PB83-163956
Mobility of Organic Compounds from

Hazardous Wastes
(U.S.) Oak Ridge National Lab., TN
Prepared for



Environmental Monitoring Systems Lab,

Las Vegas, NV
Feb 83
                  U.S. DEPARTMENT OF COMMERCE
                National Technical Information Service

                              urns

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                                                   EPA-600A-83-OOI
                                                   February 1983


                                                          P333-163956
MOBILITY OF ORGANIC COMPOUNDS FROM HAZARDOUS WASTES
                        by

   D. K. Brown, M.  P.  Maskarinec, F.  W.  Larimer,
                 and C. W. Francis
           Oak Ridge National Laboratory
            Oak Ridge, Tennessee 37830
  Interagency Agreement Numbers  EPA AD-89-F-1-058
                and DOE 40-1087-80
                  Project Officer

               Llewellyn R.  Williams
            Quality Assurance Division
    Environmental  Monitoring Systems Laboratory
              Las  Vegas, Nevada 89114
    ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
        OFFICE OF RESEARCH AND DEVELOPMENT
       U.S. ENVIRONMENTAL PROTECTION AGENCY
              LAS VEGAS, NEVADA 89114

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-600A-83-OOI
2.
4. TITLE ANO SUBTITLE
MOBILITY OF ORGANIC COMPOUNDS FROM HAZARDOUS WASTES
7 AUTHORS) D. K. Brown, M. P. Maskarinec, F. W. Larimer,
and C. W. Francis, Oak Ridge National Laboratory,
Oak Ridcre, Tennessee 37830
9. PERFORMING ORGANIZATION NAME ANO ADDRESS
Environmental Monitoring Systems Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, Nevada 89114
12. SPONSORING AGENCY NAME ANO ADO
U.S. Environmental Protect!
Office of Research and Deve
Environmental Monitoring Sy
Las Vegas, Nevada 89114
RESS
on Agency--Las Vegas, NV
lopment
stems Laboratory
3. RECIPIENT'S ACCESSION NO.
p«f 3 ]63956
S REPORT DATE"
February 1983
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
ABSD1A
11. CONTRACT/GRANT NO. Iftg fjQS .
EPA AD-89-F-1-058 and
'DOE 40-1087-80
13. TYPE OF REPORT ANO PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/07
IS. SUPPLEMENTARY NOTES
Project Officer: Llewellyn R. Williams, Quality Assurance Division, Environmental
Monitoring Systems Laboratory, Las Vegas, Nevada 89114
16 ABSTRACT
The objective of this research is to develop a second generation laboratory extraction test to model the mobility of organic and inorganic
constituents from solid wastes co-disposed with municipal waste This test should more accurately and reproduc.bly model 'eachate
production for selected organic as well as inorganic constituents, than the test procedure referred to as EP promulgated by EPA in 1 980
As a first approach the capabilities of five aqueous extraction procedures to remove organ.c compounds from 1 1 solid wastes were
evaluated The extraction procedures investigated were four batch extractions using (1) de.on.zed distilled water adjusted to PH 5 with 0 5 Ji
acetic acid, (2) deiomzed distilled water, (3) detonized distilled water with a sodium cation exchange resin (4) 0 5 fid sodium citrate, and (5)
an upward-flow column extraction using deiomzed distilled water The major conclusions relative to the effectiveness of the extraction
procedures to remove organic compounds were. (1) the column procedure extracted more organic material than any of the batch
procedures, and (2) among the batch extraction procedures, deiomzed distilled water was the most aggressive medium
The most noticeable differences between the column procedure utilized and the batch procedures were the elevated levels of moderately
volatile and the nonpolar organic compounds found in the column extracts Factors contributing to these results are (1 ) the column
procedure is a completely closed extraction permitting direct collection of volatile compounds, and (2) the column extracts were not filtered
through membrane filters which are known to sorb appreciable quantities of nonpolar compounds _._,..._
Two extracting devices (magnetically stirred and rotary extractor* for conducting the EP were also compared Extracts produced by the two
extractors showed significantly different concentrations of As. Cd, Fe. Ni. and Zn. although neither method showed a consistent pattern
The proposed reverse-phase High-Pressure Liquid Chromatography protocol to assess the bioaccu-nulation potential of solid waste
extracts was found to produce only qualitative information because of nonuniformity of detector response. However, the test does provide a
useful screening method for the detection of potentially bioaccumulative organic compounds
In addressing a secondary research objective, comparison of two isolation techniques (i e . resin adsorption technique using Amberlite
XAD-2 resin and a solvent partition technique using methylene chloride) to isolate organ.c mutagens from aqueous solutions for testing in
the Ames Salmonella mutagemcity assay was conducted Although the assay results were not affected by the type of isolation technique
used, the extract.on efficiency of the resin technique was. in general, less dependent on the specific aqueous medium than was the solvent
partition
17.
». DESCRIPTORS
KEY WORDS AND DOCUMENT ANALYSIS
b.lOENTIPIERS/OPEN ENDED TERMS

18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (Thu Report!
UNCLASSIFIED
20. SECURITY CLASS (This page)
UNCLASSIFIED

c. COSATI Field/Group

21. NO. Of PAGES
203
22. PRICE
EPA Farm 2220-1 (R«v. 4-77)    PMlviou* COITION i» OBIOUBTE
                                                       i

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                                    NOTICE


     Although the research described In this article has been funded wholly or
in part by the U.S. Environmental Protection Agency through Interagency
Agreement EPA AD-89-F-1-058 to the U.S. Department of Energy, it has not been
subjected to Agency policy review and therefore does not necessarily reflect
the views of the Agency.  Mention of trade names or commercial products does
not constitute endorsement or recommendation for use.
                                     ii

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                           TABLE OF CONTENTS
LIST OF TABLES	     v
LIST OF FIGURES	    ix

ABBREVIATIONS AND SYMBOLS 	   xii

ACKNOWLEDGMENTS 	  xiii

1.  INTRODUCTION  	     1

2.  OBJECTIVES AND RATIONALE  	     5

    2.1   TASK 1:  Evaluation of Aqueous Extraction
                   Procedures to Remove Nonpolar Organic
                   Compounds from Solid Wastes  	     5

          2.1.1  Batch 1:  Environmental Protection Agency EP .  .  .     6
          2.1.2  Batch 2:  Deionized Distilled Water Extractant  .  .     6
          2.1.3  Batch 3:  Sodium-Resin Extractant	     6
          2.1.4  Batch 4:  Citrate Buffer Extractant  	     7
          2.1.5  Column	     7
    2.2   Task 2:  A Comparison of Two Sample Preparation Protocols
                   for Performing the Ames Test on Solid Waste
                   Extracts and Wastewaters 	     8

    2.3   Task 3:  Assessment of a Magnetically Stirred
                   Extractor Relative to an EPA-Approved
                   Rotary Extractor for Conducting
                   the Extraction Procedure (EP)  	     9
    2.4   Task 4:  Evaluation of the Proposed Reverse-Phase
                   High-Pressure Liquid Chromatography (HPLC)
                   Protocol for Assessing Bioaccumulation
                   Potential of Solid Waste Extracts  	    10

3.  EXPERIMENTAL	    11
    3.1   Description of Solid Wastes	.'	    11

    3.2   Methods	    14
          3.2.1  Isolation of Organic Compounds
                 from Solid Wastes  	    14
          3.2.2  Solid Waste Extraction Procedures  	    17
          3.2.3  Filtration Study (Supplemental to Task 1)  ....    28
          3.2.4  Isolation of Organics for Mutagenicity
                 Testing - Task 2	    29
          3.2.5  Assessment of Extracting Devices  for
                 Conducting the Extraction Procedure
                 (EP) - Task 3	    32
    3.3  Methods of Analysis  	    33

          3.3.1  Inorganic Analyses 	    33
          3.3.2  Organic Analyses 	    34
          3.3.3  Mutagenicity Testing 	    36
          3.3.4  Analysis of Bioaccumulative Materials in
                 Wastes and Leachates	    37
                                   iii

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                                                                    Page

4.  RESULTS	   40
    4.1   Task 1:  An Evaluation of Aqueous Extraction
                   Procedures to Remove Nonpolar Organic
                   Compounds from Solid Wastes  	   40

          4.1.1  Inorganic Analyses of Extracts 	   40
          4.1.2  Isolation of Organic Compounds in Solid Wastes . .   46
          4.1.3  Organic Analyses of Aqueous Extraction
                 Procedure Extracts 	   52
                 4.1.3.1  Dissolved Organic Carbon Results  ....   52
                 4.1.3.2  Gas Chromatography and Gas
                          Chromatography/Mass Spectrometry  ....   61
          4.1.4  Mutagenicity Testing 	   71
          4.1.5  Filtration Study 	   84
    4.2   Task 2:  Comparison of Two Sample Preparation Protocols
                   for Performing the Ames Test on Solid Waste
                   Extracts and Wastewaters 	   90
    4.3   Task 3:  An Evaluation of the Equivalence of a
                   Magnetically Stirred Extractor Relative to an
                   EPA-Approved Rotary Extractor for Conducting
                   the Extraction Procedure (EP)	   99

    4.4   Task 4:  Evaluation of the Reverse-Phase High-Pressure
                   Liquid Chromatography Protocol for Assessing
                   the Bioaccumulation Potential of Solid Waste
                   Extracts	105
5.  CONCLUSIONS	108

    5.1   Task 1:  An Evaluation of Aqueous Extraction
                   Procedures to Remove Nonpolar Organic
                   Compounds from Solid Wastes  	  108

    5.2   Task 2:  Comparison of Two Sample Preparation
                   Protocols for Performing the Ames Test on
                   Solid Waste Extracts and Wastewaters 	  ill

    5.3   Task 3:  An Evaluation of the Equivalence of a
                   Magnetically Stirred Extractor Relative
                   to an EPA-Approved Rotary Extractor for
                   Conducting the Extraction Procedure (EP)  ....  112

    5.4   Task 4:  Evaluation of the Proposed Reverse-Phase
                   High-Pressure Liquid Chromatography (HPLC)  .
                   Protocol for Assessing Bioaccumulation
                   Potential of Solid Wastes  	  113
6.  FUTURE RESEARCH	114

7.  REFERENCES	116
APPENDIX A  Quality Assurance Project Plan  	  119

APPENDIX B  FY-1982 Workplan  	  157
                                   iv

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                            LIST OF TABLES

Table                                                               Page
 1.1   Hazardous waste definition threshold levels  	      3
 3.1   Description of waste types 	     12
 3.2   Waste characteristics  	     13
 3.3   Extraction procedures:   Identification of variable
       leaching factors 	     18
 3.4   Equipment and materials used for the extraction
       procedures	     19
 3.5   Batch 1:  Extraction Procedure (EP)  extraction data   ...     23
 3.6   Batch 2:  Water extraction data	     24
 3.7   Batch 3:  Na-resin extraction data	     25
 3.8   Batch 4:  Citrate buffer extraction  data 	     26
 3.9   Measurements of pH and  electrical  conductivity in
       column extracts after passing through XAD-2 resin   ....     27
 4.1   Selected inorganic analyses  of extracts produced
       using four extraction procedures for wastes 1-6  	     41
 4.2   Inorganic analyses of water  and extraction procedure
       (EP) extracts for wastes 7 and 8	     '42
 4.3   Inorganic analyses of extraction procedure (EP),
       water, Na-resin, and citrate buffer  extracts
       for waste 9	     43
 4.4   Inorganic analyses of extraction procedure (EP),
       water, Na-resin, and citrate buffer  extracts for
       waste 10	     44
 4.5   Inorganic analyses of extraction procedure (EP),
       water, Na-resin, and citrate buffer  extracts for
       waste 11	     45
 4.6   Comparison of Fe concentrations using four
       extraction media 	     47
 4.7   Total organics recovered:  Comparison of Soxhlet
       extraction with the sequential  extraction scheme -
       gravimetric data on solid waste, organic isolates   ....     48

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Table                                                               Page
 4.8   Organic compounds Identified In solid wastes 	    51
 4.9   Dissolved organic carbon observed In selected
       aqueous waste extracts 	    56
 4.10  Comparison of dissolved organic carbon (DOC) In
       extracts filtered through glass fiber and
       polycarbonate filters  	    58
 4.11  The relative effectiveness of five aqueous
       extraction procedures to remove organic
       compounds from solid wastes  	    63
 4.12  Relative amounts of individual  compounds in solid
       waste extracts and relative ranking of the
       extraction procedures  	    66
 4.13  Results of mutagenicity testing of waste 1 extracts  ...    72
 4.14  Results of mutagenicity testing of waste 2 extracts  ...    73
 4.15  Results of mutagenicity testing of waste 3 extracts  ...    74
 4.16  Results of mutagenicity testing of waste 4 extracts  ...    75
 4.17  Results of mutagenicity testing of waste 5 extracts  ...    76
 4.18  Results of mutagenicity testing of waste 6 extracts  ...    77
 4.19  Results of mutagenicity testing of waste 9 extracts  ...    78
 4.20  Results of mutagenicity testing of waste 10 extracts ...    79
 4.21  Results of mutagenicity testing of waste 11 extracts ...    80
 4.22  Summary of mutagenic activity of solid waste isolates:
       Aqueous extract and isolates 	    81
 4.23  Organic compounds found in column extracts, with and
       without an in-line filter  	    86
 4.24  Organic compounds remaining in  a column extract after
       using four solid/liquid separation treatments  	    87
 4.25  Organic compounds remaining in  a batch water extract
       after using four solid/liquid separation treatments  ...    89

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Table                                                               Page

 4.26  Organic compounds remaining In a standard solution
       after using four treatments for separating solid
       and liquid phases	     91

 4.27  Organic compounds remaining in a standard solution
       (agitated for 24 hours) after using four solid/liquid
       phase separation treatments  	     92

 4.28  Comparison of two recovery techniques for removing
       organic mutagens from wastewaters and solid waste
       extracts	     93

 4.29  Mutagenic activity of the positive controls
       benzo(a)pyrene and 9-amino acridine  	     96

 4.30  Mutagenic activity in organic isolates:   Comparison
       of recovery techniques using benzo(a)pyrene  	     97

 4.31  Mutagenic activity in organic isolates:   Comparison
       of recovery techniques using 9-amino acridine	     98

 4.32  Distribution of variation associated with the
       variables of agitation method, replicate extraction,
       and analytical procedure 	    103

 4.33  Mean (x) concentrations and statistical  differences
       of selected inorganics using a magnetic  stirrer
       (2 agitation rates) and a rotary extractor 	    104

 4.34  Bioaccumulation data on solid waste isolates:  Aqueous
       extracts and organic isolates  	    106

 B-l   Amount of extract needed for various analyses
       and biotests	    169

 B-2   Major equipment needs and estimated costs for
       performing a batch vs column extraction   	    171

 B-3   Description and preliminary information  relative to
       industrial wastes to be used in the study	    173
                                 vn

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                            LIST OF FIGURES
Figures                                                             Page

  3.1   Scheme for proximate analysis of solid  wastes  and
        sludges by sequential extraction 	    15

  3.2   Apparatus used for isolation  of volatiles	    16

  3.3   Column extraction apparatus  	    22

  3.4   Extraction procedures for environmental  water  samples   .  .    30

  3.5   Partition coefficients of known compounds  plotted
        against log retention times  	    38

  4.1   Chromatograms for waste 2 - Soxhlet extract (A), and
        sequential extraction extracts:   acids  (B), bases  (C),
        and neutrals (D)	    49

  4.2   Chromatograms for waste 11 -  Soxhlet extract (A) and
        sequential extraction extracts:   acids  (B), bases  (C),
        and neutrals (D)	    50

  4.3   Chromatogram of waste 2 (aged four years in a  tightly
        covered landfill):  Volatile  organic compounds  	    53

  4.4   Chromatograms of volatile organic compounds for
        waste 3 (A) and waste, 9 (B)	    54

  4.5   Dissolved organic carbon (DOC) found in water
        extracts over the 24-h extraction time	    59

  4.6   Dissolved organic carbon (DOC) found in Na-resin
        extracts over the 24-h extraction time	    60

  4.7   Chromatograms of waste 10 column extracts  -
        replicate 1 (1) and replicate 3 (2)	    65

  4.8   Chromatograms of volatile organics from waste  2
        extracts:  Citrate buffer extract (a) and  Na-resin
        extract (b)	    67

  4.9   Chromatograms of volatile organics in water extracts
        from waste 2:  Open vessel (a) versus closed
        vessel (b), and distilled-in-glass water blank  (c)  . .  .  .    69

 4.10   High and low stirrer speed values for waste 12:
        Mean and standard deviation values for  four replicate
        extractions over the 24-h extraction time	100
     Preceding page blank
                                  IX

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Figures                                                            Page
 4.11    High and low stirrer speed values for waste  13:
         Mean and standard deviation values for four  replicate
         extractions over the 24-h extraction time  	  101
 A-l     Project organization and responsibilities  	  126
 A-2     Disciplines and activity areas  	  137
 A-3     The research data management components  	  140
 A-4     Sample and processing analysis  	  141
 A-5     Corrective action plan	149
 A-6     Quality assurance program organization chart  	  151
 A-7     Analytical Chemistry Division QA assessment  schedule   .  .  152
 B-l     Schematic of lysimeter containing residential
         and commercial  wastes 	  179
 B-2     Flow diagram for lysimeter study  	  180

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               ABBREVIATIONS AND SYMBOLS

AAS     Atomic Absorption Spectroscopy
BaP     Benzo(a)pyrene
DDE     2,2-bis-(p-chlorophenyl)-l, 1-dichloroethylene
DMSO    Dimethyl sulfoxide
DOC     Dissolved organic carbon
EP      Extraction Procedure (40 CFR 261.24)
EPA     U.S. Environmental Protection Agency
GC      Gas Chromatography
GC/MS   Gas Chromatography/Mass Spectrometry
HPLC    High-Pressure Liquid Chromatography
K-D     Kuderna-Danish
MeClp   Methylene chloride
NEIC    National Enforcement Investigations Center
NIPDWS  National Interim Primary Drinking Water Standards
ORNL    Oak Ridge National Laboratory
PTFE    Polytetrafluoroethylene
Pa      Pascals
RCRA    Resource Conservation and Recovery Act
rpm     Revolutions per minute
S       Siemens
TCO     Total Chromatographable Organic Compounds
                           xi

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                            ACKNOWLEDGMENTS

    The authors wish to acknowledge the technical  assistance of
J. W. Gooch (Environmental Sciences Division),  R.  W.  Harvey (Analytical
Chemistry Division), and S. Severs (SCUU Science Semester
participant).   Appreciation is also expressed to N. M.  Ferguson
(Analytical Chemistry Division), J. C. Goyert,  and R. H.  Strand
(Environmental Sciences Division) for their research  contributions,  as
well as to M.  R. Guerin (Analytical Chemistry .Division),  S. E.  Herbes,
and T. Tamura (Environmental Sciences Division) for their helpful
suggestions for improvement of this report. A  special  thanks goes to
L. W. Littleton, D. D. Rhew, and others in the  Environmental  Sciences
Division Word Processing Center for their assistance  in preparing  this
report.  Finally, the helpful suggestions and assistance  during the
course of this project from the following individuals are greatly
appreciated:  L. R. Williams of EPA, Environmental Monitoring Systems
Laboratory, Las Vegas, Nevada; and D. Friedman  and T. A.  Kimmell of
EPA, Office of Solid Waste, Washington, D. C.
                                  xii

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                        SECTION 1:   INTRODUCTION

     The disposal of municipal and industrial waste in landfills is a
widely used waste management practice in the United States.  It has
become evident during the past few years that there has been serious
environmental damage and possible adverse human health effects because
of improper disposal of hazardous waste in landfills.   Under the
Resource Conservation and Recovery Act (RCRA) of 1976  (PL94-580),
Congress directed the Environmental Protection Agency  (EPA) to
promulgate regulations to protect human health and the environment from
improper management of solid wastes.
     Under Section 3001 of RCRA, Identification and Listing of
Hazardous Waste, EPA is charged with identifying which industrial
wastes pose a hazard to human health or the environment if these wastes
are improperly managed.  On May 19, 1980 (EPA 1980b),  EPA promulgated
regulations that identified a number of properties of  hazardous waste,
which, if exhibited by a waste, would indicate that the waste requires
controlled management.  Under these regulations,  toxicity of wastes is
determined by the Extraction Procedure Toxicity Characteristic
(40 CFR 261.24) which employs an Extraction Procedure  (EP) to predict
the degree to which toxic species might leach out of the waste and
contaminate groundwater if the waste was disposed of in a nonsecure
municipal landfill.  The EP is a 24-h extraction  procedure using 0.5  N^
acetic acid to adjust downward, if possible,  the  pH of the solid waste
suspension to pH 5.0 (EPA 1980d).  Additional  information with regard
to the development of the EP can be found in  the  EP Toxicity
Characteristic Background Document (EPA 1980a).

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     The EP results in an extract that is analyzed  for the  eight metals
(As, Ba, Cd, Cr Pb, Hg, Se, and Ag),  four pesticides  (Endrin,  Lindane,
Methoxychlor, and Toxaphene), and two herbicides  [2,4-D and 2,4,5-TP
(Si 1 vex)] for which National Interim  Primary Drinking Water Standards
(NIPDWS) (EPA 1979a) have been established.   Hazardous waste definition
threshold levels (Table 1.1) have been established  for each of the
species taking into account attenuative processes expected  to  occur
during the movement of leachate through the  underlying strata  and
groundwater aquifer.
     The EP is considered to be a first-order approximation which
primarily models the leaching action  of the  low molecular weight
carboxylic acids generated in an actively decomposing municipal  waste
landfill.  Acetic acid is added to distilled water  to make  up  the
extracting medium used in the EP.  The acetic acid  primarily affects
the leaching of metals from an industrial  waste.  The higher molecular
weight organics that are expected to  be present in  municipal landfill
leachates, and thought to affect the  Teachability of  nonpolar  organics,
are not currently modeled by the EP.   This perceived  limitation is  the
impetus behind the current research.
     The primary objective of this research  is to develop a second
generation test for mobility that will  more  accurately and  reproducibly
model leachate production, for organic as well as inorganic
constituents, in the previously described disposal  environment.   A
second important objective of this research  program is that the mobility
test developed be compatible with subsequent biological  testing.

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    TABLE  1.1.   HAZARDOUS WASTE DEFINITION THRESHOLD LEVELS*
Contaminant
Arsenic
Barium
Cadmium
Chromium (IV)
Lead
Mercury
Selenium
Silver
Maximum
concentration (mg/L)
5.00
100.00
1.00
5.00
5.00
0.20
1.00
5.00
Endrin (1,2,3,4,10,10-hexachloro-l ,
  7-epoxy-l ,4,4a,5,6,7,8,
  8a-octahydro-l ,  4-endo,  endo-5,
  8-dimethano naphthalene)                                 0.020

Lindane (l»2,3,4,5,6-hexachlorocyclohexane,
  gamma isomer)                                           0.40

Methoxychlor (l,l,l-trichloro-2,2-bis
  [p-methoxyphenyl] ethane)                               10.00
Toxaphene (CioHioCls* technical
  chlorinated camphene, 67-69% chlorine)                   0.50

2,4-0, (2, 4-0 ichlorophenoxy acetic  acid)                   10.00

2,4,5-TP; Silvex (2,4,5-Trichlorophenoxypropionic
  acid)                                                   1.00
Source:  40 CFR 261.24

Concentrations are 100 times the NIPDWS values.

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     Work toward these objectives has centered in four separate but
related tasks as follows:
     Task 1:  An evaluation of aqueous extraction procedures  to remove
              nonpolar organic compounds from solid  wastes.
     Task 2:  A comparison of two sample preparation protocols  for
              performing the Ames Test on solid  waste extracts  and
              wastewaters.
     Task 3:  An evaluation of the equivalence of a  magnetically
              stirred extractor relative to  an EPA-approved rotary
              extractor for conducting the EP.
     Task 4:  Evaluation of the proposed reverse-phase High Pressure
              Liquid Chromatography (HPLC) protocol  for assessing  the
              bioaccumulation potential  of solid waste extracts.

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                 SECTION 2:  OBJECTIVES AND RATIONALE

2.1  Task 1:   An Evaluation of Aqueous Extraction Procedures to Remove
              Nonpolar Organic Compounds from Solid Wastes
     The primary objective of Task 1  was to assess the capabilities  of
five selected aqueous extraction procedures to remove organic compounds
from 11 solid wastes known to contain significant quantities of organic
compounds.  Other objectives included (1) analyzing the solid waste
extracts for selected inorganic constituents known to be present in  the
samples and (2) mutagenicity-testing of the extracts.  Mutagenicity
testing was included to evaluate any differences in aggressiveness
toward organic compounds among extraction procedures that might not  be
detected by 6C/MS analyses; for example, the ability of an extraction
procedure to extract high molecular weight mutagens from solid wastes.
     A desirable, relevant extraction procedure should accurately and
reliably model leachate production in the landfill situation, be
relatively simple and economical to perform,  and yield an extract that
can be applied to biological assays.   The five extraction procedures
selected for this study were four batch extractions and an upward flow
column extraction.   The following extractants were used:
     Batch 1:   Deionized distilled water adjusted to pH 5 with
               0.5  N acetic acid (EP).
     Batch 2:   Deionized distilled water.
     Batch 3:   Deionized distilled water with a sodium cation exchange
               resin.

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     Batch 4:  0.5 M soc.ium citrate buffer.
     Column:   Deionized distilled water.
A rationale for each procedure follows.

2.1.1  Batch 1:  Environmental Protection  Agency EP
     The EP (EPA 1980b) is the test procedure promulgated by EPA under
RCRA to determine if an unacceptably high  level  of groundwater
contamination might result if an industrial  waste is disposed of in a
municipal landfill.  The high ionic strength of  the extracting solution
and/or the method of membrane filtering the  aqueous extract limits the
recovery of organic compounds from a solid waste extract.  The acetic
acid used in the EP may also confound the  interpretation of the
phytotoxicity and aquatic toxicity assays  (Epler et al.  1980).

2.1.2  Batch 2:  Deionized Distilled Water Extractant
     Deionized distilled water, because it introduces no extraneous
interferences, is a reliable extractant to evaluate the  toxicity of
solid waste extracts in phytotoxicity and  aquatic toxicity assays.   In
addition, distilled water at relatively high liquidisolid ratios tends
to solubilize organics from solid wastes more efficiently than other
aqueous extractants (McKown et al. 1980).  For example,  solutions
containing citrate and acetate salts at high concentrations can enhance
flocculation over dispersion.

2.1.3  Batch 3:  Sodium-Resin Extractant
     The solubility of organic compounds in  groundwater  is largely
dependent on the "hardness" or "softness"  of the water.   Medium- and
long-chain organic acids are solubilized when the "hard" calcium

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(or iron) is replaced by "soft" sodium.   This  is the basic  principle in
the extraction of fulvic and humic acids from  soils by soil  scientists
(Schnitzer and Kahn 1972) (i.e., create  a dispersed condition  by
substituting Na+ for the dominant Ca+ and Fe    ions).   Conventionally,
this is accomplished using 0.1 J4 NaOH.  However, the high pH (11-12)
does not represent environmental conditions.   A sodium saturated
chelating resin, added to a suspension displaces the dominant  cations
with sodium without significantly changing the pH of the suspension.
The organic compounds are dispersed from the solid matrices, in effect
solubilizing them in an aqueous environment.
2.1.4  Batch 4:  Citrate Buffer Extractant
     For certain solid wastes citrate buffer (0.5 M sodium  citrate) was
observed to be more aggressive than acetate or distilled water in
leaching both organic compounds and metals; however,  distilled water
was the overall leaching medium of choice (McKown et al. 1980).  The
citrate butter was included because of an existing data base with
citrate, the structural similiarity of citrate to other carboxylic acid
esters present in municipal waste leachates, and the known  capacity of
citrate for complexing metals.
2.1.5  Column
     An upward flow column extraction procedure was developed  as a
possible alternative to a batch extraction.  Deionized  distilled water
is pumped upward through solid wastes packed in a glass column.
Nonpolar organic compounds are collected directly on  XAD-2  resin in

-------
series with the solid waste column; polar organic compounds  remain  in
the eluent.  Advantages of this system include:
     (1)  no time-consuming filtration step is needed,
     (2)  the extraction system is completely closed  until the  organic
          compounds are collected, thus loss of volatiles will  be
          minimized,
     (3)  concentration of organic compounds is possible,
     (4)  column extraction of solid wastes more closely simulates  the
          physical landfill leaching process, and
     (5)  column give dynamic data.

2.2  Task 2:  A Comparison of Two Sample Preparation  Protocols  for
              Performing the Ames Test on Solid Waste Extracts  and
              Wastewaters
     The objective of this work was to compare two techniques for
isolating organic mutagens from solid waste leachates and wastewaters
for testing in the Ames Salmonella mutagenicity assay (Epler et al.
1980).  The two recovery techniques compared were a resin adsorption
technique using Amberlite XAD-2 resin and a solvent partition technique
using methylene chloride.  The XAD-2 resin technique  has been used
extensively at the Oak Ridge National Laboratory (ORNL) (Epler  et al.
1980) and at EPA's Health Effects Research Laboratory at Research
Triangle Park, North Carolina, while the solvent partition scheme is
the one recently developed by the National  Enforcement Investigations
Center (NEIC), Denver, Colorado (EPA 1980c).  The objective  of  this
task was to determine if significant differences were obtained  in the
Ames Salmonella mutagenicity assay when using either  of the  two
preparation protocols.

-------
2.3  Task 3:  Assessment of a Magnetically Stirred Extractor Relative
              to an EPA-Approved Rotary Extractor for Conducting the
              Extraction Procedure (EP)
     The objective of this task was to compare a magnetically stirred
extractor to an EPA-approved rotary extractor for conducting the EP.
An acceptable extractor to conduct the EP was described in "Test
Methods for Evaluating Solid Hastes - Physical/Chemical Methods"
(EPA 1980) as "...one which will prevent stratification of a waste
sample and extraction fluid and will  insure that all  sample surfaces
continuously contact well mixed extraction fluid.  Among 'the acceptable
extractors are:  (1) stirrers and (2) tumblers.   Stirrers  consist of a
container in which the waste/extraction fluid mixture is agitated by
spinning blades.  Rotators agitate by turning a  sample container end
over end through a 360° revolution."
     The magnetically stirred extractor consists of a glass vessel  and
polytetrafluoroethylene (PTFE)-coated stirring bar in concert with a
commercially available magnetic stirrer readily  available  in most
laboratories.  This design appeared to satisfy all of the  above
requirements.  The magnetically stirred extractor offers certain
advantages in that, in contrast to the rotary extractor design, the pH
of the suspension can be automatically adjusted.  In  addition,  the
glass vessel and PTFE-coated magnetic stir bar eliminates  the
possibility of contamination by the spinning stainless steel  blades
used in several of the EP extractor designs.

