Table Of ContentTotal Petroleum Hydrocarbon Criteria Working Group Series
Volume 4
Development of Fraction
Specific Reference Doses
(RfDs) and Reference
Concentrations (RfCs) for
Total Petroleum
Hydrocarbons (TPH)
Development of Fraction
Specific Reference Doses
(RfDs) and Reference
Concentrations (RfCs) for
Total Petroleum
Hydrocarbons (TPH)
Total Petroleum Hydrocarbon Criteria Working Group Series
Volume 4
Development of Fraction
Specific Reference Doses
(RfDs) and Reference
Concentrations (RfCs) for
Total Petroleum
Hydrocarbons (TPH)
PREPARED FOR: PREPARED BY:
Chevron, British Petroleum, and the Exxon Biomedical Sciences, Inc.:
Total Petroleum Hydrocarbon D.A. Edwards, Ph.D.
Criteria Working Group M.D. Andriot, Ph.D.
M.A. Amoruso, Ph.D.
A.C. Tummey
C.J. Bevan, Ph.D.
A. Tveit, Ph.D.
L.A. Hayes, M.S., MLS
EA Engineering, Science, and
Technology, Inc.:
S.H. Youngren, Ph.D.
Remediation Technologies, Inc.:
D.V. Nakles, Ph.D.
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CONTENTS
PREFACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
I. INTRODUCTION/BACKGROUND . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
A. Hazard Assessment for TPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1. Methodology for Human Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Ecological Considerations and Assessment of New Toxicity Data . . . . 4
B. Evaluation of Toxicity Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1. USEPA Methodology for RfD/RfC Development . . . . . . . . . . . . . . . . . 5
2. Prioritization of Toxicity Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
II. SUMMARY/CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
III. EVALUATION OF AROMATIC FRACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
A. C - C and C - C Aromatic Fraction . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5 6 >7 8
1. Oral . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2. Inhalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
B. C - C , C - C , and C - C Aromatic Fraction . . . . . . . . . . . . . . . . 12
8 10 >10 12 >12 16
1. Oral . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
2. Inhalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
C. C - C and C - C Aromatic Fraction . . . . . . . . . . . . . . . . . . . . . . . 14
>16 21 >21 35
1. Oral . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2. Inhalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
D. Overall Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
IV. EVALUATION OF ALIPHATIC FRACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
A. C - C and C - C Aliphatic Fraction . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5 6 >7 8
1. n-Heptane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2. Commercial Hexane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3. Other C - C Alkane/Cycloalkane Compounds . . . . . . . . . . . . . . . . . 17
5 8
4. Proposed Composition-Weighted RfD for TPH Fraction
Containing C - C or C - C Aliphatics . . . . . . . . . . . . . . . . . . . . . . 19
5 8 6 8
v
B. C - C , C - C , and C - C Aliphatic Fraction . . . . . . . . . . . . . . . . 21
8 10 >10 12 >12 16
1. Summary of Inhalation Studies on
Dearomatized Petroleum Streams and JP-8 . . . . . . . . . . . . . . . . . . 22
2. Summary of Oral Gavage Studies on
Petroleum Streams and JP-8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3. Summary and Conclusions for Oral RfDs and Inhalation RfCs . . . . . . 28
C. C - C and C - C Aliphatic Fraction . . . . . . . . . . . . . . . . . . . . . . . 29
>16 21 >21 35
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2. Data Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3. Rationale for RfD Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
APPENDICES
A. Literature Review (Individual Compounds) . . . . . . . . . . . . . . . . . . . . . . . 43
Attachment I - Results of Total Petroleum Hydrocarbons
(TPH) Literature Search . . . . . . . . . . . . . . . . . . . . . . . . 47
Attachment II - EBSI Modified Deliverable . . . . . . . . . . . . . . . . . . . . . . 53
B. Toxicity Summaries for Both Aromatic and Aliphatic
Constituents in the C to C Carbon Range . . . . . . . . . . . . . . . . . . . . . . 81
4 22
C. Review of American Petroleum Institute (API’s)
Toxicity Data on Selected Refinery Streams . . . . . . . . . . . . . . . . . . . . 101
Attachment I - Composition Data on Selected Refinery Streams . . . . . 123
vi
PREFACE
This document is fourth in a series from the Total Petroleum Hydrocarbon
Criteria Working Group (TPHCWG). The Working Group was formed in 1993
based on the observation that widely different clean-up requirements were being
used by states at sites that were contaminated with hydrocarbon materials such as
fuels, lubricating oils, and crude oils. These requirements were usually in the form
of concentrations of total petroleum hydrocarbon, otherwise known as TPH, and
ranged from 10 to over 10,000 milligrams of hydrocarbons per kilogram of soil.
