EPA/600/R-03/072
July 2003
Characteristics of Spilled Oils, Fuels, and Petroleum
Products:
1. Composition and Properties of Selected Oils
Zhendi Wang, B.P. Hollebone, M. Fingas, B. Fieldhouse,
L. Sigouin, M. Landriault, P. Smith, J. Noonan, and G. Thouin
Emergencies Science and Technology Division
Environmental Technology Centre
Environment Canada
335 River Road, Ottawa, Ontario
James W. Weaver
Project Officer
Ecosystems Research Division
Athens, Georgia 30605
National Exposure Research Laboratory
Office of Research and Development
United States Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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Notice
The U.S. Environmental Protection Agency through its Office of Research and Development funded
and managed the research described here under contract (1D-5859-NAFX) to Environment Canada.
It has been subjected to the Agency's peer and administrative review and has been approved for
publication as an EPA document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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Foreword
The National Exposure Research Laboratory's Ecosystems Research Division (ERD) in Athens,
Georgia, conducts research on organic and inorganic chemicals, greenhouse gas biogeochemical cycles,
and land use perturbations that create direct and indirect, chemical and non-chemical stresses,
exposures, and potential risks to humans and ecosystems. ERD develops, tests, applies and provides
technical support for exposure and ecosystem response models used for assessing and managing risks
to humans and ecosystems, within a watershed / regional context.
The Regulatory Support Branch (RSB) conducts problem-driven and applied research, develops
technology tools, and provides technical support to customer Program and Regional Offices, States,
Municipalities, and Tribes. Models are distributed and supported via the EPA Center for Exposure
Assessment Modeling (CEAM) and through access to Internet tools (www.epa.gov/athens/onsite).
At the request of the US EPA Oil Program Center, ERD is developing an oil spill model that focusses
on fate and transport of oil components under various response scenarios. Since crude oils and
petroleum products are composed of many chemicals that have varying physical properties, data are
required to characterize these fluids for use in models. The data presented in this report provide input
to compositional models by characterizing oil composition by several approaches, but also by providing
physical transport properties at corresponding levels of weathering and temperature. EPA expects
these data to be useful both for modeling and to provide a resource for the oil spill response community
as a whole.
Rosemarie C. Russo, Ph.D.
Director
Ecosystems Research Division
Athens, Georgia
in
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Abstract
Multicomponent composition and corresponding physical properties data of crude oils and petroleum
products are needed as input to environmental fate simulations. Complete sets of such data, however,
are not available in the literature due to the complexity and expense of making the measurements.
Environment Canada has previously developed a database of various physical and chemical properties
of crude oils and petroleum products. In this cooperative project, ten "typical" crude oils and refined
products in common use or transport were identified for subsequent characterization. Measured oil
physical properties include API gravity, density, sulphur content, water content, flash point, pour point,
viscosity, surface and interfacial tension, adhesion, the equation for predicting evaporation, emulsion
formation, and simulated boiling point distribution. The chemical composition of the oils are quantified
for hydrocarbon groups, volatile organic compounds, n-alkane distribution, distribution of alkylated
polyaromatic hydrocarbon (PAH) homologues and other EPA priority PAHs, and biomarker
concentrations. This project will provide the most complete and comprehensive database for the
selected oils to date. The new composition data will be integrated into the existing Environment Canada
oil properties database. The results will be made available to the public both on the world wide web
and as a database on disc.
IV
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Table of Contents
Notice ii
Foreword iii
Abstract iv
1. Introduction 1
2. List of Definitions 3
3. Methods for Measurement of Physical and Chemical Properties of Selected Oils 10
4. Summary of Quality Assurance and Quality Control (QA/QC) Plan 28
5. Physical Properties and Chemical Composition of Alaska North Slope Crude Oil (2002)
34
6. Physical Properties and Chemical Composition of Alberta SweetMixed Blend (ASMB, Reference
#5) 46
7. Physical Properties and Chemical Composition of Arabian Light (2000) 58
8. Physical Properties and Chemical Composition of Sockeye (2000) 70
9. Physical Properties and Chemical Composition of South Louisiana (2001) 82
10. Physical Properties and Chemical Composition of West Texas Intermediate (2002) ... 94
11. Physical Properties and Chemical Composition of Fuel Oil No. 2/Diesel (2002) 106
12. Physical Properties and Chemical Composition of Fuel Oil No. 5 (2000) 118
13. Physical Properties and Chemical Composition of Heavy Fuel Oil 6303 (2002) 129
14. Physical Properties and Chemical Composition of Orimulsion-400 (2001) 140
15. Trace Metals 148
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16. References 149
17. Appendices 153
1 Chemical Abstract Service (CAS) Registry Numbers for Selected Analytes 153
2 Oil Chemical Analysis Protocol 156
3 GC Chromatograms for Alaska North Slope Crude Oil 157
4 GC Chromatograms for Alberta Sweet Mixed Blend #5 Crude Oil 170
5 GC Chromatograms for Arabian Light Crude Oil 182
6 GC Chromatograms for Sockeye Crude Oil 194
7 GC Chromatograms for South Louisiana Crude Oil 208
8 GC Chromatograms for West Texas Intermediate Crude Oil 220
9 GC Chromatograms for Fuel Oil Number 2 231
10 GC Chromatograms for Fuel Oil Number 5 245
11 GC Chromatograms for HFO 6303 257
12 GC Chromatograms for Orimulsion-400 270
VI
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1. Introduction
During any oil spill incident, the properties of the spilled oil, including the oil phase composition and
oil compositional changes due to weathering, ideally would be known immediately, so that models could
be used to predict the environmental impacts of the spill or various treatment alternatives. Unfortunately,
the properties routinely measured by oil producers and refiners are not the ones that on-scene commanders
need to know most urgently. Oil producers and refiners typically do not know to what extent or at what
rate their oils will evaporate; the detailed chemical composition of the oil and its differential compositional
changes overtime; how these changes affect its behavior and fate in the environment; the viscosity of the
oil at ambient temperature as it evaporates; if the oil likely to sink or submerge; if the use of chemical
dispersants can enhance its dispersion; if emulsions will form; the hazard to on-site personnel during
cleanup; or the oil toxicity to marine or aquatic organisms.
Since 1984, the Emergencies Science and Technology Division (ESTD) of Environment Canada
has continued to develop a database on various physical-chemical properties of crude oils and petroleum
products. This database addresses the properties and behaviors listed in the previous paragraph and can
be queried via the internet at www.etcgntre.org/spills^ Through many years endeavor, the oil properties
database now contains information on over 400 oils from all over the world. Environment Canada is the
largest single source of data in the oil properties database.
The U. S. EPA's immediate interest in developing a database of properties and compositions is for
use in supporting the development of models for application to accidental spills and releases of petroleum
hydrocarbons and other multicomponent oils. This multicomponent composition data is not typically
available in the literature nor immediately available on an incident-specific basis due to the complexity and
expense of making the measurements. Thus the creation of a database containing both physical property
and composition data for various conditions of weathering would be useful for emergency response
modeling. In this situation the data could be used for simulation of an example oil that would be chosen for
its similarity to the spilled oil. This approach recognizes that performing detailed characterization of an oil
during an emergency is more than unlikely. It would further be desirable to have access to similar data for
planning purposes in advance of spills.
Ten representative oils and refined petroleum products with spill potential were chosen after
discussion with the US EPA. These oils were collected from various sources. For each oil, the properties
presented are those that determine its environmental behavior and effects. Whenever possible, ESTD has
used standard test methods, such as those of the American Society for Testing and Materials (ASTM), to
obtain oil property data. The physical property measurements include API gravity, density, sulphur, water
content, flash point, pour point, viscosity, vapor pressure, surface tension, and adhesion. Many oil analytical
methods have been developed by ESTD specifically to determine environmentally-significant individual
components, oil hydrocarbon groups, and chemical properties. These include methods for determining
evaporation equations, emulsion formation and characterization, measuring chemical dispersibility,
measuring volatile organic compounds, important saturated and biomarker compounds, and environmentally
hazardous PAH compounds. Because evaporative loss results in significant changes in physical properties
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and chemical composition of spilled oils, we measure most properties not only for fresh oils, but also for
evaporated oils prepared in the lab to represent various degrees of evaporation. Upon the completion of
the proj ect, a complete set of physical properties and comprehensive multicomponent data on important
chemical composition of the selected oils will be provided and integrated into the existing ESTD database.
Finally, the unique information produced from this proj ect is intended by EPA to advance the state-of-the-
art of oil spill modeling. As such it will be available to the public through the Internet at
www.etcentre.org/spills.
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2. List of Definitions
Acyclic: A compound with straight or branched carbon-carbon linkages but without cyclic (ring)
structures.
Adhesion: The degree to which an oil will coat a surface, expressed as the mass of oil adhering per unit
area. A test has been developed for a standard surface that gives a semi-quantitative measure of this
property.
Aliphatics: Hydrocarbons in petroleum that contain saturated and/or single unsaturated bonds and elute
during chromatography using non-polar solvents such hexane. It includes alkanes and alkenes, but not
aromatics.
Alkane (Paraffin): A group of hydrocarbons composed of only carbon and hydrogen with no double
bonds or aromaticity. They are said tobe "saturated" with hydrogen. They may by straight-chain (normal),
branched or cyclic. The smallest alkane is methane (CH4), the next, ethane (CH3CH3), then propane
(CH3CH2CH3), and so on.
Alkene (Olefin): An unsaturated hydrocarbon, containing only hydrogen and carbon with one or more
double bonds, but having no aromaticity. Alkenes are nottypically found in crude oils, but can occur as
a result of heating.
Alkyl Groups: ^hydrocarbon functional group (QH^+i) obtained by dropping one hydrogen from fully
saturated compound; e.g., methyl (-CH3), ethyl (-CH2CH3), propyl (-CH2CH2CH3), or isopropyl
[(CH3)2CH-].
API Gravity: An American Petroleum Institute measure of density for petroleum:
API Gravity = [141.5/(spedfie gravity at 15.6 °C) - 131.5]
Fresh water has a gravity of 10 ° API. The scale is commercially important for ranking oil quality. Heavy,
inexpensive oils are < 25 ° API; medium oils are 25 to 3 5 ° API; light, commercially-valuable oils are 3 5
to 45 °APL.
Aromatics: Cyclic, planar hydrocarbon compounds that are stabilized by a delocalized TT-electron
system. They include such compounds as the BTEXgroup (benzene, toluene, ethylbenze and the three
xylene isomers), polycyclic aromatic hydrocarbons (PAHs, such as naphthalene), and some heterocyclic
aromatics such as the di-benzothiophenes.
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Asphaltenes: A complex mixture of heavy organic compounds precipitated from oil s and bitumens by
natural processes or in laboratory by addition of excess w-pentane, or w-hexane. After precipitation of
asphaltenes, the remaining oil or bitumen consists of saturates, aromatics, and resins. Asphaltenes are
so named because they make up the largest percentage of the asphalt used to pave roads.
Biological Marker (Biomarker): Complex organic compounds composed of carbon, hydrogen, and
other elements which are found in oil, bitumen, rocks, and sediments and which have undergone little or
no change in structure from their parent organic molecules in living organisms. Most, but not all, biomarkers
are isoprenoids, composed of isoprene subunits. Biomarkers include pristane, phytane, triterpanes,
steranes, porphyrins, and other compounds. These compounds are typically analyzed by GC/MS.
Bitumen: Mixture ofhydrocarbons of natural or pyrogenous origin or a combination of both. Unlike oil,
bitumen is indigenous to the fine-grained rock in which it is found.
Boiling Point: The temperature at which a liquid begins to boil. That is, it is the temperature at which the
vapour pressure of a liquid is equal to the atmospheric or external pressure. It is measured at standard
pressure. The boiling point distributions of crude oils and petroleum products may be in a range from 3 0
°C to 700 °C.
BTEX: The collective name given to benzene, toluene, ethylbenzene and the xylene isomers (p-,m-, and
o-xylene).
Carbon Preference Index (CPI): The ratio of odd to even w-alkanes. Odd/even CPI alkanes are
equally abundant in petroleum but not in biological material. A CPI near 1 is an indication of petroleum.
Check Standard: An analyte with a well-characterized property of interest, e.g., concentration, density,
etc... used to verify method, instrument and operator performance during regular operation. Check
standards may be obtained from a certified supplier, may be a pure sub stance with properties obtained
from the literature or may be developed in-house.
Chemical Dispersion: In relation to oil spills, this term refers to the creation of oil-in-water emulsions
by the use of chemical dispersants made for this purpose.
Complex Modulus: The complex modulus is a measure of the overall resistance of a material to flow
under an applied stress, in units offeree per unit area. It combines viscosity and elasticity elements to
provide a measure of "stiffness", or resistance to flow. The complex modulus is more useful than viscosity
for assessing the physical behaviour of very non-Newtonian materials such as emulsions.
Cycloalkanes (Naphthene, Cycloparaffin): A saturated, cyclic compound containing only carbon and
hydrogen. One of the simplest cycloalkanes is cyclohexane (C6H12). Steranes and triterpanes are branched
naphthenes consisting of multiple condensed five- or six-carbon rings.
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Density: The mass per unit volume of a substance. Density is temperature-dependent, generally
decreasing with temperature. The density of oil relative to water, its specific gravity, governs whether a
particular oil will float on water. Most fresh crude oils and fuels will float on water. Bitumen and certain
residual fuel oils, however, may have densities greater than water at some temperature ranges and may
submerge in water. The density of a spilled oil will also increase with time as components are lost due to
weathering.
Dispersants or Chemical Dispersants: Chemicals that reduce the surface tension between water and
a hydrophobic substance such as oil. In the case of an oil spill, dispersants facilitate the breakup and
dispersal of an oil slick throughout the water column in the form of an oil-in-water emulsion. Chemical
dispersants can only be used in areas where biological damage will not occur and must be approved for
use by government regulatory agencies.
Emulsion: A stable mixture of two immiscible liquids, consisting of a continuous phase and a dispersed
phase. Oil and water can form both oil-in-water and water-in-oil emulsions. The former is termed a
dispersion, while emulsion implies the latter. Water-in-oil emulsions formed from petroleum and brine can
be grouped into four stability classes: stable, aformal emulsion that will persist indefinitely; meso-stable,
which gradually degrade over time due to a lack of one or more stabilizing factors; entrained water, a
mechanical mixture characterized by high viscosity of the petroleum component which impedes separation
of the two phases; and unstable, which are mixtures that rapidly separate into immiscible layers.
Emulsion stability is generally accompanied by a marked increase mviscosity and elasticity, over that of
the parent oil which significantly changes behaviour. Coupled with the increased volume due to the
introduction of brine, emulsion formation has a large effect on the choice of countermeasures employed to
combat a spill.
Emulsification: The process of emulsion formation, typically by mechanical mixing. In the environment,
emulsions are most often formed as a result of wave action. Chemical agents can be used to prevent the
formation of emulsions or to "break" the emulsions to their component oil and water phases.
Equipment Blank: A sample of analyte-free media which has been used to rinse the sampling equipment.
It is collected after completion of decontamination and prior to sampling. This blank is useful in documenting
and controlling the preparation of the sampling and laboratory equipment.
"Fingerprint": A chromatographic signature of relative intensities used in oil-oil or oil-source rock
correlations. Mass chromatograms ofstemnes or terpanes are examples ofjingerprints that can be used
for qualitative or quantitative comparison of oils.
Flash Point: The temperature at which the vapour over a liquid will ignite when exposed to an ignition
source. A liquid is considered to be flammable if its flash point is less than 60 °C.
Flashpointis an extremely important factor in relation to the safety of spill cleanup operations. Gasoline
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and other light fuels can ignite under most ambient conditions and therefore are a serious hazard when
spilled. Many freshly spilled crude oils also have \owflashpoints until the lighter components have
evaporated or dispersed.
GC-MS: Gas chromatography-mass spectrometry.
GC-TPH: GC detectable total petroleum hydrocarbons, thatisthe sum of all GC-resolved and unresolved
hydrocarbons. The resolvable hydrocarbons appear as peaks and the unresolvable hydrocarbons appear
as the area between the lower baseline and the curve defining the base of resolvable peaks.
Hydrocarbon: A hydrocarbon is an organic compound containing only hydrogen and carbon.
Hydrocarbons are the principal constituents of crude oils and refined petroleum products. Oil hydrocarbons
can be grouped into four major classes of compounds: saturates (including waxes)., aromatics,
asphaltenes, and resins.
Hopane: Pentacyclic hydrocarbons of the triterpane group believed to be derived primarily from
bacteriohopanoids in bacterial membranes.
Interfacial Tension: The net energy per unit area at the interface of two substances, such as oil and water
or oil and air. The air/liquid interfacial tension is often referred to as surface tension. The SI units for
interfacial tension are milliNewtons per meter (mN/m). The higher the interfacial tension., the less
attractive the two surfaces are to each other and the more size of the interface will be minimized. Low
surface tensions can drive the spreading of one fluid on another. The surface tension of an oil, together its
viscosity, affects the rate at which spilled oil will spread over a water surface or into the ground.
Internal Standard (IS): A pure analyte added to a sample extract in a known amount, which is used to
measure the relative responses of other analytes and surrogates that are components of the same solution.
The internal standard must be an analyte that is not a sample component.
PAHs: Polycyclic aromatic hydrocarbons. MkylatedPAHs are alkyl group derivatives of the parent
PAHs. The five target alkylated PAHs referred to in this report are the alkylated naphthalene,
phenanthrene, dibenzothiophene, fluorene, and chrysene series.
Polar Compounds: An organic compound with distinct regions of positive and negative charge. Polar
compounds include alcohols, such as sterols, and some aromatics, such as monoaromatic-steroids.
Because of their polarity, these compounds are more soluble in polar solvents, including water, compared
to non-polar compounds of similar molecular structure.
Pour Point: The lowest temperature at which an oil will appear to flow under ambient pressure over a
period of five seconds. Thepour point of crude oils generally varies from -60 °C to 30 °C. Lighter oils
with low viscosities generally have lower pour points.
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Resins: This is the name given to a large group of polar compounds in oil. These include hetero-
substitutedarowato, acids, ketones, alcohols and monoaromatic steroids. Because of their polarity, these
compounds are more soluble mpolar solvents, including water, than the non-polar compounds, such as
waxes and aromatics, of similar molecular weight. They are largely responsible for oil adhesion.
RRF: Relative response factor.
Saturates (Saturated Fraction): Nonammatichydrocarbons in petroleum. This grouping includes both
normal and branched alkanes (paraffins), and cycloalkanes (naphthenes).
SIM (Selecting Ion Monitoring): Mass spectrometric monitoring of a specific mass/charge (m/z) ratio.
The 57Mmode offers better sensitivity than can be obtained using the full scan mode.
Solubility: The amount of a substance (solute) that dissolves in a given amount of another substance
(solvent). Particularly relevant to oil spill cleanup is the measure of how much and the composition of oil
which will dissolve in the water column. This is important as the soluble fractions of the oil are often toxic
to aquatic life, especially at high concentrations. Thesolubilify of oil in water is very low, generally less than
1 parts per million (ppm).
Steranes: A class of tetracyclic, saturated biomarkers constructed from six isoprene subunits (~C30).
Steranes are derived from sterols, which are important membrane and hormone components in eukaryotic
organisms. Most commonly used Steranes are in the range of C26 to C30 and are detected using m/z 217
mass chromatograms.
Surrogate Analyte: A pure analyte that is extremely unlikely to be found in any sample, which is added
to a sample aliquot in a known amount and is measured with the same procedures used to measure other
components. The purpose ofasurrogate analyte is to monitor the method performance with each sample.
Terpanes: A broad class of complex branched, cyclic alkane biomarkers including hopanes and tricyclic
compounds. They are commonly monitored using m/z 191 mass chromatograms.
Triterpanes: A class of cyclic saturated biomarkers constructed from six isoprene subunits. Cyclic
terpane compounds containing two, four, and six isoprene subunits are called monoterpane (C10),
diterpane (C20) and triterpane (C30), respectively.
Total n-alkanes: The sum of all resolved n-alkanes (from C8 to C40 plus pristane and phytane).
Total 5 Alkylated PAH Homologues: The sum of the 5 target PAHs (naphthalene, phenanthrene,
dibenzothiophene, fluorene, chry sene) and their alkylated (Q to C4) homologues, as determined by GC-
MS. These 5 target alkylated PAH homologous series are oil-characteristic aromatic compounds.
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Total Aromatics: The sum of all resolved and unresolved aromatic hydrocarbons including the total of
BTEX and other alkyl benzene compounds, total 5 target alkylated PAH homologues, and other EPA
priority PAHs.
Total Saturates: The sum of all resolved and unresolved aliphatic hydrocarbons including the total n-
alkanes, branched alkanes, and cyclic saturates.
Vapour Pressure: A measure of how oil partitions between the liquid and gas phases, or the partial
pressure of a vapour above a liquid oil at a fixed temperature.
Viscosity: Viscosity is the resistance of a fluid to shear, movement or flow. The viscosity of an oil is a
function of its composition. In general, the greater the fraction of saturates and aromatics and the lower
the amount ofasphaltenes and resins, the lower the viscosity. As oil weathers, the evaporation of the
lighter components leads to increased viscosity. Viscosity also increases with decreased temperature, and
decreases with increased temperature.
The viscosity of an ideal, non-interacting fluid does not change with shear rate. Such fluids are called
Newtonian. Most crude oils and oil products are Newtonian. The viscosity of non-Newtonian materials
may vary with shear rate, as well as duration of shear. Oils with high woe content are often non-Newtonian,
and stable water-in-oil emulsions are always non-Newtonian. A material that exhibits a decrease in
viscosity with shear stress is termed pseudoplastic, while those that exhibit a decrease in viscosity with time
of applied shear force are referred to as thixotropic. Both effects are caused by internal interactions of the
molecules and larger structures in the fluid which change with the movement of the material under applied
stress. Generally, non-Newtonian oils are pseudoplastic, while emulsions maybe either thixotropic or
pseudoplastic.
In terms of oil spill cleanup, viscous oils do not spread rapidly, do not penetrate soils as rapidly, and affect
the ability of pumps and skimmers to handle the oil.
Volatile Organic Compounds (VOC): Organic compounds with high vapour pressures at normal
temperatures. VOCs include light saturates and aromatics, such as pentane, hexane, BTEX and other
lighter substituted benzene compounds, which can make up to a few percent of the total mass of some
crude oils.
Waxes: Waxes are predominately straight-chain saturates with melting points above 20 °C (generally,
the w-alkanes C18 and heavier).
Weathering: Processes related to the physical and chemical actions of air, water and organisms after oil
spill. The major weathering processes include evaporation, dissolution, dispersion, photochemical oxidation,
water-in-oil emulsification, microbial degradation, adsorption onto suspended particulate materials,
interaction with mineral fines, sinking, sedimentation, and formation of tar balls.
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UCM: GC unresolved complex mixture of hydrocarbons. The UCM appear as the "envelope" or hump
area between the solvent baseline and the curve defining the base of resolvable peaks.
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3. Methods for Measurement of Physical and Chemical Properties of
Selected Oils
3.1 Selection and Collection of Oils
Ten oils and refined petroleum products with significant potential to be spilled in U. S. waters were
chosenbased on discussion with the US EPA. These oils were collected by ESTD from various
oil companies and refineries in North America. The oils include: Alberta Sweet Mix Blend
(Reference #5), ArabianLight, South Louisiana, West Texas Intermediate, Sockeye, Alaska North
Slope, Fuel Oil No.2, Fuel Oil No.5 ("Bunker B"), Heavy Fuel Oil 6303 ("Bunker C"), and
Orimulsion-400.
3.2 Instruments
The maj or instruments used to determine the oil physical properties and chemical composition are
the following:
•Oil Weathering System (Wheaton Spin-Vap -10)
•GC-MS (HP)
•GC-FID (HP)
•XRF (Spectro Titan)
•Vi scorneter (ThermoHaake VT550)
•Rheometer (ThermoHaake RheoStress 300)
•Density meter (Anton Parr DMA 48)
•Flash point analyzer (Herzog HFP360/362)
•Vapor pressure tester (Herzog HVP970)
•Karl Fisher automatic titrator (Metrohm)
•Tensiometer (Kriiss K10)
3.3 Evaporation (Weathering) of Oils
A laboratory oil-weathering technique by rotary evaporation is used by Emergencies Science and
Technology Division to artificially weather oils with varying degrees of weight loss. The oil-
weathering system consists of a WheatonN-10 Spin Vap with a 10 L flask, an integral water bath
(capacity 14L), a HaakeF3-CH circulating bath and a Millipore vacuum pump (Figure 1). The
bath temperature can be set from 20 °C to 100 °C ± 0.5 °C. The rotation speed can be
continuously varied from 10 to 135 rpm.
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Figure 1 Rotary evaporator used
for artificial weathering of oils.