-------
2.4  Task 4;  Evaluation of the Proposed  Reverse-Phase  High-Pressure
              Liquid Chromatography (HPLC)  Protocol  for Assessing
              Bioaccumulation Potential of  Solid Waste  Extracts
     The objective of this task was to evaluate the  analytical
constraints and interpretations associated  with using the  proposed
reverse-phase High-Pressure Liquid Chromatography  (HPLC) protocol
(EPA 1978a and EPA 19785) to assess the bioaccumulation potential of
solid waste extracts.  It has been shown  that  there  is  a relationship
between octanol/water partition coefficients and bioaccumulation
potential (i.e., compounds with high octanol/water partition
coefficients have the potential to biologically accumulate) and between
octanol/water partition coefficients and  the log of  reverse-phase HPLC
retention times.  Plotting the log of reverse-phase  HPLC retention
times of solid waste extracts (from Task  1) against  the log of the
octanol/water partition coefficients of known  compounds should provide
a method to estimate the potential for the  components in the  solid
waste extracts to accumulate in biological  tissues.
                                   10

-------
                       SECTION 3:  EXPERIMENTAL
                   3.1  Description of Solid Wastes

     Eleven solid wastes from a variety of industries were obtained  for
use in Task 1.  The particular wastes were selected because they were
thought to contain toxic organic compounds.  Table 3.1  contains  a short
description of the wastes used for Task 1  and other studies.   Wastes  1
through 6 were taken from actual  landfills.  Corresponding landfill
leachates were also sampled in a related study comparing  the solid
waste EP extracts with the landfill leachates (Brown et al. 1981).
Waste samples 7 through 11 are oily in nature and  were  selected  based
on a prediction that this oily component would challenge  the extraction
procedures.  Wastes 7 and 8 changed physically (i.e., the oily
components separated from the remainder of the sample)  during the
course of the study.   For this reason, not all  extractions were
performed on these wastes.
     Two additional waste samples (12 and 13) were selected for  use  in
Task 3.  Both were selected because they contained Teachable  inorganic
elements and were expected to pose stirring problems with the magnetic
stirrer.  An additional waste (14) was utilized for the supplementary
filtration study in Task 1.
     General sample information,  such as water content  and general
physical description  of wastes 1  to 14,  is presented in Table 3.2.
Water content was determined by gas chromatography as described  by
Shultz and Spears (1966).
                                  11

-------
                   TABLE 3.1.  DESCRIPTION OF  WASTES
  Waste                         Waste description
Used for Task 1:
   1        Sludge from the production  of feed  additives  and  veterinary
            Pharmaceuticals
   2        Sludge from the treatment of a municipal  sewage,  a  cannery
            waste, and tannery wastes
   3        Paper mill sludge
   4        Municipal refuse and local  industrial waste (plastic
            laminate and electronics  waste)
   5        Paper mill, paper trimmings, and related  wastes
   6        Municipal wastewater treatment sludge mixed with  local
            industrial waste (plastic and textile mill)
   7        Wastewater treatment sludge from a  metal  processing plant
   8        Untreated washing sludge  from a metal bearing factory
   9        Wastewater treatment sludge from a  coal conversion plant
  10        Filter cake from a coal conversion  biological treatment
            plant
  11        Centrifuged heavy oil  residuals from a coal conversion
            wastewater treatment plant
Used for Task 3:
  12        Ash  from a coal conversion  facility
  13        Fly  ash from a coal-fired power plant
Used for Filtration Study:
  14        Vacuum bottoms from a coal  conversion facility
                                  12

-------
                   TABLE 3.2.   WASTE CHARACTERISTICS
Waste
  Water
 content3
(weight %)
       Waste characteristics
   1

   2
   33

   55


   56
Yellowish green, dark;  pasty texture

Dark grey sludge containing hair,  hide,
etc.; strong odor

Dark brown, nearly opaque, sandy sludge;
noticeable aroma
4
5
6
7
8
9
10
11
12
13
14
77
62
60
ndb
nd
50
41
59
nd
nd
<1.0
Sawdust-like texture; yellow-orange
Like flaked cardboard; dark purple
Very dark gray, clay-like consistency;
strong odor
Watery, dark brown; slightly aromatic
Dark brown, thick, oily liquid; oily odor
Black, oily sludge; rubbery consistency
Charcoal gray, sandy, and granular;
irritating odor
Black, oily sludge; irritating odor
Hard granular solid containing Cd, Fe,
and Ni .
Fine solid, high in magnetite, contains
As, Cd, and Zn
Dark -colored dry powdery solid.
 As determined by the method of Shultz and Spears  (1966).

3nd = not determined.
                                   13

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     Many of the wastes, because they cjntained  significant quantities
of organic compounds, had the potential  to change during  the course of
the study due to biological activity.  To slow down  such  changes,  each
waste was thoroughly mixed and subsampled into 200-  to  500-g
quantities.  The subsamples were placed in glass containers and  frozen
at -15°C.  Samples were thawed in the refrigerator (4°C)  the day prior
to extraction.

                             3.2  Methods

3.2.1  Isolation of Organic Compounds in Solid Wastes
     Identification of the major organic constituents from  the wastes
was carried out using the following  two procedures:
     (1)  Twenty-four-hour Soxhlet extraction  with methylene chloride,
          followed by volume reduction in a Kuderna-Danish  (K-0)
          evaporator (EPA 1980d).
     (2)  A three-step sequential extraction procedure  developed at
          ORNL (Fig. 3.1; Maskarinec and Harvey  1982).
The isolates from procedures (1) and (2) were  compared  by gravimetry as
well as by gas chromatography.
     Volatile organic compounds were determined  in selected wastes
using the apparatus shown in Fig. 3.2.  This apparatus  is a simple
modification of the existing purge and trap devices  that  allows  the
purging of solid materials without dissolution in water (Brazell and
Maskarinec 1981).
                                  14

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                                                               ORNL DWG 81  20042R ESD
                      VOLUME REDUCED
                      TO 10 mL IK D)
VOLUME REDUCED TO 10 mL (K D)     ACID
                                                          REDUCED TO 100 mL (K D)
Fig. 3.1.   Scheme for proximate analysis of  solid wastes and sludges by
            sequential extraction.
                                      15

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                                ORNL-OWG 81-6937
            TENAX
           HEAT
        SHRINKABLE,
          TEFLON
           HEAT
        SHRINKABLE
          TEFLON
      GLASS WOOL
   OR SINTERED FRIT
GLASS WOOL
                                     CONDENSER
Fig.  3.2.  Apparatus used  for  isolation of volatiles.
                        16

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3.2.2  Solid Waste Extraction Procedures
     In this study, five aqueous extraction procedures were evaluated
and compared for ability to extract both Inorganic and organic
components.  Table 3.3 contains a listing of the five extraction
procedures, with a compilation of variable leaching factors.   Table  3.4
contains a listing of equipment and materials used for the five
extraction methods.  All extractions were carried out to  a liquid  to
solid ratio of 20:1.
     The EP was performed according to the current regulatory protocol
(EPA 1980d), using 185 g of wastes.  Wastes were placed in borosilicate
glass vessels with 2.96 L of deionized distilled water (ASTM, Type I
Reagent Water).  The vessel was fabricated at ORNL from 6.35-mm-thick,
152.4-cm-i.d. (inside diameter) flanged glass pipe that could hold up
to 4.0 L of solution.  A fitted vessel  cover was constructed  of
plexiglass, with holes cut in it to admit a pH electrode  and  tubing
(for adding acid).  The solid waste suspensions were agitated for  24 h
using a magnetic stirrer and 76.2-mm PTFE-coated stir bar.  During the
24-h extraction, the pH of the solution was automatically adjusted to
pH 5 using 0.5 N acetic acid.  A maximum amount of 4 ml of acid per
gram of waste extracted is specified in the protocol.   If less than  the
maximum amount of acid was used during extraction, the extract was
diluted with deionized distilled water to a final  1:20 solid:liquid
ratio prior to filtering.
     The water extractions were performed as in the EP with the
exception that 3.7 L of deionized distilled water (ASTM,  Type I  Reagent
Water) were initially added to 185 g of waste (1:20 solid:liquid
ratio).  There was no pH adjustment during extraction.
                                  17

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                               TABLE 3.3.  EXTRACTION PROCEDURES:  IDENTIFICATION OF VARIABLE LEACHING FACTORS
oo
                                                                       Variable factors3
Extraction
1. Batch 1: EP
Initial
leaching medium
Deionized distilled
waterb
Mode of
extraction
Batch:
magnetically
stirred
PH
adjustment
Adjust to pH 5
with 0.5 N
acetic acid -
maximum limit of
2-meq/g sample
Treatment of leachate solution
for extract analysis
Pressure-filtered through
0.4-um Nuclepore filter
              2. Batch 2:  Water  Deionized distilled
                                  waterb
              3. Batch 3:         Deionized distilled
                 Na-resln         water0 with 1-g
                                  calculated dry wt
                                  Chelex 100/10-g
                                  sample

              4. Batch 4:         0.5 M citrate buffer
                 Citrate buffer
              5. Up-flow column   Deionized distilled
                                  water0
Batch:
magnetically
stirred

Batch:
magnetically
stirred
Batch:
rotary
extractor

Column:
upward flow
None
Pressure-filtered through
0.4-um Nuclepore filter
Adjust to pH 7    Pressure-filtered through
with 0.1 N HC1    0.4-um Nuclepore filter
None
None
Pressure-filtered through
0.4-um Nuclepore filter
Leachate from column directly
passed through XAO-2 resin
              aFactors such as particle size (<9.5 mm), extraction at room temperature,  extraction time (24 h for
               batch extractions or until an effect 1:20 solid:liquid ratio contact is reached for column extraction),
               one extraction on each waste, and effective 1:20 solid:liquid ratio remained constant.

              °ASTM, Type I Reagent Water.

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        TABLE 3.4.  EQUIPMENT AND MATERIALS USED FOR THE EXTRACTION PROCEDURES
Item
Manufacture or supplier3
Catalog Number
Magnetic stlrrer
Teflon stir bar
pH controller
pH electrode
Filtration apparatus
Filters       0.40-Qn pore size
              0.8-Qn pore size
              3.0-Qn pore size
Pre-filters   P40
              P80
              P100
              P300
Drain disc
Rotary extractor
Glass column
Pump
Sea sand, sieve distribution:
  20 to 35 mesh - 8X;
  36 to 50 mesh - SIX;
  51 to 60 mesh - 18%;
  61 to 70 mesh - 7%;
  71 to 100 mesh - 13%;
  and  100 mesh - 3X.
  Cole-Partner                            C-4817-00
  Cole-Panner                            C-4612-30
  Chemtrix                               45AR
  Leeds & Northrop                       117493
  Mil 11pore Corp.                        YT30-142-HU
  Nuclepore Corp.                        112207
  Nuclepore Corp.                        112209
  Nuclepore Corp.                        112212
  Nuclepore Corp.                        211703
  Nuclepore Corp.                        211705
  Nuclepore Corp.                        211707
  Nuclepore Corp.                        211708
  Nuclepore Corp.                        231700
  Associated Design & Mfg.  Co.            3740-6-BRE
  Glenco Scientific                      3400-D-25X45
  Lab.  Data Control, Div. of  Milton  Roy  2396-57
  Fisher Scientific                      S-25
aUse of a specific manufacturer or supplier  does  not  imply the endorsement by either
 Oak Ridge National Laboratory or  the  U.S. Environmental Protection Agency.
                                        19

-------
     The sodium resin displacement extraction was  also  performed  in  the
same manner as the EP.  Initially, 2.96 L  of deionized  distilled  water
(ASTM, Type I Reagent Water) and 92.5 g of Chelex  100 resin  (Bio  Rad
Laboratories, 100-200 mesh,  sodium form) was added to 185  g  of  sample.
The suspension was adjusted  to pH 7 using  0.1 N. HC1.  This pH
adjustment was performed to  make the final  extract more suitable  for
phytotoxicity and aquatic toxicity bioassays.   The final extract  was
also diluted to a final  1:20 solid:liquid  ratio prior to filtration.
     The citrate buffer extractions were performed according to the
procedure of McKown et al. (1980).  This procedure specified the  use of
a rotary extractor which tumbles solid waste suspensions end-over-end
in closed glass containers.   A 75-g sample was  placed in the glass
container with 1.5 L of 0.5  M citrate buffer.   The tumbling  rate  was
29 rpm.
     Following a 24-h extraction using the above-mentioned batch
procedures, the component solid and liquid phases were  separated  by
pressure filtration at 5.2 X 105 Pa (75 psi), and the final  extract
was passed through a 0.4-um  polycarbonate  filter (Nuclepore).   In
most cases, a series of filters having decreasing pore  sizes was  needed
in the filter stack.  Even though the filter stack was  changed, as
deemed necessary, some suspensions took considerable time  to filter
(as much as 1-2 days).
     For column extraction,  100 g of solid waste was thoroughly mixed
with 100 g of acid-washed sea sand to increase  the hydraulic
conductivity of the samples.  A glass column 2.5 cm i.d. and 45 cm long
(with plungers on each end adjustable to the varying bulk  density of
                                  20

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the samples) was packed with the solid waste/sand mixture.   A 2.5-cm
layer of sand was placed on each end of the column.   Figure  3.3
schematically shows the column extraction apparatus.   For this study,
deionized distilled water (ASTM, Type I Reagent Water,  passed through
XAD-2 resin to remove trace organic material)  was pumped upward  through
the solid waste/sand mixture until  2 L had passed through the sample.
A relief valve, set at 5.1 x 105 Pa (60 psi) was used to avoid unsafe
stresses on the glass column.  The  column effluent was  passed through  a
10-um pore size PTFE cloth (located on the top plunger) and  then
directly through an XAD-2 resin cartridge (16.8 ml) for collection  of
organic compounds.
     The pH, amount of acid added during extraction  (for extractions
requiring pH adjustment), and electrical  conductivity were recorded on
the 11 samples during each of the five extraction procedures
(Tables 3.5-3.9).  Solution pH is an important factor when considering
dissolution/precipitation and sorption reactions that may be occurring
during extraction.  These data are  provided as accessory information on
the wastes (e.g., the solid waste's buffering  capacity).
     Following extraction, all samples were stored and  preserved
according to the desired analysis as follows:
     (1)  organic compounds - stored in glass  containers and
          refrigerated at 4°C,
     (2)  Hg analysis - placed in glass volumetric flask with
          dichromate/nitric acid preservative,
                                  21

-------
                                          ORNL-DWG 81-13761AESO
           RELIEF
           VALVE
           (60 psi)
                                                     RESIN FOR
                                                     COLLECTION
                                                     OF ORGANIC
                                                     COMPOUNDS
       POSITIVE
       DISPLACEMENT
       PISTON PUMP
XAD-2 RESIN
    CLEANUP)
                    EXTRACT
H20
            Fig.  3.3.  Column  extraction apparatus.
                             22

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                                                              TABLE I.S.  BATCH  1:  EP EXTRACTION DATA
ro
LO
Initial
solution
pH (1:16
Replication solld:solution
Waste Number ratio)
1 8.
2 1 7.
2 7.
3 7.
4 7.
5 7.
6 S.
7b
8 6.
9 7.
10 1 12.
2 12.
3 11.
7
5
1
1
5
4
3

5
0
0
0
6
11 5.6
Acetic
acid initially
added
(meq/g
sample)
2.
0.
0.
2.
0.
0.
0.

0.
0.
2.
2.
2.
Oa
65
54
Oa
03
04
02

36
23
0"
Oa
Oa
0.02
Total
acetic acid
added
(meq/g
sample)
2.
0.
0.
2.
0.
0.
0.

0.
0.
2.
2.
2.
o«
79
68
Oa
07
11
12

38
38
0"
Oa
0*
0.03


PH
6.
5.
5.
6.
4.
4.
5.

5.
5.
12.
11.
12.
1
0
0
0
8
7
0

1
1
0
9
2
5.2

Electrical
conductivity
(uS/cm)
2750
2440
2150
3300
498
150
100

2750
418
6575
7600
7550
85
Final EP extract

Color
Transparent.
Translucent,

Transparent,
Transparent,
Transparent,
Transparent,

Transparent,
Transparent,
Transparent,
Transparent,
Transparent,
Transparent,
dark yellow
colorless

yellow-grey
pale yellow
colorless
yellow

green tint
colorless
pale yellow
pale yellow
pale yellow
pale yellow tint
               aMaximuin amount  allowed  (4 ml  acid/g sample).


               bNot  extracted.

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TABLE 3.6.   BATCH 2:   MATER  EXTRACTION DATA
Waste
1
2
3
4
5
6
7
8
9
10
11
Initial
solution
pH
8.
8.
6.
7.
6.
6.
6.
8.
7.
11.
5.
8
0
6
8
8
3
1
1
5
7
9
Final
solution
pH (before
filtering
8
7
7
7
7
6
6
8
6
12
5
.8
.8
.1
.0
.0
.4
.6
.8
.3
.4
.8
1
i
8
8
7
6
7
6
6
8
6
12
6

PH
.8
.0
.0
.8
.4
.7
.0
.2
.5
.0
.0
Final
Electrical
conductivity
(uS/crn)
2000
1620
820
410
252
1500
121
150
307
6620
69
filtered extract

Color
Transparent,
Transparent,
Opaque, tan
Transparent,
Transparent,
yellow-orange
yellow-green

pink
pink
Opaque, yellow-brown
Transparent,
Transparent,
Transparent,
Transparent,
Transparent,
colorless
pale-gold
colorless
gold
pale yellow
                   24

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                                                             TABLE 3.7.  BATCH 3:  Na-RESIN  EXTRACTION DATA
INJ
in
Waste
1
2
3
4
5
6
7
8
9
10
11
Blank
Initial
solution
PH
8
8
6
7
7
5
6
7
7
11
5
4
.3
.2
.9
.4
.6
.3
.1
.3
.5
.4
.8
.8
Solution pH
after
resin addition
7
7
7
7
8
5
7
8
7
11
6
9
.0
.8
.5
.9
.1
.9
.8
.3
.8
.5
.3
.5
Amount of
HC1 added to
adjust solution
to pH 7
(meq/g sample)
n
0
0
0
.0
.006
.072
.014
0.028
0
.0
0.027
0
0
0
0
0
.032
.009
.4
.028
.022
Final
pH
(before
filterim
6.8
7.1
7.1
7.1
7.2
5.9
7.0
7.1
6.5
12.4
7.0
7.15
Final filtered extract
I) PH
7.0
7.4
7.5
7.2
7.7
6.4
7.2
7.4
7.2
12.1
7.2
7.0
Electrical
conductivity
(uS/cm) Color
2700
2125
1160
428
425
782
460
345
450
7750
450
165
Transparent,
Transparent,
Translucent,
Transparent,
Transparent,
Translucent.
Transparent,
Transparent,
Transparent,
Transparent,
Transparent,
Transparent,
yellow-orange
colorless
gold
apple cider colored
pale orange
pale yellow
tan
tan
black tint
pale gold
pale yellow
colorless

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         TABLE 3.8.  BATCH 4:  CITRATE BUFFER EXTRACTION DATA
Waste
1
2
3
4
5
6
7a
8
9
10
11
Final pH
filtered
extract
4.5
7.2
8.0
5.1
5.4
5.4

5.0
5.1
12.3
5.3
Electrical
conductivity
(uS/cm)
7555
7600
5300
5200
5800
6100

5800
5850
10800
ndb
Color
Transparent, yellow
Transparent, pale yellow
Opaque, dark brown/black
Transparent, yellow
Transparent, pale orange
Transparent, yellow

Transparent, pale gold
Transparent, pale yellow
Transparent, amber
Transparent, apple cider colored
"Not extracted.
3nd = not determined.
                                  26

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  TABLE  3.9.  MEASUREMENTS OF pH AND
  ELECTRICAL CONDUCTIVITY IN COLUMN
       EXTRACTS AFTER PASSING
         THROUGH XAD-2 RESIN
Electricity
conductivity
Waste Replication pH (uS/cm)
1
2
3
4
5
6
9
10

1
2

1
2



1
2
3
7.9
7.6
7.2
6.9
7.8
6.4
6.8
6.5
7.4
12.1
10.8
10.5
1999
1500
910
1175
741
560
388
1025
550
6150
4900
2460
11                    5.2           20
                  27

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     (3)  all other metals - placed In plastic containers,  preserved
          with Ultrex nitric acid (solution  pH < 2)  and refrigerated
          at 4°C (EPA 1979b), and
     (4)  volatile organic compounds - stored in 25-mL glass bottles
          with no head space at  4°C.
3.2.3  Filtration Study (Supplemental  to Task 1)
     A filtration study was conducted  to determine if decreased levels
of organic compounds measured in the batch extract resulted from
sorption of nonpolar organic compounds during filtration through  a
0.4-urn nominal pore size membrane filters.   As described earlier, the
column extracts were passed through a  10-ym  pore size PTFE  cloth  at
the top of the column before the collection  of organics on  an XAD-2
resin.  The two objectives of the filtration study were to  determine if
the XAD-2 resin had collected entrained organic particulates (less than
10 urn) from the column that might be filtered out if filtered through
a 0.4-um membrane filter and to  examine the  recovery of organic
compounds in four solid/liquid phase separation treatments.  The  four
separation treatments were:
     (1)  filtration through a precombusted  glass fiber filter  (Whatman
          GF/F, approximately 0.7-um pore size),
     (2)  filtration through a Nuclepore filter  (polycarbonate,
          0.4-um pore size),
     (3)  filtration through a Millipore filter  (type HA -  mixed  esters
          of cellulose, 0.4-um pore size), and
     (4)  centrifugation (in 250-nt glass bottles, 400 times gravity
          for 1 h).
                                  28

-------
     Using 100-g samples of waste 14,  four extractions were conducted
as follows with deionized distilled water as the extractant:
     (1)  column extraction performed as described in Section 3.2.2
          (i.e., extract from the column passed directly  through  a
          16.8-mL XAD-2 resin cartridge),
     (2)  column extraction performed  like (1)  above, except  a glasc
          fiber filter was placed in line prior to the effluent passing
          through the XAD-2 resin cartridge,
     (3)  column extraction performed  like (1)  above with the effluent
          subjected to the above listed four solid/liquid phase
          separation treatments, and
     (4)  batch extraction was performed on the rotary extractor; the
          suspension then subjected to the four solid/liquid  phase
          separation treatments.
     In addition, 4 L of a standard solution were prepared with known
organic compounds at concentrations of 10 ppm.   Two liters of this
solution were then immediately subjected to the same four separation
treatments.  The remaining 2 L of this standard solution  from above
were agitated for 24 h with the rotary extractor.  The solution was
then subjected to the four solid/liquid phase separation  treatments.

3.2.4  Isolation of Organics for Mutagenicity Testing - Task  2
     Two recovery techniques (Fig. 3.4), a resin adsorption technique
(Epler et al. 1980) using Amberlite XAD-2 resin (resin cartridges as
used in Task 1) and a solvent partition technique using methylene
chloride (EPA 1980c), were compared for the isolation of  organic
mutagens from aqueous solutions.  Two  known mutagens were used as
                                  29

-------
                                                                  ORNL-OWG 81 20041 ESO
                            LITER SAMPLE
                      DIVIDE INTO 2 EQUAL PORTIONS
                       BASE NEUTRAL EXTRACTION
                           ADJUST TO pH 12
EXTRACT EACH ALIQUOT WITH SO. 30 AND 30 mL MeCL,
OR PASS THROUGH XAD 2 COLUMN
1
AQUEOUS PHASE
I
ACID EXTRACTION
ADJUST TO QH 2
EXTRACT EACH ALIQUOT WITH
100. 60. AND 60 mL MeCI, OR
PASS THROUGH XAD 2 RESIN
1
t t
SOLVENT PHASE/RESIN
1
1
T
DRY WITH Na,SO4
1
»
CONC IN K D
1 ,
PHASE






AQUEOUS PHASE SOLVENT PHASE/RESIN PHASE EXCHANGE INTO ACETONE
* 1
DISCARD DRY WITH Na,SO,
1
CONC IN K D
1
T
FINAL VOL • 10 m
f
75 mL
*
L



EXCHANGE ACETONE
FOR 15 mL DMSO
BY
EXCHANGE INTO ACETONE ROTOEVAPORATION
FINAL VOL • 10 mL
I
T
75 mL
*


AMES TEST







EXCHANGE ACETONE FOR
IS mL DMSO BY
ROTOEVAPORATION
1
AMES TEST
*' ACID FRACTION







                                                                       BASE/NEUTRAL
                                                                        FRACTION
Fig.  3.4.   Extraction  procedures for environmental water  samples.
                                     30

-------
markers, representing the base (9-amino acridine)  and neutral
[benzo(a)pyrene] chemical classes.  The mutagens were purified to the
highest possible level and dissolved in dimethysulfoxide (1  mg/mL).
The aqueous media included:
     (1) distilled water,
     (2) a solid waste EP extract (waste 10),
     (3) a "real-world" landfill  leachate (from waste 3),  and
     (4) an industrial wastewater.
All aqueous media and all extraction blanks were tested for  indigenous
mutagenic effects.  These four aqueous media were  chosen to  give  large
variety, both in terms of physical characteristics and possible
chemical interferences.
     Mutagens were added to each aqueous medium in an amount sufficient
to give an unambiguous response in the Ames test (1  mg/L of  water).   A
sufficient volume (4 L) of each aqueous medium was used for  both
recovery techniques (eight 500-ml aliquots:  2 replicates  x  2  treatments
x 2 mutagens).  Since the required level of BaP was  in exess of its
solubility, the mutagen was added directly to the  aqueous  medium
contained in a separatory funnel.  The funnel was  shaken once,  the pH
was adjusted, and the extraction  was begun immediately.  The separatory
funnel/resin system was not disconnected until the extraction  was
completed.   Thus, any components  precipitated out  by pH adjustment or
sorbed onto the funnel were extracted with the organic solvent.   The
same procedure was used for the 9-amino acridine.  An analysis  of
variance was performed to determine significant differences  between the
recovery techniques.  The recovery of benzo(a)pyrene (containing  tracer
                                  31

-------
levels of   C-labeled benzo(a)pyrene below mutagenic ranio-activation
threshold values) was measured by liquid scintillation counting as well
as by reverse-phase HPLC.  The 9-amino-acridine recovery was measured
by fluorescence spectrometry at several dilutions using the standard
addition method.
3.2.5  Assessment of Extracting Devices for Conducting the EP - Task 3
     Two extracting devices (magnetically stirred and rotary extractor)
were compared for Task 3.  The magnetically stirred extractor at both a
high and low mixing rate and the rotary extractor at 29 rpm were
examined for conducting the EP (EPA 1980b and EPA 1980d).  The low
mixing rate utilized in the magnetic stirrer was the lowest speed that
could be achieved while still keeping solids suspended, and the high
mixing rate utilized was the highest speed at which the stir bar could
be controlled.
     A factorially designed experiment was conducted using the three
mixing rates, two wastes (Nos. 12 and 13), four extraction replicates,
and three analytical determinations of each extract.  Two statistical
treatments of the data were performed (SAS Institute, Inc., 1979):
variance component analysis and the Duncan's multiple range test.
     Stirrer-speed determinations using the magnetic stirrer were made
using a low-frequency tachometer designed at ORNL.  A description of
this device follows.  A photon coupled interrupter module was installed
in the magnetic stirrer, beneath the plate.  A disc with 64 slits was
attached to the magnet shaft in the stirrer.  As the magnet rotates,
the disc over an optical sensor (utilizing infrared) generates
64 pulses for each revolution.  The pulses are fed into a three-channel
                                   32

-------
low-frequency tachometer where, using integrated circuitry,  each  of  the
64 pulses is converted to a d.c. voltage (equal  to 1  rpm).   The output
is then transferred to a strip chart recorder.

                       3.3  Methods of Analysis

3.3.1  Inorganic Analyses
     All extracts analyzed for inorganic constituents were treated
according to standard methods (EPA 1979b) and were directly  analyzed
for metals by fTameless graphite furnace atomic  absorption spectroscopy
(AAS) with the following exceptions:
     (1)  extracts for Hg determination were preserved by addition to a
          nitric acid/dichromate solution and worked  up for  cold  vapor
          flameless AAS (Feldman 1974),
     (2)  Se was chelated with 5-nitro-o-phenylene diamine and
          extracted with toluene before analysis (Talmi and  Andren
          1974), and
     (3)  As was determined by an arsine accumulation-helium glow
          detector procedure (Feldman 1979).
Samples were analyzed by the method of standard  addition (EPA 1979b).
     Because the primary focus of this study was organic content  of
various solid waste extracts, only selected elements  believed to  be  in
high concentrations were examined in the batch-type extractions.   The
elements were generally limited to those found in the NIPDWS (EPA
1979a) because they are used to identify toxic constituents  in EP
                               o
extracts.  However, Fe, Ni, SO. , and Zn were measured in selected
extracts as well.
                                   33

-------
3.3.2  Organic Analyses
     The organic analysis of the various aqueous batch extracts was
carried out by first adjusting the aqueous extract to pH 6.8 using
phosphate buffer and to a conductivity of 20 mS/cm using sodium
chloride.  The adjusted extract (500 ml) was then passed through a
cartridge containing 4.2 ml XAD-2 resin (XAD-2 resin was obtained in
pre-cleaned, pre-filled form from Isolab, Inc.,  Akron, Ohio).   Previous
work (Epler et al. 1980) had shown that these conditions were effective
for the extraction of nonpolar organic compounds, of primary interest
in this work.  This extraction technique effectively excludes the
acetic acid used in the EP and the citric acid used as an alternative
test extractant.  In addition, the XAD technique avoids the problems
often encountered in the solvent partition techniques where high
concentrations of organic acids (such as acetic and citric acids) tend
to produce stabel emulsions, complicating the separation of the aqueous
and nonaqueous phases.
     The column extracts were isolated directly on 16.8-mL XAD-2 resin
(see Fig. 3.3) that had previously been cleaned  by successive Soxhlet
extraction with water, methanol, acetone, and water.  Each batch of
resin was examined for nonpolar organic contaminants.
     Organic compounds were eluted from the XAD-2 resin cartridge (used
for batch extractions) with 15 ml of acetone and 5 ml of methylene
chloride (60 ml acetone and 20 ml methylene chloride was used for the
column cartridge).  Solvent containing the eluted material  was then
concentrated to 1 mL using a Kuderna-Danish (K-D) evaporator.   The
extract containers were rinsed with the eluting  solvent prior to
desorption of the resin.
                                   34

-------
     An exception to the above procedure was made in the filtration
study (Section 3.2.3).  In this case resin from each XAD-2 cartridge
(through which a column extract had passed) was emptied into a 150-ml
beaker.  Fifty milliliters of acetone/methylene chloride (50/50
mixture) were added, and the mixture was placed in an ultrasonic bath
for 15 min.  A 1-mL aliquot was removed and spiked with azulene as an
internal standard.  This aliquot was analyzed by gas chromatography.
     Aliquots (500 ml) of all other aqueous extracts were spiked with
azulene, adjusted to pH 12 with NaOH, and extracted three times with
50 mL methylene chloride.  The pH was then adjusted to pH 2 with HC1
and extracted three times with 50 ml methylene chloride.  The methylene
chloride extracts were combined, dried over anhydrous sodium sulfate,
and reduced in volume using a K-D evaporator.  The standard solutions
were reduced to 1 ml and the solid waste extracts to 10 ml, since
higher levels of organic compounds were present in the solid waste
extracts.   In all cases, the final concentration of the internal
standard was 10 ppm.  The extracts were analyzed by gas chromatography.
One solid  waste extract was also analyzed by gas chromatography/mass
spectrometry to confirm the presence of the identified compounds.
     The organic concentrates were analyzed by gas chromatography using
fused silica capillary columns (30-m-long x 0.25-mm-i.d. columns coated
with SE-52 stationary phase from J&W Scientific).  Gas chromatography
was performed using a Hewlett-Packard Model 5736A gas chromatograph
with a Model 18835B Grob-type split/splitless injection system.   The
splitless injection technique was used throughout this work.
                                   35

-------
Quantitation was obtained using a Hewlett-Packard Model  3390A recording
integrator.  Gas chromatography/mass spectrometry was performed using a
Hewlett-Packard Model  5985 gas chromatograph/mass spectrometer/data
system in the electron impact mode.  Volatile organic compounds in
selected extracts were isolated by purge and  trap procedures (Zlatkis
et al. 1981) and analyzed by gas chromatography,  as above.   The
combustion-infrared method (EPA 1979b)  was used to determine dissolved
organic carbon (DOC) concentrations.  The ORNL in-house  quality
assurance program, which was used throughout  this study,  indicates a
coefficient of variation of less than 8% by this  DOC method.

