DRAFT
C0701-1TOC/UST
2/5/88 1
CHARACTERISTIC WASTE DESIGNATION OF SOILS
CONTAMINATED WITH PETROLEUM PRODUCTS
DRAFT REPORT
FEBRUARY 5, 1988
EPA Contract No. 68-01-7381
MRI Project No. 8900-07-54
Prepared for:
Mr. Michael R. Ka11nosk1
Policy and Standards Division
Office of Underground Storage Tanks
U. S. Environmental Protection Agency
401 M Street SW
Washington, O.C. 20460
-------
' L--~ /
Rl$
MIDWEST RESEARCH INSTITUTE
Suite 35!
401 Harrison Oaks Boulevari
Carv N C 275'
April 6, 1988
Mr. James DeLong
Third Floor
1029 Vermont Avenue, N.W.
Washington, D.C. 20005
Dear Mr. DeLong,
Mr. Michael Kal1nosk1 of the U.S. EPA Office of Underground Storage
Tanks requested that I send to you a copy of the report our office
prepared entitled "Characteristic Waste Designation of Soils Contaminated
With Petroleum Products." This draft report has not been through complete
peer review. This review process 1s currently being conducted and the
revised final report 1s anticipated to be 1n the OUST docket on April 15,
1988. Should you have any questions about the content of this report,
please call me at (919)467-5215 or Michael Kal1nosk1 at (202)382-7989.
Sincerely
iwnet H. Dean
Environmental Scientist
-------
DRAFT
C0701-1T0C/UST
2/5/88 11
PREFACE
This report describes work performed by Midwest Research Institute
(MRI) under EPA Contract No. 68-01-7383, MRI Project Number 8900-57-L.
This work Involved the performance of the Toxicity Characteristic Leaching
Procedure on two son types that had been contaminated with petroleum
products, as well as a discussion of the regulatory impacts of the
results. This report has been prepared 1n accordance with directions
provided by the Office of Underground Storage Tanks, U. S. Environmental
Protection Agency.
APPROVED BY:
MIDWEST RESEARCH INSTITUTE
Lloyd T. Taylor
Director
11
-------
DRAFT
C0701-1T0C/UST
2/5/88 111
TABLE OF CONTENTS
Page
LIST OF FIGURES
LIST OF TABLES
EXECUTIVE SUMMARY 1
SECTION 1.0 INTRODUCTION 3
SECTION 2.0 DATA PRESENTATION 5
2.1 SOIL CHARACTERIZATION 5
2.2 CONTAMINATED SOIL PREPARATION 5
2.3 FUEL CHARACTERIZATION 5
2.4 CONTAMINATED SOIL CHARACTERIZATION 6
2.5 IGNITABILITY CHARACTERISTIC TESTS 7
2.6 TOXICITY CHARACTERISTIC LEACHING PROCEDURES
(TCLP) TEST 7
SECTION 3.0 REGULATORY ANALYSIS 9
3.1 IGNITABILITY CHARACTERISTIC 9
3.2 TOXICITY CHARACTERISTIC 9
3.3 IMPACTS OF THE PROPOSED TC REGULATION 9
3.4 IMPACT OF TOXICITY CHARACTERISTIC ON THE
HAZARDOUS SUBSTANCE TANKS 10
3.5 APPENDIX VIII IMPACTS 11
3.6 CERCLA REPORTABLE QUANTITY IMPACTS 12
SECTION 5.0 REFERENCES 14
APPENDIX A. TCLP ANALYSIS RESULTS AND QA/QC PROCEDURES A-l
A.l MATERIALS AND METHODS A-l
A.1.1 Soil Characterization A-l
A. 1.2 Sqo1l/Fuel Products Mixing A-2
A.1.3 Determination of Characteristic of
Ign1tab1l1ty of Fuel-Contaminated
Soils A-2
A.1.4 Toxic Characteristic Leaching Procedure
(TCLP) A-3
A.1.5 Analysis A-3
111
-------
DRAFT
C0701-1T0C/UST
2/5/88 1v
TABLE OF CONTENTS
Page
A.2 RESULTS AND DISCUSSION A-5
A.2.1 Soil Characterization A-5
A.2.2 Soil/Fuel Product Mixing Results A-6
A.2.3 Characteristic of Ign1tab1l1ty Results... A-6
A.2.4 Analytical Results A-6
A.3 QUALITY ASSURANCE/QUALITY CONTROL A-14
A.3.1 Volatile Organic QA/QC A-15
A.3.2 SemlvolUe QA/QC A-17
A.4 REFERENCES FOR APPENDIX A A-21
1 v
-------
DRAFT
C0701-1T0C/UST
2/5/88 v
LIST OF FIGURES
Page
Figure A-l. Leachate/nomlnal soil concentration plots of
volatile aromatic analytes 1n Action topsoll/
diesel mixtures A-
Flgure A-2. Leachate/nomlnal soil concentration plots of
semivolatile aromatic analytes 1n Action topsoll/
diesel mixtures A-
Flgure A-3. Leachate/nomlnal soil concentration plots of
semlvolatlle aromatic analytes 1n Action topsoll/
diesel mixtures A-
Flgure A-4. Leachate/nomlnal soil concentration plots of
volatile aromatic analytes 1n Action topsoll/
gasoline mixtures A-
Flgure A-5. Leachate/nomlnal soil concentration plots of
semlvolatlle aromatic analytes 1n Action topsoll/
gasoline mixtures A-
Flgure A-6. Leachate/nomlnal soil concentration plots of
volatile aromatic analytes 1n Kaw River soil/
diesel mixtures A-
Flgure A-7. Leachate/nomlnal soil concentration plots of
semlvolatlle aromatic analytes 1n Kaw River soil/
diesel mixtures A-
Flgure A-8. Leachate/nomlnal soil concentration plots of
semlvolatlle aromatic analytes 1n Kaw River soil/
diesel mixtures A-
Flgure A-9. Leachate/nomlnal soil concentration plots of
volatile aromatic analytes in Kaw River soil/
gasoline mixtures A-
Flgure A-10. Leachate/nomlnal soil concentration plots of
semlvolatlle aromatic analytes 1n Kaw River soil/
gasoline mixtures A-
v
-------
DRAFT
C0701-1T0C/UST
2/5/88 v1
LIST OF TABLES
Page
TABLE 1. SOIL CHARACTERIZATION RESULTS FOR KAW RIVER SOIL
AND ACTION TOPSOIL
TABLE 2. CONCENTRATIONS OF THE SOIL/FUEL PRODUCT MIXTURES
TABLE 3. VOLATILE AND SEMIVOLATILE ORGANIC TARGET ANALYTE
CONCENTRATIONS IN UNLEADED GASOLINE, DIESEL FUEL,
AND NO. 6 FUEL OIL
TABLE 4. IGNITABILITY TEST RESULTS FOR FUEL CONTAMINATED
SOILS
TABLE 5. CONCENTRATIONS OF PROPOSED TCLP COMPOUNDS IN GASOLINE
CONTAMINATED SOIL SAMPLES AND LEACHATE
TABLE 6. PROJECTED HAZARDOUS SOIL CONCENTRATIONS OF PURE
TOLUENE AND BENZENE
TABLE 7. HAZARDOUS SUBSTANCES STORED IN UST's BY NUMBER
OF TANKS
TABLE 8. CONCENTRATIONS AND REPORTABLE QUANTITIES OF HAZARDOUS
SUBSTANCES FOUND IN PETROLEUM PRODUCTS
TABLE A-l. SOIL CHARACTERIZATION RESULTS FOR KAW RIVER SOIL AND.. A-
ACTION TOPSOIL
TABLE A-2. CONCENTRATIONS OF SOIL/FUEL PRODUCT MIXTURES A-
TABLE A-3. IGNITABILITY TEST RESULTS FOR FUEL CONTAMINATED
SOILS A-
TABLE A-4. VOLATILE AND SEMIVOLATILE ORGANIC TARGET ANALYTE
CONCENTRATIONS IN UNLEADED GASOLINE, DIESEL FUEL,
AND NO. 6 FUEL OIL A-
TABLE A-5. THEORETICAL CONCENTRATIONS OF SELECTED TARGET
ANALYTES IN ACTION TOPSOIL/FUEL MIXTURES AT THE
VARIOUS NOMINAL CONCENTRATIONS A-
TABLE A-6. THEORETICAL CONCENTRATIONS OF SELECTED TARGET
ANALYTES IN KAW RIVER SOIL/FUEL MIXTURES AT THE
VARIOUS NOMINAL CONCENTRATIONS A-
TABLE A-7. CONCENTRATIONS OF CONTAMINATED ACTION TOPSOIL
LEACHATE A-
v1
-------
DRAFT
C0701-1T0C/UST
2/5/88 v11
LIST OF TABLES (continued)
Page
TABLE A-8. CONCENTRATIONS OF CONTAMINATED KAW RIVER SOIL
LEACHATE A-
TABLE A-9. RESULTS OF RECOVERY CALCULATIONS FOR TCLP OF FUEL-
CONTAMINATED ACTION TOPSOIL A-
TABLE A-10. RESULTS OF RECOVERY CALCULATIONS FOR TCLP OF FUEL-
CONTAMINATED KAW RIVER SOIL A-
v i 1
-------
DRAFT
C0701-1/UST
2/5/88
EXECUTIVE SUMMARY
BACKGROUND
The quantity of soil contaminated by releases of petroleum products
froai underground storage tanks 1s potentially very large. These soils
could be classified as hazardous waste based on the "conta1ned-1n" policy
defined by OSW 1f they exhibit a hazardous characteristic. Under existing
regulations, the characteristic that soil contaminated with fuel products
1s likely to exhibit 1s that of 1gn1tab1l1ty. However, 1n June 1986, EPA
proposed amending Its hazardous waste Identification regulations by
expanding the Toxicity Characteristic to Include additional chemicals,
several of which are constituents of fuel products.
OBJECTIVE
The objectives of this study were to determine 1f soils contaminated
with petroleum products would be classified as hazardous under the
1gn1tab1l1ty characteristic or the proposed toxicity characteristic, to
examine the Implications of regulating these soils as hazardous waste, and
to develop recommendations for regulating these soils. To determine
whether soils were hazardous, sandy and clayey soil samples were
contaminated with up to 10,000 ppm of unleaded gasoline, dlesel fuel, and
No. 6 fuel oil. The samples were subjected to both the 1gn1tab111ty and
toxicity characteristic test procedures. Toxicity characteristic
leachates were analyzed for selected RCRA hazardous products, RCRA
Appendix VIII compounds, and compounds subject to proposed CERCLA
reportable quantity requirements.
RESULTS OF CHARACTERISTIC TESTS
• None of the contaminated soils exhibited the 1gn1tab1l1ty
characteristic.
• Benzene concentrations 1n leachates from some gasoline
contaminated soils exceeded the proposed TCLP regulatory level of
70 ug/L. Hazardous leachate was produced from sandy soil contaminated
with 1,000 to 10,000 ppm of gasoline. No other gasoline constituents
exceeded proposed regulatory levels. However, for the most contaminated
sandy soil sample, the toluene concentration was within 10 percent of the
proposed regulatory level of 14,400 ug/L.
1
-------
DRAFT
C0701-1/UST
2/5/88
• Leachates from soil contaminated with up to 10,000 ppm of dlesel
fuel and No. 6 fuel oil did not exceed any of the proposed TCLP regulatory
levels.
• Napthalene was the only Appendix VIII compound (other than benzene
and toluene) that was detected 1n TCLP leachates. It was detected 1n
leachates from both sandy and clayey soils contaminated with each of the
fuels.
EFFECT OF REGULATIONS ON CONTAMINATED SOIL MANAGEMENT
• Soil contaminated up to Its saturation point by a fuel product
release would not be hazardous based on the 1gnitab1l1ty characteristic.
• The quantity of contaminated soil that could be classified as
hazardous under the toxicity characteristic 1s not known, but 1t 1s
estimated that 33,000 UST systems containing gasoline may be leaking.
Thus, 1t might be necessary to manage a very large quantity of hazardous
soil 1f the proposed TCLP amendment 1s promulgated.
• Because benzene, a volatile compound, was the only constituent
detected 1n the TCLP leachates above proposed regulatory levels, treatment
techniques such as air stripping and vacuum extraction could be viable
alternatives to disposal of the hazardous soil 1n Subtitle C landfills.
• Releases from UST's containing benzene or toluene as pure product
may produce a larger quantity of contaminated soil than an equivalent
volumetric release of gasoline.
• Because napthalene, an Appendix VIII constituent, was detected 1n
the leachates from soils contaminated with each of the fuels, an
Implementing Agency could classify as hazardous those soils that would not
be hazardous under the toxicity characteristic.
• Fuel releases that did not generate hazardous soils could still be
subject to proposed CERCLA reportable quantity requirements. Gasoline
releases of about 100 gallons would contain a reportable quantity of
benzene. Diesel fuel and No. 6 fuel oil releases of 27,000 gallons and
125,000 gallons, respectively, would contain reportable quantities of
napthalene.
2
-------
DRAFT
C0701-1/UST
2/5/88
1.0 INTRODUCTION
The U. S. Environmental Protection Agency (EPA) Office of Underground
Storage Tanks (OUST) 1s responsible for developing programs for regulating
underground storage tanks that contain petroleum products and hazardous
substances. Under Subtitle I of the Resource Conservation and Recovery
Act (RCRA), the EPA must promulgate standards for release detection,
recordkeeping, reporting, corrective action, and closure for new and
existing tanks. They must also promulgate standards for design, construc-
tion, Installation, and compatibility of new tanks.
To develop these standards 1t 1s Important to know what
concentrations of contaminants 1n soils constitute a hazard and what the
Implications are of regulating such soils as hazardous waste. Currently,
soils contaminated with petroleum products could be classified as
hazardous 1f they were to fall the criteria for the 1gn1tab1l1ty
characteristic (40 CFR 261.21). Also, these soils could be classified as
hazardous 1f they were to fall existing toxicity characteristics. The
current toxicity characteristic leaching procedure or the EP toxicity
procedure 1s based on levels of metals and pesticides. The only metal of
concern to petroleum product tank owners would be lead and 1t 1s not
expected to be present 1n significant enough concentrations to result 1n
test failure. However, the toxicity characteristic proposed by the Office
of Solid Waste (OSW) (51 FR 21648, June 13, 1986) Includes a number of new
organic compounds. Some of these compounds, such as benzene and toluene,
are commonly found 1n petroleum products. The proposed criteria for
defining hazardous wastes (51 FR 21648, June 13, 1986) also Include a test
for determining the mobility (by leaching) of toxic organic and Inorganic
constituents 1n wastes: the toxicity characteristic leaching procedure
(TCLP). Regulatory levels for selected constituents 1n TCLP extracts are
stipulated as part of the criteria for defining hazardous wastes.
There currently are no data available on the concentration of
toxicity characteristic contaminants 1n petroleum-contaminated soils
therefore, 1t 1s unclear whether soils contaminated by leaking UST's will
pass or fall a characteristics test. Other Issues that remain are the
quantity of soils requiring disposal at a Subtitle C facility under a
3
-------
DRAFT
C0701-1/UST
2/5/88
Toxicity Characteristic (TC) classification or other regulatory
classification mechanism, and the environmental and economic impacts of
both disposal and alternatives to disposal. The EPA initiated this study
to help resolve these Issues.