The following evaporation procedure is used to evaporate oils:
(1) The water bath of distilled water is brought to a temperature of 80 °C.
(2) The empty rotary flask is weighed, approximately 2 L of oil added and the flask
reweighed.
(3) The flask is mounted on the apparatus and the flask partially immersed in the water
bath and spun at full speed, 135 rpm. A constant flow of air of 13 L/min through the flask
is maintained by the vacuum pump;
(4) At set intervals, the sample flask is removed and weighed. Periodically, a sample of
about 1 g is removed for chemical analysis.
(5) When evaporation is stopped (i.e. overnight and weekends), the flask is sealed and
stored at 5 °C. After removal and prior to restarting, the flask is weighed to ensure that no
evaporation has occurred during storage.
Typically, three weathered fractions are prepared for each oil sample. The initial weathering period
is 48 hours, a duration chosen to simulate the eventual final state of an oil in the environment. In
addition, intermediate fractions of approximately one- and two-thirds of the 48 hour loss by weight
are prepared.
The exact time taken to prepare these intermediate fractions is determined by estimation from the
measured fractional mass-loss as a function of time for the 48-hour sample. The fraction mass-loss
is calculated as:
%weathering = (mi - m^ / (mt - m^ x 100%,
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where, %weathering is the percentage evaporative mass-loss over the 48 hour period, mt is the
initial mass of the flask and oil, m/is the final mass of the flask and oil, and me is the mass of the
empty flask. A graph of%weathering as a function of time is plotted using the interval weighing
data.
The times for one-third (t]/3) and two-thirds (t2/3) of the final mass loss are interpolated from the
time- weathering graph. Typical times for t1/3 range from 30 minutes to 2 hours, for t2/3, 8 to 12
hours.
This technique allows for precise control of the evaporative weight loss for a target oil, and can be
directly correlated to compositional changes of the target weathered oil . By tracking weight loss
as a function of time, an equation for predicting evaporation can be found. Also, from this same
graph, it is possible to determine a point at which the evaporation rate i s sufficiently slow that the
oil may be considered to have achieved the maximum evaporative loss likely to be observed under
the conditions of a marine spill.
3. 4 Equation(s) for Predicting Evaporation
The evaporation kinetics, reported as percentage mass loss as a function of time, are determined
for each oil by measuring the weight loss over time from a shallow dish (Fingas 97, Fingas 98a,
Fingas 01). Approximately 20 g of oil is weighed into a 139mm petri dish. Measurements are
conducted in a climate-controlled chamber at 1 5 °C. Temperatures are monitored by a digital
thermometer. The oil weight is recorded by an electronic balance accurate to 0.01 g at
geometrically increasing intervals and collected on a computer logging system. Near the anticipated
end of the run, the measurement interval is reset such that the number of points near the beginning
and end of the run are approximately equal. The evaporation period can last from a few days for
light oils to weeks for heavier products.
The time versus weight loss data series are fitted to a set of simple equations. From long
experience (Fingas 98a, Fingas 01), either a square-root or a natural logarithm function is chosen
as the simplest, most representative equation for evaporative mass loss. The best-fit equations have
the form:
%Ev = (A+BT)\nt
%Ev = (A+BT)t1'2
where: %Ev is weight-percent evaporated, Tis the oil surface temperature (°C), t is time (in
minutes), and A and B are constants fitted to the measured data.
The apparatus is periodically checked by conducting a run with a 15-g mass in place of the oil.
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3.5 Method for Determining Sulphur Content
The mass fraction of atomic sulphur in oil is determined using X-ray fluorescence by closely
following ASTM method D 4294.
The XRF spectrometer is calibrated using a duplicate series of six NIST sulphur-in-oil standards.
A linear calibration chart is prepared from the twelve standard measurements. Single element
standards are used to calibrate and remove chlorine interference in the sulphur signal. Instrument
and operator performance is monitored by a triplicate measurement of a check standard consisting
of a known crude oil. Check standard measurements are tracked on a quality control chart.
Approximately 3 g of oil is weighed out into 31mm HDPE XRF cells, sealed with 0.25 mm thick
mylar film. The sealed cells are measured on a Spectro Titan XRF spectrometer. Each unknown
is measured in triplicate and the mean reported as the final value.
3.6 Method for Determining Water Content
The mass fraction of water in oil or an emulsion, expressed as a percentage, is determined by Karl
Fischer titration using a Metrohm 701 automatic titrator. The method used closely follows ASTM
method D 4377. The Karl Fischer reaction is an amine-catalyzed reduction of water in a
methanolic solution:
CH3OH + SO2 + RN - [RNH]+ [SO3CH3]-
2RN + H2O + I2 + [RNH]SO3CH3 - [RNH]+ [SO4CH3]- + 2 [RNH]+ r
The amine, RN, or mixture of amines is proprietary to each manufacturer.
A sample of oil or emulsionin the range of 50 to 100 mg is accurately weighed and introduced to
the reaction vessel of the autotitrator. A solution of 1:1:2 (by volume) mixture of
methanol:chloroform:toluene is used as a working fluid. The autotitrator is loaded with 5-mg/mL,
pyri dine-free Karl Fischer reagent from a certified supplier. Samples are repeated in triplicate and
the mean reported as the water percentage. The instrument calibration is checked by a series of
five replicate titrations of 25 |IL of distilled, deionized water.
3.7 Method for Determining Flash Point
The flash point of an oil or product sample, in degrees Celcius, is determined by one of two
methods, depending on the sample. Lower viscosity samples, including light fuel oils and most
crudes, are measured using a Herzog FIFP 362 TAG2 analyzer (Figure 2), following ASTM
method D1310. Heavier samples, such as intermediate and heavy fuel oils or highly weather crude
oils, are measured using a Herzog 360 Pensky-Martens analyser, following ASTM D 93.
13
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In b oth methods, 50 to 70 mL of sample is measured into the flash point cup (Figure 3 ), then the
method program initiated. Pre-cooling of the instrument is necessary for subambient flash points.
Samples are repeated in triplicate and the mean reported. Flash points below -10 °C or above 110
°C are confirmed in duplicate and reported as outside of the measurable temperature range.
Figure 2 Flashpoint
tester.
Figure 3 Flashpoint tester cup in TAG configuration.
Reagent-grade/>-xylene is periodically measured by both the TAG2 and the Pensky-Martens
methods as a check on instrument and operator performance. A control chart is kept of the results.
3.8 Method for Determining Pour Point
The pour point of an oil sample, in degrees Celsius, is determined by following ASTM method D
97. Two aliquots of sample are poured into test j ars (as described by ASTM D 97), stopped and
fixed with ASTM 5C or 6C thermometers, as appropriate.
Pour point is determined, as described in ASTMD97, by tilting the test j ar to the horizontal and
observing the flow of the sample past the fill mark on the jar. IfnoflowisvisibleafterS seconds,
the pour point is considered to have been reached. When the pour point is reached, 3 °C is added
to the temperature recorded. The average of the two measurements is reported as the pour point.
If the samples are below their pour point at room temperature, then they are heated to 50 °C in a
glycol-filled heat bath. The bath temperature is lowered until the pour pointis reached. If samples
are liquid at room temperature, they are cooled in the glycol bath to -5 °C, and measured at
intervals as described by ASTM method D 97. Further cooling, if required, is done first to -20 °C
and then -30 °C in a series of refrigerators and finally to -56 °C in an acetone/dry ice bath.
14
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3.9 Method for Determining Density and API Gravity
The density of an oil sample, in g/mL, is measured using an Anton Parr DMA 48 digital density
meter following ASTM method D 5002 (Figure 4). Measurements are performed at 0.0 °C and
15.0 °C. The instrument is calibrated using air and distilled, deionized water at each temperature.
Method and operator performance is monitored by periodic measurement of a check standard fo
/>-xylene at 15.0 °C. A method control chart is kept of these measurements.
Figure 4 Digital densitometer taking a reading.
Densities are corrected for sample viscosity, as specified by the instrument manufacturer.
Measurements are repeated in triplicate and the mean reported as the density.
API gravity (API 82) is calculated using the standard formulaforthe specific gravity of an oil at 60
°F (15.56 °C). The oil density at 15.56 °C is estimated by exponential extrapolation from the 15.0
°C and 0.0 °C data points. This is converted to specific gravity by division by the density of water
at 15.5 °C, using the following equation:
s.g.15-56 = p° exp [ ( In p15 - In p° )/15 x 15.56 ] / p (H2O)1556
where: s.g.15-56 is the specific gravity of the oil or product at 15.56 °C (60 °F), p° and p15 are the
measured oil densities at 0 °C and 15 °C, respectively, and p (H2O)15 56 is the literature value for
the density of water at 15.56 °C. The API Gravity is then determined using the formula (API 82):
API = 141.5 / (s.g.1^6) - 131.5
15
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3.10 Method for Determining Dynamic Viscosity
The dynamic viscosity of an oil sample, in mPa. s or cP, is measured using a Thermo-Haake VT5 50
viscometer using standardNV and SV1 cup-and-spindle sensors (Figure 5). Measurements are
made at 0.0 °C and 15.0 °C. The instrument i s calibrated with ASTM-traceable standards at 15.0
°C. Check standards of pure ethyl ene glycol and glycerine are used to validate the NV and S VI
methods respectively. Control charts are kept for each set of sensors, based on the ethyl ene glycol
measurements at 15.0 °C for the NV sensors and glycerine measurements at 20.0 °C for the S VI
sensors.
Figure 5
Viscometer.
From a qualitative observationofthe oil either the NV or the S VI sensor is chosen to measure the
sample. The NV sensor is used for oils with viscosities below 100 cP, the SV1 sensor, for oils
above 70 cP. In both cases, the measurement cup is filled with 9.1 mL of sample. The sensor is
mounted onto the instrument and the sample volume is adjusted to the proper level. The sample is
allowed to equilibrate for 15 minutes for 15.0 °C measurements, or 30 minutes at 0.0 °C. Samples
and sensors are kept chilled at the appropriate temperature prior to use.
For the NV sensor, the rotational shear rate is set at 1000/s, the S VI sensor at 50/s. If the oil is
observed to be non-Newtonian, single samples are run at shear rates of 1/s, 10/s and 50/s. In all
cases, the sensors are ramped up to speed over a period of five minutes. The viscosity is measured
for a subsequent five minutes, sampled once per second. The viscosity reported is that at time zero
of the second, constant-shear rate interval. This may be obtained by the mean of the constant-shear
rate interval data or by linear fit to the time-viscosity series if friction-heating has occurred during
the measurement. For Newtonian samples, triplicate measurements are averaged and the mean
reported as the absolute or dynamic viscosity. For non-Newtonian samples, viscosities are
reported for each of the three shear rates.
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3.11 Method for the Evaluation of the Stability of Emulsions Formed from Saline and Oils
and Oil Products
Water-in-oil emulsions are formed in 2.2-litre fluorinated vessels on an end-over-end rotary mixer
(Associated Design, VA) at a nominal rotational speed of 50 RPM (Jokuty 95, Fingas 98b).
(1) A 600-mL volume of salt water (3.3% w/v NaCl) is dispensed into a mixing vessel.
(2) A 30-mL aliquot of oil is added to each vessel for a 1:20 oil:water ratio.
(3) The vessels are sealed and placed in the rotary mixer such that the cap of each mixing
vessel follows, rather than leads, the direction of rotation. The rotary mixer is kept in a
temperature controlled cold room at 15 °C .
(4) The vessels and their contents are allowed to stand for approximately 4 hours before
rotation begins, then mixed continuously for 12 hours.
(5) At the conclusion of the mixing time, the emulsions are collected from the vessels for
measurement of water content, viscosity and the complex modulus. The emulsions are
stored in the cold room at 15 °C for one week, then observed for changes in physical
appearance.
Emulsions are classified into one of four stability classes: unstable, entrained water, meso-stable
(Figure 6) and stable (Figure 7). Water content for the emulsions is measured using method 5.6
Method for Determining Water Content. The complex modulus is measured on an RS300
RheoStress rheometer using a 35 mm plate-plate geometry. A stress sweep is performed in the
range 100 to 10,000 mPa in the forced oscillation mode at a frequency of 1 Hz. The complex
modulus value in the linear viscoelastic region is reported.
Figure 6 Meso-stable emulsion of
Alberta Sweet Mix Blend #5
(ASMB#5) and 33%o brine.
Figure 7 Stable emulsion of Sockeye
(1991) and 33%0 brine.
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3.12 Method for Determining the Chemical Dispersibility of an Oil or Oil Product
This method determines the relative ranking of effectiveness for the dispersibility of an oil sample
by the surfactant Corexit 9500. This method follows closely ASTM F2059.
A pre-mix of 1:25.0 dispersantoil is made up by adding oil to lOOmg of dispersant (approximately
2.5OmL of oil in total).
Six si de-spout Erlenmeyer flasks, as described in ASTMF2059, containing 120 mL of 33%o brine
are placed into an incubator-shaker. An aliquot of 100 |IL of premix is added to the surface of the
liquid in each flask, care being taken to not disturb the bulk brine. The flasks are mechanically
shaken at 20.0 °C with a rotation speed of 150 rpm for exactly 20 minutes (Figure 8). The
solutions are allowed to settle for 10 minutes.
Figure 8 Shaker flasks for dispersant effectiveness testing in
shaker/incubator.
Using the side spout, 3 0 mL of the oil-in-water phase is transferred to a 250 mL separatory funnel,
first clearing the spout by draining 3 mL of liquid. The 3 0 mL aliquot is extracted with 3^5 mL of
70:30 (v:v) dichloromethane:pentane, collected into a 25-mL graduated cylinder (Figure 9).
Sample analysis done using a GC/FID to determine the oil concentration in the solvent. A 900 |IL
aliquot ofthe 15-mL solvent extract is combined with 100 |IL ofinternal standard (200 ppm of
5-oc-androstane in hexane) in a crimp-top injection vial and shaken well. Total petroleum
hydrocarbon content ofthe sample is quantified by the internal standard method using the total
resolved peak area (RPA) and the average hydrocarbon response factor over the entire analytical
range:
18
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RPH =
-I.S.
/RRF x20 xJ5 x 120/30/0.9
WhereRPHis the resolved petroleum hydrocarbon (mg/mL), ATOTAL is the total resolved peak
area, ALS_ is the internal standard peak area and RRFis the average relative response factor for a
series of alkane standards covering the analytical range.
Figure 9 Aqueous to methylene chloride extraction for
dispersant effectiveness testing.
The method is calibrated using a series of six oil-in-solvent mixtures prepared from the premix for
each oil. The volume of premix dispersant/oil solution for each standard is selected to represent a
percentage efficiency of the dispersed oil. The volume of the premix is then carefully applied to the
surface of the brine in a shaker flask and shaken exactly as one of the samples, as described
previously. Upon removal from the shaker however, the entire contents of the flask is transferred
to the separatory funnel. This is extracted with 3 x20 mL of 70:30 (v:v) dichloromethane:pentane
and made up to 60 mL. Chromatographic quantitation is then performed using the formula:
RPH = ATOTAL/ALS. /RRF x20 x 60 x 120 /120 /0.9
The RPH values as a function of %effectiveness for the calibration standards are plotted. The
sample RPH values are then used to determine the %effectiveness of the dispersant.
The results of this test provide a means of ranking effectiveness of dispersant/oil combinations
relative to each other, but do not directly imply the effectiveness for any other specific conditions.
This is due to the broad range of parameters affecting dispersant effectiveness: turbulent energy,
time of mixing, dosage rate, brine salinity, temperature, evaporative loss, dilution, settling time and
thoroughness of the mixing between dispersant and oil.
19
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3.13 Method for the Determination of the Hydrocarbon Group Constituents
The asphaltene and resin mass fractions (Speight 91) of an oil or oil product are determined
gravimetrically. The asphaltene precipitation is a minor variation on the procedure given in ASTM
methodD 2007. The saturate fraction (Fl) and aromatic fraction (F2) are calculated by mass-
balance from the total petroleum hydrocarbon measurement, method 3.17, following. Wax content
is determined by summing the individual areas for thew-alkanes n-C 18 upto n-CUom the simulated
boiling point chromatograms, obtained in method 3.16.
A 60 mL quantity ofw-pentane is added to a pre-weighed sample of approximately 5g of oil. The
flask is shaken well and allowed to stand for 30 minutes. The sample is filtered through a 0.45-|lm
membrane using a minimum of rinsings of w-pentane. The precipitate is allowed to dry then
weighed. The weight of the precipitate as a fraction of the initial oil sample weight i s reported as
the percentage asphaltenes (Figure 10).
The filtrate from the precipitation, the "maltene" fraction, is recovered and made up to 100 mL with
w-pentane. A15-g, 1 -cm diameter column of activated silica gel is prepared. The top of the column
is protected by a 1 -cm layer of sodium sulphate. A 5-mL aliquot of the maltene fraction is loaded
onto the column. A 60-mL volume of 1:1 (v:v) benzene:hexane is eluted through the column and
discarded. A 60-mL volume of methanol, followed by a 60-mL volume of dichloromethane are
eluted through the column and combined. The methanol/dichloromethane fractions are reduced by
rotary evaporation and blown down to dryness under nitrogen. The mass fraction of this dried
eluent, compensating for the volume fraction used, is reported as the percentage of resins in the
sample (Figure 11).
Measurements are repeated three times for each sample and the means are reported as the final
values.
Figure 10 Asphaltenes after filtering and
drying.
20
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Figure 11 Resin samples being reduced under dry
nitrogen.
3.14 Method of Determining Adhesion
An analytical balance is prepared by hanging an ASTM method D 6 standard penetrometer needle
from the balance hook and allowing the apparatus to stabilize and tare. Approximately 80 mL of
oil sample is poured into a 100-mL beaker. The beaker is elevated until the oil reaches the top of
the stainless steel needle, but not touching the brass support shaft. The needle is kept immersed in
oil for 30 seconds. The beaker is then lowered until the needle is clear of the oil. The system is left
undisturbed, closed inside a draft shield. After 30 minutes the weight of the oil adhering to the
needle is recorded. The mass of the oil divided by the surface area of the needle is the adhesion
of the oil in g/cm2. Four measurements are taken for each oil sample and the mean reported as the
final value (Jokuty 96).
3.15 Method of Determining Surface and Interfacial Tensions
Surface and interfacial tensions, in mN/m, are measured using a Kriiss K10 Tensiometer by the
de Noiiy ring method (Figures 12 and 13). The experimental method used follows closely ASTM
method D 971. The instrument calibration is checked using a vendor-supplied weight. Method and
operator performance is monitored by periodic measurement of the surface tension ofp-xylene at
15 °C. A control chart is kept of the history of check standard measurements.
21
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Figure 12 Digital
tensiometer.
Figure 13 Close-up of du Nouy ring interfacial tension
measurement of 33%o brine and diesel
For sample/air surface tensions, the measurement ring is first zeroed in air. A small amount of
sample, approximately 15 mL, is poured into a 43-mm diameter vessel. The ring is dipped into the
sample to a depth of no more than 5 mm, then pulled up such that it is just visible on the surface
of the liquid. The system is allowed to rest for 30 seconds. The measurement is initiated,
automatically terminating when the upward pulling force on the ring just balances the downward
force exerted by the liquid. The apparent surface tension, O^p, is recorded.
For sample/water and sample/brine (3.3% w/vNaCl) interfacial tensions, the ring is zeroed in the
sample at a depth of not more than 5 mm. The ring is removed and cleaned. A25-mL volume of
water or brine is dispensed into a 43-mm diameter vessel. The ring is dipped 5 mm into the
aqueous phase. A 10-mL to 15-mL volume of sample is carefully poured down the side of the
vessel wall, with great care taken so as to disturb the aqueous/oil interface as little as possible. The
ring is then raised to the bottom on the interface and the system is allowed to rest for exactly 3 0
seconds. The measurement is started and the apparent interfacial tension is recorded, O^p, when
the force balance is reached.
The apparent surface tension is corrected for mass of the upper phase lifted by the ring during
measurement using the Zuidema and Waters correction:
0.7250+.
[1.452(7
APP
C\D-d)
+0.04534—
1.679
R/r I
22
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where: O is the interfacial tension, O^p is the instrument scale reading, C is the ring diameter,/)
is the density of the lower phase, dis the density of the upper phase, R is the radius of the du Noiiy
ring, and r is the radius of the ring wire. Measurements are made at 0.0 °C and 15.0 °C and
repeated in triplicate. Samples, aqueous phases and glassware are all kept at temperature for a
minimum of 30 minutes before measurement. The mean of at least three corrected interfacial
tensions is reported as the measured value.
3.16 Method for Determining the Simulated Boiling Point Distribution
This analysis is performed on an Analytical Controls SIMDIS analyser, a modified Hewlett-
Packard 5890 series II gas chromatograph. The system has a custom cryogenically-cooled inlet
and a high-temperature column. Reference and calibration mixtures are run according to Analytical
Controls specifications.
Oil samples are made up as 2% (m/m) solutions in carbon disulphide. An aliquot of 0.5 |IL is
injected into the inlet. The inlet temperature program runs from 40 °C to 430 °C a 70 °C per
minute. The oven temperature program runs from -20 °C for 1 min, ramp at 10 °C/min to 43 0 °C,
and hold for 3 minutes at this final temperature. The flame ionization detector operates at 430 °C.
The Analytical Controls Software outputs a series of simulated boiling point ranges as a function
of temperature and has the option of producing a "wax report" for the relative abundances of all
w-alkanes in the oil sample.
3.17 Method for the Determination of Individual (n-Alkanes and Isoprenoids) and Total
Petroleum Hydrocarbons (TPH), Polycyclic Aromatic Hydrocarbons (PAHs) and
Biomarker Triterpanes andSteranes in Oil and Oil-spill-related Environmental Samples
(Water, Particulates and Soils/Sediments)
A chromatographic column with a PTFE-stopcock (10.5 mm ID. x 200 mm length) is plugged
with borosilicate glass wool at the bottom, and serially rinsed with methanol, hexane and
dichloromethane, and allowed to dry. The column is dry-packed with 3 grams of activated silica
gel with tapping to settle the silica gel, and topped with about 0.5 cm anhydrous sodium sulphate.
The column is conditioned with 20 mL of hexane, and the eluent is discarded. Just prior to
exposure of the sodium sulphate layer to air, a 200 |IL of crude oil solution containing
approximately 16 mg of oil (-80 mg/mL in hexane) is quantitatively transferred onto the column
using an additional 3 mL of hexane to complete the transfer. All eluentuptothispointisdiscarded.
Twelve mL of hexane is used to elute aliphatic hydrocarbons, and 15 mL of 50% benzene in
hexane (v/v) is used to elute aromatic hydrocarbons.
Half of the hexane fraction (labelled "F1") is used for analysis of aliphatics, triterpanes and steranes;
half of the 50% benzene fraction is labelled "F2" and used for analysis of targetPAHs and alkylated
PAH homologues. The remaining half of F1 and F2 is combined into a fraction (labelled as "F3")
23
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and used for the determination of total petroleum hydrocarbons (TPH). These three fractions are
concentrated under a stream of nitrogen to appropriate volumes, spiked with internal standards (5-
oc-androstane for GC-TPH and n-alkane determination, d 14-terphenyl for PAH analysis, and C30-
(3(3-hopane for biomarker analysis), and then adjusted to accurate preinj ection volume of 0. 5 mL
for GC-MS and GC-FID analysis (see Figure 1 for oil analysis protocol).
The concentrations of individual n-alkanes, selected isoprenoids such as pristane and phytane, and
total petroleum hydrocarbons are determined by high resolution capillary GC/FID using the
following equation:
A. WK D
Concentration ({lg/g)=2x
AIS RR^ Ws
where:
As = Response for the analyte in the sample, units may be in area counts or
peak height.
AIS = Response for the internal standard in the sample, units same as \.
WIS = Amount (|ig) of internal standard added to the sample.
D = Dilution factor. If dilution was made on the sample prior to analysis. If no
dilution was made, D = 1, dimensionless.
Ws = Weight of sample extracted, g. Either a dry or wet weight may be used,
depending upon the specific application of the data.
Note that Fl and F2 are split in half for analyses, so the final concentration of
individual analytes must be multiplied by 2 in the Equation.
Prior to sample analysis, the instrument is calibrated using a standard solution, which is composed
of C8 through C34 n-alkanes, and 5-oc-androstane as the internal standard. A 5-point calibration
is established demonstrating the linear range of the analysis. The relative response factor (RRF) for
each hydrocarbon component is calculated relative to the internal standard. Total GC detectable
petroleum hydrocarbons (TPH), defined as the sum of resolved plus unresolved aliphatic and
aromatic hydrocarbons, is quantified by the internal standard method using the baseline corrected
total area of the chromatogram . The RRF used for the determination of TPH is the average of the
n-alkane relative response factors over the entire analytical range.