3.3.3  Mutagenicity testing
     Mutagenicity testing was carried out under both Tasks  1 and 2.
Under Task 1, the Salmonella/microsome  mutagenicity assay was applied
in an abbreviated screening mode to Soxhlet isolates, acid/base/neutral
fractions obtained through sequential extraction, and the five aqueous
extraction procedure extracts generated from  Task 1.  The general
methodology for the Salmonel1a/microsome assay has been  described
elsewhere (Epler et al. 1980).  In a screening mode, this assay is
restricted to two Salmonella typhimurium strains;  TA100, with a hisG
base-pair substitution, uvrB and rfa factors, and the pKMlOl plasmid;
and TA98, the hisD frameshift, also carrying  the  uvrB and rfa factors
and the pKMlOl plasmid.  The tested strains were  used without metabolic
activation as well as with addition of  microsomal preparations from
both phenobarbital and Aroclor-1254-induced rats  (henceforth referred
to as phenobarbital activation and Aroclor activation).
                                  36

-------
     Organic concentrates were prepared by methods identical  to thosa
used for chemical analysis (Section 3.3.2) except that the isolates
were dried under a nitrogen stream.  The residue was then dissolved  in
2 ml of dimethylsulfoxide (DMSO).
     Under Task 2, the two sample preparation protocols (Section 3.2.4,
Section 4.2) were compared using the Ames test (the full  five-strain
Ames plate assay procedure, with and without metabolic activation) on
solid waste leachates and wastewaters.  The general methodology has
been described elsewhere (Epler et al. 1980).  This procedure was
slightly modified to conform to the EPA/NEIC protocol  (EPA 1980c) for
conducting the Salmonel1 a/microsome assay.  The criterion used of
"positive" test was the modified two-fold rule, i.e.  a positive
dose-response with a revertant value—for at least one of the test
material doses—at least twice that of the spontaneous revertant value
(solvent control).

3.3.4  Analysis of Bioaccumulative Materials in Wastes and Leachates
     Soxhlet isolates, acid/base/neutral  fractions obtained through
sequential extractions of the wastes, as well as organic  concentrates
from the five aqueous extraction procedures were tested for
bioaccumulation potential (EPA 1978) in Task 4.
     Basically, the method involves chromatography of  a series of
compounds of known octanol/water partition coefficients on a
reverse-phase HPLC system, using ultraviolet (UV)  detection.   When
plotting the partition coefficient of known compounds  against the log
retention time, a straight line is obtained (as shown  in  Fig.  3.5) that
can be used to extrapolate back to the partition coefficients of
                                  37

-------
~ 5
cc
UJ

< 4
0
O
                                    ORNL-DWG 81-9417
           I     I
I     I
          PHENANTHRENT
                           O-DICHLOROBENZENE
                       TJROMOBENZENE
                    BENZENE
      -^ACETONE
           I     I     I
I
I     I     I      I
     0.1   0.2   0.3  0.4   0.5   0.6   0.7  0.8

                 LOG  RETENTION TIME (min)
                    0.9   1.0
 Fig. 3.5.  Partition coefficients of known compounds plotted against log
         retention times.
                          38

-------
unknown compounds.  Constituents of an unknown mixture,  having partition
coefficients equal to or greater than log P = 3,  are defined  (EPA 1978a
and 1978b) as being potentially bioaccumulative.
     All samples were stored, refrigerated, at 4°C to avoid evaporation
and decomposition.  Each sample was injected onto a Zorbax*
octadecylsilane column (4.6 mm x 25 cm) by use of a loop injector with
a 20-uL sample loop.  An 85:15 methanol-water mobile phase was degassed
and pumped through the system using a Chromatix constant-flow pump at a
rate of 1 mL/min.  A Laboratory Data Control  ultraviolet absorbance
monitor at 254 nm was employed.
     A standard solution was prepared using acetone, benzene,
bromobenzene, orthodichlorobenzene, phenanthrene, and
2,2-bis-(p-chlorophenyl)-l,l-dichloroethylene (DDE).  The quantity of
each compound was varied to produce peaks approximately  25% of the
recorder scale (approximately 100 yg/mL).  Preliminary standard runs
were made with each compound in a 3:1 acetone-cyclohexane solution to
determine optimum peak heights.  The acetone-cyclohexane solution was
diluted in the final standard with methanol to decrease  the size of the
acetone solvent peak while maintaining the solubility of the DDE.
     Retention times of standard compounds were recorded each  day. The
bromobenzene peak was selected as an external  standard for
semi-quantitative comparison with sample peaks to account for  day-to-day
variation in instrumental response.  Plots were made of  log P
(octanol/water partition coefficient) versus  log  retention time for
extrapolation.  The 500 to 1 concentration factor was used for aqueous
extracts, with lower concentration factors applied to the waste isolates.
                                   39

-------
                          SECTION  4:   RESULTS

4.1  Task 1;   An Evaluation of Aqueous Extraction  Procedures  to Remove
              Nonpolar Organic Compounds  from  Solid Wastes
4.1.1  Inorganic Analyses of Extracts
     The analytical results for selected  inorganic components (NIPDWS
metals) in the four batch extracts (EP, water, Na-resin,  and  citrate
buffer) for wastes 1 through 6 are presented in Table  4.1.  The citrate
buffer extracts contained higher concentrations of all  metals except
for Ba in waste 1 and Cr in waste  4.   In  addition, Ba  was present  in
the citrate buffer extracts in considerably higher concentrations  than
in the other batch extracts for wastes 2  through 6.  The  EP
consistently produced extracts containing the  second highest  levels of
metals (except Ba in waste 5).  The water and  Na-resin extractions
yielded extracts containing comparable levels  of metals.
     All NIPDWS elements were analyzed in the  water extracts  of
wastes 7 and 8 and the EP extract from waste 8 (Table  4.2).   Neither of
these wastes contained levels of metals that warranted further analyses
of these wastes for inorganic constituents.
     Inorganic analyses of the four batch extracts for wastes 9, 10,
and  11 are presented in Tables 4.3, 4.4,  and 4.5,  respectively.  Three
EP extractions were performed on sample 10 for the organic  isolation
study  (Task 2, see Section 3.2.4)  to  produce necessary quantities  of
extract.  The three extracts were analyzed separately  for inorganic
elements.
     Extracts from wastes 9, 10, and  11 were also  examined  for Fe, Ni,
and  Zn, because such coal-related wastes  are expected  to  contain these
                                  40

-------
  TABLE 4.1.  SELECTED INORGANIC ANALYSES OF  EXTRACTS  PRODUCED  USING
           FOUR EXTRACTION PROCEDURES FOR WASTE SAMPLES 1-6
Extraction procedure3
Waste Element
1 As
Ba
2 Ba
Cr
3 As
Ba
Cr
4 Ba
Cr
5 Ba
6 Ba
EP

65,000
150
144 + 51C
3,940 +_ 1,216C
3.0
660
18
400
180
1,500
650
Water Na-resin

37,000b- 84,000b
79 100
310 210
131 180
0.54 0.8
590 390
8.9 1.3
460 190
163 160
470 190
460 430
Citrate
buffer

156,000b
35
730
17,400
21
990
510
l,100a
34
1,430
3,000
aSingle determination.
 Exceeds EP threshold concentrations as in 40 CFR  261.24.

°Mean and standard deviation of replicate extractions  (n=2).
                                  41

-------
  TABLE 4.2.  INORGANIC ANALYSES OF WATER
     AND EP EXTRACTS FOR WASTES 7 AND 8
Water extraction3
Element
Ag
As
Ba
Cd
Cr
Hg
Pb
Se
Waste 7

<0.01
4.7
210
0.13
2.6
0.008
4.1
<0.5
Waste 8

<0.01
0.4
520
0.63
2.2
0.004
2.1
<0.5
EPa
Waste 8

<0.01
2.9
370
0.91
13
0.02
11
<1
aSingle determination.
                      42

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    TABLE 4.3.   INORGANIC ANALYSES  OF  EP, WATER, NA-RESIN,
            AND CITRATE  BUFFER  EXTRACTS FOR WASTE 9
Extraction procedure3
Element
Ag
As
Ba
Cd
Cr
Hg
Pb
Se
Fe
Ni
Zn
s°;
EP

0.1
1.7
160
0.73
2.6
0.04
2.6
1.8
4.0
5.9
543
69,000
Water

<0.1
0.65
120
<0.02
0.51
nd
0.99
<2
8.1
<1
70
70,000
Na-resin
. 110/1 - - - -
yg/u
<0.1
3.0
130
<0.02
0.56
nd
2.0
2.3
22
<1
15
nd
Citrate
buffer

ndb
13
600
nd
98
nd
nd
5.0
16,300
140
3383
nd
 Single determination.

}nd =  not determined.
                              43

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   TABLE 4.4.   INORGANIC ANALYSES OF  EP,  WATER,  NA-RESIN,
          AND CITRATE BUFFER EXTRACTS FOR WASTE 10

Element


Ag
As
Ba
Cd
Cr
Hg
Pb
Se
Fe
Ni
Zn

. EPa
(x + S.O.)


38C
8.3 + 1.6
147. + 5.8
<0.1
5.4 + 2.5
0.06b
16.5 + 13.4
4.6 1 0.8
11+7
25 i 4
30 + 27
Extraction
Waterb
. - - iia/l -

<0. 1
0.7
160
<0.1
3.8
ndd
n
4.9
8.8
21
19
procedure
Na-resin


<0.1
0.6
130
0.67
6.7
nd
8.7
4.3
4.4
46
7.5

Citrate.
buffer0


0.28
3.6
170
1.8
42
nd
43
12
16,500
62
63
aThree extractions were performed.   Values  (means  and  standard
 deviations) reported are based  on  single determinations on each
 of the the 3 extracts.
bSingle determination.
cHighest value reported, all  other  values less than
 detection limit.
dnd = not determined.
                             44

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TABLE 4.5.   INORGANIC ANALYSES OF EP, WATER, NA-RESIN,
       AND CITRATE BUFFER EXTRACTS FOR WASTE 11
Extraction procedure3
El ement
Ag
As
Ba
Cd
Cr
Hg
Pb
Se
Fe
Ni
Zn
EP

0.03
0.3
335
0.97
<0.7
<0.01
1.4
<0.5
1,830
130
220
Water
- - - - IIO/I
0.05
0.5
306
0.38
<0.7
ndb
1.3
<0.5
320
70
84
Na-resin

0.16
1.2
222
0.24
<0.7
nd
<1
<0.5
45
7
9.6
Citrate
buffer

0.42
225
777
5.2
483
nd
263
1.8
83,000
330
570
aSingle determination.

 nd = not determined.
                          45

-------
metals.  Extract data for wastes 9,  10,  and 11  showed  consistently
higher concentrations of metals in the citrate  buffer  extracts.   In
several cases (Cr in sample 9, Se in sample 10,  and  As,  Cr,  and  Pb in
sample 11), the citrate buffer extraction produced levels  in excess of
the NIPDWS concentrations.  In general,  higher  concentrations of Ba,
Cd, Cr, Pb, and Se were noted in the citrate buffer  extracts.
     The higher extraction efficiency for metals by  the  citrate  buffer
extraction may be explained in part  by the large quantities  of Fe
released with this extractant (Table 4.6).  The high complexing
capacity of citrate for Fe tends to  solubilize  Fe from iron-solid phase
matrices, thus releasing associated  metals from the  solid  phase.

4.1.2  Isolation of Organic Compounds from Wastes
     The isolates produced by the Soxhlet extraction and the three-step
sequential extraction procedure were compared by gravimetry  as well  as
by gas chromatography (see Section 3.2.1).  The gravimetric  data are
shown in Table 4.7.  The three-step  sequential  extraction  scheme
consistently extracted more organic  material from the  wastes than did
the Soxhlet.  The major organic components of the wastes were isolated
by both techniques.  Figures 4.1 and 4.2 indicate the  complexity  of the
waste isolates.  For identification  of the major organic compounds  in
the wastes, it was sufficient to analyze only the Soxhlet  extracts  by
gas chromatography/mass spectrometry.  Table 4.8 lists the compounds
which were identified confidently in each of the waste isolates.   In
most cases where identifications were made,  appropriate  standards were
not available, and identification was made by comparison with reference
spectra.  The compounds are listed in order of decreasing concentration.
                                   46

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   TABLE 4.6.  COMPARISON OF FE CONCENTRATIONS
           USING FOUR EXTRACTION MEDIA3

Waste

1
2
3
4
5
6
9
10
11

EP

0.009
0.12
1.55
0.035
0.77
0.99
0.004
0.01
1.8

Water

0.001
0.059
0.41
0.037
0.036
0.24
0.008
0.008
0.32
Fe
Na-resin

0.001
0.070
0.14
0.013
0.028
0.076
0.022
0.004
0.045

Citrate
buffer

25
10.5
8.7
0.51
3.3
32
16.3
16.5
83
aSingle determination.
                        47

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TABLE 4.7.  TOTAL ORGANICS RECOVERED:   COMPARISON OF SOXHLET
     EXTRACTION WITH THE SEQUENTIAL EXTRACTION  SCHEME -
      GRAVIMETRIC DATA ON SOLID WASTE  ORGANIC ISOLATES
Sequential extraction
Waste

1
2
3
4
5
6
9
10
11
Acids


0.74
2.4
6.5
3.5
1.6
1.0
2.7
0.25
0.48
Bases


4.4
0.15
0.2
0.1
0.2
0.2
0.24
0.4
0.31
Neutral s
C rt 1 1 H lalAC^O

38.4
14.9
24.0
58.2
26.6
60.6
368
16
344
Soxhlet


12.1
3.0
1.3
21.0
14.2
11.2
151
4.1
25.8
                             48

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                                                    «*/WB 81-4545
              I
JJUL
ulwLjL_A.
             78   86   106   126    146   166   186   206   226
                 1    1    i
    I   1   1  .1
Fig.  4.1.  Chromatograms for waste 2 - Soxhlet extract (A),  ana
          sequential extraction extracts:   acids (B), bases  (C), and
          neutrals  (D).  Injection temperature  - 300°C,  detector
          temperature - 300°C, carrier gas - \\2 at 1.2 mL/min.
                                49

-------
                                               ORNL-OWG 81-15954
       B
       C
             \iM
                                      TEHP CC)
Fig. 4.2.  Chromatograms for waste 11 - Soxhlet extract (A) and
           sequential extraction extracts:  acids (B), bases (C), and
           neutrals (D).  Conditions as in Fig. 4.1.
                                   50

-------
       TABLE 4.8.  ORGANIC COMPOUNDS IDENTIFIED IN SOLID WASTES3
  Waste                   Compounds


   1    Nitroanilineb

   2    Hydrocarbons (19)c, cresolb, indoleb, methyl  indoles (2)c,
        phthalates (3)c, nonyl phenols (5)c, decanoic acid,
        phenanthreneb

   3    Aliphatic hydrocarbons, cresolb,  naphthaleneb, hydroxy indole

   4    Tributyrin, p_-hydroxy benzaldehyde (2)c,  methylene bisphenol
        (2)c, hydroxy benzyl alcohol, phenol0, hydroxy benzoic acid,
        biphenol (2)c, fluorantheneb, bicresol (Tentative), piperonal

   5    Aliphatic hydrocarbons, cresolb,  methyl indole, hydroxy indole,
        methoxy indole

   6    Aliphatic hydrocarbons, siloxanes, dioctylphthalateb,  cresolb,
        indoleb, dibutylphthalateb, methyl indole,  butyric acid,
        phenyl acetic acid, octanoic acid, decanoic acid

   9    Methyl fluorantheneb, methyl biphenylb, trimethylnaphthalene,b
        biphenylb, various aliphatic hydrocarbons

   10   Biphenyl^, 05 phenol, C] tetrahydronaphthalene, C]  naphthalene
        (2)b, tetrahydronaphthalene, minor components, C3  hydroxy
        biphenyl ^ hiphenyl (2)c,  isopropyl cyclohexane,  C3 benzenes
        (3)c, indane, naphthalene,b hydroxy anthracene, acenaphtheneb,
        CTI biphenyl, dibenzofuran, fluorene, phenanthreneb,
        hydroxy fluorene, C] phenanthrene (2)b»c, methoxyphenanthrene

   11   Biphenyl ether, biphenyl0,  phenanthreneb, tetrahydronaphthalene,
        cresol", €3 phenol, xylenols (3)c, phenyl phenol,  tplyl phenol
        (5)c, Ctj phenol, bipiyridyl, acridine + benzoquinol ines,
        dibenzofuran, acenaphtheneb, fluoreneb, dibenzothiopheneb,
        phenanthrenec, fluorantheneb, pyreneb
Compounds identified in Soxhlet isolates in  order of  decreasing
 concentration.

 Comparison with authentic standards.

cNumber of isomers detected.
                                   51

-------
Comparison of the gravimetric data with the total  area of the
chromatogram indicated that 15 to 20% of the mass  was eluted under
these chromatographic conditions.
     The organic content of the wastes varied considerably, as was
expected, although wastes 2, 3, 5, and 6 contained similar compounds,
predominantly hydrocarbons and carboxylic acids.   The acids in these
wastes probably resulted from decomposing municipal  refuse (these
wastes were obtained from landfills that also received municipal
waste), while the hydrocarbons may have resulted from oil  disposal.
Waste 1 contained nitroaniline, which constituted  about 99% of all
organic material present.  Waste 4 contained exclusively phenolic
compounds plus tributyrin.  These compounds resulted from a phenoxy
resin plastic manufacturing process.  Wastes 9, 10,  and 11  contained
similar compounds; each waste resulted from a coal conversion process.
Thus, the major constituents of these wastes are phenols,  aromatic
heterocycles, and aromatic hydrocarbons.
     Volatile organic compounds were determined (see Section 3.2.1)  for
wastes 2, 3, and 9 (Figs. 4.3 and 4.4).  Volatile  compounds included
hydrocarbons, phenols, and sulfur compounds.  Figure 4.3 shows that
volatile compounds from waste 2 could be detected  after aging 4 years
in a carefully covered landfill.

4.1.3  Organic Analyses of Aqueous Extraction Procedure Extracts
4.1.3.1.  Dissolved Organic Carbon Results
     Earlier studies of solid waste extracts (from batch extraction
procedures) indicated that a screening procedure for the presence of
water-soluble organic compounds would be desirable (Epler et al.  1980).
                                   52

-------
                                                                                    ORNL-DWG 81-9582
01
                                                            40
                                                        TIME (min)
                     Fig.  4.3.   Chromatogram of waste 2 (aged four years in a tightly covered  landfill) -
                                volatile organic compounds.  Conditions as in Fig. 4.1.

-------
                                                     ORNL-OWG 81-9305
             B
                           I
I
I
  80      70      60      50      40      30
                               TIME(min)
               20
                10
Fig.  4.4.   Chromatograms of volatile organic compounds for waste 3 (A)
           and waste 9 (B).
                                  54

-------
Such a screening protocol would reduce the laboratory time for
preparing and analyzing extracts for organic constituents.  Dissolved
organic carbon (DOC) analysis is an appropriate method for screening
extracts for organic constituents.  However, it cannot be used for
extraction procedures that use organic acids (e.g.,  acetic acid used in
the EP or citric acid) unless very high concentrations of other organic
compounds are present above the acid background levels in the extract.
     The water and Na-resin batch extracts were also examined for DOC
concentrations.  In addition to the batch procedure  extracts, the
column extracts, after passing.through XAD-2 resin,  were analyzed for
DOC to screen for organic compounds not retained by  the XAD-2 resin
(e.g., very polar organic compounds).
     The concentrations of DOC found in extracts of  the water,
Na-resin, and column (after passing the XAD-2 resin) procedures for  the
11 wastes tested are shown in Table 4.9.   All  wastes contained
detectable quantities of organic components.  There  was no significant
statistical  difference in quantities of DOC extracted between the water
and Na-resin procedures (SAS Institute, Inc. 1979).   Although the
column extracts were not analyzed for the specific organic compound
present, previous studies with XAD-2 resin indicate  that polar
compounds, e.g. dicarboxylic acids, nonextractable with organic solvent
accounted for the levels of DOC observed (Epler et al.  1980).  Column
extracts from waste 14 did not contain extractable organic compounds
above 10 yg/L (Section 4.1.3.2).
     As DOC analysis requires filtration at the submicron level,  it  was
necessary to evaluate the effect of filter type.  Therefore,  all  water
                                  55

-------
  TABLE 4.9.   DISSOLVED  ORGANIC CARBON (DOC) OBSERVED
          IN  SELECTED AQUEOUS WASTE EXTRACTS3
Extraction
Waste
1
2
3
4
5
6
7
8
9
10
11
Water

198
457
207
254
92
552
134
42
13
54
46
Na-resin

155
494
178
353
64
406
37
48
13
39
28
Column - after passing
through XAD-2

80
206
246
31 9b
268
423
nec
ne
10
50
ndd
filtered through glass fiber  filters (Whatman GF/F,
 precombusted 0.7 pm).
 Average of two replicates.
cne = not extracted.
 nd = not determined.
                          56

-------
and Na-resin suspensions were filtered using two types of filters:   a
polycarbonate membrane filter (Nuclepore, 0.4 ym) and a precombusted
glass-fiber filter (0.7 urn).  The glass-fiber-filtered extracts were
expected to be higher in DOC due to sorption of organics on
polycarbonate filters as well as passage of submicron particles
(0.4-0.7 urn) through the glass fiber filter.  However, as Table 4.10
shows, this was generally not the case.  In cases where large (order of
magnitude) differences were found in DOC values (e.g., the Na-resin
extracts from wastes 3 and 9),'the polycarbonate-filtered extracts
contained the higher level.  Statistical analysis (SAS Institute, Inc.,
1979) of data in Table 4.10 showed that there was no difference in
DOC values between glass-fiber- and membrane-filtered extracts.
     To determine whether changes fn the DOC values during the 24-h
extractions, warranted consideration of a shorter extraction  time,
25-mL aliquots (one aliquot for each sampling time) were drawn from the
extraction vessel immediately after the wastes were thoroughly mixed
and at 1-, 2-, 4-, 8-, and 24-h intervals.   Figures 4.5 and 4.6
graphically describe concentrations of DOC  found in the water and
Na-resin extracts, respectively.  These plots show there was  no
consistent pattern of increase or decrease  in DOC values with respect
to time.  In general, the wastes that contained appreciable levels  of
volatile organics (wastes 2 and 3) decreased in concentrations of DOC
over the extraction time.  This phenomenon  might be expected  because
the extraction vessel was not sealed.
                                  57

-------
     TABLE 4.10.  COMPARISON OF DOC IN EXTRACTS  FILTERED
        THROUGH GLASS FIBER AND POLYCARBONATE  FILTERS
Mater extracts
Waste
1
2
3
4
5
6
7
8
9
10
11
GFb

198
457
207
254
92
552
134
42
13
54
46
NFC

212
505
337
243
72
544
29
45
10
56
49
Na-resin
Displacement extracts
GFb

155
494
178
353
64
406
37
48
13
39
28
NFC

124
437
1740
280
44
480
30
42
no
40
46
aSingle value determinations.
 Glass fiber filter (Whatman GF/F,  precombusted,  «0.7 um).
°Polycarbonate filter (Nuclepore, 0.4 ym).
                             58

-------
                                         ORNL-OWG 81-13763RESD
     500 ^S_2.
          O
•6-
•2-
        •6
        •2
                                     WATER EXTRACTION
                                 I
                I
                         8
        12      16
        TIME  (h)
20
24      26
Fig. 4.5.  DOC found in water extracts over the 24-h extraction time.
                               59

-------
                                            ORNL-DWG 81-13764RESD
1VJUW
500
i
200
|
^
o»
1 100
i «
CD i
% so :
o 1
ORGANIC
r\>
o
DISSOLVED
» ro ui O
1
(
1 1 1 1 1 1
s-s-^rirrrr.'glrrrrrra^.
3^6/"-*-3- ""~~~--6
3 3- — -._, 	 4
rr*-4~- -^-.-::;.^_^
I^rS-.o..--""6 	 	 	 5
^x« "5"j.v._ 	 — 8 _
o, JO\HO - « ,.1 _ _V.V_Vr _-_ .- — ,10
7X
.9 	
	 - 	 9
9
	 9-~ 	
/ Na-RESIN
9' EXTRACTION
{-
1 1 1 1 1 1
D 4 8 12 16 20 24 2
TIME (h)
Fig. 4.6.   DOC  found  in Na-resin extracts over the 24-h extraction  time,
                                  60

-------
     Because the DOC values changed over time for each sample,  a linear
regression analysis was performed to determine if these changes were
significant over time (SAS Institute, Inc. 1979).  The following waste
extracts showed a statistically significant change (P < 0.05)  in DOC
(slope of linear regression different from zero) over the 24-h
extraction time:
     (1) the water extracts from wastes 7 and 8 increased in  DOC over
         time,
     (2) the Na-resin extract from waste 4 increased, and
     (3) the Na-resin extracts from wastes 2 and 3 decreased  in DOC
         over time.
Although waste 9 did not show a statistically significant change over
24 h in DOC concentration by water extraction, there  was  a large drop
in DOC concentrations (from 120 to 20 ug/L) in the first  4 h.
     During the first 8-h of extraction, only the Na-resin extract from
waste 9 increased in DOC.  Overall, the majority of wastes extracted
did not significantly change in DOC content over the  extraction period.
With the exception of the water extraction of waste 7,  there were no
significant differences observed between 8- and 24-h  extraction times,
suggesting that 8-h extraction may be as effective as the 24-h
extraction, at least for the analysis of DOC.

