United States Effluent Guidelines
Environmental Protection Division January 1981
Agency Washington. D.C.
Development of
Methodology for the
Evaluation of Solid Wastes
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January, 1981
FINAL REPORT
ON
DEVELOPMENT OF METHODOLOGY FOR
THE EVALUATION OF SOLID WASTES
Volume I
by
M. M.-McKown, J. S. Warner, R. M. Riggin,
M. P. Miller, R. E. Heffelfinger, B. C. Garrett,
G. A. Jungclaus and T. A. Bishop
Battelle
Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
Contract Number: 68-03-2552
Industrial Environmental Research Laboratory
Cincinnati, Ohio
Project Officers: M. Carter
D. Neptune
EFFLUENT GUIDELINES DIVISION
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C.
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DISCLAIMER
This report has been reviewed by the Effluent Guidelines Division, U.S.
Environmental Protection Agency, and approved for publication. Mention of
trade names or commercial products does not constitute endorsement or
recommendation for use.
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FOREWORD
On May 19, 1980*(45 FR 33122) the Environmental Protection Agency promul-
gated criteria for identifying wastes which pose a potential hazard to human
health or the environment if improperly managed. These criteria were promul-
gated under the authority of Section 3001 of the Resource Conservation and
Recovery Act (PL 94-580). During the development of these criteria, EPA
needed to establish methodology to evaluate wastes relative to the aspects
of potential mobility of toxic components (leaching) from the wastes and
total content of toxic species in the waste. This report is divided into two
volumes. Volume I is an evaluation of test methodology for the potential
mobility of toxic components from wastes, and volume II is an evaluation of
test methodology for the content of extractable toxic species present in
wastes.
During the development of the regulations, EPA found that there was per-
vasive evidence that the contamination of groundwater through the leaching
of waste contaminants from land disposed wastes is one of the most prevalent
pathways by which toxic waste constituents migrate to the environment. EPA
addressed this problem by developing a-test procedure, called the Extraction'
Procedure, (40 CFR Part 261.24) to identify wastes from which hazardous
concentrations of particular toxic constituents are likely to leach into the
groundwater under conditions of improper management. The particular condi-
tion of improper management modelled by this procedure is codisposal of
toxic wastes in an actively decomposing municipal landfill. EPA realized in
making its codisposal assumption that actively decomposing municipal waste
landfills generate more aggressive leachate media than other landfills.
EPA conducted a number of studies to develop the Extraction Procedure.
These studies were aimed at developing a leaching medium that would model the
leachate generated by actively decomposing refuse, yet have a low inherent
biological toxicity. Low toxicity was necessary so that bioassay procedures
could be employed to measure the presence of significant concentrations of
toxic species in the resulting extract. The Agency found that it could not
incorporate all the desired properties into the extraction media given the
Congressional and Court-mandated deadlines. Thus, only the acidic nature of
municipal landfill leachate was incorporated into the Extraction Procedure
promulgated on May 19, 1980.
Volume I of this report describes one of several studies being conducted
by the Agency to evaluate and improve leachate test methodology to be applied
to wastes in an actively decomposing municipal landfill. Much emphasis in
this work was placed on studying the leachability of organic components of
wastes.
iii
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As part of an overall study to characterize wastes, EPA is evaluating
analytical methods for both leachable components and total content of wastes.
Volume II of this report presents part of the work performed to date in this
area.
iv
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ABSTRACT
Battelle's Columbus Laboratories conducted this research program to de-
velop a method for assessing potential mobility of organic compounds from a
waste codisposed in a municipal landfill.' Inorganic constituents were moni-
tored to provide a basis for comparison with previous research in the field
using distilled water, 0.5 N acetic acid titration (EPA extraction procedure-
EP), and other leaching media. A literature survey and contacts with key
scientists served as the basis for assessing state-of-the-art leachate re-
search. A quality assurance study to assess the precision and accuracy of
analytical methods to be used to evaluate the leachates and wastes was con-
ducted prior to initiation of leachate research.
From a total of 23 wastes collected for the program, 6 samples were se-
lected for evaluation. Initial assessment of the effect of the mixing device
design and the effect of leaching media upon leachabillty of organic and
inorganic constituents was accomplished using a dewatered (25 percent solid)
public owned treatment works (POTW) sludge. The EP was used to evaluate a
stirring-type mixing device (made by ADMCo) and a tumbling-type mixing device
(designed by NBS for EPA). The NBS tumbler was selected for all subsequent
studies on the basis of (1) superior leaching ability for volatile organics,
(2) comparable leaching ability for metals and semivolatile organics, (3)
ease of operation, and (A) ability to handle a wider range of sample types.
Seven of the 17 leaching media were selected for additional studies on the
basis of the results of this initial task. These media were distilled water,
acetic acid (EP), 0.1 M acetate buffer (pH 4), two pH 5 sodium citrate
buffers (0.02 M and 0.05 M), and 0.01 M sodium citrate (pH 5). Five wastes
were leached with each of these seven media. The five wastes were a baghouse
dust, an unidentified organic still bottom, an ink pigment waste, a pharma-
ceutical waste, and a coal gasification tar. The observed effect of leaching
medium composition on organic mobility was slight, whereas the effect on
metal mobility was frequently very large and concentration dependent. Com-
parable results were obtained with the EP and 0.1 M acetate buffer while the
addition of citrate generally increased mobility of metals dramatically.
There was no significant difference in mobility of metals or organics by
adding hydrosulfite or surfactant, respectively.
Quality assurance measures adopted for the program included spikes, three
or five replicates, blanks and appropriate calibration/performance standards.
Descriptive statistics, including mean recoveries, standard deviation and
relative standard deviations were augmented by comparisons of secondary char-
acteristics to evaluate the leaching results.
An interlaboratory comparison study of the potential mobility procedure
developed by Battelle and the total content method developed by Southern
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Research Institute (SoRI) was performed jointly by both laboratories. The
ink pigment and still bottoms wastes were used for the interlaboratory com-
parison of the methods. The data for metal analyses were comparable using
atomic absorption spectrophotometry or inductively coupled argon plasma. The
comparison of volatile organic analyses was excellent especially when one
considers that Battelle used a carbon disulfide extraction method with analy-
sis by gas chromatography and SoRI used purge and trap EPA Method 624 that
involves analysis by combined gas chromatography-mass spectrometry. Data for
semivolatile organic constituents obtained by both laboratories using EPA
Method 625 were also comparable.
The advantages and disadvantages of the various analytical methods used
throughout the program to determine metals and organics are discussed in
detail. It was concluded that the leaching procedure and analytical methods
used meet all of the original objectives of the program including feasibility
of Implementation at a cost of under $1850 per sample.
The solid waste leaching procedure developed on this program when used
with distilled water as the leaching medium is recommended for the prepa-
ration of a leachate that can be used to assess the potential mobility of
organic components from solid wastes codisposed with municipal wastes in a
landfill except when the waste contains significant amounts of immiscible and
nondispersible oils. The carbon disulfide extraction procedure with analysis
by glass capillary column gas chromatography as used on this program is
recommended as an optional procedure for the determination of volatile
organics in solid wastes and solid waste leachates. The modified Method 625
used for this program, involving a single extraction under acidic conditions
and the determination of both neutral and acidic semivolatile components in a
single GC-MS run using a glass capillary column, is recommended as an
optional procedure for the determination of semivolatile organics in solid
wastes and solid waste leachates.
We recommend that future research programs be undertaken to.:
• Develop protocols and procedures for dealing with oily wastes
• Develop a relatively simple solid waste extraction method that will
give good recoveries of low levels of the polar and"acidic semi-
volatile organics as well as the less polar neutral components, and
• Conduct an interlaboratory validation study of the leaching procedure,
leachate analysis methods, and total content analysis methods,
involving a number of wastes selected to represent waste types and six
or more laboratories.
This report was submitted in fulfillment of Contract No. 68-03-2552 by
Battelle's Columbus Laboratories under sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from January 1 to August 29,
1980.
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CONTENTS
Page
FOREWORD iii
ABSTRACT v
FIGURES x
TABLES xi
ACKNOWLEDGEMENT xv
I. INTRODUCTION 1
Task 1. Procurement of Waste Samples : . . . . 2
Task 2. Physical Compatibility of Wastes 3
Task 3. Comparison of Extraction Precision 3
Task 4. Effect of Leachate Media on Waste 3
Task 5. Effect of Waste on Leachate Composition 4
Task 6. Interlaboratory Comparison 4
II. CONCLUSIONS 5
III. RECOMMENDATIONS 7
IV. LITERATURE REVIEW 9
V. EXPERIMENTAL 15
Sample Collection and Selection 15
Physical Compatibility 17
Leachate Generation 17
Procedures for Inorganic Analyses 19
Instrumentation 20
Sample Preparation 20
Procedures for Organic Analyses 21
Volatile Organic Analysis 21
Semivolatile Organic Analysis 22
Statistical Considerations 23
vii
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CONTENTS (Continued)
Quality Assurance 23
Experimental Design • • 24
Documentation 24
Analytical Quality Control. 25
VI. RESULTS 31
Sample Characterization 31
Sample Selection 31
Extractor Evaluation (Task 3) 33
Effect of Media (Task 4) 33
Effect of Waste Type (Task 5) 39
Interlaboratory Comparison Study (Task 6) 48
Leachate Analyses 62
Total Content . 71
Comparison of Leaching Efficiency . . . 81
Statistical Treatment of the Data 88
VII. QUALITY ASSURANCE 89
Volatile Organics 89
Semivolatile Organics 91
Metals 97
VIII. DISCUSSION 103
Selection of Wastes 103
Selection of Leaching Media 104
Leachate Analysis Methods 105
Metal Analyses 105
Volatile Organic Compounds 106
Semivolatile Organic Compounds 107
Total Content Analysis Methods . 107
Metal Analyses 107
Volatile Organic Analyses 108
Semivolatile Organics 109
Feasibility of Implementation 109
Leaching Method 109
Total Content Method Ill
Cost to Implement Ill
viii
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CONTENTS (Continued)
Page
REFERENCES 113
APPENDIX
SOLID WASTE LEACHING PROCEDURE A-l
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FIGURES
1.
2.
3.
4.
•*.
6.
7.
8.
9.
10.
11.
12.
Reconstructed Gas Chromatogram (RGC) for Volatile
RGC for Ink Pigment Leachate
RGC for Coal Gasification Tar Leachate
RGC for Semivolatile Organics in Pharmaceutical Waste Leachate.
Gas Chromatogram of C&2 Extract of Still Bottoms Leachate . . .
Page
. . 18
. . 49
. . 50
. . 51
. . 52
. . 53
. . 54
. . 55
. . 56
. . 57
. . 72
. . 73
13. Gas Chromatogram of C$2 Extract of Still Bottoms for
Total Content Analysis ....................... 82
14. Gas Chromatogram of CS£ Extract of Ink Pigment
for Total Content Analysis ............. ........ 83
x
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TABLES
Page
Number
1. Critical Variables in a Leaching Method 11
2. Frequency of Test Variable Specifications in
Published Leaching Procedures 12
3. Description of Waste Samples Received for the Study 16
&. Physical Characteristics of Waste Samples 32
5. Data for Extractor Evaluation—Task 3 34
6. Description of Leaching Media 35
7. Comparison of Leachates from Dewatered POTW Sludge 36
8. Precision of Analysis of Leachates from Dewatered POTW Sludge ... 37
9. Volatile Organic Content of Selected Leachates
Using EPA Method 624 41
10. Composition of Leachates from Baghouse Dust 42
11. Composition of Leachates from Still Bottoms 43
12. Composition of Leachates from Ink Pigment Waste 44
13. Composition of Leachates from Pharmaceutical Waste 45
14. Composition of Leachates from Coal Gasification Tar Waste 46
15. Composition of Standard Solution A 58
16. Composition of Standard Solution B 59
17. Composition of Standard Solution C 60
18. Composition of Standard Solution D 61
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TABLES (Continued).
19. Composition of Standard Solutions Used for Spiking in
Total Semivolatile Organic Content Analyses . . . 63
20. ICAP Analysis of Leachates for Solid Wastes (Battelle) 64
21. Battelle AA and ICAP Data Comparison—Leachate 65
22. Recovery of Metals Spiked into Leachates from
Solid Wastes (Battelle) 66
23. Interlaboratory Comparative Data from AAS Analysis
of Metals in Ink Pigment and Still Bottoms 67
24. Volatile Organic Content of Leachates from
Solid Wastes (Battelle) 68
25. Interlaboratory Comparative Data from Analysis of
Volatile Organics in Ink Pigment and Still Bottoms 69
26. Interlaboratory Comparative Data from Analysis of
Semivolatile Organics in Still Bottoms 74
27. Interlaboratory Comparative Data from Analysis of
Semivolatile Organics in Ink Pigment 75
28. Recovery of Semivolatile Organics Spiked into
Leachates from Still Bottoms 76
29. Recovery of Semivolatile Organics Spiked into
Leachates from Ink Pigment 77
30. Total Metals Content of Solid Wastes (Battelle) 78
31. Recovery of Metals Spiked into Solid Wastes (Battelle) 79
32. Total Volatile Organic Content of Solid Wastes (Battelle) 80
33. Recovery of Semivolatile Organics Spiked into
Still Bottoms Based on Total Content Analysis ..... 84
xii
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TABLES (Continued)
Page
34. Recovery of Semivolatile Organics Spiked into
Ink Pigment Based on Total Content Analysis 86
35. Precision Data for GC-MS Analysis of Volatile
Organics in Water Using EPA Method 624 90
36. Precision Data for GC-MS Analysis of Volatile
Organics by Direct Injection of Standard 92
37. Precision Data for GC-MS Analysis of Volatile
Organics in a POTW Sludge Supernatant Using EPA Method 624 93
38. Precision Data for GC-MS Analysis of Semivolatile
Organics in Standard Solutions . . 94
39. Precision Data for GC-MS Analysis of Semivolatile
Organics Using a Packed Column Over a Period of 4 Weeks 95
40. Precision Data for GC-MS Analysis of Semivolatile
Organics Using a Capillary Column Over a Period of 2 Weeks 96
41. Precision Data for ICAP Analysis of Metals in Distilled Water ... 98
42. Precision Data for ICAP analysis of Metals in a
Distilled Water Leachate from a POTW Sludge 99
43. Precision Data for AAS Analysis of Metals in Distilled Water. . . . 100
44. Precision Data for AAS Analysis of Metals in a
Distilled Water Leachate from a POTW Sludge 101
45. Estimated Costs for Analysis of Ten Samples Using the
Solid Waste Leaching Procedure 112
xiii-xiv
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ACKNOWLEDGMENTS
The assistance and technical support provided by the Task Officers for
this program, Mr. Mike Carter and Dr. Dean Neptune of the Effluent Guidelines
Division, is appreciated by Battelle. We are indebted to Mr. David Friedman
and Dr. Jim Poppiti of the Office of Solid Waste who provided valuable
technical direction.
The cooperation and technical guidance of Dr. Gene Meier, EMSL-Las Vegas,
which significantly enhanced the quality of this research program is grate-
fully acknowledged.
The Battelle researchers appreciated this opportunity to interact and
collaborate with Chip Miller, Ruby James and Walt Dixon of Southern Research
Institute who conducted the total content research effort. The staff of the
Center for Analytical Chemistry, National Bureau of Standards, is acknowl-
edged for providing the NBS tumbler extractors and for helpful technical
discussions.
Mr. Ray Smithson and Mr. Ron Clark of Battelle provided management assis-
tance that was invaluable to the project. Ms. Linda Delma's professional
contributions in production and organization of weekly reports and coordina-
tion of program activities are appreciated by program participants.
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SECTION I
INTRODUCTION
The EPA's Office of Solid Wastes (OSW) of the Office of Water and Waste
Management is required by the Resource Conservation and Recovery Act of 1976
(RCRA) to identify wastes that may be hazardous and to select those wastes
which require special management. The EPA specifies an extraction procedure
(EP) involving the use of acetic acid to assess the leachability of certain
toxic organic compounds and chemical elements from wastes for use in
determining whether a waste is a hazardous waste under RCRA"). The
research effort by Battelle's Columbus Laboratories described here, entitled,
"Development of Methodology for the Evaluation of Solid Wastes", was
established by the OSW and the Effluent Guidelines Division (EGD) of EPA to
continue development of the potential mobility procedure and to evaluate
methods for the total content of toxic compounds in waste materials covered
by the RCRA legislation. Major emphasis was placed on potential mobility of
organic compounds; metal analyses were also conducted so that additional
valuable comparisons with EP results could be realized.
Several criteria were designated by EPA for development of a leaching
procedure. The method developed had to be:
• Technically sound
e Feasible and practical to implement
• Designed to simulate the leachability expected to occur in municipal
landfill environments
• Within the capabilities of a production-type laboratory
• Cost no more than $1,850 per sample analysis when performed routinely.
The municipal landfill environment was targeted since the mode of disposal of
interest to OSW is codisposal of a given waste in a municipal landfill.
Battelle performed two tasks prior to.initiation of leaching research.
First, a state-of-the art literature search was conducted. Because Battelle
researchers were familiar with the analytical approaches for leaching method
development, an exhaustive literature search was unnecessary. Key publica-
tions and information were assembled by referring to latest editions of EPA
reports and methods and searching recent selected technical journals. Per-
sonal contacts, including scientists currently active in this area of
research, EPA researchers, and appropriate ASTM members presently associated
with development of leaching methods, were relied upon to supplement printed
information. '
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Second, based on this survey, several analytical techniques were identi-
fied that would be required for the research program. Since a variety of
factors would be examined throughout the course of the study, the inherent
analytical method variabilities were established prior to use by performing
an exhaustive analytical method precision study. A detailed description of
this study is presented in the Quality Assurance section of this report for:
• Atomic Absorption Spectrophotometry (AAS)
• Inductively Coupled Argon Plasma Spectrometry (1CAP)
• Gas Chromatography.(GC)
• Gas Chromatography-Mass Spectrometry (GC-MS),
^
as applied to the analysis of 'the leachates from dewatered sludge from a
Public Owned Treatment Works (POTW).
The research program that was designed included six subtasks to be
conducted concurrently when possible. These subtasks were:
Task 1. Procurement of Waste Samples
Task 2. Physical Compatibility of Wastes
Task 3. Comparison of Extractor Precision
Task 4. Effect of Leaching Media on Waste
Task 5. Effect of Waste on Leachate Composition
Task 6. Interlaboratory Comparison Study.
The scope of each task, to be described in detail in this report, will be
summarized here.
TASK 1. PROCUREMENT OF WASTE SAMPLES
The requirement that the leaching procedure developed must be applicable
for a broad range of wastes made it mandatory that a spectrum of wastes that
are difficult to handle be obtained for examination. The most complex
samples were sought so that the worst case waste could be included in the
method development phase. The criteria used to select waste samples
included:
High percent solid content
High total organic content
Large number of organic compounds present at high concentration
High total inorganic content
Wide pH range.
The wastes selected for study included one or more meeting each criterion
and, preferably, wastes meeting more than one of these criteria. A special
attempt was made to obtain wastes representative of anticipated industrial
problem wastes.
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TASK 2. PHYSICAL COMPATIBILITY OF WASTES
The research performed for developing a leaching method required the
evaluation of a variety of leaching media applied to numerous solid wastes.
This evaluation could be accomplished only if the wastes studied were com-
patible throughout the conduct of the method. Thus, each waste obtained from
the sources identified was evaluated according to the ability and ease of:
• Separation by centrifugation
• Separation by filtration, and
• Dispersion in extraction device.
Based upon these observations, eight wastes were selected for further study
which would challenge the centrifugation, filtration, and extraction steps.
TASK 3. COMPARISON OF EXTRACTION PRECISION
Two extraction devices were considered for the program based upon the
literature search:
(1) Stirrer Extractor-Associated Design and Manufacturing Company
(ADMCo)
(2) Tumbler extractor developed for EPA by the National Bureau of
Standards (NBS).
These two devices were used to extract the dewatered POTW sludge using
EPA's extraction procedure (EP). Any differences in the precision of the
data obtained or losses of analytes of interest that might be attributed to
the extraction equipment were identified in this manner.
TASK A. EFFECT OF LEACHING MEDIA ON WASTE
Based upon the survey of scientists and published literature, Battelle
researchers selected seventeen candidate leaching media which met one or all
of the following criteria:
• Likely to be present in or simulate components present in a municipal
landfill
• Nontoxic for bioassay
• Minimum analytical interference potential for organic and inorganic
analysis.
The dewatered POTW sludge was leached with each of these media and analyzed
for organic and inorganic priority pollutant compounds to assess efficiency
and applicability of each medium.
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TASK 5. EFFECT OF WASTE ON LEACHATE COMPOSITION
The results from Task 4 and supplementary information regarding the
chemical nature of each medium were evaluated to select a small number of
media for study with a variety of solid wastes. In this manner, it was
possible to determine if the type of waste affected the relative analytical
results obtained by using the leaching procedure with a variety of media.
TASK 6. INTERLABORATORY COMPARISON
Two research organizations participated in this study. Battelle's
Columbus Laboratories (BCL) developed the potential mobility or leaching
procedure, and Southern Research Institute (SoRI) developed the total content
method. The final task of this program required the participation of both
laboratories. Samples and analytical methods were exchanged and both
organizations performed the leachate procedure and analysis for total content
in order to obtain comparative data.
The research program discussed in detail in this report was completed in
only 6 months due to the urgency of the EPA's need for defensible analytical
methodology in this important area. Therefore, the Conclusions and
Recommendations sections of this report include several suggestions for
future research. Battelle recommends that extensive interlaboratory valida-
tion studies be conducted for both the potential mobility and total content
methods.
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SECTION II
CONCLUSIONS
The types of waste covered by the Resource Conservation and Recovery Act
vary considerably in respect to composition and physical properties. The
wastes selected for the program included a variety of wastes high in solids
content and containing significant amounts of organic and inorganic
pollutants.
The leaching media studied included dilute acetic acid as used in the
EPA Extraction Procedure (EP), distilled water, and 15 additional .media
selected to provide variable conditions that might occur in a municipal
landfill. The distilled water leachate was as'effective as the other media
in leaching organic components and does not interfere with either bioassay
or analytical procedures.
The results obtained using 0.1M sodium acetate buffer, pH 4.0, were
similar to the results obtained using the EP for the leaching of metals. The
EP using a tumbler-type extractor was found to be a reproducible means of
generating leachates from many types of wastes. The stirrer extractor was
shown to be inadequate since significant losses of volatile organic compounds
were observed. Citrate buffer was often more aggressive than acetate buffer
for the leaching of metals. The aggressiveness of buffered acidic and
reducing media toward leaching of metals was highly metal and sample
dependent.
The results of the interlaboratory comparison study conducted jointly by
Battelle and Southern Research Institute indicate that the solid waste
leaching procedure developed for this study is reproducible. The procedure
is easy to use and is suitable for many types of wastes and analytes. How-
ever, the procedure does not provide for obtaining a representative aliquot
of a two-phase liquid leachate that would result from leaching an oily waste.
Although the leaching media studied were selected to mimic conditions
occurring in a municipal landfill, the degree to which this procedure repro-
duces the leaching of organics in a codisposal environment is unknown at this
time.
5-6
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SECTION III
RECOMMENDATIONS
The solid waste leaching procedure developed on this program is recom-
mended for the preparation of a leachate that can be used to assess the
potential mobility of chemical components from a solid waste placed in a
landfill. More specifically it is recommended that the procedure be used
with distilled water as the leaching medium for generation of a leachate
which can be analyzed to assess the potential mobility of organic components
from a solid waste codisposed with municipal wastes in a landfill.
The procedure can be used to prepare leachates of various different types
of wastes to compare the potential mobilities of organic components from
those wastes. It should be recognized, however, that the composition of
leachates produced from a waste in the field can be affected very signifi-
cantly by uncontrolled factors such as amount of rainfall, evaporation rates,
water flow rates and water flow profiles at a landfill site. Consequently,
the composition of an actual leachate produced from a waste in the field
should not be expected to be the same as a leachate generated in the
laboratory under controlled conditions.
It should also be recognized that although the leachability of organic
components was not significantly affected by the leaching medium composition,
the leachability of inorganic components was very drastically affected by
leaching medium composition. Therefore, if it is desired to determine the
site specific leachability of inorganic components, it is recommended that
the leaching medium be carefully selected based on the composition of the
waste, the composition and relative amount of material codisposed with the
waste, the composition of the soil mixed with the waste, the chemical and
biological reactions that can be expected in the particular landfill
situation, and the water flow profiles that can be expected.
One aspect of the solid waste leaching procedure that was not studied in
this program is the potential removal of soluble organic components by
adsorption by the membrane filter used in the filtration step. It is very
possible that the relatively lipophilic cellulose ester filter used will
remove significant amounts of soluble components, especially the less polar
components. However, if the filtration step is omitted, relatively high
concentrations of organic compounds may remain in the leachate as part of the
particulate matter that is not removed by centrifugation. It is therefore
recommended that the adsorption of low levels of soluble organics by cellu-
lose ester membrane filters and the use of less lipophilic final filters,
e.g. glass fiber or regenerated cellulose filters, be studied in a future
research program.
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For reasons discussed elsewhere, the solid waste leaching procedure
developed in this program is not suitable for use with wastes that contain
significant amounts of immiscible and nondispersable oils. Since such oily
wastes are relatively common, it is recommended that future efforts include
the development of protocols and procedures for dealing with oily wastes.
This effort should be combined with the membrane filter study because im-
miscible oils or solvents can be very detrimental to cellulose ester filters.
The analytical procedures used on this program for the determination of
volatile and semivolatile organics often deviated considerably from EPA
Methods 624 and 625 in order to achieve improvements in cost effectiveness.
However, the quality of the data obtained, in terms of both precision and
accuracy (percent recovery) was not sacrificed. Consequently, it is recom-
mended that the CS2 extraction method with GC-FID analysis for volatile
organics be accepted as an optional method for both leachate analyses and
total content analyses for solid waste studies whenever possible. It is
recognized that in some cases the presence of large amounts of interferences
may preclude the use of any method other than a GC-MS procedure.
It is also recommended that the modified methylene chloride extraction
procedure, employing a single extraction under acidic conditions and a single
GC-MS run using a glass capillary column, be accepted as an optional
procedure for the analysis of semivolatile organic priority pollutants in
leachates in all cases except when benzidine is of specific interest. It
should be recognized, however, that Method 625 is not reliable for the
determination of low levels of benzidine unless special modifications are
made to prevent the oxidative degradation of benzidine.
For the extraction of semivolatile organics from solid wastes for total
content analyses, it is recommended that a single neutral/acid fraction for
analysis by glass capillary column GC-MS be accepted as an optional proce-
dure. Furthermore, it is recommended that the homogenization-extraction be
performed without the addition of water and in the presence of a drying agent
to enhance the recoveries of polar components. This step could be coupled
with Soxhlet extraction to achieve an exhaustive extraction, if desired.
Finally, it is recommended that cleanup steps in addition to GPC be studied
in an effort to prevent the precipitation during the concentration step of
material that might adsorb and thus remove components of interest.
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SECTION IV
LITERATURE REVIEW
Prior to initiating laboratory investigations, a literature search was
conducted to examine the current state-of-the-art in leaching methods.
Because this study was primarily concerned with the potential mobility of .
organic constitutents of wastes, particular attention was paid to previous
research dealing with leaching of organic compounds. The search provided
pertinent information about the characteristics of the leaching media that
have been used, the leaching test conditions that have been-specified, and
the extent to which precise control of these conditions has been maintained.
Finally, the search examined which leaching test conditions have been pre- •
viously studied and what results have been obtained.
Because Battelle researchers were familiar with .leaching methods and the
associated analytical techniques, an exhaustive search of the literature on
leachates was unnecessary. Due to this previous experience, attention was
focused on the latest developments in the leaching field. The resources used
during the literature search included
• Computerized retrieval of published abstracts using key word searching
of the Chemical Abstracts Envirolines, National Technical Information
Service, and Pollution Abstracts data files.
• Active searching of most recent government publications and pro-
fessional journals for articles too current for inclusion in the files
of abstracting services.
• Personal contact with scientists currently'active in the fields of
leaching medium selection, leaching methology development, and leach-
ate characterization. The individuals contacted included government
and academic researchers and ASTM members presently devoted to
leaching method studies.
The literature search reinforced the belief that the majority of
investigations into leachability of constituents from solid wastes have been
confined to studying the inorganic constituents. Earlier studies that did .
include an assessment of the mobility of organic constituents.usually
presented data for organic compounds as "Total Organic Content" or as other
general classes of compounds, such as tannins and lignins^|3). Only more
recently have researchers attempted to analyze for specific organic
constituents.
-------
Robertson, et al., investigated various organic compounds that were being
leached from a sanitary landfill'^'; Burrows and Rowe-studied the ether-
soluble constituents in landfill leachates^); and Jones, et al. , examined
halogenated organic compounds leached from wastes'^).
The chemical and physical nature of leachates has been studied exten-
sively, and comprehensive reviews have been published^,8), Ideally, the
leaching medium and test conditions used in a leaching test should reproduce
the actual leachate and conditions to be encountered at the field disposal
site, because the chemical composition of a leaching medium is highly site
specific. The leachate percolating through a particular waste reflects the
composition of all the materials through which that leachate has travelled
and depends on such site characteristics as annual rainfall volume and com-
position, evapotranspiration, biological activity, and the nature of the
surrounding soil and wastes^"'.
Because of the diversity of the site conditions that are encountered in
the field, no single leaching medium can accurately reproduce the compo-
sition of the actual leachate to be found in all situations. However, the
factors that influence leaching medium composition have been identified
(lable 1), and the relative influence of leaching activity can be estimated.
The predominant factors inherent to leaching medium composition that directly
relate to leaching ability are the proton and electron environments^'"^'
and the presence of solubilizing agents^^, 13).
The proton and electron environments have been determined for natural
envi ronments' ^) and landfill leachates^ > ^> *^) by measuring the pH,
redox potential, ionic strength, and buffering capacity. Lowenbach has
evaluated the extent to which various leaching media have incorporated these
factors^^O.