Quantitation of target PAHs, alkylated PAH, and dibenzothiophene homologues is performed on
GC/MS in SIM mode with RRFs for each compound determined during instrument calibration. The
ions monitored are 128, 142, 156, 170, and 184 for alkyl homologues of naphthalene; 178, 192,
206, 220, and 234 for phenanthrene alkyl series; 184, 198, 212, and 226 for dibenzothiophene
alkyl series; and 166, 180, 194 and 208 for fluorene alkyl series. The RRF for target PAH
compounds are calculated from authentic standards. PAH alkyl homologues are quantified by using
the straight baseline integration of each level of alkylation. Although the alkylated homologue groups
can be quantified using the RRF of the respective unsubstituted parent PAH compounds, it is
24
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preferable to obtain the RRFs directly from alkylatedPAH standards, if they are commercially
available. In this project, the RRFs obtained from 1-methyl-naphthalene, 2-methyl-naphthalene,
2,6-dimethyl-naphthalene, 2,3,5-trimethyl-naphthalene, and 1-methyl-phenanthrene are used for
quantitation of 1-methyl-naphthalene, 2-methyl-naphthalene, C2-naphthalene, C3-naphthalene, and
Q-phenanthrene in oil, respectively. The RRFs of 2,3,5-trimethyl-naphthalene and 1-methyl-
phenanthrene are used for quantification of C4-naphthalene, and C2-, C3-, and C4-phenanthrenes
respectively. The selection criteria for the integration and reporting of each alkylated homologue
are based primarily on pattern recognition and the presence of selected confirmation ions.
The average RRF for the biomaker compound C3017(3(H) 21 oc(H)-hopane is determined relative
to the internal standard C3017(3(H)21(3(H)-hopane. The average RRF for C3017(3(H)21 oc(H)-
hopane (m/z 191) is used for quantitation of C3017oc(H) 21 (3(H)-hopane and other triterpanes
in the oil sample. For quantitation of steranes, the RRF of C29 20R ocaoc-ethylcholestane
monitored at m/z 217 is determined relative to C3017(3(H) 21 (3(H)-hopane monitored at m/z 191,
and then the average RRF of C29 20R aaoc-ethylcholestane is used for estimation of sterane
compounds in the oil.
3.18 Analytical Method for Identification of BTEX Compounds and Alkyl Benzenes and
Direct Determination of BTEX and (BTEX + C3-benzenes) in Oils and Refined Products
by Gas Chromatography /Mass Spectrometry
The identification of BTEX and other alkyl substituted benzene components in oils are
accomplished based on mass spectral data, comparison of GC retention data with reference
standards, and calculation of retention index values and comparison with those reported in the
literature.
Quantitation of BTEX and (BTEX+C3-benzenes) is accomplished by GC/MS using an internal
standard method. The strict quality control measures are used in order to guarantee the precision
and accuracy of analytical data. The GC/MS is carefully maintained and tuned daily to achieve the
required sensitivity. Prior to sample analysis, the instrumentis calibrated using a standard solution
that is composed of 5 BTEX compounds, 6 C3-benzene compounds, 2 C4-, 2 C5-, 1 C6- and 1
Cy-benzene compounds. The internal standard used is d10-ethylbenzene. A 5-point calibration
curve that demonstrates the linear range (0.01 ppm to 200 ppm) of the analysis is established for
each target compound. The RRFs for each compounds are calculated relative to the internal
standard.
Oil samples are directly weighed and dissolved in n-pentane (without using any solvent evaporation
and concentration step, which may result in the loss of BTEX compounds) to an approximately
concentration of 2 mg/mL for GC/MS analysis. To achieve improved precision and accuracy of
analytical data, the following refinements are implemented in addition to the routine quality control
measures: (1) The oil solutions in vials are tightly capped to avoid any possible loss of volatile
BTEX compounds, and are then put in a refrigerator for 3 0 minutes to precipitate the asphaltenes
25
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to the bottom of the vials in order to void performance deterioration of the column due to
introduction of asphaltenes; (2) Blanks and calibration check standards are analyzed before and
after each sample batch (about 7-10 samples) to monitor analysis precision; (3) C3-benzenes in
oil are quantified using the RRF directly obtained from the respective individual C3-benzene
standards instead of using the RRF obtained from benzene or Ci/C2 substituted benzenes.
The concentration of the analyte of interest in the sample is determined using the following equation:
As Wis D
Concentration (jig I g)=
where:
As = Response for the analyte in the sample, units may be in area counts or
peak height.
AIS = Response for the internal standard in the sample, units same as As.
WIS = Amount (|ig) of internal standard added to the sample.
D = Dilution factor, if dilution was made on the sample prior to analysis. If no
dilution is made, D = 1. Dimensionless.
Ws = Weight of sample, in g.
The extensive qualitative and quantitative information obtained pertaining to alkylbenzenes is useful
for evaluating weathering behaviour, potential toxicity, composition and concentration changes of
oil in the short term following a spill. The data canbe al soused to evaluate the fate and transport
of alkylated benzene compounds and other petroleum hydrocarbons in the environment and to
assess the possible biological effects and damage of the spill to the environment and natural
resources.
3. 19 Method for the Determination of Trace Metals in Oil Samples
The metal content of an oil or oil product is determined by oxidation of the oil in hot acid,
dissolution in aqueous solution then measurement by inductively-coupled plasma atomic emission
spectroscopy (ICP-AES).
The oil sample is warmed in a water bath and mixed thoroughly . Approximately 1 g of sample is
weighed into a 1 50 mL teflonbeaker. To the oil is added 0.5 mL of concentrated nitric acid and
1.5 mL of concentrated hydrochloric acid. The beaker is covered and heated on a 120 °C
hotplate. Thebeakeris swirled gently until the mixture begins to fume. A further amount of 0.5 mL
of concentrated nitric acid and 1 . 5 mL of concentrated hydrochloric acid is added to the beaker.
The beaker is recovered and heated until approximately 0.5 mL of the mixture remains.
The acid-mixture is quantitatively filtered into a glass test tube through aNumber 4 Whatman filter
with a deionized water rinse. The solution is made up to 10.00 mL. The solution is mixed
26
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thoroughly by vortex and submitted to the ICP-AES for analysis.
The ICP-AES is calibrated with commercial multi-element aqueous standards and verified using
a certified aqueous reference standard. The 29 metal analytes are determined from each respective
calibration chart and corrected for the 10:1 dilution in sample preparation. Duplicate measurements
are made for each sample. Method blanks, matrix blanks, and blind standards were included with
the analyte samples to ensure method performance.
The ICP-AES analysis was performed under contract to Environment Canada by Caduceon
Environmental Laboratories of Ottawa, Canada.
3.20 Method for the Sample Handling, Storage and Disposal of Oil and Oil Products
This method describes the procedures for the safe and non-destructive manipulation and sampling
ofhydrocarbon unknowns. Procedures are outlined for the reception and disbursal of samples to
and from the laboratory, the handling of oil to avoid damaging the sample, the techniques necessary
to obtain a representative sample and the safe storage and disposal of oil.
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4. Summary of Quality Assurance and Quality Control (QA/QC) Plan
4.1 Quality Assurance Statement
As a federal government science and technology institute it has been one of our fundamental operating
principles that the Oil Research Laboratory of the Emergencies Science and Technology Division (ESTD)
of Environment Canada should set an example by adopting the most stringent standards possible for our
work. A critical part of our official Mission Statement is to provide "specialized sampling and analytical
expertise and services of the highest standards". Quality management has always been a fundamental
element of our programs. We continue to refine our quality procedures and protocols whenever new
information and processes become available. Our quality program is certified through SCC-CAEAL, the
Standards Council of Canada/Canadian Association for Environmental Analytical Laboratories.
Participation in the SCC-CAEAL accreditation program provides us a systematic, internationally
recognized quality system. A quality web site has been created which provides staff with easy and fast
access to all current and approved quality system documentation. The Emergencies Science and
Technology Division QA/QC system includes the following:
-Laboratory profile, mission and organization;
-Quality system;
-Personnel;
-Methodology;
-Service, equipment and supplies;
-Facilities;
-Sample management;
-Data management;
-Work load management.
4.2 Quality Assurance in Chemical Composition Methods
The Oil Research Laboratory at Emergencies Science and Technology Division presently performs the
following chemical measurements for crude oils, oil products, and oil-spill-related environmental samples:
total petroleum hydrocarbons (TPH), total saturates, total aromatics, w-alkane distribution, oil-characteristic
alkylated PAH homologous series, and other EPA priority PAHs, BTEX and alkyl-benzene compounds,
biomarker triterpanes and steranes. The methods of "Analytical Method for Identification of BTEX
Compounds andAlkyl'Benzenes and DirectDetermination of BTEX and (BTEX + C3-benzenes) in
Oils and Refined Products by Gas Chromatography/Mass Spectrometry" and "Analytical Method
for the Determination of Individual n-Alkanes andlsoprenoids and Total Petroleum Hydrocarbons
(TPH), Polycyclic Aromatic Hydrocarbons (PAHs), andBiomarker Triterpanes and Steranes in Oils,
Petroleum Products, and Oil-spill-related Environmental Samples " have been approved by SCC and
CAEAL and have become official ETC methods.
28
-------
Chromatographic techniques are used for analyses of oil chemical compositions. In addition to a formal
quality control program, a number of specific measures have been added to the processing of oil samples
to monitor quality control and to aid in assessment of the data quality with respect to the proj ect obj ectives.
An important part of this is the evaluation of specific QC samples for accuracy, precision, and potential
contamination. Before sample analysis, a five point initial calibration composed of the target oil components
(for example, n-alkanes and EPA priority PAHs) are established, demonstrating the linear range of the
analyses. Check standards at the mid-point of the established calibration curves are run before and after
each analytical batch of samples (7-10 samples) to validate the integrity of the initial calibration. The method
of internal standards (such as EPA Method 8000 for PAH analysis) using the average relative response
factors (RRF) generated from the linear initial calibration is used to quantify the target oil compounds. The
RRF stability is a key factor in maintaining the quality of the analysis. Mass discrimination, that is the
reduced response of high molecular weight components, must be carefully monitored. If there is a problem
with mass discrimination, it can be minimized by trimming the capillary column and by replacing the quartz
liner in the inj ection port. All samples and quality control samples are spiked with appropriate surrogate
compounds to measure individual sample matrix effects associated with sample preparation and analysis.
Method detect! on limits (MDL) studies of target compounds are performed according to the procedure
described in the EPA protocol titled "Definition and Procedure for the Determination of the Method
Detection Limit" (Code of Federal Regulations 40 CFR Part 136). Control charts of standards are
prepared and monitored. Validations of analytes in the control chart should be no more than 25% from
historical average.
Trace metal analysis was performed under contract by Caduceon Environmental Laboratories, a CAEAL-
certfied laboratory in Ottawa, Canada. Each batch of samples contained reagent blanks, method duplicates
and matrix-matched reference materials. Blind standards were also submitted with the oils for analysis. The
ICP-AES was calibrated using commercial standards and verified against a certified reference standard.
4.3 Quality Assurance in Physical Property Methods
The ESTD Oil Research Laboratory performs the following physical property measurements on crude oils
and oil products: adhesion, boiling point distribution, density/API gravity, dispersibility, evaporation
equation, flash point, hydrocarbon group analysis, sulphur content, surface and interfacial tensions,
vi scosity, and water content. Many of these procedures are ASTM standard methods, and must meet the
reproducibility and repeatability of the appropriate method. Others, however, are methods developed in-
house and control systems are defined for them in the standard operating procedures (SOP) for those
methods. The following table details the measurement procedures:
Adhesion In-house Method
Boiling Point Distribution Commercial Package
Density/API Gravity ASTM D5002
Dispersibility ASTMF2059
Evaporation Equation In-house Method
Flash Point ASTM D93 and ASTM D56
29
-------
Hydrocarbon Group Analysis In-house Method
Pour Point ASTMD97
Sulphur Content ASTM D4294
Surface and Interfacial Tensions ASTM D971
Viscosity In-house Method
Water Content ASTM D4377
Two physical property methods are considered semi-quantitative: adhesion and pour point. For these
methods, although the range of variability in the results is closely monitored, no calibrations, blanks or check
standards are preformed. Note that while pour point is measured according to ASTM D97, no calibration
or check standard is specified by that method. While the ASTM D97 reproducibility requirements are
achieved, no further controls for pour point are used in the Emergencies Science and Technology Division
Oil Research Laboratory.
Several physical property methods rely on a single instrument and involve a simple measurement with little
sample manipulation. These measurements include: density/API gravity, the development of the evaporation
equation, flash point, sulphur content, surface and interfacial tensions, viscosity and water content. For all
of these methods, the instruments are calibrated as directed by the manufacturer or the appropriate ASTM
method with chemical and/or gravimetric standards as appropriate. In addition, instrumental and operator
performance is monitored by periodic measurement of check standards. A log is kept for each instrument,
in which calibration and check standard measurements are recorded. The check standard measurements
are monitored closely. Failure of the check standard measurement to fall within the smaller of either a
historical 95% confidence limit or the appropriate ASTM required repeatability results in an investigation
of the procedure. This investigation includes recalibration and measurement of the check standard until the
desired precision and accuracy is reached.
Finally, the last class of physical property methods involve significant sample preparation, followed by a
measurement by gas chromatography or gravimetry. These methods include: boiling point distribution,
dispersibility, and hydrocarbon group analysis. The boiling point distribution is measured using a commercial
package provided by Analytical Controls. The quality control for this procedure involves the minimization
of the variance of a check sample chromatogram. The dispersibility test is defined by ASTMF2059 and
uses the calibration and standard procedure defined by that method. The hydrocarbon group analysis is
carried out under the same protocols as described for the other chromatographic techniques previously.
4.4 Example Method Quality Control Procedures
As examples, the QA/QC procedures followtaken from atypical physical property method, for Surface
and Interfacial Tension (see method 5.15), and from the chemical composition method for determination
ofthe oil characteristic alkylatedPAHhomologues and other EPA priority unsubstituted PAH compounds
(see method 5.17):
30
-------
From the Standard Operating Procedure for the determination of the oil characteristic
alkylatedPAH homologues and other EPA priority unsubstituted PAH compounds:
14. QUALITY CONTROL
14.1 Each laboratory that uses this method is required to operate a formal quality control program. The
minimum requirements of this program consist of an initial demonstration of laboratory capability
and the analysis of spiked samples as a continuing check on performance.
The laboratory is required to maintain performance records to define the quality of data that is
generated. Ongoing performance checks must be compared with established performance criteria
to determine if the results of analyses are within accuracy and precision limits expected of the
method.
14.2 The reliability of this method is dependent on the quality control procedures followed with each
analytical batch (approximately 7-10 samples), one procedure blank, one check standard, and one
standard oil are analyzed.
14.3 Initial Calibration and Continuing Calibration Check
14.3.1 Prior to the use of this method, a five-point response factor calibration curve must be
established showing the linear range of the analysis. Each calibration standard is
analyzed and the response factor (RRF) for each compound at each concentration level
is calculated.
14.3.2 A check standard at about the mid-point of the established calibration curve must be
analyzed before and after each set of up to 7 samples or once per working day, whichever
is more frequent, in order to determine the response factors for the analytes of interest
relative to the initial calibration. The PAH calibration standard (NIST SRM 1491)
contains 24 PAH compounds plus dibenzothiophene and 4 deuderated PAH surrogate
compounds, d 14-terphenyl is added to purified sample extract prior to GC/MS analysis as
an internal standard.
14.3.3 The percent difference between the response factors in the check standard and those of the
initial calibration is calculated using Equation 9:
(RRF7-RRFr)
Difference(%)=- - - - — xlOO% (9)
where:
RRFj = Average response factor from the initial calibration
RRFC = Response factor from continuing calibration
If the difference of response factors is within 20%, analyses may proceed. If not, a five-point
calibration curve must be repeated for that compound prior to analysis of the sample.
14.3.4 RRF stability is a key factor in maintaining the quality of the analysis. Mass
discrimination, that is the reduced response of high molecular weight compounds, must be
carefully monitored. The ratio of RRF ofn-C32 to n-C21 should not be allowed to fall below
80% in the check standard. If there is a problem with mass discrimination, it can be
reduced by trimming the first 20 cm of the capillary column and by replacing the quartz
31
-------
liner in the injection port.
14.4 Procedural Blank Analysis
14.5 Surrogate Compounds Analysis
14.5.1 All samples and quality control samples are required to be spiked with surrogate o-
terphenyl (OTP). OTP is spiked into sample prior to extraction. This will measure
individual sample matrix effects associated with sample preparation and analysis.
Recovery of surrogate OTP should be within 60% to 120%. If the recovery for any
surrogate standard does not fall within the control limits for method performance, the
following corrective actions can be taken:
(1) Check calculations to ensure there are no errors.
(2) Check instrument performance and initial standard and surrogate solutions for
degradation, contamination or other possible problems.
(3) reanalyze the sample or extract if the steps above fail to reveal a problem. Ifreanalysis
yields surrogate recoveries within the stated limits, the reanalysis data will be used.
14.5.2 If the surrogate could not be measured because the sample diluted prior to analysis, or
surrogate co-elutes with a compound, no corrective action needs be taken.
14.6 A control chart of the standard should be prepared and monitored. Variations of analytes in the
control chart should be no more than 25% from historical average.
14.7 Detection Limit
Under optimum conditions an instrumental detection limit of 8 pg/\lL per PAH target analyte (mean
value) can be achieved.
14.8 GC Resolution
The target compounds, surrogate and internal standards must be resolved from one another and
from interfering compounds. Potential problems may arise from the lack of baseline resolution of
these compounds. Corrective action must be taken to correct resolution problem, i.e. rerun samples
with a different temperature program.
From the Standard Operating Procedure for the determination of surface and interfacial
tensions:
10 QUALITY CONTROL
10.1 Each laboratory that uses this method is required to operate a formal quality control program. The
minimum requirements of this program consist of an initial demonstration of laboratory capability
and the analysis of reference standards as a continuing check on performance.
10.2 The laboratory is required to maintain performance records to define the quality of data that is
generated. Ongoing performance checks must be compared with established performance criteria
to determine if the results of analyses are within accuracy and precision limits expected of the
method.
10.3 Before performing any analysis, the analyst must demonstrate the ability to generate acceptable
accuracy and precision with this method.
32
-------
10.4 A method log book is maintained, containing all instrumental maintenance and calibration and
check standard measurements.
10.5 The instrument is calibrated using a standard weight provided by the manufacturer. The instrument
calibration is checked before each batch of samples and recorded in the log book. If the instrument
calibration is outside the manufacturer's parameters, the cause must be investigated and the fault
corrected.
10.6 A check standard ofp-xylene is used to define the operating characteristics of the instrument. Before
each batch of samples is measured, a sample of reagent grade p-xylene is measured in triplicate at
15 °C. These measurements are noted in the instrument log book and tracked to ensure instrument
and operator performance.
10.7 If the check standard falls outside the historical 95% confidence limit, as tracked by a control plot,
the instrument function and/or operator technique is corrected as necessary. ASTM method D971
requires a repeatability of 4%, approximately ±1.2 mN/m. Measurements are not to be taken until
the check standard measurements fall within the acceptable range for accuracy and precision.
33
-------
5. Physical Properties and Chemical Composition of Alaska North Slope
Crude Oil (2002)
5.1 Origin: Alaska, U. S. A (the oil was drawn as a line sample off the TAPS pipeline where
it spurs off to the Petrostar Refinery in Valdez on March 19, 2002)
Synonyms: ANS
Appearance: Brown-black, light, little odour, fine black particulates dispersed through-out
liquid.
Values are reported for the fresh oil and for artificially weathered fractions of 10.0%, 22.5% and
30.5% loss by weight.
5.2 API Gravity
30.89 (calc)
5.3 Equation for Predicting Evaporation
%Ev = ( 2.86+ 0.045 T)\nt
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
5.4 Sulphur Content
Weathering
(weight %)
0
10.0
22.5
30.5
Sulphur
(weight %)
1.11 (n=3)
1.20 (n=3)
1.38 (n=3)
1.50 (n=3)
5.5 Water Content
Weathering
(weight %)
0
10.0
22.5
30.5
Water
(volume %)
<0.1 (n=3)
<0.1 (n=3)
<0.1 (n=3)
<0.1 (n=3)
34
-------
5.6 Flash Point
Weathering
(weight %)
0
10.0
22.5
30.5
Flash Point
(°C)
<-8
19
75
115
(n=3)
(n=3)
(n=3)
(n=3)
5.7 Density
Weathering
(weight %)
0
10.0
22.5
30.5
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.8777
0.8663
0.9054
0.8940
0.9303
0.9189
0.9457
0.9340
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
5.8 Pour Point
Weathering
(weight %)
0
10.0
22.5
30.5
Pour Point
(°Q
-32
-20
-9
-6
(n=2)
(n=2)
(n=2)
(n=2)
35
-------
5.9 Dynamic Viscosity
Weathering
(weight %)
0
10.0
22.5
30.5
Temperature Viscosity
(°C) (cP)
0 23.2
15 11.5
0 76.7
15 31.8
0 614
15 152
0 4230
15 624.7
(n=3)
(n=3)
(n=3)
(n=3)
(n=2)
(n=3)
(n=2)
(n=2)
5.10 Chemical Dispersibility
Weathering
(weight %)
0
10.0
22.5
30.5
Chemical Dispersibility
using Corexit 9500 ( %)
47
45
34
15
(n=6)
(n=6)
(n=6)
(n=6)
5.11 Adhesion
Weathering
(weight %)
0
10.0
22.5
30.5
Adhesion
(g/m2)
20
35
38
40
(n=4)
(n=4)
(n=4)
(n=4)
36
-------
5.12 Surface and Interfacial Tensions
5.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
10.0
22.5
30.5
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
27.3
26.4
29.8
28.4
31.2
30.4
33.1
31.8
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
5.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
10.0
22.5
30.5
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
22.5
20.2
25.3
23.1
26.8
24.2
30.1
25.6
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
37
-------
5.12.3 Oil/Fresh Water Inter facial Tension
Weathering
(weight %)
0
10.0
22.5
30.5
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
26.7
23.6
28.1
25.5
30.8
27.7
33.2
30.2
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
5.13 Emulsion Formation
Weathering
(weight %)
0
10.0
22.5
30.5
Visual Stability
Unstable
Unstable
Unstable
Mesostable
Complex Modulus
(Pa)
155
Emulsion
Water Content (%)
72.9
38
-------
5.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 10.0% 22.5% 30.5%
weathered weathered weathered weathered
2.5
3.9
6.5
10.0
13.4
16.6
19.8
22.6
25.2
32.6
40.7
49.5
57.7
66.0
72.8
79.0
84.1
88.4
0.1
0.5
1.4
3.6
6.6
9.8
13.1
16.3
19.2
27.4
36.4
46.1
55.3
64.5
72.1
79.0
84.7
89.5
0.1
0.6
2.0
4.4
7.3
16.6
27.0
38.2
48.7
59.3
68.2
76.0
82.6
88.0
0.5
7.5
18.7
31.1
42.8
54.5
64.2
72.8
79.9
85.8
39
-------
5.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
75.0
15.0
6.1
4.0
2.6
10.0%
weathered
72.1
16.0
7.4
4.4
2.9
22.5%
weathered
69.2
16.5
8.9
5.4
3.3
30.5%
weathered
64.8
18.5
10.3
6.4
3.6
5.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 30.5%
weathered weathered
2866
5928
1319
6187
5620
16300
21920
0
0
0
0
30
0
30
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
40
-------
5.17 tt-Alkane Distribution
n-Alkane Component
w-C8
w-C9
w-CIO
w-Cll
w-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
H-C18
Phytane
H-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-C30
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
w-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
5.55
4.29
4.13
3.98
3.71
3.57
3.42
3.28
3.15
3.06
1.89
2.68
1.41
2.32
2.11
1.96
1.90
1.79
1.65
1.47
1.27
0.97
0.78
0.70
0.56
0.44
0.31
0.27
0.24
0.22
0.11
0.09
0.07
0.05
0.03
0.02
63.4
1.62
1.9
1.35
0.9
(mg/g oil)
30.5%
weathered
0.73
2.51
3.80
4.58
4.34
4.05
4.00
2.41
3.46
1.80
2.93
2.71
2.50
2.45
2.34
2.16
1.94
1.73
1.28
1.03
0.98
0.69
0.60
0.43
0.33
0.31
0.25
0.14
0.13
0.10
0.07
0.06
0.04
56.9
1.66
1.92
1.34
1.0
41
-------
ANS Fresh
6 -i
5 -
4 -
3 -
2 -
1 -
0 -
oo
o
o o o o
B
0)
O CM
CM CM
O O
c\ic\ic\icococococo^r
OOOOOOOOO
ANS 30.5% w
_ 5 -1
o 4 .
1 3
d 2-
o
0 -
!!