4.1.3.2  Gas Chromatography and Gas Chromatography/Mass Spectrometry
     Using GC and GC/MS analysis, the extracts produced from the five
extraction procedures were compared in two ways.   First,  the total area
of each of the chromatograms (excluding the solvent peak)  was compared,
as a measure of the total mass extracted.   Because of the  low levels of
                                   61

-------
organic compounds present in most of the extracts,  gravimetry was  not
useful.  Second, the quantities of individual compounds extracted  by
the various media were compared.  While it was  not  possible to obtain
absolute quantitative data on the individual compounds, the equivalent
treatment of all extracts ensures a reliable relative comparison.
Blanks were run by carrying the media through all extraction and
analytical operations.  Appendix A contains quality control procedures
used at ORNL for organic analyses as well  as inorganic analyses.
     The data for total chromatographable organic content  for each of
the extraction procedure extracts are shown in  Table 4.11.
Additionally, an estimate of the total chromatographable organic
concentration is given for each EP extract. This estimate  is based on
average integrator response for aliphatic hydrocarbons and  should  only
be used to make relative comparisons between samples.
     To evaluate the relative effectiveness of  the  extraction procedures
to extract organic compounds, each extraction procedure was ranked from
lowest to highest (1 to 5) for each waste (Table 4.11).  This ranking
scheme was used to statistically detect significant  differences
(P < 0.05) among extraction procedures across wastes using  a
completely randomized design (by extraction procedure).  Applying  this
ranking scheme, the following conclusions  can be made  relative to  the
effectiveness of the five extraction procedures to  remove
chromatographable organic compounds:
     (1)  The up-flow column was more aggressive than  any of the batch
          extraction procedures.
                                  62

-------
   TABLE  4.11.  THE RELATIVE EFFECTIVENESS OF FIVE AQUEOUS EXTRACTION
       PROCEDURES TO REMOVE ORGANIC COMPOUNDS FROM SOLID WASTES
Extraction procedure
Waste
1
2
3
4
5
6
9
10
11
Mean
rank
score0
EP

1.0 (1)-
1.0 (3)
1.0 (2)
1.0 (3)
1.0 (3)
1.0 (1)
Ob (1)
1.0 (3)
1.0 (4)
2.33
Water
. . . TTfl i
3.1 (3)
0.79 (2)
0.5 (3)
1.1 (4)
3.6 (4)
37 (4)
1.0 (4)
1.5 (4)
0.49 (2)
3.33+
Na-
resin
/s EP (rank'
8.7 (4)
1.4 (4)
0.32 (1)
0.84 (2)
0.07 (1)
2.6 (2)
0.42 (2)
0.67 (1)
0.40 (1)
2.00
Citrate
buffer
a\ 	
i
2.6 (2.).
0.10 (1)
2.0 (4)
0.45 (1)
0.14 (2)
4.2 (3)
0.44 (3)
0.90 (2)
0.69 (3)
2.33
1
t(
Column

22 (5)
6.7 (5)
7.3 (5)
6.3 (5)
4.1 (5)
49 (5)
4.7 (5)
2.3 (5)
8.9 (5)
5.00*
Estimated
jtal in EP
(yg/L)
328
224
31
340
700
6
37b
754
2740

aRanking of each extraction procedure from lowest  to  highest  (1 to 5)
 for each waste sample.

bTotal in distilled water, as no detectable peaks  were observed in
 the EP extract.

cMean rank scores without the same superscript  are significantly
 different (P < 0.05)  by Duncan's multiple range test.
                                  63

-------
     (2) Among batch extraction procedures, deionized distilled water
         was the most aggressive extracting medium.
     (3) No statistical differences were observed among the EP, citrate
         buffer, and Na-resin batch extraction  procedures.
     The column extraction procedure was replicated  three times using
waste 10.  The total chromatographable organic  compounds (total area of
the chromatographs as measured in integrator counts, a dimensionaless
unit) for the three replicate column extractions  were:   replicate  1:
2.5 x 107, replicate 2:  2.7 x 107, and replicate 3:  3.2 x 107.   The
coefficient of variation associated with these  three replicates was 13%.
These data suggest that the extractions were in reasonably close
agreement in terms of organic matter extracted.  Chromatograms of  the
first and third extractions were quite comparable relative to  organic
compounds present (Fig. 4.7).  Furthermore, the extract after  passing
through the resin cartridge was analyzed by the method  described in
Section 3.3.2 (solvent partition at basic and acidic pH).  No
extractable organic compounds were detected above 10 ug/L.
     For individual organic compounds, data are shown in Table 4.12.
Conclusions 1 and 2 developed above for total chromatographable organic
compounds apply to individual compounds as well.   Interestingly, it
seems that the sample matrix is a major factor  in individual compound
differences between the four batch extraction procedure extracts.
Cresol, for example, was extracted more effectively  by  the water
procedure on wastes 2, 3, and 6, but by the EP  on wastes 4 and 11.
     Volatile organic compounds were also determined on selected
samples.  Figure 4.8 shows the results of the analysis  of volatiles
                                   64

-------
                                                               OR ML DWG 81 21534
                                             1
  70
         86
                106
               H—
                20
        TEMPERATURE (°C)
 126      146      166     186
H	1	1	h-
 30       40      SO     60
           TIME (mm)
 206
—I—
                                                             226
                                                                         250
         10
 70
        80
Fig. 4.7.   Chromatograms  of waste  10 column extracts - replicate 1  (1)
            and replicate  3 (2).  Conditions as  in  Fig. 4.1.
                                     65

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  TABLE 4.12.   RELATIVE AMOUNTS OF INDIVIDUAL COMPOUNDS  IN  SOLID WASTE
       EXTRACTS AND RELATIVE RANKING OF THE EXTRACTION PROCEDURES
Extraction procedure3
Na- Citrate
Waste
1
2




3


4






5


W

6






9
10



11





Mean
and =
Compound
Nitroamline
Cresol
Indole
Methyl indole
Decanoic acid
Phenanthrene
Cresol
Naphthalene
Hydroxyindole
Phenol
Cresol
o-hydroxy benz-
aldehyde
Tributyrin
Methyl ene bisphenol
Chrysene
Naphthalene
Methyl indole
Hydroxyindole

Methoxyindole
Phenol
Butyric acid
Cresol
Decanoic acid
Phenyl acetic acid
Indole
Methyl indole
(No peaks identified)
C3 pyridine
Naphthalene
Quinoline
1 -methyl naphthalene
Cresol
Xylenol
Quinoline
£3 phenol
Naphthol
Blphenyl
rank scoreb
not detected.
EP
1.0
1.0
1.0
1.0
1.0
1.0
1.0
nd
1.0
1.0
1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0

1.0
nd
1.0
1.0
1.0
1.0
1.0
1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
2.08

Water
2.0
1.6
1.6
0.76
1.1
2.0
1.6
1.0
0.13
2.2
0.72

1.0
1.6
0.87
15
2.0
2.0
0.70

2.3
1
25
12
16
49
16
13

4.7
3.2
5.6
2.0
0.33
0.10
0.52
0.71
0.70
3.5
3.13

resin
5.6
1.0
2.2
1.1
1.0
1.8
3.2
nd
0.07
0.88
0.91

0.20
1.8
0.57
16
nd
nd
0.04

0.11
0.10
6.8
1.3
8.5
1.6
10
1.2

3.1
1.4
1.3
1.2
0.68
0.13
1.1
0.68
0.51
2.8
*T
2.44

buffer
3.6
0.02
1.1
0.98
1.3
0.58
0.28
0.82
0.15
1.6
0.55

0.96
1.6
0.97
7.4
nd
1.4
0.13

0.12
0.63
4.5
6.3
9.7
1.8
7.9
3.0

3.9
1.6
2.3
1.5
1.3
0.51
0.74
0.68
0.58
0.85
2.49

Co 1 umn
13
36
41
14
5.1
21
20
26
1.1
21
12

2.3
3.6
4.6
16
7.5
5.3
0.99

1.9
6.6
nd
1100
22
51
20
15

13
15
6.7
6.7
15
9.6
4.3
8.7
8.8
17
4.87*

bMean rank scores without the same  superscript are significantly
 different (P < 0.05)  by Duncan's multiple range test.
                                   66

-------
            (a)
                                  I
                                            ORNL-DWG 81-9581
                                               JuL
                             II  .   LUjbJL
          60
50
40      30

 TIME(min)
20
Fig. 4.8.   Chromatograms of volatile organics from waste 2 extracts
          citrate buffer extract  (a) and Na-resin extract (b).
          Conditions as in Fig. 4.1.
                              67

-------
from the citrate buffer extract and the Na-resin  extract  from waste 2.
The citrate buffer extract clearly contained  higher  levels  of volatile
organic compounds.  Similar results were obtained on wastes 3,  9,  10,
and 11.  While the mechanism of extraction  of organic compounds using
these two media was expected to be similar, there is a fundamental
difference:  the citrate buffer extraction  is conducted in  a sealed
tumbler while the Na-resin extraction is conducted in a stirred vessel
which is not airtight.  To assess if the differences noted  were
actually due to the difference between the  rotary extractor and the
stirred vessels, or a result of the different extraction  media,  the
distilled water extract of waste 2 was repeated in a sealed system.
The results are shown in Fig. 4.9.  The sealed vessel  extract again
contained much higher levels of organic volatiles, although not quite
as high as in the citrate buffer extract, implying that both factors
(vessel type and extracting media) are involved.   Further examination
of this phenomenon is recommended.
     In summary, the column extraction procedure  was found  to be the
most effective means of extracting nonpolar organic  compounds.   The
most noticeable differences are in the levels of  moderately volatile
compounds (e.g., phenol  and cresol) and in  the levels  of  the nonpolar
compounds (e.g., phenanthrene).
     Factors contributing to the observed higher  yields of  organic
compounds from the column procedure are:
     (1) the column procedure is a closed system  allowing for sorption
         of the moderately volatile compounds  directly on the XAO-2
         resin, and
                                   68

-------
                                      ORNL-DWG 64-9583
      (a)
       (c)
                                              ILL
         60
                50
40     30

 TIME(min)
                                    20
                                           <0
Fig. 4.9.  Chromatograms  of  volatile organics in water
           extracts from  waste 2 - open vessel (a)
           versus closed  vessel  (b), and distilled in
           glass water  blank (c).   Conditions as in
           Fig. 4.1.
                          69

-------
     (2) the column extracts were not filtered  using  membrane  filters
         which are known to sorb appreciable quantities of  nonpolar
         organic compounds (evidence relative to  this effect  is
         presented in Section 4.1.5).
It is important to point out that the major objective of this  work  was
to develop an aqueous extraction procedure that simulated real-world
conditions.  The goal was to identify a procedure that was  significantly
better, in terms of removal of organic compounds, than the  present  EP,
and one that could be used for a variety of wastes.   The upflow  column
procedure appears to be such a procedure.  However, the reasons  for
removal of greater quantities of organic compounds by this  procedure
are yet undetermined.  Two of the contributing  factors are  suggested
above.  In a supplemental study, an experiment  was conducted,  using
waste 14, to evaluate the influence of membrane filtering on  column
extracts.
     The relative ranking of the extraction procedures to remove
organic compounds from solid wastes (Tables 4.11  and  4.12)  indicate
that water is a significantly (P < 0.05) better extracting  medium
than the EP (acetic acid), Na-resin (sodium saturated system), or
citrate buffer (0.5 fl sodium citrate).  It appears that a medium low in
ionic strength, such as deionized distilled water, enhances
solubilization and mobility of organic compounds  from solid wastes.
McKown et al. (1980) observed a similar solvent action with water.
This solvent action in combination with the up-flow column  procedure--
which provides a continuous fresh supply of deionized distilled
water—may be the primary mechanism responsible for the greater  removal
                                  70

-------
of organic compounds by the column procedure.  Work in FY-lfi82 is
intended to evaluate in greater detail  the chemical mechanisms and/or
operational processes that are responsible for the observed difference
in quantities of organic compounds extracted by batch  and column
procedures.
     The majority of the data presented here suggest that the physical
apparatus, i.e. extraction vessel  employed, has a greater effect on  the
organic content of the resulting extracts than the aqueous medium
tested.
4.1.4  Mutagenicity Testing
     For comparative purposes, the Salmonella/microsome assay results
obtained with the various extracts from a given waste  are reported
together in Tables 4.13 - 4.21.  The results of mutagenicity testing
are summarized in Table 4.22.  The modified two-fold increase rule was
used as an indicator of positive mutagenic test response (EPA 1980c).
A sample was considered toxic if in any test the background  lawn was
absent at two or more consecutive dose  levels.  As the presence of
cytotoxicity can alter or mask the apparent mutagenic  response,  tests
showing toxicity are noted.
     Of the nine wastes examined (1-6,  9-11), seven were found to
possess mutagenic activity in at least  one extract or  isolate.   Only
wastes 4 and 6 were without detectable  genetic activity.
     The results of mutagenic testing of waste 1  isolates  and extracts
are shown in Table 4.13.  Among the aqueous extracts,  a positive
response was elicited, in the TA 98 strain of Salmonella typhimurium
with the water, citrate buffer, and Na-resin extracts.   The  Soxhlet
                                   71

-------
                                                               TABLE 4.13. RESULTS OF NUTAGENICITY TESTING OF HASTE  1 EXTRACTS
-j
ro
Volume 01
DMSO tesi
solution
luL/plale


) EPa
Revertants/plate
TA 98
Uater*
Citrate Na-
buffer* resin"
Column1
Sequential extraction
Soxhlet6 Acid6 8asec Neutral"
EP4
Mater1
Citrate
buffer*
TA 100
Na-
resin Column
So»hletb
Sequential extraction
Acldc Base0 Neutral"
Phenobarbital activation
75
SO
25
10
0
T«
T
52
54
20
T
T
79
111
24
T
59
45
42
20
42
31
38
30
15
S3
54
80
70
44
94
83
63
55
22
T
109
85
50
18
20
27
32
19
26
78
61
35
21
14
T
T
176
191
137
T
377
380
348
282
T
107
109
150
126
114
204
170
192
186
65
79
120
139
162
242
210
201
137
119
106
135
124
102
115
107
121
115
141
115
119
157
145
124
83
Aroclor activation
75
50
25
10
0

75
SO
25
10
0
T
T
T
33
21


T


14
T
T
106
97
14


T


21
30
39
55
27
31


T


20
40
49
44
36
26


28


19
53
54
67
61
53


17


45
70
59
44
41
30

138
62
60
54
20
T
94
72
44
20


150


19
23
29
24
27
24


22


31
60
49
35
26
16
No activation

32


29
T
T
T
167
138


T


163
T
T
326
325
202


T


166
T
T
119
153
78


T


142
T
196
211
196
149


148


177
T
56
104
178
169


T


167
186
173
142
136
108

252
199
167
170
144
102
98
113
108
128


119


107
135
159
142
152
143


106


137
115
141
120
112
91


99


91
                 a250 |iL of aqueous extract/uL of DMSO test solution.
                 bl  mg solid waste/uL of DMSO test solution.
                 C3  019 solid waste/uL of DMSO test solution.
                 d300 ug solid waste/Ml  of  ONSO test  solution.
                 'T  = toxic.

-------
                                                               TABLE 4.14.  RESULTS OF MUTAGENICITY TESTING OF WASTE 2 EXTRACTS
-•J
C*>
Volume o
OHSO tesi
solution
(uL/plate
F

) EP*
Revertants/plate
TA 98
Water*
Citrate Ka-
buffer* resin"
Sequential
Column*
Soxhlet" Acfdc
extraction
Basec Neutral*1
EPa Water*
Citrate
buffer*
Ha-
res In*
TA 100
Column*
Soxhletb
Sequential extraction
Acid0 Basec Neutral*1
Phenobarbltal activation
75
SO
25
10
0
21
18
15
20
17
168
154
165
137
151
71
71
29
19
21
72
44
42
28
16
IS
16
27
26
16
19
10
20
29
16
T6
16
12
10
22
15
17
17
16
20
32
36
18
18
26
74
81
73
80
94
153
290
308
220
226
107
120
94
83
86
149
169
169
83
112
T
T
148
142
141
59
69
93
103
93
T
T
T
117
150
120
106
94
107
99
113
121
82
106
119
Aroclor activation
75
50
25
10
0

50
0
27
29
23
23
19

19
22
71
99
82
67
74

20
28
52
40
29
32
30

15
8
34
39
32
30
17

18
16
29
27
30
32
18

19
42
20
24
21
18
18

6
14
T
T
13
19
32

T
15
26
IS
14
18
IS

20
16
32
32
26
24
23
No activation
33
14
85
82
94
86
133

93
99
227
193
188
215
178

141
194
T
156
194
125
119

117
104
T
142
92
78
200

94
200
T
T
T
149
125

T
120
T
T
T
T
114

T
119
T
T
T
T
153

T
179
98
107
86
113
122

121
106
120
128
113
124
115

114
141
                  250 uL of aqueous extract/Ml of DNSO test solution.
                 bl  mg solid waste/wL of DMSO test solution.
                  3  ng solid waste/uL of DMSO test solution.
                 d300 ug solid  waste/id of DMSO test  solution.
                 er  » toxic.

-------
                                               TABLE  4.15. RESULTS OF MUTAGENICITY TESTING OF WASTE 3 EXTRACTS
\lo\ume ol
OMSO tesl
solution
(uL/plate


) EP*
Revertants/plate
TA 98
Water*
curate Na-
buffer* resin*
Column*
Sequential
Soxhletb Acid0 Basec
extraction C i tra te
Neutral*1 EPa Water* buffer
TA 100
Na-
resin* Column* Soxhlet
Sequential extraction
Acidc Base0 Neutral"
Phenobarbltal activation
75
50
25
10
0
T
19
22
31
19
284
284
243
ISO
44
29
27
22
18
20
32
30
31
18
22
29
39
31
33
43
22
23
23
17
24
18
17
24
17
14
11
7
14
18
12
14
21
13
20
16
T
T
130
138
197
488
420
365
350
247
136
142
94
154
137
161
141
180
137
167
106
121
137
120
126
97
98
96
103
83
107
136
109
104
83
85
108
84
98
89
83
133
107
105
112
Aroclor activation
75
50
25
10
0

50
0
T
21
25
20
40

23
32
154
104
89
61
65

122
37
21
26
29
29
21

16
14
52
34
32
29
28

18
58
40
35
29
40
42

14
30
21
18
27
16
22

7
8
10
17
19
15
26

5
12
11
14
16
14
11

13
10
26
20
20
15
23
No activation
16
18
T
42
73
ins
142

8?
171
346
277
221
152
188

247
179
138
161
143
106
138

169
163
174
180
134
91
154

149
110
139
121
119
123
149

108
121
85
93
102
112
89

104
95
ndf
113
113
99
91

91
114
94
77
78
107
81

107
110
102
110
85
106
91

114
134
*2SO pL of aqueous extract/uL of DMSO test solution.
bl mg solid waste/Ml of OMSO test solution.
C3 109 solid xaste/uL of OMSO test solution.
d300 ug solid waste/uL of OMSO test solution.
6T - toxic.
 nd • not  determined.

-------
                                              TABLE 4.16.  RESULTS  OF MUTAGEH1CITY  TESTING OF WASTE  4  EXTRACTS
Volume oi
DHSO tesi
solution
(uL/plate
f

) EP*
Revertants/plate
TA 98
Water*
Citrate Na-
buffer* resin"
Column"
Sequential extraction
Soxh 1 etb Acidc Base' Neutral"
EP"
Citrate
Water* buffer*
Ha-
res In*
TA 100
Coliwi"
Soxhletb
Sequential extraction
Addc Basec Neutral"
Phenobarbital activation
75
SO
25
10
0

75
50
25
10
0
14
19
14
19
18

20
21
26
31
26
163
175
155
167
112

T
55
57
67
57
38
33
35
57
58

41
36
34
59
43
IB
17
20
21
16

19
19
22
17
21
16
16
17
30
22

19
27
28
16
28
Te
9
25
17
13

T
T
15
8
26
T
17
17
23
26

22
11
31
15
23
12
9
18
12
15
Aroclor
15
20
16
22
12
12
10
14
12
9
activation
17
17
14
20
14
105
91
85
107
85

85
92
113
92
97
T
355
341
363
363

T
260
201
310
204
T
113
160
106
89

T
162
203
179
146
T
162
120
125
82

T
T
135
138
99
T
T
T
165
151

T
T
T
171
149
T
T
85
64
90

T
T
92
72
59
T
T
T
133
119

T
T
111
176
115
111
75
106
112
116

110
116
95
108
108
86
92
97
76
70

109
88
83
89
103
No activation
50
0
13
20
T
24
T
28
15
20
T
29
3
8
11
14
10
13
15
18
93
90
T
106
T
124
T
108
T
122
53
93
T
141
95
105
68
67
*250 uL of aqueous extract/uL of DHSO test solution.
bl ng solid waste/uL of DHSO test solution.
C3 rug solid waste/uL of DNSO test solution.
d300 ug solid waste/uL of DHSO test solution.
8T • toxic.

-------
                                              TABLE 4.17.  RESULTS OF NUTAGEN1CITY TESTING OF  HASTE  5 EXTRACTS
Volume ol
DMSO tesl
solution
(uL/plate


) EP1
Revertants/plate
TA 98
Citrate Na- Sequential extraction
Water1 buffer1 resin1 Colum1 Soxhlet1 Acid1 Base1 Neutral1
EP1
Water1
TA 100
Citrate Na-
buffer1 resin1 Column1
Sequential extraction
Soxhletb Acidc Base0 Neutrald
Phenobarbltal activation
75
50
25
10
0
15
13
21
12
18
154
165
180
164
85
74
58
42
67
51
50
47
13
30
30
18
22
18
18
32
34
35
35
25
15
22
20
18
16
14
110
63
46
33
22
15
13
11
12
9
75
83
98
74
85
362
335
404
249
322
129
158
188
133
123
185
178
146
163
148
122
160
153
136
141
111
135
113
159
109
94
114
83
115
83
166
178
182
172
150
61
56
68
66
70
Aroclor activation
75
50
25
10
0

50
0
18
22
18
21
26

20
12
85
82
87
91
83

30
29
76
53
44
42
25

24
22
43
21
34
29
37

46
37
34
29
28
30
29

19
29
22
32
22
25
21

17
18
24
24
15
20
26

10
18
24
25
37
32
32
Np_
24
15
15
16
11
10
14
activation
6
IB
99
105
94
107
97

96
90
229
253
215
216
268

180
238
Te
94
71
99
79

119
121
154
135
146
127
113

T
186
162
154
160
148
180

117
165
109
150
95
117
97

110
121
104
99
107
115
91

110
134
150
151
190
137
153

121
179
55
54
72
75
103

62
67
a250 uL of aqueous extract/uL of DMSO test solution.
bl rng solid waste/uL of ONSO test solution.
C3 mg solid waste/Ml of DMSO test solution.
d300 ug solid Haite/uL of DMSO test solution.
eT • toxic.

-------
                                              TABLE  4.18.  RESULTS OF HUTAGENICITY  TESTING OF WASTE 6 EXTRACTS
Volume c
DNSO tes
solutloi
(uL/plati
,f

s) EP*
Reverlants/plate
TA 93
Water1
Citrate Na-
buffer* resin1 Column8 Soxhletb
Sequential extraction
Acidc Basec Neutral*1 EPa Water*
Citrate
buffer*
Na-
resln*
TA 100
Column'
Soxhlet"
Sequential extraction
Acidc Base0 Neutral*1
Phenobarbltal activation
75
SO
25
10
0
T
T
T
33
19
97
167
151
161
155
T
59
33
41
37
35
33
30
20
22
28
29
31
44
44
18
20
14
20
17
12
16
10
20
18
42
17
22
19
20
no'
nd
nd
nd
nd
T
T
T
138
128
T
T
334
328
352
T
T
T
T
116
169
160
119
191
167
138
137
169
168
220
57
89
86
82
60
63
136
130
86
115
106
126
90
108
118
nd
nd
nd
nd
nd
Aroclor activation
75
50
25
10
0

50
0
T
T
23
22
20

T
28
91
94
106
96
68

T
22
T
40
37
28
37

T
37
T
39
26
14
28

16
58
35
33
35
45
44

30
47
T
35
15
23
9

18
14
22
18
21
24
23

16
15
10
16
12
12
20

11
14
nd
nd
nd
nd
nd
NO activation
nd
nd
T
T
T
135
138

T
116
T
T
219
239
233

T
169
T
T
T
136
113

T
186
T
T
160
180
154

70
110
163
192
240
243
227

118
136
99
82
60
88
61

43
109
T
T
80
103
119

81
123
88
102
103
75
75

81
96
nd
nd
nd
nd
nd

nd
nd
*250 id. of aqueous extrut/uL of DNSO test  solution.
bl ag solid waste/uL of DNSO test solution.
C3 mq solid Mtte/uL of DHSO test solution.
d300 ug solid Haste/id, of OHSO test  solution.
*T • toxic.
fnd - not deUratned.

-------
                                                                   TABLE 4.19. RESULTS OF HUTAGENIC TESTING OF WASTE  9 EXTRACTS
oo
Volume
DHSO te
solutic
(uL/plal

it
>n
te) EP*
Revert ants/plate
TA 98
Water*
Citrate
buffer*
Na-
resin*
Column*
Soxhletb
Sequential extraction Citrate
Acid0 Basec Neutral" EP* Water* buffer*
TA 100
Na-
resln* Column* Soxhlet"
Sequential extraction
Acidc Basec Neutral*1
Phenobarbital activation
75
50
25
10
0

75
50
25
10
0
57
40
64
61
48

37
42
39
55
69
TO
41
33
46
40

T
39
44
46
41
43
38
55
44
48

48
39
49
47
42
45
48
39
53
40

45
32
39
42
41
7
13
8
16
17

T
18
15
14
18
41
33
41
47
17

T
T
T
47
27
£5
58
60
52
47

T
T
T
39
28
T
53
41
71
47
Aroclor
46
52
46
59
28
57 206
43 187
35 202
32 191
19 168
activation
54 193
40 177
30 199
32 162
20 188
160
162
181
165
216

187
206
160
165
152
174
215
226
217
201

234
199
174
173
175
161
167
165
175
216

T
167
182
205
152
86
61
70
74
117

T
99
78
91
118
T
T
117
112
104

T
T
T
107
98
T
T
227
220
173

T
T
T
231
182
187
187
150
216
173

207
160
188
20S
182
162
165
163
135
174

173
160
151
163
98
No activation
50
0
35
54
20
34
51
43
30
34
T
6
T
29
T
35
26
35
33 220
28 233
121
191
207
229
163
191
T
82
T
192


204
192
92
103
                   a250 uL of aqueous extract/uL of OHSO test solution.
                   bl  tug solid Maste/uL of DMSO test solution.
                   C3  mg solid waste/pL of DHSO test solution.
                    300 119 solid waste/uL of DHSO test solution.
                   eT  • toxic.

-------
                                                                 TABLE 4.20.   RESULTS Of HUTAGENICITY TESTING OF WASTE 10 EXTRACTS
VO
Volune
OMSO te
solutli
(uL/plat


»n
tej EP*
Revertants/plate
TA 98
Citrate Ma-
Water* buffer* resin*
Colum*
Soxhlet
Sequential extraction Citrate
b Acid0 Basec Neutral" EP* Water* buffer*
Pnenobarbital
75
SO
25
10
0
Te
T
T
44
17
T
T
58
41
52
T
T
T
45
22
T
T
35
33
16
T
T
94
78
42
T
93
94
78
22
T
609
556
97
39
T
T
T
T
22
T
60
61
52
42
activation
T I
T T
T T
156 T
109 1 10

T
T
T
T
154
Na-
resln*

T
T
T
117
111
TA 100
Colum*

T
T
T
149
1)2
Soxhlet"

r
T
T
T
199
Sequential extraction
Acid0 Basec Neutral"

T
670
645
536
167

r
T
T
T
91

T
T
T
T
106
Aroclpr activation
75
50
25
10
0
T
T
T
31
13
T
T
T
42
43
T
T
T
T
28
T
T
119
4B
8
T
T
70
70
31
T
T
156
202
22
T
T
T
T
48
T
T
T
54
42
T
T
T
T
35
T T
T T
T T
T T
96 91
T
T
T
T
167
T
T
T
108
94
T
T
T
117
108
T
T
T
T
192
T
T
T
229
126
T
T
T
I
153
T
T
T
T
123
No activation
50
0
T
7
T
42
T
58
T
17
T
42
T
21
T
40
T
27
T
44
T 109
94 76
T
110
T
71
T
111
ISO
105
T
159
T
153
T
99
                   *250 uL of aqueous extract/id, of ONSO test solution.
                   bl Big solid Naste/ut. of ONSO test solution.
                   C3 ng soltd naste/uL of DMSO test solution.
                   d300 ug solid waste/uL of DHSO test solution.
                   eT • toxic.

-------
                                                                TABLE 4.21. RESULTS OF HUTAGENICITY TESTING OF  WASTE  11 EXTRACTS
00
o
Revertants/Plate


Cone.
(ul/plate) EPa

Water


TA 98

Citrate Na-
a buffer resin" Column2 Soxhlet





Sequential extraction
" Acid0
Basec
Neutrald EPa

Citrate
Water" buffer9

Na-
resina
TA 100
Column9

Soxhletb



Sequential extraction
Acidc Base0 Neutrald
Phenobarbltal activation
7.5
S.O
2.5
1.0
0
110
92
46
30
19
39
52
45
27
16
71
57
54
49
42
Te
45
46
70
22
T
T
17
21
20
T
T
T
13
27
17
17
17
33
26
232
161
57
18
21
T
T
T
28
21
T
T
117
93
85
T
71
136
119
80
163
213
169
152
150
119
109
125
123
106
T
T
T
54
62
T
T
T
T
113
T
120
109
138
107
205
160
176
105
104
T
T


71
Aroclor activation
7.5
5.0
2.5
1.0
0

S.O
0
98
59
53
29
20

7
4
74
52
27
29
18

9
7
80
86
48
39
40

42
30
T
T
110
97
29

27
22
T
T
14
29
26

T
18
T
T
T
14
22

T
3
26
46
20
34
20

T
15
125
68
35
19
41

21
15
T
T
T
T
15
No
T
8
T
T
T
78
65
activation
T
40
T
T
78
79
74

95
30
156
165
214
176
135

120
95
151
109
182
143
110

T
85
T
T
58
48
73

T
46
T
T
T
T
45

T
122
T
T
119
140
94

T
65
T
T
T
T
202

T
90
T
T
T
T
47

T
116
                  a2SO pL of aqueous extract/luL of DHSO test solution.
                  bl mg solid waste/uL of OMSO test solution.
                  C3 mg solid vaste/uL of DNSO test solution.
                  d300 ug solid waste/uL of OMSO test solution.
                  eT • toxic.

-------
  TABLE 4.22.  SUMMARY OF MUTAGENIC ACTIVITY OF SOLID UASTE
      ISOLATES:  AQUEOUS EXTRACTS AND ORGANIC ISOLATES*
Aqueous extracts
Organic isolates
Sequential
extraction
Waste
1
2
3
4
5
6
9
10
11
Q.
LU
T
NE
T
NE
NE
T
NE
T
M
s_
V
•»->
£
M
NE
M
NE
NE
T
NE
T
M


-------
isolate, as well as the acid and neutral  fractions  from the  sequential
extraction, also gave a mutagenic response in TA 98.   The Soxhlet
isolate and the acid fraction were direct mutagens, whereas  the
remainder of the mutagenic extracts of this waste required metabolic
activation.
     Waste 2 displayed mutagenic activity in the citrate buffer and
Na-resin extracts (Table 4.14).   The positive response was confined to
TA 98 and required metabolic activation.   The column  extract and
Soxhlet isolate and the acid fraction from sequential  extraction were
toxic, particularly toward TA 100.
     Mutagenic activity detected in waste 3 was  restricted to the water
extract (Table 4.15).  Significant activity in TA 98  was noted with the
phenobarbital-induced activation system,  as well  as in the absence of
metabolic activation.  Results obtained with TA  98  (Aroclor  activation)
and with TA 100 (with and without activation) treated with water extract
support the positive observation noted with TA98/phenobarbital
activated.  No other extract or  isolate elicited a  mutagenic response.
     As noted above, no mutagenic activity was observed with any of the
isolate or extracts from waste 4 (Table 4.16).  Toxicity was seen,
however, with the Na-resin and column extracts,  Soxhlet isolate,  and
the acid fraction from sequential extraction, which made mutagenicity
impossible to detect.
     Two samples from waste 5 gave a positive response with  TA 98:  the
citrate buffer extract (with Aroclor activation)  and  the base fraction
from sequential extraction (with phenobarbital activation) (Table 4.17).
No other activities were noted;  waste 5 extracts  and  isolates were
essentially nontoxic in these assays.
                                  82

-------
     No mutagenic response was observed with extracts and Isolates  of
waste 6 (Table 4.18).  Significant cytotoxicity was noted with the  EP,
water, citrate buffer extracts, and the acid fraction.  The neutral
fraction from sequential extraction was not available for testing.
     Only one extract or isolate of waste 9 (the neutral fraction from
sequential extraction) gave a positive mutagenic response
(Table 4.19).  This isolate was mutagenic in the presence of metabolic
activation (either microsome preparation) in strain TA 98.  The Soxhlet
isolate and acid fraction were toxic.
     Several samples from waste 10 were genetically active
(Table 4.20).  The Na-resin extract was mutagenic in TA 98 with Aroclor
activation, while the Soxhlet isolate and column extract were active in
TA 98 with phenobarbital activation.  The data suggest that either
activation system will accommodate the mutagenic agent(s) in these
samples.  A striking response was obtained with the acid fraction from
sequential extraction.  This fraction was mutagenic (with phenobarbital
activation) in TA 98 and TA 100.  All of the extracts and isolates  from
this waste were toxic at high dose levels.
     The samples of the final waste assayed, waste 11, were
sufficiently toxic that the dose range was lowered tenfold to bring
survival up to a reasonable level for a meaningful  assay (Table 4.21).
The EP, water, Na-resin extracts, and the base fraction gave positive
mutagenic responses in TA 98 with metabolic activation.  The column
extract, Soxhlet isolate, acid fraction, and neutral fraction were
toxic.  Even at an additional 10-fold reductions, the column extract
was still toxic at the higher dose levels.
                                   83

-------
     In summary, seven of the nine wastes  possessed  detectable
mutagenic activity in one or more extracts or isolates (Table 4.22).
It is interesting to note that the organic isolates  produced  by
methylene chloride Soxhlet extraction and  the three-step sequential
extraction procedure showed mutagenic activity in  two  and five of the
wastes tested, respectively.  On the other hand,  six of the nine wastes
were found to possess mutagenic activity by using  the  less aggressive
aqueous extracting procedures.  The Na-resin extracts  accounted for
four of the seven positives.  Water and citrate buffer revealed three
of the wastes (but not the same three) to  contain  mutagenic activity
while the EP and the column (which extracted the greatest quantities  of
chromatographable organic compounds) procedures revealed only one of
the eleven wastes to contain mutagenic activity (again not the same
waste).  These data demonstrate the difficulties  in  establishing a
single procedure or media that will be universally successful  (with a
broad variety of wastes) in providing an extract that  allows
unambiguous testing of mutagenicity.  The  sequential extraction
procedures has the advantage of separating active  components  into
separate fractions.  In this way the confounding effects of
cytotoxicity and mutagenicity are frequently resolved  and information
about the nature of the mutagen is obtained.