Specific objectives of this study were to determine whether soils
contaminated with petroleum products would be defined as hazardous waste
under the 1gn1tab1l1ty characteristic or the TC criteria proposed by OSW
and to evaluate the Impact of the regulation through estimation of the
potential volume of soil affected by both petroleum products and hazardous
substances. Two different types of soil were contaminated with three
different petroleum products (unleaded gasoline, No. 2 dlesel fuel, and
No. 6 fuel oil) at several concentration levels and subjected to both the
1gn1tab1l1ty and TCLP tests. The TCLP extracts were analyzed and the
results were examined to determine which contaminated soils would be
defined as hazardous.
This report presents the results of the 1gn1tab1l1ty characteristic
test and the analytical results for the petroleum products and the TCLP
extracts. The report also discusses the regulatory Implications of the
results and presents recommendations for resolving related Issues. The
experimental procedures used to generate the data, the quality
assurance/quality control (QA/QC) procedures followed, and the results of
QA/QC performed during sample preparation and analysis are presented 1n
the Appendix.
4
-------
DRAFT
C0701-1/UST
2/5/88
2.0 DATA PRESENTATION
2.1 SOIL CHARACTERIZATION
Two different types of soils were used to determine the mobility of
petroleum products mixed 1n soil. The first soil was a light-colored,
f1ne-gra1ned, sandy river soil obtained from Kaw Sand Company. The second
soil was dark and loamy with a higher apparent clay content than the Kaw
soil. This soil was obtained from Action Topsoll. Each soil was charac-
terized for Its water content. The Action Topsoll and Kaw River soil were
13.5 and 10.1 percent water by weight, respectively. A rough particle
size characterization (percent sand, silt, and clay) was also performed on
each soil using a method based on an American Society of Testing and
Materials method. Both soils were approximately 50 percent silt, but
their sand and clay contents were different. The Action Topsoll was
3.7 percent sand and 41 percent clay while the Kaw River soil was
45 percent sand and 4 percent clay. Table 1 presents the results of these
characterization tests. Appendix A contains more detail on the analytical
procedures used for the characterization tests.
2.2 CONTAMINATED SOIL PREPARATION
Three different types of fuel products (unleaded gasoline, dlesel
oil, and No. 6 fuel oil) were mixed with the two soils described above.
Each soil was spiked with each of the fuel products at five different
nominal concentration levels (10,000, 5,000, 1,000, 100, and 10 ppm). The
actual fuel concentrations 1n each of the mixtures are presented In
Table 2. These values were used to estimate the pre-TCLP, or theoretical,
concentration of each analyte 1n the soil and to perform subsequent
comparisons with the TCLP extract concentrations. A detailed discussion
of the product mixing procedures 1s presented 1n Appendix A.
2.3 FUEL CHARACTERIZATION
The data obtained from the analysis of the three fuels for their
volatile and semlvolatlle organic composition are presented 1n Table 3.
The compounds are on either the proposed TCLP 11st (51 FR 21648),
Appendix VIII compounds 11st, and/or CERCLA 11st of hazardous*substances
for which there are reportable quantity requirements. The results for
analyses of additional semlvolatlles are presented 1n Appendix A.
5
-------
DRAFT
C0701-1/UST
2/5/88
The unleaded gasoline was, as expected, very rich 1n volatile
aromatic hydrocarbons. The most abundant was toluene, followed by
m-xylene, o- and p-xylene, benzene, and ethylbenzene. In contrast to very
high levels of volatile organic compounds 1n gasoline, relatively low
levels of semlvolatlles were observed 1n this fuel. Only naphthalene
(198 ug/g) was detected at a level significantly higher than the
quantitation limit.
Diesel fuel had lower levels of volatile aromatic compounds than the
gasoline; m-xylene and o- and p-xylene were the most abundant volatile
aromatlcs at approximately 650 ug/g. Toluene and ethylbenzene were
detected at between 310 and 360 ug/g, and benzene was detected, but at a
concentration lower than the quantitation limit. The most abundant
semlvolatlle aromatic compound 1n dlesel fuel also was napthalene
(658 ug/g).
No. 6 fuel oil had lower concentrations of volatile aromatic
hydrocarbons than gasoline and dlesel fuel. The most concentrated
analytes were m-xylene (69 ug/g), o- and p-xylene (65 ug/g), and toluene
(60 ug/g). Ethylbenzene and benzene were detected at less than 25 ug/g.
The most abundant semlvolatlle organlcs were large four-ring aromatlcs
(benzo[a]anthracene and chrysene), with significantly lower concentrations
of naphthalene. The latter 1s expected to Impact TCLP extracts more than
the more abundant large aromatlcs due to significant differences 1n their
aqueous solubilities.
2.4 CONTAMINATED SOIL CHARACTERIZATION
The theoretical concentrations of each target analyte 1n Action
Topsoll and Kaw River soil were obtained by multiplying the concentration
of every analyte found 1n each fuel times the actual concentration of that
fuel 1n each soil. For example, 1f the concentration of benzene 1n
unleaded gasoline was 13,800 ug/g, and 1f the concentration of gasoline 1n
Kaw River soil (nominal concentration of 100 ppm) was 0.103 g/kg, then the
theoretical concentration of benzene 1n this contaminated soil would be:
13,800 ug/gx0.103 g/kg = 1,421 ug/kg
In the absence of data validating these theoretical.concentrations, 1t
will be assumed that minimal evaporative losses of all analytes
occurred. This may not be a valid assumption, especially for the volatile
6
-------
DRAFT
C0701-1/UST
2/5/88
organic compounds. However, every possible measure was taken to minimize
any such possible losses.
2.5 IGNITABILITY CHARACTERISTIC TESTS
To determine whether fuel-contaminated soil would be 1gn1table, both
soil types were tested using the two most concentrated gasoline
contaminated samples and the most concentrated samples contaminated with
dlesel fuel and No. 6 fuel oil. The samples were contacted with the flame
of a low-flame bunsen burner and observed during and after flame contact
for any flashing or sustained combustion. This procedure 1s based on
guidance provided 1n SW 846, Volume 1C, Chapter 7, Section 7.1.2.2. A
summary of the results 1s presented 1n Table 4. Flashing or sustained
combustion was not observed 1n any of the samples. Thus, none of the
samples exhibited the characteristic of 1gn1tab111ty.
2.6 TOXICITY CHARACTERISTIC LEACHING PROCEDURES (TCLP) TEST
Samples of the fuel-contaminated soils were subjected to the TCLP
protocol described 1n the Federal Register (Volume 51, No. 216,
November 7, 1986). An acetate buffer solution was used as the leaching
medium. The results of the analyses of the TCLP leachates obtained from
gasoline-contaminated Kaw River soil samples are presented 1n Table 5.
The actual fuel concentrations 1n the soil, the theoretical analyte
concentrations, and the proposed regulatory levels also are presented 1n
Table 5. The leachates from Kaw River soil containing 1,000, 5,000, and
10,000 ppm of gasoline and from Action topsoll containing 10,000 ppm of
gasoline exceeded the proposed regulatory level for benzene of 70 ug/L.
Toluene leachate concentrations were high 1n the same samples, but only
the leachate from the most contaminated sample approached the regulatory
level of 14,400 ug/L. The only semlvolatlles on the proposed TCLP 11st
that were detectable 1n gasoline were 3-and 4-methylphenol. However,
these compounds were not detected 1n the leachates.
The results of the analyses of the TCLP leachates obtained from
Action topsoll samples are also presented 1n Table 5. As with the Kaw
River samples, benzene was the only analyte that exceeded the proposed
TCLP regulatory levels 1n any of the samples. The leachate from the
Action topsoll sample contaminated with 10,000 ppm of gasoline contained
109 ug/L and 1t was the only leachate to exceed the proposed regulatory
level.
7
-------
DRAFT
C0701-1/UST
2/5/88
The difference 1n volatlles concentrations 1n the leachates (shown 1n
Table 5 and Tables A-7 and A-8) for similar concentrations 1n the soil
Indicates that volatlles bind with Action topsoll (a clayey soil) much
more effectively than they bind with Kaw River soil (a sandy soil). This
effect 1s represented by the extraction efficiency which 1s a measurement
of the percentage of the analyte 1n the soil sample that 1s extracted to
the leachate. As the concentration of the analyte Increases 1n the Action
topsoll, the extraction efficiency Increases. This Indicates that the
capacity of the soil to bind with the analytes 1s reduced as the concen-
tration of the analyte 1n the soil increases. However, the extraction
efficiency of volatlles from Kaw River soil remains constant or decreases
which may Indicate that the binding effect is not a function of the
concentration 1n this soil and that some of the analytes approach satura-
tion 1n the leaching fluid at the higher concentrations 1n the soil.
The leachates from soils contaminated with dlesel fuel and No. 6 fuel
oil did not exceed any of the proposed TCLP regulatory levels, except for
three questionable data points. The benzene concentration of 42.9 yg/L 1n
the leachate from the Kaw River soil sample contaminated with 10,000 ppm
of dlesel fuel came the closest to the proposed regulatory level of
70 yg/L. Toluene leachate concentrations were at least three orders of
magnitude below the proposed regulatory level of 14,400 yg/L for all
samples. With the exception of the questionable data, the extraction
efficiencies of volatlles were much higher than those from the gasoline-
contaminated samples, but they followed the same trends. A complete
presentation of all of the data is presented in Appendix A.
8
-------
DRAFT
C0701-1/UST
2/5/88
3.0 REGULATORY ANALYSIS
Soils contaminated with petroleum products that exhibit a hazardous
characteristic could be classified as hazardous wastes based on the
"contalned-ln" policy defined by OSW.1 This study was conducted to
determine whether soils contaminated with fuel products would be hazardous
based on the 1gn1tab1l1ty characteristic or the proposed TCLP
characteristic. In addition, fuels contain compounds that are listed
hazardous wastes 1f discarded, RCRA Appendix VIII hazardous compounds, and
hazardous substances subject to CERCLA reportable quantity requirements.
The Impacts of these regulations on the management of soil contaminated
with fuel products and the test results of this study are discussed below.
3.1 IGNITABILITY CHARACTERISTIC
Based on the results of this study, soils contaminated with up to
10,000 ppm of gasoline, dlesel fuel, or No. 6 fuel oil would not be
Ignltable. Higher concentrations were not tested, but 10,000 ppm 1s close
to the saturation point. Thus, most soil contaminated by a fuel product
release would not be hazardous based on the 1gn1tab1l1ty characteristic.
3.2 TOXICITY CHARACTERISTIC
The results of this study Indicate that some soils contaminated with
gasoline, would be considered hazardous waste because they fall the
proposed TCLP test. At the same concentrations, however, soils
contaminated with dlesel fuel and No. 6 fuel oil did not exhibit the
toxicity characteristic. The acetate leaching medium used 1n the proposed
TCLP test 1s representative of that found 1n a landfill. The actual
leaching potential for the TC compounds 1n petroleum products could differ
from the results of the TCLP test, because the actual leaching medium at a
release location 1s likely to be rainwater.
3.3 IMPACTS OF THE PROPOSED TC REGULATION
The experiments conducted 1n this study also Indicated that the
concentrations of gasoline that would be hazardous varied with the type of
soil tested. Thus, the volume of hazardous soil generated from a leaking
UST depends on the national distribution of soil types as well as the
number of releases and the average quantity of a release. At this time,
only the number of releases can be estimated. Based on survey results
9
-------
DRAFT
C0701-1/UST
2/5/88
presented 1n the proposed underground storage tank (UST) rules, 1t was
estimated that releases could exist at about 10 percent of the
193,000 retail gasoline facilities nationally (52 FR 12662). If 1t 1s
assumed that gasoline also 1s stored 1n 50 percent of the 651,000 petro-
leum storage UST's 1n other Industry sectors and that 10 percent of these
tanks are leaking, a total of about 33,000 UST systems containing gasoline
may be leaking nationwide. Because the soil type distribution and the
quantity of gasoline released per site are not known, 1t 1s difficult to
estimate the quantity of hazardous soil nationwide. However, it 1s clear
that the quantity of hazardous soil may be extremely large. The land ban
on disposal of hazardous waste and the potential volume of hazardous soil
make excavation and disposal in a Subtitle C landfill an unlikely soil
management option. However, because benzene was the only gasoline
constituent that made the soil hazardous, other treatment options (e.g.,
vacuum extraction and aeration) are available and could be used to
eliminate the hazard by reducing the benzene concentration. Because the
treated soil will no longer exhibit the toxic characteristic, 1t can be
managed 1n any manner consistent with State regulations. Most States
currently use subjective criteria (such as odor) to establish disposal
options. These criteria may be more stringent than RCRA regulations.
Thus, 1f the State criteria are retained, disposal of soil that 1s
nonhazardous according to RCRA may still be restricted by State
regulations.
3.4 IMPACT OF TOXICITY CHARACTERISTIC ON THE HAZARDOUS SUBSTANCE TANKS
Toluene and benzene are hazardous substances on the 11st of proposed
toxicity characteristic contaminants that are derived from petroleum and
also are stored as pure products 1n UST's. Notification reports from New
York, California, and Iowa and a report by the Chemical Manufacturers
Association Indicated that the number of tanks storing toluene 1s greater
than that for any other hazardous compound and 1s more than an order of
2
magnitude greater than the number storing benzene. The proposed rules
for UST's Indicate that there are about 54,000 tanks storing hazardous
substances nationwide (52 FR 12662). Although the total number of tanks
storing toluene and benzene 1s not known, 1t 1s likely that several
thousand contain toluene. The concentrations of pure toluene and benzene
10
-------
DRAFT
C0701-1/UST
2/5/88
1n the soil that would result 1n a hazardous waste designation based on
the proposed TCLP procedure could be estimated using the results of this
study. Table 6 shows the toluene and benzene soil concentrations, TCLP
concentrations, proposed TCLP hazardous concentrations, and projected
hazardous soil concentrations for soils contaminated with gasoline. The
ratios of leachate concentrations from gasoline-contaminated soils to the
proposed hazardous TCLP concentrations were equated with the corresponding
soil concentration ratios to estimate the hazardous soil concentrations.
Gasoline tests were used because they contained more of both toluene and
benzene than the other fuels. As shown 1n Table 6, soil contaminated with
toluene concentrations of 600 to 3,200 ppm or with benzene concentrations
of 4 to 89 ppm would be characterized as hazardous waste. The range 1s
presented because the hazardous substance concentration 1s a function of
the soil type.
A number of other TC substances are stored 1n UST's so that releases
from these tanks, depending on the volume of the release and the type of
the soil, have the potential of contaminating significant volumes of soil
that would then necessitate treatment and/or disposal as hazardous
waste. Table 7 presents a 11st of these hazardous substances ranked by
numbers of tanks.
3.5 APPENDIX VIII IMPACTS
Fuel products contain several substances that are not on the proposed
TCLP or CERCLA reportable quantity lists, but that are listed 1n
Appendix VIII of RCRA (see Table 3). Wastes that contain these substances
could be considered hazardous 1f 1t 1s determined that the substance poses
a substantial threat to human health and the environment when Improperly
treated, stored, transported, disposed, or otherwise 'managed' (40 CFR
261.10). The determination of what 1s hazardous 1s based on a considera-
tion of many factors, one of which the potential for constituents of the
waste to migrate Into the environment under plausible types of Improper
management. Napthalene was the only Appendix VIII compound (other than
benzene and toluene) contained 1n fuels that was detected 1n the TCLP
leachates. In many cases, 1t was detected 1n leachates that did not
exceed the proposed TCLP regulatory levels for benzene. Thus, an
Implementing Agency could classify additional soils as hazardous based on
the migration potential of napthalene.