H ^ ^
• i i i
n n
111 llllllllf,
\ 1 I l- 1 \ 1 l- l- I i II II 11 II II i 1 H n • •
DO O CN| ^" CO QJ QJ C) CN| ^~ CO CO O CN| ^~ CO CO O
O T- T- T- T- £= CCNCNCNCNCNCOCOCOCOCO^r
'OOOOrorooOOOOOOOOOO
1^1 1 1 1 (f. ^Z 1 1 1 1 1 1 1 1 1 1 1
D. CL
Figure 5.1 w-Alkane Distribution for Alaska North Slope crude oil (mg/g
oil)
42
-------
5.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
261
1015
1800
1702
815
5594
209
666
710
486
296
2368
122
225
318
265
931
142
328
447
379
1295
48
74
99
84
306
10493
1.49
0.76
1 : 0.65 : 0.34
134.71
12.03
13.03
2.88
2.88
8.40
4.64
5.14
0.50
10.28
2.26
3.01
0.13
0.63
3.13
204
30.5%
weathered
167
1288
2716
2575
1174
7919
295
932
988
707
432
3354
174
319
456
362
1312
197
449
647
525
1819
68
107
141
115
430
14834
1.41
0.76
1 : 0.65 : 0.34
176.9
18.43
20.02
4.55
3.81
11.92
8.11
7.49
0.70
14.74
3.69
4.42
0.25
1.02
4.91
281
43
-------
ANS Fresh
_ 5000 n
•f^ 3000 -
a 2000 -
g 1000 -
° 0
.illi .
17°]P]
Q.
m
n n n n
° •£ Z Z £ o_ o_
Q_ i i CD ' '
co T- co jz •*- co
Z 0 0 Q. 0 0
Other
CD n
N Q
1 5
Q
EPA Priority PAHs
en S' m
en
n n _ • • •
Q Li. Li. ^ O
CO O CN -C -A
o o o o o
CL
0)
m
O
CO
O
ANS
^>
o
^)
3:
d
o
O
30.5% w
5000 n
4000 -
3000 -
2000 -
1000 -
0 -
J
m T—
Z 0
?5§ ] n Other EPA Priority PAHs
100 j ;;
Q- 0 rr <; o n_ n_
en o (5 ^- ro
< m -Q en
en
1 n n 11 PI n -BIBB n n PI n
Z CQ.CL NQQLLLL >* O
cO-c^co ajT-coocN-c-^
OQ.OOJ2OOOOOO
Q
n.
D)
en
O
CO
O
Figure 5.2 PAH Distribution for Alaska North Slope crude oil (|ig/g oil)
44
-------
5.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
65.6
40.8
77.6
116.6
46.9
33.0
34.2
21.6
21.6
13.3
15.1
8.6
20.9
28.5
73.6
84.2
702
30.5%
weathered
91.8
57.8
104.6
161.1
64.1
46.1
46.5
30.9
31.0
19.3
21.0
12.4
31.8
43.0
103.2
113.8
978
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
1.61
0.56
0.35
0.67
1.42
1.58
1.62
1.76
0.73
0.87
1.59
0.57
0.36
0.65
1.39
1.51
1.60
1.70
0.74
0.91
45
-------
6. Physical Properties and Chemical Composition of Alberta Sweet Mixed
Blend (ASMB, Reference #5)
6.1 Origin: Alberta, Canada (ESTD storage, originally from ESSO, Alberta, Canada)
Synonyms: ASMB #5
Values are reported for the fresh oil and for artificially weathered fractions of 12.6%, 24.3% and
36.8% loss by weight.
6.2 API Gravity
35.72 (calc)
6.3 Equation for Predicting Evaporation
%Ev=(3.35+0.045 T)\nt
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
6.4 Sulphur Content
Weathering
(weight %)
0
12.6
24.3
36.8
Sulphur
(weight %)
0.63 (n=3)
0.70 (n=3)
0.78 (n=3)
0.89 (n=3)
6.5 Water Content
Weathering
(weight %)
0
12.6
24.3
36.8
Water
(volume%)
0.1 (n=3)
O.I (n=3)
0.1 (n=3)
O.I (n=3)
46
-------
6.6 Flash Point
Weathering
(weight %)
0
12.6
24.3
36.8
Flash Point
(°C)
-4.3
27.8
67.8
>110
(n=2)
(n=3)
(n=3)
(n=2)
6.7 Density
Weathering
(weight %)
0
12.6
24.3
36.8
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.8536
0.8404
0.8805
0.8676
0.8987
0.8852
0.9151
0.9017
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
6.8 Pour Point
Weathering
(weight %)
0
12.6
24.3
36.8
Pour Point
(°Q
-18
-12
-12
9
(n=2)
(n=2)
(n=2)
(n=2)
47
-------
6.9 Dynamic Viscosity
Weathering Temperature Viscosity
(weight %) (°C) (cP)
0 0 23.6
15 6.1
12.6 0 45.3
15 13.8
24.3 0 D=l 14170
D=10 1802
D=100 310
15 31.5
36.8 0 D=l 41690
D = 10 6097
D = 100 897
15 123.2
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
6.10 Chemical Dispersibility
Weathering Chemical Dispersibility
(weight %) using Corexit 9500 ( %)
0 28.1
12.6 26.6
24.3 17.2
36.8 10.9
(n=6)
(n=6)
(n=6)
(n=6)
48
-------
6.11 Adhesion
Weathering
(weight %)
0
12.6
24.3
36.8
Adhesion
(g/m2)
4.8
25.0
33.6
43.7
(n=3)
(n=4)
(n=4)
(n=3)
6.12 Surface and Interfacial Tensions
6.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
12.6
24.3
36.8
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
28.3
25.5
29.1
27.2
30.1
28.0
31.1
29.9
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
49
-------
6.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
12.6
24.3
36.8
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
19.2
23.1
29.0
23.1
21.1
24.1
20.1
23.2
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
6.12.3 Oil/Fresh Water Interfacial Tension
Weathering
(weight %)
0
12.6
24.3
36.8
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
30.7
14.3
33.9
16.0
31.1
15.3
32.7
14.3
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
6.13 Emulsion Formation
Weathering
(weight %)
0
12.6
24.3
36.8
Visual Stability
Meso
Meso
Stable
Stable
Complex Modulus
(Pa)
133
409
630
1025
Emulsion
Water Content (%)
89.6
92.9
87.7
86.0
50
-------
6.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight
0% 12.6%
weathered weathered
2.4
3.8
6.5
10.2
13.6
17.4
21.5
25.9
29.7
39.4
49.5
59.5
68.0
76.0
82.2
86.6
90.4
93.1
0.2
0.8
1.6
3.4
6.1
9.5
13.8
18.2
22.4
32.8
43.5
54.5
63.5
72.1
78.9
84.0
87.7
90.4
Fraction (%)
24.3%
weathered
0.1
0.1
0.1
0.2
1.1
3.4
7.2
11.4
23.1
35.5
48.1
58.6
68.7
76.5
82.4
86.6
89.7
36.8%
weathered
0.1
1.1
10.4
24.5
39.3
51.6
63.4
72.7
79.7
84.7
88.3
51
-------
6.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
77.3
16.8
4.2
1.7
3.2
12.6%
weathered
77.0
15.7
5.4
2.0
3.5
24.3%
weathered
76.5
15.4
5.7
2.4
4.0
36.8%
weathered
72.4
18.0
6.5
3.1
4.4
6.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 36.8%
weathered weathered
2261
5308
1646
8954
1240
18170
30570
0
10
0
0
110
10
120
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
52
-------
6.17 tt-Alkane Distribution
n-Alkane Component
n-C8
n-C9
n-CIO
n-Cll
n-C12
n-C13
n-C14
n-C15
n-C16
n-C17
Pristane
n-C18
Phytane
n-C19
n-C20
n-C21
n-C22
n-C23
n-C24
n-C25
n-C26
n-C27
n-C28
n-C29
n-C30
n-C31
n-C32
n-C33
n-C34
n-C35
n-C36
n-C37
n-C38
n-C39
n-C40
n-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
5.52
5.09
5.02
4.45
4.43
4.37
4.57
4.18
3.85
2.45
3.14
1.96
3.01
2.80
2.56
2 29
2.02
1.86
1.75
1.56
1.30
1.14
1.03
0.76
0.66
0.44
0.35
0.29
0.24
0.10
0.08
0.05
0.04
0.03
78.8
1.58
1.61
1.25
0.96
(mg/g oil)
36.8%
weathered
1.39
4.12
5.93
5.92
6.98
6.69
6.16
4.05
5.19
3.28
4.85
4.33
4.13
3.72
3.34
2.96
2.83
2.44
2.07
1.83
1.66
1.28
1.06
0.74
0.52
0.49
0.43
0.18
0.12
0.09
0.06
0.05
88.9
1.52
1.58
1.23
1.04
53
-------
6 -,
=• 5 -
o
5> 4 -
"3)
£ 3-
¥ 2-
o „
0 1 -
n
U
3)
J
i
C
T
t
!
J
0
t
!
0
J
LT
c
c
^
)
ASM B #5 (Fresh)
: H F|
''''• i ^ n ''''• '- ^10
: : : |:| : : : 1 || |::| 1:1 PI
: : || : : 1 H II II 1 1 fl Fl PI
M ; 1 M Ml 1 II ll II 1 I i II I B . . .
r^oo O5^-coLor^O5^-coLor^O5^-
oooooooooooooo
II 1 1 1 1 1 1 1 1 1 1 1 1
CC CCCCCCCCCCCC
8 -,
~ 7 -
o 6-
E 4-
"3" 3-
c 0
o 2 -
O -|
n
U
^ n
• ;; ;;
I ^ ^
1 ;; !;
r
O) T- CO if
^ O O C
c c c
ASM B #5 (36.8% w)
:: F1
11 n ;; i pi H
;; ;; ;; ;i pi ;; ;; \ ;; pi
!! !! !! i; !! 1 I \ 1 I I 1 i pi n
\ \ 1 \ \ \ \ \ \ \ I lllllllilranpi
5OOOOOOOOOOOOOO
1 1 1 1 1 1 1 1 1 1 1 1 1 1
Figure 6.1 w-Alkane Distribution for Alberta Sweet Mixed Blend #5 crude
oil (mg/g oil)
54
-------
6.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
245
987
1769
1734
763
5498
141
559
642
456
294
2092
121
219
298
201
839
81
189
289
295
854
29
62
100
92
282
9565
1.75
0.95
1:0.74:0.28
70.8
7.61
15.95
2.09
2.45
18.28
2.94
2.94
0.49
8.71
0.86
1.72
0.74
1.25
2.94
140
36.8%
weathered
153
1209
2662
2830
1311
8165
235
924
1052
748
487
3446
201
360
501
333
1395
133
317
475
481
1405
49
107
169
159
483
14895
1.65
0.95
1:0.76:0.28
99.5
11.97
26.31
3.87
4.24
21.57
5.36
4.61
0.62
15.21
1.25
2.62
0.75
1.8
4.36
203
55
-------
ASMB #5
Fresh
3000 -,
= 2500 -
o) 2000 -
a isoo -
£ 1000 -
0 500-
0-
n
-A
1
100 Other EPA Priority PAHs
50 -H
o II 1-1 m
Q-0Q:<2-Q-Q-Q-
-------
6.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
48.4
25.5
57.0
87.7
33.4
31.7
24.9
17.4
15.2
10.7
10.1
6.3
26.1
23.8
51.5
60.2
530
36.8%
weathered
83.0
43.1
103.6
155.9
58.5
54.6
40.4
28.8
25.6
17.7
17.7
10.4
46.1
42.2
87.3
107.5
922
Diagnostic Ratios
C23/C24
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
1.90
0.55
0.29
0.65
1.05
1.44
1.43
1.60
1.93
0.53
0.28
0.66
1.07
1.40
1.45
1.69
57
-------
7. Physical Properties and Chemical Composition of Arabian Light (2000)
7.1 Origin: Saudi Arabia (Sampled from Irving Oil Refinery, St. John, NB, 2000)
Synonyms: None
Values are reported for thefresh oil and for artificially weathered fractions of 9.2%, 17.6% and
26.0% loss by weight.
7.2 API Gravity
31.30 (calc)
7.3 Equation for Predicting Evaporation
%Ev =(2.4 + 0.045 7) In t
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
7.4 Sulphur Content
Weathering
(weight %)
0
9.2
17.6
26.0
Sulphur
(weight %)
1.93 (n=3)
2.17 (n=3)
2.36 (n=3)
2.60 (n=3)
7.5 Water Content
Weathering
(weight %)
0
9.2
17.6
26.0
Water
(volume %)
<0.1 (n=3)
<0.1 (n=3)
<0.1 (n=3)
O.I (n=3)
58
-------
7.6 Flash Point
Weathering
(weight %)
0
9.2
17.6
26.0
7.7 Density
Weathering
(weight %)
Flash Point
Temperature
36.5
71.7
Density
(g/mL)
(n=2)
(n=3)
(n=3)
(n=2)
0
9.2
17.6
26.0
0
15
0
15
0
15
0
15
0.8776
0.8641
0.8994
0.8660
0.9154
0.9028
0.9321
0.9193
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
7.8 Pour Point
Weathering
(weight %)
0
9.2
17.6
26.0
Pour Point
-21
-15
-8
-9
(n=2)
(n=2)
(n=l)
(n=2)
59
-------
7.9 Dynamic Viscosity
Weathering
(weight %)
0
9.2
17.6
26.0
Temperature Viscosity
(°C) (cP)
0 32.6
15 13.0
0 77.6
15 27.4
0 D=l 3546
D=10 1073
D=100 368
15 59.9
0 D=l 17190
D=10 3869
D=100 1096
15 173.7
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
7.10 Chemical Dispersibility
Weathering
(weight %)
0
9.2
17.6
26.0
Chemical Dispersibility
using Corexit 9500 ( %)
19.0
13.8
10.0
7.9
(n=6)
(n=6)
(n=6)
(n=6)
7.11 Adhesion
Weathering
(weight %)
0
9.2
17.6
26.0
Adhesion
(g/m2)
17
28
30
35
(n=3)
(n=3)
(n=4)
(n=3)
60
-------
7.12 Surface and Interfacial Tensions
7.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
9.2
17.6
26.0
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
27.2
26.0
29.2
27.9
30.6
28.4
30.9
30.2
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
7.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
9.2
17.6
26.0
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
21.3
21.6
22.2
22.8
16.4
24.6
26.8
20.4
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
61
-------
7.12.3 Oil/Fresh Water Inter facial Tension
Weathering
(weight %)
0
9.2
17.6
26.0
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
23.5
23.8
22.4
22.0
28.3
25.7
30.1
22.4
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
7.13 Emulsion Formation
Weathering
(weight %)
0
9.2
17.6
26.0
Visual Stability
Meso
Meso
Stable
Stable
Complex Modulus
(Pa)
92.7
212
274
503
Emulsion
Water Content (%)
91.1
88.6
83.8
83.8
62
-------
7.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 9.2% 17.6% 26.0%
weathered weathered weathered weathered
1.1
1.3
1.7
4.7
6.8
9.6
12.6
15.9
19.1
26.8
35.1
43.7
51.4
58.9
65.5
71.4
76.2
80.1
1.2
2.9
5.3
8.2
11.7
15.0
23.5
32.4
41.7
50.1
58.2
65.4
71.8
77.0
81.2
0.1
0.6
2.0
4.7
8.0
17.3
27.3
37.7
47.0
56.1
64.0
71.1
76.8
81.4
0.2
1.2
8.6
19.4
30.9
41.4
51.5
60.5
68.5
75.0
80.2
63
-------
7.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
75.5
15.2
5.7
3.6
2.7
9.2%
weathered
73.3
16.9
6.0
3.8
2.9
17.6%
weathered
72.4
16.7
6.6
4.3
3.2
26.0%
weathered
70.1
16.3
8.8
4.8
3.6
7.16 Volatile Organic Compounds
Concentration
(ug/g oil)
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
0%
weathered
979
3050
1995
4927
8620
10950
19570
26.0%
weathered
11
74
434
1508
6520
2030
8550
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
64
-------
7.17 tt-Alkane Distribution
n-Alkane Component
n-C8
n-C9
n-CIO
n-Cll
n-C12
n-C13
n-C14
n-C15
n-C16
n-C17
Pristane
n-C18
Phytane
n-C19
n-C20
n-C21
n-C22
n-C23
n-C24
n-C25
n-C26
n-C27
n-C28
n-C29
n-C30
n-C31
n-C32
n-C33
n-C34
n-C35
n-C36
n-C37
n-C38
n-C39
n-C40
n-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
6.87
7.61
7.25
7.00
6.41
5.93
5.62
5.30
4.76
3.99
0.57
3.42
1.13
2.79
2.57
2 24
1.98
1.57
1.43
1.12
1.00
0.80
0.71
0.58
0.48
0.40
0.29
0.21
0.18
0.15
0.08
0.06
0.05
0.03
0.02
84.6
6.95
3.03
0.51
0.93
(mg/g oil)
26.0%
weathered
0.29
2.47
5.41
6.56
7.13
7.14
6.46
5.51
0.79
4.55
1.51
3.88
3.43
3.17
2.62
2.19
2.01
1.54
1.38
1.16
1.02
0.92
0.69
0.61
0.42
0.29
0.24
0.19
0.11
0.06
0.05
0.04
0.03
73.9
6.99
3.02
0.52
1.00
65
-------
Arabian Light Fresh
8 -,
~ 7 -
o 6-
•2* 5 -
0) J
E 4-
o" 3-
c 0
o 2 -
O -|
n
;; F
.
! p
n
:
:: r
I
ii JL
1 1 1 1 II 1 llllininr,o______
Qt-t-t-t-t-t-CNCNCNCNCNCOCOCOCOCO^r
'OOOOOOOOOOOOOOOOO
8 -,
=• 7 -
o 6 -
1! 5-
E 4 -
o" 3-
o 2-
0 -i .
n -
ri
J
O) T- CO
c 9 9
Arabian Light 26.0% w
n
'- '- '- 1
1! 11 llliliFlFln..
ooooooooooooooo
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Figure 7.1 w-Alkane Distribution for Arabian Light crude oil (mg/g oil)
66
-------
7.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
50.3
391.7
1123.3
1542.2
831.2
3939
51.2
293.0
384.5
310.2
257.1
1296
147.7
438.8
770.3
675.9
2033
35.2
94.6
183.9
199.0
513
13.0
29.5
54.4
69.8
167
7947
0.98
0.55
1 : 0.87: 0.57
7.83
7.83
2.86
0.99
0.27
4.10
0.50
1.61
0.99
4.22
1.24
0.00
0.52
0.49
1.86
37
26.0%
weathered
25.7
332.5
903.8
1739.9
1000.2
4002
64.1
367.5
488.0
393.1
328.2
1641
181.2
544.4
980.6
856.6
2563
40.4
117.7
222.1
251.9
632
16.8
37.9
72.7
90.1
217
9055
0.97
0.55
1 :0.88 :0.57
8.79
8.66
3.22
1.73
0.37
5.07
1.98
2.48
1.11
5.69
1.99
0.00
0.74
1.12
2.23
43
67
-------
Arabian Lig
Fresh
2000 -,
o 1500 -
a 1000 -
1 500-
n
ht
1
1 5
•
^
c<
C
7
-)
\
c D
j= -
CL C.
10] Other EPA Priority PAHs
n n
0 1 1 HI._il_n-|l|._r,.B
< m ^ co co
co
llll Jill __HH
D- NQQLLLL £-OO
;oEooooooo
Q
Arabian Light
26.0% w
2000 -,
0 1500 -
a 1000 -
0
o 500-
o
0-
n
1 5
10 ., Other EPA Priority PAHs
D[-i
0 n n
llrin II n n n II . _ n
Q- Q) LL ^ 2" Q_ Q- Q_
CQ Q ro -— ' ro ~ D)
<^ CQ -° CQ CQ
n n
_nllnn •II I
Z C CL CL NQQU-LL £>OO
co _c ^— co o)T— COOCM-CT— co
Oo_OO-QOOOOOoO
b
Figure 7.2 PAH Distribution for Arabian Light crude oil (|ig/g oil)
68
-------
7.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
17.7
6.6
152.2
124.6
79.9
65.7
48.1
29.8
27.0
17.8
14.4
8.8
42.6
36.5
35.1
55.1
762
26.0%
weathered
21.6
7.9
184.2
148.9
96.5
77.3
57.2
36.7
32.5
21.9
17.5
11.1
51.3
43.8
40.4
67.6
917
Diagnostic Ratios
C23/C24
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
2.70
0.14
0.05
1.22
1.22
1.62
1.51
1.63
2.72
0.14
0.05
1.24
1.25
1.56
1.49
1.58
69
-------
8. Physical Properties and Chemical Composition of Sockeye (2000)
8.1 Origin: California, U.S.A. (Via U.S. Dept. Int., M.M.S., OHMSETT, NJ)
Synonyms: Sockeye Sour
Appearance: Black, heavy, sticky, sour odour.
Values are reported for the fresh oil and for artificially weathered fractions of 6.9%, 13.0% and
19.8% loss by weight.
8.2 API Gravity
19.32 (calc)
8.3 Equation for Predicting Evaporation
%Ev =(1-52+ 0.045 T)\nt
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
8.4 Sulphur Content
Weathering
(weight %)
0
6.9
13.0
19.8
Sulphur
(weight %)
4.51 (n=3)
4.95 (n=3)
5.19 (n=3)
5.47 (n=3)
8.5 Water Content
Weathering
(weight %)
0
6.9
13.0
19.8
Water
(volume%)
0.8 (n=3)
0.1 (n=3)
0.1 (n=3)
<0.1 (n=3)
70
-------
8.6 Flash Point
Weathering
(weight %)
0
6.9
13.0
19.8
Flash Point
(°C)
-4
35
72
>110
(n=4)
(n=3)
(n=3)
(n=2)
8.7 Density
Weathering
(weight %)
0
6.9
13.0
19.8
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.9465
0.9354
0.9642
0.9537
0.9798
0.9692
0.9951
0.9839
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
8.8 Pour Point
Weathering
(weight %)
0
6.9
13.0
19.8
Pour Point
(°Q
-25
-18
2
13
(n=2)
(n=2)
(n=2)
(n=2)
71
-------
8.9 Dynamic Viscosity
Weathering
(weight %)
0
6.9
13.0
19.8
Temperature Viscosity
(°C) (cP)
0 3220
15 761
0 13600
15 2720
0 143000*
15 15100
0 5300000*
15 274000"
* Measured at a shear rate of 1 s"1 with a 60mm a cone and plate sensor.
** Measured under static conditions with a 60mm cone and plate sensor, applied
8.10 Chemical Dispersibility
Weathering
(weight %)
0
6.9
13.0
19.8
Chemical Dispersibility
using Corexit 9500 ( %)
11.8
9.6
10.1
8.9
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
shear stress of 100 Pa
(n=6)
(n=6)
(n=6)
(n=6)
8.11 Adhesion
Weathering
(weight %)
0
6.9
13.0
19.8
Adhesion
(g/m2)
70
70
90
350
(n=4)
(n=4)
(n=4)
(n=4)
72
-------
8.12 Surface and Interfacial Tensions
8.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
6.9
13.0
19.8
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
30.1
28.8
NM
31.3
NM
32.2
NM
NM
(n=4)
(n=4)
(n=3)
(n=3)
8.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
6.9
13.0
19.8
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
23.0
21.9
NM
23.1
NM
NM
NM
NM
(n=3)
(n=3)
(n=3)
73
-------
8.12.3 Oil/Fresh Water Inter facial Tension
Weathering
(weight %)
0
6.9
13.0
19.8
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
23.7
21.4
NM
24.9
NM
NM
NM
NM
(n=3)
(n=3)
(n=3)
8.13 Emulsion Formation
Weathering
(weight %)
0
6.9
13.0
19.8
Visual Stability Complex Modulus
(Pa)
Meso-stable
Meso-stable
Entrained Water
Entrained Water
183
251
391
1298
Emulsion
Water Content (%)
75.6
73.3
53.4
17.7
74
-------
8.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 6.9% 13.0% 19.8%
weathered weathered weathered weathered
0.4
0.4
1.5
3.3
5.1
7.1
9.2
11.3
13.2
18.9
24.7
30.9
36.8
43.3
50.1
57.3
63.5
69.2
0.1
0.7
1.6
3.1
5.0
7.1
9.2
15.4
21.6
28.3
34.6
41.7
49.0
56.6
63.2
69.1
0.2
0.9
2.3
4.1
10.5
17.1
24.2
30.9
28.5
46.4
54.9
62.1
68.5
0.4
4.6
11.3
19.0
26.3
34.6
43.4
52.9
60.9
68.0
75
-------
8.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
49.2
17.2
15.1
18.5
1.6
6.9%
weathered
46.2
17.6
16.4
19.8
1.7
13.0%
weathered
44.4
18.0
17.1
20.5
1.8
19.8%
weathered
40.3
18.0
17.2
24.5
2.1
8.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 19.8%
weathered weathered
1343
2031
974
3880
5810
8230
14040
9
12
0
1
70
20
90
f'Xylenes" include o-, m-, and/>-xylene isomers.
f f "C3-Benzenes" include eight isomers.