Solubilizing agents include constituents such as complexing agents
(hydroxyl ion, ammonia, EDTA), colloidal constituents (micelles or surfac-
tants), and organic constituents (melanic materials, humic acids). These
agents have a profound effect upon the mobility of inorganic and organic
constituents of the waste, even when the agents are present at low con-
centrations. Most analyses of field leachates have failed to examine the
possible presence of such agents, although some of the more recently
developed leaching media have incorporated solubilizing agents^l^,18).
The analytical techniques used in the leaching procedures^19-21) nave
been studied extensively^^"™', and the instrumental methods for use in
analyzing the wastes and leachates have been investigated by several
researchers'31~38). The report of Lowenbach provides a detailed summary of
the procedures for over 30 available or proposed leaching methods^l^).
These leaching methods were evaluated with regard to the critical variables
given in Table 1. A summary of the leaching variables for these proposed
methods is presented in Table 2^»-^'.
The studies of Ham and associates provide a comprehensive evaluation of
the effects produced by systematically varying each of the leaching condi-
tions given in Table 1(8,9,17,18,40,41)_ The studles of Lowenbach and Ham
10
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TABLE 1. CRITICAL VARIABLES IN A LEACHING METHOD
I. Leaching Medium Composition
A. Proton and Electron Environment
1) pH
2) Redox potential (pe or Eh)
3) Ionic strength
4) Buffering capacity
B. Presence of Solubilizing Agents
1) Chelating agents
2) Complexing agents
3) Colloidal constituents
4) Organic constituents
II. Leaching Conditions
A. Contact Area/Particle Size
B. Method of Mixing
C. Mixing Time
D. Temperature Control
E. Number of Leachings on the Same Solid
F. Number of Leachings with the Same Liquid
G. Solid to Liquid Ratio
11
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TABLE 2. FREQUENCY OF TEST VARIABLE SPECIFICATIONS
IN PUBLISHED LEACHING PROCEDURES
Number of Published Leaching
Procedures Specifying the
Critical Leaching Variable Test Variable(a)
I. LEACHING MEDIUM COMPOSITION
HO (distilled, deionized, distilled-deionized,
^ or unspecified) 17
H20 with pH adjustment or simple acid base 5
Site specific 1
Acetate buffer 1
Synthetic municipal landfill leachate 1
Synthetic natural rainwater 1
Bacterial nutrient media 1
Tests with more than one leachate 5
II. LEACHING CONDITIONS
A. Contact Area/Particle Size
10 Mesh 1
45-60 Mesh 2
100-200 Mesh 1
Unspecified 28
B. Temperature
20°C "If Required" 1
95°C 2
Unspecified or Room Temperature 29
C. Method Mixing
Mechanical Shaker 12
Mechanical Stirrer 8
Stir and Settle 3
Gas Agitator 3
Special Apparatus A
No Mixing 2
12
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TABLE 2. (CONTINUED)
Critical Leaching Variable
Number of Published Leaching
Procedures Specifying the
Test Variable(a)
D. Time of Mixing
<1 Hour
1-24 Hours
24 Hours
48 Hours
72' Hours
>72 Hours
To Equilibrium
E. Number of Leachings on Same Solid
1
3
5
7
10
Several
F. Number of Leachings with Same Medium
1
G. Solid to Liquid Ratio
5
7
11
3
2
2
2
24
1
1
1
2
3
31
1
1:<4
1:4
1:5
1:6
1:7
1:9
1:10
1:>10
Varied
Calculated
5
5
3
2
1
1
4
6
2
3
(a) A total of 32 published leaching procedures were compared.
13
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and associates were relied upon very heavily by researchers at Battelle in
assessing what leaching media had been developed and what conditions had been
recommended.
Once the search for leaching media and leaching conditions had been
completed, the results from these past studies were critically evaluated.
This evaluation was used to select the leaching media for use in the
appropriate subtasks of this overall research program and the analytical
techniques for use with the leaching method.
14
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SECTION V
EXPERIMENTAL
SAMPLE COLLECTION AND SELECTION
Samples of sludges and other industrial wastes were collected at the
initiation of the project from a variety of industries with emphasis given to
samples known to contain high levels of solvent-extractable organic compo-
nents or expected to cause problems during leachate generation or analysis.
It was believed that the most complex samples available should be used for
method development so that any method developed would be applicable to all
sample types. The samples obtained are listed in Table 3. These samples
include oily wastes, aqueous sludges, inorganic solids and organic solids.
Some of the wastes had dense solids separated from the liquid phase, some
contained no liquid phase, and one was gelatinous.
Some samples were collected specifically for this project at the waste
generation site. These samples were preserved at 4°C prior to leachate
generation. Two exceptions are the baghouse dust and fly ash samples which
were not refrigerated. Many of the samples were provided by a commercial
hazardous waste disposal facility and were received in five gallon plastic
pails. Since these wastes had been exposed to ambient temperature for
several months or more, no refrigeration was deemed necessary.
The pH and percent solids content were determined for all wastes
received. For samples containing sufficient liquid, the pH was determined on
the liquid phase. For solid samples or for those containing only small
amounts of liquid, equal weights of sample and distilled water were mixed in
a slurry and the pH was determined on the mixture after five minutes. All pH
measurements were taken using an Orion Model 501 pH meter with a combination
pH electrode. In some cases, oil in the waste caused difficulties in
obtaining an accurate pH measurement.
For the determination of percent solids in the waste, a 100-g portion of
the well-mixed waste was dried at 105°C overnight. The sample was weighed
after cooling and the percent solids calculated from the remaining solid.
Many of the samples as received were inhomogeneous. In order to ensure
that all replicate determinations performed would test the precision of the
method and not the homogeneity of the waste, the wastes were thoroughly mixed
prior to collection of an aliquot for leaching experiments. The method of
mixing varied depending on the waste type. In some cases, a Teflon^-coated
spatula was used to stir the waste as thoroughly as possible. A motor-
driven, Teflon^-coated stirrer was used when feasible. Still, because of
15
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TABLE 3. DESCRIPTION OF WASTE SAMPLES RECEIVED FOR THE STUDY
Description
POTW Raw Sludge
POTW Dewatered, Chemically-treated
Sludge
Electroplating Sludge
Latex Paint Sludge
Lime Slurry Treatment Sludge
Food Processing Sludge
Coke Plant Sludge
Still Bottom, Organic
Fly Ash
Baghouse Dust
Pulp and Paper Sludge
Coal Gasification Coal Tar Waste
Oil Refining Oil Waste
Machine Operation Waste
Ink Pigment Waste
Steel Mill Spent Acid
Alkaline Cleaning Waste
Engine Manufacturing Waste -
Oils and Coolants
Water Treatment Waste Acid Sludge
Herbicide Manufacturing Acetone -
Water Waste
Herbicide Manufacturing Acid Waste
Paint Manufacturing Waste
Pharmaceutical Waste
PH
6.5
9.7
9.0
7.8
7.2
5.6
9.0
3.6
10.9
6.3
6.5
6.8
3.6
6.8
11.3
1.3
11.4
6.8
5.9
7.5
0.6
6.8
6.5
Percent
Solids
Content
0.8
25.2
15.2
14.9
2.0
0.5
3.1
35.9
100
99.3
28.9
49.7
81.6
22.7
14.8
13.7
2.6
2.1
9.7
17.4
40.5
0.7
19.0
(a)
Category
AS
IS
AS
AS
AS
AS
AS
OS
IS
IS
OS
OS
ow
6w
AS
AS
AS
Kb
AG
AS
AS
AS
AS
(a) AS = Aqueous sludge (>80% H20); OW = oily waste (>20% oil);
IS = inorganic solid (>20% inorganic); OS = organic solid
(>20% organic).
16
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the nature of the wastes, thorough mixing was not always possible, and in-
homogeneity of the waste cannot be excluded from contributing significantly
to the overall precision obtained with the method.
Physical Compatibility
Each of the 23 wastes considered for use in this method development
program was visually evaluated and categorized. A physical description for
each waste was given according to consistency, color, and solid content. The
definition of categories used to classify the samples is 'as follows:
Aqueous Sludge (AS) - Greater than 80 percent water
Oily Waste (OW) - Greater than 20 percent oil
Inorganic Solid (IS) - Greater than 20 percent inorganic content
Organic Solid (OS) - Greater than 20 percent organic content.
The processing techniques to be used or examined for use during the
conduct of the leachate procedure included:
• Centrifugation
• Filtration
• . Stirring
• Tumbling.
If a given processing technique could obviously not be used without damage to
laboratory equipment, only a visual inspection was recorded.
The amenability of each waste to tumbling in the NBS extractor was
considered to be the most critical evaluation of physical compatibility. For
this investigation, 1500 ml of water was added to 75 gm of wastes contained
in a glass bottle. Adequate dispersion of the waste in the leaching sequence
was examined only for the most complex samples.
Leachate Generation
Two different sample extraction devices were used in this study for the
generation of leachates. One device is a stirrer-based unit manufactured by
Associated Design and Manufacturing Company, (ADMCo) Model No. 3736-M, con-
sisting of a 2-liter stainless steel beaker and a motor-driven two-blade
impeller.(^ The interior of the beaker and the impeller blades were
Teflon^ coated per Battelle's special request to prevent metal contamina-
tion from the stainless steel. The tumbler system shown in Figure 1 is
capable of tumbling four containers in an end-over-end fashion. This ex-
tracter was designed and provided by the National Bureau of Standards.
Similar units are now commercially available (Associated Design and Manu-
facturing, Model No. 3740-4-BRE).
For the generation of leachate using the ADMCo stirrer, the conventional
EPA extraction procedure was used.^D The dewatered POTW sludge was the
only sample extracted using this device. Since the sample was essentially a
wet solid, no filtration prior to sample extraction was conducted. A 100-g
portion of the well-mixed sample was placed in the 2-liter stainless steel
17
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2-liter Plastic or Glass Bottles
CO
1/15 hp Electric Motor .
Screws for Holding Bottles
FIGURE 1. NBS-DESIGN ROTARY EXTRACTOR
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beaker and 1600 ml of deionized water was added. The sample was stirred
briefly and the pH was determined. If the pH was greater than 5.0, a portion
of 0.5 N acetic acid was added and the sample was again stirred. The pH was
measured and additional acetic acid was added until the pH was 5.0 ± 0.2
or until 400 ml of 0.5 N acid was added. The sample was stirred for 24 hours
and the pH was checked periodically. Additional acetic acid solution was
added to maintain pH 5.0 unless the maximum of 400 ml had been reached. If
the pH of the solution was not less than 5.2 and the maximum amount of acid
had not been added at the end of the 24-hour extraction period, the pH was
adjusted to 5.0 ± 0.2 and the extraction was continued for an additional
four hours with pH adjustments at each one hour interval. A blank, con-
sisting of 1600 ml of deionized water plus the average amount of acetic acid
used in the samples, was carried through the procedure. In four of the five
replicate determinations on the dewatered POTW sludge, the maximum amount of
acetic acid (400 ml) was added. The final pH of the leachate was greater
than 7. However, the fifth replicate required only 150 ml of acetic acid to
remain at pH 5.0 ± 0.2. Although the sample was mixed as thoroughly as
possible prior to obtaining aliquots, sample inhomogeneity is suspected to be
the cause of this variation.
Upon completion of the 14-hour stirring period, additional deionized
water was added as required such that the total volume of deionized water and
acetic acid added was equal to 2.0 liters. An aliquot for analysis of purge-
able organic compounds was collected and refrigerated prior to analysis. The
remaining sample was centrifuged and an aliquot was taken for semi-volatile
organic analysis from the centrifugate and refrigerated until extraction with
methylene chloride. Samples for metals analysis were taken after pressure
filtration through a 0.45 micron Millipore membrane filter. Nitric acid
(UltrexR grade) was added to the samples for metals analysis to yield a pH
less than 2. If the dilution was greater than one percent, the dilution was
recorded and the data were adjusted accordingly. No refrigeration was
required.
Sample generation using the MBS tumblers was essentially similar to that
used with the stirrer assembly. One exception was the substitution of a
glass bottle with a Teflon^-lined screw cap (1.8 or 2.3-liter capacity) for
the stainless steel beaker. Samples were tumbled for 20 ± 2 hours. If
the standard EP was being followed, the pH was adjusted periodically
throughout the extraction to pH 5 using 0.5 N acetic acid except that in no
case was more than 4 ml of acid per gram of sample added. However, for all
other extractions, the leaching medium was added directly to the waste in a
1:20 ratio of mass of waste to leachate volume and no additional leaching
medium was added during the extraction.
This latter leaching procedure, the product of the research effort, is
presented in numbered format in Appendix A.
Procedures for Inorganic Analyses
Analysis for inorganic constituents was performed by two techniques;
atomic absorption spectroscopy (AAS) and inductively coupled argon plasma
spectroscopy (ICAP). Because of the relatively high detection limits
19
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required for the leachate analyses, all AAS work was performed using flame
atomization. In the total content analyses conducted in Task 6, however, the
method of graphite furnace atomization was used for some metals present at
very low levels. All mercury analyses were conducted using the cold vapor
flameless atomic absorption method.
Instrumentation
Two atomic absorption spectrometers were used for the AAS analysis, a
Perkin-Elmer Model 603 and a Perkin-Elmer Model 5000. Both units are
equipped with deuterium arc background correction capability which was used
for all analyses. These microprocessor-equipped units permit standardization
with direct readout in concentration units. Hollow cath'ode lamps were used
for all elements except arsenic, selenium, antimony, and thallium where
electrodeless discharge lamps were used. The mercury analyses were performed
on a Perkin-Elmer Model 305-B atomic absorption spectrometer equipped with a
cold vapor apparatus.
The ICAP unit used for this study was a Jarrell-Ash Model 965 equipped
with 30 channels and the spectrum-shifter background correction attachment.
Background correction was employed along with interelement interference
corrections for known spectral overlaps. These corrections were auto-
matically performed by the PDP-8A computer interfaced to the spectrometer.
Results for 30 elements are printed in concentration units based on the
standards run with each set. Background and interelement corrections used
are specific for each ICAP unit since the configuration of each instrument
(element, wavelength) is unique.
Sample Preparation
Sample preparation for elemental analysis of leachates was based on
standard EPA procedures in "Methods for Chemical Analysis of Water and
Wastes" EPA-600/4-79-020(42', or on the methods given for the proposed ICAP
analysis in the Federal Register (December 3, 1979).
Samples for the analysis of 22 elements (Al, B, Ba, Be, Ca, Cd, Co, Cr,
Cu, Fe, Pb, Mg, Mn, Mo, Ni, Na, Sb, Sn, Ti, V, Y, Zn) by either AAS or ICAP
were prepared using Method 4.1.3 from "Methods for Chemical Analysis of Water
and Wastes"^ ^'. This procedure involves the vigorous digestion of a
sample aliquot with nitric acid and incorporates a repeated refluxing of the
sample until digestion is deemed complete. This procedure is essentially
identical to the ICAP digestion procedure (8.3) given for total metals in the
cited Federal Register.
For analysis of four other elements (Se, Tl, Ag, As,) a second digestion
procedure was used, involving the use of nitric acid and hydrogen peroxide in
a less vigorous procedure™^'. This sample preparation was used for the
analysis of the listed metals by ICAP or AAS, as required.
Studies conducted for this program indicated no loss of added spike of
the above elements using Method 4.1.3, as long as care was taken not to take
the sample to complete dryness on heating. However, better spike recoveries
20
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were obtained for antimony using the nitric-hydrogen peroxide acid digestion
than for the HN03 procedure. In the latter stages of the project, only
Method 4.1.3 was used for the preparation of samples.
The digestion procedure used for mercury analysis is given in "Methods
for Chemical Analysis of Water and Wastes"^2)- The organomercury com-
pounds are first subjected to a I^SO^-HNC^ digestion. The mercury is
oxidized by the addition of permanganate and persulfate, with the excess
reduced with hydroxylamine. Finally, stannous sulfate is used to reduce
mercury to the elemental state and the mercury is aerated from solution in a
closed system into a cell positioned in the light path of an atomic absorp-
tion spectrophotometer. The elemental mercury vapor absorbs the radiation of
the mercury hollow cathode lamp that is passed through the cell.
PROCEDURES FOR ORGANIC ANALYSES
Volatile Organic Analysis
Analyses of the organic compounds in the solid waste leachates were
conducted for volatile organic and semivolatile organic constituents. The
volatile components were analyzed by EPA Method 624^3). ^ 5-ml aliquot of
the leachate sample for purgeable organic analysis was spiked with a three-
component internal standard and transferred to the analytical system
consisting of:
o A Tekmar Model LSC-1 Liquid Sample Concentrator fitted with a 5-ml
sample container and a 12-inch adsorbent trap containing 15.2 cm of
Tenax and 8.2 cm of silica gel
e A GC equipped with a 2 meter x 2 mm I.D. glass column packed with 1
percent SP-1000 on 60/80-mesh Carbopak B, and
e A quadrupole mass spectrometer (Finnigan Model 3200). The mass
spectrometer was controlled by an INCOS data system. The mass range
of 40 to 280 a.m.u. was scanned during the data acquisition.
Only selected leachates were screened for volatile organic components since
the semivolatile constituents were more important for assessing potential
mobility.
The volatile organic analysis of solid waste leachates for the inter-
laboratory comparison study (Task 6) was performed using a carbon disulfide
extraction procedure. A 40-ml aliquot of leachate was placed in a separatory
funnel and extracted with 2 ml of carbon disulfide (CS£) and 20 ul of meth-
anol containing 200 ug of 1,2-dichloroprdpane which served as the internal
standard. The mixture was shaken for one minute and allowed to stand for 15
minutes before an aliquot of the CS2 extract was withdrawn for analysis by
gas chromatography. A Hewlett-Packard Model 5700 GC with an FID detector was
used for analysis of the CS2 extract using a 30-m SP-2100 glass 'capillary
column. The column temperature was programmed from -10°C to 200°C at
21
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8 degrees per minute. The linear velocity through the column was 50 cm/sec
using hydrogen as the carrier gas.
The volatile organic content of solid wastes was determined by extracting
a 2-gram sample (wet weight) with 2 ml of C$2, 20 ml of water, and 20 1 of
methanol containing the internal standard (1,2-dichloropropane). Sample agi-
tation and elapsed time during the sample transfer step were minimized to
avoid loss of volatile compounds. A 50-ml centrifuge tube was used for the
extraction and capped immediately following addition of the waste and extrac-
tion media. The tube was shaken vigorously for 1 minute, centrlfuged for 15
minutes, and an aliquot withdrawn by syringe for GC analysis. The GC condi-
tions were identical to those described for leachate analysis except that the
column temperature was raised to a higher temperature (250°C) to elute high-
boiling components.
Semivolatile Organic Analysis
The method used to analyze the leachates for semivolatile organic com-
pounds is a modified version of EPA Method 625(43>. A 300-ml aliquot of
leachate was placed in a 500-ml bottle having a TeflonR-lined screw cap and
shaken with 30 g of Nad until the NaCl was dissolved. The pH was adjusted
with 6N HC1 to less than 2 and the sample was cooled to less than 28°C prior
to completely transferring the solution to a 500-ml separatory funnel. The
sample bottle was rinsed with 150 ml of methylene chloride which was added to
the separatory funnel. The separatory funnel was shaken vigorously for 2
minutes. A 100-ml aliquot of the methylene chloride extract representing
200 ml of leachate was dried and concentrated to 2 ml using the procedures
described in EPA Method 625. The concentrate was transferred to a 2-ml
septum-capped vial and mixed with 50 1 of methanol containing 100 pg of
D^-anthracene as an internal standard for the GC-MS analysis.
Due to the large number of extracts requiring GC-MS analysis for semi-
volatile organic compounds, an automatic sample injection system was used. A
Finnigan 4000 GC-MS with INCOS Data System was equipped with a Hewlett
Packard Model 7672A autosampler. The computer compound search and quantifi-
cation procedure utilized both the Finnigan INCOS computer programs, computer
programs for the OWA Finnigan GC-MS System, and programs developed at
Battelle. The GC-MS analyses were performed using a 30-meter SE-52 Methyl
silicone capillary column programmed from 50°C (2 minutes hold) to 3000C
(5.5 minutes hold) at the rate of 48C/min. The injector temperature was
270°C while both the separator oven and transfer line were maintained at
280°C. The mass range from 70 to 450 a.m.u. was scanned at a rate of 2
seconds per scan.
The mass spectra for compounds identified and quantified using the
automated search routine were also examined for accuracy by experienced mass
spectrometrists.
22
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STATISTICAL CONSIDERATIONS
During the preliminary planning stages of this method development pro-
gram, the use of formally designed experiments required for rigorous statis-
tical comparisions between the methods was ruled out because it was not
considered possible to identify and control all of the significant variables
that might be involved. Also due to the complexity and size of this project,
time and cost considerations precluded the use of such designs. In addition,
it was believed that secondary characteristics of the methods, such as the
biological effect of the leaching medium, were important properties which had
to be considered in any comparison among methods. Only more extensive exper-
iments could provide rigorous information on these secondary characteristics.
Therefore, the comparisons made between various methods and the choice made
for candidate methods were based to a significant degree on sound scientific
judgment.
However, the primary characteristics of concern were the reproducibility
of the individual method, i.e., the reproducibility of the amount of material
leached from a waste, and the analytical precision of the associated measure-
ment process. Qualitative comparisons of measures of reproducibility and
analytical precision obtained from the experimental data rather than strict
quantitative comparisons were made. Therefore, it was decided to collect the
precision data for the various leaching methods using individual experiments
based on the sound analytical principles of analyzing blanks, real samples
and spiked samples using replications. During the initial planning, it was
decided that five replications should be used in each of the experiments.
The choice of five was not based on any objective statistical criteria, but
rather on the basis that five replications should provide sufficient informa-
tion on the sources of variability to qualitatively compare the methods.
During the course of the program, It became evident that the difference in
potential mobility observed for the media examined were sufficiently great
that means rather than coefficients of variation could be used for compari-
son. It was therefore decided to reduce the number of replications to three.
In view of the fact that comparisons among methods in terms of precision were
made in a qualitative way, and that the analytical method repeatabilities
were grossly smaller than the repeatability of mobility of different leachate
media, the use of three replications was judged to be adequate.
The decisions about the relative behavior of the various leaching methods
applied to the various sample wastes were based on several basis summary
statistics and sound scientific judgment. The basis summary statistics in-
cluded average background, average observed spike value, percent spike re-
covery, standard deviations and relative standard deviations. The scientific
judgment required to assess the important qualitative characteristics of the
leaching methods was provided by Battelle scientists.
QUALITY ASSURANCE
The quality assurance activities of this program were those associated
with experimental design, sample tracking, documentation, and analytical
quality control.
23
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Experimental Design
The considerations for experimental design were based on the program
objective of developing a technically sound, practical waste leaching pro-
cedure that will simulate natural leachability and will be within the capa-
bilities of a production-type laboratory. In addition, the experimental
design was controlled by the significant number of experiments to be accom-
plished in a short time (6 months).
The leaching procedures were compared in various ways, as described in
other sections of this report, and much of the comparison was in terms of
amount leached and repeatability of the amount leached. Thus, in effect, the
comparisons made were results of analytical determinations of selected metals
and organic compounds in leachates.
In order to assess the variability contributed by the leaching process
including any effect contributed by sample inhomogeneity, it was necessary to
determine the variability contributed by the analysis process. This task was
accomplished by conducting replicate analyses of spiked distilled water stan-
dards. Statistical analysis of these data included relative standard devia-
tion and percent recovery for inorganic and organic compounds of interest
added at three concentration levels.
Documentation
Documentation included sample"identification and tracking, sample
labeling, and experimental records. Because of the large number of leachates
to be generated, a carefully designed sample logging and tracking system was
implemented in order to ensure an efficient and accurate flow of samples
through the many steps of the procedure. Upon receipt, each waste sample
was assigned a unique laboratory identification number which was recorded in
a master laboratory record book (LRB). Laboratory record cards were prepared
and are permanently filed by project number with cross references to all
laboratory notebooks used.
Since the project involved repeated use of the same waste with as many as
seventeen different leaching media, further identification had to be pro-
vided to eliminate any ambiguity. Thus, each individual leachate was
assigned a unique identifier code. This code was based on the laboratory
record book number and page number on which that experiment was permanently
recorded. All replicates were recorded on the same page and were assigned
sequential numbers. For example, 35704-16-3 refers to a particular leachate
with all conditions recorded in laboratory record book 35704 on page 16. The
-3 indicates this leachate is the third replicate. On that page are recorded
all pertinent information including what waste sample was leached, the
leaching solution used, the extractor used, the initial and final pH of the
leachate, and any other observations for that sample.
Three separate samples were obtained from each leachate generated and
analyzed for metals, volatile organic compounds, and semivolatile organic
compounds, respectively. For meTsls and volatiles analyses, the leachate
number was adequate identif icat; on. Fof sc-.-i volatile organic analysis each
24
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sample required a solvent extraction prior to analysis. Each extract was
assigned an additional number according to the lab book in which the extrac-
tion was recorded. The leachate numbers were cross-referenced in this book.
As implied above, documentation included a record of all experimental
work done and all resulting data. Data that resulted from a print-out from
an instrument are filed and identified to refer to a laboratory record book
where the experiment is described. The filed print-out can also be traced
from information in LRBs. The LRBs used in this program are numbered 35692,
35704, 35785,' 35900 and 36125. These books are part of the permanent program
file.
Data.report forms were designed clearly and completely to identify the
data in terms of sample, sample type, sample number, leaching media, leaching
method, spike level, replication number and analysis method. The data on
these forms were entered into the computer where means, precisions and
recoveries were calculated. Before doing any calculations, a computer print-
out was compared to data on the data sheets to ascertain completeness and
accuracy. The results of computer calculations were verified to be true and
accurate by comparison to results of manual calculations on a set of data.
Analytical Quality' Control
Analytical quality control (QC) included use of approved methods pre-
viously published by the EPA(42-45). The quality control recommendations
found in the referenced documents were followed in addition to general
Battelle QC procedures.
Specifically QC activities consisted of daily calibration of equipment,
daily analysis of blanks, periodic use of QC standards (one standard for
every four samples for organic determinations and one standard for every
seven samples for metals determinations) and daily use of decafluorotriphenyl
phosphine (DFTPP) to check the tuning of the quadrupole mass spectrometer.
At the beginning of the method development program, precision was deter-
mined for each analysis method utilized. These precision data were useful in
setting criteria for performance of QC standards and as a basis of comparison
for results of leaching experiments. In the case of metals analyses, the
result was expected to agree within 5 percent relative to the expected
value—otherwise the system was recalibrated. For organic analyses the
calculated reponse factor of a check standard was expected to agree within
three standard deviations of the expected reponse factor. If not within that
range the system was recalibrated. The results' of these controls and checks
are part of the documented experimental effort.
Reagent chemicals used in this program were analytical grade or dis-
tilled in glass and while purity was not checked on individual chemicals, the
purity was verified to be appropriate through results of method blank
determinations.
Standards used for the inorganic analyses were obtained from two differ-
ent sources—Fisher Scientific and Spex Industries, Inc. Each standard
25
-------
solution used in this program was prepared individually by dilution of a
Fisher stock solution (not serially diluted to obtain various concentrations)
and compared periodically to standards prepared from Spex high purity solids
(> 99.99 percent pure).
Calibration standards were prepared biweekly from stock solutions which
were checked for contamination from other elements by ICAP. A solution
containing the same element prepared using Spex solid standards was also
analyzed by ICAP. Contamination was verified if only one of the standards
produced a signal for some other element. However, an interelement inter-
ference was identified if both standards produced a signal for some element
of the same apparent concentration. Interelement interference corrections
were based on three determinations at a single concentration level shown to
be within the linear range for that element.
Standards for organic analyses were obtained from many sources. These
compounds were kept in a locked repository and the purity was monitored by
various techniques depending on the use. A record was kept for each refer-
ence compound that includes source, date of purchase, and purity information.
The purity information included when purity was monitored, the method of
monitoring and the results. Primary stock standard solutions were made from
these pure compounds by dissolving a known mass of the compound in a known
volume of solvent. These stock standards were diluted to achieve appropriate
concentrations.
Inorganic Analysis Routine
To verify that an instrument was operating correctly and within the
expected performance limits, an appropriate standard was included within
every seven samples. For ICAP analysis of standard solutions, the determined
values agreed with the known concentration of the standard within ± 5
percent. If the value obtained was outside these limits, the instrument was
restandardized prior to continuing the analyses. Any samples analyzed after
an acceptable standard check and before the unacceptable check were repeated.
An identical protocol was used for flame atomic absorption using single
element standards rather than the multi-element standards used for ICAP. For
flameless atomic absorption, the acceptable limits for standard checks were
± 10 percent, due to the less precise nature of these analyses.
Spiked samples, with the spike added prior to sample preparation, were
prepared and analyzed with each set of replicates for a given waste and
leachate combination. The samples to be spiked were selected randomly. For
all ICAP and atomic absorption analyses, the spike recoveries were expected
to be within LOO ± 10 percent of the amount added, where spike recovery
was calculated by
(sample + spike added) - (sample)
spike added x 100/8
However, for flameless AA analyses used in the total content determinations,
the method of standard additions was used in all cases as required in the
26
-------
method. Each leachate was prepared in quintuplicate or triplicate thus, no
further replication was required.
Standard solutions prepared from dilutions of commercially available
stock solutions were used for calibration of all instruments. As an addi-
tional check on standard purity, stock solutions were compared periodically
from two different sources (Fisher Scientific or Spex Industries, Inc.). All
required standards from both sources were available in the laboratory since
all of these analyses are routinely performed at Battelle.
To properly exercise the power of simultaneous,, multi-element analysis by
ICAP, special precautions were required. These included the recognition and
correction of interelement interferences and the use of background correc-
tion. Both procedures are routinely employed in the laboratory.
Similarly, fundamental knowledge of atomic absorption principles and
techniques were required to produce valid results, especially when graphite
furnace work was required. The experience in this laboratory is extensive
with both ICAP and AAS, and enabled the strict adherence to the Quality
Assurance plan.
The studies for precision and accuracy of metals analyses were done using
one operator for each step. That is, a different person was responsible for
each of the following steps: preparation of calibration standards, prepara-
tion of spiking solutions, generation of leachates, sample digestion, ICAP
analysis, and AAS analysis. An exception to this scheme was for the analysis
of mercury in which case one operator carried out all steps except the leach-
ate generation. Observation and supervision of the whole process, from
formulation of standards to data review and management, was the responsi-
bility of one professional chemist.