11
-------
DRAFT
C0701-1/UST
2/5/88
3.6 CERCLA REPORTABLE QUANTITY IMPACTS
Petroleum product releases that would not result 1n hazardous soils
may still be large enough to be subject to proposed CERCLA reportable
quantity requirements. Table 8 shows the concentration of the volatHes
and napthalene (the only semlvolatlle 1n petroleum on the CERCLA 11st) 1n
gasoline, dlesel fuel, and Ho. 6 fuel oil. The reportable quantity of
each constituent and the release volume of each fuel that would contain
the reportable quantity of each constituent also are shown 1n Table 7.
For gasoline, benzene 1s the constituent that would exceed the limit
first; the reportable quantity would be contained 1n a little over
100 gallons. Reportable quantities of dlesel fuel and No. 6 fuel oil
would not be exceeded until about 27,000 gallons and 125,000 gallons were
released, respectively. These release volumes are based on the quantity
of napthalene 1n these products because napthalene would exceed the
reportable quantity first.
12
-------
DRAFT
C0701-1/UST
2/5/88
5.0 REFERENCES
1. Memorandum from M. Williams, EPA:0SW, to P. Tobln, EPA:WHD,
Region IV. November 13, 1986. RCRA regulatory status of contaminated
ground water.
2. Camp Dresser and McKee, Inc. Draft Evaluation of Hazardous Substances
Most Frequently Stored 1n Underground Tanks. Prepared for the Office
of Underground Storage Tanks, U. S. Environmental Protection Agency.
June 1987.
14
-------
DRAFT
c0701-lal/UST
2/05/88 1
TABLE 1.
SOIL CHARACTERIZATION RESULTS
AND ACTION TOPSOIL
FOR KAW RIVER SOIL
Component concentrations, percent4
Action topsoll Kaw River soil
Water, wt/wt
13.5
10.1
Sand
3.7
45
S1lt
55
51
Clay
41
4.0
aSand, silt, and clay concentrations reported on a dry basis.
-------
DRAFT
c0701-la3/UST
2/03/87 1
TABLE 2. CONCENTRATIONS OF THE SOIL/FUEL PRODUCT MIXTURES
Saaple No.
Soi 1
Samp 10 description
Nominal fuel
Fuel concentration
type in soil, jig/g
Amount
of fuel
added, U9
Total
amount
of fuel*
soi1, g
Final con-
centration,
yg/g
7035/36
Act 1on
Diesel
10
1,960
200
9.8
7033/34
Action
Diesel
100
20,610
200
103
7029/30
Action
Diesel
1,000
200,000
200
1,000
7051/52
Action
Oiesel
1,000
200,000
202
991
7027/28
Action
D1ese1
5,000
1,000,000
200
5,000
7025/26
Action
Diesel
10,000
2,010,000
200
10,000
7059/60
Action
Fuel oi1
10
1,600
200
8.0
7023/24
Action
Fuel oi1
100
20,400
213
96
7057/58
Action
Fuel oi1
1,000
210,000
205
1,030
7055/56
Action
Fuel oi1
5,000
1,070,000
201
5,330
7053/54
Action
Fuel oi1
10,000
2,040,000
200
10,200
7011/12
Action
Gas
10
2,040
200
10.2
7009/10
Action
Gas
100
19,910
200
100
7005/6
Action
Gas
1,000
200,000
200
1,000
7007/8
Action
Gas
1,000
200,000
200
1,000
7003/4
Action
Gas
5,000
1,020,000
200
5,100
7001/2
Action
Gas
10,000
2,030,000
200
10,100
7045/46
Ksm
Diesel
10
2,100
200
10.5
7037/38
Kaw
Oiesel
100
20,120
200
101
7043/44
Kaw
Diesel
1,000
190,000
200
950
7041/42
Kaw
Diesel
5,000
980,000
200
4,890
7039/40
Kaw
Diesel
10,000
2,010,000
200
10,100
7069/70
Kaw
Fuel oi1
10
2,100
200
10.5
7021/22
Kaw
Fuel oi1
100
20,600
200
103
7067/68
Kaw
Fuel oi1
1,000
220,000
201
1,100
7065/66
Kaw
Fuel oi1
5,000
1,060,000
200
5,300
7063/64
Kaw
Fuel oil
10,000
2,040,000
200
10,200
7019/20
Kaw
Gas
10
2,600
200
130
7049/50
Kaw
Gas
100
20,600
200
103
7017/18
Kaw
Gas
100
21,700
201
108
7031/32
Kaw
Gas
1,000
230,000
200
1,150
7073/74
Kaw
Gas
1,000
210,000
200
1,050
7015/16
Kaw
Gas
5,000
980,000
200
4,900
7047/48
Kaw
Gas
10,000
2,000,000
200
10,000
7013/14
Kaw
Gas
10,000
2,010,000
200
10,000
-------
DRAFT
c0701-la3/UST
2/03/87 2
TABLE 3. VOLATILE AND SEMIVOLATILE ORGANIC TARGET ANALYTE
CONCENTRATIONS IN UNLEADED GASOLINE, DIESEL FUEL, AND NO. 6 FUEL OIL
GasolIne,
ug/g
Diesel,
yg/g
No. 6 fuel oi
yg/g
Volatile organic compounds
Carbon dlsulfIdea
Benzene8 c
Toluene8 c
Ethyl benzene8
ni-Xy lene®
o~ and p-Xylenee
hdP
13,800
58,000
12,500
33,100
32,100
NO
TR
359
312
669
638
NO
10.0
60.4
21.7
69.0
65.2
Quantitation limit
500
125
6.00
Sew IvoI atIle organic compounds
Phenol
2-Methylphenola
3- and 4-Methylphenola
Nitrobenzene8
PyrIdIne8
FIuoranthenec
Benzo(a)pyrenec
BenzoIb J~Ik)fIuoranthenec
BenzoIa]anthracene0
Chrysenec
2,4-0IoethyIphenoIc
Indenod ,2,3-cdlpyrene°
Naphthalene0
01 benz(a,h1 anthracene0
W)
NO
34.6
NO
NO
2.36
W)
4.55
2.20
2.01
4.69
NO
198
NO
NO
5.47
3.49
NO
NO
NO
NO
NO
NO
168
8.42
NO
658
HD
NO
NO
NO
W
NO
W)
775
663
9,810
21,200
NO
237
142
NO
Quant I tat i on Unit (base/neutraIs)
Quantitation limit (phenols)
2.00
2.00
113
2.00
453
2.00
?Analyte is listed in the proposed TCLP rules (51 FR 21648, June 13, 1986).
3 analyte not detected.
°AnaIyte is IIsted In Append I * VIII.
a trace; analyte was detected, but at a concentration below the quantitation limit.
aAnalyte is a CERCIA hazardous substance subject to reportable quantity requirements.
-------
DRAFT
c0701-lal/UST
2/05/88 2
TABLE 4. IGNITABILITY TEST RESULTS FOR FUEL CONTAMINATED SOILS
son
Fuel
type
Fuel
concentra-
tion, ppm
Flash
point
Sustained
combustion
Action
Gasoline
10,100
None
None
Action
Gasoline
5,100
None
None
Kaw
Gasoline
10,000
None
None
Kaw
Gasoline
4,900
None
None
Action
Diesel
10,000
None
None
Kaw
Diesel
10,100
None
None
Action
Fuel oil
10,200
None
None
Kaw
Fuel oil
10,200
None
None
-------
I T
cU/01-la6/UST
12/23/87 2
TABLE 5. CONCENTRATIONS OF PROPOSED TCLP COMPOUNDS IN GASOLINE-CONTAMINATED SOIL SAMPLES AND LEACHATE
Analytes
Actual
concentration
of gasoline
in sol 1, )g/g
Theoret i ca1
concentration
of analyte In
contaminated
soil, )g/ga
Concentration of
analyte In TCLP
leachate, )g/L
Extraction
efticlency,
percent recovery
Proposed TCLP
regu1atory
1 eve 1, ) g/L
Kaw
Benzene
103
1,050
4,900
10,000
1.42
14.5
67.6
138
31.6
241
1,660
2,380
44.5
33.3
49.3
34.5
70
Toluene
4,900
10,000
284
580
8,420
13,100
59.6
45.2
14,400
3- and 4-methylphenol
10,000
0.35
NDd
0
10,000
Action topsoi1
Benzene
5,100
10,100
70.4
140
TRC
109
0
1.56
70
Toluene
5,100
10,100
296
589
417
2,620
2.83
8.90
14,400
3- and 4-methylphenol
10,100
0.35
NO
0
10,000
Assumes that minimal losses from volatilization occurred. This may not be valid, especially for the volatile organic
compounds. However, every attempt was made to minimize volatilization.
ND = not detected.
CTR = trace; analyte was detected, but the concentration was less than the 2.0 )g/L quantitation limit.
-------
DRAFT
c0701-la5/UST
1/4/88 2
TABLE 6. PROJECTED HAZARDOUS SOIL CONCENTRATIONS OF PURE TOLUENE AND BENZENE
Noainal
Toluene
Benzene
Soil type
gasolIne
concen-
tration In
the toil, ppa
Actual
TCLP concen-
tration. ppb
Hazardous
TCLP concen-
tration. ppb
Actual
concentration
in soil, ppa
Projected
hazardous
(oil concen-
tration, ppa
Actual
TCLP concen-
tration. ppb
Hazardous
TCLP concen-
tration, ppb
Actual
concentration
In soil, ppa
Projected
hazardous
soil concen-
tration, ppa
Km River
1.000
1.480
14.400
60.9
S92
241
70
14.5
4.2
S.000
8.420
14.400
284
486
1.660
70
67.6
2.9
10.000
13.100
14,400
580
638
2,380
70
118
4.1
Action Topsoll
1.000
7.62
14.400
58
109,606
5.000
417
14.400
296
10.221
--
--
-
10.000
2.620
14,400
586
3,220
109
70
139
89
-------
DRAFT
c0701-lal/UST
2/05/88 3
TABLE 7. HAZARDOUS SUBSTANCES STORED IN UST'S BY NUMBER OF TANKS®
No. of
Rank
Compound
tanksD
1
Toluene
450
2
Methyl ethyl ketone
261
3
Methylene chloride
112
4
1t1,1-Tr1ch1oroethane
86
5
T etrach1oroethy1ene
36
6
Trlchloroethylene
24
7
Benzene
20
8
Chlorobenzene
16
9
Acrylon1tr1le
10
10
Vinyl chloride
6
11
Pentachlorophenol
3
12
Carbon disulfide
2
13
Lead-containing water
1
14
Water containing mercury
1
15
Chromate rinse
1
^Reference 2.
^Numbers represent results of surveys In California, Iowa, and New York,
and some additional Information from the Chemical Manufacturer's
Association.
-------
FT
w„/01-la4/UST
2/03/88 2
TABLE 8. CONCENTRATIONS AND REPORTABLE QUANTITIES OF HAZARDOUS SUBSTANCES FOUND IN PETROLEUM PRODUCTS
Analyto
Concentration In fuel, ppm
Gasoline Diesel Fuel oil No. 6
Reportable
quantity, lb
Quantity of fuel containing
reportable quantity of analyte. gallons8
Gasoline Diesel t-uei olI no. 6
Vol at Iles
Benzene 13,800 Trace
Toluene 56,000 3S9
Ethyl benzene 12,500 312
Xylene 65,200 1,307
10.0
60.4
21.7
134.2
10
1,000
1,000
1,000
129
13,070
14,250
2,730
500,000
570,000
140,000
180,000
2,900,000
8,200,000
1,300,000
Semlvolatlles
Napthalene
198
658
142
100
89,950
27,000
Assumes that the densities of dlesel fuel and No. 6 fuel oil are 42 lb/ft , the same as that of gasoline.
125,000
-------
DRAFT
C0701-1A/UST
2/3/88
APPENDIX A. TCLP ANALYSIS RESULTS AND QA/QC PROCEDURES
A.l MATERIALS AND METHODS
A.1.1 Soil Characterization
Two different types of soils were used to determine the mobility of
petroleum products mixed 1n soil. The first soil was a light-colored,
fine-grained sandy soil obtained from Kaw Sand Company (Lawrence,
Kansas). A second soil was obtained from Action Topsoll (Olathe,
Kansas). The Action soil was dark and loamy with a higher apparent clay
content than the Kaw soil. Both soils are commercially available.
Each soil was characterized for its water content. Approximately
10 g of each soil was transferred to tared beakers and placed 1n an oven
(100°C). The beakers were weighed at 2-h Intervals until two consecutive
weighings gave the same result.
A rough particle size characterization (percent sand, silt, and clay)
was performed on each soil using a method based loosely on ASTM Standard
Method D422. Ten grams of each soil were mixed with 15 mL of a 0.2-g/mL
solution of Calgon detergent to promote clay dispersion. The soll/Calgon
mix was diluted to 125 mL with delonlzed water. The mixture was shaken
for approximately 1 h on a rotary shaker and wet-s1eved through a 230-mesh
sieve to separate sand-size particles from s1It- and clay-sized
particles. The liquid was drained through a large funnel Into a 1-L
graduated cylinder. The sand-size particles remaining on the sieve were
washed with delonlzed water, with the fine particle-conta1n1ng washings
drained into the graduated cylinder to a maximum volume of 1 L. The sand-
sized particles were oven-dried and weighed. The suspended particles 1n
the graduated cylinder were mixed thoroughly using a perforated rubber
stopper on a stainless steel rod. After 20 s, a volumetric plpet was
Inserted to a depth of 20 cm and a 20-mL aliquot was collected and
A-l
-------
DRAFT
C0701-1A/UST
2/3/88
dispensed Into a 50-mL tared beaker. The silt- and clay-sized particles
thus collected were dried 1n an oven and weighed. The same procedure was
repeated for clay-sized particles after 123 m1n, but at a depth of
10 on. The weights for each of the f1ner-than-sand sized particles were
corrected for the Calgon and the total volume from which they were
sampled, and the s11t content corrected for its clay content.
A.1.2 Soil/Fuel Products Mixing
Three different types of fuel products were mixed with the two soils
described above. Unleaded gasoline and dlesel oil were obtained from a
Fairway 011 gasoline station (Shawnee, Kansas) 1n June 1987. Fuel oil
No. 6 was obtained from Consolidated Fuel 011 Co. (Riverside, Missouri) 1n
May 1987.
Each soil was spiked with each of the fuel products at five different
nominal concentration levels. These concentrations were 10,000, 5,000,
1,000, 100, and 10 ppm. A small amount (10-20 g) of the soil was supple-
mented with the appropriate amount of the fuel product (2, 20, 200, 1,000,
and 2,000 mg) so that when the weight of the mix was made up to 200 g, the
actual concentration would be close to the nominal concentration. The
mixing was done 1n precleaned, 32-oz laboratory jars which were modified
by a glassblower so that portions of the glass wall were pushed into glass
fingers extending Into the containers' cavity. These glass fingers
promoted more efficient mixing of the soil and the fuel when the sealed
jars were rotated 1n a tumbling table (1 h). At the end of the mixing
period, they were stored at -10°C. This procedure worked well for the
1ow-v1scos1ty liquid fuels (gasoline and dlesel), but the viscous fuel oil
did not mix well and produced clumps. As an alternative, the soil and
fuel oil were dispensed Into unmodified 32-oz laboratory jars and placed
directly Into a freezer (-10°C) for several hours. At the end of this
time, three ceramic balls (l-1n diameter) were placed 1n the jar, and the
jar was rotated for 3 to 4 h. This procedure broke the solidified clumps
of fuel oil and effectively mixed them into the soil.