Members of the group jointly recognized that the numerical standard was not
based on a scientific assessment of human health risk and they established the fol-
lowing goal for their effort:
To develop scientifically defensible information for establishing soil cleanup lev-
els that are protective of human health at hydrocarbon contaminated sites.
The Working Group is guided by a steering committee consisting of representa-
tives from industry, government, and academia. Some of the active participants
among the more than 400 involved, include the Gas Research Institute, the
Petroleum Environmental Research Forum, several major petroleum companies
including Chevron, Exxon, and Shell, the American Petroleum Institute, the
Association of American Railroads, several state governments (i.e., Washington,
Texas, Colorado, Hawaii, Louisiana, New Mexico), the U.S. Environmental
Protection Agency, the Department of Defense, and many consulting firms such as
EA Engineering, Science and Technology.
An overlying theme to this document is the importance of exposure potential
when defining human health risk. The fate and transport of a chemical or mixture
defines the exposure route and, in conjunction with receptor properties, concen-
trations at receptors. If fate and transport is not considered, unrealistic human
health risks could be calculated, resulting in misinformed decisions about site
clean-up, regulatory guidance, etc.
This document summarizes the methods used to delineate TPH into equivalent
carbon number fractions based on fate and transport considerations. The input into
the fraction method included composition data on many common fuels and petro-
leum products. This information is provided in detail in Volume 2 of the Working
Group reports. Once the fractions were defined, fraction-specific values of relevant
physical-chemical properties were calculated based on correlations to boiling point.
Companion volumes include Volume 1 which provides an overview of the com-
plexities of petroleum hydrocarbon characterization and risk assessment and a dis-
cussion on the analytical methods available. In addition to descriptions about gen-
eral analytical methods we have also provided a summary of a proposed GC-based
analytical method developed by the Working Group that reports hydrocarbon
results in equivalent carbon number groups or fractions.
vii
To complete the risk-based approach, the Working Group has also selected tox-
icity criteria (e.g., Reference Doses) for each of the defined fate and transport frac-
tions. The evaluation of the toxicology research database and rationale behind the
toxicity criteria selected is described in detail in Volume 4, “Development of
Fraction-Specific Toxicity Criteria for Total Petroleum Hydrocarbons (TPH)” (in
preparation). The analytical method, fate and transport considerations and toxici-
ty criteria are the technical elements which fit into a risk-based framework for
determining human health based criteria at petroleum hydrocarbon contaminat-
ed sites. The group selected the American Society for Testing and Materials
(ASTM) Risk Based Corrective Action - RBCA framework as an example of how
these elements can be used to calculate risk-based screening levels driven by non-
cancer human health risk for petroleum contaminated sites. We hope you find this
document to be useful in your efforts to evaluate and determine acceptable risk-
based criteria at petroleum sites.
viii
ACKNOWLEDGMENTS
The publication of this volume of the Total Petroleum Hydrocarbon Criteria
Working Group Methodology would not have been possible without the hard work
and dedication of individuals and organizations across the public and private sec-
tors. Specifically, we would like to acknowledge the following members of the
TPHCWG steering committee.
Beth Albertson*, Friedman and Bruya
Roger Andes and Christopher P.L. Barkan, Association of American Railroads
Bruce Bauman, Roger Claff, Judith Shaw and Lorraine Twedock, API
Barbara Brooks, Hawaii Department of Health
Deborah Edwards and Joan Tell, Exxon Biomedical Sciences, Inc.