Standards, leachates and spikes were prepared and analyzed over a period
of several days. The order of analyses was randomized so each days run
included all concentration levels. The results of all QC determinations were
reported along with the associated data set.
Organic Analysis Routine
High concentrations of some purgeable compounds may cause carryover from
one sample to the next sample, invalidating the data for the next analysis.
This situation occurred for the organic still bottom leachate sample. To
analyze a method blank following each sample would be costly and impractical
for such a heavy sample load.
For determination of purgeable compounds the routine procedure adopted
was to alternate the Tekmar glass fit after each run. After running a sample
and emptying the sampler, the sampler was rinsed with methanol and distilled
water, and dried in a glassware oven at 100°C. Another sampler which had
been drying in the oven was used for the next run. The sampler was cooled
before attaching it to the Tekmar Liquid Sample Concentrator and adding the
next sample.
27
-------
In order to insure quality control, the following procedures were used on
a daily basis:
(1) Instrument checked (Finnigan 3200), tune with FC-43
calibration compound.
(2) Instrument calibrated (m/e 20-510; 2.95 sec up, 0.05
sec down, scan parameters).
(3) Method blank analyzed (5.0 ml freshly purged water
plus 5.0 ul spike of the 50 ng/ vi 1 three-component
internal standard solution (50 ppb; m/e 46-260 scan
range for the sample runs).
(4) A spiked 100 ppb standard solution was analyzed.
(5) The next four samples, spiked at the 50-ppb level
with the three-component internal standard solution
were analyzed.
(6) Another spiked standard containing 20 ppb of the 27
compounds of interest was analyzed.
(7) The next four samples were analyzed followed by
another standard at the 100-ppb level.
For the GC-MS analysis of samples for semivolatiles samples were run in
the following sequence (1.0 yl injected):
80 ng/pl standard
4 samples
20 ng/ul standard
4 samples
80 ng/ul standard
4 samples
200 ng/ul standard
4 samples
REPEAT SEQUENCE
This sequence allowed for analysis of an 80 ng/yl standard every eight runs
and permitted 16 samples to be analyzed for every 20 runs. Response factors
(RFs) were recalculated for each standard run and the data were tabulated.
The RF from the 80-ng standards was used to quantify the sample components.
The analysis methods precision studies were conducted over a period of two
days while the precisions calculated during sample analyses encompass a
period of four weeks. The operation of the instruments was done by a single
analyst while standards were made and samples prepared by several other
operators.
Precision and accuracy were assessed first of all for the analytical
method through replicate analyses of standards carried through the analysis
28
-------
procedure. Precision was calculated as relative standard deviation as
follows:
r n
S = Standard Deviation
I (x. - x)2
n-1
1/2
n
I x.
1
x = Mean
RSD = Relative Std Dev = -£- x 100.
x
Accuracy was calculated in terms of percent recovery of a compound added
(spiked) to water and leachates as follows:
Percent Reco'very
(sample + spike) - (sample)
spike
Secondly, the protocol of leaching included replicate leachings of the
same waste with the same leaching medium. The results of analyses of these
replicated leaching solutions were used to estimate the repeatability of
leaching by calculation of relative standard deviation as above. In
addition, one of the replicated leaching solutions was spiked with compounds
and metals of interest in order to calculate a percent recovery also as
above. The replicated leachings thus provided information on the effect of
the leached materials on analytical performance.
29-30
-------
SECTION VI
RESULTS
SAMPLE CHARACTERIZATION
The pH and percent solids content of each waste were determined upon re-
ceipt as part of Task 1. These results and the classification codes assigned
to each waste have already been given in Table 3. The physical compatibility
assessments of each waste for the leaching processes (centrifugation, filtra-
tion, stirring, tumbling) are reported in Table 4. Also included is a
description of each waste according to appearance (color, solid content).
SAMPLE SELECTION
From a total of 23 waste samples collected, eight samples were initially
selected for further study:
Latex paint
Still bottoms
Baghouse dust
Coal gasification tar
Ink pigment
POTW dewatered sludge
Herbicide acetone and water
Herbicide acid
The criteria for selection of the wastes included:
(1) Estimation of organic content and variety of organic compounds
expected
(2) Range of pH
(3) Range of solid content
(4) Complexity of matrix from both physical and chemical considerations
(5) Category of waste
When the herbicide acetone and the herbicide acid were mixed with water
for the initial leaching experiments, it was found that both were completely
soluble. Thus, these two wastes were eliminated from consideration and the
pharmaceutical waste was substituted for study. It was anticipated that the
latex paint sample would be high in organic content. Since this sample
proved to be low in organic content, no further analyses were performed.
31
-------
TABLE 4. PHYSICAL CHARACTERISTICS OF WASTE SAMPLES
10
Sample
Raw POTW
Dewatered POTW
Electroplating
Latex Paint
Lime Slurry
Food Processing
Coke Plant
Still Bottoms
Fly Ash
Baghouse
Pulp/Paper
Coal Tar
Oil Refining
Machine Op.
Ink Pigment
Pickle Acid
Alkaline
Engine Mfg
Water Treatment
Herbicide- Acetone
Herbicide-Acid
Paint Mfg
Pharmaceutical
Category
(a)
AS
IS
IS
AS
AS
AS
AS
OS
IS
IS
OS
OS
OW
OW
AS
AS
AS
AS
AS
AS
AS
AS
AS
Amenability to Given Processing Technique (b)
Centrl- Filtra-
fugatlon tlon Stirring Tumbling
/ No / /
/ / / /
/ / / /
/ No / /
/ / / /
/ / / /
/ / No /
/ / / /
/ . / / /
/ / / /
No No No /
/ No / J
/ No / /
No No / /
/ / / /
/ / / /
/ No •/ /
/ No / /
/ / / /
/ / / /
/ No / /
/ No / /
Physical Description of Sample
Thin dark green aqueous
suspension
Dark wet cake
Dark wet cake
Thick milky aqueous suspension
Thin tan' aqueous suspension
Thin tan aqueous suspension
Thin dark aqueous suspension
Thick black chunky aqueous slurry
Fine tan powder
Fine dark brown powder
Brown wet fibrous lumpy cake
Black viscous tar with water
layer
Medium viscosity dark oil with
sediment
Brown oil-water mixture i25% oil
Pourable black jelly
Thin brown aqueous suspension
Thin tan aqueous suspension
Thin gray aqueous suspension
with oil
Thick brown aqueous suspension
with granules
Dark red-brown aqueous solution
Thin gray aqueous suspension
Thin milky gray-green aqueous
suspension
Gelatinous red-brown stinky,
aqueous suspension
(a) AS = aqueous sludge (>80% 1I20) ; OW
OS = organic solid (>20% organic).
(b) Check mark indicates "yes".
oily waste (>20Z oil) ; IS = inorganic solid (>20% inorganic) ;
-------
EXTRACTOR EVALUATION (TASK 3)
The two extractors, ADMCo stirrer and NBS tumbler, were used in a
parallel leaching experiment to determine if any differences in the
analytical results would be obtained. The dewatered POTW sludge was leached
using the EP medium and the leaching methods described previously. Five
replicate extractions and a blank were processed using both techniques. The
leachates were analyzed for both organic and inorganic constituents. The
average and standard deviation for each analyte found in significant quan-
tities are presented in Table 5. The metal analysis data for the NBS timber
are generally more precise than for the ADMCo extractor. For the analysis of
22 elements leached using the ADMCo unit, the average relative standard
deviation was 37 percent, while for the NBS tumbler the average RSD for the
same 22 elements was 28 percent. Significant losses of volatile organic com-
pounds, such as toluene, chlorobenzene, and ethylbenzene, occurred when the
ADMCo extractor was used. Comparable results were obtained for less volatile
compounds such as phenanthrene.
Based on the analytical results obtained for Task 3 and the simpler
operation of the NBS tumbler, only the NBS tumbler was used for leaching
method development in Tasks 4 and 5 .
EFFECT OF MEDIA (TASK 4)
The objective of this task was to compare the effectiveness- of various
aqueous media for leaching organic components as well as inorganic components
from a solid waste sample. The solid waste sample chosen for this task was a
chemically dewatered municipal sludge sample (POTW sludge) having a solids
content of 25 percent. This sample was chosen since it was known to contain
significant levels of a wide range of organic compounds as well as metals.
Several aqueous media (listed in Table 6) having widely varying chemical
characteristics (pH, ionic strength, surfactant levels, and oxidation
potential) were evaluated. Since the focus of this study was on codisposal
of wastes, rather than monodisposal, slightly acidic (pH 4-6) media were
selected. Distilled water was also evaluated as a reference point for
comparison of data.
The data obtained are given in Table 7 and the precision of the replicate
leachings is given in Table 8. Organic components present in the leachate
from POTW sludge included toluene, chlorobenzene, ethylbenzene, 1,4-dichlor-
obenzene, 1,2,4-trichlorobenzene, naphthalene, acenaphthene, fluorene,
phenanthrene, and various phthalates. No phenols were found in the leachates
above the detection limit (-50 ug/liter).
Examination of the data in Table 7 reveals that the only significant
effect of leaching medium on mobility of organic compounds is the somewhat
greater leaching ability of citrate relative to both distilled water and
acetate buffer. The POTW sludge used contained very high levels of iron
resulting from chemical dewatering with ferric chloride and lime. The
citrate-containing leaching media gave leachates containing extremely high
levels of iron, nearly 0.1 percent. The high levels of the ferric citrate
33
-------
TABLE 5. DATA FOR EXTRACTOR EVALUATION ~ TASK 3
Amount of
Analyte
Al
B
Ba
Cd
Co
Cr
Cu
Fe
Pb
Mn
Mo
Hi
Na
Sn
V
Y
Zn
Se
Tl
Ag
AS
Sb
Toluene
Chlorobenzene
Echylbenzene
1, 4-Dichlorobenzene
1, 2,4-Trichlorobenzene
Naphchalene
Acenaphchene
Fluorene
2, 4-Dinitrotoluene
Phenanchrene
Dibutyl Phthalate
Bis(2-ethylhexyl) Phthalate
Analyte Found.
ADMCO
440 ± 190
210 ± 54
930 ± 450
42 + 18
57 ± 24
94 ± 26
37 ± 11
3700 ± 2000
110 ± 62
3200 ± 1700
47 + 26
580 ± 300
15500 ± 1200
> 120 ± 22
44 ± 10
18 + 10
2300 ± 1200
90 ± 53
670 ± 100
9 ± 2
210 ± 51
98 ± 22
1.5 ± 0.3
0.4 ± 0.1
1.5 ± 0.4
4 ± 1
100 + 33
10 ± 3
3 ± 1
2 ± 1
7 ± 4
13 ± 4
230 ± 40
12 ± 7
uR/li Using Given Extractor
NBS
860 ± 540
390 ± 100
1200 ± 170
63 ± 15
71 ± 11
120 ± 54
66 ± 24
6700 ± 7400
170 ± 71
4100 ± 580
36 ± 4
670 ± 130
16000 ± 1700
130 ± 16
47 + 6
43 ± 16
3300 ± 910
120. ± 23
830 ± 91
12 ± 4
250 ± 43
110 ± 16
61 ± 7
29 ± 4
34 ± 7
34 + 24
180 ± 18
25 ± 3
2 + 1
1 ± 1
10+6
16 ± 2
250 ± 63
20 ± 6
34
-------
TABLE 6 . DESCRIPTION OF LEACHING MEDIA
Medium
Contents per Liter of Medium(a)
EP Acetic Acid Titration
0.1M Sodium Acetate, pH 4
0.1M Sodium Citrate, pH 4
0.1M Sodium Citrate, pH 5
0.05M Sodium Hydrosulfite
0.05M Sodium Citrate, pH 4
0.1M Ammonium Citrate, pH 4
0.1M Sodium Butyrate, pH 4
0.02M Ferrous sulfate and
0.1M Sodium Citrate, pH 5
U Wise Synthetic Leachate
0.05M Sodium Hydrosulfite, and
0.1M Sodium Citrate, pH 5
0.01% Igepal
0.01% Igepal CO-630, and
0.1M Sodium Citrate, pH 5
0.05M Sodium Citrate, pH 5
0.02M Sodium Citrate, pH 5
0.01% .Igepal, and
0.05M Sodium Citrate, pH 5
0.05M Sodium Hydrosulfite and
0.05M Sodium Citrate, pH 5
0 to 400 ml acetic acid
5.7 ml acetic acid and 8.2 g sodium acetate
21 g citric acid monohydrate and 4.8 g
sodium hydroxide
21 g citric acid monohydrate and 8 g sodium
hydroxide
8.7 g sodium hydrosulfite
10.5 g citric acid monohydrate and 2.4 g
sodium hydroxide
8.6 g'citric acid monohydrate and 13.3 g
ammonium dibasic citrate
8.8 g butyric acid and 0.7 g sodium
hydroxide
21 g citric acid monohydrate, 5.6 g ferrous
sulfate heptahydrate, and 9.4 g sodium
hydroxide '
1.05 g pyrogallol, 6.9 g ferrous sulfate
heptahydrate, 20.4 g sodium acetate tri-
hydrate, 8.6 ml acetic acid, and
3.8 g glycine
8.7 g sodium hydrosulfite, 21 g citric acid
monohydrate, and 16.7 sodium hydroxide
0.1 g Igepal CO-630
0.1'g Igepal CO-630, 21 g citric acid mono-
hydrate, and 8 g sodium hydroxide
10.5 g citric acid monohydrate and 4 g
sodium hydroxide
4.2 g sodium citrate monohydrate and 1.6 g
sodium hydroxide
0.1 g Igepal CO-630, 10.5 g citric acid
monohydrate, and 4.0 g sodium hydroxide
8.7 g sodium hydrosulfite, 10.5 g citric
acid monohydrate, and 4.0 g sodium
hydroxide
(a) Distilled, deionized water used to prepare all media.
(b) Igepal CO-630 is a registered trademark of GAF Corporation.
35
-------
TABLE 7. COMPARISON OF LEACHATES FROM DEWATERET) POTW SI.imfiF.
co
en
Amount Relative Amount (*iW Found Using Given Leaching Mudlumlc)
Annlyto
Al
B
Ba
Co
Fc
Mn
Mo
Sn
Cd
Cd
Cr
Cr
Cu
Cu
Pb
Pb
Nl
HI
Zn
Zn
To,u(f)
ClBz
EtBz
pUCBz
TCBz
Naph
Acne
Fluo
Phcn
BEHP
(a)
(b)
(c)
(d)
(e)
Found (b)
Analy- Using 0.1M 0.1M 0.1M
sis Distilled NaOAc NaClt NaClt O.OSM
Method Water, ug/l EP pU 4 pll 4 pll 5 Na2S204
ICAP 480 1.6 0.5 106 89 0.2
ICAP 46 8.5 4.1 IS 13 3
ICAP 70 17 17 40 60 0.3
ICAP 7 10 9.2 24 23 2.8
ICAP 2000 3.3 2;3 265 252 . 1.1
ICAP 35 117 109 146 143 29
ICAP 57 0.6 0.7 5.6 5.3 2.3
ICAP 21 6.2 5.7 56 41 4.3
ICAP <5(e) 13 7 20 17 3
FAAS <20(e) 3 2 5 3 ND
ICAP 29 2.9 3.1 131 124 2.5
FAAS <100(e) ND ND 45 58 ND
ICAP 53 0.9 0.5 6.0 13 0.3
FAAS <50(e) 2 ND 6 14 ND
ICAP 88 1.9 0.9 86 78 0.7
FAAS <200(e) ND ND 49 44 ND
ICAP <50(e) 13 12 24 22 2
FAAS <100(e) B 7 14 13 ND
ICAP 63 51 37 95 85 ND
FAAS 73 45 36 90 79 0.3
CC-MS 65 0.9 O.B 0.6 NA NA
CC-MS 33 0.9 0.8 0.6 NA NA
GC-HS 33 1.0 0.8 0.8 NA NA
CC-MS 20 1.7 1.0 1.5 1.6 0.9
CC-MS 180 1.0 1.0 2.4 2.8 0.8
CC-MS 27 0.9 0.9 1.2 1.2 0.9
GC-MS 3 0.7 0.7 3.0 3.3 3.0
GC-HS 3 0.3 1.0 1.3 1.7 1.0
CC-MS 15 1.1 1.0 3.5 4.0 0.7
GC-HS 16 1.3 1.0 7.5 1.6 0.5
Relative to the amount found using distilled water.
Average of five runs.
0.05M
NaClt
pll 4
89
12
23
20
235
131
4.6
34
11
2
106
35
5.0
S
53
29
20
11
69
63
0.5
0.5
0.6
1.4
2.8
1.1
2.7
2.3
4.4
12
0.1M
NII4Clt
pH 4
108
13
49
23
240
140
5.3
54
20
6
124
40
10
10
91
38
26
13
92
85
NA
NA
NA
1.3
2.2
1.0
2.0
1.3
3.3
8.1
FeS04 H
0.1M 0.1M U Uls
NaOBu NaClt SL
pll 4
0.
4.
16
8.
1.
114
1.
7.
5
1
3.
ND
0.
9
1.
ND
12
6
25
22
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
(f)
More complete descriptions of leaching media are given In Table 6.
High blank value Interfered with the determination.
Relative amounts based on detection limit for these elements
NA - Not analyzed. ND - Not detected.
pH 5 pll 4.5
7 93 27
6 22 6.5
21 2.6
9 13 2.8
4 (d) (d)
ISO 128
0 4.2 2.5
1 40 20
ND 22
ND 3
8 131 31
53 13
5 ND ND
2 ND
6 5.3 16
ND 6
17 26
B 10
14 73
36 70
NA NA
NA NA
NA NA
1.3 1.1
1.9 1.2
0.9 0.7
2.0 0.7
1.0 0.7
2.4 0.9
7.5 1.1
•Tolu - toluene
ClBz - chlorobenzene
EtBz - ethylbcnzene
lajSjO^
0.1M
NaClt
pH 5
100
24
21
23
220
143
6.1
48
32
6
134
39
42
44
91
39
30
14
122
103
NA
NA
NA
0.7
1.2
0.4
2.0
0.7
2.1
6.3
0.01Z
Igepal
CO-630
0.5
1.2
8.1
ND
0.3
0.6
1.1
0.9
ND
ND
0.7
ND
0.2
ND
ND
ND
ND
ND
3.8
2.9
NA
NA
NA
1.2
1.0
1.0
ND
1.0
0.9
1.1
pDCBz- 1,4-dlchlorobenzene
TCBz - 1,2,4-trlchlorobenzene
Igepal
0.1M
NaClt
pH 5
100
22
55
21
220
143
S.6
52
18
3
131
37
8.9
11
91
39
26
12
82
75
NA
NA
NA
2.9
5.6
2.4
8.3
4.3
10
31
Naph
Acne
Fluo
Phen
BEHP
0.05M
NaClt
pH 5
71
18
23
16
175
117
S.I
37
ND
ND
37
27
6.8
8
24
B
16
7
17
15
NA
NA
NA
2.2
2.8
1.4
2.0
4.0
3.7
33
0.02M
NaClt
pH 5
0.4
6.8
8.9
2.0
13
26
1.7
4.1
3
NA
4.3
NA
0.1
NA
0.9
NA
0.8
NA
7.4
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Na2S204
O.OSM
NaClt
pH 5
91
28
27
37
250
1S7
6.3
74
33
NA
143
NA
25
NA
80
NA
2.8
NA
182
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
- naphthalene
- acenaphthene
- fluorene
- phenanthrene
- bla(2-ethylhexyl) phthalate
-------
TABLE 8. PRECISION OF ANALYSIS OF LEACHATES FROM DEWATERED POTW SLUDGE
U)
===^=
ndard D
Annly- 0.1M O.IM 0.1M
ala NoOAc NaCit NaClt 0.05M
Analytc Method II20 EP pll 4 pll 4 pll 5 Nn2S204
Al 1CAP 54 63 38
B ICAP 26 25 10
Bo ICAP 34 14 6
Co ICAP 14 15 5
Fo ICAP 55 110 77
Mn ICAP 37 14 . 2
Ho ICAP 7 11 10
Sn ICAP 29 12 6
Cd ICAP ND 24 16
Cd FAAS ND 21 12
Cr ICAP 48 45 4
Cr FAAS ND ND ND
Cu ICAP 50. 36 12
Cu FAAS ND 11 ND
Pb ICAP 25 42 60
Pb FAAS ND ND ND
Nl ICAP ND 19 4
Nl FAAS ND 17 5
Zn ICAP 49 28 14
Zn FAAS 30 29 14
Tolu CC-HS 6 12 9
ClBz GC-MS 11 13 4
EcDz GC-MS 10 19 7
pDCBz GC-MS 13 71 29
TCBz GC-MS 8 10 24
Naph GC-MS 1 12 25
Acne GC-MS 66 50 25
Fluo GC-MS 66 100 33
Phcn GC-MS 38 16 24
RF.IIP GC-MS 46 32 42
' '
5 5
4 5
4 6
5 3
6 2
6 4
5 4
3 1
9 10
13 9
5 4
6 3
44 11
46 8
6 5
5 4
7 4
6 5
6 4
5 3
15 NA
16 NA
16 NA
10 13
7 16
19 33
26 30
25 20
6 20
9 30
- —
19
5
31
15
60
16
5
11
21
ND
4
ND
58
ND
9
ND
19
ND
ND
9
HA
NA
NA
12
7
4
66
33
9
39
(a) Average of five runs.
(b) More complete descriptions of the leaching media ore
(c) High blank value Interfered with the determination.
NA = Not analyzed ND - Not detected.
, ,
0.05M
NaClt
pll 4
4
3
9
0
3
3
3
5
16
33
3
4
8
11
5
7
6
3
2
2
19
16
9
10
15
9
18
35
17
13
^^^^^^
given
ont") of
0.1M
NlljClt
pll 4
1
2
3
0
3
3
2
4
5
9
2
6
31
33
4
6
4
3
2
4
NA
NA
NA
10
13
13
42
13
14
12
^s^^^^^^
In Table
Amount
0.1M
NaOBu
pll 4
39
7
8
4
83
5
14
4
18
19
5
ND
56
36
14
ND
6
6
27
28
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
"
6.
Pound Uslne Given Leadline Medlum
-------
complex may have had more of an effect on the mobility of organic compounds
than the citrate itself. The addition of 0.01 percent Igepal (a nonionic
surfactant), acetate buffer, or 0.05 M sodium hydrosulfite (a reducing agent)
did not alter the mobility of organics relative to that obtained using
distilled water. However, the addition of 0.01 percent Igepal in combination
with citrate buffer appeared to give a somewhat greater mobility of organics
relative to that observed for either Igepal or citrate alone. The effect is
best indicated by comparing the results from 0.05 M citrate with those from
Igepal plus 0.1 M citrate in Table 7. The extract from the butyrate con-
taining leaching medium could not be concentrated below 10 ml because of the
high amount of butyric acid present. GC-MS analysis was not run on the con-
centrate to avoid contaminating the mass spectrometer. However, GC analysis
was conducted and visual examination of the chromatograms revealed that the
butyrate gave no significant increase in leachability of organics over the
acetate buffer.
The University of Wisconsin "Synthetic Leachate'^17,18) was foun
-------
• 0.05 M sodium citrate buffer, pH 5
• 0.02 M Sodium citrate buffer, pH 5
• 0.01 M Igepal +0.05 M sodium citrate buffer, pH 5
• 0.05 M Na2S204 + 0.05 M sodium citrate buffer, pH 5
Distilled water and the EP were chosen as reference points, since these media
are currently in widespread use in the other laboratories. The 0.1 M acetate
buffer (pH4) was chosen because it simulates the EP and gave comparable re-
sults to the EP but is much easier to accomplish since titration of the
sample to maintain a particular pH level is not necessary. The 0.05 M
citrate buffer (pH5) was selected because it was more aggressive than either
acetate or distilled water in leaching both organics and metals. It was
decided to add 0.02 M citrate buffer to the list (it was not used in Task 4)
because it is desirable to reduce the concentration of "additives" to the
leaching medium as much as possible. This medium was expected to be more
aggressive than acetate but somewhat less aggressive than the higher level
citrate buffer and less toxic in bioassay studies.
Although the nonionic surfactant (Igepal) was found to have little effect
on mobility of organics from POTW sludge it was selected for further study
(organics only) on other wastes since any effect could be highly dependent oa
the nature of the waste sample (e.g. tars and oils should be more readily
extracted into a leaching medium having surfactant present). N32S204
was selected for evaluation (in conjunction with citrate buffer) in order to
assess the significance of added reducing agent mobility of metals (organics
were not determined for this medium) from a variety of waste types.
EFFECT OF WASTE TYPE (TASK 5)
The objective of this task was to evaluate the mobility of organic
components and metals from several representative wastes using the leaching
media selected on the basis of the data obtained in Task 4. The wastes
selected are listed below:
Baghouse dust
Still bottoms
Ink pigment waste
Pharmaceutical waste
Coal gasification tar.
The physical nature of these waste samples has been tabulated in this section
of the report (table 5). This group of waste samples was selected for de-
tailed study since these wastes represent a wide variety of waste categories
having a range of physical properties.
Baghouse dust was a finely divided solid containing essentially no water
and only trace levels of organics. When suspended in water the baghouse dust
sample gave a neutral pH. The still bottom sample was a solid residue, high
in organic content having approximately 40 percent solids and a pH of 3-4.
The ink pigment waste was an alkaline (pH 11) gelatinous material having
approximately 15 percent solids and a relatively high level of organics. The
39
-------
pharmaceutical waste was a foul-smelling aqueous sludge having approximately
20 percent solids and a neutral pH. The coal gasification tar was totally
organic and approximately 50 percent of the material was volatilized at 100°C
overnight (the conditions used to obtain a residue for percent solids
determination).
The results obtained for the various leaching media on each waste sample
are presented in Tables 9 to 14. The data obtained for each waste are dis-
cussed below. The still bottoms leachate contained very large amounts of
several chlorinated volatile compounds, as shown in Table 9, and approxima-
tely the same levels of these compounds were leached using distilled water
and Igepal/citrate buffer. Coal tar leachate contained significant levels of
benzene and several alkylated derivatives. Ink pigment leachate contained
significant levels of both chlorinated and nonchlorinated volatile organics.
Pharmaceutical waste leachate contained only a low level of trichloroethane
while latex paint leachate contained low levels of several chlorinated
organics.
The leachates from baghouse dust had low levels of four organic priority
pollutants (phenanthrene, fluoranthene, pyrene, and phenol) and significant
quantities of several metals, especially Al, Ba, Cr, Mn, Mo, Ni, Sn, and Zn.
The distilled water leachate gave the highest level of organic compounds
except for fluoranthene and pyrene where the Igepal/citrate medium gave
larger values. However, the levels of all the organics were quite low and
highly variable, making it difficult to assign any significance to the
differences observed between leaching media.
In general, the distilled water leachate from baghouse dust contained
much lower levels of metals than any of the other leachates (Table 10). The
EP gave much higher levels (relative to distilled water) of Mn, Ba, Ni, Sn,
and Zn, but actually gave a lower level of Cr. Mo was present at essentially
the same level in all leaching media. Acetate buffer (0.1 M, pH 4) gave
metal levels comparable to the EP. Both 0.02 M and 0.05 M citrate buffer, pH
5, gave much higher levels of most of the metals, especially Ba, Cd, Cu, Fe,
Ni, and Zn, than either the EP or distilled water. The leachate obtained
using the higher concentration (0.05 M) citrate contained 2-3 times higher
levels of many metals than the leachate obtained using the 0.02 M citrate
medium. The addition of hydrosulfite to the 0.05 M citrate medium increased
the levels of most metals leached by as much as a factor of two.
The leachates from still bottoms contained significant levels of several
organic priority pollutants, as shown in Table 11. In addition, high levels
of Al, Ba, Cr, Cu, Fe, Mn, Ni, and Zn were observed. Because the distilled
water leachate was acidic (less than pH 5), the EP and distilled water
leaching process were identical for this sample. The levels of organics were
determined in the EP/distilled water, 0.05 M citrate, and 0.05 M citrate/0.01
percent Igepal. Inspection of the data in Table 11 reveals that citrate,
with or without Igepal, gave comparable or lower levels of most organics than
distilled water/EP. The only exception was phenol, which was present at a
five-fold higher level in the citrate buffer not containing Igepal. However,
the high PvSD (75 percent) for this value casts considerable doubt on its
significance.
40
-------
TABLE 9. VOLATILE ORGANIC CONTENT OF SELECTED LEACHATES USING EPA METHOD 624
Component
Methylene Chloride
1,1-Dichloroethene
1 , 1-Dichloroethane
trans-l,2-Dichloroethene
Chloroform
1, 2-Dichloroethane
1 , 1, 1-Tr ichloroethane
Carbon tetrachloride
Trichloroethene
Benzene
1,1, 2-Tr ichloroethane
1,1.2, 2-Tetrachloroe thane
Tetrachloroethene
Toluene
Chlorobenzene
Ethylbenzene
Latex Paint(
(H20)
14
ND
25
11
7
35
6
ND
20
ND
84
ND
ND
ND
ND
ND
_• Concentration ot uomponent
a) Ink Pigment^) Pharmaceutical^8)
(H20) (H20)
1,000
110
12
11
12
ND
120
ND
750
190
ND
150
180
1.850
15
1.300
ND
ND
ND.