A.1.3 Determination of Characteristic of Iqn1tab111ty of Fuel-
Contamlnated Soils
The fuel-contaminated soils were allowed to come to room temperature,
and 10 to 20 g was transferred to a clean watch glass. The flame of a
A-2
-------
DRAFT
C0701-1A/UST
2/3/88
low-flame Bunsen burner was allowed to contact the samples for 2 s and
then removed. The sample was observed during and after flame contact for
any flashing or sustained combustion of the samples. If no flashing or
sustained combustion occurred, the above procedure was repeated three
times. This procedure 1s based on the guidance provided 1n SW 846,
Vol. 1C, Chapter 7, Section 7.1.2.2.
A.1.4 Toxic Characteristic Leaching Procedure (TCLP)
Samples were subjected to the TCLP protocol according to the
procedures described In the Federal Register (Volume 51, No. 216,
November 7, 1986). Acetate was used as the leaching fluid.
The TCLP for volatile organlcs was performed using a 90-mm zero
headspace extractor (ZHE). Two of the devices were purchased from
MllUpore Corporation, and four other similar devices were constructed by
a local machine shop. The samples were added to the ZHE cold and allowed
to warm up inside the device (with zero headspace) before commencing
filtration. The fuel-contaminated soils were previously determined to
have no free liquid, and thus no filtrates were collected. Leaching
solution was pumped Into the ZHE from a graduated cylinder using a piston
pump (Cole Parmer R-7115-60). After the 18-h extraction period, the
leachate was collected 1n glass, gastlght syringes (50 mL); the first
portion collected was discarded, and the second portion was dispensed Into
vials with no headspace. These 1eachate-conta1n1ng vials were stored 1n
charcoal-filled paint cans. The V1ton 0-r1ngs on the ZHE were cleaned
with methanol and oven-dried.
A portion of the fuel-contaminated soils was Introduced Into flint-
glass 1-gal containers which had been previously treated 1n a 50 percent
HN03 bath (12 h minimum). The appropriate volume of leaching fluid was
then added. Leachates were allowed to settle for 1 h after the TCLP
extraction and then filtered using the 142-mm high-pressure filtration
device.
A.1.5 Analysis
A.1.5.1 Volatile Organic Analysis. Volatile organic compounds 1n the
samples were analyzed according to the procedures 1n Methods 5030 and 8240
from SW-846. Nonaqueous samples (soil blanks and fuels) were dispersed 1n
tetraglyme prior to analysis. The samples were analyzed by purge-trap-
A-3
-------
DRAFT
C0701-1A/UST
2/3/88
desorb 6C/MS using a Flnnigan/MAT CH4 magnetic sector mass spectrometer
controlled by an INCOS data system.
The following minor method deviations were necessary to analyze these
samples:
1. D„-l,2-D1bromoethane was used as the second Internal standard
rather than the recommended l,4-d1fluorobenzene. Du-1,2-D1bromoethane 1s
stable, available 1n pure form, demonstrates good purging efficiency,
yields fragmentation patterns with Intense 1ons at m/z 111 and 113, and
elutes near the middle of the chromatographic run.
2. O10-Ethylbenzene was used as a surrogate 1n addition to the
suggested D„-l,2-d1chloroethane, D8-toluene, and BFB (bromofluorobenzene).
3. The response factor for the SPCC bromoform was calculated using
the Internal standard 0^-1,2-dlbromoethane. Method 8240 uses l,4-d1-
fluorobenzene as the corresponding Internal standard. The minimum RF
criterion for bromoform (RF >0.250) was achieved during analysis.
4. The matrix spiking solution consisted of all of the volatile
target compounds.
5. The GC/MS operating conditions were changed so that the final
column temperature was 225°C rather than 220°C. This allowed the xylenes
to elute with better chromatography.
6. The samples were not screened by GC/FIO. Rather, the samples
were reanalyzed by PTD-GC/MS 1f necessary using an appropriate dilution.
7. Mass spectra of target compound "hits" from the INCOS target
compound analysis (TCA) routine results were visually checked and the
Identification of the compound confirmed. For a compound to be a target
compound candidate In the TCA routine, 1t had to elute at the correct
retention time, and have characteristic 1on response. Mass lists for the
1ons with greater than 10 percent relative abundance were not printed or
checked; 1t would not have provided any better compound Identification nor
would 1t have been an effective use of time.
A.1.5.2 SemlvolatHe Organic Analyses. Sem1volat1le organlcs were
solvent-extracted from the fuels, soils, and TCLP extracts using
SW-846-3580 (Waste Dilution, for fuels), SW-846-3520 (Continuous Liquid/
liquid Extraction, for leachates), or SW-846-3540 (Soxhlet Extraction, for
solid samples). Prior to subjecting the samples to solvent extraction,
A-4
-------
DRAFT
C0701-1A/UST
2/3/88
they were spiked with surrogate standards. All of the fuel sample
extracts were cleaned up using SW-846-3650 (Ac1d/Base-Neutral Cleanup).
The base neutral extract of each sample was fractionated using
SW-846-3611; the resulting aromatic fraction was combined with the addle
extract. The sample extracts were concentrated using Kuderna-Danlsh (KD)
glassware. Each sample extract and dilutions thereof were screened using
GC/FID to determine the optimal concentration for GC/MS analysis.
The GC/MS analyses were performed on a F1nn1gan/MAT 5100 quadrupole
mass spectrometer controlled by an INCOS data system. The analyses were
as per SW-846-8270 with the following exceptions:
1. The fused silica capillary column used had a 0.25-ym film
thickness rather than the specified 1.0-ym thickness. The latter column
may cause excessive "bleeding" of the stationary phase at the temperatures
required to elute polycycllc aromatic hydrocarbons (PAHs), adversely
affecting chromatographic quality.
2. The final temperature of the GC temperature program was 300°C
rather than the specified 270°C. This temperature was held until benzo-
Ig,h,1]perylene eluted. No problem was noted 1n the separation of
d1 benz[a,h]anthracene, 1ndeno[l,2,3,cd]pyrene, and benzo[g,h,1jperylene.
3. Mass spectra of target compound "hits" from the INCOS target
compound analysis (TCA) routine results were visually checked and the
Identification of the compound confirmed. For a compound to be a target
compound candidate 1n the TCA routine, 1t had to elute at the correct
retention time, and have characteristic 1on response. Mass lists for the
1ons with greater than 10 percent relative abundance were not printed or
checked; 1t would not have provided any better compound Identification nor
would It have been an effective use of time.
4. Two sets of components were poorly resolved under the
chromatographic conditions employed for the analysis of these samples and
are reported as a combined value. These analytes were m- and p-cresol (3-
and 4-methylphenol), and benzo[b]- and benzo[k]f1uoranthene. Since these
analytes were not found 1n the samples, this Impacts only on calibration
results.
A-5
-------
DRAFT
C0701-1A/UST
2/3/88
A.2 RESULTS AND DISCUSSION
A.2.1 Soil Characterization
Table A-l presents the results of the soil characterization studies
performed on the two soils used during this study. The data indicate that
Kaw River soil was characterized by having a very low clay content, with
sand and silt 1n approximately equal proportions. The Action topsoll had
a very low sand content, with the bulk of the material split approximately
equally between silt- and clay-sized particles. Both soils had about
13.5 percent (wt/wt) water content; however, the Kaw River soil had
clumping problems during mixing with the fuels, and 1t was dried 1n an
oven to a 10 percent (wt/wt) water content, which effectively avoided the
clumping problem.
A.2.2 Soil/Fuel Product Mixing Results
The actual and nominal concentrations of the soil/fuel product mixes
are presented 1n Table A-2. The actual values were used to estimate the
pre-TCLP concentration of each analyte 1n the soil, and to perform
subsequent comparisons with the TCLP extract concentrations.
A.2.3 Characteristic of Iqn1tab1l1ty Results
The results for the 1gn1tab1l1ty test are presented 1n Table A-3;
none of the fuel product-contaminated soils were 1gn1table. A limited
number of samples were used for this test: the two most concentrated
gasol1ne/so1l mixtures, and the most concentrated dlesel and fuel o1l/so1l
mixtures for both soils. If any of the above had been determined to be
1gn1tab1e, additional samples would have been analyzed.
A.2.4 Analytical Results
A.2.4.1 Quantitation Limits. The reliable detection limits-
hereafter referred to as quantitation limits—for volatile organic
compounds not detected 1n the samples were estimated from the sample
preparation procedures and from the Instrumental detection 11m1t. For
aqueous samples, the quantitation limit of a compound (10 ng on-column
from a 5.0-mL sample aliquot) 1s:
. 2 ng/mL - 2 Ug/L
A-6
-------
DRAFT
C0701-1A/UST
2/3/88
For tetraglyme extracts, 1f a 10.0-g sample Is dispersed 1n tetraglyme to
a final volume of 25 mL (25,000 uL), and a 20-yL portion 1s taken for
purge-trap-desorb (PTD) analysis, the quantitation limit for a compound
(10 ng on-column) would be:
(10 ng/20QHL)x 25tOOO HL a lf250 ng/g = L25 vg/g
The quantitation limits of target semlvolatlle compounds not detected
1n the samples were estimated from the sample preparation procedures and
the Instrumental detection limit. For example, suppose that 10 g of
sample were extracted and the extract concentrated to 5 mL. The smallest
amount of any target analyte that could be accurately quantified using the
average response factor from the calibration curve would need to have a
concentration no lower than the lowest calibration standard 1n the curve
(1.0 ug/mL). The estimated sample quantitation limit was calculated as
follows:
I"? ;^pi° extracted* = " ^
These values were corrected for any required dilutions that occurred
during sample preparation as determined by screening with gas
chromatography/flame Ionization detection (GC/FID).
A.2.4.2 Results of Fuels Analysis. The data obtained from the
analysis of the three fuels (unleaded gasoline, dlesel, No. 6 fuel oil)
for their volatile and semlvolatlle organic composition are presented 1n
Table A-4.
The unleaded gasoline was, as expected, very rich 1n volatile
aromatic hydrocarbons. The most abundant was toluene, followed by
m-xylene, o- and p-xylene, benzene and ethylbenzene. All of the
concentrations were above 10,000 ug/g, which was significantly higher than
the quantitation limit for the analysis of this fuel. Carbon disulfide
was not detected 1n gasoline. In contrast to very high levels of volatile
organic compounds 1n gasoline, relatively low levels of semlvolatlles were
observed 1n this fuel. Only two target analytes were detected at levels
significantly higher than the quantitation 11mlt—naphthalene (198 yg/g)
and 2-methylnaphthalene (259 ug/g).
A-7
-------
DRAFT
C0701-1A/UST
2/3/88
Diesel fuel had lower levels of volatile aromatic compounds than the
gasoline; m-xylene and o- and p-xylene were the most abundant volatile
aromatlcs at approximately 650 ug/g. Toluene and ethylbenzene were
detected at between 310 and 360 ug/g. and benzene was detected, but at a
concentration lower than the quantitation limit. The semlvolatHe
aromatic compounds were more abundant 1n dlesel fuel than 1n gasoline,
especially two- and three-ring aromatlcs (Mphenyl, naphthalene, 2-methyl-
naphthalene, fluorene, and phenanthrene), and the most concentrated were
2-methylnaphthalene (2,800 ug/g), phenanthrene (1,250 ug/g) and
naphthalene (658 ug/g).
No. 6 fuel oil had lower concentrations of volatile aromatic
hydrocarbons than gasoline and dlesel fuel. The most concentrated
analytes were m-xylene (69 ug/g). o- and p-xylene (65 ug/g). and toluene
(60 ug/g). Ethylbenzene and benzene were detected at less than 25 ug/g.
The most abundant semlvolatlle organlcs were four-ring aromatlcs
(benzola]anthracene, chrysene, pyrene), with significantly lower
concentrations of naphthalene and 2-methylnaphthalene. The latter two are
expected to Impact TCLP extracts more than the more abundant large
aromatlcs due to significant differences 1n their aqueous solubilities.
For example, methyl naphthalene has an approximate solubility (1n water) of
25 mg/L compared to pyrene, which has an approximate solubility of
0.15 mg/L.1"3
The theoretical concentrations for each target analyte 1n each fuel-
contaminated soil are presented 1n Table A-5 for Action topsoll and 1n
Table A-6 for Kaw River soil. These values were obtained by multiplying
the concentration of every analyte found 1n each fuel times the actual
concentration of that fuel In each soil. For example, 1f the
concentration of benzene 1n unleaded gasoline was 13,800 ug/g. and 1f the
concentration of gasoline 1n Kaw River soil (nominal concentration of
100 ppra) was 0.103 g/kg, then the theoretical concentration of benzene 1n
this contaminated soil would be:
13,800 ug/gx0.103 g/kg = 1,421 ug/kg
A-8
-------
DRAFT
C0701-1A/UST
2/3/88
Only those analytes that were detected 1n all the fuels above the
quantitation limit are reported 1n this table. Appendix VIII compounds
and those compounds Identified as toxicity characteristic contaminants 1n
Table C-l of the TCLP proposed rules (51 CFR 21648, June 13, 1986) are
flagged as such 1n the table. In the absence of data validating these
theoretical concentrations, 1t will be assumed that minimal losses of all
analytes occurred. This may not be a valid assumption, especially for the
volatile organic compounds. Every possible measure was taken to minimize
any such possible losses.
A.2.4.3 TCLP Extracts.
A.2.4.3.1 Action topsoll. The results of the analyses of the TCLP
leachates obtained from fuel-contaminated Action topsoll samples are
presented 1n Table A-7. For convenience, only those analytes that were
consistently detected 1n more than one TCLP extract of the same soil/fuel
combination are reported 1n Table A-7. A complete table with all of the
target analytes 1s Included 1n Appendix A. For some of the fuel/soil
mixtures, not all of the leachates produced were analyzed. Whether to
analyze for semivolatile organlcs was determined after screening the
extracts by GC/FID. In the case of volatile organlcs, the rapid
turnaround of GC/MS reports permitted real-time evaluation of the trends,
and whether or not 1t was necessary to analyze the next lower
concentration leachate.
The Action topsoll/dlesel leachates indicated that, for volatile
aromatlcs, the soil with the highest fuel concentration produced the most
concentrated leachates. Thus, m-xylene and o- and p-xylene showed their
highest concentrations 1n the leachate resulting from the 10,000-ppm
fuel/soil mixture. There was at least a two-fold decrease 1n concen-
tration to the 5,000-ppm leachate, and at least a ten-fold decrease 1n
concentration from the 5,000- to the 1,000-ppm leachate. These differ-
ences closely parallel the differences between the levels of fuel
contamination 1n each soil and are Interpreted as being significant. This
pattern was not observed for the semivolatile aromatic compounds
studied. The difference between the 10,000-ppm and the 5,000-ppm
leachates for all of the reported semivolatile organlcs was not
significant. However, the difference between most of the semlvolatile
A-9
-------
DRAFT
C0701-1A/UST
2/3/88
analytes was significant between the 5,000- and the 1,000-ppm leachates.
