API 4593 : 1994

Executive summary
1.0 Introduction
2.0 Methods
2.1 Chemical classes considered
2.2 Selection of candidate chemicals for detailed
         evaluation
2.2.1 Chemical composition of petroleum products
2.2.2 Physical/chemical properties
2.2.3 Mammalian and aquatic toxicology
2.2.4 Transport and fate
2.2.5 Analysis
2.2.6 Information needs
2.3 Chemicals evaluated in greater detail
3.0 Chemical composition and properties of petroleum
         products
3.1 General properties
3.2 Crude petroleum
3.2.1 Complexity of crude oil
3.2.2 Alkanes
3.2.3 Aromatic hydrocarbons
3.2.4 Organic compounds containing sulfur, nitrogen or
         oxygen
3.2.5 Resins and asphaltenes
3.2.6 The saturated hydrocarbon assemblage
3.2.7 The aromatic/heterocyclic assemblage
3.3 Gasoline
3.3.1 Refining
3.3.2 Composition
3.4 Middle distillate fuels
3.4.1 Refining
3.4.2 Jet fuels
3.4.3 Kerosene
3.4.4 Heating oils
3.4.5 Diesel fuels
3.5 Residual petroleum products
3.6 Used lubricating oils
3.7 Petroleum chemicals chosen for further evaluation
4.0 Sources and fates of selected compounds in soils
         and groundwater
4.1 Petroleum-derived chemicals in soils and groundwater
4.1.1 Petroleum consumption
4.1.2 Releases to soil and groundwater
4.2 Petroleum-type chemicals from other sources in soils
4.2.1 Other fossil fuels
4.2.2 Pyrosynthesis
4.2.3 Biosynthesis
4.3 Concentrations of hydrocarbons in soils
4.4 Fates of hydrocarbons in soils and groundwater
4.4.1 Distribution of hydrocarbon assemblage in soils
4.4.2 Migration
4.4.3 Evaporation
4.4.4 Dissolution
4.4.5 Photooxidation
4.4.6 Biodegradation
4.4.7 Fate of compounds of concern in soils
5.0 Subsurface transport of petroleum hydrocarbons
5.1 Introduction
5.2 General subsurface transport processes
5.2.1 NAPL transport processes
5.2.2 Partitioning
5.2.3 Dissolved and gaseous phase transport processes
5.2.4 Special conditions
5.3 Relative subsurface transport for selected petroleum
         hydrocarbon constituents
5.3.1 NAPL transport
5.3.2 NAPL partitioning
5.3.3 Dissolved phase partitioning
5.3.4 Dissolved phase transport process
5.3.4.1 Retardation approach
5.3.4.2 EPA HRS mobility approach
5.4 Summary
6.0 Biological effects
6.1 Introduction
6.2 Aquatic toxicology
6.2.1 Toxicity of petroleum products to aquatic organisms
6.2.2 Bioavailability of petroleum hydrocarbons to aquatic
         organisms
6.3 Mammalian toxicology
6.3.1 Benz(a)anthracene
6.3.2 Benzo(a)pyrene
6.3.3 5-Methylchrysene
6.3.4 1-Methylphenanthrene
6.3.5 Dibenzothiophene
6.3.6 1,2,4-Trimethylbenzene
6.3.7 Naphthalene
6.3.8 2-Methylnaphthalene
6.3.9 Cyclohexane
6.3.10 n-Hexane
6.3.11 2,3-Dimethylbutane
6.3.12 2,2-Dimethylpentane
6.4 Summary
7.0 Analysis of petroleum hydrocarbons in soil and
         groundwater
7.1 Standard analytical methods
7.2 Volatile hydrocarbons
7.3 Semivolatile hydrocarbons
8.0 Information gaps and recommendations
8.1 Physical/chemical parameter values
8.2 Equilibrium between petroleum products and soil water
8.3 Bulk migration of petroleum products through soils
8.4 Human toxicology of abundant chemicals in petroleum
         products
9.0 References
List of Appendices
Appendix A - Petroleum hydrocarbon composition data
Appendix B - Physical/chemical properties of petroleum
             compounds
Appendix C - Toxicity data summary
TABLE
3-1 The saturated (alkane) hydrocarbon distribution of
         two crude and two refined oils. Concentrations are
         in weight percent
3-2 Physical/chemical parameter values
4-1 Physical properties of crude, refined, residual, and
         waste oil that affect their behaviour in soils
4-2 Solubility of crude, refined and residual petroleum
         products and the most abundant aromatic hydrocarbons
         in their water-soluble fractions.
5-1 Regression equations for the estimation of Koc
5-2 Koc, Kd, and R values for the compounds of interest
         and BTEX
5-3 Numerical results of three-phase partitioning
         calculations
5-4 Numerical results of two-phase partitioning
         calculations
5-5 Assigned values for mobility in the EPA hazard ranking
         system
5-7 Compound categorization based on relative subsurface
         mobility
6-1 Acute toxicity to freshwater organisms of water-soluble
         fractions of selected crude and refined petroleum
         products
7-1 Volatile hydrocarbons
7-2 PAH and Alkyl homologue PAH target compounds
FIGURE
3-1 Structure of the most abundant classes of organic
         chemicals in crude and refined petroleum
3-2 Boiling point range of fractions of crude petroleum
4-1 Gasoline evaporation from sea surface, assuming
         20MPH wind, 10degreesC temperature, 1000 BBL, boomed
         area 34,000sq ft.
4-2 Evaporation of forties crude oil, 0.835g/ml, 32.7
         percent distilled at 180 degrees C
4-3 Bacterial degradation of naphthalene, effect of
         oxygen in sediments
5-1 Triangular diagram used to illustrate equilibrium
         partitioning (compound X is partitioned 70 percent
         onto soil, 20 percent into air, and 10 percent into
         water)
5-2 Triangular diagram displaying the expected
         partitioning between air, water, and soil for a
         soil of relatively low organic carbon content
5-3 Triangular diagram displaying the expected
         partitioning between air, water, and soil for a soil
         of relatively high organic carbon content
5-4 Diagram displaying the expected partitioning
         between water and soil for a soil of relatively low
         organic carbon content
5-5 Diagram displaying the expected partitioning between
         water and soil for a soil of relatively high
         organic carbon content
5-6 Graphical display of retardation factors calculated
         for two different soil types
5-7 Graphical display of mobility values that would
         apply for each compound using the EPA hazard ranking
         system
6-1 Relationship between aqueous solubility of
         petroleum hydrocarbons and their toxicity to
         freshwater organisms
6-2 Relationship between Log Kow of selected PAH and
         sulfur heterocytics and bioconcentration factors
         (BCF) in freshwater animals
7-1 Extraction procedure for sediment and soil samples
7-2 Extraction procedure for groundwater samples
7-3a Extract cleanup column procedure
7-3b Procedure for fractionation by extracts of
         environmental samples containing hydrocarbons by
         HPLC to obtain F1 (saturated), F2 (aromatic), and
         F3 (polar) fractions for gas chromatic analysis
7-4 Instrumental procedures for analysis of cleaned up
         extracts of environmental samples by gas
         chromatography with quantification by mass
         spectrometry