ND
ND
ND
12
ND
ND
ND
ND
ND
ND
9
ND
ND
Still Bottoms(b) Still Bottoms(b) Coal Tar(b) Coal Tar
-------
TABLE 10. COMPOSITION OF LEACHATES FROM BAGHOUSE DUST
Amount Found
Using
Distilled
Mater
Analyte
Al
B
Ba
Cd
Co
Cr
Cu
Fe
Pb
Mn
Mo
Nl
Sn
Ti
V
Y
Zn
Phen
Fluan
Pyr
Phol
Mg/lU)
557
237
11
c5
8
1020
<10
207
74
68
35600
<50
<10
2
81
<5
12
18
13
8
8
RSD
13
20
9
_
7
2
_
15
5
6
1
-
_
_
1
_
51
100
96
96
18
Relative Amount (RA)(a) Found & Percent Relative Std Dev (RSD) Using Given Leaching Medium(b>
EP
RA
1.1
1.6
16
>21
4.8
0.2
ND
2.9
3.5
2340
0.9
>5
>31
2.5
1.3
ND
129
0.3
0.4
0.4
0.9
0.1M NaOAc,
pH 4.0
RSD
10
15
55
65
19
20
_
58
24
86
48
59
17
10
6
_
167
16
20
22
57
RA
1.5
0.6
27
>20
3.6
0.1
>2
6.1
3.0
1900
0.5
>6
>24
3.5
0.9
ND
100
0.3
0.3
0.3
0.5
RSD
4
9
4
11
5
8
1
29
5
_
11
5
3
7
4
_
12
10
10
10
35
0.05M NaCit,
pH 5.0
RA
6.6
8.1
78
>59
5.8
3.3
>340
475
21
3470
0.8
>22
>34
29
28
>21
53000
0.4
0.4
0.3
0.3
RSD
12
6
53
9
-
6
6
11
22
6
10
11
17
10
8
9
12
13
25
10
60
0.02M NaClt,
pH 5.0
RA
11
2.9
87
>24
ND
2.4
>260
208
17
1940
1.2
>6
>36
ND
13
ND
22000
NA
NA
NA
NA
RSD
11
19
66
10
-
2
6
10
49
8
11
26
14
-
10
_
7
_
-
-
—
0.05M Na 2S2°4 +
0.05M NaClt,
pH 5.0
RA
4.5
5.4
78
>11
15
5.6
>7
1150
14
6560.
1.1
>66
>45
ND
41
>17
78000
NA
NA
NA
NA
RSD
10
20
1
10
14
3
16
5
12
3
12
4
1
-
3
13
1
-
-
-
~
O.OUIgepal-t
0.05M NaClt,
pH 5.0
RA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.6
1.6
2.4
0.6
RSD
_
-
-
-
-
—
-
-
—
-
-
—
-
-
~
-
—
18
22
46
12
(a) Relative to amount found using distilled water.
(b) More complete description of the leaching media are given in Table 6.
(c) Average of three runs; blank value has been subtracted.
(d) Phen - phenanthrene; Fluan - fluoranthene; Pyr - pyrene; Phol - phenol.
NA = Not analyzed.
ND = Not detected.
RSD = Relative standard deviation.
-------
TABLE 11. COMPOSITION OF LEACHATES FROM STILL BOTTOMS
U>
Amount Found
Using
Distilled
Water
Analyte
Al
B
Ba
Co
Cr
Cu
Fe
Pb
Mn
Mo
Ni
Ti
V
Zn
Hg
pDCBz
BCEE
oDCB
HCEt
HCBud
TCBz
HCBz
Phen
Phol
MgA(c)
2620
373
1100
<50
<100
174000
249000
<500
2690
<100
1150
<50
<50
3550
<1
35
32
15
58
178
29
<5
6
340
RSD
19
11
3
—
_
11
11
-
4
—
7
-
_
10
-
15
82
13
33
88
75
_
75
10
Relative Arat
EP
RA RSD
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
(RA)
Found &
0.1M NaOAc,
pH 4.0
RA
1.6
1.9
0.1
ND
ND
1.2
1.0
ND
1.0
ND
1.0
ND
?1
1.0
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
RSD
5
8
12
_
-
13
3
-
3
_
2
-
13
9
-
_
_
-
_
-
-
_
-
-
Percent
Relative Std Dev (RSD) Using Given Leaching Medium^)
0.05M NaCit,
pH 5.0
RA
5.0
2.0
1.9
>2
>8
1.3
1.5
>2
1.0
ND
1.4
>7
>3
1.7
ND
0.9
ND
0.9
0.9
0.4
0.3
ND
0.3
3.8
RSD
6
15
0
14
5
4
1
8
1
_
1
4
12
3
-
14
-
11
19
15
6
_
99
75
0.02M
PH
RA
6.5
2.0
1.2
>2
>8
1.3
1.5
>2
1.0
ND
1.5
>7
>2
1.8
>1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NaCit ,
5.0
RSD
2
12
50
3
15
7
2
16
5
_
23
12
12
8
14
-
-
-
_
-
-
-
-
—
0.05M Na2S204 +
0.05M NaCit,
pll 5.0
RA
4.5
1.9
0.2
>2
>10
1.3
1.7
>2
1.1
>1
1.5
>7
>3
3.2
>16
NA
NA
NA
NA
NA
NA
NA
NA
NA .
RSD
6
7
15
12
2
4
1
0
3
12
3
4
2
4
31
-
-
-
_
-
-
-
-
™
0.01%Igepal +
0.05M NaCit,
pll 5.0
RA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1.2
1.7
1.2
1.1
0.3
0.5
>1
ND
0.9
RSD
-
-
—
-
-
-
-
-
—
-
-
—
-
-
—
2
5
3
8
18
5
29
-
7
(a) Relative to amount found using distilled water.
(b) More complete descriptions of the leaching media are given in Table
(c) Average of three runs; blank value has been subtracted.
(d) pDCBz - 1,4-dichlorobenzene HCEt - hexachloroethane
BCEE - bis(2-chloroethyl)cther . HCBud - hexachlorobutadiene
oDCB - 1,2-dlchlorobenzene TCBz - 1.2,4-trichlorobenzene
NA = Not analyzed.
6. ND = Not detected.
RSD = Relative standard deviation.
HCBz - hexachlorobenzene
Phen - phenanthrene
Phol - phenol.
-------
TABLE 12. COMPOSITION OF LEACHATES FROM INK PIGMENT WASTE
Amount Found Relative Amt (RA)
Using
Distilled
Water EP
Analytc Mg/l(c> RSD RA
Al 11300 4 0.3
B 3790 3 1.0
Ba 573 B 4.3
Cd <5 - >3
Co <5 - >5
Cr 1050 4 0.5
Cu 383 7 0.1
Fe 3910 14 0.3
Pb 5690 5 0.6
Mn 110 10 7.6
Ho 487 2 0.3
Nl <50 - >2
Sn 46 10 3.9
Tl 85 17 0.3
V 10 22 3.0
Zn 110 27 14
PDCBz(d) 310 3 0.7
oDCBz 550 3 0.7
Naph 810 7 0.6
Acny 100 32 0.7
Acne 56 27 0.9
Fluo 110 22 0.7
Phen 290 28 1.0
Fluan 88 20 1.3
Pyr 76 28 1.0
BEIIP 620 14 0.7
Chry 49 45 1.0
DOPh 92 9 1.0
BbkF 32 44 2.2
Phol 2100 9 0.9
PCP 96 59 0.5
(a) Kulatlvu to amount found using
(b) Mare complete descriptions of
Found & Percent Relative Std Dcv (RSD) Using Clvcn Leaching Medium^1)
0.1M NaOAc, 0.05M
RSD
5
14
5
3
9
7
15
35
20
7
B
a
3,
6
9
15
46
47
28
25
29
25
24
24
23
8
41
28
14
27
29
Pll
RA
0.4
0.8
3.6
>2
>3
0.7
0.1
0.3
0.8
10
0.4
>J
2.1
0.3
1.8
13
0.6
0.7
0.7
0.5
0.5
1.1
2.6
2.8
2.5
0.5
0.4
0.4
0.2
2.1
ND
4.0
RSD
13
6
8
13
11
2
14
14
19
21
20
20
10
10
22
8
8
8
5
10
15
22
26
31
31
31
62
31
67
58
-
pll
RA
1.4
1.1
6.0
>2
>4
1.2
0.1
1.8
1.3
11
0.9
Jl
2.5
1.0
3.3
1.4
0.8
0.8
0.8
0.9
0.9
2.1
5.9
7.2
7.5
0.9
7.3
0.9
11
1.0
,1.3
NaClt,
5.0
RSD
9
11
34
5
7
16
26
15
16
22
4
8
1
18
8
37
3
3
2
7
2
6
6
3
4
4
33
5
13
5
13
0.05M Na2S204+ 0.01ZIgcpal +
0.02H NaClt. 0.05M NaClt. 0.05M NaClt.
pll 5.0
RA
0.5
0.8
2.4
ND
ND
0.8
ND
0.5
0.4
1.6
0.8
ND
ND
ND
ND
6.5
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
distilled water.
tilt!
(c) Average of three runs; blank value
(d) pDCBz - 1.4-dichlorohenzene
oUCUz - 1.2-dichlurobenzcnc
Naph - naphthalene
Acny - acenaphythylcni:
leaching media are given
has been
subtracted
In Table
6.
RSD
14
14
5
_
-
8
_
12
29
23
5
-
_
-
-
2
_
-
-
_
-
-
_
-
-
_
-
-
_
-
-
Pll 5.0
RA
1.4
1.0
0.2
ND
ND
1.3
ND
2.1
1.0
11
0.9
ND
ND
ND
ND
7.3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
RSD
6
7
21
_
-
4
_
-
4
11
6
-
_
-
-
6
_
-
-
-
-
-
_
-
-
_
-
-
.
-
-
pll 5.
RA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.7
0.7
0.7
0.6
0.6
1.3
1.4
0.6
0.6
0.8
0.8
0.7
3.4
1.0
1.0
,0
RSD
_
-
-
_
-
-
_
-
-
_
-
-
_
-
-
-
21
17
23
48
47
67
82
68
35
33
42
32
150
6
29
NA = Not analyzed.
ND = Not detected.
RSD <• Relative standard
Fluo - fluorene
Phun - pliunnnrhruiic
Fluan - fl
iiuranthene
Try - pyrene
Chry
UOPli
BbkF
Phol
- chrysune
- dloctyl
- bcnzo(b
- phenol
deviation.
phthalatc
&/or k)fluoranthcne
Acnu -
- lils(2-ethylliexy])phthaliil:e I'CP - pentachlorophenul.
-------
TABLE 13. COMPOSITION OF LEACHATES FROM PHARMACEUTICAL WASTE
Amount Found
Relative Amt
Using
Distilled
Water
Analyte
Al
B
Ba
Cu
Fe
Mn
Zn
Phol
pg/H(c)
<40
209
785
27
72
20
809
410
RSD
_
6
1
25
14
3
5
130
EP
RA
ND
0.4
0.1
0.2
1.4
13
<0.1
0.5
RSD
_
7
3
5
11
1
23
23
(RA)
Found & Percent
0.1H NaOAc,
pH
RA
>5
0.4
ND
ND
2.2
24
0.3
NA
4.0
RSD
19
51
-
-
37
7
47
-
Relative Std Dev (RSD) Using Given Leaching Medium^
0.05M NaCit.
pH 5
RA
>15
3.6
0.8
ND
46
37
2.4
0.6
.0
RSD
3
13
71
-
32
30
13
3
0.02M NaCit,
pit 5.0
RA
>10
0.8
1.0
1.6
28
25
1.4
NA
RSD
16
34
78
89
34
5
35
-
0.05M Na2S204 +
0.05M NaCit,
pit 5.
RA
>12
0.4
0.2
9.6
33
24
0.9
NA
.0
RSD
13
6
9
6
5
7
3
-
0.01%Igepal +
0.05M NaCit,
pH
RA
NA
NA
NA
NA
NA
NA
NA
0.5
5.0
RSD
-
-
-
-
-
-
-
9
(a) Relative to amount found using distilled water.
(b) More complete descriptions of the leaching media are given in Table 6.
(c) Average of three runs; blank value has been subtracted.
(d) Phol = phenol.
NA = Not analyzed.
ND = Not detected.
RSD = Relative standard deviation.
-------
TABLE 14. COMPOSITION OF LEACHATES FROM COAL GASIFICATION COAL TAR WASTE
Amount Found
Using
Distilled
Water
Naph
Acne
Fluo
Phen
-P-
CT> Fluan
Pry
Chry
BbkF
Phol
DMP
1 Wg/K
2,100
970
570
930
270
210
160
130
12,000
5,200
RSD
5
10
49
22
32
25
75
44
25
29
Relative Amount (RA)
-------
The data in Table 11 for metals again illustrate the greater leaching
ability of citrate relative to either distilled water or acetate buffer.
However, the effect of citrate was'not as pronounced for the still bottom
sample as it was for the baghouse dust sample. The addition of hydrosulfite
to the citrate buffer had no significant effect on .the mobility of metals in
the still bottoms sample. The 0.02 M and 0.05 M citrate buffers gave
virtually identical levels for metals in the still bottom sample.
The data for the ink pigment sample are shown in Table 12. High levels
of many organic priority pollutants and metals were observed in the leachates
from this sample. For organics other than PNAs, the leaching medium composi-
tion had very little effect. Benzo(k)fluoranthene was present at a higher
level in the citrate medium, both with and without Igepal added. However,
several other PNAs (fluoranthene, phenanthrene, fluorene, pyrene, and chry-
sene) were elevated in the citrate medium alone but not in the Igepal/citrate
medium. This result indicates that the differences observed are not signifi-
cant and probably could not be reproduced. Lower molecular weight PNAs
(naphthalene, acenaphthene, and acenaphthalene) were present at comparable
levels in-all leaching media.
The data in Table 12 for metals reveal that the EP and 0.1 M acetate
buffer, pH 4, gave comparable results for all metals. The levels of several
metals (Al, Cu, Cr, Fe, Pb, and Mo) were lower in the EP than in distilled
water, while several other metals (Ba, Cd, Co, Mn, Sn, V, and Zn) were high
in the EP. Citrate does not give significantly higher levels of any of the
metals relative to acetate or the EP. The addition of hydrosulfite did not
significantly affect the leachate content. Since this waste was highly
alkaline, the distilled water leachate actually represents an alkaline
leaching condition, which may help to explain the results obtained for
certain metals.
The data obtained for pharmaceutical waste are presented in Table 13.
Only one priority pollutant organic compound, phenol, was found in the
leachate of this waste. The level of phenol was highest in the distilled
water leachate with all of the other leachates, including the EP, containing
approximately 50 percent of the amount found in distilled water. Significant
levels of Al, B, Ba, Cu, Fe, Mn, and Zn were found in the pharmaceutical
waste leachates (Al was not found in the distilled water leachate). Al, Mn,
and Fe were elevated, relative to distilled water, in all the leachates ex-
cept the EP in which only Mn was significantly elevated. Acetate buffer gave
slightly higher metal levels than the EP and citrate gave greatly increased
levels of Al and Fe. The effect of added hydrosulfite was negligible except
that a lower level of B and a higher level of Cu were obtained relative to
0.05 M citrate alone.
The data for coal gasification tar are presented in Table 14. These
leachates were analyzed for organics but'not for metals because of relatively
high organic content of the material. In general, distilled water gave high-
er levels of the organic components present (PNAs and phenol) than any of the
other media. Organic levels in the EP were approximately 2 to 5 times less
than for distilled water, and 0.05 M citrate contained substantially lower
levels than the EP. The addition of Igepal to 0.05 M citrate increased the
47
-------
level of organics leached somewhat, but lower levels than distilled water
were still observed.
Representative reconstructed gas chromatograms for both volatile and
semivolatile organic analysis reported in Tables 9-14 for the five samples
are presented in Figures 2 to 10 (volatiles were not determined in the
baghouse dust samples) .
The diverse nature of the wastes studied and the relatively limited
current understanding of the parameters affecting mobility of chemical
constituents in solid wastes makes it difficult to summarize the results in
such a way that predictions can be made as to what results to anticipate in
other experimental situations. However, several relatively concise state-
ments can be made concerning the overall results obtained in this task:
(1) The effect of leaching medium composition on organic mobility is
slight whereas the effect on metal mobility is frequently very
large.
(2) The EP and 0.1 M acetate buffer, pH 4, gave comparable results for
both organics and metals in all of the wastes studied.
(3) While the addition of citrate generally increases the mobility of
metals, the increase relative to distilled water, can vary from
negligible to 105 times.
(4) The addition of hydrosulfite does not generally affect the mobility
of metals to a significant extent.
(5) The addition of surfactant does not generally affect the mobility of
organics to a significant extent.
(6) The total amount of metals leached from a given quantity of waste
using citrate is dependent upon the citrate concentration, with high
concentration of citrate leaching more metals.
INTERLABORATORY COMPARISON STUDY (TASK 6)
Battelle and SoRI conducted an interlaboratory comparison of the poten-
tial mobility and total content methods using the ink pigment and still
bottoms wastes. In order to ensure that sample inhomogeneity was minimized,
the wastes were remixed at Battelle and ten 75-g samples and a 200-g sample
were prepared for each laboratory. The leachates from five of the 75-g
samples were used for metal analysis and the leachates from the remaining
five 75-g samples were used for organic, determinations. The 200-g sample was
used for total content analyses. These samples were shipped and stored at 0°
to 5°C until use.
It was decided that both laboratories would use the same source of organ-
ic standards for spiking experiments to eliminate any analytical variabili-
ties due to differences in compound purity. The standards used for spiking
48
-------
100.0-1
VO
RIC.
8
100
5:00
-r
2
-**
200
10:00
300
15:00
11
400
20:00
10
A.
1. Ethyl Chloride
2. 1.1-Dichloroethylene
3. 1,1-Dichloroethane
4. 1.2-Dichloroethylene
5. Chloroform
6. 1.2-Dichloroethane
7. 1,1.1-Trichloroethane
8. Trichloroethylene
9. 1.1.2-Trichloroethane
10. 2-Bromo-1-Chloropropane (Int. Std.
11. 1,1,1,2-Tetrachloroethane
12. 1.1,2,2-Tetrachloroethane
13. Unknown Chloro Cpd
12
T
500
25:00
13
JL
600
30:00
—I ' 1
700 800 Scan Number
35:00 40: OOTime. Minutes
FIGURE 2. RECONSTRUCTED GAS CHROMATOGRAM FOR VOLATILE ORGANICS IN STILL BOTTOMS LEACHATE
-------
100.0-1
Ul
o
RIC-
100
5:00
1. Methylene Chloride
2. 1.1.1-Trichloroethane
3. Trichloroethylene
4. Benzene
5. 2-Bromo-1-Chloropropane (Int. Std.)
6.1,1.2.2-Tetrachloroethane
7. Toluene
8. Chlorobenzene
9. Ethylbenzehe
10. Xylene
11. Xylene
12. Dichlorobenzene
200
10:00
300
15:00
5
•A A ~
D
IU
9
12
l/l
500
25:00
600
30:00
700
35:00
800 Scan Number
40:00 Time. Minutes
FIGURE 3. RECONSTRUCTED GAS CHROMATOGRAM FOR VOLATILE ORGANICS IN INK PIGMENT LEACHATE
-------
100.6-
RIC.
*ju
I Scan
I No.
1
4;
255 "°§
1 319 \
76 12:: IjH |\ ,291^ |\_343 39^|\..
2
445
1 '*76
VJUJ
172
189
255
272
291
303
319
343
394
408
422
445
476
519
545
569
578
648
648
I
J\
569 \\
i A. 607 I
^J^^^J ^
i 1 i 1 i 1 i 1 i 1 i 1 i
1'3'i 2u(i 3iM 4.00 500 6Dd
5:ij'.i 18:QO 15:00 20:00 25:OiJ 30:00
Description
Methylene chloride
Acetone
Bromochloromethane (IS)
1 , 1-Dichloroethane
1 , 2-Dichloroethy lene
Chloroform
1 , 2-Dichloroethane
1,1, 1-Trichloroethane
Dimethyl disulfide
Trichloroethylene
1,1, 2-Tr Ichloroe thane
2-Bromo-l-chloropropane (IS)
1,1,1, 2-Tetrachloroe thane
1,1,2,2-Tetrachloroethane
Toluene
Dichlorocyclobutane
Dimethyl hexene
Benzonitrile
Z22^
1 ' 1
700 806 SCAN
35:00 -»'J:CiLt TIME
FIGURE 4. RECONSTRUCTED GAS CHROMATOGRAM FOR VOLATILE ORGANICS IN
PHARMACEUTICAL WASTE LEACHATE
-------
MC.
Scan
No.
168
189
206
252
341
362
417
446
490
525
547
608
653
680
701
759
417
Description
Methylene chloride
Acetone
Carbon disulfide
Bromochloromethane (IS)
1,1,1-Trichloroethane
Thiophene
Benzene
2-bromo-l-chloropropane (IS)
Methyl thiophene
1,4-Dichloiobutane (IS)
Toluene
Ethyl benzene
Benzonltrile
Cyclooctatetraene
Xylene
Benzofuran
T
luu
5:00
128 168 206
T
1:00
10:00
252
i
362
300
341
T
300
15:00
759
—r
•400
20:09
•14C
i
500
25:00
—I
608
30:68
700
35:00
880 SCAN
40:00 TIME
FIGURE 5. RECONSTRUCTED GAS CHROMATOGRAM FOR VOLATILE ORGANICS IN
COAL GASIFICATION TAR LEACHATE
-------
103.3-1
OJ
RIC_
Scan
No. Description
164 04 alkyl benzene
263 Naphthalene
345 Diphenylether
377 Acenaphthene
415 Diethyl phthalate
438 Silicone
452 Silicone
470 d10-Anthracene (IS)
507 Dlbutyl phthalate
534 Phenanthrenedione
545 Fluoranthene
560 Pyrene
585 Silicone
608 Silicone
622 Bis(2-ethylhexyl) phthalate
630 Silicone
656 Hydrocarbon
164
tea
5:08
260
10:68
I
308
15:88
400
20:00
500
25:00
I
£00
38:00
l
708
35:00
800 SCAN
40:00 TIME
FIGURE 6. RECONSTRUCTED GAS CHROMATOGRAM FOR SEMIVOLATILE ORGANICS IN BAGHOUSE DUST LEACHATE
-------
100.00-1
Ln
RIC.
1. Trichloroethylene
2. 1.1.2.2-Tetrachloroethane
3. Tetrachloroethylene
4. Hexachloroethane
5. Hexachlorobutadiene
6. Biphenyl
7. Diphenyl Ether
8. D,o-Anthracene (Int. Std.)
Scan Number
4&-.Q& time. Minutes
FIGURE 7. RECONSTRUCTED GAS CHROMATOGRAM FOR SEMIVOLATILE ORGANICS IN STILL BOTTOMS LEACHATE
-------
100.00-,
Ln
Ln
RIC-
1. 1,4-Dichlorobenzene
2. 1,2-Dichlorobenzene
3. Naphthalene
4. Methylethylphenol
5. Methylnaphthalene
6. Dio-Anthracene (Int. Std.)
7. Fluoranthene
8. Pyrene
9. Bis-(2-Ethylhexyl) Phthalate
100
5:00
200
10:00
—I
300
15:00
400
20:00
500
25:00
600
30:00
700 800 s.can Number
35:00 40:00 Time- Mi
FIGURE 8. RECONSTRUCTED GAS CHROMATOGRAM FOR SEMIVOLATILE ORGANICS IN INK PIGMENT LEACHATE
-------
Description
Ul
Acetic acid
2-Methylbutanoic acid
Pentanoic acid
Phenol
2-Phenylethanol
Methyl phenol
1-Phenylethanol
Benzole acid
Phenyl propanolc acid
d^Q-Anthracene
Tetradecanoic acid
Fatty acid estei
Dodecylbenzene
Unknown, MW 260
Unknown, MW 260
860 SCAN
TIME
FIGURE 9. RECONSTRUCTED GAS CHROMATOGRAM FOR SEMIVOLATILE ORGANICS IN PHARMACEUTICAL WASTE LEACHATE
-------
100.0-1
227
Ul
RIC.
Scan
No.
137 TrinethyIbenzene
Description
I
2ii i
)ft4
153
k 137^
• • •"** m^
1
\
199
|j
||
1
i
I
1
249
1
III
1 .
II II II
1 U<
f±.— v—
2b6
j
*"^-25
8
326
273
/303
/
300
/
I
i
III
II
L
'( CO
r
1 A
w
1
II
366
CO **>
i f**
A
1
i
T\I
4G7
CM |
(7) 1
163 Dihydroindene
177 Benzofuran
184 Phenol
199 Indene
211 Methyl phenol
227 Methyl phenol
234 Dimethyl phenol
249 Dimethyl phenol
258 Dimethyl phenol
266 Naphthalene
273 Benzo(b)thiophene
277 Phenylacetaldehyde
293 Trimethylphenol
300 Pyridinedicarbonitrile
303 Methyl naphthalene
312 Methyl naphthalene
326 Indole
338 Unknown mixture
354 Methyl Indole
366 Acenaphthylene
381 Dimethyl phthalate
384 Dibenzofuran
392 Naphthalenol
396 Methyl cinnoline
471 407 Fluorene
CQ J II
" fit
i |j II
II III 1 1
i III
433
vw
420 Unknown
471 d10-Anthracene (IS)
483 Isoquinoline
497 Carbazole
546 Fluoranthene
562 Pyrene
437 642 Chrysene, benzo(a)anthra
_ 741 MW 252 PAH
rn
CO
f 546
1
1
I)
562
II
„,
I 642
1 1 ul n \ \ o «i.
v yv 5je rt
« \lr WWV^^JSL^^^J^^^
5:60
18:03
360
15:90
20:00
500
25:00
600
30:00
700
35:00
800 SCAN
40:00 TIME
FIGURE 10. RECONSTRUCTED GAS CHROMATOGRAM FOR SEMIVOLATILE ORGANICS IN COAL TAR LEACHATE
-------
TABLE 15. COMPOSITION OF STANDARD SOLUTION A
Compound
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
N-Nitrosodimethylamine
N-Nitrosodipropylamine
Nitrobenzene
Isophorone
Acenaphthylene
Dimethyl phthalate
2, 6-Dinitro toluene
Fluorene
2 , 4-Dinitro toluene
Diethyl phthalate
Dibutyl phthalate
Fluoranthene
Pyrene
Chrysene
Dioctyl phthalate
Benzo(k) f luoranthene
Concentration,
ug/ml(a)
250
50
50
250
50
50
50
250
250
250
50
250
50
250
250
50
In 1:1 methanol:2-propanol.
58
-------
TABLE 16. COMPOSITION OF STANDARD SOLUTION B
Compound
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
1, 4-Dichlorobenzene
Bis ( 2-chloroethyl) ether
1, 2-Dichlorobenzene
Bis ( 2-chloroisopropyl) ether
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Hexachlorocyclopentadiene
4-Chlorophenyl phenyl ether
Hexachlorobenzene
4-Bromophenyl phenyl ether
4, 4 '-DDE
Endrin
2,4,2',4'-Tetrachlorobiphenyl
2,4,6)2t,4f,6 '-Hexachlorobiphenyl
g-BHC (lindane)
4, 4 '-ODD
Concentration,
yg/ml(a)
500
100
100
500
500
100
100
100
500
500
500
500
500
100
100
100
(a) In methanol.
59
-------
TABLE 17. COMPOSITION OF STANDARD SOLUTION C
Compound
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Benzidine
3 , 3 '-Dichlorobenzidine
Phenol
2, 4-Dimethylphenol
2-Chlorophenol
2 , 4-Dichlorophenol
2, 4-Dinitrophenol
4-Nitrophenol
2,4,6-Trichlorophenol
Pentachlorophenol
Concentration,
100
500
1000
100
500
100
500
100
500
100
(a) In methanol.
60
-------
TABLE 18. COMPOSITION OF STANDARD SOLUTION D
Concentration,
Compound ug/ml(a)
1. Methylene chloride 50
2. 1,1-Dichloroethene 10
3. 1,1-Dichloroethane 10
4. trans-l,2-Dichloroethene 50
5. Chloroform. 10
6. 1,2-Dichloroethane 50
7. 1,1,1-Trichloroethane 10
8. Carbon tetrachloride 50
9. Trichloroethene 50
10. Benzene 50
11. 1,1,2-Trichloroethane 10
12. 1,1,2,2-Tetrachloroethane 10
13. Tetrachloroethene 50
14. Toluene 50
15. Chlorobenzene . 50
16. Ethylbenzene 50
(a) In methanol.
61
-------
leachates for organic analysis were prepared as four separate spiking solu-
tions by Battelle and shipped in ampules to SoRI. The concentration of com-
pounds used for each of the four solutions, designated as Solutions A, B, C,
and D, is shown in Tables 15-18. For the semivolatile organics analyses,
600 ul of Solution A, 300 ul of Solution B, and 300 ul of Solution C were
used to spike 300 ml of leachate. Solution D was used to spike the leachates
for volatile organic analysis, 2 yl for 40 ml of leachate from still bottoms
and 200 ul for 40 ml of leachate from ink pigment.
The standards used for spiking samples for total semivolatiles organic
content analysis were prepared as five separate solutions by SoRI and shipped
in ampules to Battelle. The concentrations of compounds in these solutions
are given in Table 19. Different mixtures of the solutions were used to
spike ink pigment and still bottoms based on the total content of the wastes
measured by SoRI.
Each of the ten 75-g samples of ink pigment waste and still bottoms was
leached using the Solid Waste Leaching Procedure with 0.1M sodium acetate,
pH 4 buffer, as the leaching medium. The buffered medium was selected
instead of the EP medium or distilled water to minimize differences due to
anomalous pH behavior.
Both laboratories rigidly followed the same analysis scheme regarding
amount of sample and size of aliquots used for each analysis. The leachates
generated for inorganic analysis were divided following final filtration to
give three 30-ml aliquots. One of the aliquots was analyzed without spiking;
one was spiked at low levels; and one was spiked at high levels.
The leachates targeted for organic analyses were divided following
centrifugation but prior to filtration. Two 40-ml aliquots were placed in
glass vials for volatile organic analysis; one of these aliquots was analyzed
without spiking and one was analyzed with spiking. The remaining leachate
was filtered and two 300-ml aliquots were collected for spiked and unspiked
semivolatile organic analysis.
Leachate Analyses
The analysis of replicate leachates for metals was conducted by flame
and/or flameless AAS and ICAP at Battelle and AAS at SoRI. The intralabora-
tory precision may be assessed by examining the percent relative standard
deviation (RSD) obtained for the five replicates. The data obtained by
Battelle using ICAP are presented in Table 20. The RSDs generally were in
the 5 percent range with approximately one third of the values in the 20 to
40 percent range. Comparable quantitative results were obtained by Battelle
for AA and ICAP as shown in Table 21, however, the levels of these metals
were frequently below the detection limit. The recovery of metals spiked
into the leachates of ink pigment and still bottoms was excellent (Table 22).