Only one analyte was detected 1n the 100-ppm leachate, and 1t too shows a
significant decrease 1n concentration from the next most concentrated
leachate.
These data can be visualized better by plotting leachate
concentrations against the nominal fuel/soil concentrations. The volatile
organlcs from the so1l/d1esel mixture (Figure A-l) suggest that the
leaching fluid will extract increasing amounts of these compounds 1f they
are used to test more highly contaminated soils than used for this
study. On the other hand, the semlvolatlles from this fuel/soil mix
(Figures A-2 and A-3) Indicate that these leaching solutions are
approaching (or have approached) a saturation point 1n their capacity to
extract higher levels of these compounds from Increasingly more
concentrated fuel/soil mixtures. For example, an Increase 1n the
fuel/so11 concentration above the 10,000«ppm level would probably result
1n Increased leachate concentrations for toluene (Figure A-l), but an
Increase above 5,000 ppm would not produce an Increased leachate
concentration for 2-methylnaphthalene (Figure A-3).
The results for the Action topsoll/fuel oil No. 6 combination do not
provide much trend information because only two leachates were analyzed
based on observations made during GC screening of the extracts. Some of
the same trends discussed above for semlvolatlle aromatlcs were seen, with
the 5,000- and 10,000-ppm leachates exhibiting nonsignificant differ-
ences. Most of the volatlles exhibited the same patterns discussed
observed for the Action topsoll/dlesel combination. However, benzene and
toluene lend some confusion to the pattern.
The patterns that were observed for the dlesel/Actlon topsoll mixture
are apparent for the volatlles 1n the Action topsoll/unleaded gasoline
leachates (Figure A-4). There was at least a two-fold difference 1n
concentrations between the 10,000- and the 5,000-ppm leachates, and no
less than a 45-fold difference between the 5,000- and the 1,000-ppm
leachates. The 100-ppm leachates had no detectable analytes. Only two
semlvolatlle aromatlcs were present 1n the leachates: naphthalene and
2-methylnaphthalene (Figure A-5). There was a less than two-fold differ-
ence 1n concentration between the two most concentrated leachates, but at
least a four-fold difference between the 5,000- and 1,000-ppm leachates.
A-10
-------
DRAFT
C0701-1A/UST
2/3/88
These patterns are not unexpected given the differences 1n solubility
between various aromatic hydrocarbons. For example, the solubility of
toluene (538 mg/L) 1s significantly higher than that of naphthalene
(31.5 mg/L), which 1n turn 1s significantly higher than that of blphenyl
(5.9 mg/L).1'2 Higher aromatic hydrocarbons (I.e., three or more rings)
have solubilities of less than 1 mg/L.3
A.2.4.3.2 Kaw River soil. The results of the analyses of TCLP
leachates obtained from fuel-contaminated Kaw River soils are presented in
Table A-8. Only those analytes that were consistently detected 1n more
than one leachate of the same soil/fuel combination are presented. A
complete table with all of the target analytes detected 1n all of the
leachates 1s presented 1n Appendix B. For some of the fuel/soil mixtures,
not all of the leachates produced were analyzed. For semlvolatlle
organlcs, whether to analyze the extracts was determined after screening
the extracts by GC/FID. In the case of volatile organlcs, the rapid
turnaround of GC/MS reports permitted real-time evaluation of the trends,
and whether or not 1t was necessary to analyze the next lower
concentration leachate.
The Kaw River so1l/d1esel leachates exhibited similar patterns to
those previously discussed for the Action topsoll (Figures A-6, A-7, and
A-8). There were discrepancies between the trends observed for
ethylbenzene and the xylenes at most concentrations and those for benzene
and toluene. First, the 1,000 ppm leachate results for toluene and, most
noticeably, for benzene appear to break the pattern of the other volatile
analytes. Second, the 10 ppm leachate concentrations are totally out of
line with the established patterns, and may be attributed to analytical
problems (e.g., contamination) with this leachate. The remaining values
for benzene and toluene, and all values for the other volatlles support
the observations made for Action topsoll.
Only three leachates were analyzed for the Kaw River soil/fuel oil
No. 6 mixture. To a large extent, these leachates support the patterns
observed for other soil/fuel mixtures. All of the leachates analyzed for
the Kaw River so1l/gasol1ne mixtures (Figures A-9 and A-10) also support
the arguments presented above.
A—11
-------
DRAFT
C0701-1A/UST
2/3/88
The Action topsoll and Kaw River soil leachates exhibit a potentially
Important difference. The slope of the leachate/soll plots decreased for
Kaw River leachates at lower nominal soil concentrations than for the
Action topsoll leachates. Even though the numerical difference between
the Kaw and Action soil leachates at most nominal concentrations was
small, the trend was consistent for most of the analytes studied. This
suggests that the sandy Kaw River soil allows leaching of contaminants
more readily than the Action topsoll.
A.2.4.3.3 Regulatory levels and leachate concentrations of
contaminated soils. Table C-l of the TCLP proposed rules (51 CFR 21648,
June 13, 1986) Indicates that, of all of the compounds targeted and
detected 1n the leachates during this study, only benzene and toluene
affect the classification of contaminated soils as hazardous waste. The
regulatory levels are 70 yg/L for benzene and 14,400 yg/L for toluene.
These levels were exceeded 1n the 10,000-ppm Action topsoll/gasoline
leachate (Table A-7) and 1n the 1,000-, 5,000-, and 10,000-ppm Kaw river
soil/gasoline leachates.
A.2.4.3.4 Efficiency of TCLP extraction. TCLP 1s an extraction
procedure, and 1f the Initial waste concentrations for each analyte are
known, the percent recovery of each analyte can be calculated. This
recovery can be a useful Indicator of the efficiency of TCLP 1n mobilizing
the various contaminants from a waste. If the calculated theoretical
concentration of m-xylene 1n the Action topsoll/dlesel fuel 5,000-ppm mix-
ture was 3,345 yg/kg (this calculation was described 1n Section 3.4.2),
and 1f 9.95 g of this soil/fuel mixture was used for TCLP, then the
Initial amount of m-xylene 1n the system 1s given by:
3,345 yg/kgxO.00995 kg = 33.3 yg of m-xylene
Similarly, 1f 200 mL of leachate had a concentration of 47.6 yg/L,
the total amount of m-xylene extracted by TCLP would be given by:
47.6 yg/Lx0.200 L = 9.52 yg of m-xylene 1n total leachate
A-12
-------
DRAFT
C0701-1A/UST
2/3/88
The leaching efficiency of m-xylene from this particular system 1s
calculated as follows:
9.52 ug of m-xylene 1n leachate = 28 g Dercent recoverv
33.3 pg of m-xylene 1n waste Percent recovery
These values also Incorporate the efficiency and accuracy of the
sample preparation and analysis.
Table A-9 shows the TCLP leaching efficiency for the Action
topsoll/fuel mixtures. Some analytes were not expected to be in the
contaminated soil because they were not detected 1n the neat fuel. In
these cases, the recovery calculation would have required a division by
zero, which 1s not processable (HP). If the analyte was expected to be 1n
the contaminated soil, but was not found 1n the leachates, then the
recovery would have been zero.
The results Indicate that, for volatile aromatlcs, the leaching
(extraction) efficiency increased with Increasing Initial soil
concentration. The most efficient extractions were those involving No. 6
fuel oil-contaminated soils, possibly because the Initially lower analyte
concentrations 1n the soil did not allow saturation of the leaching
fluid. The least efficient TCLP extractions were those which Involved
gasoline contaminated soils, probably because of the high Initial
concentrations of the analytes which may have permitted relatively rapid
saturation of the leaching fluid. For semivolatHe aromatlcs, the maximum
extraction efficiency was seen at lower levels of fuel/soil concentra-
tions. For example, the dlesel contaminated Action topsoll leachates had
maximum extraction efficiency 1n the 1,000 ppm soil. Some recovery values
1n Table A-9 appear to be unusually high. These will be discussed below.
Table A-10 presents the recovery results for the fuel-contaminated
Kaw River soils. The volatile aronatlcs 1n the dlesel contaminated soil
show that the maximum extraction efficiency occurred 1n the 1,000 ppm
leachates, 1n which nearly all of the material in the soil was
extracted. With the exception of the 1,000 ppm No. 6 fuel oil leachate,
the No. 6 fuel oil contaminated Kaw soil showed almost complete extraction
of the volatile analytes. The gasoline contaminated soils showed that the
10 ppm and the 100 ppm leachates were the most efficient in extracting
A-13
-------
DRAFT
C0701-1A/UST
2/3/88
volatile analytes from the soil. For semlvolatlles, the highest
recoveries were seen 1n the 1,000 ppm leachates for dlesel, and 1n the
1,000 ppm leachate for No. 6 fuel oil.
Some of the analytes presented 1n Table A-9 and A-10 exhibited
extremely high recoveries, Indicating analytical problems (e.g., sample
contamination, matrix effects); these values are flagged 1n the tables.
For some of the vol atlies, these problems were probably related to the
analysis of the leachates, because the unusually high recoveries affect
only some of the analytes or some samples of a soil/fuel set. In the case
of gasoline/soil semlvolatlles and fuel o1l/so1l volatlles, 1n which high
recoveries were observed for all of the analytes for both of the soil
types, 1t 1s possible that the results of the analysis of the neat fuel
may be underestimated. These observations are supported by QC results
(see section 4.0) for the analysis of the neat fuels. Surrogate
recoveries for volatlles analysis of No. 6 fuel oil were low, as were
surrogate recoveries for semlvolatlles analysis of gasoline. These
observations may clarify some of the apparent outliers discussed
previously for leachate concentrations. Benzene and toluene
concentrations for both nominal concentrations of Action topso1l/No. 6
fuel oil (Table A-7) were probably Inaccurate. Similarly, the Kaw River
so11/No. 6 fuel oil 1,000-ppm leachate and benzene 1n the 1,000-ppm Kaw
River so1l/d1esel leachate may be Inaccurate (Table A-8).
The leaching (extraction) efficiencies discussed above may highlight
the differences mentioned above 1n the ability of contaminants to be
leached from the different types of soil studied. In general, extraction
efficiencies were higher at lower nominal concentrations 1n Kaw River soil
than 1n Action topsoll. For example, 1n the Action so1l/d1esel leachates,
a maximum of 30 percent of the volatile contaminants were leached from
10,000 ppm soil, whereas the corresponding Kaw River soil leachates showed
approximately 100 percent recovery from the 1,000 ppm leachates. This
trend was observed 1n most of the other leachates.
A.3 QUALITY ASSURANCE/QUALITY CONTROL
This section reports the QA/QC procedures followed during this study
and the QA/QC results obtained during the course of sample preparation and
analysis. The QA/QC data assist 1n establishing the quality and validity
A-14
-------
DRAFT
C0701-1A/UST
2/3/88
of the sample analysis data. The data quality objectives (DQOs) for this
study were as follows:
1. Analytical precision—30 percent relative percent difference
(RPD) for duplicate analyses.
2. Analytical accuracy«70 to 130 percent of true value for QA check
samples and 70 to 130 percent recovery for surrogates and matrix spikes.
The QA activities performed during this study Include:
1. Surrogate recoveries—used to evaluate analytical accuracy and
extraction efficiency.
2. Matrix spikes—to establish accuracy of the analysis procedures
as well as matrix effects.
3. Duplicates and matrix spike duplicates—to establish analytical
precision.
4. Method blanks—to evaluate potential contamination during sample
preparation and analysis.
5. QA check samples—a blind sample prepared independently of the
analysis team to check analytical Instrumentation and data Interpretation.
Specific QA/QC procedures, deviations, and analysis results are
described 1n the following sections.
A.3.1 Volatile Organic QA/QC
A.3.1.1 GC/MS Considerations. The GC/MS performance criteria for
the analysis of volatlles specified 1n SW-846-8240 were used. The 1on
abundance ratios of BFB (bromofluorobenzene) were compared on a dally
basis with the 1on abundance criteria from Method 8240, and the Instrument
was tuned 1f necessary. The BFB had to be analyzed by direct Injection
rather than by purge-trap-desorb because the BFB coeluted with a silicon
peak apparently originating from the 3 percent 0V-1 packing 1n the
analytical adsorbent trap. When the peaks coeluted, the Interference
caused the criteria not to be met.
The analyses were performed on a F1nn1gan MAT CH4 magnetic sector
GC/MS. A five-point calibration curve was constructed using mixed
calibration standard solutions at 2, 10, 40, 70, and 115 yg/mL.
Calibration standards were prepared from EPA repository chemicals and from
the highest purity commercially available chemicals. All standards were
assigned a unique number for Identification and tracking purposes. The
A-15
-------
DRAFT
C0701-1A/UST
2/3/88
calibration standard mixes were prepared In methanol according to
SW-846-8240. Five microliters of these solutions were added to 5.0 mL of
reagent water. The average response factors (RFs) obtained for the
calibration check compounds (CCCs), target analytes, and surrogate
recovery compounds deviated by less than 30 percent (relative standard
deviation) of the average RF. The RFs for the system performance check
compounds (SPCCs) exceeded the minimum RF.
A mid-level (40 ug/mL) standard was analyzed before and after
analyzing samples each day, and at the end of every 12-h period. This
standard contained the target analytes, surrogates standards, BFB, SPCCs,
and CCCs. The BFB 1on abundance ratios were compared on a dally basis
with the 1on abundance criteria from Method 8240, and the Instrument was
tuned 1f necessary. The SPCCs were checked to assure that the minimum RF
had been met. The response factors of the CCCs were examined to determine
1f they were within 25 percent of the average RF per Method 8240. All
criteria specified 1n Method 8240 were met on every day of analysis.
The extracted 1on current profile (EICP) areas for the Internal
standards were monitored as the samples were analyzed. Internal standard
area counts were consistent (-50 to +100 percent) between standard checks.
A.3.1.2 Quality Control Volatile Analysis Results.
A.3.1.2.1 Surrogate recoveries. Volatile organic surrogate recoveries
for all the samples analyzed are presented 1n Table A-ll. More than
95 percent of the surrogate data points met recovery DQOs (70 to
130 percent). However, the five surrogates that did not meet DQOs were 1n
two samples.
A.3.1.2.2 Duplicate precision and matrix spike recovery. All of the
1,000 ppm leachates were analyzed for volatile organlcs 1n duplicate and
as a matrix spike. The results are presented 1n Tables A-12 through
A-16. Each one of these leachates was part of a separate batch of samples
extracted by TCLP.
More than 95 percent of the analytes met precision DQOs established
for this study (30 percent RPD), and all of the analytes met accuracy DQOs
(70 to 130 percent recovery).
A.3.1.2.3 Method blanks. Ho volatile organic target compounds were
detected 1n the Instrument (system) blanks or 1n the method blanks. The
A-16
-------
DRAFT
C0701-1A/UST
2/3/88
system blanks consisted of organic-free purge water spiked with Internal
standards.
A.3.1.2.4 MRI QA check sample. The results of the analysis of an MRI
QA check sample, typically used to check the analytical instrumentation
and the analyst's data Interpretation are summarized 1n Table A-17. All
of the analytes were within DQOs for check samples (70 to 130 percent of
true values).