76
-------
8.17 tt-Alkane Distribution
n-Alkane Component
w-C8
w-C9
w-CIO
w-Cll
w-C12
w-C13
w-C14
w-C15
w-C16
H-C17
Pristane
H-C18
Phytane
w-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-C30
H-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
w-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
1.27
0.95
0.85
1.02
1.14
1.37
1.43
1.54
1.52
1.32
1.68
1.19
1.79
1.08
1.02
0.91
0.81
0.71
0.65
0.59
0.51
0.30
0.30
0.30
0.28
0.23
0.15
0.14
0.23
0.33
0.07
0.08
0.07
0.03
0.02
25.9
0.78
0.66
0.94
0.95
(mg/g oil)
19.8%
weathered
0.13
0.63
1.08
1.52
1.73
1.76
1.55
1.90
1.41
2.11
1.25
1.20
1.09
0.97
0.85
0.75
0.71
0.60
0.37
0.36
0.36
0.29
0.28
0.17
0.17
0.24
0.39
0.10
0.10
0.08
0.04
0.02
242
0.82
0.67
0.90
1.00
77
-------
— 251
02.0-
•5*
Ito-
go.5-
2 0.0-
n
I U U
i i i
00 O
i (_)
c
Sockeye Fresh
n fl
n
1 [1 nn
ifjnnn
llllllllllllllnnnnnnnnn
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
CNJ^CQ OJOJOCN'Nj-CQCOOCN'Nj-CQCOO
T- T- T- CCC\JC\JC\JC\JC\JCOCOCOCOCO-f
0005500000000000
i i i TO 3>i i i i i i i i i i i i
C C C •— f-* CCCCCCCCCCC
Q- Q-
= 2.5 n
«20-
0) ,-c
e 1-5'
o 1.0-
§0.5-
0.0-
n n
n 1
Sockeye IQ^/oW
1
PI
II II II 11 n n n n n n n n fl _
COOCNJ-^CQ 0) CDOCNJ-^CDOOOCNJ-^CDOOO
Q T- T- T- T- C CC\JC\JC\JC\JC\JCOCOCOCOCO'vr
;i.oooo55ooooooooooo
C i i i i ^) >^ i i i i i i i i i i i
Q- Q-
Figure 8.1 w-Alkane Distribution for Sockeye Crude Oil (mg/g oil)
78
-------
8.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
111
511
1057
1144
599
3424
60
237
319
283
179
1078
34
86
155
128
404
13
39
68
64
183
5
11
22
22
61
5149
1.35
1.09
1 : 0.89 :0.36
34.23
6.72
7.70
2.20
1.22
5.01
3.18
0.98
0.40
1.59
0.49
19.32
0.00
0.12
0.86
84
19.8%
weathered
72
560
1272
1541
824
4269
76
314
424
362
241
1417
45
117
216
171
550
17
50
89
84
239
7
15
29
29
81
6556
1.33
1.10
1 : 0.89 :0.35
38.98
8.99
10.37
3.12
1.62
6.75
4.25
1.12
0.50
2.50
0.50
25.98
0.00
0.20
1.00
106
79
-------
Sockeye
Fresh
2000 -
'o
5> 1500 -
7 1000 -
c
8 500-
-i
Sockeye
19.8%w
1800 -,
= 1600 -
a) 1400-
o) 1200 -
•3 1000 -
6 800 -
o 600 -
0 400 -
200 -
n
£ +
£ 0
1
r
J
Q- ,1
™ 0
<
<
-
•7
i
*5
J
Z
-o
J
f
d Q
n 1
^° 1 Other EPA priority PAHs
40 -
n
10 - 11 _
0IIllBB_ •mil _ II
m < co S" co co1
CO
i n n
Q
40 1 Other EPA priority PAHs
30 - n
20 n
10 n i-i _
CQ
I I I I I I I ^-, l~l I I PI ^, n n „ „
Q
Figure 8.2 PAH Distribution for Sockeye crude oil (|lg/g oil)
80
-------
8.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
46.2
31.3
61.2
99.5
38.7
40.6
27.5
18.9
18.8
12.8
8.4
5.7
6.9
35.4
207.8
151.7
811
19.8%
weathered
57.7
38.9
78.2
126.5
52.3
54.4
36.9
25.3
26.3
18.1
11.9
8.0
8.7
42.9
262.1
191.4
1039
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
1.48
0.46
0.31
0.62
0.95
1.45
1.47
1.47
0.19
1.37
1.48
0.46
0.31
0.62
0.96
1.46
1.46
1.48
0.20
1.37
81
-------
9. Physical Properties and Chemical Composition of South Louisiana
(2001)
9.1 Origin: Baton Rouge, Louisiana, U.S.A. (Exxon-Mobil)
Synonyms: Louisiana
Values are reported for the fresh oil and for artificially weathered fractions of 10.9%, 19.7% and
27.7% loss by weight.
9.2 API Gravity
32.72 (calc)
9.3 Equation for Predicting Evaporation
%Ev =(2.74 + 0.045 7) In t
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
9.4 Sulphur Content
Weathering
(weight %)
0
10.9
19.7
27.7
Sulphur
(weight %)
0.49 (n=3)
0.71 (n=3)
0.79 (n=3)
0.88 (n=3)
9.5 Water Content
Weathering
(weight %)
0
10.9
19.7
27.7
Water
(volume %)
O.I (n=3)
0.1 (n=3)
O.I (n=3)
O.I C«=3J
82
-------
9.6 Flash Point
Weathering
(weight %)
0
10.9
19.7
27.7
Flash Point
<-10 (n=2)
42.3 (n=3)
80.7 (n=3)
>110 (n=2)
9.7 Density
Weathering
(weight %)
0
10.9
19.7
27.7
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.8668
0.8562
0.8888
0.8770
0.9025
0.8906
0.9135
0.9018
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
9.8 Pour Point
Weathering
(weight %)
0
10.9
19.7
27.7
Pour Point
(°Q
-41
-19
-14
-11
(n=2)
(n=2)
(n=l)
(n=2)
83
-------
9.9 Dynamic Viscosity
Weathering
(weight %)
0
10.9
19.7
27.7
Temperature Viscosity
(°C) (cP)
0 18.5
15 10.1
0 54.8
15 23.7
0 217.3
15 48.9
0 515.9
15 141.0
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=2)
(n=3)
(n=3)
9.10 Chemical Dispersibility
Weathering
(weight %)
0
10.9
19.7
27.7
Chemical Dispersibility
using Corexit 9500 ( %)
26.5
23.5
15.8
10.3
(n=6)
(n=6)
(n=6)
(n=6)
9.11 Adhesion
Weathering
(weight %)
0
10.9
19.7
27.7
Adhesion
(g/m2)
24
34
50
28
(n=4)
(n=4)
(n=5)
(n=4)
84
-------
9.12 Surface and Interfacial Tensions
9.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
10.9
19.7
27.7
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
28.3
26.1
29.3
28.1
30.4
29.4
31.1
29.8
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
9.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
10.9
19.7
27.7
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
20.9
16.8
22.0
19.4
22.0
22.2
20.6
18.4
(n=2)
(n=3)
(n=3)
(n=2)
(n=3)
(n=2)
(n=4)
(n=3)
85
-------
9.12.3 Oil/Fresh Water Inter facial Tension
Weathering
(weight %)
0
10.9
19.7
27.7
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
20.8
15.5
25.2
15.8
25.3
22.3
24.7
21.9
(n=3)
(n=2)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
9.13 Emulsion Formation
Weathering
(weight %)
0
10.9
19.7
27.7
Visual Stability
Unstable
Unstable
Unstable
Unstable
Complex Modulus Emulsion
(Pa) Water Content (%)
86
-------
9.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 10.9% 19.7% 27.7%
weathered weathered weathered weathered
1.2
1.6
2.1
5.6
8.2
11.1
14.1
17.5
20.6
29.8
39.9
49.7
58.1
65.8
72.0
77.1
80.9
83.8
0.9
2.4
4.8
7.8
11.4
14.9
25.2
36.6
47.7
57.0
65.7
72.7
78.5
82.8
86.0
0.1
0.4
1.6
4.0
7.2
18.1
30.6
42.8
53.1
62.7
70.4
76.7
81.5
85.0
0.1
0.3
1.4
10.6
24.1
37.5
49.0
59.6
68.2
75.2
80.5
84.5
87
-------
9.15 Hydrocarbon Groups
Concentration
(°/o)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
80.8
12.6
5.9
0.8
1.7
10.9%
weathered
80.4
12.3
6.4
0.9
1.8
19.7%
weathered
78.4
12.5
8.0
1.1
2.0
27.7%
weathered
77.3
13.3
8.0
1.5
2.2
9.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 27.7%
weathered weathered
1598
3552
891
6164
6680
12210
18890
0
10
0
2
190
12
202
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
88
-------
9.17 tt-Alkane Distribution
n-Alkane Component
w-C8
H-C9
H-C10
H-C11
H-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
w-C18
Phytane
w-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-CSO
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
H-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
4.33
4.12
4.12
4.56
4.25
4.14
3.81
3.88
3.48
3.05
2.10
2.24
1.35
2.00
1.70
1.55
1.33
1.13
1.03
0.92
0.72
0.54
0.49
0.42
0.38
0.31
0.23
0.18
0.16
0.15
0.08
0.07
0.05
0.04
0.03
0.02
59.0
1.45
1.65
1.55
0.95
(mg/g oil)
27.7%
weathered
0.21
1.81
3.81
4.94
5.19
5.29
4.75
4.13
2.76
3.11
1.84
2.61
2.27
2.11
1.81
1.58
1.44
1.28
1.08
0.78
0.70
0.62
0.54
0.46
0.34
0.27
0.24
0.20
0.12
0.10
0.08
0.07
0.05
0.04
56.7
1.50
1.68
1.49
1.02
89
-------
South Louisiana Fresh
51
4-
3-
2-
1 -
c
'• n
II | 1 ri
MM ;; 1 M 1 1 r, r.
1 I \ I I I \ 11 I 11 IlIiiiHElEln...
X3OCM-*CD ,
o
CM
O
CM
CM
O
CM
O
CD
CM
O
00
CM
O
O
CO
O
CM
CO
O
CO
O
CD
CO
O
00
CO
O
O
•*
O
Figure 9.1 w-Alkane Distribution for South Louisiana Crude Oil (mg/g oil)
90
-------
9.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
248.6
952.7
1500.1
1765.7
886.3
5353
134.4
569.8
654.6
427.4
251.8
2038
40.0
125.7
237.4
205.5
609
67.3
181.7
291.4
246.0
804
23.0
58.8
81.6
69.1
233
9037
1.63
1.00
1:0.62:0.31
94.32
8.15
17.90
2.47
3.70
8.64
5.19
2.10
0.37
4.07
0.49
30.37
0.50
0.86
1.23
180
27.7%
weathered
164.1
1058.9
1965.6
2403.6
1222.3
6815
188.3
777.8
887.1
574.6
349.6
2777
55.4
172.4
323.1
272.6
823
94.8
253.2
396.4
354.1
1098
30.4
80.1
108.4
90.7
310
11823
1.59
1.01
1:0.61:0.31
120.60
10.70
24.27
3.61
5.10
11.33
6.35
3.73
1.24
5.97
0.62
38.95
1.12
1.12
1.99
237
91
-------
South Louisiana
2500 n
2000 -
1500 -
1000 -
500 -
0 -
Fresh
n
150 1 Other EPA Priority PAH
" 1 n
< m S' CQ CQ
CQ
1 .111* mBn _Rii ...
to" -A co .c •>- co aJT-ooocNi-c-^-co
ZOOQ-OO.QOOOOOOO
Q
South Louisiana
/
3000 n
2500 -
2000 -
1500 -
1000 -
500 -
0 -
27.7% w
|
-J,
150 1 Other EPA Priority PAH
75J
0 III ^H_____ _ •
mSE
-------
9.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
16.9
11.2
59.9
81.5
31.0
27.5
20.1
13.6
12.2
8.8
6.1
4.4
19.0
23.1
65.0
72.8
473
27.7%
weathered
22.7
14.7
75.9
105.6
40.2
35.7
25.1
17.4
15.4
10.5
7.3
5.2
24.3
30.3
85.8
94.3
610
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
1.50
0.21
0.14
0.73
1.13
1.48
1.39
1.37
0.82
0.89
1.54
0.21
0.14
0.72
1.13
1.44
1.46
1.41
0.80
0.91
93
-------
10. Physical Properties and Chemical Composition of West Texas
Intermediate (2002)
10.1 Origin: Galveston, Texas, U.S.A. (Via Texas A & M)
Synonyms: None
Values are reported for the fresh oil and for artificially weathered fractions of 10.1%, 21.0% and
31.7% loss by weight.
10.2 API Gravity
34.38 (calc)
10.3 Equation for Predicting Evaporation
%Ev=(3.08 + 0.045 T)\nt
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
10.4 Sulphur Content
Weathering
(weight %)
0
10.1
21.0
31.7
Sulphur
(weight %)
0.86 (n=3)
1.01 (n=3)
1.11 (n=3)
1.24 (n=3)
10.5 Water Content
Weathering
(weight %)
0
10.1
21.0
31.7
Water
(volume%)
O.I (n=3)
O.I (n=3)
0.1 (n=3)
O.I (n=3)
94
-------
10.6 Flash Point
Weathering
(weight %)
0
10.1
21.0
31.7
Flash Point
<-10 (n=2)
32.8 (n=3)
66. 0 (n=3)
>110 (n=2)
10.7 Density
Weathering
(weight %)
0
10.1
21.0
31.7
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.8594
0.8474
0.8792
0.8665
0.8956
0.8827
0.9103
0.8973
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
10.8 Pour Point
Weathering
(weight %)
0
10.1
21.0
31.7
Pour Point
(°Q
-22
-12
1
7
(n=2)
(n=2)
(n=2)
(n=2)
95
-------
10.9 Dynamic Viscosity
Weathering
(weight %)
0
10.1
21.0
31.7
Temperature Viscosity
(°C) (cP)
0 19.2
15 8.6
0 42.1
15 16.4
0 253.6
15 37.5
0 853.6
15 112.3
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
10.10 Chemical Dispersibility
Weathering
(weight %)
0
10.1
21.0
31.7
Chemical Dispersibility
using Corexit 9500 ( %)
27.7
23.6
13.3
12.8
(n=6)
(n=6)
(n=6)
(n=6)
10.11 Adhesion
Weathering
(weight %)
0
10.1
21.0
31.7
Adhesion
(g/m2)
12.4
16.8
27.6
33.2
(n=3)
(n=4)
(n=4)
(n=3)
96
-------
10.12 Surface and Interfacial Tensions
10.12.1
Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
10.1
21.0
31.7
70.72.2 Oil/Brine
Weathering
(weight %)
0
10.1
21.0
31.7
Temperature
(°Q
0
15
0
15
0
15
0
15
(33%o) Interfacial
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
27.4
26.0
28.7
27.6
29.7
28.7
31.4
29.2
Tension
Surface Tension
(mN/m)
18.8
15.6
19.4
14.6
19.2
12.6
19.9
17.3
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
97
-------
10.12.3
Oil/Fresh Water Interfacial Tension
Weathering
(weight %)
0
10.1
21.0
31.7
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
19.3
15.8
19.9
18.1
21.0
17.2
22.7
17.1
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
10.13 Emulsion Formation
Weathering
(weight %)
0
10.1
21.0
31.7
Visual Stability Complex Modulus Emulsion
(Pa) Water Content (%)
Unstable
Unstable
Mesostable 19.1
Mesostable 81.9
82.7
83.6
98
-------
10.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 10.1% 21.0% 31.7%
weathered weathered weathered weathered
0.7
0.7
1.0
5.5
8.9
12.6
16.2
20.0
23.5
32.4
41.2
50.0
57.5
64.6
70.7
75.8
79.8
82.8
1.8
4.2
7.5
11.2
15.3
19.2
29.0
38.9
48.7
57.0
64.9
71.7
77.4
81.8
85.2
0.1
0.9
2.8
6.2
10.1
21.1
32.3
43.4
52.9
61.9
69.6
76.2
81.2
85.0
0.4
1.9
11.4
23.7
36.2
47.0
57.2
66.0
73.4
79.1
83.3
99
-------
10.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
78.5
14.8
6.0
0.7
2.8
10.1%
weathered
78.6
13.7
6.9
0.8
3.1
21.0%
weathered
76.3
14.6
8.0
1.1
3.4
31.7%
weathered
74.8
13.8
9.9
1.6
4.0
10.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 31.7%
weathered weathered
4026
7395
4845
7105
10190
23370
33560
0
13
0
1
310
14
324
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
100
-------
10.17 tt-Alkane Distribution
n-Alkane Component
w-C8
H-C9
H-C10
H-C11
H-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
w-C18
Phytane
w-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-CSO
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
H-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
7.08
6.80
7.59
7.84
6.72
6.57
5.93
5.53
5.02
4.76
1.99
3.39
1.85
3.38
2.78
2.51
2.35
1.92
1.73
1.52
1.33
1.07
1.02
0.88
0.71
0.57
0.45
0.34
0.31
0.28
0.14
0.10
0.08
0.06
0.04
0.02
94.7
2.40
1.83
1.07
0.95
(mg/g oil)
31.7%
weathered
0.43
3.31
6.21
8.20
8.10
7.94
7.19
6.77
2.79
4.76
2.56
4.74
3.87
3.56
3.37
2.78
2.52
2.28
1.93
1.57
1.54
1.33
1.04
0.86
0.67
0.52
0.51
0.45
0.22
0.16
0.13
0.10
0.08
0.05
92.5
2.43
1.86
1.09
1.05
101
-------
West Texas Intermediate Fresh
10
8
6 -\
4
2 ^
0
n n n
CO
o
O>
o
o
O
CM
O
CM
O
CM
O
o
CO
O
CO
CO
O
CD
CO
O
CT>
CO
O
West Texas Intermediate 31.7%w
10
8
6 -\
4
2 ^
0
111
Finn
CO
O
O)
O
O
O
CN
O
CN
O
CN
O
o
CO
O
CO
CO
O
CD
CO
O
CT>
CO
O
Figure 10.1 w-Alkane Distribution for West Texas Intermediate crude oil
(mg/g oil)
102
-------
10.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
292.6
951.6
1451.7
1546.3
929.5
5172
125.2
358.9
350.6
264.5
196.2
1295
139.0
207.1
268.4
201.2
826
48.9
108.6
160.7
140.2
458
13.5
22.5
32.7
31.4
100
7841
1.27
0.72
1:0.94:0.46
68.45
11.08
8.84
1.00
2.12
6.72
1.24
1.37
0.37
3.48
0.25
0.12
0.18
0.18
0.50
106
31.7%
weathered
212.8
1056.6
1517.0
2025.8
1257.2
6069
176.6
505.3
510.9
372.6
278.7
1844
194.6
293.1
377.6
279.8
1145
63.0
141.3
208.8
186.5
600
19.3
31.8
47.5
47.0
146
9804
1.22
0.71
1:0.95:0.46
82.79
14.09
11.47
1.87
3.12
10.22
1.50
1.75
0.37
5.24
0.33
0.20
0.25
0.25
0.69
135
103
-------
West Texas Intermediate 15° other EPA Priority PAH
2000 -
1500 -
1000 -
500 -
0 -
Fresh
1
T
75 - _
Q-0iE<2'D-^D-
CQ
I Eiliil ralil _raHnn
£ =r =r S - CO _c T- CO (D-^-COOCM-Ci-CO
ZOOQ.OO-QOOOOOOO
Q
West Texas Intermediate 150 -| other EPA Priority PAH
2000 -
1500 -
1000 -
500 -
o -
31.7%w
i ;;
75 "1
< m S^ m m
^ m
Jill Bill -eBB ___
•C Z Z CQ-CL NQQLLLL >-OO
ZOO^OO-QOOOOOoO
Q
Figure 10.2 PAH Distribution for West Texas Intermediate crude oil (|-lg/g
oil)
104
-------
10.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
42.5
23.7
53.5
74.7
33.2
31.2
26.5
17.9
14.9
9.8
9.2
5.8
16.5
21.8
63.3
79.0
524
31.7%
weathered
62.6
34.5
75.7
104.4
47.6
45.1
38.3
26.0
21.7
14.3
13.8
8.9
23.9
30.7
92.7
114.1
755
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
1.80
0.57
0.32
0.72
1.06
1.48
1.52
1.57
0.76
0.80
1.81
0.60
0.33
0.73
1.06
1.47
1.52
1.55
0.78
0.81
105
-------
11. Physical Properties and Chemical Composition of Fuel Oil No. 2/Diesel
(2002)
11.1 Origin: Local Retailer, Ontario, Canada (Stinsons' Gas)
Synonyms: "Summer" Diesel, Fuel Oil No. 2
Appearance: Golden-coloured, light, characteristic "fuel" odour.
Values are reported for the fresh oil and for artificially weathered fractions of7.2%, 14.2% and
22.0% loss by weight.
11.2 API Gravity
37.52 (calc)
11.3 Equation for Predicting Evaporation
%Ev =( 0.02 + 0.013 7) sqrt(f)
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
11.4 Sulphur Content
Weathering
(weight %)
0
7.2
14.2
22.0
Sulphur
(weight %)
0.09 (n=3)
0.10 (n=3)
0.10 (n=3)
0.10 (n=3)
11.5 Water Content
Weathering
(weight %)
0
7.2
14.2
22.0
Water
(volume %)
O.I (n=3)
O.I (n=3)
0.1 (n=3)
O.I fw=5j
106
-------
11.6 Flash Point
Weathering
(weight %)
0
7.2
14.2
22.0
Flash Point
(°C)
54
65
76
85
(n=2)
(n=2)
(n=2)
(n=2)
11.7 Density
Weathering
(weight %)
0
7.2
14.2
22.0
Temperature
(°Q
0
15
0
15
0
15
0
15
Density
(g/mL)
0.8423
0.8310
0.8468
0.8350
0.8493
0.8383
0.8524
0.8416
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
11.8 Pour Point
Weathering
(weight %)
0
7.2
14.2
22.0
Pour Point
(°Q
-50
-49
-43
-41
(n=2)
(n=2)
(n=2)
(n=2)
107
-------
11.9 Dynamic Viscosity
Weathering Temperature Viscosity
(weight %) (°C) (cP)
0 0 4.08
15 2.76
7.2 0 4.55
15 3.27
14.2 0 5.16
15 3.42
22.0 0 5.59
15 4.18
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=2)
(n=3)
(n=2)
11.10 Chemical Dispersibility
Weathering Chemical Dispersibility
(weight %) using Corexit 9500 ( %)
0 72
7.2 71
14.2 64
22.0 66
(n=6)
(n=6)
(n=6)
(n=6)
11.11 Adhesion
Weathering Adhesion
(weight %) (g/m2)
0 2
7.2 12
14.2 13
22.0 8
(n=4)
(n=4)
(n=3)
(n=4)
108
-------
11.12 Surface and Interfacial Tensions
11.12.1
Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
7.2
14.2
22.0
77.72.2 Oil/Brine
Weathering
(weight %)
0
7.2
14.2
22.0
Temperature
(°Q
0
15
0
15
0
15
0
15
(33%o) Interfacial
Temperature
(°Q
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
28.7
27.5
28.8
27.7
28.6
28.1
29.3
28.3
Tension
Surface Tension
(mN/m)
21.5
18.1
24.8
19.5
26.6
20.7
28.5
21.9
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=8)
(n=3)
(n=3)
(n=2)
(n=3)
(n=3)
(n=3)
109
-------
11.12.3
Oil/Fresh Water Interfacial Tension
Weathering
(weight %)
0
7.2
14.2
22.0
Temperature
(°C)
0
15
0
15
0
15
0
15
Surface Tension
(mN/m)
25.0
21.6
28.1
23.9
28.5
24.3
29.1
25.7
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=3)
(n=2)
11.13 Emulsion Formation
Weathering
(weight %)
0
7.2
14.2
22.0
Visual Stability
Unstable
Unstable
Unstable
Unstable
Complex Modulus Emulsion
(Pa) Water Content (%)
110
-------
11.14 Boiling Point Distribution
Boiling Point
(°Q
40
60
80
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
Cumulative Weight Fraction (%)
0% 7.2% 14.2% 22.0%
weathered weathered weathered weathered
0.2
0.5
1.2
2.8
7.8
16.4
26.8
57.4
84.1
96.4
97.9
98.1
98.2
98.3
98.4
98.6
0.1
0.1
0.1
0.7
4.0
11.8
22.4
55.4
84.5
98.1
99.7
99.9
0.1
1.4 0.3
7.1 3.2
17.0 11.2
51.7 46.7
83.3 81.4
98.1 97.8
99.8 99.7
111
-------
11.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
88.2
10.2
1.7
0.0
1.7
7.2%
weathered
86.1
11.9
2.0
0.0
1.8
14.2%
weathered
86.1
11.7
2.2
0.0
2.0
22.0%
weathered
85.6
11.4
3.0
0.0
1.8
11.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes}|
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 22.0%
weathered weathered
136
1024
619
3774
13780
5550
19330
0
0
0
7
2260
7
2267
fNote that the "Xylenes" include o-, m-, and/>-xylene isomers.
f f Note that the "C3-Benzenes" include eight isomers.