4.1.5  Filtration Study
     One of the major objectives of the filtration study was  to
determine if the filtration of batch extracts  (through 0.4-pm pore
size membrane filters) was responsible for the large differences in
concentration of organic compounds noted between the batch and column
                                   84

-------
extraction procedures (the column extracts were no* filtered using  the
0.4-um pore size membrane filters).  To do this,  a series  of
experiments were conducted as outlined In Section 3.2.3.
     Small differences In amounts of organic compounds were  found In
the column extracts produced from experiments 1 and 2 (Table 4.23).   In
this experiment, the extracts were passed directly through XAD-2 resin,
with and without an in-line glass fiber filter.  These data  suggest
that entrained organic particles that can pass through the PTFE cloth
i.e., < 10 urn, but would be retained by a glass-fiber filter i.e.,
> 0.7 ym, either do not represent a significant input to the XAD-2
resin or pass through it without being adsorbed with  the waste tested
(waste 14).
     A column extract was also subjected to four  separation  treatments
(Table 4.24).  In this case, the glass fiber filter retained  less
organic material, judged by analyzing GC-elutable compounds  in the
filtrate, than did any of the other treatments.  Compounds such as
naphthol, phenanthrene, and benzo(a)anthracene were not detected in
the extract filtered through the Millipore filter,  nor was
benzo(a)anthracene detected in the extract filtered through  the
Nuclepore filter.  Thus, Millipore filters appear to  be more  sorptive
for some classes of nonpolar organic compounds than do the Nuclepore
filters.  Sorption in this case appears to be related to filter type
(material) rather than nominal pore size.
     A comparison of the quantities of organic compounds found in the
glass-fiber-filtered extracts collected directly  from the  column on
XAD-2 resin (Table 4.23, approximately 25,500 ug/100  g) versus those
                                  85

-------
       TABLE 4.23.  ORGANIC COMPOUNDS FOUND IN
          COLUMN EXTRACTS, WITH AND WITHOUT
                  AN IN-LINE FILTER3
Compound
    Without
    filter
  With
filterb
Naphthalene
Quinoline
Naphthol
Dibenzothiophene
Phenanthrene
Benzo(a)anthracene
    Totaic
	 - ug/100 g waste 	
       945                 1275
        50                  305
        70                   80
        30                   50
        40                   65
       300                  155
    21,900               25,500
aUsing waste sample 14,  extracts collected directly
 from column on  XAD-2 resin.
bGlass fiber filter (precombusted,  Whatman GF/F,
 0.7 urn) placed on  top  of column.
cTotal = all elutable compounds using GC.
                          86

-------
     TABLE 4.24.   ORGANIC  COMPOUNDS  REMAINING  IN A COLUMN EXTRACT
         AFTER USING FOUR SOLID/LIQUID SEPARATION  TREATMENTS3
Compound

£-cresol
Naphthalene
Qu incline
Naphthol
Dibenzothiophene
Phenanthrene
Carbazole
Benzo( a) anthracene
Totald

Glass fiber
(0.7-um)


9648
5052
1376
392
336
400
104
208
91,200
Filtered
Nuclepore
(0.4-um)
- - - no/inn

1948
2756
412
80
64
76
76
nd
66,320

Mi Hi pore
(0.45-ym)


1632
2228
428
ndc
68
nd
168
nd
68,200
Centrifugedb


1496
2108
400
72
28
44
40
nd
60,640
 Using waste 14.
3Centrifuged in open  250-mL  glass  bottles, 400 times gravity for 1 h.
"nd - not  detected.
 Total  = all  elutable compounds using GC.
                                  87

-------
collected from the column and Isolated using  a  solvent partition
technique (Table 4.24, ca. 60,000 to 90,000 ug/100  g), suggests that
the in-line XAD-2 resin cartridge (16.8 ml) may not be the  most
effective means of collecting organic compounds.  For example, for the
waste tested (No. 14) approximately three to  four times more  elutable
compounds were detected using the solvent partition method  to isolate
and concentrate organic compounds from the aqueous  effluent.  The
treatment of the internal standard (azulene)  was  different  for these
two extracts (in the case of the column/XAD-2 system, the internal
standard was added after resin extraction;  with the solvent extraction
system the azulene was added to the aqueous phase prior to
extraction).  However, in view of the high  recoveries (> 75%)
normally obtained for azulene, it is unlikely that  the large
differences in organic chemical levels noted  between the two  isolation
techniques can be attributed to differences in  the  handling of the
internal standard.
     Amounts of organic compounds observed  among  the batch  extracts
after the four separation treatments can be found in Table  4.25.
Phenanthrene was again not detected in any  of the extracts  filtered
through the Millipore filters.   It is interesting  to note  that
benzo(a)anthracene was not found in any of  the  batch extracts,
regardless of the filter type used, while it  was  observed in  the
glass-fiber-filtered column extract (see Table  4.24).  In all cases,
where extracts were filtered through glass  fiber  filters, the column
extract contained greater quantities of organic compounds than did the
extracts from the batch procedures.
                                  88

-------
   TABLE  4.25.   ORGANIC COMPOUNDS REMAINING IN A BATCH WATER EXTRACT
         AFTER  USING FOUR SOLID/LIQUID SEPARATION TREATMENTS3

Compound


£-cresol
Naphthalene
Qu incline
Naphthol
Dibenzothiophene
Phenanthrene
Carbazole
Benzo(a) anthracene
Total d
F
Glass fiber
(0.7-um)


3056
4564
100
96
60
168
64
nd
43,240
Mltered
Nuclepore
(0.4-um)
_ iin/lflf

4380
3032
100
80
48
60
56
nd
45,280

Millipore
(0.45-un)


3376
4784
108
60
36
nd
48
nd
46,000

Centrifugedb


3856
4520
104
132
64
168
64
nd
44,400
aUsing waste 14.
bCentrifuged in open 250-mL glass bottles,  400 times  gravity  for  1  h.
cnd = not detected.
 Total = all elutable compounds using GC.
                                  89

-------
     When £ standard solution containing known  concentrations  of
selected organic compounds was subjected to the different  solid/liquid
separation treatments, differing amounts of organic compounds  were also
found (Table 4.26).  In general, the glass fiber filter exhibited lower
sorption properties.  Again, certain organic compounds
[dibenzothiophene, phenanthrene, and benzo(a)pyrene]  were  not  found in
the Millipore-filtered sample from any extract  (<1 yg/L).   Additional
losses of organic compounds were seen when the  standard solution was
agitated for 24 h (Table 4.27).   This loss is probably  due to  sorption
of the compounds on the glass container walls.   This  may also  explain
the loss of organics in the centrifuged samples (i.e.,  samples were
centrifuged in glass bottles).  Volatilization  may also have occurred
in the centrifuged samples.

4.2  Task 2:  Comparison of Two  Sample Preparation Protocols for
              Performing the Ames Test on Solid Waste Extracts and
              Wastewaters
     The results of the recovery study comparing isolation of  two
organic compounds [benzo(a)pyrene (BaP) and 9-amino-acridine]  from
extracts and wastewaters using the XAD resin adsorption and solvent
partition techniques are shown in Table 4.28.   The BaP  recovery  values
are somewhat confounded by the fact that the added BaP  was well  in
excess of its water solubility (1  mg/L added relative to a water
solubility of below 10 yg/L). Thus, the recovery data  for solvent
partition showed an unexpected distribution of  BAP into the acid
fraction, implying that three extractions with  methylene chloride were
not sufficient to remove all of  the BAP into the base/neutral
                                  90

-------
    TABLE  4.26.   ORGANIC  COMPOUNDS  REMAINING  IN A STANDARD SOLUTION
           AFTER USING FOUR TREATMENTS FOR SEPARATING SOLID
                          AND LIQUID PHASES3

Compound


Phenol
p_-cresol
Naphthalene
Qu incline
Naphthol
Dibenzothiophene
Phenanthrene
Carbazole
Fluoranthene
Benzo(a)anthracene

Glass fiber
(0.7-um)


7.8
8.6
5.8
6.3
6.6
9.2
9.7
11.6
7.4
4.4
Filtered
Nuclepore
(0.4-um)


7.8
8.8
1.3
6.7
7.7
9.7
11.5
2.0
8.8
3.8

Millipore
(0.45-um)


7.7
8.1
1.0
5.2
7.0
ndc
nd
1.3
nd
nd

Centrifugedb
• -

6.0
9.2
6.1
7.0
7.9
6.7
5.9
6.6
7.8
5.7
Approximately 10 ppm of each compound added  to prepare  standard
 solution.
 Centrifuged in open 250-mL glass bottles,  400  times  gravity for  1 h.
cnd = not detected at 1  mg/L.
                                   91

-------
   TABLE 4.27.  ORGANIC COMPOUNDS REMAINING IN A STANDARD SOLUTION
     (AGITATED FOR 24 HOURS) AFTER USING FOUR SOLID/LIQUID PHASE
                        SEPARATION TREATMENTS*

Compound


Phenol
£-cresol
Naphthalene
Qu incline
Naphthol
Dibenzothiophene
Phenanthrene
Carbazole
Fluoranthene
Benzo(a)anthracene

Glass fiber
(0.7-um)


7.2
8.1
5.2
5.3
6.3
4.6
4.7
4.8
3.4
2.1
Filtered
Nuclepore
(0.4-um)


5.9
8.3
2.9
4.9
7.4
4.3
4.3
4.5
2.6
1.8

Millipore
(0.45-um)


4.2
6.7
3.2
5.4
5.3
ndc
nd
1.8
nd
nd

Centrifugedb


4.3
8.2
3.4
7.0.
8.2
4.8
5.1
5.5
4.6
3.2
Approximately 10 ppm of each compound  added to prepared standard
 solution;  standard solution  was  agitated for 24 h.

 Centrifuged in 250-mL glass  bottles, 400 times gravity for 1 h.

cnd - not detected at 1 mg/L.
                                  92

-------
  TABLE 4.28.  COMPARISON OF TWO ISOLATION TECHNIQUES FOR REMOVING
     ORGANIC MUTAGENS FROM WASTEWATERS AND SOLID WASTE EXTRACTS



XAD-2 resin
Aqueous medium
Water
EPC
Leachate
Wastewater6
Water
EPC
Leachate
Wastewater6
Base/
neutral

77.0
87.5
85.0
83.0
78.0
83.5
78.5
85.5
Acid

1.5
3.0
1.5
4.5
0.0
2.0
1.0
0.0
% recovery3


Solvent partition
Base/
Total neutral

78.5 50.0
90.5 55.5
86.5 27.5
87.5 83.0
9 -ami no acridine^ -
78.0 93.5
85.5 72.5
79.5 74.0
85.5 96.5
Acid

22.0
24.5
7.5
7.5
0.0
0.0
0.0
0.0
Total

72.0
80.0
35.0
90.5
93.5
72.5
74.0
96.5
al mg/L of mutagen added, average of two replicates.
bRecovery measured using both HPLC and scintillation  counting
 (results agreed +_2%).
cSolid waste extract using the EPA-EP with waste 10.
^A waste leachate collected at a landfill containing  waste  3.
eCoal conversion wastewater.
^Recovery measured using fluorescence spectrophotometry.
                                 93

-------
fraction.  However, for the soluble 9-amino-acridine,  the  recovery
distribution was excellent.
     Using Duncan's multiple range test,  the only significant
difference (P < 0.05) in recovery of the  BaP or  9-amino-acridine
between the two isolation techniques was  noted with  BaP  in landfill
leachate.  Significant precipitation and  subsequent  emulsion formation
took place using the solvent partition technique, which  could  account
for the difference noted.  There were also some  significant differences
(P < 0.05) in the recovery of BaP and 9-amino-acridine by  the  solvent
partition technique, depending on the type of aqueous  medium spiked
with these chemicals.  For example, in addition  to the very low
recovery of BaP in the landfill leachate  (35%),  the  recovery of BaP
from the water and EP extract (72 and 80% recovery,  respectively) was
significantly lower than its recovery by  solvent partition from coal
conversion wastewater (90.5% recovery).  The nature  of the aqueous
medium also affected the recovery of 9-amino-acridine.  In this case,
the recovery from the EP extract and landfill  leachate (72.5 and 74.0%,
respectively) was significantly (P < 0.05) lower than  that recovered
from the water or coal conversion wastewater (93.5 and 96.5%,
respectively).  In contrast, there were no observed  differences in the
recovery of either BaP (range 77.0% to 90.5%) or 9-amino-acridine
(78.0% to 85.5%) among the aqueous media  using the XAD-2 resin
technique.  These data suggest that the XAD-2 resin  technique  is
preferable to solvent partition if a wide range  of aqueous media are to
be investigated.
                                  94

-------
     Mutagenicity testing results of the positive controls and the
organic isolates from the recovery study are shown in Tables 4.29
to 4.31.  The mutagenic activity was directly related to the chemical
distribution of benzo(a)pyrene and 9-amino-acridine.   There was no
indication of interference from other organic species present in the
extracts.
     Aqueous media spiked with 9-amino-acridine were directly mutagenic
when tested with TA1537.  When assayed with metabolic activation
applied, activity was also seen with TA1538, TA98, and TA100.
     The benzo(a)pyrene-spiked extracts showed no mutagenic activity
with any strain in the absence of metabolic activation.  Strong
positive responses were observed in TA1537, TA1538,  TA98,  and TA100
when metabolic activation was applied.  Qualitatively, the mutagenic
activity of the spiked extracts was identical  to the  results obtained
with the positive control samples of 9-amino acridine and
benzo(a)pyrene.
     In summary, there was no major difference in the ability of the
two techniques to recover BaP or 9-amino-acridine from wastewaters.
The single observed difference was the very poor recovery  of BaP in the
landfill leachate by the solvent partition  technique  (35%  recovery
compared to 86.5% recovery by XAD-2).   However,  in the solvent
partition technique, recovery appeared to be dependent on  the aqueous
medium.  Recovery by the XAD-2 technique, on the other hand, was
observed to be independent of the aqueous matrix.  Furthermore,  the
resin isolation procedure (XAD-2 resin) is  superior,  from  a practical
standpoint, for the following reasons:
                                  95

-------
TABLE 4.29.  MUTAGENIC ACTIVITY OF THE POSITIVE CONTROLS
           BENZO(A)PYRENE AND 9-AMINO ACRIDINE

Compound


Benzo(a)pyrene (25 ng/uL)
With activation
Without activation
9-amino acridine (25 ng/yL)
With activation
Without activation
Strain
TAT 535 TA1537 TAT 538 TA98



0 9.5 13.1 7.4
0000

0 1.4 2.0 1.7
0 3.1 0 0

TA100



4.2
0

0.9
0
                            96

-------
 TABLE 4.30.  MUTAGENIC ACTIVITY IN ORGANIC ISOLATES:   COMPARISON
            OF  RECOVERY TECHNIQUES  USING BENZO(A)PYRENE


Aqueous medium

Water
EP
Leachate
Wastewater

Resin
Base/neutral
TAT 537
7.0
8.1
6.9
7.4
Revertants/uLa

Solvent partition
Acid Base/neutral
, Aroclor activation
0 4.0
0 5.6
0 4.7
0 4.4
Acid

0.3b
1.2
1.4
1.3
TA1538, Aroclor activation
Water
EP
Leachate
Wastewater
11.5
11.5
10.2
11.2
0 4.5
0 5.4
0 4.6
0 4.7
3.8b
3.0
2.6
2.2
TA98, Aroclor activation
Water
EP
Leachate
Wastewater

Water
EP
Leachate
Wastewater
8.0
8.7
8.1
8.9
TA100.
5.7
4.6
8.2
3.8
0 5.4
0 6.4
0 6.9
0 7.3
Aroclor activation
0 3.8
0 2.9
0 5.0
0 3.5
1.5"
1.9
2.6
2.4

0.8b
1.8
2.1
1.6
aAverage of two replicates.

bSingle determination.
                               97

-------
TABLE 4.31.  MUTAGENIC ACTIVITY IN ORGANIC  ISOLATES:   COMPARISON
         OF  RECOVERY  TECHNIQUES USING 9-AMINO ACRIDINE
Revertants/uL3

Aqueous medium
Resin
Base/neutral
Solvent partition
Acid Base/neutral
Acid
TA1537, No activation
Water
EP
Leachate
Wastewater

Water
EP
Leachate
Wastewater

Water
EP
Leachate
Wastewater

Water
EP
Leachate
Wastewater
1.7
2.2
2.7
1.6
TA1538,
0.7
0.8
1.3
1.1
TA98,
0.8
0.9
1.4
1.2
TA100,
1.0
1.3
1.2
0.9
0
0
0
0
Aroclor
0
0
0
0
Aroclor
0
0
0
0
Aroclor
0
0
0
0
2.4
2.4
2.1
2.2
activation
0.9
1.2
1.1
0.8
activation
1.7
0.5
1.0
0.9
activation
1.4
0.6
1.7
0.9
0
0
0
0

0
0
Ob
0

0
0
Ob
0

0
0
0
0
  aAverage of two replicates.

  bSingle determination.
                               98

-------
     (1)  It is technically simpler, and a series of XAD columns can be
          used to facilitate handling large numbers of samples.
     (2)  There are no problems with emulsion formation.  Emulsions may
          pose severe problems in solvent partition techniques with
          "dirty" water samples, e.g. the real-world landfill  leachate.
     (3)  It is more economical; much less solvent is consumed.
However, the resin procedure has limitations.  If significant
precipitation occurs during pH adjustment, flow of water through the
column can be impeded, increasing extraction time.  Also batch-to-batch
variability in the resin, as well as contamination, requires that
extensive clean-up of the resin is necessary to ensure reproducibility.

4.3  Task 3;  An Evaluation of the Equivalence of Magnetically Stirred
              Extractor Relative to an EPA-Approved Rotary Extractor
              for Conducting the EP
     A magnetically stirred extractor and a rotary extractor were
compared for conducting the EP.  Using the low frequency tachometer
(see Section 3.2.5), the stirring rates for the magnetically stirred
extractor were recorded every hour during the 24-h extraction  for
wastes 12 and 13.  Figures 4.10 and 4.11 present the mean speed  and the
standard deviation found for the four replicate EP extractions during
the extraction period.  Waste 12 was a very hard granular solid, and
427 rpm represented the lowest mean rate (over the 24 h)  required to
keep the solids suspended.  Waste 13 was a powdery solid, high in
magnetite, which was expected to load the magnetic stirrer.  Even so, a
lower mean 24-h stirring rate of 342 rpm was obtained.   In  both  cases,
the stirring speed gradually increased for 1  to 2 h after adding the
solids to the extractor.  The stirring rate was reproducible between
                                  99

-------
                                             ORNL-DWG 81-21532 ESD
   700
   600
   500
,>••••{
                  -«~l f
   200
   100
                 
-------
                                                    ORNL-DWG 81-21533 ESD
 Q.


Q
ill
LU
cc

tt
CC
    700
    600
    500
   400
    300
   200
    100
                                    12        16

                                   TIME (h)
                                                       20
24
Fig. 4.11.  High and low stirrer speed values for waste 13 - mean and
            standard deviation values for four replicate extractions
            over the 24-h extraction time.
                                  101

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the four replicate runs of each 24-h extraction;  for example,  the
coefficients of variation (calculated each hour for the four
extractions) for wastes 12 and 13 were 6 and  3% for the highest speed
and 12 and 5% for the lowest speed, respectively.
     The percent variation associated with the  variables of agitation
method, replicate extractions, and analytical procedure was determined
using variance component analysis (Table 4.32).   The major source of
variation was associated with the agitation method (39-95%), although
the amount differed depending on the waste and  element.   The amount  of
variation associated with extraction replicates and analytical
procedure also differed according to waste and  element,  ranging from
5.0 to 39.1% for extraction replicates and 0.3  to 22.0% for analytical
procedure.
     Mean inorganic concentrations for wastes 12 and 13 and statistical
differences found between agitation methods are  shown in Table  4.33.
In all cases, the magnetic stirrer agitation method produced
statistically (P < 0.05) different inorganic concentrations than the
rotary extractor.  Neither method showed consistently higher
concentrations.  For waste 12, the rotary extraction method extracted
greater amounts of Cd, while Fe and Ni concentrations were higher using
the magnetic stirrer at either stirring rate.   For waste 13,
concentrations of As were highest using the rotary extractor; Cd
concentrations were highest using the magnetic  stirrer,  and Zn  values
were lowest using the high-speed magnetic stirrer.  It is interesting
to note that concentrations of a more volatile element such as  As are
considerably reduced when using the open magnetic stirrer system versus
                                  102

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       TABLE 4.32.  DISTRIBUTION OF VARIATION ASSOCIATED WITH
      THE VARIABLES OF AGITATION METHOD, REPLICATE EXTRACTION,
                      AND ANALYTICAL PROCEDURE3
Sample


12



13


Variable


Agitation method
Agitation replicates
Analytical procedure

Agitation method
Agitation replicates
Analytical procedure


_Cd_
38.9
39.1
22.0
As_
94.7
5.0
0.3
Element

%_ _
_F_e__
78.7
17.1
4.2
_Cd_
59.4
26.7
13.9


Ni
71.9
10.9
17.2
In
71.9
6.0
22.1
aDetermined using variance component  analysis  (SAS  Institute,  Inc.,
 1979).
                                 103

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    TABLE 4.33.   MEAN (x)  CONCENTRATIONS AND STATISTICAL DIFFERENCES
        OF SELECTED INORGANIC  COMPOUNDS USING A MAGNETIC STIRRER
               (2 AGITATION RATES) AND A ROTARY EXTRACTOR3
Waste



12



13


Agitation



Magnetic stirrer - high speed
Magnetic stirrer - low speed
Rotary extractor

Magnetic stirrer - high speed
Magnetic stirrer - low speed
Rotary extractor



Cd
66*
70+
76
As
99*
343+
548
Element
iin/l

fe_
36+
47
22*
Ci
91 +
91 +
78*



Ni
207 7+
2042+
1777*
_Zn
564*
1084
880"""
aValues within a sample for a  particular element that have different
 superscripts  are significantly different (P  < 0.05), as determined
 using Duncan's multiple range test  (SAS Institute,  Inc., 1979).
                                 104

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the closed rotary system.   This is  also supported  by the  fact  that
high-speed stirring produced lower  As concentrations than did  the
slower stirring speed.   Concentrations of the other elements
investigated also differed between  the high- and low-speed stirring
rates; where statistical differences  were found  (for Cd,  Fe, Zn), the
high-speed magnetic stirrer yielded lower amounts.
     In summary, differences can be expected in  inorganic contaminant
concentrations when using  a magnetic  stirrer extractor versus  rotary
extractor.  Neither method will yield consistently higher
concentrations than the other.   However, because the concentrations of
elements in these samples  were  very low (ppb-range), it is recommended
that additional samples containing  higher levels of extractable
constituents be studied.  If volatile constituents are of interest, the
closed rotary extractor may be  the  preferred method, although  this
system does not allow for  automatic pH adjustment.

4.4  Task 4:  An Evaluation of  the  Reverse-Phase High-Pressure Liquid
              Chromatography (HPLC) Protocol  for Assessing the
              Bioaccumulation Potential of Solid Waste Extracts
     Nine wastes were tested for bioaccumulative materials using  the
bioaccumulation potential  test  as described in Section 3.3.4.  The
materials tested were the  organic isolates from  the Soxhlet and
sequential extraction fractions, and  the organic concentrates  from the
five aqueous extraction procedures  on the nine wastes.  Table  4.34
illustrates data collected in terms of the number of chromatographic
peaks found with retention times equal to or greater than log  P = 3.0
as well as the total peak  area  with respect to bromobenzene.   All
wastes, with the exception of wastes  1 and 3 were  found to contain
                                  105

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           TABLE  4.34.   BIOACCUMULATION DATA ON SOLID WASTE ISOLATES:
                     AQUEOUS EXTRACTS AND  ORGANIC  ISOLATES*
Aqueous extracts


Waste
1
2
3
4
5
6
7
8
9


Q.

0
0
0
0
0
0
ned
0
0


i.
Ol
-u
ID

0
0
0
0
0
0
0
0
0


c
in
ia
_ _ _ M,,n
0
0
0
0
0
0
0
3/12.3
0
t-

-------
bioaccumulative materials, as Identified in  the  Soxhlet  isolates  and
sequential extraction fractions, but none of these materials  were
observed in the organic concentrates from the aqueous  batch extraction
tests.  An exception was waste 8 which contained by far  the highest
levels of these components.  The low quantities  of bioaccumulative
compounds observed in the batch extracts are probably  due in  large
measure to the low water solubility of the bioaccumulative compounds
which promotes their loss by adsorption on the membrane  filters
utilized in the batch extractions.
     Considering the highly lipiphilic nature of bioaccumulative
materials, it is interesting to note that significant  levels  of these
materials were isolated in the column extracts.   In almost all cases,
the materials found to be bioaccumulative in the solid wastes (by
Soxhlet and sequential extraction)  were also found in  the column
extracts.  Among the aqueous extraction procedures, only the  column
procedure is effective for the detection of  bioaccumulative materials,
using the current methodology.
     The bioaccumulation potential  test itself has several drawbacks.
No UV detector is not universal (therefore,  nonabsorbing materials such
as chlorinated aliphatic compounds  may be missed) nor  is the  response
of the UV detector uniform (highly  absorbing materials may be given too
high a ranking).  Therefore, information obtained is essentially
qualitative.  However, the test does provide a useful  screening method
for the detection of potential bioaccumulative organic compounds  in the
wastes as well as in the extracts.
                                  107

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                        SECTION 5.   CONCLUSIONS

5.1  Task 1;   An Evaluation of Extraction Procedures  to Remove
              Nonpolar Organic Compounds from Solid Wastes
     The primary objective of Task  1 was to  assess the capabilities  of
five selected extraction procedures to remove organic compounds from
11 solid wastes.  Other objectives  included  mutagenicity  testing of  the
extracts and examining the solid wastes for  organic compounds (Soxhlet
and sequential extraction) and the  solid waste extracts for  selected
inorganic constituents.  The five extraction procedures used were four
batch extractions and an upward flow column  extraction.   The following
extracting media were used:
     (1)  Batch 1:  EP, acetic acid, pH 5.0,
     (2)  Batch 2:  deionized distilled water,
     (3)  Batch 3:  deionized distilled water with a  sodium
                    displacement resin, and
     (4)  Batch 4:  0.5 M citrate buffer,
     (5)  Column:  deionized distilled water.
     The following conclusions are  based on  data presented for  Task  1:
     •   For the four batch extractions, the citrate  buffer  extracts
         consistently showed highest concentrations of inorganic
         compounds.
     •   Of the two methods compared for identification of organics  in
         the waste samples (Soxhlet extraction with methylene chloride
         and a three-step sequential extraction procedure developed  at
         ORNL), the three-step sequential extraction  scheme  consistently
         extracted more organic material than did the Soxhlet extraction.
                                  108

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No significant differences in organic concentrations (based on
DOC levels) were found between water and Na-resin extracts.
No significant differences were found in DOC values between
glass fiber and Nuclepore-filtered extracts from the water and
Na-resin extracts.
Total chromatographable organic (TCO) content data for the
five extraction procedures revealed that the column procedure
extracted more organic material than did any of the batch
extraction procedures.
When the five extraction procedures were ranked from lowest to
highest (1 to 5) for the ability to extract total
chromatographable organics (TCO),  the column procedure
produced extracts higher in TCO and selected organic compounds
than batch extracts (P < 0.05).
Of the four batch extraction procedures, the water procedure
extracted the highest levels of TCO and selected organic
compounds (P < 0.05).
No significant differences in the ability to extract organic
compounds were observed among the EP, Na-resin, citrate buffer
extractions.
In general, the column leaching procedure was the most
aggressive means of extracting organic compounds from solid
wastes.  The most noticeable differences between the column
procedure and the batch procedures were the levels of
moderately volatile compounds and  the nonpolar compounds found
in the extracts.
                         109

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The five extraction procedure extracts,  as well  as the Soxhlet
solid waste Isolate and the solid waste  Isolates produced from
the sequential procedure,  were compatible with the
Salmonella/microsome assay.
Of the nine wastes examined,  seven yielded organic Isolates
that possessed detectable mutagenic  activity.  The
Salmonel1 a/microsome mutagenicity assay  performance comparison
with the nine wastes Indicated that, of  the five aqueous
extraction procedures,  the Na-resin  extraction was the most
effective extraction, revealing four of  the mutagenic
activities detected.
Six mutagenic waste components were  identified  (from five
wastes) by the sequential  extraction method. This method has
the great advantage of (1) indicating the class  fractions
harboring the active components and  (2)  revealing multiple
mutagenic components.
Only one of the nine EP extracts examined exhibited mutagenic
activity.
The coefficient of variation  associated  with replicating the
column extraction procedure was 13%.
The use of glass fiber filters for the separation of solid and
aqueous phases allows higher  recovery of organic compounds
than filtering with Nuclepore and Millipore filters.
For a single waste, the column extraction procedure extracted
greater quantities of total chromatographable organic
compounds than a closed batch extraction,  even when the
extracts were filtered through the same  filter type.
                         110

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5.?.  Task 2:  Comparison of Two Sample Preparation Protocols for
              Performing the Ames Test on Solid Waste Extracts  and
              Wastewaters
     The objective of Task 2 was to compare two techniques  for  the
isolation of organic mutagens for performing the Ames test  on solid
waste extracts and wastewaters.  The two recovery techniques were a
resin absorption technique using Amberlite XAD-2 resin and  a solvent
partition technique using methylene chloride.  Two mutagens were
examined, benzo(a)pyrene and 9-amino acridine.   The following was
concluded:
         There were no major differences.in the ability of  the  two
         techniques to recover BaP or 9-amino acridine from wastewater.
         One exception was the very poor recovery of BaP in the
         landfill leachate by the solvent partition technique.
         The recovery of BaP and 9-amino acridine was dependent on the
         aqueous matrix using the solvent partition technique.
         Recovery of the mutagens by the XAD-2  technique was
         independent of the aqueous matrix.
         The various aqueous matrices employed  did not appear to  modify
         the amount of mutagenic activity attributable to
         benzo(a)pyrene and 9-amino acridine.
         From a laboratory performance standpoint, the resin isolation
         procedure was considered superior.
         The resin procedure, has its limitations.  If significant
         precipitation occurs during pH adjustment, flow of water
         through the column XAD-2 cartridge can be impeded.
                                  Ill