A.3.2 SemlvolatHe QA/QC
A.3.2.1 GC/MS Considerations. GC/MS performance criteria for the
analysis of semlvolatlles established in SW-846-8370 were used. The
Instrument was tuned on a dally basis with a solution of DFTPP (50 yg/mL)
per the Key Ion and Abundance Criteria set forth 1n Method 8270. A
mixture of the SPCCs and the tuning standards (4,4'-DDT, benzidine,
pentachlorophenol) was analyzed dally to monitor the RFs of the SPCCs
(minimum RF = 0.05), to monitor GC column performance (benzidine and
pentachlorophenol), and to verify Injection port Inertness (4,4'-0DT). A
s1x-po1nt calibration curve was constructed using mixed calibration
standard solutions which contained the CCCs, target analyses not Included
1n the CCCs, and the surrogate standards; the concentrations ranged from
1.0 to 150 yg/mL. The curve was accepted 1f the percent relative standard
deviation (percent RSD) did not deviate by more than 30 percent from the
average RF of each Individual CCC. A mid-level standard (50 yg/mL) was
run every day of operation, and the RFs of the CCCs checked to determine
1f they were within 30 percent of the average RF per Method 8270. If such
was not the case, the GC/MS system was checked, and 1f necessary, a new
calibration curve was constructed. No more than 12 h of continuous GC/MS
analyses were performed without recallbratlon of the Instrument (DFTPP,
SPCC, and dally standard). Before Injection, the GC/MS analyst spiked
1.0 mL of each sample with 10 yL of a 4,000-yg/mL mixed Internal standard
solution as specified 1n Method 8270.
Specific deviations from this present protocol were occasionally
necessary as described below:
1. The most concentrated calibration standard (150 yg/mL) of the
s1x-po1nt curve for 2-fluorophenol, D5-pheno1, 2-methylphenol, 3- and
4-methylphenol, anthracene, l,4-d1chlorobenzene (CCC), phenol and
A-17
-------
DRAFT
C0701-1A/UST
2/3/88
2-fluorob1phenyl slightly saturated the SC/MS detector,, resulting 1n lower
relative response factors than for the other standard?. If the high point
had been removed from the s1x-po1nt curves, tixe average RFs for the
resulting f1ve-po1nt curves (1.0 to 50 pg/mL) would fcave decreased by less
than 5 percent. However, 1f any of these analytes had appeared 1n the
sables above 50 ug/mL, the concentration would have been outside the
linear calibration range of the Instrument. It was therefore deemed best
to accept the lower relative response factors; the reported sample
concentrations may be overestimated by no more than 5 percent.
2. On a number of occasions, the response factor for pyridine 1n the
dally standard was more than 30 percent of the average response factor of
the curve. This 1s not expected to impact the data because pyridine was
not detected 1n any sample.
3. The minimum response factor criteria for 2,4-d1n1trophenol (SPCC)
were not met on 3 out of 9 GC/MS analysis days. On all occasions that
2,4-din1trophenol failed to meet criteria, the RF was more than 85 percent
of the minimum RF.
4. A number of calibration check compounds cause difficulty
achieving consistent response factor data. During the analysis of these
sables, two phenolic and three nonphenollc components of the CCC mix were
found to be extremely difficult to bring into compliance with the
established criteria. These problem compounds were:
All the target analytes were checked on a dally basis, and with the
exception noted above, they were always within 30 percent of the average
RF.
A.3.2.2 Surrogate Recoveries. Sem1volat1le organic surrogate
recoveries are summarized 1n Table A-18. A large number of the surrogate
recoveries were outside project DQOs (70 to 130 percent recovery).
CCC
Failure frequency
(percent of analysis days)
Pentachlorophenol
2-N1trophenol
D1phenylam1ne
D1-n-octylphthalate
Hexach1orobutad1ene
11
11
56
78
11
A-18
-------
DRAFT
C0701-1A/UST
2/3/88
However, a number of factors need to be considered when evaluating these
data. First, some of the base/neutral surrogates employed (and required
by SW-846) are poor choices for surrogate standards, especially when
alumina cleanup of the extracts 1s required. For example, both
D5-n1trobenzene and 2-fluorob1phenyl have, because of their functional
groups, a larger charge associated to their molecules. When passing
through the fractionation column necessary to separate aliphatic
Interferences from the aromatic compounds, these two surrogates Interact
more strongly with the alumina, and may be more strongly retained than the
less charged PAHs. This results 1n low and variable recoveries of these
compounds. These two compounds are not structurally related to PAHs and
do not behave like them. Second, project DQOs for semlvolatlle surrogate
recoveries were extremely tight; a more reasonable range would have been
between 50 to 130 percent.
The phenolic surrogates (2-fluorophenol, D5-phenol, and
2,4,6-trlbromophenol) showed that 61, 64, and 27 percent of the data
points, respectively, did not meet surrogate recovery DQOs (Table A-18).
The average recovery was between 58 to 81 percent, and only 2-fluorophenol
had an unacceptable spread 1n the surrogate recoveries (-50 percent
RSD). If a wider range of 50 to 130 percent recovery had been used for
DQOs, only 9 to 20 percent of the data points for surrogate recoveries
would have been outside DQOs. This suggests that a large proportion of
the surrogates that missed DQOs were between 50 and 70 percent recovery.
The base/neutral surrogates (D5-n1trobenzene, 2-fluorob1phenyl,
Dl0-pyrene, and Dllt-p-terphenyl) present a different case because of the
additional fractionation step to which the base/neutral extracts were sub-
jected. As was discussed above, 05-n1trobenzene and 2-fluorob1phenyl are
not truly amenable to fractionation, and this 1s reflected 1n the
surrogate recoveries. Project DQOs for surrogate recoveries were missed
for more than 80 percent of the surrogate data points for D5-n1trobenzene
and 2-fluorob1phenyl. The average recoveries were low and the spread of
the data was wide, especially for Ds-n1trobenzene (as Indicated by percent
RSD). The use of a wider surrogate recovery range (50 to 130 percent) for
DQOs would not have Improved the number of data points meeting DQOs
significantly. The other base/neutral surrogates employed (D10-pyrene and
A-19
-------
DRAFT
C0701-1A/UST
2/3/88
Dllf-p-terphenyl) had acceptable average recoveries, although the spread
for Dllf-p-terphenyl was wide. Approximately 23 to 32 percent of the data
points for these compounds did not meet project DQOs. However, an
increase of the DQO range to between 50 to 130 percent recovery would have
resulted in fewer than 15 percent of the data points to miss DQOs.
A.3.2.3 Matrix Spike Recoveries and Duplicate Precision. The matrix
spike recovery and duplicate precision results for the analysis of the
neat fuels used 1n this study are presented 1n Tables A-19 and A-20.
Analysis of dlesel fuel 1n duplicate (Table A-19) Indicates that more than
95 percent of the analytes met precision DQOs. However, the differences
between the two replicates suggests lower precision than this because a
number of analytes detected in one replicate were not detected 1n the
other. The difference between the quantitation limits for these samples
Indicates that most of the analytes should not have been seen 1n the
second replicate. Only 2-methylnaphthalene was above the quantitation
limit for the second replicate, and thus should have been detected.
Therefore, only 2 out of 23 analytes (phenanthrene and 2-methyl-
naphthalene) did not meet met precision DQOs. Table A-20 summarizes
matrix spike recovery of analytes spiked Into gasoline. More than
60 percent of the analytes did not meet recovery DQOs, suggesting matrix
interferences.
Tables A-21 through A-25 summarize the matrix spike recovery and
duplicate precision results for the TCLP leachates analyzed. The
1,000 ppm leachate of each fuel/soil mixture was selected as the QC sample
for each TCLP batch, and was analyzed as a matrix spike and 1n some cases
matrix spike duplicate. Approximately 31 percent of the analytes did not
meet matrix spike recovery DQOs, and about 23 percent of the duplicates
did not meet precision DQOs.
A.3.2.4 Method Blanks. Table A-26 presents the concentrations of
the semlvolatlle organic target analytes found 1n the method blanks. All
the reported values for the samples were corrected for the concentration
found 1n the blanks.
A-20
-------
DRAFT
C0701-1A/UST
2/3/88
A.3.2.5 MRI QA Check Sample. The results of the analysis of an MRI
QA check sample, which 1s used to check the analytical Instrumentation and
data Interpretation, are summarized 1n Table A-27. All of the analytes
met accuracy DQOs.
A.4 REFERENCES FOR APPENDIX A
1. McAullffe, C. 1963. Solubility of C1-C9 hydrocarbons 1n water.
Nature. 200:1092-1093.
2. Bohon, R. L.# and W. F. Clausen. 1951. The solubility of aromatic
hydrocarbons 1n water. J. Amer. Chem. Soc. 73:1571-1578.
3. Tlssot, B. P., and D. H. Welte. 1984. Petroleum Formation and
Occurrence. Sprlnger-Verlag. New York. p. 315.
A-21
-------
DRAFT
C0701-1A1/UST
12/22/87 1
TABLE A-l. SOIL CHARACTERIZATION RESULTS FOR KAW RIVER SOIL
AND ACTION TOPSOIL
Component concentrations, percent
Action topsoll Kaw River soil
Water, wt/wt 13.5 10.1
Sand 3.7 45
S1lt 55 51
Clay 41 4.0
-------
DRAFT
C0701-1A3/UST
12/2/87 1
TABLE A-2. CONCENTRATIONS OF THE SOIL/FUEL PRODUCT MIXTURES
Sataple No.
Description (soil/
fuel noalnal concen-
tration in ppm)
Amount
of fuel
added, ug
Total amount
of fuel and
soil, g
Final
concentration,
g/kg*
7035/36
Action/diesel 10
1,960
200
0.00980
7033/34
Action/diesel 100
20,610
200
0.103
7029/30
Actlon/dlesel 1,000
200,000
200
1.00
705 J/52
Actlon/dlesel 1,000
200,000
202
0.991
7027/28
Action/diesel 5,000
1,000,000
200
5.00
7025/26
Action/diesel 10,000
2,010,000
200
10.0
7059/60
Action/fuel oil 10
1,600
200
0.00800
7023/24
Action/fuel oil 100
20,400
213
0.0960
7057/58
Action/fuel oil 1,000
210,000
205
1.03
7055/56
Action/fuel oil 5,000
1,070,000
201
5.33
7053/54
Action/fuel oil 10,000
2,040,000
200
10.2
7011/12
Action/gas 10
2,040
200
0.0102
7009/10
Action/gas 100
19,910
200
0.100
7005/6
Action/gas 1,000
200,000
200
1.00
7007/8
Action/gas 1,000
200,000
200
1.00
7003/4
Action/gas 5,000
1,020,000
200
5.10
7001/2
Action/gas 10,000
2,030,000
200
10.1
7045/46
Kaw/diesel 10
2,100
200
0.0105
7037/38
Kaw/diesel 100
20,120
200
0.101
7043/44
Kaw/dlesel 1,000
190,000
200
0.950
7041/42
Kaw/diesel 5,000
980,000
200
4.89
7039/40
KaM/Diesel 10,000
2,010,000
200
10.1
7069/70
KaN/fuel oil 10
2,100
200
0.0105
7021/22
Kaw/fuel oil 100
20,600
200
0.103
7067/68
Kaw/fuel oil 1,000
220,000
201
1.10
7065/66
Kaw/fuel oil 5,000
1,060,000
200
5.30
7063/64
Kaw/fuel oil 10,000
2,040,000
200
10.2
7019/20
Kaw/gas 10
2,600
200
0.0130
7049/50
Kaw/gas 100
20,600
200
0.103
7017/18
Kaw/gas 100
21,700
201
0.108
7031/32
Kaw/gas 1,000
230,000
200
1.15
7073/74
Kaw/gas 1,000
210,000
200
1.05
7015/16
Kaw/gas 5,000
980,000
200
4.90
7047/48
Kaw/gas 10,000
2,000,000
200
10.0
7013/14
Kaw/gas 10,000
2,010,000
200
10.0
"Final concentration (gAg) * Amo"n''' of
Amount of
fuel added (ug) n
fuel+soil (g) 1
1.000 gAq
1,000,000 ug/g
-------
DRAFT
C0701-1A1/UST
12/2Z/87 2
TABLE A-3. IGNITABILITY TEST RESULTS FOR FUEL CONTAMINATED SOILS
Fuel
Fuel concentra- Flash Sustained
Soil type tlon, ppm point combustion
Action
Gasoline
10,100
None
None
Action
Gasoline
5,100
None
None
Kaw
Gasoline
10,000
None
None
Kaw
Gasoline
4,900
None
None
Action
Diesel
10,000
None
None
Kaw
Diesel
10,100
None
None
Action
Fuel oil
10,200
None
None
Kaw
Fuel oil
10,200
None
None
-------
DRAFT
C0701-1A3/UST
12/2/87 2
TABLE A-4. VOLATILE AND SEMIVOLATILE ORGANIC TARGET ANALYTE
CONCENTRATIONS IN UNLEADED GASOLINE, DIESEL FUEL, AND NO. 6 FUEL OIL
GasolIne,
ug/g
Diesel,
ug/g
No. 6 fuel oi
yg/g
Volatile organic compounds
Carbon dIsuIfI do
Benzene
ToIuene
Ethylbenzene
m-Xylene
o- and p-Xylene
Quantitation limit
ND
13,800
58,000
12,500
33,100
32,100
500
NO
TR
359
312
669
638
125
NO
10.0
60.4
21.7
69.0
65.2
6.00
SemivoI at Ile organic compounds
Phenol
Acenaphthene
FIuoranthene
8enzofa)pyrene
Acenaphthylene
Anthracene
Benzo(b1~{k J fIuoranthene
Benzolg.h,I]fIuoranthene
Benzo[aI anthracene
Blphenyl
Chrysene
Olbenz[a,hi anthracene
2,4-0 i aethy I p heno I
FIuorene
Indeno(1,2,3-cd J pyrene
2-MethyI phenol
3- and 4-MethyI phenol
2-MethyI naphtha Iene
Naphthalene
Nitrobenzene
Phenanthrene
Pyrene
Pyridine
ND
2.36
ND
m
TRb
4.55
UD
2.20
5.28
2.01
4.69
2.92
ND
NO
34.6
259
198
M)
6.57
NO
W)
W)
f©
NO
NO
NO
TR
NO
NO
NO
249
168
W>
8.42
467
ND
5.47
3.49
2,800
658
ND
1,250
205
W)
ND
f©
NO
775
ND
ND
663
M
9,810
NO
21,200
ND
NO
NO
237
ND
W)
461
142
ND
506
8,710
NO
Quantitation limit (base/neutrals)
Quantitation limit (phenols)
2.00
2.00
113
2.00
453
2.00
^ND = analyte not detected.
TR = analyte detected, but at a concentration lower than the quantitation limit.