112
-------
11.17 tt-Alkane Distribution
n-Alkane Component
w-C8
H-C9
H-C10
H-C11
H-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
w-C18
Phytane
w-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-CSO
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
H-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
1.15
4.24
10.93
13.43
13.23
13.02
12.33
11.98
10.96
9.22
3.81
6.72
2.52
4.72
3.01
1.70
0.85
0.41
0.19
0.09
0.04
0.02
0.02
0.01
0.01
0.01
124.6
1.58
1.61
1.25
0.99
(mg/g oil)
22.0%
weathered
3.96
11.79
15.25
16.51
15.77
15.58
13.70
11.37
4.82
8.20
3.10
5.88
3.74
2.11
1.06
0.52
0.24
0.11
0.05
0.03
0.02
0.01
0.01
0.01
133.8
1.52
1.58
1.23
1.03
113
-------
Diesel (Fresh)
18
_. 15
I 12
1 9
d 6
0 o
0 3
0
i||
.lllll
1 n
:\:\n i
1 ^ l HllIlH..__
OOOOIM-CD (n mOCMM-CQOOOCMM-CQOOO
C3 1-1-1-1- r- f-oirMrMOirMcococococoM-
JLOOOOroroOOOOOOOOOOO
Ql CL
Diesel 22.0% w
18 -,
— 15 -
0
D) 12 -
D)
E 9 -
o 6-
S 3-
0 -
p.
J.
- ri
n Jn
^OOOOroroOOOOOOOOOOO
Q_ Q_
Figure 11.1 Alkane Distribution for Fuel Oil No. 2 (Diesel) (mg/g oil)
114
-------
11.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
820
3664
6927
6636
2805
20852
437
1000
617
185
53
2293
65
110
99
38
312
567
799
756
360
2481
0.02
0.03
0.04
0.00
0.09
25938
1.56
1.50
1 :0.35 :0.16
839.73
34.87
153.55
13.08
6.60
30.88
0.25
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1080
22.0%
weathered
677
3968
8101
8163
3427
24337
557
1262
769
237
65
2890
82
137
123
50
392
713
1025
961
458
3157
0.03
0.04
0.04
0.00
0.12
30776
1.53
1.52
1 :0.36 :0.17
1072.40
42.29
187.34
14.09
8.48
38.84
0.28
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1364
115
-------
Diesel Fresh
9000 -i
=- 7500 -
'o
5> 6000 -
O)
3 4500 -
o
o 3000 -
O
1500 -
_
_
n
1000 -, Other EPA Priority PAHs
800 - 1-1
600 -
400 -
20° - 1 1 n
Q.0r£<2~0-0-0-
m < (g g co m
n fl n . nfirin
cc T- co _c T- co ^T-COO^^T-CO
2OOQ-OO-QOOOOOOQ
Q
Diesel
22.0% w
9000 -
= 7500 -
D)
"3) 6000 -
a.
o 4500 -
c
0 3000 -
1500 -
"
•
n
1 50° -i Other EPA Priority PAHs
1000 - [-1
500 -
0 ' '
m < en ^n m m*
CQ
nfln» n n n •
-nZZ CQ.Q. NQQU-LL >>OO
Q. i i 0 i iCii ' ' ^ i i
oj •<- co _c T- co
-------
11.19 Biomarker Concentrations
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
Concentration (ug/g oil)
0% 22.0%
weathered weathered
4.0
1.4
5.3
1.8
3.0
2.9
Note: except for the C23 and C24 terpanes,
no other biomarkers were detected.
117
-------
12. Physical Properties and Chemical Composition of Fuel Oil No. 5 (2000)
12.1 Origin: New Jersey, U.S.A, (Via U.S. Dept. Int., M.M.S., OHMSETT, NJ, 2000)
Synonyms: Bunker B
Appearance: Black, heavy, sticky, little odour.
Values are reported for the fresh oil and for an artificially weathered fraction of 7.2% loss by
weight.
12.2 API Gravity
11.55 (calc)
12.3 Equation for Predicting Evaporation
%Ev = (-0.14+ 0.013 T)tm
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
12.4 Sulphur Content
Weathering
(weight %)
0
7.2
Sulphur
(weight %)
1.00 (n=3)
1.08 (n=3)
12.5 Water Content
Weathering
(weight %)
0
7.2
Water
(volume%)
3.1 (n=3)
<0.1 (n=3)
118
-------
12.6 Flash Point
Weathering
(weight %)
0
7.2
Flash Point
(°C)
94
136
(n=3)
(n=3)
12.7 Density
Weathering
(weight %)
0
7.2
Temperature
(°C)
0
15
0
15
Density
(g/mL)
1.0034
0.9883
1.0160
1.0032
(n=3)
(n=3)
(n=3)
(n=3)
12.8 Pour Point
Weathering
(weight %)
0
7.2
Pour Point
(°C)
-19
-3
(n=2)
(n=2)
119
-------
12.9 Dynamic Viscosity
Weathering
(weight %)
0
7.2
Temperature
(°C)
0
15
0
15
Viscosity
(cP)
18600
1410
72000
4530
(n=3)
(n=3)
(n=3)
(n=3)
12.10 Chemical Dispersibility
Weathering
(weight %)
0
7.2
Chemical Dispersibility
using Corexit 9500 ( %)
15
7
(n=6)
(n=6)
12.11 Adhesion
Weathering
(weight %)
0
7.2
Adhesion
(g/m2)
34
47
(n=4)
(n=4)
120
-------
12.12 Surface and Interfacial Tensions
12.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering Temperature Surface Tension
(weight %) (°C) (mN/m)
0 0 NM
15 NM
7.2 0 NM
15 NM
12.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
7.2
Temperature
(°C)
0
15
0
15
Surface Tension
(mN/m)
NM
NM
NM
NM
f NM: not measurable
12.12.3 Oil/Fresh Water Interfacial Tension
Weathering Temperature Surface Tension
(weight %) (°C) (mN/m)
0 0 NM
15 NM
7.2 0 NM
15 NM
121
-------
12.13 Emulsion Formation
Weathering
(weight %)
0
7.2
Visual Stability
Stable
Stable
Complex Modulus
(Pa)
1590
2490
Emulsion
Water Content (%)
78.3
72.8
12.14 Boiling Point Distribution
Cumulative Weight Fraction (%)
Boiling Point 0% 7.2%
(°C) weathered weathered
40
60
on
oU
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
0.1
0.2
0.6
1.3
2.3
7.2
14.6
24.4
39.9
55.8
66.2
74.0
80.4
85.6
0.2
3.8
11.3
21.7
38.0
55.0
66.2
74.5
81.5
86.9
122
-------
12.15 Hydrocarbon Groups
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
Concentration
(weight %)
0% 7
.2%
weathered weathered
44.2
39.5
8.0
8.4
2.3
39.9
39.1
8.3
12.8
2.5
12.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 7.2%
weathered weathered
0 0
149 0
124 1
612 2
1750 30
890 0
2640 30
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
123
-------
12.17 tt-Alkane Distribution
n-Alkane Component
w-C8
H-C9
H-C10
H-C11
H-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
w-C18
Phytane
w-C19
w-C20
w-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-CSO
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
H-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
0.34
0.54
0.74
1.01
1.35
1.71
1.89
2 22
2.03
1.11
1.79
0.76
1.70
1.55
1.70
1.85
2.25
2.46
2.47
2.08
1.77
1.34
1.01
0.58
0.37
0.21
0.14
0.11
0.07
0.06
0.04
0.02
0.01
37.3
1.83
2.35
1.45
1.02
(mg/g oil)
7.2%
weathered
0.1
0.49
1.08
1.60
2.11
2.53
2.38
1.27
2.10
0.88
1.90
1.90
2.00
2.23
2.73
2.98
3.03
2.55
2.20
1.66
1.26
0.70
0.48
0.26
0.17
0.12
0.09
0.07
0.06
0.03
0.02
0.02
41
1.87
2.39
1.45
1.02
124
-------
3.0 -I
I 2.0-
0)
y 1.0-
o
0 0.5-
0.0-
-f
00 O OM
"99
Fuel #5 Fresh
:
1 n
I 1
J
\ n
iln
1 1 1 1 N n n PI PI ™
•^-(D CD (DOOM-^-tDOOOOM-^-tDOOO
OOjSjSOOOOOOOOOOO
cL o.
3.5 -,
=- 3.0 -
I 2.5-
|> 2.0 -
~ 1-5-
o 1.0 -
° 0.5-
0.0 -
nl
00 O CM
£=99
Fuel #5 7.25% w
ill
n
Illi
1 H
M M F
II ___
?££!8SS888SS88S
OOro^OOOOOOOOOOO
ol £
Figure 12.1 w-Alkane Distribution for Fuel Oil No. 5 (mg/g oil)
125
-------
12.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
236
2048
4790
5001
2385
14460
848
4274
6974
6610
4074
22779
92
295
610
582
1579
357
1021
1809
1799
4986
920
2808
4676
3482
11887
55692
1.88
1.63
1 : 1.00 :0.27
132.98
33.69
167.50
217.67
80.43
552.67
551.51
125.74
34.08
221.23
449.35
159.07
25.15
68.56
83.87
2863
7.2%
weathered
128
1722
4708
5288
2736
14582
895
4533
7362
6971
4369
24130
99
315
661
638
1713
370
1075
1936
1888
5269
965
3195
4923
3598
12681
58375
1.81
1.59
1 : 0.99 : 0.26
123.02
34.29
168.82
224.82
84.89
563.19
530.94
132.61
39.74
224.46
459.47
180.00
27.70
74.10
87.05
2975
126
-------
Fuel #5 Fresh
8000 -,
s* ynnn
~ / uuu ~
0
o) 6000 -
2 5000 -
o 4000 -
o 3000 -
2000 -
1000 -
n
\j
1000-1 Other EPA Priority PAHs
500 1_ . • F1P1- n Fl ,-,
Q. m [T < -O- CL CL
CQ O ro ^ ro
CO
Jl
II I
T
n ^
1;;
I
^^^z^°rV99^5. £-9
|"oo£ooEoo""oo
Q
CL
D)
CQ
O
O
Fuel #5
7.25% w
8000 -,
= 7000 -
o
D) 6000 -
2 5000 -
o 4000 -
0 3000 -
2000 -
1000 -
o
. 1
.d z z
s- - "
^ o o
1000
500
0
-i Other EPA Priority PA Hs
CO o m ^ ra
< CD g CD
1
1 |
1=1 Fj
_-•• .ill 1
CL CL
;
dtLCL NQQLJ-LJ- >0
foo^oooooo
Q
D)
CD
O
oS
o
Figure 12.2 PAH Distribution for Fuel Oil No. 5 (|ig/g oil)
127
-------
12.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
49.7
20.1
71.0
67.6
17.6
16.9
11.5
10.2
7.0
4.4
4.0
2.3
21.7
16.2
17.2
18.0
355
7.2%
weathered
53.6
22.7
74.8
71.8
19.4
19.2
12.6
11.4
7.3
4.7
4.7
2.7
22.6
16.3
18.6
19.2
381
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
2.47
0.74
0.30
1.05
1.04
1.12
1.58
1.78
1.34
0.96
2.36
0.75
0.32
1.04
1.01
1.11
1.55
1.76
1.39
0.97
128
-------
13. Physical Properties and Chemical Composition of Heavy Fuel Oil 6303
(2002)
13.1 Origin: Imperial Oil Ltd., Nova Scotia, Canada (2002)
Synonyms: Bunker C, Land Bunker
Appearance: Black, heavy, sticky, little odour.
Values are reported for the fresh oil and for an artificially weathered fraction of 2.5% loss by
weight.
13.2 API Gravity
11.47 (calc)
13.3 Equation for Predicting Evaporation
%Ev = (-0.16+ 0.013 T)tm
Where: %Ev = weight percent evaporated; T= surface temperature (°C); / = time (minutes)
13.4 Sulphur Content
Weathering
(weight %)
0
2.5
Sulphur
(weight %)
1.48 (n=3)
1.50 (n=3)
13.5 Water Content
Weathering
(weight %)
0
2.5
Water
(volume%)
0.1 (n=3)
<0.1 (n=3)
129
-------
13.6 Flash Point
Weathering
(weight %)
0
2.5
Flash Point
(°Q
111
133
(n=3)
(n=3)
13.7 Density
Weathering
(weight %)
0
2.5
Temperature
(°Q
0
15
0
15
Density
(g/mL)
1.0015
0.9888
1.0101
0.9988
(n=3)
(n=3)
(n=3)
(n=3)
13.8 Pour Point
Weathering
(weight %)
0
2.5
Pour Point
(°C)
-1
11
(n=2)
(n=2)
130
-------
13.9 Dynamic Viscosity
Weathering
(weight %)
0
2.5
Temperature
(°Q
0
15
0
15
Viscosity
(cP)
241000
22800
3600000
149000
(n=3)
(n=3)
(n=3)
(n=3)
13.10 Chemical Dispersibility
Weathering
(weight %)
0
2.5
Chemical Dispersibility
using Corexit 9500 ( %)
9
6
(n=6)
(n=6)
13.11 Adhesion
Weathering
(weight %)
0
2.5
Adhesion
(g/m2)
100
240
(n=4)
(n=4)
131
-------
13.12 Surface and Interfacial Tensions
13.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering Temperature Surface Tension
(weight %) (°C) (mN/m)
0 0 NM
15 NM
2.5 0 NM
15 NM
13.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering
(weight %)
0
2.5
Temperature
(°C)
0
15
0
15
Surface Tension
(mN/m)
NM
NM
NM
NM
f NM: not measurable
13.12.3 Oil/Fresh Water Interfacial Tension
Weathering Temperature Surface Tension
(weight %) CQ (mN/m)
0 0 NM
15 NM
2.5 0 NM
15 NM
132
-------
13.13 Emulsion Formation
Weathering
(weight %)
Visual Stability
Complex Modulus
(Pa)
Emulsion
Water Content (%)
0
2.5
Entrained
Entrained
752
984
57.7
24.1
13.14 Boiling Point Distribution
Cumulative Weight Fraction (%)
Boiling Point 0% 2.5%
(°C) weathered weathered
40
60
100
120
140
160
180
200
250
300
350
400
450
500
550
600
650
0.1
0.2
0.3
0.6
1.2
5.5
12.5
23.3
33.5
38.8
41.2
45.3
55.7
70.1
0.2
3.5
10.2
21.2
31.5
37.0
39.7
44.1
54.8
69.6
133
-------
13.15 Hydrocarbon Groups
Concentration
(weight %)
Component
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
0%
weathered
42.5
29.0
15.5
13.0
2.5
2.5%
weathered
38.8
26.9
16.6
17.7
2.7
13.16 Volatile Organic Compounds
Component
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes}
Total BTEX
Total BTEX and C3-
Benzenes}
Concentration
(ug/g oil)
0% 2.5%
weathered weathered
40 0
136 0
58 0
396 0
940 50
630 0
1570 50
f'Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
134
-------
13.17 tt-Alkane Distribution
n-Alkane Component
w-C8
w-C9
w-CIO
w-Cll
w-C12
w-C13
w-C14
w-C15
w-C16
w-CIV
Pristane
w-C18
Phytane
H-C19
w-C20
H-C21
w-C22
w-C23
w-C24
w-C25
w-C26
w-C27
w-C28
w-C29
w-C30
w-C31
w-C32
w-C33
w-C34
w-C35
w-C36
w-C37
w-C38
w-C39
w-C40
w-C41
TOTAL
C17/PRISTANE
C18/PHYTANE
PRISTANE/PHYTANE
CPI
Concentration
0%
weathered
0.09
0.19
0.41
0.68
0.99
1.21
1.43
1.78
2.00
2.20
2.17
1.85
2.26
2.14
1.85
1.49
1.36
1.23
1.00
0.67
0.44
0.31
0.20
0.11
0.07
0.04
0.02
0.02
28.2
0.91
1.17
1.19
1.00
(mg/g oil)
2.5%
weathered
0.10
0.42
0.71
1.23
1.59
2.07
2.33
2.55
2.62
2.24
2.66
2.48
2.18
1.78
1.63
1.51
1.23
0.84
0.57
0.38
0.25
0.13
0.09
0.04
0.02
0.02
31.7
0.91
1.17
1.14
0.99
135
-------
HFO-6303 Fresh
2.50 -,
° 2.00 -
O)
^ 1.50-
g 1.00-
o
0 0.50 -
0.00 -
1 ^ i
PI M M i
n i 1 MM MM !
-•lili Miiii
i|
::::::__
I MM Hi
MM 1 I \ |!J 1 1 § • _ _
X1O(N^-(D
-------
13.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
0%
weathered
140
1250
2861
2886
1422
8558
422
1870
2910
3107
2211
10520
108
315
620
701
1744
224
565
978
936
2703
376
1173
1806
1379
4733
28258
1.86
1.39
1 : 1.01 :0.37
69.22
19.74
92.54
95.99
41.09
226.28
198.27
53.42
11.84
93.03
151.14
48.37
9.50
21.84
28.62
1161
2.5%
weathered
89
1091
2806
2956
1509
8450
458
2029
3171
3376
2459
11492
115
335
665
766
1881
233
600
1015
963
2811
415
1274
1961
1397
5047
29682
1.83
1.4
1 : 1.03 : 0.37
66.79
19.87
93.24
99.34
44.52
247.88
210.88
57.21
13.29
99.94
164.81
57.33
10.10
24.30
29 92
1239
137
-------
HFO-6303
Fresh
_ 6000 -,
o 5000 -
D)
en 4000 -
^ 3000 -
o 2000 -
O
1000 -
o
IBl M
€. z
2 0
1 .[
30
20
10
I
1 0 1
co .c T;
O Q. O
D -
D -
D -
Other EPA Priority PAHs
n „ PI HI „ 1 1 n _ HI 1 •=• _.
Q-(iirr<-O-CLCLCL
m o ra & ra — en
< co -° co m
on
=
I 1 _ H a 1 -ail D 1 1 1
Q- NQQU-LL £-OO
oS S^oSooj-c^oS
O-QOOC-)C-)CJOO
b
HFO-6303
2.5% w
6000 -,
D)
o> 4000 -
o 3000 -
c
0 2000 -
1000 -
0 -
.1
.c Z
1 5
^
<*
c
soo , Other EPA Priority PAHs
150 -
0
• _ 1 i n III 1 P1_llpl___
CO O oj — 01 D)
< rn -Q CQ CO
CO
i m I
II Jl
i pi
II J 1 1
; CCLCLNQQLJ-LJ- £• O O
5
Figure 13.2 PAH Distribution for HFO 6303 (Bunker C) (|lg/g oil)
138
-------
13.19 Biomarker Concentrations
Concentration (ug/g oil)
Biomarker
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
0%
weathered
92.3
45.9
14.4
11.5
3.7
3.3
3.2
2.0
1.5
1.2
1.1
0.9
5.7
1.6
10.7
5.5
204
2.5%
weathered
106.4
51.8
15.1
12.7
4.0
3.7
3.6
2.3
1.6
1.3
1.2
1.0
6.5
1.9
12.6
6.2
232
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
2.01
8.01
3.99
1.25
1.11
1.58
1.21
1.28
3.69
1.94
2.10
8.40
4.10
1.20
1.10
1.60
1.23
1.27
3.39
2.04
139
-------
14. Physical Properties and Chemical Composition of Orimulsion-400 (2001)
14.1 Origin: Bitor America Corporation, Venezuela (2001)
Synonyms: None
Appearance: Black, easily-poured, very sticky, no odour.
Values are reported for the fresh product only. Note that some of the composition results are
reported both as bitumen only, /'. e. dried product, and as Orimulsion-400, as calculated using the
measured water mass fraction of section 15.5 below.
14.2 API Gravity
8.63 (calc)
14.3 Equation for Predicting Evaporation
Not Measured
14.4 Sulphur Content
Weathering Sulphur
(weight %) (weight %)
0 2.00* (n=3)
*Note: Including water. Dried bitumen is 2.8%.
14.5 Water Content
Weathering Water
(weight %) (volume%)
0 28 (n=5)
140
-------
14.6 Flash Point
Weathering
(weight %)
Flash Point
0
>320*
(n=2)
*Note: After water had completely boiled-off sample was cooled and re-tested. The
residual bitumen flashed between 130 and 140°C.
14.7 Density
Weathering
(weight %)
Temperature
Density
(g/mL)
0
0
15
1.0155
1.0093
(n=3)
(n=3)
14.8 Pour Point
Weathering
(weight %)
0
14.9 Dynamic Viscosity
Pour Point
Weathering
(weight %)
0
Temperature
(°C)
0
15
Viscosity
(cP)
330
256
(n=3)
(n=3)
141
-------
14.10 Chemical Dispersibility
Weathering Chemical Dispersibility
(weight %) using Corexit 9500 ( %)
0 100* (n=6)
*Note: Orimulsion-400 is an oil-in-water dispersion.
14.11 Adhesion
Weathering
(weight %)
0
Adhesion
(g/m2)
90
(n=6)
14.12 Surface and Interfacial Tensions
14.12.1 Surface Tension (Oil/Air Interfacial Tension)
Weathering
(weight %)
0
Temperature
(°C)
0
15
Surface Tension
(mN/m)
NM
36.3
(n=3)
14.12.2 Oil/Brine (33%o) Interfacial Tension
Weathering Temperature Surface Tension
(weight %) (°C) (mN/m)
0 0 NM
15 NM
|NM: not measurable
142
-------
14.12.3
Oil/Fresh Water Interfacial Tension
Weathering
(weight %)
0
Temperature
0
15
Surface Tension
(mN/m)
NM
NM
14.13 Emulsion Formation
Weathering Visual Stability Complex Modulus Emulsion
(weight %) (Pa) Water Content (%)
0
Unstable*
*Note: Dispersion in water; bitumen settled-out on vessel walls.
14.14 Boiling Point Distribution
The boiling point distribution of Orimulsion was not measured.
14.15 Hydrocarbon Groups
Component
Concentration
(weight %)
Orimulsion-400 Orimulsion-400
(after water content
correction)
Saturates
Aromatic s
Resins
Asphaltenes
Waxes
32.1
19.7
9.6
10.6
NM
44.6
27.3
13.3
14.8
NM
143
-------
14.16 Volatile Organic Compounds
Concentration
(ug/g oil)
Orimulsion-400
Component
Orimulsion-400*
(after water
content correction)
Benzene
Toluene
Ethylbenzene
Xylenesf
C3-Benzenes{
Total BTEX
Total BTEX and C3-
Benzenes}
16
29
22
29
80
100
180
22
41
31
40
120
130
250
f "Xylenes" include o-, m-, and/>-xylene isomers.
}"C3-Benzenes" include eight isomers.
*Data for Bitumen were obtained by correction for the
water content (28%) from the data for the original Orimulsion-400.
14.17 tt-Alkane Distribution
No w-Alkanes were detected.
144
-------
14.18 PAH Distribution
Concentration (ug/g oil)
Alkylated PAH
Naphthalene
CO-N
Cl-N
C2-N
C3-N
C4-N
Sum
Phenanthrene
CO-P
Cl-P
C2-P
C3-P
C4-P
Sum
Dibenzothiophene
CO-D
Cl-D
C2-D
C3-D
Sum
Fluorene
CO-F
Cl-F
C2-F
C3-F
Sum
Chrysene
co-c
Cl-C
C2-C
C3-C
Sum
TOTAL
2-m-N/l-m-N
(3+2-m/phen)/(4-/9-+lm-phen)
4-m:2/3m:l-m-DBT
Other PAHs
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1 ,2,3cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
TOTAL
Orimulsion-400
5
31
90
143
212
482
28
86
231
286
183
814
10
39
140
264
454
12
41
145
212
410
10
24
45
52
131
2291
1.51
1.02
1 :0.83 : 1.20
2.38
0.71
6.90
2.97
1.78
4.40
2.14
1.31
0.12
2.14
2.50
6.07
0.00
0.24
1.55
35
Orimulsion-400*
8
43
125
199
295
670
39
119
320
397
255
1131
14
55
194
367
630
16
57
202
294
569
14
33
63
72
182
3182
1.51
1.02
1 :0.83 : 1.20
3.30
0.99
9.58
4.13
2.48
6.11
2.97
1.82
0.17
2.97
3.47
8.43
0.00
0.33
2.15
49
'Data for Bitumen were obtained by correction for the
water content (28%) from the data for the original Orimulsion-400.