John Fitzgerald, Massachusetts Department of Environmental Protection
Kathy Garland*, New Mexico EMNRD
Joseph Greenblott and Bruce Peirano, US EPA
John Gustafson, Bruce Krewinghaus, Ross MacDonald, Ileana Rhodes, Shell
Development Company
Keith Hoddinott, US Army
Jim Holler, Agency for Toxic Substances and Disease Registry
Paul Kostecki and Tom Potter, University of Massachusetts, Amherst
William Kucharski*, GECCO Inc.
Mark Laughman, Louisiana Department of Environmental Quality
Katherine Kurtz, Navy Environmental Health Center
David Linz*, LinzTech
David Nakles, RETEC
Doug Orem and Susan Youngren, EA Environmental Science and Engineering
Wade Weisman*, US Air Force Armstrong Lab.
Robert Wilkenfeld*, Chevron
* members of Executive Committee
The TPHCWG would like to thank the following reviewers for their helpful sug-
gestions and comments: Jane Sutherlin, LADEQ; James Evans, GRI; Peter Miasek,
Imperial Oil; Bill Lowery, NJDEP; Adolfo Silva, Petro Canada; Daniel Smith, USAF;
and Fred Reitman, Texaco.
Additionally, we would like to commend Donna Voorhees (Menzie-Cura) and
Tamlyn Oliver (AEHS) for their adept assistance in editing and publication of this
document.
ix
I. INTRODUCTION/BACKGROUND
The purpose of Volume 4 is to provide the basis for the development of fraction-spe-
cific reference doses/concentrations (RfDs/RfCs) for total petroleum hydrocarbon
(TPH). The development of fraction-specific RfDs/RfCs provides for the hazard
assessment of the TPH in the TPHCWG’s risk assessment methodology (Figure 1).
The selection of the most appropriate method for evaluating the risk of TPH is
described below. The methodology selected was termed the indicator/surrogate
approach, which is consistent with U.S. Environmental Protection Agency (USEPA)
methodology and is illustrated in Figure 2 (USEPA, 1986). The indicators referred
to are the single compounds within petroleum which are known to be carcinogens
and which are evaluated/regulated individually (either federally or at state level).
The surrogates for which RfDs/RfCs are developed are noncarcinogenic mixtures
(fractions) which represent the mass of petroleum remaining after evaluation of the
carcinogenic indicators. Indicators are evaluated first because their presence (even
in relatively low concentrations) will drive a cleanup, due to their greater relative
potency. The hazard assessment for TPH fractions would be utilized where indica-
tor compounds are not present or are below regulatory criteria.
A. HAZARD ASSESSMENT FOR TPH
1. Methodology for Human Health
In order to develop a human health-based method for deriving cleanup levels for petro-
leum hydrocarbons in soil and groundwater, the authors surveyed the scientific litera-
ture to identify methods used to assess the potential health effects of petroleum hydro-
carbons. Over 30 scientific papers and reports were reviewed and the citations can be
found in the General section of the reference list. Based on this review, the approach-
es fit into two general categories: (1) use of toxicity data for the whole mixture or parent
product (e.g., diesel fuel, gasoline, jet fuel, etc.) and (2) use of an indicator surrogate
approach to assess the risk and toxicity posed by the mixture. The strengths, weakness-
es, and the applicability of these scientific approaches were evaluated.
Ideally, a hazard assessment should be conducted utilizing data on the mixture
to which the receptor of concern is exposed. Utilizing data on the actual mixture
present accurately accounts for the interactive effects of all components in the
mixture. (Michelson and Boyce, 1993; Krewski and Thomas, 1992; WSDE, 1994;
Warshawsky et al., 1993). Currently, these data are not available. The data which
are available are (1) data on some whole mixtures or parent products (e.g., gaso-
line, jet fuel and mineral oil), (2) data on some individual compounds (indicators;
e.g., benzene, benzo[a]pyrene) and (3) data on some fraction-specific mixtures.
Toxicity data on whole mixtures or parent products are only available for gaso-
line, jet fuel, and mineral oil. Thus for other parent products (such as bunker fuel,
diesel, lube oils, etc.) a whole mixture approach is not appropriate.
In addition, once in the environment the parent product separates into fractions
based on differences in fate and transport (Volume 3, TPHCWG methodology).
The mixture to which a receptor is exposed will vary with space, time, and by media.
Thus, a whole mixture approach would not be appropriate for a weathered release.
1