The average percent recovery for analysis by AA and ICAP was 102 and 96, re-
spectively. A comparison of BCL and SoRI metals data by AAS for both total
content and leachates is given in Table 23. The interlaboratory agreement is
considered very good.
62
-------
TABLE 19. COMPOSITION OF STANDARD SOLUTIONS USED FOR SPIKING
IN TOTAL SEMIVOLATILE ORGANIC CONTENT ANALYSIS
Compound
1, 3-Dichlorobenzene
1, 4-Dichlorobenzene
1, 2-Dichlorobenzene
Hexachloroe thane
Bis (2-chloroethy 1) ether
Bis(2-chloroisopropyl)ether
Hexachlorobutadiene
Nitrobenzene
Naphthalene
1 , 2, 4-Tr ichlorobenzene
Bis (2-chloroethoxy )methane
N-nitrosodi-n-propylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Acenaphthene
Dimethyl Phthalate
2,6-Dinitrotoluene
Fluorene
2,4-Dinitrotoluene
1, 2-Diphenylhydrazine
4-Chlorophenyl Phenyl Ether
Diethyl Phthalate
N-Nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl Phenyl Ether
Phenanthrene
Di-n-butyl Phthalate
Fluoranthene
Pyrene
Benzidine
Butylbenzyl Phthalate
Bis(2-ethylhexyl) Phthalate
Benzo (a) anthracene
3,3' -Dichlorobenzene
Di-n-octyl Phthalate
Benzo (b) f luoranthene/
Benzo (k) f luoranthene
Benzo(a)pyrene
Benzo (ghi) pery lene
Dibenzo (ah) anthracene
Ind eno ( 1 , 2 , 3-cd ) py rene
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4 -D ime thy Ipheno 1
2 , 4-Dichlorophenol
2,4, 6-Tr ichlorophenol
4-Chloro-3-methylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Pentachlorophenol
4-Nitrophenol
Anthracene
Concentration, mg/ml, in Given Solution
K H G I A-So
0.166
1.625 0.877
0.429 1.504
2.00
14.35
2.01 .0.802
0.136 3.010
1.034
2.02 0.605
2.00
2.02
2.015
20.10 1.510
0.503
2.01
1.004
2.03 1.016
2.00
0.553
1.522
2.048
2.119
2.01
0.184 3.022
1.01
2.01
1.07
1.12
1.03
1.00
10.03 0.407
10.05
10.00 0.263 2.425
10.04 0.426
10.11
10.06
10.02
10.00
10.04
10.02 1-520
10.02 1-207
2.208
J
0.854
1.096
1.002
1.002
1.000
1.023
1.001
1.100
1.012
0.960
1.008
1.006
1.007
1.004
1.004
1.109
1.000
0.807
1.033
1.014
1.005
1.004
1.009
1.009
1.006
0.010
1.013
0.011
0.010
0.010
0.011
0.010
0.005
1.004
63
-------
TABLE 20. ICAP ANALYSIS OF LEACHATES FOR SOLID WASTES
(BATTELLE)
Amount Found for
Ink Pigment (a)
Element
Al
B
Ba
Be
Ca
Co
Fe
Mg
Mn
Mo
Sn
Ti
V
Y
Se
Tl
Ag
As
Sb
Cd
Cr
Cu
Pb
Ni
Zn
vg/fc
5,720
. 4,080
1,810
. <1
29,500
14
1,550
227,000
1,100
406
<30
75
<5
<5
<150
<400
<10
<100
< 100
< 5
710
52
5,070
<50
940
RSD
5.8
1.9
5.8
—
6.9
21
7.1
1.4
5.9
4.2
—
28
—
—
—
—
—
—
—
—
5.3
44
4.3
-=-
4.6
Amount Found for
Still Bottoms^3)
ug/fc
<200
<100
1,640
<5
130,000
< 25
50,500
' 9,420
2,570
<50
<150
<25
<25
<25
<750
<2,000
<50
<500
< 500
<25
<50
13,300
<250
1,620
4r080
RSD
__
—
13
—
7.6
—
0.4
5.4
5.3
—
—
—
—
—
—
—
—
—
—
—
—
41
—
32
26
(a) The values given for the last six elements, Cd, Cr, Cu, Pb, Ni and Zn,
are the averages of five replicates. The values given for all other
elements are the averages of 15 replicates.
64
-------
TABLE 21. BATTELLE AA AND ICAP DATA COMPARISON--LEACHATE(a>
Ink Pigment (yg/1) Still Bottoms (ug/1)
Element
Cd
Cr
Cu
Pb
Ni
Zn
AA
<20
830
<50
5290
<100
1110
ICAP
<5
710
52
5070
<50
940
AA
<20
<100
12,500
. <200
1200
4360
ICAP
<25
<50
13,300
<250
1620
4080
(a) Precision was comparable for both AA and ICAP.
65
-------
TABLE 22. RECOVERY OF METALS SPIKED INTO LEACHATES FROM SOLID WASTES
(BATTELLE)
en
Element
INK PIGMENT
Cd
Cr
Cu
Pb
Nl
Zn
Analytical
Method
ICAP
AA
ICAP
AA
ICAP
AA
ICAP
AA
ICAP
AA
ICAP
AA
Amount Found
In Uiis piked
Sample, tig/1
<5
<20
710
830
52
<50
5,070
5,290
<50
<100
940-
1,110
Amount Spiked, pg/1
High
Level
100
100
2.000
2,000
100
100
10,000
10,000
200
200
2.000
2,000
Lou
Level
500
500
10,000
10,000
500
500
25,000
25,000
1,000
1,000
10,000
10,000
RSD
-------
TABLE 23. INTERLABORATORY COMPARATIVE DATA FROM AAS ANALYSIS OF
METALS IN INK PIGMENT AND STILL BOTTOMS
Total Content. ug/g(b)
Compound(
Battelle
Cols Labs
Southern
Res Inst
AVR
Leachate Content.
Battelle
Cols Labs
Southern
Res Inst
AVR
Leaching
Efficiency,
Percent
(c)
INK PIGMENTS
Chromium
Copper
Lead
Zinc
55
7
250
24
55
10
240
26
55
9
245
25
830
<50
5,290
1,110
340
<50
7,540
1,560
590
<50
6,420
1,340
21
54
107
STILL BOTTOMS
Chromium
Copper
Lead
Nickel
Zinc
55
640
21
130
160
39
880
22
91
220
47
760
22
110
190
<100
12,500
<200
1,200
4,360
23
23,600
270
1,450
5,790
__
18,000
—
1,320
5,080
•••V
47
—
24
53
(a) Only metals detected by both research institutes are reported here for comparison purposes.
(b) The values given are the averages of five replicate runs.
(b) The leaching efficiency represents the percent of the total content that was leached out by the
solid waste leaching procedure. A single batch leaching with 1000 ml of 0.1 N NaOAc buffer,
pH 4.0, per 50 gram of waste was used. The leaching efficiency was calculated as follows:
% Leaching efficiency
Avg. Leachate Content (yg/1)
50 (g of waste/1)
x
100
Avg. Total Content (yg/g of waste)
-------
TABLE 24. VOLATILE ORGANIC CONTENT OF LEACHATES FROM
SOLID WASTES (BATTELLE)
Compound
STILL BOTTOMS
trans-1, 2-Dichloroethene
1, 1-Dichloroe thane
Chloroform
1, 2-Dichloroe thane
1, 1, 1-Trichloroethane
Benzene
Carbon tecrachloride .
Trichloroechene
1,1, 2-Tr ichloroe thane
Toluene
Tetrachloroethene
Ethylbenzene
INK PIGMENT
trans-1 , 2-Dichloroethene
1, 2-Dichloroe thane
1,1, 1-Trichloroethane
Benzene
Carbon tetrachloride
Tr ichloroe thene
1,1, 1-Trichloroethane
Toluene
Tetrachloroethene
Ethylbenzene
Amount
Spiked,
Pg/1
230,000
50,000
50,000
250,000
50,000
250,000
250,000
250,000
50,000
250,000
250,000
250,000
2,500
2,500
500
2,500
2,500
2,500
500
2,500
2,500
2,500
Amount Found in
Unspiked Sample (a'
Ug/1 RSD(b)
19,000
158,000
15,000
99,000
15,000
54
1,600
190,000
360,000
94
150,000
<30
<100
<100
<400
490
<500
740
<200
4,300
330
2,700
55
21
20
16
15
24
16
11
11
15
13
~ .
—
—
—
30
—
28
—
27
20
25
Amount Found in
Spiked Sample
Ug/1 5sT>(b)
210,000
144,000
56,000
270,000
65,000
240,000
240,000
420,000
320,000
260,000
390,000
270,000
1,000
1,300
470
2,700
1,700
3,000
410
5,900
2,900
5,100
11
14
10
4
8
8
10
7
7
8
7
7
23
10
50
3 .
15
4
12
3
2
6
Percent
Recovery
76
(c)
82
68
100
96
95
92
<«0
104
96
108
40
52
94
76
68
90
82
64
104
96
(a) Average of five replicates.
(b) Percent relative standard deviation.
(c) Could not be determined because spike level was much lower than the background level.
68
-------
TABLE 25. INTERLABORATORY COMPARATIVE DATA FROM ANALYSIS OF
VOLATILE ORGANICS IN INK PIGMENT AND STILL BOTTOMS
Total Content.
Compound
Battelle
Cols Labs
Southern
Res Inst
Avg
Leachate Content. yg/l(a)
Battelle
Cols Labs
Southern
Res Inst
Avg
Leaching
Efficiency,
Percent
(b
INK PIGMENT
Benzene
Trichloroethene
Toluene
Tetrachloroethene
Ethylbenzene
6
11
68
11
89
3
6
52
4
57
5
9
64
8
73
490
740
4,300
330
2,700
430
760
3,200
530
1,720
460
750
3,750
430
2,210
184
167
117
108
61
STILL BOTTOMS
1,1-Dichloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
Trichloroethene
1,1,2-Trichloroethane
Toluene
Tetrachloroethene
730
760
280
5,800
7,600
21
34,000
2,170
1,500
350
5,770
7,180
29
17,200
1,450
1,130
315
5,790
7,400
25
25,700
158,000
99,000
15,000
190,000
360,000
94
150,000
171,000
96,800
23,700
150,000
268,000
490
144,000
165,000
98,000
19,400
170,000
314,000
290
147,000
226
173
123
59
85
23
11
(a) The values given are the averages of five replicate runs.
(b) The leaching efficiency represents the percent of the total content that was leached.out by the
solid waste leaching procedure. A single batch leaching with 1000 ml of 0.1 N NaOAc buffer,
pH 4.0, per 50 gram of waste was used. The leaching efficiency was calculated as follows:
% Leaching efficiency =
Avg. Leachate' Content (yg/1)
50 (g of waste/1)
x
100
Avg. Total Content (yg/g of waste)
-------
The volatile organic content of leachates of the still bottoms and ink
pigment measured by Battelle is presented in Table 24. The RSD was 15 per-
cent or less in most cases. The percent recovery of spikes varied from 40 to
108, however, most recoveries were in the 80 to 105 percent range. The com-
parison of Battelle's data with SoRI's, for both total content and leachates,
is shown in Table 25. These data are remarkably similar, especially since
the two laboratories used different analytical methods for measurement.
Battelle used a CS2 extraction followed by GC-FID, while SoRI used Method
625 which is a purge and trap technique with detection by GC-MS.
The CS2 extraction method used by Battelle is similar to the EPA sol-
vent extraction method used for trihalomethanes in drinking water, except for
the following three major changes: (1) an SP-2100 glass capillary column was
used instead of a packed column—the improved resolution minimized the possi-
bility of interferences and the much higher temperature permitted most of the
high-boiling compounds to be eluted from the column at the end of each run;
(2) a flame ionization detector was used instead of an electron capture
detector—this change permitted aromatic hydrocarbons to be detected in
addition to halocarbons; and (3) CS2 was used as the solvent instead of
isooctane—this selection minimized the solvent peak and permitted compounds
as low-boiling as trans-1,2-dichloroethene, b.p. 48°C, to be resolved from
the solvent. The main disadvantage of the CS2 extraction method is that it
does not resolve methylene chloride and lower boiling compounds from the
solvent peak. A second disadvantage is that CS2 cannot be used with a
flame ionization detector when significant amounts of €5 to Cg saturated
and olefinic hydrocarbons or other interferences are present as in a
gasoline-containing sample. A saturated hydrocarbon solvent and an electron
capture detector or photoionization detector would need to be used in such
cases.
The C&2 extraction method offers the following important advantages
over the purge and trap GC-MS method:
(1) Requires less operator time—one person can easily extract 25 to 50
or more samples per day.
(2) Readily automated using automatic samplers in common use.
(3) Uses much less expensive instrumentation—GC instead of computerized
GC-MS .
(4) Quality control is easier to maintain because of the larger number
of runs that can be completed per day.
(5) Samples with extremely high levels of volatiles have much less of an
adverse effect on the instrumentation.
(6) Able to determine higher-boiling components; any of the CS2~
extractable semivolatiles can be determined along with volatile
constituents for samples that do not contain significant
interferences.
70
-------
The above advantages all contribute to the CS2 extraction method being
quicker and less costly than the purge and trap GC-MS method. The data
presented in Table 25 indicate that the results obtained from the two methods
in this program are comparable. Representative gas chromatograms of CS2
extracts from leachates of ink pigment and still bottoms are shown in Figures
11 and 12, respectively. The volatile priority pollutants identified on the
basis of retention times and quantified on the basis of peak areas are listed
in the legends. In nearly every case the peaks are sharp and well resolved
from neighboring peaks. The chromatograms also show that much higher-boiling
components, in fact, any of the CS2~extractable semivolatiles, could be
determined along with the volatile components in one run if there were no
significant interferences. The detection limit achieved relative to that of
the semivolatiles method would be higher by a factor of 10 because the
concentration factor is only 20 instead of 200. Nevertheless, the detection
limit is generally about 20 to 100 ug/1 which is adequate for most solid
waste studies.
The semivolatile organic analyses of the leachates are more difficult to
evaluate and compare due to the large number and diverse types of compounds
involved. The still bottoms leachate contained few semivolatile compounds
and these constituents were present at levels too low for quantitative
comparison. Both laboratories identified phenol in this leachate. In con-
trast, the ink pigment leachate contained over a dozen semivolatile priority
pollutants. A comparison of data obtained by Battelle and Southern Research
Institute (SoRI) shown in Tables 26 and 27, shows good agreement in most
cases. The Battelle and SoRI data for the spiked leachates are given in
Tables 28 and 29. The RSD for the five replicate determinations varied from
5 to 113 with most values being around 20 to 40 percent for both labora-
tories. Recoveries generally were 50 to 120 percent with a few compounds
having relatively poor recoveries (e.g. certain phenols). Benzidine was not
recovered because only acidic conditions were used for the extractions.
Total Content
The analysis for total metals in the ink pigment and still bottom wastes
is reported in Table 30. Both ICAP and AA results are included in Table 30
for silver, arsenic, antimony, cadmium, chromium, copper, lead, nickel, and
zinc. These data agree well and generally the RSD is lower for ICAP. The
percent recovery of spikes shown in Table 31 is good for most metals except
those present in concentrations at or near the minimum detection limit.
The total volatile organic content measured by the CS2~GC/FID method
adapted for this study by Battelle is tabulated in Table 32. The RSD for
replicate analyses and the percent recovery averaged 13 and 78 percent, re-
spectively. The low recoveries are usually associated with the high back-
ground concentrations for which an inadequate amount of spikes was added, or
compounds present at or near the detection limit. The comparison of Battelle
and SoRI VOA data using the two different analytical methods was shown in
Table 25. The excellent agreement observed suggests that either of these
methods is suitable for volatile organic analysis of wastes. The advantages
of the CS2 extraction method discussed for leachates also apply to use for
the total content studies. Representative gas chromatograms of CS2
71
-------
ro
Ik2 11
4X
/3
'
\
6
]
r
\
_j-
11
\
10
1
12
1,1 -Dichloroethane (160.000 //g/l)
1.2-Dichloroethylene (19.000//g/l)
Chloroform (15.0OO//g/l)
1.2 Dichloroethane (1 OO.OOO //g/l)
1,1.1 -Trichloroethane (15.00O //g/l)
Benzene (50 //g/l)
7. 1,2-Dichloropropane (Int. Std.)
8. Trichloroethylene (1 90.000 //g/l)
9. 1,1,2-Trichloroethane (360.OOO //g/l)
10. Toluene (90//g/l)
11. Tetrachloroethylene (15O.OOO //g/l)
12. 1.1.2,2-Tetrachloroethane(2O.OOO//g/l)
1.
2.
3.
4.
5.
6.
FIGURE 11. GAS CHROMATOGRAM OF CS™ EXTRACT OF STILL BOTTOMS LEACHATE
-------
6
\|
JUU
•v
vr
1. Benzene (490 /ug/l)
2. 1.2-Dichloropropane (Int. Std.)
3. Trichloroethylene (740 //g/l)
4. Toluene (4300 /ug/l)
5. Tetrachloroethylene (33O A/g/l)
6. Ethylbenzene (27OO//g/l)
FIGURE 12. GAS CHROMATOGRAM OF CS2 EXTRACT OF INK PIGMENT LEACHATE
-------
TABLE 26. INTERLABORATORY COMPARATIVE DATA FROM ANALYSIS OF
SEMIVOLATILE ORGANICS IN STILL BOTTOMS.
Compound
1, 3-Dichlorobenzehe
1,4-Dichlorobenzene
1, 2-Dichlorobenzene
Hexachloroe thane
Hexachlorobutadiene
1,2, 4-Tr±chlorobenzene
Naphthalene
Hexachlorocyclopentadiene
4-Chlorophenyl Phenyl Ether
Hexachlorobenzene
BIs(2-ethylhexyl) Phthalate
Di-n-octyl Phthalate
Phenol
Total
Battelle
Cols Labs
3
15
13
219
283
29
6
9
6
175
14
3
4
Content, ug/g(fl)
Southern
Res Inst
5
36
12
181
328
17
4
2
8
134
3
7
6
Avg
4
26
13
200
306
23
5
6
7
155
9
5
5
Leachate
Battelle
Cols Labs
0
28
31
25
0
6
4
0
0
0
14
7
281
Content,
Southern
Res Inst
0
0
0
0
0
0
0
0
0
0
0
0
195
ug/l(a)
Avg
0
14
16
13
0
3
2
0
0
0
7
4
238
Leaching ,,.
Efficiency, '
%
0
1.1
2.5
0.1
0
0.3
0.8
0
0
0
1.6
1.6
95.2
(a) The values given are the averages of five replicate runs.
(b) The leaching efficiency represents the percent of the total content that was leached out by the solid
waste leaching procedure. A single batch leaching .with 1000 ml of 0.1 N NaOAc buffer, pH 4.0, per 50
gram of waste was used. The leaching efficiency was calculated as follows:
„ T . . ff. , _ Avg. Leachate Content (ug/1) 100
% Leaching efficiency - 5Q(g Qf waste/1) * Avg< Total content (ug/g of waste)
-------
TABLE 27. INTERLABORATORY COMPARATIVE DATA FROM ANALYSIS OF
SEMIVOLATILF. ORGANICS IN INK PIGMENT
-J
Ul
Total Content, ug/g(a)
Compound
1,4-Dichlorobenzene
1 , 2-Dichlorobenzene
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Di-n-octyl Phthalate
Benzo(b and/or k)fluoranthene
Benzo(a)pyrene
Phenol
Pentachlorophenol
Battelle
Cols Labs
7
23
26
6
4
10
28
12
13
7
37
9
6
45
4
Southern
Res Inst •
34
40
95
18
11
22
58
12
7
8
45
5
7
68
3
Avg
21
32
61
12
8
16
43
12
10
8
41
7
7
57
4
Leachate
Battelle
Cols Labs
92
260
320
9
5
3
0
0
0
0
18
0
0
2700
0
Content, \i
Southern
Res Labs
79
250
560
45
14
13
2
0
0
0
52
0
0
3100
0
g/1(a)
Avg
86
255
440
27
10
8
1
0
0
0
35
0
0
2900
0
Leaching . .
Efficiency, '
8.2
15.9
14.4
4.5
2.5
1.0
0.1
0
0
0
1.7
0
0
102
0
(a) The values given are the averages of five replicate runs.
(b) The leaching . efficiency represents the percent of the total content that was leached out by the solid
waste leaching procedure. A single batch leaching with 1000 ml of 0.1N NaOAc buffer, pH 4.0, per 50 '
gram of waste was used. The leaching efficiency was calculated as follows:
„ _ . . ... . Avg. Leachate Content(ug/1) 100
% Leaching efficiency = —p
50(g of waste/1)
Avg. Total Content (yg/g of waste)
-------
TABLE 28. RECOVERY OF SEMIVOLATILE ORGANICS SPIKED
INTO LEACHATES FROM STILL BOTTOMS
1.
2.
3.
4.
5.
6.
7.
3.
9.
10.
11.
12.
13.
14.
15.
16.
17.
IB.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
(a)
(b)
Compound
1 , 4-Diehlorobenzene
Bis(2-chloroechyl)ether
1, 2-Olehlorobenzene
Bis (2-chloroisopropy 1 ) ether
N-nltrosodipropylanine
Nitrobenzene
Hexachlorobutadiene
1, 2.4-Trichlorobenzene
lEophorone
Hexachlorocyclopentadiene
Acenaphchylene
Dimethyl Phthalate
2 , 6-Dinitro toluene
4-Chlorophenyl Phenyl Ether
Fluorene
2 , 4-Dinitro toluene
Diethyl Phchalate
Hexachlorobenzene
4-Bromophenyl Phenyl Ether
Dlbutyl Phthalate
Fluoranthene
Pyrene
Benzldine
Butyl Benzyl Phthalate
Chrysene
3,3' -Dlchlorobenzidine
Dioctyl Phchalate
BenzoCb and/or k)fluoranchene
letrachlorobiphenyl
4, 4 '-DDE
Endrin
Hexachlorobiphenyl
Y-BHC (Lindane)
4,4'-DDD
2-Chlorophenol
Phenol
2 , 4-Dlaethy Iphenol
2,4-Dlchlorophenol
2,4, 6-Tr Ichloropheno 1
2 , 4-Dinltrophenol
Pentachlorophenol
4-Nl»ophenol
Amount
Spiked,
lig/1
500
100
100
500
100
100
500
100
500
100
100
100
100
100
500
500
500
500
500
100
500
100
100
100
500
500
500
100
500
500
500
100
100
100
500
1000
100
100
500
500.
100
100
Percent relative standard deviation of
Avg. ant. in 5 spiked runs -
AVK. amt
RSD(a) of
Amount Found
BCL
17
25
15
24
45
15
17
13
22
53
7
B
—
20
8
31.
12
8
12
16
13
12
—
—
16
61
38
22
14
11
33
15
24
23
17
26
14
20
11
—
41
—
SoRI
43
19
33
9
—
34
21
14
15
36
23
12
33
14
13
24
22
16
16
20
13
17
57
—
19
50
19
113
—
—
—
—
—
—
18
12
31
—
. 15
15
—
24
five replicate
. in 5 unsoiked
Percent
Recovery (b)
BCL
55
105
57
114
61
58
70.
51 '
95
135
47
37
0
38
45
87
49
118
41
45
38
5*3
0
SA
67
24
102
47
76
NA
170
59
80
66
74
71
39
61
58
0
36
0
runs.
runs
SoRI
82
210
89
108
0
150
73
207
102
71
100
90
74
188
102
70
222
131
123
105
112
100
. 14
—
160
35
160
390
HA
170
NA
HA
NA
NA
36
118
33
0
20
42
0
46
x 100
Amount spiked
NA = Not analyzed.
76
-------
TABLE 29. RECOVERY.OF SEMIVOLATILE ORGANICS SPIKED
INTO LEACHATES FROM INK PIGMENT
Compound
1. 1,4-Dichlorobenzene
2. Bis(2-chloroethyl)ether
3. 1,2-Dlchlorobenzene
4. Bis(2-chloroisopropyl)ether
S. N-nlciosodipropylamlne
6. Nitrobenzene
7. Hexachlorobutadiene
8. 1,2,4-Trichlorobenzene
9. Isophorone
10 . Hexachloroeyclopencadiene
11. Acenaphchylene
12. Dimethyl Fhthalace
13. 2.6-Dinltrotoluene
14. 4-Chlorophenyl Phenyl Ether
15 . Fluorene
16. 2, 4-Dinitro toluene
17. Diethyl Fhthalate
18. N-nitrosodiphenylamine
19 . Hexachlorobenzene
20. 4-Bronophenyl Phenyl Ether
21. Dlbutyl Phthalate
22. Fluoranthene
23. Pyrene
24. Benzidine
25. Chrysene
26. 3,3'-Dlchlorobenzldlne
27. Dioctyl Phthalate
28. Benzo(b and/or k) f luoranthene
29. Tetrachloroblphenyl
30. 4,4'-DDE
31. Endrin
32. Hexachloroblphenyl
33. Y-BHC (Lindane)
34. 4,4'-DDD
35. 2-Chlorophenol
36. Phenol
37. 2,4-Dlmethylphenol
38. 2,4-Dlchlorophenol
39 . 2,4, 6-Trlchlorophenol
40. 2,4-Dinltrophenol
41. Pentachlorophenol
42. 4-Nltrophenol
Amount
Spiked,
US/1
500
100
100
500
100
100
500
100
500
100
100
100
100
100
500
500
500
100
500
500
100
500
100
100
500
500
500
100
500
500
500
100
100
100
500
1000
100
500
500
500
100
100
(a) Percent relative standard deviation of
(b) Percent recovery =
Avg. amt. in 5 spiked runs -
Avg. ant
RSD(a) of
Amount Found
BCL
17
28
24
15
27
24
24
13
13
38
11
11
—
22
17
11
11
—
28
28
33
31
30
—
37
45
39
35
34
34
36
34
26
37
14
15
14
16
11
—
16
—
SoRI
15
15
12
12
34
—
14
13
14
7
16
12
—
24
21
22
—
—
5
7
8
10
12
—
7
10
27
10
—
—
—
—
—
—
29
13
21
20
13
11
58
24
five replicate
. in 5 unspiked
Percent
Recovery(b)
BCL
67
195
80
92
58
95
88
97
84
28
109
67
0
79
85
125
90
NA
147
72
31
52
73
0
69
78
63
57
98
72
92
76
110
66
127
89
197
153
138
0
97
0
runs.
runs
SoRI
67
160
20
77
134
0
95
80
89
91
105
120
83
80
79
78
0
0
46
116
80
86
310
0
50
18
94
56
NA
NA
NA
NA
NA
NA
26
34
78
78
120
98
82
105
« 100
amount spiked
NA - Not analyzed.
77
-------
TABLE 30. TOTAL METALS CONTENT OF SOLID WASTES
(BATTELLE)
Element
AT
B
Ba
Be
Ca
Co
Fe
Mg
Mn
Mo
Sn
Ti
V
Y
Se
Tl
Ag
Ag
As
As
Sb
Sb
Cd
Cd
Cr
Cr
Cu
Cu
Pb
Pb
Ni
Ni
Zn
Zn
Hg
Analytical
Method
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
GFAAS
ICAP
GFAAS
ICAP
GFAAS
ICAP
GFAAS
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
ICAP
GFAAS
ICAP
FAAS
CVAAS
Amount Found in
Ink Pigment Wastea
ug/g RSD
440
110
44
<0.1
735
<0.1
300
4,800
35
10
<0.6
4.9
3.2
<0.1
, <3
<8
<0.2
NA
3.3
NA
<0.2
0.3
<0.1
0.2
46
55
6
6.7
222
254
1
1.5
19
24
NA
5.0
2.4
6.8
—
11
—
20
3.8
28
3.8
—
15
62
—
—
—
—
—
14
—
—
18
~
26
3.3
2.9
15
9.0
2.0
—
—
27
5.8
17
—
Amount Found in
Still Bottoms3
fg/g
1,160
13
77
<0.1
2.910
<0.5
10,480
1,090
69
<1
<3
9.1
5.3
0.6
<15
<40
<1
. 1
17
1.6
<10
NA
<0.5
NA
47
55
630
636
20
21
130
129
154
163
0.7
RSD
9.0
11
10
—
24
—
6.7
6.1
25
—
—
1.4
9.1
16
—
—
~
—
19
9
—
—
—
—
7.9
7.4
3.2
3.6
20
20
5.5
5.7
8.4
4.7
12
(a) The values given for the last 10 elements Ag, As, Sb, Cd, Cr, Cu, Pb,
Ni, Zn, and Hg, are the averages of five replicates. The values for
all other elements are the averages of 15 replicates.
NA = Not analyzed.
78
-------
TABLE 31. RECOVERY OF METALS SPIKED INTO SOLID WASTE
(BATTELLE)
Element
INK PIGMENT
Cd
Cd
Cd
Cr
Cr
Cu
Cu
Pb
Fb
Ni
Nl
Ni
Zn
Zn
Sb
Analytical
Method
ICAP
FAAS
GFAAS
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
GFAAS
ICAP
FAAS
GFAAS
Amount Found'8)
in unspiked
Sample ug/g
<0.1
<0.2
0.2
46
55
6
6.7
222
254
1
<1
1.5
19
24
0.3
RSD^C' of Amount Found
Amount Spiked, us/a In Spiked Sample
Low
Level
0.1
0.2
0.2
50
50
25
25
250
250
1
1
1
25
25
1
High
Level
1
1
—
250
250
100
100
1,000
1.000
5
5
5
100
100
5
Low
Level
—
12
20
0.9
1.0
3.7
3.4
1.2
1.1
11
12
28
1.2
2.2
16
High
Level
*
94
6.9
—
2.9
2.8
5.3
2.7
2.0
3.1
9.0
3.4
4.5
3.8
2.1
11
Percent
Low
Level
(b)
200
255
98
92
96
101
94
98
110
100
250
100
100
54
Recovery
High
Level
72
130
—
98
115
98
94
90
100
90
118
109
99
102
84
STILL BOTTOMS
Cr
Cr
Cu
Cu
Pb
Pb
Ni
Nl
Zn
Zn _
Be
Ag
Ag
As
As
Hg
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
ICAP
FAAS
ICAP
ICAP
GFAAS
ICAP
GFAAS
CVAAS
47
55
630
636
20
21
130
129
154
163
<0.1
<1
0.1
15
1.6
0.7
25
25
250
250
25
25
100
100
100
100
0.1
0.5
0.5
2
2
2
100
100
1,000
1.000
100
100
500
500
500
500
0.5
2
.2
10
10
10
4.5
2.0
5.6
3.3
6.4
3.8
3.6
1.1
7.0
3.4
—
—
44
13
6.2
5.4
3.0
2.6
l.B
1.6
7.2
4.2
1.4
2.9
6.0
6.4
55
—
31
5.2
5.8
7.2
96
116
94
99
100
104
92
96
97
108
200
(b)
84
—
64
96
101
112
92
95
104
98
97
96
108
107
200
(b)
37
60
62
73
(a) Average of five replicates.