-------
5.3  Task 3;  An Evaluation of the Equivalence  of  a  Magnetically
              Stirred Extractor Relative to an  EPA-Approved  Rotary
              Extractor for Conducting the EP
     The objective of Task 3 was to compare a magnetically stirred
extractor with an EPA-approved rotary extractor for  conducting  the EP.
The conclusions were as follows:
     •   The high and low stirring rates obtained  using  the
         magnetically stirred extractor between replicate extractions
         of two wastes showed low variability.   Coefficient  of
         variation values for the two wastes were  6  and  3% for  the high
         speed and 12 and 5% for the low speed.
     •   The percent variation (determined using variance component
         analysis) associated with the variables of  agitation method,
         replicate extractions, and analytical  analysis  differed
         depending on the waste and metal. The major  source of
         variation, however, was associated with the agitation  method,
         ranging from 39 to 95%.
         The magnetic stirrer agitation method  produced  statistically
         different inorganic concentrations than the rotary  extractor.
         Neither method showed consistently higher concentrations.
         If volatile constituents are of interest, the sealed rotary
         extractor is the preferred method, although this system does
         not allow for automatic pH adjustment.
                                  112

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5.4  Task 4;  Evaluation of the Proposed Reverse-Phase High-Pressure
              Liquid Chromatography (HPi.C)  Protocol  for Assessing
              Bioaccumulation Potential of  Solid Waste Extracts
     The objective of Task 4 was to evaluate the proposed  reverse-phase
High-Pressure Liquid Chromatography (HPLC)  protocol  (EPA 1978) to
assess the bioaccumulation potential of solid waste  extracts.  Soxhlet
extracts, acid/base/neutral fractions from  the sequential  extraction
procedure, and the organic isolates from the aqueous extracts of the
five extraction procedures produced in Task 1 were tested  for
bioaccumulative material.  The following was concluded:
         Of the five aqueous extraction procedures,  only the column
         extraction produced extracts that  contained bioaccumulative
         material.
         A majority of the Soxhlet isolates and sequential  extraction
         procedure fractions of the solid wastes contained
         bioaccumulative organics.
         The bioaccumulation test itself has several drawbacks; the
         UV detector is not universal (therefore, nonabsorbing
         materials may be missed) and the response of the  UV detector
         is not uniform.
         The present bioaccumulation protocol can provide  a screening
         method for the detection of potentially bioaccumulative
         organic compounds in the wastes as well  as  in their leachates.
                                  113

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                      SECTION 6.   FUTURE  RESEARCH

     Further research should be conducted to determine  if the up-flow
column extraction procedure Is superior to batch-mode extractions for  a
variety of wastes and extracting media.   It appears that one of the
major faults in the batch-mode extractions is the filtration step:
(1) it is very time consuming for  some samples, and (2) the filtration
using 0.40- to 0.45-ym membrane filters appears to sorb significant
quantities of certain organic compounds.  It was demonstrated that
up-flow column extracts not filtered  through membrane filters contained
significantly greater quantities of total chromatographable organic
compounds than batch extractions which were filtered through 0.4-ym
pore size filters.  When water was used as the common extracting medium
for a single waste in both the up-flow column and a batch-mode
extraction, the total quantity of  elutable organic compounds by gas
chromatography was 1.4 to 2.1 times higher using the up-flow column.
The quantity of organic compounds  varied  according to the method of
liquid/solid phase separation and  type of filter.  Further experiments
should be conducted to confirm if  this is typical for a variety of
wastes and possibly for different  classes of extracting media.
     Regardless of which type of extraction procedure is found to be
superior for extracting organic compounds (either up-flow column or
batch extraction), its relevance to simulating the leaching of organic
and inorganic constituents from wastes co-disposed in a municipal
landfill environment needs to be established.  The present EP was
conceived as a first-order approximation  to simulate leaching action of
                                  114

-------
the low molecular weight carboxylic acids generated In an actively
decomposing municipal landfill.  It uses acetic acid,  the carboxylic
acid most prevalent In municipal waste landfill leachate.  The acetic
acid, because of Its weak acidic character,  plays  a dominant  role  in
the leaching of metals; however, its role relative to  the removal  of
polar and nonpolar organic compounds from wastes is unclear.   Acetic
acid also was not compatible with a variety of biotesting procedures
(Epler et al. 1980).  Thus, the limitations  of acetic  acid as an
extracting medium were the impetus behind this past year's research.
     Future research needs to (1) confirm the  aggressiveness  of the
up-flow column to remove organic and inorganic constituents from a
variety of wastes using selected leaching media, and (2)  test the
effectiveness of the up-flow and batch-mode  extractions to simulate
leaching by municipal waste leachate.   The objective of this  research
is to develop a second generation test for mobility, henceforth known
as EP-III, that will more accurately and reproducibly  model leachate
production, for inorganic as well as organic constituents, in a
co-disposal municipal landfill.  A workplan  with these objectives  is
appended (Appendix B).
                                  115

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                            7.  REFERENCES

Brazell, R. S., and M. P. Maskarinec.  1981.   Dynamic Headspace
     Analysis of Solid Waste Materials.   J.  High  Resolut.  Chromatogr.
     Chromatogr. Comm. 4:404-405.
Brown, D. K., C. W. Francis, M. P. Maskarinec, and F. W.  Larimer.
     1981.  Toxicity of Leachates, Comparison  of  Extraction  Procedure
     Extracts and Landfill Leachates.  ORNL/TM-7563.   Oak  Ridge
     National Laboratory, Oak Ridge, Tennessee.
Environmental Protection Agency (EPA).  1980a. Background Document.
     Section 261.24 - EP Toxicity  Characteristic.   Office  of Solid
     Waste, Environmental Protection Agency, Washington,  D.C.
Environmental Protection Agency (EPA).  1980b. Identification  and
     Listing of Hazardous Waste.  _IN Environmental  Protection Agency
     Hazardous Waste Management System.   40 CFR 261.24.
Environmental Protection Agency (EPA).  1980c. Microbial  Bioassay for
     Toxic and Hazardous Material.  EPA-330/9-80-002,  Office of
     Enforcement, EPA, Denver, Colorado.
Environmental Protection Agency (EPA).  1980d. Test  Methods for
     Evaluating Solid Waste, Physical/Chemical Methods.   SW-846,
     U.S. Environmental Protection Agency, Washington, D.C.
Environmental Protection Agency (EPA).  1979a. National  Interim
     Primary Drinking Water Regulations. 40 CFR  141.
                                  116

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Environmental Protection Agency (EPA).  1979b.  Methods for Chemical
     Analysis of Water and Wastes.   EPA-600/4-79-010,  Environmental
     Monitoring and Support Laboratory, Office of Research and
     Development, U.S. Environmental  Protection Agency, Cincinnati,
     Ohio.  460 pp.
Environmental Protection Agency (EPA).  1978a.  Hazardous  Waste:
     Proposed Guidelines and Regulations and Proposal  on Identification
     and Listing.  Fed. Regist. 43:58966.
Environmental Protection Agency (EPA).  1978b.  Identification  and
     Listing of Hazardous Waste.  Advanced Notice of Proposed
     Rulemaking.  Fed. Regist.  43:59025-59026.
Epler, J. L., F. W. Larimer, T. K.  Rao, E. M. Burnett, W.  H. Griest,
     M. R. Guerin, M.  P. Maskarinec,  0. A. Brown,  N.  T. Edwards,
     C. W. Gehrs, R. E. Millemann,  B. R. Parkhurst,  B. M.  Ross-Todd,
     D. S. Shriner, and H. W. Wilson, Jr.   1980.   Toxicity of
     Leachates.  EPA-600/2-80-057,  Office of Research and  Development,
     U.S. Environmental Protection  Agency, Washington, D.C.  134  pp.
Feldman, C.  1974.  Perchloric  Acid Procedure for Wet-Ashing Organics
     for the Determination of Mercury (and Other Metals).   Anal.  Chem.
     46:1606-1609.
Feldman, C.  1979.  Improvements in the Arsine Accumulation - Helium
     Glow Detector Procedures for Determining Traces  of Arsenic.  Anal.
     Chem. 51:664-669.
                                  117

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Kam, R., M. A. Anderson, R. Stegman,  and R.  Stanforth.   1979.
     Background Study on the Development of  a  Standard  Leaching  Test.
     EPA-600/2-79-109, Office of Research and  Development.
     U.S. Environmental Protection Agency, Cincinnati,  Ohio.
Maskarinec, M. P., and R. W. Harvey.   1982.  Screening  of Sludges and
     Solid Wastes for Organic Compounds.  Int.  J.  Environ.  Anal.  Chem.
     11:53-60
McKown, M. M., J. S. Warner, R. M. Riggin, M.  P. Miller,
     R. E. Heffelfinger, B. C. Garrett,  and  G.  A.  Jungclaus.   1980.
     Development of Methodology for the  Analysis of  Solid Wastes.
     Draft Final Report to U.S. EPA,  Washington, D.C.
SAS Institute, Inc.  1979.  SAS User's Guide.   Cary,  North  Carolina.
Schnitzer, M., and S. U. Kahn.  1972. Humic Substances in  the
     Environment.  Chapter 2, pp. 9-27.   IN  Extraction, Fractionation,
     and Publication of Humic Acids.   Marcel Dekker,  Inc.,  New York.
Shultz, F. J., and A. W. Spears.  1966.   Determination  of Moisture in
     Total Particulate Matter.  Tob.  Sci. 10:75-76.
Talmi, Y., and A. W. Andren.  1974.  Determination of Selenium in
     Environmental Samples Using Gas  Chromatography with a  Microwave
     Emission Spectrometric Detection System.   Anal.  Chem.  46:2122-2126.
Zlatkis, A., R. S. Braze!1, and C. Poole.  1981.   The Role  of  Organic
     Volatile Profiles in Clinical Diagnosis.   Clin.  Chem.
     27(6):789-797.
                                  118

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                              APPENDIX A


                    QUALITY ASSURANCE PROJECT PLAN

                                  For

                    "Toxicity of Leachates  Project"

                     Oak Ridge National  Laboratory
                      Oak Ridge, Tennessee   37830

                            Revision No. 1

                            April 15, 1982
                        Interagency Agreements
                            DOE 40-1087-80
                          USEPA AD-89-F-1-058
APPROVAL:

ORNL Project Manager: 	Date:
                            C.  W.  Francis
ORNL QA Coordinator (ESD): 	Date:
                            M.  H.  Shanks
ORNL QA Coordinator (ACD):	Date:
                            L.  T.  Corbin
EPA Project Officer: 	Date:
                            Llewellyn R.  Williams
EPA QA Officer: 	        	Date:_
                            John Santolucito
                                  119

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                           Table of Contents
Section Description
1.0 Project Description
2.0 Project Organization and
Pages Revisions Date
3 1 4-15-82
2 1 4-15-82
 3.0
 4.0
 5.0
 6.0

 7.0
 8.0

 9.0
10.0
11.0
12.0


13.0
Responsibility
QA Objectives in Terms of
Precision, Accuracy, Complete-
ness, Representativeness, and
Comparability
  3.1 Organic Analyses
  3.2 Inorganic Analyses
Sampling Procedures
Sample Custody
Calibration Procedures and
Frequency
Analytical Procedures              3
  7.1 Extraction and Concentration
  7.2 Analytical Chromatography
  7.3 Gas Chromatography/Mass Spectrometry
  7.4 Atomic Absorption (AA) Spectrometry
  7.5 Inductively Coupled Plasma Atomic
      Emission Spectrometry (ICP)
Data Analysis, Validation, and     6
Reporting
Internal Quality Control Checks    1
Performance and Systems Audits     1
Preventative Maintenance           1
Specific Procedures to be          2
Used to Routinely Assess
Data Precision, Accuracy, and
Completeness
Corrective Action                  3
4-15-82
4-15-82
4-15-82
4-15-82

4-15-82
4-15-82

4-15-82
4-15-82
4-15-82
4-15-82


4-15-82
                                  120

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Section       Description                  Pages    Revisions     Date

14.0      Quality Assurance Reports  to        5          1       4-15-82
          Management

15.0      References                         1          1       4-15-82

16.0      Distribution  List                  1
                                  121

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1.  Project Description
     The objective of the research is to develop a laboratory extraction
test for solid wastes that:   (1)  models the leaching  action  a waste
would undergo when disposed of, along with a municipal  waste, in a
municipal waste landfill following a 95/5 (weight fraction of municipal
and industrial waste) co-disposal scenario, (2)  is compatible in aquatic
toxicity and phytotoxicity testing protocol, and (3)  is relatively
inexpensive to conduct in terms of time, equipment, and personnel.  The
extraction test will be henceforth referred to as EP-III.
     The project involves research in both the  laboratory  and field.
The laboratory work is centered on evaluating the extraction conditions
that are most aggressive in removing inorganic  and organic constituents
from four selected industrial wastes by a particular  municipal  waste
leachate (MWL).  Municipal waste leachate has been obtained  from a
lysimeter located at the U.S. Army Corps of Engineers Waterways
Experiment Station (WES), Vicksburg, Mississippi, for this work.  The
extraction procedure (column aerobic, column anaerobic, or rotary
batch) found to be most aggressive will serve as baseline  data to be
simulated by the laboratory method developed for EP-III.  The
laboratory variables to be investigated in this  phase of the work will
consist of the type of extraction procedure (up-flow  column  or batch
rotary)  and type of extraction media (acetate buffer, CCL-saturated
water, distilled water, or synthetic leachate).   The  experiment will
consist  of a factorial arrangement of 11 treatments and four industrial
wastes in a randomized block design with two blocks (time) per
                                  122

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treatment-waste combination.  The 11 treatments will  consist of the
eight (procedure x media) laboratory methods plus the three  WES/MWL
extractions.
     The field work will test the ability of various  laboratory
extraction methods to simulate the leaching characteristics  of
industrial wastes in large-scale field lysimeter experiments containing
wastes in a 95% municipal to 5% industrial  scenario and will  evaluate
the aggressiveness relative to age of a municipal waste  leachate to
extract contaminants from industrial wastes.
     Municipal waste leachate from two large-scale lysimeters (1.8 m in
diameter and 3.6 m in height) will  be diverted to 16  columns  per
lysimeter containing four industrial wastes (the same wastes  used in
the laboratory studies).  For each  lysimeter,  one-half of the columns
(4 wastes x 2 replicates) will be used to compare the 95% municipal and
5% industrial waste scenario to the laboratory extraction studies.  The
remaining columns will be used to evaluate the relative aggressiveness
of the municipal waste leachate as  a function  of age  of the  leachate.
The projected work schedule is presented in Table 1.
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                   TABLE 1.   PROJECTED WORK SCHEDULE
             Milestone                                   Projected Date

1.  Laboratory study
      WES municipal  leachate procured                     Jan. 27, 1982
      Industrial  wastes (8)  procured                      May 15, 1982
      Proximate analysis of  wastes initiated              May 15, 1982
      Select sastes  (4) for  laboratory  and
        field studies                                    May 31, 1982
      Laboratory extractions started
        (88 extractions)                                 June 1, 1982
      Laboratory extractions completed                    Sept. 1, 1982
      Inorganic and  organic  analysis of
        extracts completed                               Sept. 15, 1982
      Statistical analyses completed                      Oct. 15, 1982

2.  Field Study
      Municipal refuse obtained and lysimeters packed     Feb. 23, 1982
      Industrial  waste columns packed for laboratory
        Comparison and aggressiveness of MWL, begin
        leaching                                         June 15, 1982
      Laboratory comparison, leaching completed           Aug. 10, 1982
      Inorganic and  organic  analyses of leachates
        from laboratory comparison completed              Sept. 1, 1982
      Aggressiveness of MWL, leaching completed           Sept. 15, 1982
      Inorganic and  organic  analyses of leachates
        from aggressiveness  of MWL completed              Oct. 1, 1982
      Statisical analyses completed, aggressiveness
        of MWL                                           Oct. 15, 1982

3.  Draft report on  laboratory and field studies          Jan. 1, 1983
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2.  Project Organization and Responsibility
     The project directly involves personnel from two Divisions at
Oak Ridge National Laboratory (ORNL):   (1)  the Environmental  Sciences
Division (ESD) and (2) the Analytical  Chemistry Division (ACD).  The
Environmental Sciences Division is responsible for conducting the solid
waste extractions, developing experimental  design, performing
statistical analysis, and interpretating environmentally related data.
The Analytical Chemistry Division is responsible for inorganic and
organic analyses of the leachates and  extracts.  The project  is managed
from the Environmental Sciences Division (Fig. A-l).
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                                                                        ORNL-OWG 82-11556
 LABORATORY SPECIALIST
     J W GOOCH, JR
                                        ORNL
                                   PROJECT MANAGER

                                     C W FRANCIS
CHEMICAL ANAYSIS
R W HARVEY'
N M FERGUSON*
0 R HEINE*
                             ENVIRONMENTAL SCIENCES
                           EARTH SCIENCES SECTION HEAD
                                   T TAMURA
SOLID WASTE
EXTRACTIONS



CHEMICAL
ANALYSIS

QA OFFICER
ESD
M H SHANKS



QA OFFICER
ACO
L T COR8IN*

PRINCIPAL INVESTIGATOR
D K BROWN


PRINCIPAL INVESTIGATOR
M P MASKARINEC*



DATA
MANAGEMENT


PRINCIPAL INVESTIGATOR
JC GOYERT
•ANALYTICAL CHEMISTRY DIVISION
           Fig.  A-l.   Project organization and  responsibilities.
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3.  QA Objectives in Terms of Precision. Accuracy,  Completeness,
    Representativeness, and Comparability
3.1  Organic Analyses
     Standard methods are in place for the classes  of organic compounds
expected to occur in the solid waste extracts:   PAH's,  phenols,
purgeable halocarbons, and aliphatic hydrocarbons.   The isolation of
the organic compounds is performed according to EPA methods  624
and 625.  By using check standards (externally  prepared)  and periodic
repetitive analyses of selected extracts as well  as National  Bureau  of
Standards (NBS) prepared samples, QA objectives for these parameters
have been established as follows:
     A.  Precision - The relative standard deviation of repetitive
         measurements on a sample should not exceed that  achieved in
         methods development/evaluation studies.  This  value has  been
         determined to be ±10% for organic analyses.
     B.  Accuracy - The analytical data obtained  from the application
         of each analytical  inethod to a check standard  (of different
         concentration than the calibration standards)  should agree
         within ±15% of the true value defined  by its gravimetric
         preparation.  Analytical results for samples also examined  by
         other EPA contractors should agree statistically at  the  90%
         confidence limits.
     C.  Completness - At least 80% of all possible analytical
         measurements should meet QA objectives.
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3.2  Inorganic Analyses
     Elemental inorganic analyses will be conducted by atomic
absorption (AA) spectroscopy (equipped with fTameless  graphite  furnace)
and Inductively Coupled Plasma (ICP) methodologies. All  samples  by AA
will be conducted according to standard methods (USEPA 1979)  except for
Hg, Se, and As analyses which will be conducted as described  in Section
7.4.  For AA and ICP analyses the QA objectives are as follows:
     A.  Precision - The relative standard deviation of repetitive
         measurements will  vary from element to element and as  a
         function of detection (the closer to the detection limit the
         higher the deviation).  For samples containing elements  ten
         times the detection limit the objective is <  ±15%, while for
         samples near the detection limit the objective is ±100%.
     B.  Accuracy - Using known standards furnished by EPA, the
         accuracy for inorganic analyses is expected to be ±15% at
         levels ten times the detection limit.  Near the detection
         limit the accuracy may decrease to 100 to 200%.
     C.  Completeness - At least 90% of all possible analytical
         measurements should meet QA objectives.
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4.  Sampling Procedures
     Municipal refuse leachate has been obtained from the Corps of
Engineers Waterways Experimental Station (WES) in Vicksburg,
Mississippi.  The municipal refuse leachate was collected in  3.4-L
Teflon*-lined cans under pressure (using helium) in a sealed  glovebox
with a helium atmosphere.  This leachate (approximately 125 L)  will  be
kept anaerobic and will  be refrigerated at 4°C until  use.  Aliquots  of
the municipal refuse leachate will be analyzed throughout the
extraction experiments to assess any changes in the chemical  nature  of
the samples.
     The industrial wastes are being obtained through EPA's Washington
Headquarters, Office of Solid Waste, Todd Kimrnell  (coordinator).   The
wastes are being shipped to ORNL in 208-L (55-gal) drums.  Wastes  in
the drums will be thoroughly mixed before subsampling for individual
extractions.  A universal sampling procedure will  not be applicable  in
obtaining representative subsamples from the drums.  The types  of
wastes range from a total liquid to slurry and dry solid.  Therefore,
each waste will  be examined, and a specific sampling  procedure  will  be
documented.  When applicable, the drum will be placed on a drum roller
to obtain a thorough mixing of the waste sample.  Subsample from the
drums will be analyzed for physicochemical properties to ensure
adequate mixing and sampling procedures.
     Municipal wastes will be collected at local municipalities and
sorted to desired composition for the large-scale  lysimeter studies.
Sampling history, conditions, and procedures will  be  recorded in
ORNL-registered laboratory notebooks.
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5.  Samples Custody
     The bulk industrial wastes [208-L (55-gal)  drums]  and  municipal
refuse leachate will be stored in a locked,  refrigerated  cargo  trailer
(ORNL Bldg. 7038).  The trailer is located in  a  locked  fenced area;
only authorized personnel are allowed access.  The  trailer  was
purchased and is operated for the EPA Synfuels Repository Project
(DOE Activity No. 40-740-78).  It is maintained  at  a constant 4°C
temperature.  The air temperature is continually recorded in the
trailer with the recorder paper being changed  monthly;  the  chart papers
are kept in a permanent file by W. Griest (ACD).
     All wastes, leachates, laboratory-derived extracts,  extraction
procedures used to obtain extracts, and important laboratory variables
will be identified by a unique six-digit sample  identifier  code.  For
example, sample code 1CIN21 may represent:  reconnaissance  study using
oil-reclaiming clay extracted aerobically in a column extraction -
extraction replicate 2 and aliquot 1 analytical  analysis.  All  persons
involved with the experiments will use the same  identifier  code for  a
particular sample.  The sample identifier code will be  established by
D. K. Brown who is in charge of the repository of waste samples.
D. K. Brown also initiates sample extractions.  All sample  information
will be logged into the data management system using the  Project
Results Tracking System (PRTS) (Strand et al.  1981; and Strand  et al.,
in review).  Information will be kept concerning sample delivery,  dates
of extraction, dates for submission for analytical  analyses,  completion
dates of the analyses, and results of analyses.   The PRTS is  a  complete
record-keeping system that allows information  to be obtained  concerning
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the status of the project; the system also allows  statistical  analyses
of the data without any data transferring (see Section 8).
     In addition, a registered ORNL technical  notebook will  be kept  for
the solid wastes and leachate samples.  A record will  be kept  as
subsamples are taken from the storage area in  terms  of what  samples
were taken and by whom, quantities removed, and for  what purpose.
     In terms of waste disposal,  separate labeled  containers will  be
kept for liquid (extracts, washwater contacting solids, etc.)  and  solid
(spent wastes, filters, etc.) wastes.  Wastes  will be  handled  and
disposed of according to ORNL's Environmental  Protection Manual  and
Hazardous Materials:  Management  and Control.   These manuals are
in-house reference manuals that are updated as needed  by ORNL's
Department of Environmental  Management (T.  W.  Oakes, Department  Head).
Waste disposal will be handled upon advice by  each Division's
Environmental Protection Officer.
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6.  Calibration Procedures and Frequency
     Each analytical Instrument will be recalibrated by the operating
Analytical Chemistry personnel before samples  are analyzed.  Flame
atomic absorption will be checked after analysis of six samples.
Standard addition techniques will be used for  graphite furnace analysis.
Commercial standards prepared for atomic absorption analysis by Fisher
Scientific Co. will be used for preparation of calibration solutions.
For inductively coupled plasma-atomic emission spectroscopy the
calibration and analysis of the samples will be performed according to
EPA method 200.7 [Martin and Kopp (ed.)» Inductively Coupled
Plasma-Atomic Emission Spectrometric Method for Trace Element Analysis
of Water and Wastes, Environmental Monitoring  and Support Laboratory,
Cincinnati, Ohio].  Single and multielement standards obtained from
SPEX Industries (Metuchen, New Jersey) as well as certified reference
samples (e.g., EPA or NBS) will be used to check the instrument
calibration.
     Instrument standardization will be conducted by subjecting an
aliquot of the standard solution to the analytical  procedures in  the
same manner as a sample aliquot and by calibrating the observed
instrument response for each standard constituent to the known
concentration of that constituent.  Matrix effects will be checked by
spiking samples and alternate method checks.   Any observed matrix
effects will be corrected.
     Standardization of organic analysis will  be conducted using
appropriate NBS materials (PAH's, phenols) on  a biweekly basis.
Periodic quality control samples will be used  for a wet chemical
operations check.
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7.  Analytical Procedures
7.1  Extraction and Concentration
     All solvent partition/concentration steps are carried out using
internal standards.  The internal standards (azulene, fluorophenol,  and
  C-cresol) are added prior to extraction and are used as a measure
of recovery as well as for instrumental calibration.  A sample blank
(distilled water + internal standards) is run with each set of sample
analyses (up to a maximum of eight).

7.2  Analytical Chromatography
     A standard mixture (containing the above-mentioned internal
standards) is analyzed with each sample set (all  samples received  on a
given date, maximum of eight samples) to verify the response of the
instrument, the retention time of the internal  standard, and the
integration parameters.  If any parameter varies  more than 10% from  the
previous standard analysis, corrective action is  taken.   Such action
might include recalibration, detector cleaning, column replacement,  etc.

7.3  Gas Chromatography/Mass Spectrometry
     Instrumental variables (tuning parameters, etc.) are checked  and
recorded daily.  Calibration curves are checked with each sample set
(as above).