-------
T
J1-1A9/UST
2/3/88 2
TABLE A-5. THEORETICAL CONCENTRATIONS OF SELECTED TARGET ANALYTES IN
ACTION TOPSOIL/FUEL MIXTURES AT THE VARIOUS NOMINAL CONCENTRATIONS®
Soil/fuel mixture Actlon/dlesel Action/fuel oil Action/gasoline
Noatnal concentration, ppa
loo
1.000
5.000
10.000
5.000
10.000
100
1,000
5.000
10,000
Volatile oraanic coapounds. llg/kg
Benzene'1
N/Ac
N/A
K/A
N/A
53.3
102
1.374
13.797
70.369
140.063
Toluene6
37.0
356
1,795
3,608
322
616
5.774
57,986
295,756
568,671
Ethylbenzene
32.1
309
1,560
3.135
116
221
1.244
12,497
63.740
126.869
¦-Xylene
6B.9
663
3,345
6.723
368
704
3,295
33,092
168,785
335,948
o- and p-Xylene
65. 7
632
3,190
6,412
348
665
3,196
32,092
163.685
325,799
Seal vol at lie oraanic coapounds. llq/kg
Fluoranthene*'
Beiuo[a)pyrene<'
K/A
N/A
N/A
N/A
N/A
N/A
0.235
2.36
12.0
23.9
N/A
N/A
N/A
N/A
4.169
7,976
NO
NO
NO
NO
Be «o[b]*[k] fluoranthene"1
Benzolajanthracene1'
N/A
N/A
N/A
N/A
3.53S
6,762
0.453
4.55
23.2
46.2
M/A
N/A
N/A
N/A
52.300
100.052
0.219
2.20
11.2
22.3
Bi phenyl
25.6
247
1,245
2,502
N/A
N/A
0.525
5.28
26.9
53.6
Chrysened
17.3
166
840
1.66B
113.024
216.218
0.200
2.01
10.2
20.4
2.4-01atthylphenold
0.867
8.35
42.1
84.6
N/A
N/A
0.466
4.68
23.9
47.6
Fluorene
48.1
463
2.335
4,693
N/A
N/A
0.291
2.92
14.9
29.7
Indenol1,2,3-cd]pyrened
N/A
N/A
N/A
N/A
1,264
2.417
N/Ac
N/A
N/A
N/A
2-Nethylphenol®
0.563
5.42
27.3
55.0
N/A
N/A
N/A
N/A
N/A
N/A
3- and 4-Methylphenolb
0.359
3.46
17.4
35.1
N/A
K/A
3.44
34.5
176
351
2-Nethylnaphthalene
288
2,774
14.000
28,139
2.458
4.702
25.7
259
1,319
2.625
Naphthalene*'
67.8
652
3,290
6,613
757
1,448
19.7
198
1,010
2,010
Phenanthrene
129
1,239
6.250
12,562
2,698
5,161
0.654
6.57
33.5
66.7
Pyrene
21.1
203
1.025
2,060
46,436
88,833
N/A
N/A
N/A
N/A
jjAnalyte theoretical concentration (llg/kg) • analyte concentration In neat fuel (llg/g)xconcentration of fuel In toll (a/kg).
Analyte is lilted In Table C-l of the TCIP proposed rules (51 CFR 21648, June 13, 1986)
°N/A • not applicable; analyte was not detected In the neat fuel.
''Analyte Is listed In Appendix VIII.
-------
DRAFT
C0701-1A9/UST
2/3/88 3
TABLE A-6. THEORETICAL CONCENTRATIONS OF SELECTED TARGET ANALYTES IN KAW RIVER SOIL/FUEL MIXTURES AT
THE VARIOUS NOMINAL CONCENTRATIONS®
Soil/fuel alxture Kaw/dlesel Kaw/fuel oil Kaw/qasol 1ne
Noalnal concentration, ppa 10 100 1.000 5,000 10.000 1.000 S.000 10,000 10 100 1.000 5.000 10.000
Itolatlle organic ccapounifa. Ua/ka
Benzene1*
N/Ac
N/A
N/A
N/A
N/A
11.0
53.0
102
142
1.421
14
.489
67.613
137,966
Toluene1*
3.77
36.1
341
1.757
3,608
66.2
320
616
597
5,972
60
.897
284.172
579,855
Ethylbenzene
3.28
31.4
296
1.527
3,136
23.8
115
221
129
1.287
13
.124
61.244
124.969
•-Xylene
7.02
67.3
635
3.275
6.723
75.7
366
704
341
3,408
34
.753
162.174
330,917
0- and p-Xylene
6.70
64.2
606
3.123
6,412
71.5
346
665
331
3.305
33
.703
157.274
320.920
>¦1 volatile organic coapounds.
Uq/kq
Fluoranthene''
Beruo(a]pyrened
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
0.0243
0. 243
2.48
11.6
23.6
N/A
N/A
N/A
N/A
N/A
857
4.145
7,977
NO
NO
NO
NO
NO
Benzo[bl+|k)f1uoranthened
N/A
tyA
N/A
N/A
N/A
727
3,514
6.763
0.0468
0. 468
4.78
22.3
45.5
Benzol a) anthracene*'
N/A
N/A
N/A
N/A
N/A
10.756
51.996
100.072
0.0227
0.227
2.31
10.8
22.0
B1phenyl
2.61
25.0
237
1,219
2,502
N/A
N/A
N/A
0.0543
0. 543
5.54
25.9
52.8
Chrysened
1.76
16.9
160
822
1.688
23.244
112.366
216.262
0.0207
0.207
2.11
9.85
20.1
2,4-01aethy1phenold
0.0884
0.847
8.00
41.2
84.6
N/A
N/A
N/A
0.0482
0. 482
4.92
23.0
46. B
Fluorene
Indeno[1,2,3-cd]pyrened
4.90
47.0
444
2.286
4.693
N/A
N/A
N/A
0.0301
0.301
3.07
14.3
29.2
N/A
N/A
N/A
N/A
N/A
260
1.256
2.418
N/Ac
N/A
N/A
N/A
N/A
2-Hethyl phenol'*
0.0574
0.550
5.19
26.8
55.0
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
3- and 4-Hethylphenol'*
0.0366
0.351
3.31
17.1
35.1
N/A
N/A
N/A
0.356
3.56
36.3
169
345.4S
2-Methylnaphthalene
29.4
282
2.660
13.706
28,140
505
2,443
4.703
2.66
26.6
272
1,267
2.586
Naphthalene
6.91
66.2
625
3,221
6,613
156
753
1.449
2.04
20.4
208
970
1.980
Phenanthrene
13.1
126
1.187
6.119
12.563
555
2,682
5.162
0.0677
0.677
6.90
32.2
65.7
Pyrene
2.15
20.6
195
1.003
2.060
9,550
46.165
88.851
N/A
N/A
N/A
N/A
N/A
jjAnalyte theoretical concentration (P9/kg) • analyte concentration In neat fuel (P9/9) « concentration of fuel In soil (9/kg).
Analyte is listed In Table C-l of the TCLP proposed rules (51 CFR 21648, June 13, 1986)
°N/A ¦ not applicable; analyte was not detected In the neat fuel.
dAnalyte is lilted In Appendix VIII.
-------
*FT
wd701-lA6/UST
12/1/87 2
TABLE A-7. CONCENTRATIONS OF CONTAMINATED ACTION TOPSOIL LEACHATES
Act I On/d I ase I Actloil/f U6l Ol I ActlQn/imcAl I ha
Nominal concentration, ppra 100 1 ,000 5,000 10,000 5,000 10,000 100 TJOOO——5(00Q 10,000
Volatile organic compounds.
M/l
Benzene
Toluene
Ethyl benzene
m-Xylene
o- and p-Xylene
NAa
NA
NA
NA
NA
NO
TR
TR
3.57
4.30
TRC
11.7
20.8
47.6
51.0
4.04
62.2
52.0
106
110
115*
52.9d
5.44
14.4
13.4
17.3
47.9
13.8
39.6
40.0
NO
TR
NO
NO
TR
TR
7.62
6.38
22.2
28.6
TR
417
402
1,220
1,340
109
2,620
1,210
3,460
3,670
Quantitation limit
NA
2.00
2.00
2.00
2.00
2.00
2.00
5.00
50.0
50.0
Semi vol at 1le orqanic compounds,
ya/i
Acenaphthene
Bi phenyl
F1uorene
2-Methylnaphthalene
Naphthalene
Phenanthrene
ND
NO
NO
3.00
NO
NO
3.33
6.66
4.45
84.6
27.1
3.81
6.14
11.7
9.02
269
112
11.1
6.93
15.6
11.9
251
174
13.7
NO
TR
NO
11.6
10.1
2.79
NO
2.76
TR
19.1
16.7
3.01
NO
NO
NO
ND
NO
NO
NO
TR
ND
54.2
63.2
NO
ND
TR
ND
246
253
ND
ND
TR
ND
350
448
NO
Quantitation limit
2.00
2.41
2.00
2.04
2.22
2.04
2.05
2.25
3.09
10.1
cND = analyto not detected.
dTR = analyte detected, but at a concentration lower than the quantitation limit.
Potentially inaccurate results; see text for discussion.
-------
DRAFT
C0701-1A9/UST
2/3/88 4
TABLE A-8. CONCENTRATIONS OF CONTAMINATED KAM RIVER SOIL LEACHATE
Soil/fuel «1xture Kaw/dlesel Haw/fuel oil Kaw/oasolIne
Ncmlnal concentration, ppa 10 100 1.000 5.000 10.000 1.000 5.000 10.000 10 100 1,000 5.000 10,000
Volatile organic compounds. Ug/L
Benzene
60.9s
2.04
51.8®
7.45
42. <
8.96
6.26
11.1
TR
31.6
241
1.660
2,380
Toluene
17.7®
2.09
51.6a
36.7
66.4
11.7
13.4
38.0
15.9
209
1,480
8,420
13,100
Ethylbenzene
TR6
TR
15.0
31.3
47.4
2.60
5.57
10.2
4.88
46.9
329
1,800
2,530
¦-Xylene
8.54®
TR
32.6
64.5
99.1
6.80
16.7
30.3
13.5
129
876
4,520
6.560
o- and p-Xylene
3.01s
TR
33.8
66.5
104
6.66
17.0
31.3
12.7
131
899
4,600
6.720
Quantitation 1Init
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
4.00
50.0
400
400
Seel volatile organic coapounds. llq/L
Acenaphthene
NAC
NDd
5.35
8.40
7.39
NO
TR
NO
NO
ND
ND
ND
ND
81 phenyl
NA
TR
10.6
18.6
16.3
TR
3.08
3.17
ND
ND
TR
TR
TR
Fluorene
HA
NO
7.10
11.7
9.42
TR
TR
TR
NO
ND
NO
ND
NO
2-Methylnaphthalene
NA
8.32
123
251
203
10.5
20.9
34.0
HO
10.7
106
343
439
Naphthalene
NA
4.47
40.6
131
125
6.38
13.6
16.5
TR
7.36
99.1
351
625
Phenanthrene
NA
TR
9.53
14.6
12.3
2.54
3.22
3.41
ND
NO
NO
NO
ND
Quantitation Halt HA 2.00 2.04 2.04 2.00 2.04 2.00 2.00 2.02 2.00 2.01 4.04 10.1
'Potentially Inaccurate results; see text for discussion.
**TR • analyte detected, but at a concentration lower than the quantitation liolt.
CNA ¦ saople not analyzed.
dND » analyte not detected.
-------
T
. J1-1A6/UST
12/1/87 3
TABLE A-9. RESULTS OF RECOVERY CALCULATIONS FOR TCLP OF FUEL-CONTAMINATED ACTION TOPSOIL®
Soil/fuel mixture Actlon/dlesol Action/fuel oil Actlon/qasolIne
Nominal concentration, ppm 100 HOOD TWO 10,000 57000 10,000 "TOO 1,000 5,000 10,000
VoI at 11e organ Ic compounds.
percent
Benzene
NA
NPC
NP
NP
4,310d
339d
0
0
0
Toluene
NA
O
13.1
34.6
329
156
0
0.268
2.83
Ethyl benzene
NA
0
26.8
33.3
94.0
125
0
1.04
12.6
m-Xylene
NA
10.8
28.6
31.6
78.3
113
0
1.37
14.5
o- and p-Xylene
NA
13.6
32.1
34.4
77.1
120
0
1.82
16.4
Semi vol at lie organic compounds,
percent
Biphenyl
FIuorene
NP
NP
NP
NP
NP
NP
NP
NP
0
54.0
18.8
12.5
NP
NP
0
0
0
19.2
7.73
5.07
W
NP
0
0
20.8
61.0
38.4
17.8
9.43
8.12
0
419'
0
83.2
68.1
52.6
26.7
23.1
0
639'
0
6.15
3.55
2.18
2.07
1.17
0
0
1.56
8.90
19.1
20.6
22.5
Acenaphthene NP NP NP NP NP NP NP NP NP NP
0 0
2-MethyI naphthalene 20.8 61.0 38.4 17.8 9.43 8.12 0 4l9d 373^ 278d
Naphthalene 0 83.2 68.1 52.6 26.7 23.1 0 639d 501d 446d
Phenanthrene * " "" ~ ~~
TCLP recovery percent = , .total g^unt oj analyte In leachate (ug) )0Q
b... TOTai amounT ot anaiyTe in conTaminaTea soil (ugj
CNA = sample not analyzed.
(jNP = recovery calculation not processed due to a contaminated soil concentration of 0.
Unusually high recovery; see text for details.
-------
DRAFT
C0701-1A9/UST
2/3/88 S
TABLE A-10. RESULTS OF RECOVERY CALCULATIONS FOR TCLP OF FUEL-CONTAMINATED KAM RIVER SOILa
Soil/fuel alxture Kaw/dlesel Ka
Fluorene
NA
0
32.1
10.3
4.02
HP
HP
NP
0
NP
0
0
HP
2-Hethylnaphthalene
MA
59.1
92.8
36.7
14.4
41.6
17.1
14.5
0
HP
781d
541d
ff>
Haphthalene
NA
135
130
81.5
37.8
82.0
36.2
22.8
0
NP
9S4d
724d
NP
Phenanthrene
MA
0
16.1
4.78
1.96
9.16
2.40
1.32
0
HP
0
0
W>
a total aoount of analyte In leachate (lla)
TaP recovery, percent ¦ xl00
total aoount of analyte 1n contaminated soil (VIg)
bNA • saaple not analyzed.
SlP ¦ recovery calculation not processed due to a contaminated soil concentration of 0.
''Unusually high recovery; see text for details.
-------
DRAFT
C0701-1A3/UST
12/2/87 3
TABLE A-12. QUALITY CONTROL RESULTS FOR VOLATILE ORGANIC ANALYSES:
KAW RIVER SOIL 1,000 ppm UNLEAOED GASOLINE LEACHATE
QA type (dup.. MS, MS dup.)
Matrix Matrix
spike spike
Sample, Dup., Average, RPO, a level, recovery >>
Analytes pg/l pg/L pg/L percent ug/L percent
Carbon d1su1f1de
NO
NO
25C
NA
1,340
1,250
105
Benzene
258
224
241
14
1,610
1,250
110
Toluene
1,640
1,310
1,475
22
2,550
1,250
86
Ethyl benzene
373
285
329
27
1,590
1,250
101
m-Xylene
975
777
876
23
1,980
1,250
88
o- and p-Xylene
1,010
788
899
25
3,380
2,500
99
d
Quantitation limit:
50
50
NA
NA
50
NA
NA
NA = not applicable; NO 3 not detected.
^RPD (relative percent difference) = ((Rep. I - Rep. 2)/Avg. of Rep. 1 and Rep. 2)xlOO.
cPercent recovery » ((amount found in spike - native level avg.)/amount spiked)x100.
The native level of this analyte was estimated as 50 percent of the quantitation limit for
^percent recovery calculations.
Quantitation limit * (ng of lowest standard x dilution factor)/ml of sample analyzed.