(b) Not detected.
(c) Percent relative standard deviation from five replicates.
79
-------
TABLE 32. TOTAL VOLATILE ORGANIC CONTENT OF SOLID WASTES
(BATTELLE)
Compound
STILL BOTTOMS
trans-1, 2-Dichloroethene
1 , 1-Dichlor oethane
Chloroform
1 , 2-Dichloroethane
1,1, 1-Tr ichloroechane
Benzene
Carbon cetrachloride
Trichloroethene
1,1, 2-Tr ichloroe thane
Toluene
Tetrachloroethene
Ethylbenzene
INK PIGMENT
trans-1, 2-Dichloroethene
1 , 1-Dichloroe thane
Chloroform
1 , 2-Dichloroethane
1,1, 1-Tr ichloroe thane
Benzene
Carbon tetrachloride
Trichloroethene
1,1, 2-Tr ichloroethane
Toluene
Tetrachloroethene
Ethylbenzene
Amount
Spiked,
Ug/g
5,000
1,000
1,000
5,000
1,000
5,000
5,000
5,000
1,000
5,000
5,000
5,000
50
10
10
50
10
50
50
50
10
50
50
50
Amount Found in. .
Unspiked Sample u;
Vg/g
<10
730
<5
760
280
25
<10
5,800
7,600
21
34,000
<1
<10
<10
<5
<10
<10
6
<10
11
5
68
11
89
RSD
—
16
—
12
23
10
—
11
11
8
14
—
„
—
—
—
—
17
—
13
12
15
11
10
Amount Found in
Spiked Sample
Vg/g
3,700
1,500
890
5,100
1,200
4,300
4,700
10,000
8,100
5,000
36,000
5,500
25
2.2
5.2
33
5.3
47
36
55
4.3
120
55
140
RSD
16
10
19
7
9
9
9
16
21
15
22
19
32
16
13
18
(0
11
19
12
29
17
12
16
Percent
Recovery
74
77
89
87
92
86
94
84
50
100
40
110
50
22
52
66
53
83
72
88
0
104
88
102
(a) Average of five replicates.
(b) Percent relative standard deviation.
(c) RSD not calculated because only two values were available.
80
-------
extracts of ink pigment and still bottoms are shown in Figures 13 and 14,
respectively. Although very complex patterns of large amounts of extractable
components were obtained, especially in the case of still bottoms, the vola-
tile priority pollutants of interest appear in the early portion of the
chromatograms where adequate resolution of individual components is generally
achieved. The chromatograms also show that despite the large amounts of
extractable components, most are eluted from the column during the tempera-
ture programming to 250°C that was used. The temperature could be raised to
300°C for more complete elution of high-boiling components without adversely
affecting the column. This type of thermal cleaning of the GC column cannot
be achieved when the conventional packed column for volatile organics, one
percent SP-1000 on Carbopak C, is used because of the greater retentiveness
and much lower temperature limitation of the SP-1000 column.
The unspiked sample data for semivolatile organics was shown in Tables 26
and 27. In general, the agreement between the BCL and SoRI data is very
good, with the average values seldom differing by more than a factor of two.
Spiked samples data are given in Tables 33 and 34. Recoveries were generally
50 to 150 percent, with reasonably good agreement between SoRI and BCL. How-
ever, some of the spike levels (e.g. dibenzo(a.h)-anthracene) were too low to
detect.
Comparison of Leaching Efficiency
The analysis of the leachate to determine potentially mobile or leachable
compounds, and the analysis of the solid waste, for total content of those
compounds, enables a'calculation of leaching efficiency to be made. The
leaching efficiencies are included in Table 23 for metals, Table 25 for
organics, and Tables 26 and 27 for semivolatile organics. In general, both
metals and organics were leached to a greater extent from the ink pigment
sample than from the still bottom sample. This result is probably due to the
fact that the ink pigment waste is more readily dispersed in water than the
still bottom sample and contains less insoluble material that might retain
components by adsorption.
For semivolatile organics the leaching efficiency was quite low (gener-
ally less than 10 percent) except for phenol, a highly water-soluble com-
pound for which the leaching was essentially complete. Leaching efficiency
for metals ranged from 20 to 100 percent.
The leaching efficiency data for volatile organics (Tables 26 and 27) are
interesting in that 200 percent recoveries are noted for the more volatile
compounds, and a rapid decrease in apparent leaching efficiency is observed
with increasing boiling point. We believe that the anomalously high leaching
efficiency values for the more volatile compounds is primarily due to loss of
volatiles during sample handling. Since a much smaller quantity of waste
(five grams) is weighed out and extracted for the total content determination
than for the leaching procedure, the relative loss of volatiles will be
greater in the total content method, thus resulting in a lower apparent total
content and a calculated high leaching efficiency.
81
-------
oc
ro
1. 1.1 -Dichloroethane (730/yg/g)
2. 1,2 Dichloroethylene (<1 00 /t/g/g)
3. Chloroform (<50 A/g/g)
4. 1,2-Dichloroethane (760/t/g/g)
5. 1.1,1 Trichloroethane (280 /ug/g)
6. Benzene (25 ug/g)
7. 1,2 Dichloropropane (Int. Std.)
8. Trichloroethylene (580O fjg/g)
9. 1,1,2-Trichloroethane (7600 pg/g)
10. Toluene (21 /jg/g)
11. Tetrachloroethylene (34,000 fjg/g)
12. 1,1,2,2-Tetrachloroethane (5000 fjg/g)
FIGURE 13. GAS CHROMATOGRAM OF CS2 EXTRACT OF STILL BOTTOMS FOR TOTAL CONTENT ANALYSIS
-------
1. Benzene (6 ^g/g)
2. 1,2-Dichloropropane (Int. Std.)
3. Trichloroethylene(11 fjg/g]
4. Toluene (68 pg/g)
5. Tetrachloroethylene (11 /ug/g)
6. Ethylbenzene (89 A
-------
TABLE 33.RECOVERY OF SEMIVOLATILE ORGANICS
BASED ON TOTAL CONTENT ANALYSIS
SPIKED INTO STILL BOTTOMS
Amount
Spiked ,
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
Compound
1 , 3-Dichlorobenzene
1, 4-Dichlorobenzene
Bis (2-chloroethyl) ether
1 , 2-Dichlorobenzene
Hexachloroethane
Bis(2-chloroisopropyl)ether
N-nitrosodipropylamine
Nitrobenzene
Hexachlorobutadiene
1, 2,4-Trichlorobenzene
Isophorone
Bis (2-chloroethoxy)me thane
Naphthalene
Hexachlorocyclopentadiene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Dimethyl Phthalate
2 , 6-Dinitro toluene
4-Chlorophenyl Phenyl Ether
Fluorene
2, 4-Dinitrotoluene
Diethyl Phthalate
Diphenylhydraz ine
N-Nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl Phenyl Ether
Phenanthrene
Dibutyl Phthalate
Fluoranthene
Pg/g
29.
214
2
10.0
63.
1020
10.
10.
10.
1800
140
10.
10.
27.
10.
9.
10.
2520
10.
10.
79.
10.
10.
11.
10.
10.
8.
10.
10.
10.
10.
6
0
0
1
1
1
0
1
6
1
1
1
2
0
2
1
0
0
1
3
1
1
0
RSD(a) of
Amount Found
BCL
12
6
28
11
10
14
—
6
9
16
19
7
20
—
18
7
24
~
16
19
—
24
—
—
—
22
19
32
28
SoRI
40
44
21
17
38
17
36
79
40
37
54
16
30
38
14
30
31
17
21
42
17
33
30
22
50
24
21
6
14
22
Percent
Recovery (b,c)
BCL SoRI
83
29
120
88
106
70
0
0
19
49
109
89
67
5.9
0
109
14
64
0
126
80
0
117
0
0
0
97
79
99
60
160
65
88
51
86
79
46
151
86
79
.63
208
68
38
62
67
40
100
78
66
94
87
95
134
150
240
105
42
92
102
84
-------
TABLE 33 (Continued)
Amount RSD(a) of
Spiked, Amount Found
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
Compound
Pyrene
Benzidine
Butyl Benzyl Phthalate
Bis(2-ethylhexyl) Phthalate
Chrysene/Benzo (a)anthracene
3,3' -Dichlorobenzidine
Dioctyl Phthalate
Benzo(b and/or k)fluoranthene
Benzo(a)pyrene
Indeno (1,2, 3, -c,d) Pyrene
Dibenzo (a, h) anthracene
Benzo (g,h, i)perylene
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4-Dimethylphenol
2 , 4-Dichlorophenol
2,4, 6-Trichlorophenol
4-Chloro-3-methylphenol
2 , 4-Dinitrophenol
2-Methyl-4, 6-dinitrophenol
Pentachlorophenol
4-Nitrophenol
yg/S
10.
10.
10.
33.
10.
10.
10.
22.
10.
0.
0.
10.
10.
10.
42.
10.
10.
10.
10.
10.
10.
10.
10.
1
1
1
1
1
1
1
1
4
05
10
1
0
1
9
0
1
1
0
0
0
0
0
BCL
20
—
—
32
25
45
38
29
36
—
—
48
60
—
5
10
7
5
—
—
—
16
—
SoRI .
31
50
14
44
16
89
21
15
14
—
—
20
64
00
57
101
40
45
51
—
—
28
— —
Percent
Recovery (b,c)
BCL SoRI
109
0
0
280
98
6
13
72
77
0
0
20
10
0
77
53
129
129
0
0
0
70
0
105
53
92
110
120
18
0
52
109
0
0
98
56
0
68
31
64
73
68
0
0
49
0
(a) Percent relative standard deviation of five replicate runs.
(b) Percent recovery = i
Avg. amt. in 5 spiked runs - .Avg. amt. in 5 unspiked runs x
Amount spiked
(c) The total content method described by Southern Research Institute
(SoRI) was used by Battelle's Columbus Laboratories (BCL) and SoRI.
85
-------
TABLE 34.RECOVERY OF SEMIVOLATILE ORGANICS SPIKED INTO INK PIGMENT
BASED ON TOTAL CONTENT ANALYSIS
Amount
Spiked,
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
Compound
1 , 3-Dichlorobenzene
1, 4-Dichlorobenzene
Bis (2-chloroethyl) ether
1, 2-Dichlorobenzene
Hexachloro e thane
Bis (2-chloroisopropyl) ether
N-nitrosodipropylamine
Nitrobenzene
Hexachlorobutadiene
1,2, 4-Tr ichlorob enz ene
Isophorone
Bis (2-chloroethoxy)methane
Naphthalene
Hexachlorocyclopentadiene
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Dimethyl Phthalate
2, 6-Dinitro toluene
4-Chlorophenyl Phenyl Ether
Fluorene
2, 4-Dinitro toluene
Diethyl Phthalate
Diphenylhydr az ine
N-Nitrosodiphenylamine
Hexachlor ob enz ene
4-Bromophenyl Phenyl Ether
Phenanthrene
Dibutyl Phthalate
Fluoranthene
ug/g
8.
54.
10.
85.
10.
10.
10.
50.
10.
11
10.
40.
161
10.
9.
Ill
85.
35.
10.
10.
60.
61.
11.
10.
10.
8.
10.
86.
10.
11.
5
9
0
2
0
0
0
2
2
1
3
1
6
6
2
1
0
2
0
1
0
0
1
3
2
1
2
RSD(a) of
Amount Found
BCL
28
29
41
23
51
37
—
—
69
24
44
36
16
—
—
24
24
32
—
31
37
40
36
—
—
31
30
19
32
25
SoRI
29
21
23
14
30
41
43
22
19
21
14
17
9
49
21
13
12
14
18
45
13
16
23
19
28
14
47
12
16
73
Percent
Recovery(b,c)
BCL SoRI
29
20
50
23
40
20
0
10
39
27
30
35
6
0
0
41
35
37
0
40
43
25
27
0
0
50
29
33
69
30
120
52
73
224
218
82
24
35
117
205
210
72
54
12
74
79
236
76
436
89
82
86
64
175
113
75
70
11
64
85
86
-------
TABLE 34 (Continued)
Amount RSD(a) of Percent
Spiked, Amount Found Recovery(b,c)
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
Compound
Pyrene
Benzidine
Butyl Benzyl Phthalate
Bis(2-ethylhexyl) Phthalate
Chrysene/Benzo (a) anthracene
3,3'Dichlorobenzidine
Dioctyl Phthalate
Benzo(b and/or k) f luoranthene
Benzo(a)pyrene
Indeno (1 , 2 , 3 , -c , d) Pyrene
Dibenzo (a , h) anthracene
Benzo(g,h,i)perylene
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4-Dimethylphenol
2 , 4-Dichlorophenol
2,4, 6-Trichlorophenol
4-Chloro-3-methylphenol
2, 4-Dinitrophenol
2-Methyl-4 , 6-dinitrophenol
Pentachlorophenol
4-Nitrophenol
Ug/g
116
10
10
161
60
10
10
132
61
0
0
60
30
10
13
31
10
10
10
10
10
86
79
BCL SoRI
.0
.1
.9
.1
.1
.9
.5
.1
.1
.4
.1
.1
.3
.1
.1
.0
.0
.0
34
—
—
28
36
95
40
36
34
—
—
32
24
—
15
.
15
22
30
—
—
—
25
—
7.
28
27
34
19
66
34
13
26
—
—
25
12
14
13
23
25
30
24
23
15
21
47
BCL
43
0
0
120
99
55
180
74
90
0
0
22
33
0
115
35
50
30
0
0
0
49
0
SoRI
64
9
71
26
90
82
109
49
114
0
0
137
150
117
92
51
131
125
134
140
110
73
112
(a) Percent relative standard deviation of five replicate runs.
(b) Percent recovery =
Avg. amt. in 5 spiked runs - A-yg. amt. in 5 unspiked runs
Amount spiked
(c) The total content method described by Southern Research Institute
(SoRI) was used by Battelle's Columbus Laboratories (BCL) and SoRI.
87
-------
STATISTICAL TREATMENT OF THE DATA
A large amount of important data was collected from the laboratory ex-
periments which were conducted during this program. These data were used in
an empirical manner to gain insight into the performance characteristics of
the methods studied.
Descriptive statistics, including mean recoveries, standard deviations
and relative standard deviations, were calculated. These statistics were
used to make qualitative comparisons among the various leaching methods.
Formal application of statistical tests or estimation procedures to
establish "significant" differences in performance characteristics (such as
precision) among the leaching methods is inappropriate for this program.
First, such an application requires the establishment of a well-defined set
of parameters, relating to the characteristic of interest. Secondly, if
statistical testing is required, the formal hypotheses involving the para-
meters of interest which are to be tested must be established. If the
comparisons are to be based on interval estimation techniques, then the
comparisons of interest must be specified in terms of the proper combination
of. the population parameters. No set of parameters was defined nor any
formal statistical hypotheses proposed, therefore, the retrospective
calculation of test statistics or confidence intervals is not meaningful.
This discussion does not imply that the data are not meaningful, however,
these data cannot be used in a formal inferential manner. The descriptive
statistics, such as mean recoveries and standard deviations based on repli-
cate analyses, were invaluable for empirically assessing differences in
method characteristics.
88
-------
SECTION VII
QUALITY ASSURANCE
The results of quality assurance efforts are demonstrated partly by the
documentation that included sample logging and sample traceability, and re-
cording of experimental work and experimental data. Quality assurance was
also demonstrated by results of replicate analyses of. blanks, standards and
spiked samples. These results are given in the many tables shown throughout
this report.
The quality control efforts included a study of the performance of the
analytical methods. These studies were carried out early in the program in
order not only to assess the performance but to provide information on
control limits and to provide a basis of comparison of performance of the
leaching process.
Four analysis' methods were studied including inductively coupled argon
plasma (ICAP) and atomic absorption spectrophotometry (AAS) for metals de-
termination, gas chromatography-mass spectrometry (GC-MS) for volatile or-
ganic (purgeable) compounds, and GC-MS for semivolatile organic compound
determinations.
The general scheme for these studies included replicate analyses of
blanks and spiked samples from which precision was calculated. In the case
of analysis for metals and volatile organic compounds, this early work also
included assessment of accuracy through .spike and recovery studies.
The samples (blanks and spikes) were carried through the analysis proce-
dure in order to estimate performance of the analysis procedure rather than
simply instrumental performance. In general, the performance indicated by
these- experiments was as expected based on performance measured on other
programs using the same or similar analysis methods. The relative standard
deviations of results of analyses of solutions done within 1 day are expected
to be of the order of a few percent. On the other hand, the same type
measurements done over a period of days and weeks will show greater devia-
tion. This effect is more pronounced with regard to determinations of or-
ganic compounds than for determinations of metals because the control of the
methodologies for determinations of metals is technically more advanced.
VOLATILE ORGANICS
The precision data obtained for GC-MS analysis of volatile organics in
distilled water using EPA Method 624 are given in Table 35. The response
89
-------
TABLE 35. PRECISION DATA FOR GC-MS ANALYSIS OF VOLATILE
ORGANICS IN WATER USING EPA METHOD 624
Compound
Dichlorome thane
Trichlorofluoromethane
Acrylonitrile
1, 1-Dichloroethene
1 , 1-Dichloroethane
(£)-!, 2-Dichloroechene
Trichlorome thane
1 , 2-Dichloroethane
1,1, 1-Trichloroe thane
Tetrachlorpmethane
Bromodichlorome thane
1, 2-Dichloropropane
(E)-l,3-Dichloro-l-propene
Trichloroethene
Benzene
Dibromochlorome thane
1,1, 2-Tr ichloroe thane
(Z)-l,3-Dichloro-l-propene
Tribromomethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Chlorobenzene
Ethylbenzene
Internal
Standard
Used (a)
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
C
C
C
C
C
C
C
Relative
Obtained
5 ug/1
2.05
1.79
ND
1.11
2.43
1.20
3.90
0.10
0.66
0.29
0.01
ND
0.39
0.38
1.31
0.31
0.39
0.28
0.26
0.19
0.32
0.84
1.00
0.41
Response
at Given
20 ug/1
2.43
2.52
0.34
1.44
3.28
1.57
4.59
0.16
0.66
0.49
0.04
0.01
0.55
0.48
1.39
0.45
0.42
0.40
0.42
0.30
0.44
0.95
1.19
0.54
Factor(b)
Level (c)
100 ug/1
2.94
2.34
0.43
1.62
3.80
1.53
4.28
0.23
0.52
0.59
0.06
0.03
0.65
0.52
1.48
0.53
0.45
0.54
0.55
0.35
0.49
0.98
1.30
0.57
RSD(d) of Relative Response
Factor(b) Obtained at
Given Level (c)
5 ug/1
7.8
1.9
-
2.9
1.3
1.3
3.7
11.9
6.3
3.5
0
-
3.9
4.1
7.4
1.9
3.0
2.0
4.5
3.0
4.7
4.5
1.7
3.7
20 ug/1
3.0
3.2
7.2
1.2
2.1
0.9
2.1
5.0
2.9
1.4
4.0
10.2
3.1
4.1
3.7
3.1
2.6
2.2
4.3
1.3
2.3
1.9
4.2
1.3
100 ug/1
2.2
2.6
4.5
2.2
1.6
1.9
1.2
. 5.7
1.7
. 2.2
2.7
3.9
1.4
2.4
0.6
1.5
1.3
20.1
0.4
2.2
1.9
1.9
1.4
0.2
(a) A •= Bromochloromethane; B = 2-Bromo-l-chloropropane; C • 1,4-Dichlorobutane.
All internal standards were present at 50 ug/1.
. Amount of int. std Area of conpound
(b) Relative response factor - Area of int. std x Amount of compound '
(c) Each value is an average obtained from three runs.
(d) RSD " percent relative standard deviation.
ND = Not detected.
90
-------
factors for the three different levels agree quite well in most cases and the
relative standard deviations are generally less than 10 percent. Direct
injections of standard solutions in me.thanol were also run to determine if
the purge and trap part of the analysis scheme introduced significant vari-
ations. The results, given in Table 36, indicate similar performance except
for acrylonitrile which is not purged from water completely. Recovery data
and precision data obtained from the analysis of a simulated leachate, POTW
sludge supernatant, spiked with volatile organics are given in Table 37. The
recoveries were generally greater than 75 percent and the precision was simi-
lar to that observed for spiked distilled water.
SEMIVOLATILE ORGANICS
GC-MS precision data from the analysis of calibration/spike standard
solutions of semivolatile organics were generated in two different ways:
• An initial precision study in which the standards were analyzed
repetitively
• Precision of the standard solutions interspersed with the authentic
leachate samples (one standard solution every fourth sample).
Precision data were generated using a capillary column as well as a packed
column. The precision data resulting from the initial precision study are
shown in Table 38. The base/neutral compounds were analyzed on a packed
column containing 3 percent SP-2250 on 80/100-mesh Supelcoport, and the
phenols were analyzed on a packed column containing 1 percent SP-1240-DA on
80/100-mesh Supelcoport. As can be seen from the percent relative standard
deviations, the response factors are precise and change minimally with
changes in concentration. Packed column precision data generated from
analysis of equivalent standard solutions interspersed among the samples over
a period of 4 weeks are presented in Table 39. Under these conditions the
response factors are not as precise. This result is not unexpected because
analysis of actual samples may cause-changes in the character of the column.
Also over a period of several weeks, the mass spectrometric performance may
vary somewhat, causing variations in the response factor. Somewhat unexpec-
tedly, the response factors at the two lower levels (50 and 200 ug/1) were
generally more equivalent and larger than the response factors at the high
level (500 ug/1). The medium level (200 ug/1) generally showed the lowest
percent relative standard deviation. More confidence can be placed on the
RSD for the 200 ug/1 standard because, as a result of the protocol, two of
these standards were analyzed for each of the 50 ug/1 standard and the
500 ug/1 standard. One possible reason for the lower response factors for
the 500 ug/1 levels is saturation of the electron multiplier.
Precision data for the analysis of standard solutions interspersed with
samples and analyzed on the SE-52 capillary column for Task 6 are shown in
Table 40. A modified list of compounds was used for the Task 6 studies. The
overall precision is not as good as for the packed column and the detection
of the phenols was not as good. However, the precision of the analyses at
the highest level was very good.
91
-------
TABLE 36. PRECISION DATA FOR GC-MS ANALYSIS OF VOLATILE ORGANICS
BY DIRECT INJECTION OF STANDARDS
IS)
Compound
Dlchloroncchane
Trlchlorofluoromethane
Acrylooltrlle
1 , 1-Dlchloroethene
1, 1-Dlchloroechane
(E)-l, 2-Dlchloroethene
Trlchloronechane
1 , 2-Dlchloroethane
1,1, 1-Tr ichloroethane
Tecrachloromechane
Bromod Ichloromethane
1 , 2-Dlchloropropane
( E) -1 , 3-Dlchloro-l-propene
Trlchloroethene
Benzene
Dlbromochlorooechane
1,1,2-Tr Ichloroethane
(Z)-l, 3-Dlchloro-l-propene
Trlbromonechanc
1 , 1 , 2, 2-Tetrachloroechane
Tetrachloroethene
Toluene
Chlorobenzene
Ethylbcnzene
Internal
Standard
Used (a)
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
B
B
C
C
C
C
C
C
C
Relative Response
Obtained at Given
5 Mg/1
3.87
1.33
1.30
1.42
3.30
0.97
4.44
0.09
0.54
O.SO
0.02
<0.01
0.67
0.42
1.84
0.46
0.47
1.15
0.43
0.26
0.36
0.74
1.07
0.43
20 |ig/l
3.95
1.65
1.49
1.52
3.55
1.10
4.20 .
O.'Ol
0.60
0.65
0.05
0.02
0.69
0.50
1.61
0.55
0.50
O.SS
0.55
0.33
•0.44
0.80
1.15
0.48
RSD(d) of Relative Response
Factor(b) Factor(b) Obtained at
Level (c.e) Given Level(c.e)
100 ug/1
3.92
1.62
1.52
1.42
3.46
1.08
3.96
0.19
0.51
0.59
0.06
0.23
0.60
0.46
1.34
O.SS
0.46
0.45
O.SS
0.30
0.39
0.74
1.07
0.46
5 M8/1
2.0
2.2
0.0
8.2
1.7
3.0
1.7
. 3.3
5.4
0.0
17.5
36
24
1.2
4.2
0.0
1.6
13
1.3
0.0
0.0
3.9
2.7
2.0
20 pg/1
1.3
1.7
1.9
1.9
0.0
0.0
0.0
1.6
0.0
0.0
0.0
0.0
4.2
0.0
1.8
0.0
0.6
0.0
0.0
0.9
0.7
0.0
0.0
1.2
100 ug/1
7.4
1.8
1.9
2.0
8.3
2.7
7.3
1.5
7.1
4.9
0.0
12.3
0.0
2.9
2.2
0.0
0.6
0.6
0.0
0.02
0.7
3.9
2.7
1.1
(a) A ° Bronochloromethane; B - 2-Brono-l-chloropropane; C - 1.4-Dlchlorobutane.
All Internal standards were present at 50 ug/l.
(b) Relative response factor - Amount of int. std. Area of compound
(c) Each value Is an average obtained from three runs.
(d) RSO • percent relative standard deviation.
(e) The amount of standard analyzed was converted to the corresponding levol of ug/1 In water that
would apply when EPA Method 624 la used.
-------
TABLE 37. PRECISION DATA FOR GC-MS ANALYSIS OF VOLATILE ORGANICS
IN A POTW SLUDGE SUPERNATANT USING EPA METHOD 624
Compound
Dichlorome thane
Trichlorofluorome thane
Acrylonitrile
1 , 1-Dichloroethene
1 , 1-Dichloroe thane
(E)-l,2-Dichloroethene
Trichlorome thane
1 , 2-Dichloroethane
1,1, 1-Trlchloroe thane
Tetrachlorome thane
Bromodichlorome thane
1, 2-Dichlo'ropropane
(E) -1 , 3-Dichloro-l-propene
Trichlbroethene
Benzene
Dibromochlorome thane
1,1, 2-Trichloroethane
(Z)-l, 3-Dichloro-l-propene
Tribromome thane
1,1,2, 2-Tetrachloroethane
Tetrachloroethene
Toluene
Chlorobenzene
Ethylbenzene
(a) A = Bromochlorqme thane
All internal standards
Internal
S tandard
Used (a)
A
A
A
A
A
A
A
A
B
B
B
B
B
B
. B
B
B
C
C
C
C
C
C
C
Amount Found, ug/1
in Given Sample (b)
RSD(d) of
Amount
Found in Given Sample
Unspiked Spiked(c) Unspiked
16 143
0 9
0 25.8
0 36.7
1.2 46.0
0.8 11.9
7.1 54.3
5.0 37.6
123 133
37.6
40.0
42.5
42.0
3.3 48.0
1.5 64.1
0.1 50.2
50.6
41.5
51.2
24.4 70.7
29.1 72.5
142 181
60.9 114
27.8
Spiked
8
11
6
11
8
9
7
4
10
10
9
3
9
9
9
7
8
9
9
9
10
8
6
6
Percent
Recovery(e)
of Spike
254
18
52
73
90
22
94
65
20
75
80
85
84
90
125
100
101
83
102
93
87
78
106
106
= 1,4-Dichlorobutane
Response factors obtained
previously
for all calculations.
standard deviation
Amount in spiked
sample - Amount in
uns piked sample
x 100.
50
93
-------
TABLE 38. PRECISION DATA FOR GC-MS ANALYSIS OF SEMIVOLATILE
ORGANICS IN STANDARD SOLUTIONS
VO
Compound
1,4-OlclilorobeiiEcoc
BI«(2-Clill!
eodrln
Endomilfan 3ulfal«
2-Chlorophcnal
2-NUrophenol
Phonol
2.4-Ulajeihylplienol
2.4-nichlorophunol
2.4.6-Trlclilurophcml
4-Cliloro-l-a»itbyphaiu>l
2.4-DlnltroplieBal
4.6-Dlnliro-a-creBol
reniachloroplieuol
4-Hltroplienol
(a) Utu-uiltliracciiu vdb uBod an thu Internal
Huldtlvu resDon
Search
"''
146
91
117
130 .
77
180
82
93
128
162
152
154
161
165
204
149
169
178
202
184
149
228
252
149
252
183
100
66
153
292
246
81
272
128
119
94
122
162
196
142
184
198
266
6)
standard ul a
fe faclor • —
BwlBtlvu
Obtained
50 PS/1
0.411
—
0.206
--
0.184
0.406
—
0. 364
1.0(6
0.765
1.050
0.721
0.886
0.092
0.391
0.775
0.561
0.275
0.212
—
0.411
0.146
0.080
0.546
0.121
0.119
0.164
0.206
0.074
0.105
0.255
0.011
0.052
0.303
0.179
0.314
0.217
0.329
0.259
0.224
0.056
0.114
0.222
0.0559
luvel that uorrespuiuta
HbsuuBtie Factor
•it Clven tan
200 pi/1
0.448
0.320
0.220
0.056
0.275
0.400
0.170
0.462
1.041
0.772
1.085
0.705
0.872
0.131
0.190
0.809
0.518
0.240
0.224
0.014
0.523
0.119
0.061
0.779
0.098
0.145
0.194
0.198
0.080
0.110
0.260
0.021
0.071
0.304
0.165
0.318
0.221
0.341
0.261
0.220
0.1497
0.0211
0.176
0.0521
to 250 MS/I
uni of Infernal Standard Area iif
ellc.d)
500 PB/I
0.518
0.412
0.247
~
O.U3
0.414
0.414
O.SI9
1.067
.0.799
1.057
0.712
0.892
0.175
0.194
0.825
0.548
0.215
0.22!