7.4  Atomic Absorption (AA) Spectroscopy
     All aqueous samples to be analyzed by atomic absorption (AA)
spectroscopy will be analyzed by a Perkin-Elmer Model 403 or 603
AA instrument.  Flame atomic absorption will  be used if  the  sample
contains high enough concentrations of the elements to be determined
                                  133

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accurately by this method.   If concentrations  are  lower  than  this,
graphite furnace AA will be used.   All  samples will  be preserved and
treated according to standard methods (USEPA 1979) with  the following
exceptions:
     (1)  extracts for Hg determination will be preserved by  addition
          to a nitric acid/dichromate solution and worked up  for cold
          vapor fTameless AAS (Feldman 1974),
     (2)  Se will be chelated with 5-nitro-o-phenylene diamine and
          extracted into toluene before analysis (Talmi  and Andren
          1974), and
     (3)  As will be determined by an arsine accumulation-helium glow
          detector procedure (Feldman 1979).
External reference solutions and EPA multielement  standards will be
used for instrument calibration.  All samples  will be analyzed by the
standard addition method (USEPA 1979).
7.5  Inductively Coupled Plasma-Atomic Emission Spectrometry  (ICP)
     Multielement analysis will be performed with  an Instruments SA,
Inc. model JY85 inductively coupled plasma-atomic  emission spectrometer
(ICP-AES), which contains a 1-m polychromator equipped with exit slits
centered at the most sensitive emission line (except for Na,  Li, and K)
of 35 different elements for simultaneous determinations. A  scanning
"n + 1" channel is also used either for the determination of  an
additional element or as an alternate emission line  of one of the
existing 35 elements.  This instrument is controlled by  a PDP-11/23
minicomputer, which also handles all data manipulations.
                                  134

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     The computer software provided by the manufacturer  includes
background correction, interelement correction,  and blank  subtraction
algorithms, which are included in the program that  automatically
changes samples, takes data, etc.
     Dilute aqueous solutions containing the analyte are pumped into a
cross flow nebulizer, which produces a fine aerosol.   The  aerosol  is
carried into the ICP, an extremely hot, flame-like  electrical  discharge
in argon gas, where the analyte species are thermally excited  and
spontaneously emit radiation characteristic of the  elements  present.
The radiation is measured with the polychromator and  monochromator to
determine the concentrations of elements in the  solution.
     Multielement standards from SPEX Industries (Metuchen,  New Jersey)
are used to calibrate this instrument.  At the present time,
calibration is performed once each day and periodically  checked with an
EPA or an NBS standard.
     The simultaneous multielement capability of this instrument
permits rapid, cost-effective analyses to be performed.  Accuracy is
generally better than 10% for elements whose concentrations  are more
than ten times their detection limit, while precision is usually better
than 5% relative standard deviation (RSD).
                                  135

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8.  Data Analysis. Validation, and Reporting
     All data analysis, validation, and reporting conducted for the
"Toxicity of Leachates" project will  be accomplished  through the
establishment of a Research Data Management System which incorporates a
number of computerized systems (Fig.  A-2).   Data  (inorganic and organic
analyses) will be entered into this data management system in
accordance with the sample identifier code  as  described  under
Section 5.  The ICP data will be programmed directly  by  the analyst;
other data will require formatting and entry by the data management
group.
     A software package entitled Statistical Analysis System (SAS)  is
leased by ORNL to conduct statistical analyses' of the data obtained in
the project.  This is a well-documented heavily used  package produced
by SAS Institute, Box 8000, Gary, North Carolina   27511.
     The Decision Support System (OSS) is one  component  of this system
and is designed for management-level  integration  of environmental
research data.  The DSS includes a plan of  study  documentation
component for determining ongoing research  among  different sites,  a
status component for determining the current and  proposed research
within research sites, and a criteria component for documenting the
numeric standards or limits (e.g., EPA/RCRA guidelines)  within  a
research project.
     To cope with the problem of accounting for and summarizing the
status and results of all samples taken during the project,  a Project
Results and Tracking System (PRTS) will be  included in the validation
procedures.  The PRTS is designed to  ensure that  each  sample, matched
                                  136

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                                      ORNL-DWG 82-7384 ESO
             ENVIRONMETRICS
          ENVIRONMENTAL SCIENCES
                  I

RESEARCH DATA MANAGEMENT
STATISTICS
EXPERIMENTAL DESIGN
SAMPLING DESIGN
ANALYSIS
INTERPRETATION
M
COMPUTERIZED SYSTEMS
DATA BASE MANAGEMENT
MANAGEMENT SUPPORT
SAMPLE TRACKING
QUALITY ASSURANCE
GRAPHICS
STATISTICAL COMPUTATION


Fig. A-2.   Disciplines and activity areas.
                   137

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with its corresponding characterization and effects  data,  represents an
appropriate estimate of a component of the research  design.   A PRTS, by
automating the bookkeeping procedures, reduces the time  and  effort
often needed to track large numbers of samples across research groups,
and it can provide an initial check on validity,  completeness, and/or
accuracy of the results from each sample.   Formal and detailed quality
assurance controls are also established in the Quality Assurance
System.  The Quality Assurance System is a computerized  program that
checks for the proper syntax, coding, and  variable values  using
criteria developed specifically for the type of data collected by the
investigators.
     Implementing quality assurance controls on developing and/or
extant data bases is necessary to ensure the validity of the results of
the research program.  The Quality Assurance System  for  the  Toxicity of
Leachates project has been developed to assist scientists  in detecting
potential errors in both qualitative and quantitative data.   All  major
data sheets will have a program written to ensure that the proper
syntax and variable values have been recorded and keypunched.  The
program will document all outlier and syntax errors  in the raw data
files and will provide an annotated output for resolving other
potential errors, such as values outside a variable's existing range,
improper lab identification, improper dates, etc. All error
definition, recognition, and correction will be accomplished by staff
within the program.
                                  138

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     A generalized figure representing the data flow for  the  Toxicity
of Leachates project through the Research Data Management System  is
illustrated in Fig. A-3.  As stated earlier,  a number of  generic
computerized systems have been developed to support  management
inquiries* determine the status of sample analyses and results, detect
possible errors in the data, establish computer file structure and
manipulation techniques, support graphical displays, and  provide
statistical computation procedures.  A flow diagram  showing sample
processing and analyses is presented in Fig.  A-4.   All files  are
automatically backed up weekly by staff in Computer  Sciences, UCCND.
     The criterion for flagging possible erroneous data is developed by
the investigator and is based on known or possible ranges of  values and
techniques and methodologies employed.  Outliers or  extreme data  points
are identified using an empirical  approach rather  than any formal
statistical decision rules.  The investigator first  examines  outliers
for possible measurement or transcription errors.   If these are not
present, the analyses are conducted with and  without the  outliers.
Data are graphed to investigate residual  patterns  and are only deleted
at the request of the investigator.
                                  139

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                                                              ORNL-DWG 82-7382
MANAGEMENT
 SUMMARIES
                        RESEARCH PROGRAM
                          EXPERIMENTAL
                         SAMPLE DESIGN
                                                     DECISION
                                                     SUPPORT
                                                      SYSTEM
              QUALITY
             ASSURANCE
               SYSTEM
                                                 MANAGEMENT
                                               DOCUMENTATION
                           TRACKING
                             SYSTEM
                         UPDATED. ERROR
                           FREE FILES
                            DATA BASE   \
                           MGMT SYSTEM I
                      I ORGANIZED DATA
                      V      SETS
                                        (STATISTICAL
                                        IMPUTATION
                                          SYSTEM
GRAPHICS
 SYSTEM
                                     ENVIRONMENTAL
                                        SCIENCES
INTERPRETATION
                        PROGRAM SYNTHESIS
        Fig. A-3.  The  research  data management components.
                                   140

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                                                 MIKE * MASKARINEC
                                                 JONATHANC COVERT
                                                 R WALLACE NAAVEV
                                                 JOE w GOOCH
                                                 D R HEINE
                                                 N MARION FERGUSON
                                                 L R WILLIAMS
Fig.  A-4.   Sample and processing  analysis.
                        141

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9.  Internal Quality Control Checks
     Internal quality control checks will be conducted  In AA and ICP
analyses of each set of solid waste extracts to  assess  precision and
accuracy of instrument calibration.  The checks  consist of:
(1) re-analysis of calibration standards to  confirm calibration, and
(2) analysis of check standards (these are standards of different
concentrations from the standards used to calibrate the instrument)
with each sample set.  Flame AA results should agree within  ±5% of
the true value.  For samples analyzed by graphite furnace containing
elements ten times the detection limit, the  objective is  ±10%,  while
for samples near the detection limit the objective is 100 to 200%.  If
the results do not agree within these limits,  matrix effects will  be
checked by spiking samples.
     Internal quality control checks for organic analyses will  be
conducted by inspection of the chromatographic profiles of each
standard, solid waste extract, and sample chemical  fraction. Any
unexpected/unusual chromatographic peaks or  features will  be noted and
interpreted with consideration of instrument malfunction,  sample
contamination, or true (non-artifactual) occurrence.  The  use of NBS
standard materials will be used to verify instrument performance.
     Solid waste extracts and municipal waste  leachate  analyzed by ICP
will be conducted by analyzing two replicate extracts (two aliquots
from the same solid waste extraction or leachate samples).   Periodic
blanks of the relevant extraction medium will  be subjected to the  same
procedures to determine if the samples are receiving  external
contamination.  Additional quality control methods  used during
analytical analyses are reported in Sections 3,  6,  and  7.
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10.  Performance and System Audits
     The system audit will be conducted as a part of the final  methods
development and validation work,  before the routine sample  analyses  are
initiated.  The audit will ensure that sample handling,  solid waste
extraction, fractionation, and analysis and quality control measures
are conducted properly and that data calculation, interpretation,
storage, and reporting flow correctly.
     The performance audit will include the analysis of  test materials
of concentrations unknown to the chemists performing the analysis.
This audit will be performed at least quarterly.  To implement  this
audit, ORNL has requested the EPA project officer to provide a
reference solid waste extract containing known concentrations of
organics and inorganics for analyses quarterly.  Additionally,  the ORNL
QA office has scheduled a QA audit of this project for May  of 1982 in
accordance with ORNL Procedure QA-L-8-100.
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11.  Preventative Maintenance
     The chemists assigned to the project are responsible for dally
maintenance and upkeep of the analytical  instrumentation.  Preventive
maintenance measures include periodic cleaning of instrument housing
ventilation filters, replacement of support  gas filters/impurity traps,
lubrication of moving parts, etc., as specified by the instrument
manufacturers.  Instrument repairs are conducted by the manufacturer
for those instruments still under warranty,  or by the ORNL
Instrumentation and Controls Division (I&C)  for those no longer  under
warranty.
     Spare parts for many of the instruments are kept in supply  by the
I&C Division.  The I&C Division also provides routine preventative
maintenance on electronic equipment in accordance with IPD2,
Maintenance Information System Instrumentation Manual.   The Plant and
Equipment (P&E) Division provides routine preventative maintenance on
mechanical equipment in accordance with QA-PE-18/D.1.14.
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12.  Specific Procedures to be Used Routinely to Assess
     Data Precision. Accuracy, and Completeness
     A.  Precision - Precision will be assessed by calculation  of  the
         relative standard deviation of repetitive measurements carried
         out on selected samples, as shown below:
                   RSD.
where RSD. = relative standard deviation for measurements of
             component i,
        X. = individual measurements of component i,
        X. = the average of the measurements of component i,  and
        n. = the number of measurements.

             The relative standard deviations should  not exceed those
         established in the course of analytical  methods of
         development/validation studies.

     B.  Accuracy - Analytical measurement  accuracy will be assessed in
         the Performance Audits, the Internal QC Checks, and  in the
         comparison of data on samples shared with other laboratories.
         In the first two of these measures, the analytical result will
         be compared with the true result,  and the accuracy of
         measurement of each constituent (A.) will be calculated as
         the percentage of difference between the measured value (X.)
         and the true value (T.):
                     A. = 100 (XrT.)/T
                      i         i   i  i.  ^
                                  145

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        Re-analysis of calibration  standards and analyses of check
    standards should agree to within ±15%  of the true  value.
C.  Completeness - Completeness of  data will be evaluated by
    multiplying the fraction  of samples analyzed (number of
    samples actually analyzed/number of samples planned in
    expected design which  could have been  analyzed) by the
    fraction data generated (number of actual data points
    generated per sample)  and expressing the result as a
    percentage.  A result  such as "ND" (component not  detected)  is
    considered a data point,  while  lack of an analysis due to
    instrument malfunction or sample loss  would be classified  as  a
    lack of data points.   At  least  90% of  the expected data should
    be generated.  Where possible,  reruns  of sample material or
    reanalysis of extracts will  be  performed to minimize the
    occurrence of missing  data.
                             146

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13.  Corrective Action
     The corrective action to be taken depends on the  type  of
performance deficiency.  For deficiencies uncovered  in routine  internal
quality control checks, the actions outlined in Section 9 will  be
taken.  For deficiencies discovered in data evaluation,  outlined in
Section 8, the following correction actions will be  taken:
     A.  Accuracy - Insufficient accuracy may result from factors  such
         as instrument malfunction, improper instrument calibration,
         degradation or other changes in the calibrating standards, or
         improper sample aliquotting.  The first three factors  may be
         identified by analysis of a freshly prepared  standard.  The
         last cause may be checked only be re-aliquotting the sample.
         (Aliquots will be held specifically for this  purpose.)
         Improper measurement of sample recovery also  can lead  to
         inaccuracy and can be determined only by remeasurement.
         Samples should be re-analyzed where loss of accuracy is
         uncovered.
     B.  Precision - Loss of acceptable precision may  be attributed to
         factors such as instrument malfunction or irreproducible
         aliquotting.  These causes could be checked by repetitive
         analysis of a standard and distinguished by comparing  results
         obtained in two instruments.  Re-analysis of  at least  selected
         samples would be required to remedy this deficiency.
     C.  Completeness. - Insufficient data may be caused  by  sample  loss
         (either sample mishandling or isolation procedure  failure),
         instrument breakdown, or failure to perform the analysis.  The
                                  147

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         potential  for sample loss  is  very low.   In the case of
         instrument breakdown or failure to perform the analysis, the
         sample analysis should  be  rescheduled.   Corrective action
         relative to sample loss will  be dealt with by making  an
         extraction on original  waste.
Significant quality deficiencies are reported to  upper ORNL management
throughout the ORNL QA program in accordance with procedure QA-L-6-103
(Fig. A-5).
                                  148

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14.  Quality Assurance Reports  to Management
     QA information will  be summarized  to the  EPA Project  Officer  in
each bimonthly data report.  Internally in ORNL  each  division  has  a
quality assurance program (see  Fig.  A-6). Procedures relative to
projects and programs in  the respective divisions are outlined in  the
Divisions' Quality Assurance Program:   Environmental  Sciences
Division's Quality Assurance Program (QA-ES-1-100)  and Analytical
Chemistry Division's Quality Assurance  Program.   Each project  will be
assessed and reviewed periodically.   The QA assessment review  date
schedule is included for  the Analytical Chemistry Division (see
Fig. A-7).
                                  150

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Fig. A-6.  Quality assurance program organization chart.
                           151

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                             ua
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                                      DIVISION    DOCUMENT NUMBER

                                         AC        AC-A1-1

                                         AC        AC-BO-1
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2
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AC

AC
AC

AC
AC

AC
AC
AC

AC
AC
AC


AC

AC

AC

AC


AC
AC
AC-BO-2

AC-BO-3
AC-BO-4

AC-BO-5
AC-GAL-1

AC-GAL-12
AC-GAL-1 3
AC-GAL-14

AC-GAL- 15
AC-GAL-16
AC-GAL- 17


AC-GAL-2

AC-GAL-3

AC-GAL-4

AC-GAL-5


AC-MES-1
AC-MES-10
              QA ASSESSMENT REVIEW DATE SCHEDULE
                FOR PERIOD ENDING 12/31/1981
           QA ASSESSMENT TITLE

IN-LINE ANALYTICAL SENSORS

ANALYSIS OF OCCUPATIONAL/ENVIRONMENTAL
SAMPLES

GASIFIERS FOR INDUSTRY

GENERATION AND CHEMISTRY OF AEROSOLS

SMOKING AND HEALTH

SPECIALIZED ORGANIC ANALYTICAL CHEMISTRY

BAUSCH AND LOMB SPECTROPHOTOMETER X 11783

ATOMIC ABSORPTION SPECTROPHOTOMETER(S)
P-E 403, P-E 460

TRACOR MODEL 222 GAS CHROMATOGRAPH

ASH FUSION FURNACE

INDUCTIVELY COUPLED PLASMA SPECTROMETER

LECO OXYGEN DETERMINATOR, R018

ION CHROMATOGRAPH, DIDNEX MODEL 16

FISHER TITATOR

TECHNICON AUTOANALYZERS

FLUOROPHOTOMETER - SINTERING FURNACE
(FLUOROMETRIC URANIUM EQUIP)

TEKTRONICS 4025 COMPUTER TERMINAL

OPTICAL EMISSION SPECTROMETER I - PASCHEN

DUPONT 21-490B/21-094B GAS CHROMATOGRAPH-
MASS SPECTROMETER
                                                                                                                                            SCHEDULED
ORIGINATOR
STRAIN
CATON
CATON
CATON
CATON
CATON
RICKARD
RICKARD
RICKARD
RICKARD
STEWART
LAYTON
KELLER
RICKARD
RICHARD
RICKARD
RICHARD
CHRISTIE
RAINEY
ISSUE DATE
8/28/1 981
6/03-1981
6/03/1981
6/03/1981
6/03/1981
6/03/1981
9/07/1979
10/23/1979
11/14/1979
11/12/1979
2/02/1981
2/05/1981
2/18/1981
9/07/1979
10/22/1979
10/22/1979
10/23/1979
11/08/1979

REVIEW DATE
9/01/1982
6/03/1982
6/03/1982
6/03/1982
6/03/1982
6/03/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
2/25/1982
2/05/1982
2/20/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
STATUS
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN

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DIVISION    DOCUMENT NUMBER

   AC        AC-MES-11


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AC
AC
AC
AC
AC

AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC-MES-12
AC-HES-13
AC-MES-14
AC-MES-15
AC-HES-2

AC-MES-3
AC-MES-4
AC-MES-5
AC-MES-6
AC-MES-7
AC-MES-8
AC-MES-9
AC-NRAS-1
AC-NRAS-2
AC-NRAS-3
   AC
             AC-NRAS-4
                                              QA ASSESSMENT REVIEW DATE SCHEDULE
                                                FOR PERIOD ENDING 12/31/1981
           QA ASSESSMENT TITLE

ORNL SINGLE-STATE GAS CHROMATOGRAPH-MASS
SPECTROMETER

SPARK SOURCE MASS SPECTROMETER - 2026

AEI MS-SO/DS-50 MASS SPECTROMETER-DATA
SYSTEM

ORNL THREE STAGE MASS SPECTROMETER -
ORG.

MICROMASS 1201 GAS MASS SPECTROMETER

OPTICAL EMISSION SPECTROMETER II -
WADSWORTH

ION MICROPROBE MASS SPECTROMETER

SPARK SOURCE MASS SPECTROMETER - MS-7

SPARK SOURCE MASS SPECTROMETER - MS-702R

2-STAGE MASS SPECTROMETER - RAL

SINGLE-STAGE MASS SPECTROMETER - RAL

2-STAGE MASS SPECTROMETER - TRU

3-STAGE MASS SPECTROMETER - RAL

COMPUTER BASED PULSE HEIGHT ANALYSIS
SYSTEM ND6620

OAK RIDGE RESEARCH REACTOR PNEUMATIC TUBE

COMPUTER BASED PULSE HEIGHT ANALYSIS
SYSTEM. BLDG 3042

DATA ACQUISITION SYSTEM, 110 6603, G-49.
4500S
                                                                                                      SCHEDULED
ORIGINATOR
RAINEY
CHRISTIE
RAINEY
RAINEY
SITES
CHRISTIE
CHRISTIE
CHRISTIE
CHRISTIE
SMITH
SMITH
SMITH
SMITH
EMERY
EMERY
EMERY
ISSUE DATE
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/09/1979
11/09/1979
11/09/1979
11/09/1979
2/20/1980
5/01/1980
5/01/1980
REVIEW DATE
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
STATUS
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
                                                                            SCOTT
                                                                                         5/01/1980    1/01/1982
                                                                                                                       OPEN

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                                              QA ASSESSMENT REVIEW DATE SCHEDULE
                                                FOR PERIOD ENDING 12/31/1981
DIVISION    DOCUMENT NUMBER





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AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC
AC-NRAS-S
AC-NRAS-6
AC-PM-1
AC-RMAL-1
AC-RMAL-2
AC-RHAL-3
AC-RHAL-4
AC-RMAL-5
AC-RMAL-6
AC-TRU-1
AC-TRU-2
AC-TRU-3
AC-TRU-4
AC-TRU-5
AC-TRU-6
AC-TRU-7
AC-TRU-8
AI-2
Al-3
           QA ASSESSMENT TITLE


HIGH FLUX ISOTOPE REACTOR PNEUMATIC TUBE

COMPUTER BASED PULSE HEIGHT ANALYSIS
SYSTEM AT BLDG 7900

PHYSICO-CHEMICAL ANALYSES GROUP

IN-CELL PIPET

IN-CELL ANALYTICAL BALANCE

IN-CELL FURNACE

IN-CELL SPECTROPHOTOMETER

HOT-CELL MANIPULATORS

X-RAY FLUORESCENCE ANALYZER

PULSE-HEIGHT ANALYZER

PROPORTIONAL COUNTERS

TITRATOR

BAUSCH AND LOMB SPECTROPHOTOMETER

REMOTE PIPETTOR

GEIGER-MUELLER COUNTER

GAMMA SCINTILLATION COUNTER

NEUTRON COUNTER

LASER APPLICATIONS

REMOTE PIPETTOR AND TITRATOR
                                                                          ORIGINATOR
                                                                                                      SCHEDULED
                                                                                        ISSUE DATE   REVIEW DATE
                                                                                     STATUS
BATE
BATE
RICCI
LAING
LAING
LAING
.LAING
LAING
STEWART
COOPER
COOPER
COOPER
COOPER
COOPER
COOPER
COOPER
COOPER
WHITTEN
KLATT
7/02/1980
7/02/1980
11/05/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
11/08/1979
2/02/1981
11/13/1979
11/13/1979
11/12/1979
11/12/1979
11/12/1979
11/13/1979
11/13/1979
11/13/1979
9/02/1981
9/10/1981
7/31/1982
7/31/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
2/02/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
1/01/1982
9/01/1983
10/01/1982
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN
OPEN

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15.  References
Feldman, C.  1974.  Perchloric acid procedure for wet-ashing organics
     for the determination of mercury (and other metals).   Anal.  Chem.
     46:1606-1609.
Feldman, C.  1979.  Improvements in the arsine accumulation - helium
     glow detector procedures for determining traces of arsenic.   Anal.
     Chem. 51:664-669.
Strand, R. H., M. P. Parrel!, T. K. Birchfield, C. W. Gudmundson,
     M. E. Vansuch, and H. N. Polovino.  1981.  Environmetrics for
     synfuels:  II.  A Computer-based coding scheme for coal  conversion
     research data.  ORNL/TM-7525.  25 pp.
Strand, R. H., M. P. Parrel!, K. L. Daniels, and J. C.  Goyert.
     Environmetrics of Synfuels:  IV.  Project Results  Tracking System
     (PRTS).  Oak Ridge National Laboratory, Oak Ridge, Tennessee (in
     review).
Talmi, Y., and A. W. Andren.  1974.  Determination of selenium in
     environmental samples using gas chromatography with a  microwave
     emission spectrometric detection system.  Anal. Chem.  46:2122-2126.
U.S. Environmental Protection Agency (USEPA).  1979. Methods  for
     chemical analysis of water and wastes.   EPA-600/4-79-010.
     Environmental Monitoring and Support Laboratory, Office of
     Research and Development, U.S. Environmental  Protection Agency,
     Cincinnati, Ohio.  460 pp.
                                  155

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16.  Distribution List
S. I. Auerbach, ORNL-ESD, Division Director
D. K. Brown, ORNL-ESD, Principal  Investigator
L. T. Corbin, ORNL-ACD, QA Coordinator
C. W. Francis, ORNL Project Manager
J. C. Goyert, ORNL-ACD, Principal  Investigator
M. R. Guerin, ORNL-ACD (Bio/Organic Section), Section Head
M. P. Maskarinec, ORNL-ACD, Principal  Investigator
F. H. Neill, ORNL, Director of ORNL Qualtiy Assurance Program
0. E. Reichle, ORNL-ESD, Associate Division Director
John Santolucito, EPA QA Officer,  EMSL-Las  Vegas
M. H. Shanks, ORNL-ESD, QA Coordinator
W. D. Shults, ORNL-ACD, Division Director
T. Tamura, ORNL-ESD (Earth Sciences),  Section Head
L. R. Williams, EPA Project Officer, EMSL-Las Vegas
                                  156

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                  APPENDIX  B


               FY-1982 Work Plan
             Toxicity of Leachates
                Revised 3/25/82
         Oak Ridge National Laboratory
              Oak  Ridge, Tennessee
                Project Manager

 C. W.  Francis, Environmental Sciences Division


            Principal Investigators

 D. K.  Brown, Environmental Sciences Division
 J. C. Goyert, Environmental  Sciences Division
M. P.  Maskarinec, Analytical  Chemistry Division


                Project Officer

             Llewellyn R. Williams
  Environmental  Monitoring Systems Laboratory
               Las Vegas, Nevada
             Interagency Agreements
                    Between

           U.S. Department of Energy
               DOE No. 40-1087-80

                      and

     U.S. Environmental Protection Agency
                 AD-89-F-1-058
                      157

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                           Table of Contents
Summary	     159
1.  Introduction	     165
2.  Development of EP-III	     166
    2.1  Leaching Media Requirements  	     166
    2.2  Extraction Procedures  	     168
3.  Performance Criteria for EP-III 	     170
    3.1  Laboratory Studies 	     170
         3.1.1  Waste Selection	     172
         3.1.2  Approach	     172
         3.1.3  Quality Control	     176
         3.1.4  Supplementary Study:  Compatibility  of
                Extraction Media to Toxicity Tests  	     177
    3.2  Field Studies - (95/5) Scenario  	     177
         3.2.1  Objectives and Approach	     177
         3.2.2  Laboratory Comparisons  	     178
         3.2.3  Aggressiveness of Municipal  Waste
                Leach ate over Time	     181
         3.2.4  Experimental Design and Analysis   	     181
    3.3  Basis of Calculation for Large-scale
         Lysimeter Research 	     182
4.  Work Schedule	     185
5.  References Cited  	     186
Attachment A - Protocol  for Evaluating the Aggressiveness
               of Three Treatment Procedures  	     187
Attachment B - Description of Lysimeter Study 	     189
                                  158

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                     OAK RIDGE NATIONAL LABORATORY
                        "TOXICITY OF LEACHATES"
                      Summary of FY-1982 Workplan
                           (Revised 3/25/82)
                              INTRODUCTION
     The objective of this research is to develop a second generation
laboratory extraction procedure, henceforth known as EP-III,  to  test
mobility of inorganic as well as organic constituents of industrial
wastes co-disposed with municipal wastes in a landfill  environment.
The desirable characteristics of EP-III include:
     1.  Ability to simulate leaching in a landfill  containing
         municipal (95%) and industrial (5%) wastes.
     2.  Compatibility with biological toxicity tests (mutagenic,
         aquatic, and terrestrial).
     3.  Relatively inexpensive to conduct in terms of time,  equipment,
         and personnel.
                               STRATEGY

     The strategy proposed by Oak Ridge National  Laboratory (ORNL) for
the development of EP-III will focus on:
     1.  Determining in the laboratory the quantities of inorganic and
         organic constituents leached from a variety of industrial
         wastes by a particular municipal  waste leachate.
     2.  Comparing the extraction characteristics of the above municipal
         waste leachate to those of laboratory methods  (combinations of
         extraction procedures with artificial extraction media), and
                                  159

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     r..  Testing the ability of the laboratory extraction methods to
         simulate the leaching of industrial  wastes  under field
         conditions using large-scale  lysimeters containing municipal
         (95%) and industrial (5%)  wastes.
     The proposed research will involve  both  laboratory and field
work.  The initial laboratory effort will be  directed  toward  evaluating
the extraction conditions that are  most  aggressive in  removing
inorganic and organic constituents  from  selected industrial wastes  by  a
particular municipal waste leachate.  The municipal  waste leachate
selected for this study will be obtained from a lysimeter located at
the U.S. Army Corps of Engineers Waterways Experiment  Station (WES),
Vicksburg, Mississippi.  The extraction  procedure  (column aerobic,
column anaerobic, or rotary batch)  found to be most  aggressive will
serve as baseline data to be simulated by the laboratory procedure
developed for EP-III.  The laboratory  variables to be  investigated  in
this phase of the work will consist of the type of extraction procedure
(uo-flow column or batch rotary) and type of  artificial extraction
media (acetate buffer, C02-saturated water, distilled  water,  or
synthetic leachate).
     Concentrations of inorganic and organic  constituents found  in
waste leachate from field demonstration  large-scale  lysimeter
experiments containing waste in a 95%  municipal to 5%  industrial
scenario will be compared to those  observed in the laboratory
extractions.  Results from both the laboratory and field studies will
be combined and compared so that the relationship between laboratory
extraction methods and actual field validations can  be determined.  By
                                  160

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comparing laboratory extraction tests with field validations,  the
potential toxicity of industrial wastes co-disposed with municipal
wastes can be examined and evaluated.

                           LABORATORY  STUDIES

A.  Objective:
     Establish the laboratory extraction method (procedure and medium)
that most closely simulates the leaching characteristics of a  municipal
waste leachate (MWL) in terms of organics and inorganics extracted.

B.  Approach:
     1.  Determine the amount of organic and inorganic chemical
       _  constituents removed from four different industrial wastes
         using three extraction procedures.  MWL from WES will be used
         as the extraction media and will serve as a baseline  control
         to compare against all artificial extraction media in part  2.
             The fou»- industrial wastes w'ill consist of two organic
         wastes, a waste containing both organic and inorganic
         contaminants, and a waste predominantly inorganic in  character.
             The three extraction procedures will consist of:
                 (a)  up-flow column - aerobic
                 (b)  up-flow column - anaerobic
                 (c)  rotary extractor - aerobic
     2.  Compare the results from part 1 with the amount of organic  and
         inorganic chemical constituents removed from the same four
         industrial wastes using two extraction procedures with each of
         four artificial extraction media.
                                  161

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             The two extraction procedures  will  consist  of:
                 (a)  an up-flow column and
                 (b)  a batch rotary extractor.
             The four extraction media will consist of:
                 (a)  0.1 J^ sodium acetate  buffer pH  5,
                 (b)  C02-saturated deionized  distilled  water,
                 (c)  deionized distilled water, and
                 (d)  synthetic MWL that simulates WES/MWL.

C.  Experimental Design:
     The experiment will consist of a factorial  arrangement  of
11 treatments and four industrial wastes in a  randomized block  design
with two blocks (time) per treatment-waste  combination.  The
11 treatments will consist of the eight (procedure x  media)  laboratory
methods plus the three WES/MWL extractions.

D.  Analysis:
     An analysis of variance will be conducted on the ranked sums
(Attachment A) to determine if there are any differences in  the amount
of organic and inorganic chemical constituents removed by  the various
extraction procedures and media.  Additional analyses will be conducted
to determine if there are any overall differences in: (1) the  batch
versus column extraction procedure, (2) the distilled water,  synthetic
leachate, and WES/MWL media, and (3) the interaction  among the  two
procedures and the three extraction media.  The  eight laboratory
methods (2 procedures x 4 media) will be compared to  the three  WES/MWL
extractions using a multivariate pattern analysis  to  determine  which of
                                  162

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the eight laboratory extraction methods is  most similar  in chemical
composition to the three WES/MWL extractions.   An  analysis will  also be
conducted to determine if there are any differences  in the amount  of
organics and inorganics removed by the WES/MWL  using the three
extraction procedures.

                             FIELD STUDIES

A.  Objectives:
     1.  Test the ability of various laboratory extraction methods to
         simulate the leaching characteristics  of  industrial wastes in
         large-scale field lysimeter experiments containing wastes in a
         95% municipal to 556 industrial scenario.
     2.  Evaluate the aggressiveness relative to age of  a municipal
         waste leachate to extract contaminants from industrial  wastes.

B.  Approach:
     Municipal waste leachate from two large-scale lysimeters  (1.8 m in
diameter and 3.6 m in height) will be diverted  to  16 columns/lysimeter
containing four industrial wastes (the same wastes used  in the
laboratory studies).  For each lysimeter, one-half of the columns
(4 wastes x 2 replicates) will be used to compare  the 95% municipal and
5% industrial waste scenario to the laboratory  extraction studies.  The
remaining columns will be used to evaluate  the  relative  aggressiveness
of the municipal waste leachate as a function of age of  the leachate.
                                  163

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C.  Experimental Design:
     The experiment will consist of a randomized block  design  with  four
treatments and two blocks (lysimeters).   The  experiment will be
replicated twice to test the block by treatment Interaction.

D.  Analysis:
     An analysis of variance will be conducted to determine if there
are any differences in the amount of organic  and inorganic  chemical
constituents removed from the four industrial wastes  by the municipal
waste leachate.  An analysis will also be conducted to  see  if  there are
any differences in leachate quality between the two lysimeters.   A
multivariate pattern analysis will be used to determine which  of  the
laboratory extraction methods most closely simulates  the  chemical
constituents derived from the field lysimeters.   The  results from the
laboratory studies and the field studies will be combined and
statistically analyzed to determine the laboratory method (EP-III) that
most closely simulates the mobility of inorganic as well  as organic
constituents of industrial wastes co-disposed with municipal wastes in
a landfill environment.
                                  164

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                           1.  INTRODUCTION

     To evaluate the potential  toxicity of a leachate  from an
Industrial waste that has been  co-disposed with a municipal waste,  a
laboratory extraction procedure is needed that models  the  leaching
action the waste would undergo  when disposed of with a municipal
waste.  Currently, under RCRA,  toxicity is determined  by the EP
toxicity test procedure (40 CFR 261.24).  Toxicity criteria are based
on the concentrations of eight  elements in the Primary Drinking Water
Regulations (As, Ba, Cd, Cr,  Pb,  Hg, Se, and Ag), four pesticides
(Endrin, Lindane, Methoxychlor, Toxaphene), and two herbicides  (2,4-D,
and 2,4,5-TP Si 1 vex) observed in  the extract.  The EP  is used as a
regulatory test to classify a waste relative to a landfill management
scenario.  The EP has a number  of limitations,  the most  important being
that a waste containing other toxicant materials is not  included in the
present criteria.  For example, the EP does not model  the  effects that
the higher molecular weight organics present in a municipal leachate
can have on the leaching of a solid waste.  Other experimental factors
include the effectiveness of extraction, the deficiency  of expressing
kinetic relationships of components extracted,  relevance to real-world
leachates, etc.  In terms of applying biological  testing to EP
extracts, the EP is severely limited in that the acetic  acid used in
the procedure interferes with aquatic toxicity and phytotoxicity
testing protocols (Epler et al. 1980).
     The objective of the FY-1982 research at ORNL is  to develop an
extraction test for solid wastes  that:  (1) models the leaching action
a waste would undergo when disposed of, along with a municipal waste,
                                  165

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in a municipal  waste landfill  following a 95/5  (weight  fraction  of
municipal and industrial waste) co-disposal  scenario;  and (2)  is
compatible in aquatic toxicity and phytotoxicity testing  protocol.
This proposed extraction procedure will be henceforth  referred to as
EP-III.
                       2.  DEVELOPMENT OF EP-III

The major characteristics of EP-III are:
     1.  It should simulate leaching in a landfill  containing  municipal
         (95%)  and industrial  (5%) wastes (by weight).
     2.  It has to be compatible with biological testing  protocol
         (mutagenic, aquatic,  and phytotoxic).
     3.  It should be relatively inexpensive to conduct in terms of
         time,  equipment, and  personnel.