145
-------
Orim
(befor
content c
800 -,
'o
0) 600 -
3.
d 400 -
o
0 200 -
n
ulsion
e water
orrection)
.ill
-§. z z
. 1
15 -,
8 -
Other EPA Priority PAHs
• _lHHin« H Q 1 r-,
CQ
1
1 ..il _.ll __..
C Q. Q. N Q Q LJ_ LL. &1 O O
Q
Orim
(after
content c
800 -
'o
o) 600 -
O)
_=.
o 400 -
o
0 200 -
0 -
ulsion
•water
orrection)
.-ill
- * A
Z 0 8
.!
15 -,
8 -
Other EPA Riority PAHs
H_lsr,lin. nnt
CD o ra ^- 03 ^
< m ^2 m m
I I
II .il .il ...
CCLCL NQQLLLL £^OO
QJ ' i C i i ' ' (— i i
foO-QOOOO^QQ
Q
Figure 14.1 PAH Distribution for Orimulsion-400 (|ig/g oil)
146
-------
14.19 Biomarker Concentrations
Biomarker
Concentration (ug/g oil)
Orimulsion-400 Orimulsion-400*
(after water
content
correction)
C23
C24
C29
C30
C31(S)
C31(R)
C32(S)
C32(R)
C33(S)
C33(R)
C34(S)
C34(R)
Ts
Tm
C27app steranes
C29app steranes
TOTAL
97.9
45.4
85.9
87.1
48.5
34.4
30.8
19.3
19.3
11.4
11.9
7.4
11.7
45.3
79.9
82
718
135.9
63.0
119.3
121.0
67.4
47.8
42.8
26.8
26.8
15.9
16.6
10.3
16.3
62.9
111.0
113.8
998
Diagnostic Ratios
C23/C24
C23/C30
C24/C30
C29/C30
C31(S)/C31(R)
C32(S)/C32(R)
C33(S)/C33(R)
C34(S)/C34(R)
Ts/Tm
C27app/C29app
2.16
1.12
0.52
0.99
1.41
1.60
1.69
1.61
0.26
0.98
'Data for Bitumen were obtained by correction for the water
content (28%) from the data for the original Orimulsion-400.
147
-------
15. Trace Metals
^
*>>
igr
Ba
Be 0.015
Bi 0.7
Ca 10.6
Cu 0.3 0.2
Fe 2.9 9.6
Li 1.03 0.05
Mg
Mn
Mo
Na 78
Ni 1.24 0.4
Sr
Ti
V 0.1 7.5
Zn
0.05
0.5
20.9 75.3
1.0
2.7 0.5
0.4
31 58
0.5 1.9
0.12
0.1
4.0 9.7
1.2 1.0
0.51
0.7
37.4
0.1
2.0
1.5
139
1.2
0.27
3.3
4.2
18.6
6.7
39.6
0.08
1.9
0.5
88
0.8
0.14
2.1
0.5
0.05 0.10
15.0 34.4 145.0 60.3
0.3 0.3
0.2 1.4 1.2 2.6
93 97 94 73
1.0 0.3 1.0
0.10 0.17
0.2
4.7 2.3 10.1
3.4 3.2 0.4
All metal content results reported as g/L oil.
Not detected in any samples: Ag, Al, As, Co, Cr, K, Pb, Y
148
-------
16. References
API 82 AmericanPetroleum Institute (API), Petroleum Measurement Tables - Volume XI/XII,
Philadelphia, PA, American Petroleum Institute, Washington DC, 1982.
API 92 American Petroleum Institute (APT),API Methods for Determination of Petroleum
Hydrocarbons in Soil (Revision 1), American Petroleum Institute, Washington DC, 1992.
ASTM D5 American Society for Testing and Mterials (ASTM), "Standard test method for
penetration of bituminous materials", in Annual Books of ASTM Standards Section 4 -
Construction, Volume 04.03, ASTM, West Conshohocken, PA, 1999.
ASTM D56 American Society for Testing and Materials (ASTM), "Standard test method for flash
point by Tag closed tester", in Annual Books of ASTM Standards Section 5 - Petroleum
Products, Lubricants and Fossil Fuels, Volume 05.01, ASTM, West Conshohocken, PA,
1999.
ASTM D93 American Society for Testing and Materials (ASTM), "Standard test method for flash
point by Pensky-Martens closed cup tester", in Annual Books of ASTM Standards
Section 5 - Petroleum Products, Lubricants and Fossil Fuels, Volume 05.01, ASTM,
West Conshohocken, PA, 1999.
ASTM D97 American Society for Testing and Materials (ASTM), "Standard test method for pour
point of petroleum oils", in Annual Books of ASTM Standards Section 5 - Petroleum
Products, Lubricants and Fossil Fuels, Volume 05.01, ASTM, West Conshohocken, PA,
1999.
ASTM D971 American Society for Testing and Materials (ASTM), "Standard test method for interfacial
tension of oil against water by the ring method", in Annual Books of ASTM Standards
Section 10 - Electrical Insulation and Electronics, Volume 10.03, ASTM, West
Conshohocken, PA, 1999.
ASTMD2887 American Society for Testing and Materials (ASTM), "Standard testmethod for boiling
range distribution of petroleum fractions by gas chromatography", in Annual Books of
ASTM Standards Section 5 - Petroleum Products, Lubricants and Fossil Fuels, Volume
05.02, ASTM, West Conshohocken, PA, 1999.
ASTM D3 710 American Society for Testing and Materials (ASTM)," Standard test method for boiling
range distribution of gasoline and gasoline fractions by gas chromatography", in Annual
Books of ASTM Standards Section 5 - Petroleum Products, Lubricants and Fossil Fuels,
Volume 05.02, ASTM, West Conshohocken, PA, 1999.
149
-------
ASTM D43 77 American Society for Testing and Materials (ASTM), "Standard test method for water in
crude oils by potentiometric Karl Fischer titrati on", in Annual Books of ASTM Standards
Section 5 - Petroleum Products, Lubricants and Fossil Fuels, Volume 05.02, ASTM,
West Conshohocken, PA, 1999.
ASTMD4294 American Society for Testing and Materials (ASTM), "Standard test method for sulfur in
petroleum products by energy-dispersive x-ray fluorescence spectroscopy", in Annual
Books of ASTM Standards Section 5 - Petroleum Products, Lubricants and Fossil Fuels,
Volume 05.02, ASTM, West Conshohocken, PA, 1999.
ASTM D5002 American Society for Testing and Materials (ASTM)," Standard test method for density
and relative density of crude oils by digital density analyzer", in Annual Books of ASTM
Standards Section 5 - Petroleum Products, Lubricants and Fossil Fuels, Volume 05.03,
ASTM, West Conshohocken, PA, 1999.
ASTMF2059 American Society for Testing and Materials (ASTM), "Standard test method for
Laboratory Oil Spill Dispersant Effectiveness Using The Swirling Flask", in Annual Books
of ASTM Standards Section 11 -Water and Environmental Technology, Volume 11.04,
ASTM, West Conshohocken, PA, 2001.
EPA92 U.S. EPAMethod3500A, Organic Extraction and Sample Preparation (Revision 1),
U. S. Environmental Protection Agency, Washington, DC, 1992.
EPA 94 U.S.EPA Method 363OB, Silica Gel Cleanup (Revision 2),U. S. Environmental
Protection Agency, Washington, DC, 1994.
EPA 84 U.S. EPA Method 61Q,Polynuclear Aromatic Hydrocarbons., U. S. Environmental
Protection Agency, Washington, DC, 1984.
EPA 92 U.S. EPA MethodSOOOA, Gas Chromatography (Revision 1), U. S. Environmental
Protection Agency, Washington, DC, 1992.
EPA86 U.S. EPA Methods 100 A, Polynuclear Aromatic Hydrocarbons., U. S. Environmental
Protection Agency, Washington, DC, 1986.
EPA 94 U.S. EPA Method 8260A, Volatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS): Capillary Column Technique
(Revision 1), U. S. Environmental Protection Agency, Washington, DC, 1994.
EPA 94 U.S. EPA Method 8270B, Semivolatile Organic Compounds by Gas
Chromatography'/Mass Spectrometry (GC/MS): Capillary Column Technique
(Revision 1), U. S. Environmental Protection Agency, Washington, DC, 1994.
150
-------
EPA 99 EPA Guidance for Quality Assurance Project Plans, EPA QA/G-5, U. S. EPA,
Washington, DC, 1998.
ETC 01 Quality Manual, Environmental Technology Centre, Environment Canada, Ottawa,
Ontario, 2001.
ETC 02 Wang, Z. AnalyticalMethods for Determination of Oil Components, ETC Method
No.: 5.3/1.3/M, 2002. Environmental Technology Centre, Environment Canada, Ottawa,
Ontario.
ETC 03 Wang, Z., Analytical Methods for Identification and Determination ofBTEXand
Other Alkyl Benzene Compounds, ETC Method No.: 5.3/1.2/M, 2002. Environmental
Technology Centre, Environment Canada, Ottawa, Ontario.
ETC 04 Environmental Technology Centre (ETC) web site: http://www.etc-
cte.ec.gc.ca/databases/spills_e.html. 2003.
Fingas97 Fingas, M.," Studies on the Evaporation of Crude Oil and Petroleum Products: I. The
Relationship Between Evaporation Rate and Time", J. Haz. Mat., 56, pp. 227-23 6,1997.
Fingas 98a Fingas,M., "Studies on the Evaporation of Crude Oil and Petroleum Products: II.
"Boundary Layer Regulation", J. Haz. Mat., 57, pp. 41-58, 1998.
Fingas 98b Fingas, M., B. Fieldhouse, and J. Mullin, "Studies of water-in-oil emulsions: stabilityand
oil properties", in Proceedings of the 21 st Arctic and Marine Oil Spill Program Technical
Seminar, Environment Canada, Ottawa, On, 1998, pp. 1-25.
Fingas 01 Fingas, M.,"TheEvaporati on of Oil Spills: Development and Implementation of New
PredictionMethodology", Chapter 5 mOilSpillModellingandProcesses, C.A. Brebbia,
ed., Wit Press, Southampton, U.K., pp. 111-138, 2001
Jokuty 95 Jokuty, P., M. Pings, S. Whiticar, and B. Fieldhouse, A study of viscosity and
interfacial tension of oils and emulsions, Manuscript Report EE-153, Environment
Canada, Ottawa, ON, 50 p, 1995.
Jokuty 96 Jokuty, P.,S. Whiticar, K. McRoberts, and J. Mullin, "Oil adhesion testing - recent
results", in Proceedings of the 19th Arctic and Marine Oil Spill Program Technical
Seminar, Environment Canada, Ottawa, ON, 1996, pp. 9-27.
Jokuty 99 Jokuty, P., S. Whiticar, Z. Wang, M. Fingas, B. Fieldhouse, P. Lambert and J. Mullin,
Properties of Crude Oils and Oil Products, Manuscript Report EE-165, Environmental
Protection Service, Environment Canada, Ottawa, ON, 1999.
151
-------
Peters 93 Peters, K. E., J. W. Moldowan, TheBiomarker Guide: InterpretingMolecular Fossils
in Petroleum and Ancient Sediments, Prentice Hall, Englewood Cliffs, NJ, 1993.
Speight 91 Speight, J.G., The Chemistry and Technology of Petroleum, New York, NY, Marcel
Dekker, Inc., 1991.
Wang 94 Wang, Z., M. Fingas, and K. Li, "Fractionation of ASMB Oil, Identification and
Quantitation of Aliphatic Aromatic and Biomarker Compounds by GC/FID and GC/MSD
(Part 1)", J. Chromatogr. Sci., 2, pp. 361-366, 1994.
Wang 94 Wang, Z., M. Fingas, and K. Li, "Fractionation of ASMB Oil, Identification and
Quantitation of Aliphatic Aromatic and Biomarker Compounds by GC/FID and GC/MSD
(Part 2)", J. Chromatogr. Sci., 2, pp. 367-382, 1994.
Wang 94 Wang, Z., M. Fingas, and G. Sergy, "Study of 22-year-old Arrow Oil Samples Using
Biomarker Compounds by GC/MS", Environ. Sci. Technol., 28, pp. 173 3 -1746,1994.
Wang 95 Wang, Z., M. Fingas, M. Landriault, L. Sigouin, and N. Xu, "Identification of
Alkylbenzenes and Direct Determination of BTEX and (BTEX+C3-Benzenes) in Oil by
GC/MS", Anal. Chem., 67, pp. 3491-3500, 1995.
Wang 96 Wang, Z., M. Fingas, "Separation and Characterization of Petroleum Hydrocarbons and
Surfactant in Orimulsion Dispersion Samples", Environ. Sci. Technol., 30(11), pp. 3351-
3361, 1996.
Wang 98 Wang, Z., M. Fingas, "Characterization of Alkylated Benzene Compounds and Direct
Quantitation of BTEX and (BTEX + C3-Benzenes) in Oils Using GC/MS", in The
Encyclopaedia of Environmental Analysis and Remediation (Eight Volumes), Robert.
A. Meyers (Editor-in-Chief), John Wiley & Sons, Inc., New York, NY, 1998; Vol. 2, pp
829-852.
Wang 99 Wang,Z., M. Fingas, Y.Y. Shu, L. Sigouin,M. Landriault, andP. Lambert, "Quantitative
Characterization of PAHs in Burn Residue and Soot Samples and Differentiation of
Pyrogenic PAHs from Petrogenic PAHs - the 1994 Mobile Burn Study", Environ. Sci.
Technol., 33,3100-3109.
Wang 99 Wang, Z. M. Fingas, and D. Page, "Oil Spill Identification", J. Chromatogr., 843, pp.
369-411, 1999.
Wang 00 Wang Z., M. Fingas, "Differentiation of PAHs in Burn Residue and Soot Samples and
Differentiation of Pyrogenic and Petrogenic PAHs - The 1994 and 1997 Mobile Burn
Study", in Chemistry of Diesel Fuel, C. S. Hsu, I. Mochida and C. Song (eds.), Taylor
and Francis Publishing Company, New York, 2000, Chapter 13, pp237-254.
152
-------
17. Appendices
1 Chemical Abstract Service (CAS) Registry Numbers for Selected Analytes
Compound
Benzene
Toluene
Ethylbenzene
M-Xylene
/>-Xylene
o-Xylene
Isopropylbenzene
Propylbenzene
2-ethyltoluene
3-ethyltoluene
4-ethyltoluene
1,2,4-trimethylbenzene
1,2,3 -triniethylbenzene
1,3,5-triniethylbenzene
Isoproplybenzne
1 -Methylethylbenzene
1 -Ethyl-2-methylbenzene
1 -Ethy 1-3 -methy Ibenzene
1 -Ethy 1-4-methy Ibenzene
«-buty Ibenzene
Isobuty Ibenzene
tert-Buty Ibenzene
sec-Buty Ibenzene
1 -Methyl-2-propylbenzne
1 -Methyl-3 -propy Ibenzne
1 -Methyl-4-propy Ibenzne
1 -Methyl-2-isopropy Ibenzene
1 -Methyl-3 -isopropy Ibenzene
1 -Methyl-4-isopropy Ibenzene
1,2-Diethylbenezne
1,3 -Diethy Ibenzene
1,4-Diethy Ibenzene
1 -Ethyl-2,3 -dimethylbenzene
1 -Ethyl-2,4-dimethylbenzene
2-Ethyl-1,4-dimethylbenzene
2-Ethyl-1,3 -dimethylbenzene
4-Ethyl-1,2-dimethylbenzene
1 -Ethyl-3,5-dimethylbenzene
1,2,3,4-Tetramethylbenzene
1,2,3,5-Tetramethylbenzene
1,2,4,5-Tetramethylbenzene
ar,ar-Diethylmethy Ibenzene
1 -Ethyl-2,4,5-trimethylbenzene
CAS
Number
71-43-2
108-88-3
100-41-4
108-38-3
106-42-3
95-47-6
98-82-8
103-65-1
611-14-3
620-14-4
622-96-8
95-63-6
526-73-8
108-67-8
98-82-8
98-82-8
611-14-3
620-14-4
622-96-8
104-51-8
538-93-2
98-06-6
135-98-8
1074-17-5
1074-43-7
1074-55-1
527-84-4
535-77-3
99-87-6
135-01-3
141-93-5
105-05-5
933-98-2
874-41-9
1758-88-9
354380
934-80-5
934-74-7
488-43-3
527-53-7
95-93-2
8638347
17851-27-3
ar-Ethyl-1,2,4-trimethylbenzene 54120-62-6
Pentamethy Ibenzne 700-12-9
1 -Isopropyl-2,5-dimethylbenzene 4132-72-3
1-Isopropy 1-3,5-dimethylbenzene 4706-90-5
1,3-Diethyl-5-methy Ibenzene 2050-24-0
ter/-Butyltoluene 37307
1-Ethy 1-3-isopropy 1-benzene 4920-99-4
1 -Ethyl-4-isopropyl-benzene 4218-48-8
2,4-Dimethyl-l-isopropylbenzene 4706-89-2
1 -Methyl-4-isobutylbenzene 1191151
1 -Methyl-3 -ter/-buty Ibenzene 1075-3 8-3
1 -Methy l-4-fer/-buty Ibenzene 98-51-1
(l-Ethylpropyl)-benzene 1196-58-3
(l,l-Dimethylpropyl)-benzene 2049-95-8
(1,2-Dimethylpropyl)-benzene 4481 -30-5
(2,2-Dimethylpropyl)-benzene 1007-26-7
w-Pentylbenzene 538-68-1
(l-methylbutyl)-benzene 2719-52-0
(2-methylbutyl)-benzene 3968-85-2
(3-methylbutyl)-benzene 2049-94-7
w-Hexylbenzene 1077-16-3
(l-Methylpentyl)-benzene 1508850
(2-Methylpentyl)-benzene 39916-61-5
(3 -Methy lpentyl)-benzene 54410-69-4
(l-Ethylbutyl)-benzene 4468-42-2
(2-Ethylbutyl)-benzene 19219-85-3
(1,1 -Dimethylbutyl)-benzene 1985-57-5
(1,3 -Dimethylbutyl)-benzene 19219-84-2
(2,2-Dimethylbutyl)-benzene 28080-86-6
(3,3 -Dimethylbutyl)-benzene 17314-92-0
(l-Ethyl-l-methylpropyl)-benzene 1985-97-3
(l,l,2-trimethylpropyl)-benzene 8932673
(1,2,2-trimethylpropyl)-benzene 19262-20-5
1 -Methyl-2-(l -ethylpropyl)-benzene 54410-74-1
1 -(1 -Ethylpropyl)-4-methylbenzene 22975-58-2
sec-Butylethylbenzene 28654-79-7
1,3 -Dimethyl-4-.sec-buty Ibenzene 1483 -60-9
1,4-Dimethyl-2-isobutylbenzene 55669-88-0
1,2-Dimethyl-4-ter/-buty Ibenzene 2007889
1,4-Dipropylbenzene 4815-57-0
1,2-Diisopropy Ibenzene 577-55-9
1,3 -Dimethyl-5-tert-buty Ibenzene 98-19-1
l,2,4-Trimethyl-5-isopropy Ibenzene 10222-95-4
1,2,4-Triethy Ibenzene 877-44-1
1,3,5-Triethy Ibenzene 102-25-0
1,2-Dimethyl-3,4-diethy Ibenzene 54410-75-2
153
-------
Compound
1,2-Diethyl-4,5-dimethylbenzene
l,2,4,5-Tetramethyl-3-ethylbenzene
Hexamethylbenzene
1,3 -Diisopropy Ibenzene
1,4-Diisopropy Ibenzene
Biphenyl
Acenaphthylene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Benzo(b)fluoranthrene
BenzoQfluoranthrene
Benzo(k)fluoranthrene
Benzo(j ,k)fluorene
Benzo(r,s,t)pentaphene
Benzo(a)phenanthrene
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Indeno(l,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
«-C8 (w-Octane)
n-Cg (w-Nonane)
«-C10 (w-Decane)
«-Cu (w-Undecane)
«-C12 (w-Dodecane)
«-C13 (w-Tridecane)
w-C14 (w-Tetradecane)
n-Cls (w-Pentadecane)
w-C16 (w-Hexadecane)
«-C17 (w-Heptadecane)
Pristane
«-C18 (w-Octadecane)
Phythane
w-C19 (w-Nonadecane)
«-C20 (w-Eicosane)
«-C21 (Heneicosane)
w-C22 (Docosane)
«-C23 (Tricosane)
w-C24 (Tetracosane)
w-C25 (Pentacosane)
w-C26 (Hexacosane)
w-C27 (Heptacosane)
w-C28 (Octacosane)
CAS
Number
6596821
31365-98-7
87-85-4
99-62-7
100-18-5
92-52-4
208-96-8
83-32-9
120-12-7
206-44-0
129-00-0
56-55-3
205-99-2
205-82-3
207-08-9
206-44-0
189-55-9
218-01-9
50-32-8
192-97-2
198-55-0
193-39-5
53-70-3
191-24-2
111-65-9
111-84-2
124-18-5
1120-21-4
112-40-3
629-50-5
629-59-4
629-62-9
544-76-3
629-78-7
1921-70-6
593-45-3
638-36-8
629-92-5
112-95-8
629-94-7
629-97-0
638-67-5
646-31-1
629-99-2
630-01-3
593-49-7
630-02-4
w-C29 (Nonacosane)
w-C30 (Triacontane)
w-C31 (Hentriacontane)
w-C32 (Dotriacontane)
w-C33 (Tritriacontane)
w-C34 (Tetratriacontane)
w-C35 (Pentatriacontane)
w-C36 (Hexatriacontane)
w-C37 (Heptatriacontane)
w-C38 (Octatriacontane)
w-C39 (Nonatriacontane)
w-C40 (Tetracontane)
w-C41 (Hentetracontane)
w-C42 (Dotetracontane)
w-C44 (Tetratetracontane)
w-C46 (Hexatetracontane)
w-C48 (Octatetracontane)
w-C50 (Pentacontane)
Naphthalene
1 -methylnaphthalene
2-methylnaphthalene
1 -ethylnaphthalene
2-ethylnaphthalene
2-isoproplynaphthalene
1 ,2-dimethylnaphthalene
1 ,3 -dimethylnaphthalene
1 ,4-dimethylnaphthalene
1 , 5 -dimethylnaphthalene
1 ,6-dimethylnaphthalene
1 ,7-dimethylnaphthalene
1 ,8 -dimethylnaphthalene
2,3 -dimethylnaphthalene
2,6-dimethylnaphthalene
2,7-dimethylnaphthalene
1 ,2,3 -trimethylnaphthalene
1 ,2,4-trimethylnaphthalene
1,2,5 -trimethylnaphthalene
1 ,2,6-trimethylnaphthalene
1,4,5 -trimethylnaphthalene
1 ,4,6-trimethylnaphthalene
2,3,5 -trimethylnaphthalene
Eudalene
Cadalene
2,6-diisopropylnaphthalene
Fluorene
1 -methylfluorene
2 -methylfluorene
630-03-5
638-68-6
630-04-6
544-85-4
630-05-7
14167-59-0
630-07-9
630-06-8
7194-84-5
7194-85-6
7194-86-7
4181-95-7
7194-87-8
7098-20-6
7098-22-8
7098-24-0
7098-26-2
6596-40-3
90-20-3
90-12-0
91-57-6
1127-76-0
939-27-5
2027-17-0
573-98-8
575-41-7
571-58-4
571-61-9
575-43-9
575-37-1
569-41-5
581-40-8
581-42-0
582-16-11
879-12-9
2717-42-2
641-91-8
413217
2131-41-1
2131-42-2
2245-38-7
490-65-3
483-78-3
24157-81-11
86-73-7
1730-37-6
1430-97-3
154
-------
Compound
4 -me thy Ifluorene
9 -me thy Ifluorene
1,7 -dimethy Ifluorene
9-e thy Ifluorene
Phenanthrene
1 -methylphenanthrene
2-methylphenanthrene
3 -methylphenanthrene
4-methylphenanthrene
9-methylphenanthrene
1,2-dimethylphenanthrene
1,3-dimethylphenanthrene
1,4-dimethylphenanthrene
1,6-dimethylphenanthrene
1,7-dimethylphenanthrene
1,8-dimethylphenanthrene
1,9-dimethylphenanthrene
2,3 -dimethy Iphenanthrene
2,4-dimethylphenanthrene
2,5 -dimethy Iphenanthrene
2,6-dimethylphenanthrene
2,7-dimethy Iphenanthrene
2,9-dimethy Iphenanthrene
3,5-dimethy Iphenanthrene
3,6-dimethylphenanthrene
3,9-dimethylphenanthrene
3,10-dimethylphenanthrene
4,5 -dimethy Iphenanthrene
9,10-dimethylphenanthrene
1,2,6-trimethy Iphenanthrene
1,2,8-trimethy Iphenanthrene
Retene
3 -ethy Iphenanthrene
9-ethylphenanthrene
Anthracene
1 -methylanthracene
2-methylanthracene
9-methylanthracene
2-ethylanthracene
2-(Tert-butyl)anthracene
1,2-dimethylanthracene
1,3-dimethylanthracene
1,4-dimethylanthracene
1,5-dimethy lanthracene
2,3 -dimethy lanthracene
2,7-dimethy lanthracene
9,10-dimethylanthracene
CAS
Number
1556-99-6
2523-37-7
442-66-0
2294-82-8
85-01-8
832-69-9
2531-84-2
832-71-3
832-64-4
883-20-5
20291-72-9
16664-45-2
22349-59-3
483-87-4
20291-74-1
7372-87-4
20291-73-0
3674-65-5
15254-64-5
3674-66-6
17980-16-4
1576-69-8
17980-09-5
33954-06-2
1576-67-6
66291-32-5
66291-33-6
3674-69-9
604-83-11
30436-55-6
20291-75-2
483-65-8
1576-68-7
3674-75-7
120-12-7
610-48-0
613-12-7
779-02-2
52251-71-5
18801-00-8
53666-94-7
610-46-8
781-92-0
15815-48-2
613-06-9
782-23-0
178-43-1
1 ,2,4-trimethy lanthracene
1 ,2,3 ,4-tetramethy lanthracene
Fluoranthene
1 -methylfluoranthene
2-methylfluoranthene
3 -methylfluoranthene
Pyrene
1 -methylpyrene
4-methylpyrene
Chrysene
1 -methylchry sene
2 -methylchry sene
3 -methylchry sene
4 -methylchry sene
5 -methylchry sene
6 -methylchry sene
20153-28-0
66553-01-3
206-44-0
25889-60-5
33543-31-6
1706-01-0
129-00-0
2381-21-7
531037
218-01-9
3351-28-8
3351-32-4
3351-31-3
3351-30-2
3697-24-3
1705-85-7
155
-------
2 Oil Chemical Analysis Protocol
156
-------
3 GC Chromatograms for Alaska North Slope Crude Oil
Figure A3-1
Figure A3-2
Figure A3-3
Figure A3-4
Figure A3-5
Figure A3-6
Figure A3-7
GC-FID chromatograms of faction 1 (F1) for saturates of Alaska North Slope
crude oil
GC-FID chromatograms of fraction 3 (F3) fortotal petroleum hydrocarbons
(TPH) of Alaska North Slope crude oil
GC-MS chromatograms of fraction 1 (F 1) fom-alkane distribution(m/z 85) of
Alaska North Slope crude oil
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of P AHs
of Alaska North Slope crude oil
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206, 220, 234, 198, 212, 226, 166, 180, 194, 208, 228, 242, 256, and 270) of
Alaska North Slope crude oil
GC-MS chromatograms of fraction 1(F1) forbiomarker terpane analysis (m/z
191) of Alaska North Slope crude oil
GC-MS chromatograms of fraction 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of Alaska North Slope crude oil
157
-------
, -rt'f
l
YM8 30'3i»\°
Figure A3-1
: if ; I ! l1 \ ! I
rff
CJV
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GC-FID chromatograms of fraction 1 (Fl) for saturates of Alaska
North Slope crude oil
158
-------
-
Figure A3-2
r-» -- '
ANS.'iO
GC-FID chromatograms of fraction 3 (F3) for total petroleum
hydrocarbons (TPH) of Alaska North Slope crude oil
159
-------
fat- 85
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Figure A3-3
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution
(m/z 85) of Alaska North Slope crude oil
160
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138
Figure A3-5a Extracted ion GC-MS chromatograms offraction 2 (F2) for determination of
the 5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of
Alaska North Slope crude oil (Peaks are labelled for naphthalene, N, the
alkylted naphthalenes, C;-N, C2-N, C3-N, C4-N, and dibenzothiophene, D).