-------
DRAFT
C0701-1A3/UST
12/2/87 4
TABLE A-13. QUALITY CONTROL RESULTS FOR VOLATILE ORGANIC ANALYSES:
KAW RIVER SOIL 1,000 ppm DIESEL LEACHATE
QA type (dup., MS. MS dup.)
Matr i x Matr i x
spike spike
Sample, Oup., Average, RPO, a MS, level, recovery^,
Analy+es yg/L yg/L yg/L percent wg/,|~ percent
Carbon d i su1fIde
NO
NO
1C
NA
53
50
104
Benzene
51.9
51.8
52
0.2
106
50
108
Toluene
53.4
49.8
52
7
92
50
81
Ethyl benzene
16.7
13.2
15
23
60.7
50
92
tn-Xy lene
39
26.3
33
39
79.9
50
95
o- and p-Xylene
41.9
25.8
34
48
122
100
88
Quantitation limit:'6
2
2
NA
NA
2
NA
NA
NA 3 not applicable; NO * not detected (no response for this analyte).
^RPD (relative percent difference) = ((Rep. 1 - Rep. 2)/Avg. of Rep. 1 and Rep. 2)x100.
percent recovery 3 ((amount found In spike - native level avg.)/amount spiked)x100.
ihe native level of this analyte was estimated as 50 percent of the quantitation limit for
^percent recovery calculations.
eOutside data quality objective limits.
Quantitation limit (aqueous samples) * (ng of lowest standard x dilution factor)/ml of
sample analyzed.
-------
DRAFT
C0701-1A3/UST
12/2/87 5
TABLE A-14. QUALITY CONTROL RESULTS FOR VOLATILE ORGANIC ANALYSES:
KAW RIVER SOIL 1,000 ppm NO. 6 FUEL OIL LEACHATE
QA type (dup.. MS, MS dup.)
Matrix Matrix
spike spike
Sample, Dup., Average, RPD, a MS, level, recovery^
Analytes ug/L Ug/L ug/L percent Ug/L percent
Carbon disulfide
f©
NO
1C
NA
45.2
50
88
Benzene
8.44
9.47
9
12
55.8
50
94
Toluene
11.6
11.8
12
2
59.7
50
96
Ethyl benzene
2.57
2.62
3
2
50.8
50
96
m-Xylene
6.87
6.72
3
2
52.6
50
92
o- and p-Xylene
6.46
6.85
7
7
103
100
96
Quantitation limit:"'
2
2
NA
NA
2
NA
NA
NA = not applicable; NO = not detected (no response for this analyte).
^RPO (relative percent difference) » ((Rep. I - Rep. 2)/Avg. of Rep. t and Rep. 2)x100.
cPercent recovery = ((amount found in spike - native level avg.)/amount spiked)xlOO.
The native level of this analyte Mas estimated as 50 percent of the quantitation limit for
^percent recovery calculations.
Quantitation limit (aqueous samples) = (ng of lowest standard x dilution factor)/mL of
sample analyzed.
-------
DRAFT
c0701-1A3/UST
12/2/87 6
TABLE 15. QUALITY CONTROL RESULTS FOR VOLATILE ORGANIC ANALYSES:
ACTION TOPSOIL 1,000 ppm UNLEADED GASOLINE LEACHATE
QA type (dup., MS, MS dup.)
Matrix Matrix
spike spike
Sample, Dup., Average, RPD, a MS, level, recovery^
Analytes wg/L yg/L yg/L percent lJ9/'L y9/L percent
Carbon disulfide
NO
NO
2.5C
NA
126
125
99
Benzene
TR
TR
2.5C
NA
136
125
107
Toluene
7.21
8.04
8
11
126
125
95
Ethyl benzene
6.19
6.56
6
6
127
125
97
m-Xylene
21.8
22.5
22
3
139
125
93
o- and p-Xylene
28.2
29.1
29
3
267
250
95
Quantitation limit:*1
5
5
NA
NA
5
NA
NA
NA » not applicable; NO = not detected; TR = detected, but at a level lower than the
quantitation limit.
?RPO (relative percent difference) = ((Rep. 1 - Rep. 2)/Avg. of Rep. 1 and Rep. 2)x100.
Percent recovery = ((amount found in spike - native level avg.)/amount spiked)x100.
The native level of this analyte was estimated as 50t of the quantitation Iimit for t
^recovery calculations.
Quantitation limit (aqueous samples) 3 (ng of lowest standard x dilution factor)/mL of
sample analyzed.
-------
DRAFT
C0701-1A3/UST
12/2/87 7
TABLE A-16. QUALITY CONTROL RESULTS FOR VOLATILE ORGANIC ANALYSES:
ACTION TOPSOIL 1,000 ppm DIESEL LEACHATE
QA type (dup.. MS. MS dup.)
Ana 1ytes
Sample,
ug/L
Dup.,
ug/L
Average,
ug/L
RPD. a
percent
MS,
ug/i
Matrix
spike
level,
ug/i
Matr 1 x
spike
recovery ^
percent
Carbon disulfide
ND
NO
1C
NA
53.2
50
104
Benzene
NO
NO
1c
NA
54.3
50
107
Toluene
TR
TR
1c
NA
52.9
50
104
Ethyl benzene
1.91
1.65
2
15
54.5
50
105
m-Xy1ene
3.73
3.4
4
9
55.8
50
104
0- and p-Xylene
4.69
3.9
4
18
109
' .0
105
Quantitation limlt:d
2
2
NA
NA
2
NA
NA
NA 3 not applicable; NO = not detected; TR = detected, but at a concentration below the
quantitation limit.
bRPD (relative percent difference) » ((Rep. 1 - Rep. 2)/Avg. of Rep. 1 and Rep. 2)x100.
cPercent recovery » ((amount found in spike - native level avg.)/amount spiked)xlOO.
The native level of this analyte was estimated as 50 percent of the quantitation limit for
^percent recovery calculations.
Quantitation limit (aqueous samples) » (ng of lowest standard x dilution factor)/mL of
sample analyzed. Quantitation limit (nonaqueous samples) » (ng of lowest standardxdilutlon
factorxtotal mL extract)/(|iL injection volumexg or mL samp I ex 1,000).
-------
DRAFT
C0701-1A2/UST
12/1/87 2
TABLE A-18. QUALITY CONTROL RESULTS FOR SEMIVOLATILE ORGANIC ANALYSES: SURROGATE RECOVERIES
Sample1
Recovery of surroaates
2-FPn
Ds-Ph
TBPh
DS-NB
2-FB1
Dio~Py
Dllt-Ter
80
79
115
53c
14C
54c
56c
53c
61c
81
45c
9.5C
41c
0C
86
78
120
74
51c
92
80
92
92
106
132c
44c
171°
27c
73
70
104
0C
86
95
82
75
44c
51c
35c
34c
86
84
65c
66c
69c
0C
67c
82
81
0C
88
162c
50c
87
87
62c
51c
82
90
78
83
92
60c
77
68c
75
57°
52c
30c
77
88
67c
57c
0C
56c
72
67c
94
53c
77
19c
35c
67c
47c
55c
55c
61c
0C
54c
56c
58c
0C
33c
86
54c
45c
70
72
0C
71
83
33c
60c
97
99
87
78
83
24c
53c
78
56c
69c
66c
79
25c
60c
67c
67c
64c
59c
85
57°
48c
77
73
59c
55c
82
39c
45c
76
74
0C
61c
46c
62c
23c
84
78
77
32c
84
73
52c
91
86
64c
49c
60c
0C
42c
88
74
78
70
78
0C
71
75
74
47c
35c
69c
53c
62c
67c
70
Unleaded gasoline
Unleaded gasoline (MS)
Diesel fuel
Diesel fuel - duplicate
No. 6 fuel oil
Act1on/gasol1ne 100
Act1on/gasol1ne l,000d
Act1on/gasol1ne 5,000
Act1on/gasol1ne 10,000
Act1on/d1esel 100
Act1on/d1ese1 1,000
Act1on/d1esel 5.000
Act1on/d1esel 10,000
Action/fuel oil 1,000-MS
Action/fuel oil 1,000-MSdup
Action/fuel oil 5,000
Action/fuel oil 10,000
Kaw/gasol1ne 10
Kaw/gasol1ne 100
Kaw/gasol1ne l,000d
(continued)
-------
JMFT
W01-1A2/UST
12/1/87 3
TABLE
A-18.
(continued)
Sample3
Recovery of surrogates'3
2-FPh
Ds-Ph
TBPh
DS-NB
2-FB1
Oio-Py
Dm-Ter
Blanks
58c
58c
60c
0C
63^
79
72
L
73
7°_
94
54c
47
80
81
73_
65
76
0C
35c
82
61c
0C
77
137
°r
14c
34c
32c
72
52c
127
172
106
79
77
0C
81
83
4C
42°
84
74
61c
S6r
56c
55c
56c
75
73
56c
57
53c
56c
69c
89
88
67c
62c
88
58c
26c
61°
0C
V
Average recovery
58
62
81
44
54
79
67
Percent RSD
49
27
31
91
37
26
34
Minimum value
0
17
40
0
9.5
30
0
Maximum value
98
92
162
172
106
171
99
Percent outside DQOs
61
64
27
93
82
23
32
aSample descriptions for TCLP extracts are 1n the following format: soil type/petroleuro product and
.nominal concentration (ppm).
2-FPh = 2-fluorophenol; D5-Ph = Ds-phenol; TBPh = 2,4,6-trlbromophenol; DS-NB = Ds-n1trobenzene;
2-FB1 ¦ 2-fluoroblphenyl; D10-Py = D10-pyrene; D1It-Ter = Dj„-terphenyl.
Rvalue 1s outside recovery DQOs.
Includes sample and two matrix spike duplicates.
-------
DRAFT
c0701-lA6/UST
12/1/67 4
TABLE A-21. QUALITY CONTROL RESULfS TOR S£fU VOLATILE ORGANIC ANALYSES:
KAW RIVER SOIL 1,000-ppm GASOLINE LEACHATE
_ OA type (dup,. KS. HSdup)
Analytes
vg/v
Matrix
spike
MS. lever,
JJJ/L
Matrix
spike
rscowrvti
percenr
MS
dup,
ugA
MatrIx
spike
level,
wg/C
Matrix
sp i ke
recovery j>
fwrcenr
Matrix
spffce
dupIicate
WO, c
percent
Acenaphtftene
Acenaphthy lene
Anthracene
Benzol alpyrene
Benzolb)*IkIfIuoranthene
Benzo(g,h,IIperyIene
Benz(alanthrecene
Biphenyi
Chrysene
Di benzla,h]anthracene
2,4-Olaethy Ipiienol
Fluoranthene
FIuorene
Indenoll ,2,3-cd|pyrM«
2-Met hy I f\aph tha I ene
2-ttethyI phenol
3- and 4-Metbylphenol
Naphthalene
N1trobenzene
Phenanthrene
Phenol
Pyreue
Pyridine
Quant i tat i an limit:-
5.35
1.01
1.01
1.01
1.01
1.01
1.01
10.6
1.01
1.01
1.01
1.01
7.1
1.01
123
1.01
1.01
40.6
1.01
9.53
1.01
1.01
1 .01
2.01
201
300
65"
245
300
80
20
218
300
79
278
300
92,1
16
229
500
76
195
300
Md
26 i
300
a?
379
300
126,.
"S
574
600
95
838
600
139 j
3*2
263
300
87
152
300
50
53d
222
300
74
296
300
96
29ri
9.3
NS
HAd
12.9
NS
NA
32
206
300
68
274
300
28
262
300
87
NO
300
0*
NA
NO
NS
NA
NO
NS
NA
NA
252
500
84
273
300
9!
8
2*4
300
76
290
300
94
21
243
300
81
328
300
109
30
125
MS
MA.
160
NS
NA„
25 j
137
600
79.6
600
53d
188
1200
16d
140
1200
'2d
29
231
300
60
248
300
69
12
226
300
76
228
300
76
0
222
300
71
245
300
10
241
600
40
210
600
35
14
238
300
7%
229
500
4
SD
300
or1
ND
300
0
NA
3.15
NA
NA
3.49
NA
NA
NA
NS = dot spiked; MA = rot applicable,
a
Anajytes with concentrations belon the quantitation limit were estimated to have a native level of 50 percent of the fluantftatjew
.1iralt.
percent recovery = demount found In spike - native level evg]/amount spiked)*!00.
(relative percent difference) = (IRep I - Rep 21/Avg of ftep I and Hep 2)xl00.
^Outside data quality objective Hafts.
Quantitation limit * equivalent niLA for total sample x lowest calibration standard (|ig/mL).
-------
r
1-1A6/UST
12/1/87 5
TABLE A-23.
QUALITY CONTROL RESULTS FOR SEMIVOLATILE ORGANIC ANALYSES:
KAW RIVER SOIL 1,000-ppm DIESEL LEACHATE
Analytes
QA type (dup.. MS. MSdup)
Sampl%,
wg/L
MS.
yg^L
Matrix
spike
level,
ug/L
Matrlx
spike
recovery b
percent
MS
dup..
ygA
Matrix
spike
level,
pg/f.
Matrix
spike
recovery j)
percen-r
Matrix
spike
dupIIcate
RPO. c
percent
Acenaphthene
5.35
201
300
Acenaphthylene
1.02
238
300
Anthracene
1.02
229
300
Benzol ajpyrene
1.02
261
300
Benzolb1~1k1f1uoranthene
1.02
574
600
Benzo l'g,h,l Iperyiene
1.02
263
300
Benz(a 1 anthracene
1.02
222
300
Bl phenyl
10.6
9.3
NS
Chrysene
1.02
206
300
D1benz[a,h)anthracene
1.02
262
300
2,4-D1 methy1pheno1
1.02
W)
NS
Fluoranthene
1.02
252
300
F1uorene
7.1
234
300
Indenol1,2,3-cdlpyrene
1.02
243
300
2-Methy1 naphtha 1ene
123
125
NS
2-Methy1 phenol
1.02
137
600
3- and 4-Methylphenol
1.02
188
1200
Naphthalene
40.6
221
300
Nitrobenzene
1.02
228
300
Phenanthrene
9.53
222
300
Phenol
1.02
241
600
Pyrene
1.02
238
300
Pyridine
1.02
ND
300
Quantitation limit:0
2.04
4.04
NA
65d
245
300
80
20
79
278
300
92d
16
76
195
300
65
'®d
87
379
300
126d
37d
95
838
600
139
37d
87
152
300
50
53d
74
296
300
98
29d
NAd
12.9
NS
NA
32
68
274
300
91
28
87
NO
300
NA
NA
NA
NO
NS
NA
NA
84
273
300
91
8
76
290
300
94
21
81
328
300
109
30
NAd
160
NS
NAd
25d
23d
79.6
600
,3S
53d
16°
140
1200
29
60
248
300
69
12
76
228
300
76
0
71
245
300
78d
10
40
210
600
35
14
7%
229
300
76d
4
0
NO
300
oa
NA
NA
2.03
NA
NA
NA
£|S = not spiked; NA = not applicable.
^Analytes with concentrations below the quantitation limit were estimated to have a native level of 50 of the quantitation limit.
cPercent recovery = ([amount found in spike - native level avgl/amount splked)x100.
dRPD (relative percent difference) = ([Rep 1 - Rep 2)/Avg of Rep 1 and Rep 2)x100.
^Outside data quality objective limits.
Quantitation limit = equivalent mL/L for total sample x lowest calibration standard (iig/mL).
------- |