0.011
0.575
0.151
0.094
1.041
0.119
0.148
0.22]
0.202
0.084
0.108
0.250
0.011
0.079
0.281
0.126
0.10B
0.218
0.329
0.246
0.202
0.596
0. IUO
0.0231
Coaiioiind
USD u of Belallvu Reaponaa Factor
Obtain.
5D MJ/1
6.1
9.9
«
1.1
1.9
1.9
3.1
1.8
1 .1
0.9
2.0
4.4
7.6
0.8
2.1
2.0
1.6
2.0
—
2.2
1.5
5.0
4.6
4.4
1.0
4.1
6.1
2.1
2.
2.
21.
7.
8.
7.
11.
5.
4.
3.
4.9
0.2
10.6
5.0
9.0
d at Given Level
200 m/l 500 IUJ/1
5.0 1.5
1.2
1.8
4.6 4.0
1.8
1.5
2.4
4.2
2.1
2.6
1.6
0.9
1.2
2.1
2.5
2.0
1.1
1.1
1.0
0.8
.2
.7
.5
.5
.7
4.8
~
.9
.8
__
.7
.1
.1
.8
.1
.5
.4
.5
.4
.2
.2
.1
.4
.4
.4
.1
.8
.0
0.6 2.2
4.2 4
1.7
1.6
1.9 3
1.2 1
11.7 11
2.1 1
5.7 !
4.0 1
7.9 I
4.8 1
2.4 :
1.9 1
.2
,J
.4
m j
.1
,g
.9
.6
.5
.7
.1
,1
.6
1.2 1.4
1.0 1
26.4
4.1 12
7.4 7
,
.5
.3
.1
Compound
ubl.iln.--d (ran live runt. uxci!|i| for IliOtfu I CUB plicnu.!. uh.cli t.iv (lit! uv.-ra^ of throe runt..
olum were 20. 80. and 20U n« which cor rut, pond to th« given Uvulu of W), 200. and 500 vg/1 la inUt.r
(b) Cavil v*jluv In uii j»o
(c) The tjauunti, Injucii:.]
prlgi LO ciiruci.no.
-------
TABLE 39. PRECISION DATA FOR GC-MS ANALYSIS OF SEMIVOLATILE ORGANICS
USING A PACKED COLUMN OVER A PERIOD OF 4 WEEKS (vg/1)
Relative Response
Factor Obtained at the
Given Level(a»b»c'
Percent Relative Stan-
dard Deviation Obtained
•at the Given Level
Compound
50
200
500
1,4-Dichlorobenzene
Bis ( 2-chloroethyl) ether
Hexachloroethane
N-Nitrosodipropylamine
Nitrobenzene
1,2, 4-Trichlorobenzene
Isophorone
Bis(2-chloroethoxy)methane
Naphthalene .
2-Chloronapthalene
Acenaphthylene
Acenaphthene
Dimethyl Fhthalate
2 , 6-Dinitr otoluene
4-Chlorophenyl Phenyl Ether
Diethyl Fhthalate
N-Nitrosodiphenylamine
(as Diphenylamine)
Phenanthrene (&/or Anthracene-DO)
Pyrene
Benzidine
Butyl Benzyl Fhthalate
Chrysene
3,3' -Dichlorobenzidine
Dioctyl Phthalate
Benzo(b and/or k)fluoranthene
A-BHC (Hexachlorocyclohexane)
Heptachlor
Aid r in
Heptachlor Epoxide
Tetrachlorobiphenyl
4, 4 '-DDE
Endrin
Endosulfan Sulfate
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4-Dime thy Iphenol
2 , 4-Dichlorophenol
2,4, 6-Tr ichlorophenol
4-Chloro-3-methyphenol
2 , 4-Dinitr ophenol
4 , 6-Dinitr o-o-cresol
Pentachlorophenol
4-Nitrophenol
(a) Din-anthracene was used as the
0.519
0.242
0.209
ND
0.228
0.533
ND
0.311
1.05
0.898
1.23
0.811
1.112
0.183
0.529
0.919
0.603
1.71
1.69
ND
0.625
1.25
0.369
1.12
1.21
0.195
0.128
0.169
0.141
0.509
0.447
0.028
0.109
0.295
0.182
0.200
0.173
0.372
0.294
0.221
ND
0.045
0.263
ND
internal
0.494
0.255
0.211
0.065
0.259
0.520
0.304
0.366
1.05
0.920
1.26
0.801
1.01
0.229
0.530
0.929
0.638
1.41
1.53
0.042
0.619
1.08
0.313
1.05
1.04
0.198
0.158
0.166
0.128
0.461
0.389
0.033
0.103
0.316
0.208
0.207
0.195
0.399
0.313
0.249
0.027
0.070
0.254
0.031
standard
0.354
0.192
0.154
0.033
0.190
0.354
0.153
0.259
0.691
0.616
0.838
0.528
0.682
0.159
0.348
0.596
0.420
0.932
0.997
0.014
0.393
0.667
0.176
0.728
0.624
0.133
0.115
0.114
0.093
0.300
0.260
0.019
0.066
0.330
0.225
0.211
0.211
0.398
0.309
0.266
0.075
0.151
0.254
0.035
at a level
17
29
15
-
36
12
-
37
14
12
15
11
11
24
12
20
13
13
8
-
19
22
37
13
22
9
23
43
16
8
6
60
23
9
7
12
6
9
8
8
—
64
29
—
20
25
16
32
24
15
26
20
18
16
16
14
14
18
14
16
13
7
9
25
14
23
34
25
26
11
22
29
18
9
8
32
35
10
9
5
9
9
9
5
93
28
15
32
17
37
33
10
35
17
54
29
20
19
16
18
14
16
16
16
15
13
14
41
20
29
41
16
32
20
34
37
27
11
21
60
68
10
9
7
14
10
12
10
15
9
15
14
that corresponds to
250 iig/1 in water prior to extraction.
(b) Relative response factor *> (Amt
(c) The amounts injected on column
of Int
were 20,
Std/Area
80, and
of Int Std)
200 ng which
x (Area of
Amt of
correspond
Compound/
Compound) .
to the
given levels of 50, 200, and 500 yg/1 in water prior to extraction.
(d) Average of 5 to 6 values.
(e) Average of 10 to 15 values.
ND = Not detected.
95
-------
TABLE 40. PRECISION DATA FOR GC-MS ANALYSIS OF SEMIVOLATILE ORGANICS
USING A CAPILLARY COLUMN OVER A PERIOD OF 2 WEEKS (ug/1)
Relative Response
Factor Obtained at the
Given Level(a»b»c)
Compound
50
200
500
X Relative Standard
Deviation Obtained
at the Given Level
50
200
500
Bls(2-chloroethyl)ether 0.462 0.578 0.513 11
1,4-Dichlorobenzene 0.868 0.825 0.629 2
1, 2-Dichlorobenzene 0.496 0.467 0.391 3
Bis(2-chloroisopropyl)ether 0.686 0.822 0.623 5
Hexachloroethane 0.114 0.095 0.123 6
N-nitrosodipropylamine 0.018 0.021 0.040 20
Nitrobenzene 0.083 0.107 0.058 11
Isophorone 0.360 0.564 0.629 14
Bis(2-chloroethoxy)methane 0.389 0.471 0.497 16
1,2,4-Irichlorobenzene 0.517 0.500 0.422 2
Naphthalene 1.659 1.709 1.002 5
Hexachlorobutadiene 0.260 0.251 0.211 4
Hexachlorocyclopentadiene 0.005 0.011 0.028 41
Acenaphthylene 0.999 1.081 0.939 6
Dimethyl Phthalate 0.326 0.468 0.549 21
Acenaphthene 0.827 0.930 0.794 5
2.4-Dinitrotoluene 0.008 0.013 36
Fluorene 0.878 0.977 0.792 4
4-Chlorophenyl Phenyl Ether 0.240 0.273 0.307 5
Diethyl Phthalate 0.218 0.352 0.478 17
4-Bromophenyl Phenyl Ether 0.129 0.148 0.189 1
Hexachlorobenzene 0.124 0.135 0.118 5
G-BHC (Lindane) 0.036 0.041 7
Phenanthrene 0.989 1.123 0.958 3
Dibutyl Phthalate 0.188 0.298 0.484 10
4,4'-DDE 0.097 0.126 0.162 2
Dieldrin 0.064 0.089 0.115 16
Endrin 0.002 0.006 0.007 29
4,4'-DDD 0.058 0.079 0.132 3
3,3'-Dichlorobenzidine 0.048 0.067 0.139 1
Bls(2-ethylhexyl) Phthalate 0.062 0.080 0.124 8
Dioctyl Phthalate 0.065 0.094 0.147 18
Fluoranthene 0.930 1.212 1.019 4
Chrysene 0.399 0.501 0.381 1
BenzoOOfluoranthene 0.315 0.382 0.297 6
Benzo(a)pyrene 0.340 0.423 0.299 6
Indeno(l,2,3-c,d)pyrene 0.170 0.238 0.154 4
Dibenzo(a,h)anthracene 0.211 0.330 0.186 7
Benzo(g,h,i)perylene 0.348 0.485 0.308 5
Phenol 0.160 0.527 0.288 4
2-Chlorophenol 0.063 0.290 0.303 24
2, 4-Dime thy 1 phenol 0.188 0.316 0.360 10
2,4-Dichlorophenol ND 0.147 0.126
2,4,6-Trichlorophenol ND 0.082 0.062
Pentachlorophenol ND 0.034 ND
36
23
23
45
33
33
38
42
33
13
21
6
27
11
20
10
38
7
3
21
11
15
14
2
18
11
26
39
17
21
12
15
5
11
11
13
13
16
18
53
51
36
66
72
75
3
8
4
3
4
6
14
6
3 •
2
13
4
13
7
3
10
6
1
7
1
2
6
8
3
8
8
2
3
4
1
2
4
4
3
2
1
2
1
7
3
17
26
-
(a) Dio~anthracene was used as the internal standard at the 100 ng level.
(b) Relative response factor = (Amt of Internal Standard/Area of
x (area of Compound/Amount of Compound) .
(c) The amounts injected were 20, 80, and 200 ng which correspond
levels of 50, 200, and 500 ug/1 in water prior to extraction.
(d) Average of 5 to 6 values.
(e) Average of 10 to 15 values. ND = Not detected.
Internal
to the
Standard)
given
96
-------
In calculating concentrations of compounds in waste samples and leach-
ates, average response factors were used; thus, the RSD of the response
factors obtained over several weeks gives an indication of variability in
compounds in a leachate that is attributable to variation in response factor.
In all these studies, the internal standard performance was used to judge
the validity of a particular analysis run. If the response (peak area count)
of the internal standard was different by more than a factor of two from
expected, the data for that run were ignored and the sample was reanalyzed.
METALS
The percent relative standard deviation (RSD) and percent recovery of
metals that were determined by inductively coupled argon plasma are shown in
Tables 41 and 42. The RSDs for the medium and high concentration are of the
order of 2 percent or less for most metals. Metals for which the RSD is
greater than 2 percent include boron, molybdenum, tin and antimony. The
behavior of these metals is erratic either because of blank problems (boron
in particular), because of their refractory nature (boron, molybdenum, and
tin), or because of typically poor performance (tin). Tin in acid solution
tends to precipitate as metastannic acid at the higher concentrations and may
have precipitated molybdenum by occlusion. The RSDs shown for the low
concentration range typically from about 1 to 15 percent, which is expected
because the concentrations are near the detection limits and thus more
subject to influence of variability of background than at higher concen-
trations. The RSDs above 15 percent are the result of background (blank)
concentrations that are greater than the spike concentration. Thus, the
analytical signal from the spiked concentration is overwhelmed by the blank
concentration in these cases.
The percent recovery data for the ICAP method show the recoveries of
spikes are generally in the range of 90 to 110 percent. The recoveries of a
few elements are outside this range for the same reasons that cause the
comparatively poor precision for the same elements.
The results for precision and recovery studies on the atomic absorption
spectrophotometric (AAS) method are shown in Tables 43 and 44. The pre-
cisions and recoveries at all concentrations are within the normal limits.
The relative standard deviations are somewhat higher than those shown for the
ICAP method. This result also is expected because the nebulizing system and
the excitation source for the ICAP are more stable and thus more repeatable
than the similar systems for the AAS.
The RSDs obtained for Tasks 5 and 6 (analyses of replicated leachings)
indicate expected larger RSDs as compared to the analysis method precision.
The variability of leaching is included in the calculated results from Tasks
5 and 6. The differences in RSDs appear to be a function of leaching method
rather than a function of concentration as is the case with the analysis
method studies. For example, for leachates from the baghouse dust sample,
Table 10, manganese was found at nearly the same concentration in all
97
-------
TABLE 41. PRECISION DATA FOR ICAP ANALYSIS OF METALS IN DISTILLED WATER
00
Element
Al
B
Da
De
Cd
Co
Cr
Cu
Fe
Pb
Mn
Mo
Nl
Sn
Tl
V
Y
Zn
Ag
As
Sb
Se
Tl
Amount
Found In
Blank (a>,
ug/l
271
692
6.0
1.3
0.9
1.4
5.8
43
105
20
3.1
6.4
45
-7.9(<=>
30
4.1
2.5
75
8.3
32
15
11
-59(c)
Amount Added
as Spike at
Given Level (b). vg.ll
Low
500
50
25
5
25
50
50
50
50
500
25
100
150
250
100
100
50
25
-
~
Med
2500
250
125
25
125
250
250
250
250
2500
125
500
750
1250
500
500
250
125
250
1250
1250
1250
1250
High
10000
1000
500
100
500
1000
1000
1000
1000
10000
500
2000
3000
5000
2000
2000
1000
500
1000
5000
5000
5000
5000
Amount Found
as Spike at
Given Level
-------
TABLE 42. PRECISION DATA FOR ICAP ANALYSIS OF METALS IN A
DISTILLED WATER LEACHATE FROM A POTW SLUDGE
VO
Amount Found
in Unspiked
Leachatew
Amount Added
as Spike at
Given Level(b). ug/j
Amount Found
as Spike at
Given Levelta»bJ. ue/t
Percent Recovery of
Spike at Given Level(a»°)
Percent Relative
Standard Deviation
Element
Al
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Pb
Mn
Mo
Ni
Sn
Ti
V
Y
Zn
AS
As
Sb
Se
Tl
ug/t
1390
1510
528
0.4
51
15
163
160
5300
259
972
9
250
25
36
9
8
3450
15
76
40
23
-7(0
Low
500
50
25
5
25
50
50
50
50
500
25
100
150
250
100
100
50
25
-
-
Mod
2500
250
125
25
125
250
250
250
250
2500
125
500
750
1250
500
500
250
125
250
1250
1250
1250
1250
High
10000
1000
500
100
500
1000
1000
1000
1000
10000
500
2000
3000
5000
2000
2000
1000
500
1000
5000
5000
5000
5000
Low
1890
336
553
5.9
71
65
206
101
5340
746
998
110
392
229
135
113
60
3390
—
~~
Med
3840
1030
658
28.5
174
268
409
318
5530
2730
1100
503
982
508
384
521
266
3520
91
1470
557
1390
1060
High
11300
1090
1060
111
554
1030
1170
1050
6310
10100
1513
1880
3220
2320
1220
2030
1030
4000
106
5160
2120
5400
4970
Low
98.9
-2350
99.3
110.4
81.3
100.1
87.7
-118
82.0
97.3
105.8
100.8
94.8
81.8
99.0
103.7
.103.6
-228
—
— "
Mod
97.8
-193
103.9
112.3
98.1
101.2
98.7
62.9
92.1
99.0
105.7
98.8
97.6
38.7
69.4
102.4
102.9
60.2
30.6
111.3
41.4
109.1
85.7
High
99.2
-42
105.8
111
100.5
101.4
100.4
88.9
100.7
98.2
108.2
93.3
98.9
46.0
59.1
100.9
101.9
110.9
9.1
101.7
41.6
107.6
99.6
a I. VI
Low
3.4
6.8
0.7
1.7
1.4
2.0
1.6
2.2
0.7
1.0
0.8
1.3
1.7
5.7
2.2
0.9
0.7
0.9
-
-
'.•.veil LfC V
Med
1.7
34
2.1
2.5
1.4
1.2
1.8
2.4
2.5
1.1
2.2
1.0
1.2
22.4
7.4
0.8
0.7
2.4
17.0
3.3
11.7
2.6
5.3
CJ. - — '
High
0.8
7.5
1.7
0.9
1.0
1.0
1.0
1.7
2.1
1.0
1.7
0.6
1.0
12.0
3.6
0.8
0.9
2.4
16.0
0.6
7.7
0.5
0.9
(a) Each value is the average obtained from five separate digests.
(b) Low = lOx detection limit; Med = 50x detection limit; High = 200x detection limit.
(c) Negative value indicates contamination in blank.
-------
TABLE 43. PRECISION DATA FOR AAS ANALYSIS OF METALS IN DISTILLED WATER
t-1
o
0
Element
Be .
Cd
Cr
Cu
Ni
Zn
"8
Amount Found
In Unaplked
Leachate(a),
ug/fc
<20
57
170
158
248
3340
<0.3
Amount Added
as Spike at
Given Level(b). yg.ll
Low Med • High
5
25
50
50
150
25
1.6
25
125
250
250
750
125
10
100
500
1000
1000
3000
500
25
Amount Found
as Spike at
Given Level(a.b), pg/e
Low
<20
93
240
130
360
3300
1.1
Med
29
180
440
370
720
3500
8.6
High
110
580
1300
1100
3200
4000
21
Percent Recovery of
Spike at Given Level(fl.b)
Low
—
140
136
(b)
72
(b)
71
Med
114
95
109
84
63
128
86
High
114
104
1'17
90
97
140
83
Percent Relative
Standard Deviation
at Given Level (b)
Lou
—
18
8.1
7.1
7.3
2.6
10.2
Med
4.5
6.5
19.0
4.9
6.5
3.5
4.1
High
4.8
4.4
4.1
5.2
3.6
6.0
5.6
(a) Number of replicates = 5.
(b) Spike level too low to be meaningful.
-------
TABLE 44. PRECISION DATA FOR AAS ANALYSIS OF METALS IN A
DISTILLED WATER LEACHATE FROM A POTW SLUDGE
Amount Added
as Spike at
Given Level (b). uR/fc
Element
Be
Cd
Cr
Cu
Ni
Zn
Hg
Low
5
25
50
50
150
25
1.6
Med
25
125
250
250
750
125
10
High
100
500
1000
1000
3000
500
25
Amount Found
as Spike at
Given Level(aib), gg/4
Low
<20
34
<100
<100
140
<20
1.4
Med
28
134
258
298
360
182
8.5
High
99
534
970
990
3120
520
22
Percent Recovery of
Spike at Given Level(a.b)
Low Med
. — 113
134 107
103
119
93 48
146
85 85
High .
99
107
97
99
104
104
88
Percent Relative
Standard Deviation
at Given Level (b)
Low Med
3.0
13 4.1
4.2
2.8
21 13.0
6.0
4.2 4.1
High
1.1
1.0
3.4
1.1
4.2
8.2
0
(a) Number of replications = 5.
-------
leachates (except one) but the RSDs for manganese varied from 86 percent for
the extraction procedure (EP) to less than 10 percent for sodium citrate
leachates using the NBS leaching device.
Recovery studies using spiked leachates show results (Table 22) similar
to those shown for the analysis method—usually between 90 and 110 percent
recovery. This result indicates that the elements extracted are determined
without apparent interelement interference even though the concentrations of
a few elements were relatively high. Thus, matrix interferences, if present,
were adequately controlled by the analysis system.
Improvement in assessing data quality would include replicate analyses of
replicate leachings. • This addition would add extra degrees of freedom and
would provide for opportunity for more formal statistical' evaluation of data.
Also, more could have been done in evaluating the variables in the
leaching procedure. For example, while many experiments would have been in-
volved, a study could have been made of effect of leach time, of leach tem-
perature, of solid to liquid ratio, of the number of leachings, and of the
value of adding internal standards to the waste before leaching. These ex-
periments would indicate which steps in the procedure are critical and what
degree of control is essential for each step.
102
-------
SECTION VIII
DISCUSSION
SELECTION OF WASTES
The Resource Conservation and Recovery Act covers an extremely broad
range of solid waste types in respect to composition and physical properties.
The amounts of water, solids, acids, bases, metals, total organics, extrac-
table organics, volatile organics, or immiscible oils that a waste contains
may range from less than one percent to nearly 100 percent. These
compositional differences can profoundly affect the physical properties of
the waste such as viscosity, dispersibility, wettability, filterability, and
water miscibility. Consequently the composition of a waste can profoundly
affect waste behavior in any batch leaching procedure that might be proposed
for assessing the potential mobility of components in the waste. Since an
objective of this program was the development of a solid waste leaching
procedure that would be applicable to as many different types of wastes as
possible, it was particularly important that types of wastes that might be
expected to cause problems in a leaching procedure be included in the study.
It was reasoned that if it could be demonstrated that a leaching procedure
could handle the more difficult types of wastes, it could be reasonably
expected that the procedure could handle most or all of the simple wastes
which are easier to handle.
A total of 23 different wastes became available for this program (see
Table 3). Nearly half of the wastes obtained^11' either contained at least
97 percent water or were completely miscible with water and therefore were
considered entirely unsuitable for the development of a solid waste leaching
procedure. Two of the wastes were oily wastes containing more than 20
percent oil. Since the oil would be almost completely mobile it was decided
that a total content analysis would sufficiently characterize the potential
mobility of such wastes. Consequently those two wastes were considered
inappropriate for the program. Three of the wastes, namely electroplating
sludge, fly ash, and baghouse dust, were expected to contain only trace
amounts of organic components. Since mobility of organic components was of
major importance in the program only one of these inorganic wastes, baghouse
dust, was selected for study. The pulp and paper sludge had a relatively
high solids content, 20 percent, but was excluded from the study because it
was expected to contain primarily cellulosic fiber and very few solvent
extractable organic priority pollutants.
The seven remaining wastes including baghouse dust were selected for at
least part of the study on the basis of relatively high solids content (>15
103
-------
percent) and with the exception of baghouse dust, the likelihood of con-
taining significant amounts of extractable organic compounds..
Dewatered POTW sludge from Cincinnati was selected for the Task 3 and
Task A studies because it represented a composite from many industries and
was expected to contain detectable amounts of a variety of organic and in-
organic priority pollutants. It was also available earlier in the program
than most of the other wastes that subsequently became of interest. The
organic still bottoms sample was of particular interest because it had a high
solids content and was expected to have a high extractable organic content.
This waste also represented a rather acidic waste. The coal gasification tar
waste was of interest because this viscous tar was expected to be a very
difficult material to work with in an aqueous leaching system. The ink
pigment waste was of interest because it was highly alkaline and unlike the
other wastes had a gelatinous consistency. The other two wastes selected, a
pharmaceutical waste and a latex paint sludge, had solids contents of about
15 percent and were expected to be high in extractable organic constituents.
Initial leaching studies showed that very few organic priority pollutants
were leached from these two samples. Consequently these wastes were given
less attention than the other selected wastes.
As described above, the wastes selected for the program covered a range
of pHs and physical consistencies. These wastes were high in solids content
and contained significant amounts of several organic and inorganic priority
pollutants. However, the available wastes did not include those representa-
tive of the more difficult to handle, more toxic, or more heterogeneous solid
wastes that are being generated by various industries. It would have been
helpful to have had additional such wastes available to challenge the
leaching procedure more severely.
SELECTION OF LEACHING MEDIA
The seventeen leaching media studied are described in Table 6. The
acetic acid titration, EP procedure, was used as a reference medium. The pH
and buffering capacity that it provides is intended to simulate those
parameters of municipal landfill leachates. Distilled water was used as a
second reference medium. Distilled water simulates rainwater and contains no
analytical interferences or components, such as acetate, that would be toxic
in a bioassay. The acetate and citrate buffered systems were designed to
provide a pH and acid capacity similar to that of the EP procedure when the
maximum amount of acetic acid is required. Citrate was used in place of
acetate to provide complexing ability, antioxidant or reducing activity, a
less soIvent-extractable acid, and possibly a less toxic medium. The effect
of changing pH, buffer capacity, and influence of ammonium ion was studied
using a variety of citrate media. Butyrate was used as a medium to determine
the effect of a more lipophilic component that is frequently present in
municipal landfill leachates. Ferrous sulfate and sodium hydrosulfite were
studied to determine the effect of reducing media. A detergent was studied
to simulate the effect of surface-active components such as soaps that might
be present in some landfill leachates. A nonionic detergent was used to
avoid any pH effects or inactivation by ionic species. The University of
104
-------
Wisconsin synthetic leachate was included as a medium that best simulates a
municipal landfill leachate despite the analytical interferences introduced.
It was concluded from the study that of the various media described
above, distilled water is the leaching medium of choice. It is nontoxic,
does not introduce any analytical interferences, is easy to use, and leaches
organic components as well as any of the other media studied. The various
media-containing citrate or acetate often leach much higher levels of metals
than are leached by distilled water but the increases vary over a wide range
depending upon the particular metal involved and the nature of the waste.
Ammonium citrate gave results similar to those of sodium citrate. The ammo-
nium ion would cause less analytical interference but would be considerably
more toxic in many bioassays. The addition of reducing agents or a detergent
had little significant effect. The addition of ferrous sulfate interfered
very significantly with the metal analyses. The University of Wisconsin
synthetic leachate contains this interference as well as pyrogallol which
interferes with the organic analysis and bioassays. The use of butyrate had
little effect on the leaching of metals. It also seriously interfered with
the organic analyses.
LEACHATE ANALYSIS METHODS
Metal Analyses
Methods used for sample preparation of leachates prior to analysis for
metals were taken from "Methods for Chemical Analysis of Waters and
Wastes."(42) Either Method 4.1.3 (HN(>3 digestion) or the HNC-3 -
H2^2 procedure for graphite furnace analysis was used, as described
previously.
Method 4.1.3 appeared to work well for most metals, as indicated by the
quantitative spike recoveries obtained. However less than quantitative re-
coveries were found for some elements, including molybdenum and tin. Low
recoveries for these elements occurred in the precision study with either
distilled water or POTW leachate as the matrix. The reason for low recov-
eries for these elements is not fully understood, although one possible ex-
planation is given under "Metals" in the Quality Assurance Section of this
report. Low recovery was also found for boron. It is likely that boron was
lost during the digestion step as the sample was .taken to near dryness.
It is recommended in "Sampling and Analysis Procedures for Screening of
Industrial Effluents for Priority Pollutants" that antimony be analyzed on
the sample prepared by Method 4.1.3. However, very low spike recoveries (<10
percent) were commonly found in samples prepared using this method. Con-
versely, spiked samples prepared using the HN03 - 8202 digestion recom-
mended for flameless analysis demonstrated quantitative recoveries. For this
reason, antimony was analyzed in samples prepared by the HNC-3 - H202
digestion method. Recovery of As, Sb, Se, and Tl were normally quantitative
using the HN03 - H2C>2 preparation also. Silver recovery was frequently
low, although the presence of chlorine in the samples is highly likely, re-
sulting in the precipitation of AgCl.
105
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Method 4.1.3 involves two steps that require interpretation by the
analyst. First, it is necessary to stop the digestion prior to complete
dryness of the sample. The final concentration found could be affected by
the point of termination, either due to incomplete digestion if halted too
soon or due to volatilization of some elements if allowed to become too dry.
Second, the reflux process is repeated an unspecified number of times, until
the "digestion is complete". The actual concentration found may be a
function of the number of reflux cycles used.
Volatile Organic Compounds
The CS2 extraction method used by Battelle was similar to the EPA
solvent extraction method used for trihaloraethanes in drinking water, except
for the following three major changes: (1) an SP-2100 glass capillary column
was used instead of a packed column—the improved resolution minimized the
possibility of interferences and the much higher temperature permitted most
of the high-boiling compounds to be eluted from the column at the end of each
run; (2) a flame ionization detector was used instead of an electron capture
detector—this change permitted aromatic hydrocarbons to be detected in addi-
tion to halocarbons; and (3) CSo was used as the solvent instead of
isooctane—this selection minimized the solvent peak and permitted compounds
as low-boiling as trans-1,2-dichloroethene, b.p. 48°C, to be resolved from
the solvent. The main disadvantage of the CS2 extraction method is that it
does not resolve methylene chloride and lower boiling compounds from the
solvent peak. A second disadvantage is that CS2 cannot be used with a
flame ionization detector when significant amounts of C$ to Cg saturated
and olefinic hydrocarbons or other interferences are present as in a
gasoline-containing sample. A saturated hydrocarbon solvent and an electron
capture detector or photoionization detector would need to be used in such
cases.
The CS2 extraction method offers the following important advantages
over the purge and trap GC-MS method:
(1) It requires less operator time—one person can easily extract 25 to
50 or more samples per day.
(2) It can be readily automated using automatic samplers in common use.
(3) It uses much less expensive instrumentation—GC instead of
computerized GC-MS.
(4) Quality control is easier to maintain because of the larger number
of runs that can be completed per day.
(5) Samples with extremely high levels of volatiles have much less of an
adverse effect on the instrumentation.
(6) Much higher-boiling components, in fact, any of the
CSo-extractable semivolatiles, can be determined along with the
volatile components in samples that do not contain significant
interferences.
106
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The results obtained on this program using the C&2 extraction method were
comparable to those obtained using the purge and trap method. The chromato-
graphic peaks obtained for volatile components were all sharp and well re-
solved from neighboring peaks.
The detection limit of the method is higher than the purge-and-trap
method by a factor of about 100 and higher than the semivolatiles method by a
factor of 10. Nevertheless, the detection limit is generally about 20 to
100 ug/1 which is adequate for most solid waste studies.
Semivolatile Organic Compounds
The method used for the solvent extraction of leachates and determination
of semivolatile organic priority pollutants was a simplified version of EPA
Method 625. The modifications were designed to decrease the number of steps
involved and decrease the amount of technician time required without
affecting precision or accuracy. The modifications were as follows:
(1) A 300-ml sample was used instead of 1000 ml.
(2) A single extraction with 50 ml of methylene chloride per 100 ml of
'water was used instead of three extractions each with 6 ml of •
methylene chloride per 100 ml of water.