                    2.1   Leaching Media Requirements

     A synthetic municipal landfill leaching medium is  needed  to model
leaching that occurs in a landfill where an  industrial  waste is
co-disposed with municipal refuse.  The characteristics of a municipal
landfill leachate will vary widely depending on the municipal  refuse
composition and state of decomposition.  Even for individual samples of
municipal refuse it would be impossible to duplicate the  leachate
composition over time because  of its complexity and varying stability
to biological degradation.  Laboratory leachates using  municipal refuse
and water are possible to produce; however,  reproducing such leachates
and maintaining stability are  impractical for a test protocol.   Rather
                                  166

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than attempting to define the leachate characteristics  emanating  from  a
defined standard landfill, it is more realistic to develop a synthetic
leachate that models leachate of maximum aggressiveness.   Such  a  model
leachate will also represent likely mismanagement scenarios, thus
adding a degree of conservatism in screening wastes for toxicity.
     No one synthetic leachate will model all municipal solid waste
leachates; however, some of the characteristics of the  more aggressive
leachates can be used as a model leachate.  Typical characteristics
simulating that of a municipal landfill are:  (1) low pH  (4-6),  (2)  low
redox potential (anoxic environment), (3) mild to high  ionic strength
(0.05-0.1 Mj, and (4) high complexation ability.
     A low molecular weight carboxylic acid, acetic acid,  was used  in
EP-I to acidify the solid waste suspension to pH 5.  The  EP-I satisfied
items 1 and 3 of the above listed requirements, and for most wastes it
has been shown to be more effective than water for removing toxic
metals from waste.  However, for most wastes, acetic acid  is not  as
effective as water in removing nonpolar organics, and the  acetic  acid
interferes in the phytotoxicity and aquatic toxicity tests.  Thus,
there is a need to develop a model synthetic extractant that
aggressively removes inorganic and organic contaminants from wastes and
one that can also be used in biotesting of the resulting  leachate.   Use
of a biodegradable organic acid in the EP-III has to be eliminated  from
consideration in that such an acid will inherently interfere in the
biotesting protocol.  Use of inorganic acids such as ^SO^ and  HC1
to acidify solid waste suspensions to pH 5 have also interfered in  the
phytotoxicity and aquatic toxicity tests.  One extracting  medium  that
                                  167

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appears to be a viable alternative is carbonic  acid.   It  is  an
aggressive leachate from the standpoint of acidity,  it is more
representative of the acidity source in landfills  than mineral  acids
such as HC1, HNO-, or f^SO., and under standard conditions of
temperature and pressure it should not be inhibitory in any  of  the
biological testing protocols.  Bause and McGregor  (1980)  proposed  and
evaluated this extractant using the same liquid-to-sol id  ratio  in  a
batch-type extraction as the EP (20:1) and found that  the carbonic acid
medium and EP extracted similar quantities of toxic  trace metals from
four fossil energy solid wastes.  Its effectiveness  in removing organic
compounds from solid wastes has been untested.

                      2.2  Extraction Procedures

     The agitation procedures for conducting the EP  have  varied from
using stirring paddles in stainless steel  vessels  (glass  vessels on
rotary agitators) to stirring in glass vessels  using commercially
available magnetic stirring devices.   However,  the basic  premise has
remained the same; that is, the procedure is a  batch-type extraction
using a final liquid-to-sol id ratio of 20:1 during the agitation period
of 24 h.  The basic principle is to ensure adequate mixing between the
solid and aqueous phase.  The high liquid-to-sol id ratio  (20:1)
promotes dispersion of many finely textured wastes (organic-laden
sludges, etc.) which make filtering a slow and  time-consuming effort.
To conduct a variety of toxicity tests and the  required inorganic  and
organic analysis, it is necessary to collect as  much as 6  L of  effluent
(Table B-l).  This may take as long as 1  to 2 d  to filter  some  of  the
                                  168

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          TABLE B-l.   AMOUNT OF EXTRACT NEEDED FOR
               VARIOUS ANALYSES3 AND BIOTESTS
Analyses:                                  Extract  needed  (ml)

Inorganics (NIPDWS)                                 750
Organics                                         1,000
Bioaccumulation                                     500

Biotestsb
Mutagenicity                                     1,000
Aquatic (D_. magna acute)                          1,000
Phytotoxicity (root elongation, 2 species)        1,000
      Total                                      5,250

 Assumes single determination.
 Assumes no dilution.
                             169

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samples through the 0.45-um membrane filter (even  using  a  pressure
filter apparatus at 75 psi).  Recent work at ORNL  has  shown  that  the
up-flow column extraction procedure removed more nonpolar  organic
compounds (extracts were collected directly on  XAD-2 resins) than the
20:1 batch-type extraction (the common  extraction  medium being double
distilled water).  Other work has indicated that volatile  constituents
are not as easily lost in a closed extraction system (such as the
rotary extractor) versus an open system.   The column extraction
procedure merits more research, and, contrary to previo is  beliefs,  it
is not as time-consuming nor is it as nonreproducible  relative to the
batch extractions as implied in previous  investigations.   Major
equipment costs for column extractions  appear to be comparable to batch
extractions with a rotary extractor (Table B-2).   The  important fact is
that not many investigators have experimented with an  up-flow column as
an alternative.

                  3.  PERFORMANCE CRITERIA FOR  EP-III

     The principal performance criteria for EP-III will  be (1) how well
it simulates the leaching characteristics of a  municipal waste leachate,
and (2) its compatibility with biological  toxicity testing protocols
(mutagenic, aquatic, and phytotoxic).

                        3.1   Laboratory Studies

     The objectives of the laboratory studies are  twofold:
     1.  Establish a data base that represents  the leaching
         characteristics of a municipal waste leachate (MWL) on
         industrial wastes,  and
                                  170

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         TABLE B-2.  MAJOR EQUIPMENT NEEDS  AND  ESTIMATED COSTS
             FOR PERFORMING A BATCH VS COLUMN EXTRACTION*
        Batch extraction
      Item
Estimated
  cost
                        Column extraction
Item
Estimated
  cost
Rotary extractor          $2,000
Glass vessels (32-L
  capacity)                   45
Filtration apparatus
  (pressure)               1,400
Filters (per sample)0     15-150
              Pressure pumpb           $  500
              Glass column with
                adjustable plungers       130
aAssume both are closed extractions,  with no pH  adjustments,  using
 organic-laden wastes,  to produce 6 L of extract.
Average cost for pump, prices vary from $200-2,000.
°Disposal item, number needed will vary with sample.
                                  171

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     2.  Develop a laboratory extraction method  using  a  selected
         procedure and a synthetic medium that best  simulates  the
         leaching of industrial  wastes  by MWL's.

3.1.1  Waste Selection;  Four industrial wastes  will be  utilized  for
all research.  The four wastes will  be  selected  from those  listed in
Table B-3 and will consist of two organic wastes (tentatively  Nos.  1
and 5):  a waste containing both organic and  inorganic contaminants
(either No. 3, 6, or 7 depending on bulk analyses, physical  properties,
and availability), and a waste predominantly  inorganic in character
(either No. 2, 4, or 8).  Initially major organic and  inorganic
constituents will be identified  in each waste to  target  the  important
potential contaminants.  This information will be used to select  the
four most appropriate wastes based on  (1)  classes of hazardous organic
compounds, (2) concentrations of toxic  inorganic  constituents
(predominantly those elements listed in the interim primary  drinking
water standards), (3) combinations of toxic inorganic  and organic
compounds, and (4) potential contaminants  amenable to target analyses
(i.e., those contaminants found  in the  industrial waste  that are
different or contained at concentrations sufficiently higher than that
observed in the municipal waste  leachate). Wastes will  not  be selected
relative to their compatibility  with any type of  extractor.

3.1.2  Approach;  Baseline experiments  relative to the extraction
capacity of municipal waste leachate (MWL) will be conducted using the
leachate obtained January 27, 1982,  from the  Waterways Experimental
Station (WES), Corps of Engineers, Vicksburg, Mississippi.
                                  172

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-.4
CO
                                                 TABLE B-3  DESCRIPTION AND PRELIMINARY INFORMATION RELATIVE TO THE INDUSTRIAL WASTES TO BE USED IN THE STUDY*


                                                                                                                                                           ORNL DWG 8311534
MUTE
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MUTE DESCRIPTION
WASTE OIL
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AMMONIA STILL LIME SLUDGE
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10-5 0*
HgBY
WEIGHT
                                       •COLLATED FROM INFORMATION PROVIDED BY TOOD KIMMELL. OSW/EPA HOT
                                       "NH - NONHAZARDOUS UNDER FCRA. H - HAZARDOUS

-------
Approximately 150 L of MWL in 37 3.8-L (1  gal)  containers were
collected under anaerobic conditions.   This leachate is  currently being
stored under refrigerated conditions.   It  will  be  used to extract the
four industrial wastes.  Extractions will  be conducted under  aerobic
conditions in a rotary extractor at  a  liquid to solid ratio of  20:1 and
under both anaerobic and aerobic conditions in  an  up-flow column  using
the same quantity of waste and the effluent collected when the  liquid
to solid ratio of 20:1 is reached.  The extracts will be filtered
through glass fiber filters for organic analyses (effective pore
diameter approximately 0.7 urn) and 0.45-um membrane  filters for
inorganic analyses.
     The quantities of inorganic and organic constituents removed from
the four industrial wastes with the  WES/MWL by  the most  aggressive of
the three extraction procedures will be considered most  representative
of leaching in a co-disposal  environment.   Ue have established, a
priori, a four-step protocol  for choosing  the extraction procedure that
is most aggressive across all  constituents tested.   The  first step of
the protocol ranks the concentrations  of each constituent from  least
aggressive to most aggressive.  The  second step groups all the
constituents into target categories;  NIPDWS inorganics  and/or  toxic
organics (hazardous constituents listed in Appendix  VIII, 40 CFR
261.24) and then sums the ranks within a category.   The  third step
ranks the sums within each category.  The  fourth step sums the ranks
across categories, resulting in an overall  rank sum  that is then
statistically analyzed.  A short example of such ranking is provided in
Attachment A.  These data will provide the following information:
                                  174

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     1.  Establish if significant occur between aerobic and anaerobic
         column extractions with municipal waste leachate.
     2.  Determine if differences occur between batch and column
         extractions with a number of artificial extraction media.
     3.  Establish baseline data relative to the extraction
         capabilities of a municipal waste leachate.
     The pattern (relative to concentration and distribution)  of
inorganic and organic constituents extracted by the most aggressive
extraction procedure (either anaerobic or aerobid'up-flow column or
aerobic rotary) using the WES/MWL will be compared to those patterns
obtained from the eight laboratory extraction methods (two extraction
procedures and four artificial extraction media).  The same four
industrial wastes will  be used.
     The two extraction procedures will consist of:
         (a)  an up-flow column and
         (b)  a batch rotary extractor.
     The four extraction media will consist of:
         (a)  0.1 ^ sodium acetate buffer pH 5,
         (b)  C0?-saturated deionized distilled  water,
         (c)  deionized distilled water, and
         (d)  synthetic MWL that simulates WES/MWL.
The rationale for selecting the extracting media is as  follows:
     EP-I:  The acetic  acid pH 5 extraction is a regulatory protocol
that has never been compared to the leaching capabilities of a
municipal waste leachate.  It is possible that the  EP-I  does simulate
the extraction of municipal waste leachates and  thus will  be included
for comparative purposes in the experimental  design.
                                  175

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     C0?-Saturated Deiom'zed Distilled Water;   This medium  best
simulates the pH and anoxic conditions of landfill leachates without
incorporating biodegradable organics into the medium.   It should  also
be compatible with biotesting protocols.
     Oeionized Distilled Water;   This medium is included for
comparative purposes.
     Synthetic Municipal Waste Leachate;   This  medium  which will
contain the major organic and inorganic components of  the WES municipal
waste leachate is intended to simulate the extracting  capabilities  of
the collected leachate.  Incorporation of this  medium  will  provide
information relative to the importance of organic and  inorganic
components of the WES leachate to remove  various contaminants from  the
five industrial wastes.  Tentatively, the organic components suggested
are 500 ppm each of C2> C4, and Cg carboxylic acids.
3.1.3  Quality Control;  A description of the quality  control for the
project is available in the April 15, 1982,  "Quality Assurance Project
Plan - Toxicity of Leachates Project" (Appendix A of this report).
Specifically, each 3.8-L (1 gal) aliquot  MWL collected at WES will  be
analyzed for organic (principally carboxylic acids by  high  pressure
liquid chromatography) and inorganic constituents (inductive coupled
plasma-atomic emission spectrometry, atomic  absorption spectroscopy,
and anionic chromatography).  Preliminary analysis of  the WES/MWL
indicates that target organic compounds can  be  used to assess
Teachability.  In cases where concentrations of the target  constituents
are observed in the MWL (both organic and inorganic),  these
concentrations will be subtracted from the concentrations found in  the
                                  176

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leachate produced on interacting the MWL and industrial  waste.
Duplicate analyses for organic and inorganic constituents will  be
conducted on the leachates (such analysis may not be conducted  if
analytical accuracy and precision for that analysis  is considered  to  be
less than 10%).

3.1.4  Supplementary Study;  Compatibility of Extraction Media  to
Toxicity Tests:  A supplementary study will be carried out  to determine
which of the extraction media can be used with toxicity  tests.   The
toxicity tests to be considered include:  (1) an alga growth  inhibition
test, (2) Daphnia magna acute immobilization test and reproduction
test, and (3) a fish acute toxicity test; these tests are found in the
document "OECD Guidelines for Testing of Chemicals." Extraction media
posing potential inherent toxicity characteristics will  be  tested  in  a
series of dilutions (including 1:100 and 1:000),  with at least  one of
the toxicity tests mentioned above.  This information will  aid  in
determining which of the proposed extractants satisfy the
characteristic of being compatible with bioassays.

                 3.2  Field Studies - (95/5) Scenario
3.2.1  Objectives and Approach;   The major objectives are to
(1) determine at what point in time and at what volume of leachate the
concentration of the inorganic and organic contaminants  the highest in
the leachate from the industrial  wastes, (2)  compare these
concentrations and the total extracted to that extracted under
laboratory conditions, and (3) evaluate in what stage (early, mid,  or
late) the municipal leachate is  most aggressive in removing inorganic
                                  177

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and organic contaminants from the  Industrial wastes.  The work  Involves
the use of two large-scale lysimeters (Fig. B-l,  1.8 m  in diameter  and
3.6 m in height) containing municipal waste.   Volume of municipal waste
is approximately 7.5 m , weighing  approximately 1.5 Mg. The
municipal waste was obtained from  the City of  Oak Ridge, Tennessee,  on
February 23, 1982, and consisted of a residential waste (collected  from
households) and a commercial waste (collected  from fast-order
restaurants, etc.).  These wastes  are layered  in  the lysimeter  in
layers approximately 71 cm thick (Fig. B-l).   The bottom of  the
lysimeter contains pea gravel and  silica sand  to  prevent clogging the
outlet with waste.  A detailed description of  the design is  presented
in Attachment B.  Leachate from each of these  lysimeters will be used
as influent to individual columns  containing each of the four previously
studied wastes.  There will be four columns for each industrial waste,
making a total of 16 columns for each lysimeter (2 experiments  x
industrial wastes x 2 replications) or a total  of 32 industrial waste
columns for the total experiment.   Blank sand  columns will also be  used
for quality control.
     For one-half of the columns,  the quantity of waste in each of  the
columns will correspond to the 95/5 scenario.   Leachate quality from
these columns, in terms of inorganics and organics, will be  compared to
laboratory-derived extractions (Section 3.1).   The remaining columns
will be used to evaluate the stage of aggressiveness of the  MWL as  a
function of the age of the leachate.

3.2.2  Laboratory Comparisons:  For each lysimeter, one-half of the
columns (4 wastes x 2 replicates)  will be used  to compare the 95%
                                  178

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                                                      ORNL-OWG 82.11532
                                              (T) THERMOCOUPLE
                                              W LOCATED AS
                                                  SHOWN
                                                38 cm LAYER SOIL
                                                    COMPACTED
                                                    RESIDENTIAL
                                                    COMMERCIAL
                                                    WASTE (LAYERED)
                                                    EACH LAYER
                                                    ABOUT 71 cm THICK
^ffi^^_T-S0«
                                                    SILICA SAND - 5 cm
                                                    0.13 m3 (277 kgl

                                                    PEA GRAVEL
                                                    - 38 L
                                                    TO COVER DRAIN
                                                    PIPE
                                                    GLASS WOOL
                                                    PYREX - 0.11 kj
Fig. B-l.   Schematic of lysimeter containing residential and
            commerical  wastes.
                             179

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                                               OFWL-OWG 82-11533
                              PUMP-COLE PARMER
                              10-CHANNEL MASTER-
                              FLEX
  TANK-U.S. PLASTICS CORP.
  POLYETHYLENE NO. 10120
  2082 L
           LYSIMETER
 GLASS MANIFOLD
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                                      PUMP-COLE PARMER
                                      1-CHANNEL MASTERFLEX
                             PUMPS-TECHNICON
                     COLUMNS FOR
                      INDUSTRIAL
                        WASTE
OVERFLOW
 TO DITCH
                                                    -OVERFLOW
                                                     COLLECTOR
Fig.  B-2.   Flow diagram for lysimeter study.
                        180

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municipal and 5% industrial waste scenario to the laboratory extraction
studies.  These columns will contain 3.6 kg of waste and will be leached
with the MWL until a 20:1 liquid to solid ratio is achieved (see
Section 3.3).  At the selected flow rate of 0.8 mL/min (equivalent to a
               p     I
flux of 7 mL m   min  ) this will require eight weeks (59 d).
Samples of leachate will be collected twice weekly the first four weeks
and once weekly the remaining four weeks.  Aliquots will also be
composited to ascertain a concentration of inorganics and organics in
the final 20:1 volume.

3.2.3  Aggressiveness of Municipal Waste Leachate over Time;  The
remaining columns (4 wastes x 2 replications) in the lysimeter design
will contain 0.86 kg of waste.  Leachate will be collected after 15 d
and fresh industrial waste will be substituted in the column.  Again
the final quantity of leachate collected will correspond to the 20:1
liquid to solid ratio.  This portion of the experiment is planned to
continue for 90 d (three to four changes of waste).  The quantity of
inorganic and organic constituents leached from each column of fresh
waste should provide an evaluation relative to the aggressiveness of
the municipal waste leachate with age of leachate.
3.2.4  Experimental Design and Analysis:  The experiment will consist
of a randomized block design with four treatments and two blocks
(lysimeters).  The experiment will be replicated twice to test the
block by treatment interaction.  An analysis of variance will  be
conducted to see if there are any differences in leachate aggressiveness
due to age of leachate.   A multivariate pattern analysis will  be used
                                  181

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to determine which of the laboratory extraction  methods  most  closely
simulates the chemical  constituents derived from the field  lysimeters.
The results from the laboratory and field studies will be combined and
statistically analyzed to determine the laboratory method (EP-III) that
most closely simulates the mobility of inorganic as well as organic
constituents of industrial wastes co-disposed with municipal  wastes in
a landfill environment.

      3.3  Basis of  Calculation for Large-scale lysimeter Research

     The large-scale lysimeters (1.8 m in diameter and 3.6  m  in  height,
Fig. B-l) contain approximately 7 m  of waste weighing on the order
of 1.5 Mg.  The wastes were compacted and covered with 0.4  m  of  soil  to
simulate a landfill.  Distilled water will  be continuously  added to
                                  -21                1            1
each lysimeter at a flux of 7 mL m   min   (ca.  26.5 L d   lysimeter  ).
     Leachate from each lysimeter will be collected in a 27-L sump from
which leachate will  be pumped to 16 individual industrial waste  columns
containing the eight industrial wastes replicated two times.   Leaching
by the municipal  waste leachate will  be conducted in a downward
trickling fashion.  The flow rate will be the same as that  applied to
                                                 -2      1
the surface of the large-scale lysimeters (7 mL  m  min   ).
Acid-washed sand will be mixed with the industrial waste (1:1) to
increase the hydrologic conductivity.  Leaching  will continue until  a
20:1 liquid:  solid ratio is achieved from these columns.   Leachate
will also be pumped from the sump for special laboratory extraction
studies.  Any excess leachate will be diverted to ORNL waste  treatment
facilities.  The basis of calculation is as follows:
                                  182

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                                      2
Area of large-scale lysimeter = 2.54 m
               -1  -2
Flux = 7 ml min   m
Assume 1.5 Mg of municipal waste/lysimeter,  for a 95/5  scenario
    (78.9 kg of waste is required).
A borosilicate glass column will be used for the industrial  wastes
    [15.2-in. (38.7-cm) i.d., 12 in. (30.5 cm)  high, cylindrical
    jar with a glass outlet being placed on  the bottom] will  be
                                                2
    used.  Then the area of each column (0.118  m ) times 16
           o
    (1.88 m ) represents 74.1% of the area of the lysimeter
    (1.88/2.54 x 100).  Therefore, 74.1% of  the leachate from the
    lysimeter will be required to "feed" the 16 columns containing
    the industrial wastes.  The weight of the industrial  wastes  in
    each column will be 3.61 kg (78.9 kg x 0.741  * 16)  for the
    laboratory comparison study and 0.8 kg for  the columns used  to
    evaluate the aggressiveness of the MWL with age.
The flow rate to each industrial waste column will be 0.8 ml/min
              12          2
    (7 ml min   m   x 0.118 m).  Thus, it will require at
    this flow rate 59 d to reach a 20:1 solution  to solid ratio
    (72 L) of column leachate for the comparative study.
Total quantity of each industrial  waste required  will be  as
    follows:
         Laboratory studies - 11 x 0.1 kg =  ~23 kg
         Field studies - 3.3(4) + 0.8(16) =  ~37 kg
         Reserve                          =  "40 kg
                              Total        =  ~82 kg
                              183

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     The above calculations and procedures  are basetJ  on best  available
Information relative to the physical and chemical  characteristics  of
the wastes and anticipated characteristics  of the  municipal waste
leachate.  Alterations to these procedures  may be  necessary to  obtain
the desired results.  For example,  mixing the industrial wastes with
acid wash sand is Intended to (1) increase  porosity of the waste/sand
mixture so that downflow of the municipal waste leachate can  be
conducted and (2) decrease the possibility  of "hydraulic short
circuiting" of the leachate through the relatively thin layer
(approximately 2 to 4 cm) of industrial waste.  The plan is to mix the
wastes with sand on a 1:1 weight basis.  Laboratory tests will be
conducted prior to installation of  the field columns  relative to the
applicability of the 1:1 mixture to facilitate downward flow  of
municipal waste leachate.  If 1:1 mixture is not a sufficient quantity
of sand to sustain flow, a 2:1  sand mixture will be used for  that
waste.  Experiments will also be conducted  to evaluate the capacity  of
the sand to attenuate the mobility  of inorganic and organic toxic
materials in municipal waste leachate.
                                  184

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                           4.  WORK SCHEDULE

	Milestone	              Projected  Date
1.  Laboratory study
       WES municipal leachate procured                    Jan.  27, 1982
       Industrial wastes (8) procured                     May 15, 1982
       Proximate analysis of wastes initiated             May 15, 1982
       Select wastes (4) for laboratory and
         field studies                                    May 31, 1982
       Laboratory extractions started
         (88 extractions)                                 June  1, 1982
       Laboratory extractions completed                   Sept.  1, 1982
       Inorganic and organic analysis of
         extracts completed                               Sept.  15,  1982
       Statistical analyses completed                     Oct.  15, 1982
2.  Field study
       Municipal refuse obtained and lysimeters packed     Feb.  23, 1982
       Industrial waste columns packed for laboratory
         comparison and aggressiveness of MWL,
         begin leaching                                   June  15, 1982
       Laboratory comparison, leaching completed          Aug.  10, 1982
       Inorganic and organic analyses of leachates
         from laboratory comparison completed             Sept.  1, 1982
       Aggressiveness of MWL, leaching completed          Sept.  15,  1982
       Inorganic and organic analyses of leachates
         from aggressiveness of MWL completed             Oct.  1, 1982
       Statistical analyses completed, aggressiveness
         of MWL                                           Oct.  15, 1982
3.  Draft report on laboratory and field studies          Jan.  1, 1983
                                  185

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                         5.  REFERENCES CITED

Bause, D. E., and K. T. McGregor.   1980.   Comparison of  four leachate-
     generation procedures  for solid waste characterization  in
     environmental assessment programs.   EPA-600/7-80-118.   U.S.EPA,
     Washington, D.C.
Epler, J. L.  1980.   Toxicity of Leachates.   EPA-600/2-80-057.
     U.S.EPA, Washington, D.C.
                                 186

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                      ATTACHMENT A TO APPENDIX B
             PROTOCOL FOR EVALUATING THE  AGGRESSIVENESS OF
                      THREE TREATMENT PROCEDURES
1.  Rank the concentrations  of each  constituent  extracted from least to
    most aggressive within each waste.
2.  Group the constituents into target  analysis  categories and then sum
    the ranks within a category:
       NIPDWR inorganics
       Toxic organics.
3.  Rank the sums within each  category.
4.  Sum the ranks across categories  to  obtain  an overall rank sum.
5.  Repeat 1-4 for all wastes.
6.  Statistically analyze the  rank sum.
                                  187

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     EXAMPLE OF PROTOCOL FOR EVALUATING THE AGGRESSIVENESS OF THREE
         TREATMENT  PROCEDURES FOR A PARTICULAR INDUSTRIAL WASTE

TREATMENTS               TOXIC ORGANICS                NIPPUR  INORGANICS
                         Phenol    BAP                  Hg     Cd      Pb

    1                      0.1      0.04                 0.5     10      43

    2                      8.0     0.09                 1.6     20      25

    3                      6.0     0.01                  2.0     12      68


STEP 1 - RANK THE CONCENTRATIONS OF EACH CONSTITUENT  EXTRACTED

    1                      12                    112

    2                      33                    231

    3                      21                    323


STEP 2 - GROUP THE CONSTITUENTS INTO  CATEGORIES AND SUM THE  RANKS

TREATMENTS               TOXIC  ORGANICS                 NIPPUR  INORGANICS

    1                          3                              4

    26                              6

    33                              8


STEP 3 - RANK  THE SUMS WITHIN EACH  CATEGORY

    1                          1.5                             1

    23                              2

    3                          1.5                             3


STEP 4 - SUM THE  RANKS ACROSS CATEGORIES TO OBTAIN AN OVERALL RANK SUM

TREATMENT       RANK SUM
1
2
3
2.5
5
4.5
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                      ATTACHMENT B TO APPENDIX B
                    DESCRIPTION OF LYSIMETER STUDY

     A one-line diagram of the lysimeter study setup is  depicted  in
Fig. B-2.  A detailed explanation follows.   The two large-scale
municipal waste lysimeters will be continuously watered  using  distilled
water contained in a 2080-L polyethylene storage tank  (U.S.  Plastic
Corp. Cat. No. 10120).  Water out of the storage tank  will flow from
0.5-in. (1.3-cm) PVC pipe into a glass  manifold that will direct  the
water into 10 separate master-flex pump channels (Cole Parmer  Cat.
No. C-7568-00); the pump will be equipped with pump heads and  silicone
tubing (Cole Parmer head #C-7013-20 and tubing #C-6411-41) to
accommodate a flow rate of 3.68 ml min    channel   .  Five channels
will continuously provide water to each lysimeter at 3.68 mL/min
(a total  of 18.4 mL/min or 26.5 L/d).   Each  lysimeter  will be  covered
with a 0.015-cm thick polyethylene tarp.
     Municipal waste leachate (MWL) out of each lysimeter will be
delivered to separate 27-1 glass sumps  (30.5 cm o.d. x 45.7  cm high,
Corning No. 6942) through 2.54-cm PVC pipe.   A 2.0-cm-thick  plexiglass
cover with the underside covered with Teflon* overlay  (with  holes cut
for inlets and outlets) will be fabricated to fit each sump  jar.  An
overflow pipe will be connected to the  sumps to divert any excess MWL
to ORNL waste treatment facilities; a sampling port will be  connected
to the overflow pipe to collect MWL for characterization and/or
laboratory studies.  MWL for industrial waste leaching will  be pumped
from the sump (30 mL/min) to a glass manifold using  a  masterflex  pump
(Cole Parmer pump no. 7545-10, pumphead no.  C-7016-00);  excess MWL not
                                  189

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used for industrial waste leaching will  return  to  the  sump.   The MWL
will contact Teflon* tubing except through the  pump  which  utilizes
silicone tubing [0.125-in. (0.32-cm) i.d., 0.251-in.  (0.64-cm)  o.d.,
Cole Farmer Cat. No. C-641102].   The glass manifold will contain inputs
to monitor the pH and Eh of the  MWL and  will  also  be fitted with
22 ports (Note:  All may not be  used) to aliquot the MWL to the
industrial waste columns.  Each  industrial waste column  (16 per
lysimeter plus 2 sand controls)  will receive  MWL at  a  flow rate of
0.8 mL/min.  The MWL will be pumped, using Technicon pumps (2-speed
proportioning pump) from each manifold port (each  channel  in  the pump
will connect to a port in the manifold)  through 0.125-in.  (0.32-cm)
o.d. Teflon* tubing connected to Technicon solvent flexible manifold
tubing [0.045-in. (0.11-cm) i.d. Technicon No.  1160533]; 0.125-in.
(0.32-cm) o.d. Teflon* tubing will be connected out of the pump and
will introduce the MWL to the industrial waste  columns.  The  industrial
waste columns are purchased borosilocate glass  jars  (32-L  capacity,
38.7-cm i.d. and 30.5 cm high, Corning No. 6942) with  an outlet placed
on the jar bottom.  A 2.0-cm-thick plexiglass cover with the  underside
covered with Teflon* overlay will be fabricated to seal the jar top.
Leachate out of the industrial columns will flow through Teflon*
tubing into Tedlar sampling bags.
                                  190

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