(3) The extraction was performed only under acidic conditions Instead of
under basic conditions followed by acidic conditions.
(4) A single extract containing both the neutrals and acids was analyzed
using as SE-52 glass capillary column instead of analyzing two
separate fractions, base/neutrals and acids, using a 3 percent
SP-2250 packed column and a 1 percent SP-1240-DA packed column,
respectively.
Because of the smaller sample size, the detection limit of the modified
method was higher than Method 625 by a factor of five. Also, because of the
acidic conditions used for the extraction, benzidine was not recovered. In
all other respects the results were comparable to those obtained by
Method 625. The method is therefore considered suitable for most solid
wastes.
TOTAL CONTENT ANALYSIS METHODS
Metal Analyses
The total content digestion method used for metals in Task 6 was based on
a method developed by the University of Washington and modified by Southern
Research Institute. In this method an aliquot of the solid waste is placed
in a clean glass ampule. Concentrated nitric acid is added to the ampule
which is sealed and heated at 125°C for one hour. The digested sludge is
filtered and analyzed by atomic absorption or ICAP.
107
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The method requires a short digestion period, much shorter than most
sludge digestion methods. Spike recoveries for all elements examined were
quantitative. The sealed ampule permits a higher temperature to be used than
would be acceptable with open beaker digestion, without loss of volatile
metals. Once the samples are placed in the oven, it is not necessary to
constantly monitor the progress to prevent the digestion from going to dry-
ness. Since no HC1 is used, the digestion is useful for silver. In fact,
the single digestion is recommended for all elements; a considerable reduc-
tion in the time required for preparation over alternate methods requiring as
many as four separate digestions.
A major problem encountered with the application of this method involves
the transfer of the solid waste sample to the 25 ml ampule. The open end of
the ampule is approximately one-fourth inch in diameter. For samples con-
taining only small particles, the transfer is relatively simple. However,
for solid wastes containing larger particles or for samples of a mud con-
sistency, transfer is very difficult due to the restricted opening. Accurate
weighing of the sample is also difficult, and the sample frequently sticks to
the inner walls of the ampule neck. The sample must be removed from the neck
of the ampule in order to allow proper sealing. Further, it becomes
difficult to handle a potentially hazardous solid waste using recommended
safety precautions such as rubber gloves. The sample is easily spilled on
the balance and benchtop which must be carefully cleaned to prevent safety
hazards.
Although no ampules exploded in the studies reported here, the possi-
bility of a dangerous explosion must be considered when using concentrated
nitric acid in a sealed ampule. A program initiated during the reporting of
this leaching development study included the analysis of industrial waste
using the sealed-ampule method for metals. An explosion occurred in the oven
during the heating process which resulted in loss of all samples but did not
involve personal injury or property damage. For re-analysis the ampules were
individually placed in heavy containers made from pipe sealed at both ends.
This safety precaution involves increased material costs and analysis time,
however, the safety of the analyst and equipment is guaranteed. Appropriate
safety precautions should be incorporated for this method.
Although quantitative spike recoveries were obtained for the elements
analyzed in this study, further information is required to determine whether
this method is universally applicable to all elements to be analyzed in solid
wastes.
Volatile Organic Analysis
The CS2 extraction method used for total content analysis involved
dispersing the solid waste in water and treating it in the same manner as a
leachate. This approach is the same as that used for the purge and trap
method applied to total content analysis. The advantages and disadvantages
of the CS2 extraction method already discussed for leachate analysis also
apply to total content analysis. Since much greater quantities of extrac-
table components are often encountered in total content analyses, it may be
necessary to temperature program the GC column to a higher temperature, e.g.,
10S
-------
300°C, to ensure that most of the high-boiling components are eluted prior to
the next run. The high temperature does not adversely affect the silicone
capillary column used. However, this type of thermal cleaning of the GC
column could not be achieved with the conventional packed column for volatile
organics, 1 percent SP-1000 on Carbopak C, because of greater retentiveness
and much lower temperature limitation.
The CS2 extraction method worked very well for total content analysis
and gave results that were comparable to those from the purge and trap
method. The volatile components of concern appeared in the early portion of
the chromatograra where there were fewer potential interferences.
Semivolatile Organics
The total content method for semivolatile organics involves homogeniza-
tion of the sample in the presence of water with raethylene chloride as the
extracting solution. Base/neutrals are obtained by successive extractions
under basic conditions and acids are obtained by successive extractions under
acidic conditions. The two extracts are concentrated as separate fractions
and cleaned up by gel permeation chromatography (GPC).
During the process of concentrating the extracts or while the concentrate
stands at room temperature, insoluble material often precipitates. This pre-
cipitate can have two significant adverse effects. First of all it can in-
terfere with the GPC cleanup. The precipitate settles out at the top. of the
column and causes an irreversible darkening and loss of column efficiency if
manual column operation is used or it clogs up filters and valves if an auto-
mated operation is used. Secondly, it may serve as an adsorbent to remove
some of the components of interest, especially the more polar components, and
thus seriously affect the recovery efficiencies.
Recovery efficiencies also seem to be adversely affected by the presence
of water during the extraction step. Recoveries for the more polar
components, e. g., phenols and nitroaromatics, are often very poor and
detection limits are abnormally high. The six horaogenization-centrifugation-
solvent removal steps in the method were found to be quite tedious and
time-consuming.
Despite the above disadvantages of the method, the precision and accuracy
of the method, as indicated by recoveries achieved with spiked samples, were
generally adequate except for the more polar components.
FEASIBILITY OF IMPLEMENTATION
Leaching Method
The leaching method involves: (1) leaching a portion of the solid waste
with an aqueous medium and (2) analysis of the aqueous medium for organic and
metal components. In terms of apparatus and instrumentation, the analytical
step requires: (1) extraction and concentration apparatus, (2) a packed
>MS system with associated data handling system and software
109
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package, (3) a purge and trap apparatus interfaced to the GC-MS system, and
(4) a flame atomization atonic absorption spectrometer (AAS) or an
inductively coupled argon plasma spectrometer (ICAP). For mercury, a special
cold vapor purging apparatus interfaced to the AAS is required. The
requirements for conducting the analytical phase are essentially identical to
the wastewater priority pollutant methods, which are widely employed by a
number of production-type analytical laboratories.
Because of the complex and diverse nature of leachates from solid wastes,
cross contamination between sample extracts can be a problem. This problem
was observed for the purge and trap method for determining volatile organics.
For example, the use of this apparatus for analyzing still bottoms leachate
caused severe carry-over into subsequent samples, due to the high quantity of
volatile organics present. Since it is not possible to predict which
leachates may create such problems, it is essential that the operator run
frequent system blanks and examine the data from each sample for possible
contaminants from the previous sample. The CS2 extraction procedure for
volatile organics, described in the experimental section, circumvents this
problem since the same apparatus is not used for each sample.
The method for leachate generation requires the following apparatus and
instrumentation:
• An agitation device, such as the NBS tumblers used in this study
• Bottles (2-liter capacity) with Teflon-lined caps to fit the agitation
device
• A centrifuge, medium speed, capable of holding 200-ml glass bottles
• Centrifuge bottles
• Filter holder capable of being pressurized to 75 psi
• Various prefliters and membrane filters.
Except for the agitation device and filter apparatus, this equipment is
readily available in analytical laboratories conducting organic analytical
work. Both the NBS tumblers and filter apparatus can be readily purchased
for a total cost of approximately $2500. Therefore, availability of instru-
mentation should not be a significant problem for laboratories wanting to
implement the leaching method.
The highly diverse physical and chemical nature of solid wastes can be a
problem in the leachate generation step, since a single set of procedures for
filtration, and phase separation, may not be feasible for all types of
wastes. The leachate generation method (using the NBS tumblers) described in
the Experimental Section has been carefully devised to be applicable to as
wide a range of solid waste types as possible. However, there are probably
certain types of solid wastes which will cause some difficulty.
110
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One specific example is an oily waste sample, which creates the problem
of how to obtain a representative aliquot of the oily layers or film present
at the surface of the leachate. When a thin layer or film is present, it is
sometimes feasible to vigorously agitate the waste prior to withdrawing an
aliquot for analysis, although questions always arise as to how much of the
oil phase remained on the glass surface of the original container.
Problems can also arise from the presence of relatively large chunks
(1 cm diameter or more) of debris in the sample, since this debris can cause
the glass bottles to break during agitation. This problem can be
circumvented by using polypropylene bottles, although contamination problems
may arise for organic analysis.
A general problem in the area of solid waste analysis is how to obtain a
representative sample or subsample of a solid waste. Current methods address
this topic in only a general way, but specific sampling protocols for multi-
phase wastes, for example, need to be developed. This problem does affect
the feasibility of implementing the leaching method, although accurate re-
sults cannot be obtained if a representative sample is not obtained.
Total Content Method
The apparatus and instrumentation required to conduct the total content
method are identical to that required for the leaching method, except that
the leachate generation apparatus is not required. The primary problem im-
pacting on the feasibility of the method is the highly complex nature of the
solid wastes. Certain organic compounds may be present at percent levels,
thus overwhelming the smaller components in the chromatogram and contami-
nating the mass spectrometer. This problem can be severe in the purge and
trap method for volatiles, as discussed previously for the leaching method.
COST TO IMPLEMENT
In calculating a cost to implement the leaching method several
assumptions have been made:
(1) The analysis is to be conducted on a day to day basis. Therefore
instrument installation and setup are not included in the cost
estimate. However, instrument calibration has been included.
(2) A sample batch consists of a minimum of 10 waste samples and 2
quality control samples.
(3) A technician hourly rate (including all overhead and fee) is $25 and
a professional hourly rate is $40. GC-MS instruments cost $50/hour
and AAS costs $20/hour.
(4) AAS methods for metals will be used.
The costs for various steps in the procedure are listed in Table 45 on a per
waste sample basis.
Ill
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TABLE 45. ESTIMATED COSTS FOR ANALYZING TEN SAMPLES
USING THE SOLID WASTE LEACHING PROCEDURE
Professional Technician Instrument Total
. Materials Hours Hours Cost $
Leachate
Generation $20 0.2 4.0 10 138
Organic
Analysis
Volatiles . $20 1.5 2.0 100 230
Semivolatiles
Extraction $10 0.2 2.0 68
GC-MS $5 2.0 2.0 120 , 255
Inorganic
Analysis
Sample
Preparation $10 0.2 1.0 43
Analysis $5 0.2 4.0 40 153
Hg Sample
Preparation $15 0.2 0.4 33
Hg Analysis $5 0.2 0.4 20 33
QA Review 1.5 60
Data
Coordination
Project
Supervision
$90
2.0
1.5
9.7 hrs
80
60
15.8 hrs ?290 $1163
NOTES: The use of purge and trap rather than CS2 extraction for
volatiles will result in a cost increase of about $100/sample
because lower sample throughput will be obtained.
Use of ICAP for metals other than Hg will reduce the cost
by about $75/sample.
112
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REFERENCES
(1) Federal Register. Volume 43, pp 58946-59028, (Dec. 18, 1978).
(2) Qasim, S. R., and Burchinal, J. C., "Leaching of Pollutants from
Refuse Beds", J. Sanitary Eng. Div. Am. Soc. Chem. Eng., 96, 49 (1970).
(3) Qasim, S. R., and Burchinal, J. C., "Leaching from Simulated Landfills",
J. Water Poll. Control Fed., 42_, 371 (1970).
(4) Robertson, J., Toussaint, C. R., and Jorque, M., "Organic Compounds
Entering Ground Water from a Landfill", EPA-660/2-74-077, U.S.
Environmental Protection Agency, Washington, B.C., (1974), 56 pp.
(5) Burrows, W. D., and Rowe, R. S. "Ether Soluble Constituents of
Landfill Leachates", J. Water Poll. Control Fed., 47^, 921 (1975).
(6) Jones, C. J., Hudson, B. C., McGugan, P. J., and Smith, A. G., "The
Leaching of some Halogenated Organic Compounds from Domestic Waste",
.J. Haz. Materials, ^, 227 (1978).
(7) Chian, E. S. K., and deWalle, F. B., "Evaluation of Leachate Treatment,
Volume 1 Characterization of Leachate", EPA 600/2-77-186a, U.S.
Environmental Protection Agency, Cincinnati, Ohio (1977).
(8) Ham, R., Anderson, M. A., Stegmann, R., and Stanforth, R., "Background
Study on the Development of a Standard Leaching Test", EPA-600/2-79-109,
U.S. Environmental Protection Agency, Cincinnati, Ohio (1979) 274 pp.
(9) Ham, R. K., Anderson, M. A., Stanforth, R., and Stegmann, R., "The
Development of a Leaching Test for Industrial Wastes", in Land Disposal
of Hazardous Wastes, Proceedings of the Fourth Annual Research Symposium,
at San Antonio, Texas, March 6-8, 1978, EPA-600/9-78-016, U.S.
Environmental Protection Agency, Cincinnati, Ohio (1978), pp 33-46.
(10) Lowenbach, W., "Compilation and Evaluation of Leaching Test Methods",
EPA-600/2-78-095, U.S. Environmental Protection Agency, Cincinnati,
Ohio (1978), 111 pp.
(11) Rai, D., Serne, R. J., and Swanson, J. L., "Solution Species of
Plutonium in the Environment", J. Environ. Qual., 9_> 417 (1980).
(12) Means, J. L.,Crerar, D. A., and Duguid, J. 0., "Migration of Radioactive
Wastes: Radionuclide Mobilization by Complexing Agents", Science, 200,
1477 (1978).
113
-------
(13) Means, J. L.,Kucak, T., and Crerar, D. A., "Biodegradability of NTA,
EDTA, and DTPA and Environmental Implications", Envir. Poll., Series
B, 1, 45 (1980).
(14) Baas Beckling, L. G. M., Kaplan, I. R., and Moore, D., "Limits of the
Natural Environment in terms of pH and Oxidation-Reduction Potentials",
J. Geol., 6£, 243 (1960).
(15) Johansen, 0. J. and Carlson, D. A., "Characterization of Sanitary
Landfill Leachates", Water Research, 10, 1129 (1976).
(16) Raveh, A. and Avnimelech, Y., "Leaching of Pollutants from Sanitary
Landfill Models", J. Water Poll. Control Fed, 51, 2705 (1979).
(17) Ham,R. K., Anderson, M. A., Stegmann, R., and Stanforth, R.,
"Comparison of Trace Waste Leaching Tests", EPA-600/2-79-071,
U.S. Environmental Protection Agency, Cincinnati, Ohio (1979)
234 pp.
(18) Stanforth, R., Ham, R., and Anderson, M., "Development of a Synthetic
Municipal Landfill Leachate", J. Water Poll. Control Fed., 51, 1965
(1979).
American Society of Testing Materials (ASTM) Standard Methods
(19) (a) D346-78 Standard Method of Collection and Preparation of Coke
Samples for Laboratory Analysis.
(b) D420-69 (reapproved 1975) Standard Recommended Practice for
Investigating and Sampling Soil and Rock for Engineering Purposes.
(c) D140-70 (reapproved 1976) Standard Method of Sampling Bituminous
Materials.
(d) D1452-65 (reapproved 1972) Standard Method of Soil Investigation
and Sampling by Auger Borings.
(e) D2234-76 Standard Method for Collection of a Gross Sample of Coal
(f) Proposed Method for Leaching of Waste Materials - Water Shake
Extraction Procedure.
(g) Proposed Method for Leaching of Waste Materials - Acid Shake
Extraction Procedure
(h) Subcommittee D 19.12 Position Letter to Douglas Costle, December
1, 1978.
(i) Proposed New Standard Method for the Determination of Soil
Attenuation of Materials Extracted from Solid Wastes.
(20) "Test Methods for Evaluating Solid Wastes", SW-846, U.S. Environmental
Protection Agency, Washington, D.C. (1980).
114
-------
(21) deVera, E. R., Simmons, B. P., Stephens, R. D., and Storm, D. L.,
"Samplers and Sampling Procedures for Hazardous Wastes Streams",
EPA-600/2-80-018, U.S. Environmental Protection Agency, Cincinnati,
Ohio, (1980), 78 pp.
(22) Burd, R. M., and Riddle, J. M., "Final Report, Evaluation of Solid
Waste Extraction Procedures and Various Hazard Identification Tests,
September, 1979", EPA Contract No. 68-01-4725.
(23) Electric Power Research Institute, "Proposed RCRA Extraction Procedure:
Reproducibility and Sensitivity", November 1, 1979. 29 pp.
(24) Epler, J. L., et al., "Toxicity of Leachates", EPA-600/2-80-057,
U.S. Environmental Protection Agency, Cincinnati, Ohio (1980),
142 pp.
(25) Epler, J. L., et al., "Toxicity of Leachates, Interim Progress
Report, April 1, 1978 to January 1, 1979", IAG No. DOE-1AG-40-646-77/
EPA-IGA-78-D-X0372.
(26) Feiler, H. "Fate of Priority Pollutants in Publicly Owned Treatment
Works, Pilot Study", EPA-440/1-79-300, U.S. Environmental Protection
Agency, Washington, D.C., 1979.
(27) Francis, C. W., Maskarinec, M. P., Epler, J. L., and Brown, D. K.,
"The Utility of Extraction Procedures and Toxicity Testing with
Solid Wastes" in Disposal of Hazardous Waste. Proceedings of the
Sixth Annual Research Symposium, at Chicago. Illinois. March 17-20,
1980. EPA-600/9-80-010, U.S. Environmental Protection Agency,
Cincinnati, Ohio (1980), pp 39-45.
(28) Houle, M. J., and Long, D. E., "Accelerated Testing of Waste
Leachability and Contaminant Movement in Soils", in Land Disposal
of Hazardous Wastes. Proceedings of the Fourth Annual Research
Symposium, at San Antonio. Texas. March 6-8. 1978. EPA-600/9-78-016,
U.S. Environmetnal Protection Agency, Cincinnati, Ohio (1978),
pp 152-168.
(29) Houle, M. J., and Long, D. E., "Interpreting Results from Serial
Batch Extraction Tests of Wastes and Soils", in Disposal of Hazardous
Waste. Proceedings of the Sixth Annual Research Symposium, at Chicago,
Illinois, March 17-20. 1980, EPA-600/9-80-010, U.S. Environmental
Protection Agency, Cincinnati, Ohio (1980), pp 39-45.
(30) Sun, C. C., and McAdams, J. T., "Assessment of RCRA/EP Test Results
on FBC Residue, Part II — Proposed Procedure in Federal Register,
December 18, 1978", Westinghouse R&D Center, May, 1979.
(31) Engineering Scinece, "Analysis of Selected Trace Metals in Leachate
from Selected Fossil Energy Materials, Final Report, Phase II
Collaborative Test Program", January 1980.
115
-------
(32) Midwest Research Institute, "Analytical Methods for the Analysis
of Priority Pollutant Metals in POTW Sludges", EPA Contract No.
68-03-2695, November 1979. .
(33) Midwest Research Institute, "Development of Analytical Test Procedures
for the Measurement of Organic Priority Pollutants in Sludges and
Sediments", EPA Contract No. 68-03-2695
(a) Progress Reports No. 1 to 10, August 17, 1978 to November 30, 1979.
(b) Special Reports No. 1 to 5, June 26, 1979, to June 16, 1980.
(34) Midwest Research Institute, "Effluent Guidelines Division POTW
Sampling and Analysis", EPA Contract No. 68-03-2565, Progress Reports
No. 1 to 7, July, 1978 to December, 1979.
(35) Stephens, R. D., and deVera, E. R., "Analysis of Hazardous Waste"
in Disposal of Hazardous Waste. Proceedings of the Sixth Annual
Research Symposium, at Chicago. Illinois. March 17-20. 1980.
EPA-600/9-80-010, U.S. Environmental Protection Agency, Cincinnati,
Ohio, (1980), pp 15-20.
(36) deWalle, F. B., Zeisig, T. Y., and Chian, E. S. K. "Analtyical
Methods Evaluation for Applicability in Leaching Analysis", in
Municipal Solid Waste Land Disposal, Proceedings of the Fifth
Annual Research Symposium, at Orlando. Florida. March 26-28. 1979.
EPA-600/9-79-023a, U.S. Environmental Protection Agency, Cincinnati,
Ohio (1979), pp 176-185.
(37) Warner, J. S., Jungclaus, G. A., Engel, T. M., Riggin, R. M., and
Chuang, C. C., "Analtyical Procedures for Determining Organic
Priority Pollutants in Municipal Sludges", EPA-600/2-80-030, U.S.
Environmental Protection Agency, Cincinnati, Ohio, 1980, 55pp.
(38) deWalle, F. B., Chian, E. S. K. , et al. "Presence of Priority
Pollutants in Sewage and their Removal in Sewage Treatment Plants",
Annual Report, June 1, 1978 to July 31, 1979", EPA Grant R 806102.
(39) Gulledge, W. P., and Webster, W. C., "ASTM Leachate Test Evaluation
Program", EPRI FP-1183, September 1979.
(40) Anderson, M. A., Ham, R. K., Stegmann, R., and Stanforth, R.
"Test Factors Affecting the Release of Materials from Industrial
Wastes in Leaching Tests", in Toxic and Hazardous Waste Disposal —
Stabilization/Solidification, Vol. 2, R. B. Pojasek, ed., Ann Arbor
Science, Ann Arbor, Michigan, (1979), pp. 145-168.
(41) Ham, R. K., Anderson, M. A., Stegmann, R., and Stanforth, R.,
"Comparison of Three Waste Leaching Tests, Executive Summary,
EPA-600/8-79-001, U.S. Environmental Protection Agency, Cincinnati,
Ohio, (1979), 30 pp.
116
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(42) Methods for Chemical Analysis of Water and Wastes EPA-600/4-79-020,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio,
(1979).
(43) Federal Register. Volume 44 pp 69532-69552, (December 3, 1979).
(44) Martin, T. D., and Kopp, J. F., AA Newsletter, 14, 109 (1975).
(45) "Handbook for Analytical Quality Control in Water and Wastewaters",
EPA-600/4-79-019, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio, (March 1979).
117
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APPENDIX
SOLID WASTE LEACHING PROCEDURE
(Battelle's Columbus Laboratories, November 1, 1980)
Scope and Application
This method describes a procedure for leaching waste materials with an
aqueous medium to obtain a solution that can be analyzed to determine
the components leached under the specified testing conditions.
1.2. This method is applicable to the preparation of a leachate that can be
used to assess the potential mobility of chemical components from a
solid waste placed in a landfill.
1.3. The particular aqueous leaching medium selected should reflect the most
severe conditions expected at the specific landfill site of concern.
1.4. It should not be presumed that the method will give a leachate
generated under controlled laboratory conditions that is the same as
the actual leachate produced under variable conditions from a waste in
the field.
2. Summary of Method
2.1. A 75-g sample of the waste is mixed with 1500 ml of a selected aqueous
medium in a closed container and leached by tumbling the mixture in an
end over end fashion for 20 hours.
2.2. The mixture is centrifuged and filtered to give an aqueous solution
that can be analyzed to determine the components that were leached from
the waste.
3. Interferences
3.1. Small amounts of water-immiscible oils or organic solvents present in
the waste that might contribute significantly to the potential mobility
of certain hazardous components may be removed during the
centrifugation and filtration steps. The final leachate in such a case
cannot be used to assess the total potential mobility of hazardous
components in the waste. Large amounts of water-immiscible oils or
organic solvents present in the waste may become part of the final
leachate and make it difficult or impossible to obtain representative
aliquots of the leachate for analyses. These constituents may also
destroy the cellulose ester membrane- filter used in the filtration
step. Any water-immiscible liquid phase present in a waste should be
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separated out prior to leaching and analyzed separately for total
content to determine possible influence on the potential mobility of
hazardous components.
3.2. Sample containers, centrifuge bottles, filtration assembly, reagents,
and distilled water used must be demonstrated to be free from
interferences that might be present in leachates at the minimum levels
of interest.
3.3. Significant amounts of highly volatile organic constituents, e.g. vinyl
chloride or raethylene chloride, may be inadvertently lost from the
leachate during sample transfers. However, because varying amounts of
such components will undoubtedly be lost during landfilling and
sampling, the method is not intended to retain them completely.
4. Apparatus and Materials
4.1. Tumbler: a device that is capable of holding one or more tumbler
bottles and turning them end over end approximately 30 times per
minute, such as the four-place tumbler designed by National Bureau of
Standards which is available from Associated Design and Manufacturing
Company, Alexandria, Virginia.
4.2. Tumbler bottle: 1800- to 2500-ml wide-mouth screw-cap bottle (e.g.
Wheaton'No. 348522 roller culture vessel). Caps must be lined with
Teflon.
4.3. Centrifuge: capable of holding four or more 200-ml centrifuge bottles
and operating at 2000 rpm (e.g. IEC No. 7165).
4.4. Centrifuge bottles: 200-ml screw-cap bottles (e.g. Corning No. 1261).
Cap must be lined with Teflon.
4.5. Filter holder: 142mm diameter with 1.5 liter reservoir capable of
being pressurized to 75 psi (e.g. Millipore No YT30142HW).
4.6. Glass fiber prefilter pads: fine 124-mm (e.g. Millipore No. AP15-124)
and coarse 124-mm (e.g. Millipore No. AP25-124).
4.7. Nitrocellulose membrane filter: 142-mm (e.g. Millipore No. HAWP-142).
4.8. Sample vial: 40-ml capacity with screw-cap (e.g. Pierce No. 13075).
4.9. Sample vial septum: Teflon-faced silicone (e.g. Pierce No. 12722).
4.10 Syringe: 50-ml glass hypodermic syringe with Luer-Lok tip.
4.11 Wide-bore syringe needle: 20-cm 16-guage stainless steel needle (e.g.
Bolab No. BB829).
4.12 Glass sample bottles: 500-ml or 1-liter narrow-mouth bottles with
Teflon-lined screw caps.
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4.13 Polypropylene sample bottles: 500-ml or 1-liter screw-cap bottles.
5. Reagents
5.1. Leaching media: one or more of the following solutions may be used.
5.1.1. Distilled water: water that is demonstrated to be free of organic
and inorganic interferences at the minimum levels of interest in the
subsequent leachate analyses that will be performed.
5.1.2. Acetate buffer: 0.1 M, pH 4.0; 8.2 g of sodium acetate trihydrate
(ACS) and 5.7 ml of glacial acetic acid (ACS) per liter in distilled
water.
5.1.3. Citrate buffer: 0.05 M, pH 5.0; 10.5 g of citric acid monohydrate
(ACS) and 4.0 g of sodium hydroxide (ACS) per liter in distilled
water.
5.1.4. Citrate buffer containing 0.01 percent Igepal CO-630: 0.05 M, pH
5.0; 10.5 g of citric acid monohydrate (ACS), 4.0 g of sodium
hydroxide (ACS), and 0.1 g Igepal CO-630 per liter in distilled
water. Igepal CO-630 is a nonionic detergent produced by GAP
Corporation.
5.2. Nitric acid (1 -I- 1) (ACS)
6. Sample Collection, Preservation, and Handling
6.1. A representative sample of the waste to be tested should be obtained by
using an ASTM standard method that can be applied satisfactorily (e.g.
D140-70, D346-75, D420-69, D1452-65, or D2234.-76) or by using methods
described in "Samples and Sampling Procedures for Hazardous Waste
Streams" EPA 600/2-80-018, January 1980. It is particularly important
that the sample be representative with respect to surface area and
solids contents which directly affect the leaching characteristics.
6.2. A minimum sample of 5000 g should be collected and sent to the
laboratory in a closed container that will not be attacked by the waste
material. In most cases a polypropylene container will be suitable.
6.3. Samples which have not been biologically or chemically stabilized, i.e.
those that might undergo significant biological or chemical change at
room temperature, should be maintained at 0-5°C, including shipping,
and leached within 48 hours. Stabilized samples may be shipped and
stored at room temperature.
7. Leachate Generation
7.1. Crush or cut the sample as necessary to reduce the particle size to
approximately 1 cm. Avoid excessive particle size reduction.
7.2. Take a 75-g representative sample of the waste to be tested and place
it in an extraction bottle with 1500 ml of leaching medium. Tighten
the cap on the bottle and tumble the mixture at 20-40°C for 20 ± 2
hours.
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7.3. Transfer as much of the mixture as required for subsequent analyses to
200-ml glass centrifuge bottles. Shake the mixture immediately prior
to filling the centrifuge bottles if necessary to obtain representative
samplings of any oil-water dispersions. Centrifuge at approximately
1500 RCF for 30 minutes at 20-30°C. (Note: This centrifugation step
can be deleted if the subsequent filtration step can be performed
without excessive clogging of the filters. In most cases the mixture
can simply be allowed to stand for 30 minutes and the supernatant used
for volatiles analysis and for the filtration step.)
7.4. Obtain a sample for volatiles analysis by completely filling a 40-ml
vial with the supernatant from one of the centrifuge bottles from 7.3.
Fill the sample vial in such a manner that no air bubbles pass through
the sample as the vial is being filled. If the centrifuged sample
contains any oil, organic solvent, or particulate material floating on
top of the water, use a syringe with a wide bore needle to withdraw the
sample from the water layer below such material. Do not attempt to
analyze the oil or organic solvent layer. Seal the vial with a Teflon-
faced septum and screw-cap and store it at 0-5°C in an inverted
position until the time of analysis.
7.5. Process the remaining supernatant from 7.3 for metals and semivolatiles
analysis. If a discrete oil or organic solvent layer is present trans-
fer the layer to a tared bottle using a disposable pipette, determine
the weight, and analyze it separately if necessary.
7.6. Decant the aqueous supernatant and filter it through one of each type
of glass fiber prefilters and a 0.45 y membrane filter. Determine the
weight or volume of the filtrate. Use the filtrate for semivolatiles
analyses and metals analyses. Store the portion of the filtrate that
is to be used for semivolatiles analyses in glass bottles with Teflon-
lined screw-caps at 0-5°C until time of analysis. To the portion of
the filtrate that is to be used for metals analyses add (1 + 1) HN03
to lower the pH to <2 and store at room temperature in screw-cap
polypropylene bottles.
3. Quality Control
8.1. Before leaching any waste samples, demonstrate through the complete
processing of a method blank that no analytical interferences will
result.
8.2. Process one method blank for every set or every ten samples analyzed.
8.3. For every ten samples of a single type of waste, process at least one
sample in triplicate.
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