162
-------
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Figure A3-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of
the 5 target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of
Alaska North Slope crude oil (Peaks are labelled for phenanthrene, P, and its
alkylated homologues, Q-P, C2-P, C,-P, and Q-P).
163
-------
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Figure A3-5d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of
the 5 target alkylated PAH homologues (m/z: 166, 180, 194) of Alaska North
Slope crude oil (Peaks are labelled for fluorene, F, and its alkylated
homologues, C;-F, and C2-F).
165
-------
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Figure A3-7
GC-MS chromatograms of fraction 1 (Fl) forbiomarker sterane
analysis (m/z 217/218) of Alaska North Slope crude oil
168
-------
169
-------
4 GC Chromatograms for Alberta Sweet Mixed Blend #5 Crude Oil
Figure A4-1
Figure A4-2
Figure A4-3
Figure A4-4
Figure A4-5
Figure A4-6
Figure A4-7
GC-FID chromatograms of fraction 1 (Fl) for saturates of ASMB #5 crude oil
GC-FID chromatograms of fraction 3 (F3) fortotal petroleum hydrocarbons
(TPH) of ASMB #5 crude oil
GC-MS chromatograms of fraction 1 (F1) fom-alkane distribution(m/z 85) of
ASMB #5 crude oil
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of P AHs
of ASMB #5 crude oil
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206, 220, 234, 198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of
ASMB #5 crude oil
GC-MS chromatograms offraction l(Fl)forbiomarkerterpane analysis (m/z
191) of ASMB #5 crude oil
GC-MS chromatograms offractionl (Fl) forbiomarker sterane analysis (m/z
217/218)
170
-------
W
3?ft« w
'K: 6 I- I |,M, ' I i '
Figure A4-1
GC-FID chromatograms of fraction 1 (Fl) for saturates of ASMB #5
crude oil
111
-------
AS MB Fresh
Figure A4-2
•N.SMB.
GC-FID chromatograms of fraction 3 (F3) for total petroleum
hydrocarbons (TPH) of ASMB #5 crude oil
172
-------
Ton 85
1
.'I'' 1
wx;
Figure A4-3
s. » Sf-W
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution
(m/z 85) of ASMB #5 crude oil
173
-------
Fresh
•:
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.
5 €€;
Figure A4-4
' "
ime
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of ASMB#5 crude oil
174
-------
1SJOC3!
'-5.49 !-6J>5
2ȣ3
Ion 142
il
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uoc i:«C3 ifi.K *.reo i»e:- IJKO svc: ?%'C3
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i*«« lo>ri '*'J
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Figure A4-5a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of ASMB #5 crude
oil
175
-------
Ian 178
2? jt
33 K
Ion IV2
2S25
31 « 1SA5
Ion 206
JS.Ki
Ion ?1
Jon 234
Figure A4-5b Extracted ion GC-MS chromatograms of fraction 1 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of ASMB #5 crude
oil
176
-------
•
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TiHIC
Figure A4-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of ASMB #5 crude oil
177
-------
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Figure A4-5d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of ASMB #5 crude oil
178
-------
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Figure A4-5
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Time
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of
the 5 target alkylated PAH homologues (m/z: 228, 242, 256, 270) of ASMB
#5 crude oil
179
-------
Ion
ccci:
ASMB,
:**{» as.** 3i?."»'»''&:»''%*
GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane
analysis (m/z 191) of ASMB #5 crude oil
180
-------
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iJtO 151
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5 GC Chromatograms for Arabian Light Crude Oil
Figure A5-1
Figure A5-2
Figure A5-3
Figure A5-4
Figure A5-5
Figure A5-6
Figure A5-7
GC-FID chromatograms of fraction 1 (Fl)for saturates of Arabian Light crude
oil
GC-FID chromatograms of fraction 3 (F3) fortotal petroleum hydrocarbons
(TPH of Arabian Light crude oil
GC-MS chromatograms of fraction 1 (F1) fom-alkane distribution(m/z 85) of
Arabian Light crude oil
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of Arabian Light crude oil
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206, 220, 234, 198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of
Arabian Light crude oil
GC-MS chromatograms of fraction 1 (Fl) forbiomarker terpane analysis (m/z
191) of Arabian Light crude oil
GC-MS chromatograms offractioi 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of Arabian Light crude oil
182
-------
Al.. .hesl
u
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Figure A5-1
GC-FID chromatograms of fraction 1 (Fl) for saturates of Arabian
Light crude oil
183
-------
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A I. 26".iW
Figure A5-2
GC-FID chromatograms of fraction 3 (F3) for total petroleum
hydrocarbons (TPH of Arabian Light crude oil
184
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GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
Arabian Light crude oil
185
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Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of Arabian Light crude oil
186
-------
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2 -/a
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Figure A5-5a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of Arabian Light
crude oil
187
-------
km 178
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31 3fl »•» 3W€
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Figure A5-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of Arabian Light
crude oil
188
-------
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Figure A5-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of Arabian Light crude oil
189
-------
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Figure A5-5d Extracted ion GC-MS chromatograms of fraction 1 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of Arabian Light crude oil
190
-------
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Ion 256
50 « » 34 e* it jo 31 &3 3« p s? 53 3?. $%' si o 4«: ,a 43 » * ^.se •« t»
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Figure A5-5e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of Arabian Light crude oil
191
-------
Ion 191
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GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z
191) of Arabian Light crude oil
192
-------
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GC-MS chromatograms of fraction 1 (Fl) for biomarker sterane analysis (m/z
217/218) of Arabian Light crude oil
193
-------
6 GC Chromatograms for Sockeye Crude Oil
Figure A6-1
Figure A6-2
Figure A6-3
Figure A6-4
Figure A6-5
Figure A6-6
Figure A6-7
GC-FID chromatograms of fraction 1 (Fl) for saturates of Sockeye crude oil
GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of Sockeye crude oil
GC-MS chromatograms offraction 1 (F1)forn-alkane distribution(m/z 85) of
Sockeye crude oil
Total ion GC-MS chromatograms offraction 2 (F2) for determination of P AHs
of Sockeye crude oil
Extracted ion GC-MS chromatograms offraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206, 220, 234, 198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of
Sockeye crude oil
GC-MS chromatograms offraction 1 (Fl)forbiomarkerterpane analysis (m/z
191) of Sockeye crude oil
GC-MS chromatograms offraction 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of Sockeye crude oil
194
-------
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lit
u
C*.1?1
Figure A6-la GC-FID chromatograms of fraction 1 (Fl) for saturates of Sockeye crude oil
195
-------
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i
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Figure A6-lb GC-FID chromatograms of fraction 1 (Fl) for saturates of Sockeye crude oil
196
-------
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Sockevc. 6
Figure A6-2a GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of Sockeye crude oil
197
-------
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Sock eve
*
Figure A6-2b GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of Sockeye crude oil
198
-------
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Figure A6-3
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Time
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
Sockeye crude oil
199
-------
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Sockcvc OS.
Sf'K
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Figure A6-4 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of Sockeye crude oil
200
-------
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13* 14 W
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Ion i 56
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Figure A6-5a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of Sockeye crude oil
201
-------
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Figure A6-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of Sockeye crude oil
202
-------
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Ion im
- 33 x gi je-
33 c<- »
Ion 212
iS
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ime
Figure A6-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of Sockeye crude oil
203
-------
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lot! 166
sr si; it K i? ae I
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ion 180
.
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Ion i
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ion 228
KI -12 Ms ii SO >|.-i» ia'ssi4 tv Si'ti25 X M-K3*(X !«-«! ?" CC'5-" f." i? %»!W JS
»*4'*3*14&«1-SQ
Ion 242
HaiSi*!.
ion 256
1-SX
ic .3*!;- 3r,c«oi
a «»5 s : -s* se 35 :o
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Ion 270
K- -j?>» a:?^» M K *; #3 49^9*1 .
Figure A6-5e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of Sockeye crude oil
205
-------
[on 19
e\ c,
2 KM
'Mi-OC- *3 55 *200
>...;.L ;..L..ji-..u.tU^,^,.,...,
SiKkcvc,
. « .. ,.,.'. A, J.Ji»
'»'»' "»:»'
**,«?
Figure A6-6
.I--J *JCT *2
GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z
191) of Sockeye crude oil
206
-------
Ion 21 7
Seckevc. 0%
3? £' .»-«
.IS SO 3sS 52 37 SC 31 3£- J1CO
48. 03
• f * .„ .. „ .„,»../,' .. . .
34,'>j" ^ OB 4? CO *?3Q
Ion 217
Sockcve. l*?
'
•«c» Jon 2IS
Figure A6-7
MOO !!,:-3 j?,v« 4C.CO
Timtj
GC-MS chromatograms of fraction 1 (Fl) for biomarker sterane analysis (m/z
217/218) of Sockeye crude oil
207
-------
7 GC Chromatograms for South Louisiana Crude Oil
Figure A7-1
Figure A7-2
Figure A7-3
Figure A7-4
Figure A7-5
Figure A7-6
Figure A7-7
GC-FID chromatograms of fraction 1 (Fl)for saturates of South Louisiana crude
oil
GC-FID chromatograms of fraction 3 (F3) fortotal petroleum hydrocarbons
(TPH) of South Louisiana crude oil
GC-MS chromatograms of fraction 1 (F1) fom-alkane distribution(m/z 85) of
South Louisiana crude oil
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of South Louisiana crude oil
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206,220,234,198,212,226,166,180,194,228,242,256, and 270) of South
Louisiana crude oil
GC-MS chromatograms of fraction 1(F1) forbiomarker terpane analysis (m/z
191) of South Louisiana crude oil
GC-MS chromatograms of fracton 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of South Louisiana crude oil
208
-------
si- r*rc*h
Sl
Figure A7-1
I
I it i I L I i I !: ; :
^*™-*^*wJ. JXj
GC-FID chromatograms of fraction 1 (Fl) for saturates of South
Louisiana crude oil
209
-------
SL, Fresh
Si.. 28%\v
Figure A7-2
I**™'
.»*
fc*^JUJLJ
GC-FID chromatograms of fraction 3 (F3) for total petroleum
hydrocarbons (TPH) of South Louisiana crude oil
210
-------
" " "*
S!., Fresh
V "" "*• 'ill :- I v. i- ' I 1 | . 1 ! - ; I
I
= " S-J-3 I3.J3 ifc-30 JO'^li -<|.CC
Figure A7-3
i ;t
ime
SL. 2
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
South Louisiana crude oil
211
-------
I
KSMol
SI.. Fresh
I ll ' ' i
JJJUU.WM
».W 3S.OO
'C7SC5-
Figure A7-4
MW
*^*».,-,. I-,, .k
.^j.
'SK 25.W »»
1
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of South Louisiana crude oil
212
-------
**«*; kin 128
1 sccoc-;
5&3GC;
cL
16,'CO 1TCJ -"-S'Ssl iCCO 2163
i 1
Ion 142
H ^ ... -V \ ^'"::-l^f •tn^'s"^.^"^ -^ S ¥i,;!H!^_is ; ^
td!w' li,« i£Cv 'iS.OO '?*.<» 15';?* iffe- l?,C-3 'lVcS> "liv-J '£9C3*",P.»
C 1*« f«« J ^
3-
II .03 1205 13*1 «^W 15 f:>3 15.K 1?i-3 1-JOD 50.C-3 2" .CO 22® 2T»
'.f«K'*4 lOI'I
'
. , •
" it W> tte& i
Ion 184
• ' .. ,1
- - - iSa" "V
-------
V
Ion 1 78
scccci
2f.t» 33J
, ,
Ion 1
.; i
Si CO
Ion 206
1 _^e..:^l -*, - —• .. -w- V-sfis^-"f~jw™c.-^»f—
31.&I
Ion 22(1
iiW"
.P , _ t ,..,.,!., ..,-,-*-. -,--f..-f ,.--,. ..»•
'
EC3OC* .«, -%
j ion 2*
2f.» 2?;' Ml SI X
Time
Figure A7-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of South Louisiana
crude oil
214
-------
M-3f£-
K •>*>
1ifm
Ion !9ft
ilcft 3S-:o Si.
5«: 85 -» ii«> 11 W
:*»»•
'"
Ion 212
« ;?J3 24-« if .SO »JK- 2S 50 2',-ja 3-2 53 3* GO J-i SO
km 2 26
ljfti-1
Hfr3 22 54
2TC3 3* .00 3'.5S
Time
Figure A7-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of South Louisiana crude oil
215
-------
Ion 166
-fy&S.Ci 20 » 2vi5 2t.59 UM
Ion ISC
:»acco asw ?' » 2t'M aw^sc-
Ion ]*>4
•KSK !.'K "K is\s i»'s? «&•>:•« -tftcscc.1! KS:< si:*? a^,» 2a.sftiux-3 2*5023.*
Tiin-e
Figure A7-5d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of South Louisiana crude oil
216
-------
228
3* M » il» 36« -S?-» «I
31.
-------
Tool 01
26 SC 55.
I
SL Frcsli
1
I-
-*-. •-—.' ' - * - ^-'" - "• ""• ^,:ej if {<
34'tt- t.J.W <2« "00 <6C
SL. 28%W
"-•—*•'y^'_4,\ '' ,' I;
Figure A7-6
:->SS 34.CO 42.CS «.»
Time
GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z
191) of South Louisiana crude oil
218
-------
Ion 2
SI, Fresh
.CC *X03 3*..O3
*t.CO
j&>3 •;
»8XV '"' -. -, ,•
I
I I
31 2? X 3D 43m
I r i
" CC
lor. 218
Figure Al-7
J SiOJ K:K 4ji« *».fj3 *2_64
-------
8 GC Chromatograms for West Texas Intermediate Crude Oil
Figure A8-1
Figure A8-2
Figure A8-3
Figure A8-4
Figure A8-5
Figure A8-6
Figure A8-7
GC-FID chromatograms of fraction 1 (Fl) for saturates of WestTexas
Intermediate crude oil
GC-FID chromatograms of fraction 3 (F3) fortotal petroleum hydrocarbons
(TPH) of West Texas Intermediate crude oil
GC-MS chromatograms of fraction 1 (F1) fom-alkane distribution(m/z 85) of
West Texas Intermediate crude oil
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of West Texas Intermediate crude oil
Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206,220,234, 198,212,226, 166, 180, 194, 228, 242, 256, and 270) of West
Texas Intermediate crude oil
GC-MS chromatograms of fraction 1 (Fl) forbiomarker terpane analysis (m/z
191) of West Texas Intermediate crude oil
GC-MS chromatograms of fraction 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of West Texas Intermediate crude oil
220
-------
WI.
4'
\\ T
Figure A8-1
».A.ti
.U i.,,;Jn
GC-FID chromatograms of fraction 1 (Fl) for saturates of West Texas
Intermediate crude oil
221
-------
WT, Fresh
WT
Figure A8-2
: J|!,*',f:-rfl«'!v'
GC-FID chromatograms of fraction 3 (F3) for total petroleum
hydrocarbons (TPH) of West Texas Intermediate crude oil
222
-------
iCMl
Wl.
ts.cc- Jst-J
JSOSCO
Figure A8-3
WT.. ^2'::!».
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
West Texas Intermediate crude oil
223
-------
VV1\
! G&30C
4-SSXJ;
*
??K«>
12&3M
10CC-W
wwc;
6CL I : I » - lhlflL.iLii. - I
: i lii ! %: fcii L Pi'l«- IS" *w: i '
53'cs 3% 5»; .w c* as x 4,1
\
\,f : •• *
3,>i) 21 C< iW.W W-.'X *3
Figure A8-4
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of West Texas Intermediate crude oil
224
-------
Ion 128
SOC3O
ic co
x^ *tte
co
Ion 142
'? , -f ~, .*• *. *»*•-• - -, 1- «.**•*»• «(*-», "» «- =•*, J-t*W tTmy
-mo; 2-s.K-
Ion 156
cc
r.« a-«
Ion 184
ilO
36
Time
Figure A8-5a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of West Texas
Intermediate crude oil
225
-------
I Ion 1 78
25 » 2?.«e ».» 3105
km
53 On .«.O3
Ion 220
2?.CB tSCS 2f?-W S3 CC 3I-.CC 3S 9
Uni 25-i
»<>f*>£tcj?«t;» « cc- »^c&asao
Time
Figure A8-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of West Texas
Intermediate crude oil
226
-------
*»'3 ^°11
«a«.
.-ww- /
.. • V..-. -. . -. < , !..!..'..
21 §3 »C5 S»,C4l4K: I? OS 2*50 2fe*0 Jlitt;
kin 2! 2
i'4i»5 »x ?? £? » yw
Jon 226
*"j*\-
ift» 2a"(* il» 3*i-J 2*,fc 26 !4 2?.90 £7 W 28 SC Ssfr'i 31 5C
Time
Figure A8-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z 198, 212, 226) of West Texas Intermediate
crude oil
227
-------
1KM
Ion 166
it«» '€ m 1 • » s? « 13-3 'if* 19C? 19 W »)« ?5 53 2'.K 2r» 2! 5C
*-•*«• r
'iiKC
IOTI ISO
C:>. n W IT 50
2\63 S
SOd 2'
t3» 3* »
on
t?.» #S S J* 83 S4 S* ^'50
Time
Figure A8-5d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of West Texas Intermediate
crude oil
228
-------
Ion 228
*
Ion 242
Ji r ,« 3 ! .5C i2 «» 31 'to 3S.4C- » iS^W 3* -90 58 W 34 S 5f,iC 55 5C 4«t- « « » 4 ' ,« 41 53
±!
:- •> <» 31 W 3') St »• W 3*"SC » 00 * ! '«i is
ion 270
-Bee;
2VOC 31 55 S-Ci
-------
r:;--.
•i'St
Jon
\\"T,
19 t€ 3vO .MCC
«i» 44 «l
K
15&23-
a .s-».-s ,«-- - - -™«,«*-4- ' »v *
o * , , ,----< - ,
i§«,< 3* C<
i me
; ..._ = ...„ \J.._JJ,JUw-.j.,?, . r,
Figure A8-6
S3 •» S4 K-
GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z
191) of West Texas Intermediate crude oil
230
-------
9 GC Chromatograms for Fuel Oil Number 2
WT,
***: Ion 2 1 1
:
K-X
41.oa «K
Ion 218
;"!i -.U'rsS AS.afl M C3C ^.» KVS *4r-,i -n» 4J<> ,\y
3 [Oil - 1 / I " ' •• -1" 'ftW
'
»:» 35 •» am 3§.&8 4°:
-------
Figure A9-2
Figure A9-3
Figure A9-4
Figure A9-5
Figure A9-6
Figure A9-7
GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of of Fuel Oil No. 2
GC-MS chromatograms offraction 1 (F1) forn-alkane distribution(m/z 85) of
Fuel Oil No. 2
Total ion GC-MS chromatograms offraction 2 (F2) for determination of PAHs
of Fuel Oil No. 2
Extracted ion GC-MS chromatograms offraction 2 (F2) for determination of the
5 target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192,
206, 220, 234, 198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) ofFuel
Oil No. 2
GC-MS chromatograms offraction 1 (Fl) forbiomarkerterpane analysis (m/z
191) of Fuel Oil No. 2
GC-MS chromatograms offraction 1 (Fl) forbiomarker sterane analysis (m/z
217/218) of Fuel Oil No. 2
232
-------
IJicsei, 7 2*--B
: jHm>" " -—Wi
";''*"•» *} ' L ' ' *;• '"'«," - - - .^;
Figure A9-la GC-FID chromatograms of fraction 1 (Fl) for saturates of Fuel Oil No. 2
233
-------
1-1.2%
22%
Figure A9-lb GC-FID chromatograms of fraction 1 (Fl) for saturates of Fuel Oil No. 2
234
-------
-*.
Figure A9-2a GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of of Fuel Oil No. 2
235
-------
42"*
Figure A9-2b GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of of Fuel Oil No. 2
236
-------
-I'll
f:-
scl, 0%
f-.K ','dpf. *«SC JOCC
*J CO A5 »
,
Time
Figure A9-3
22%
GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
Fuel Oil No. 2
237
-------
Dicsd.0%
atecoo
_ f-
<•*
»:$«>:
23GOC3.
5*: a
Figure A9-4
'-0 50 is.W
ll^i^i,.^
B C«0
DicscL.22%
t-SCS
line
Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs
of Fuel Oil No. 2
238
-------
Ion 12S
'S.Cfl iC'CC- 2iit« 2*0 23,-3S S*,:3
4-;C-CC»:
Ion 142
E
2i'as
ton i 56
v&
Ion 170
'!'""» U.K I2O3 !5;?3 1*.?3 '5-53 I9.?d Ti^' IS-00 II&3 21.CC 22.X li.OC 24 OC
Ion 1X4
HK 1240
"» ">3 '-3 T3
Time
?BOO T9 » I IK
Figure A9-5a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of Fuel Oil No. 2
239
-------
;
Ion 178
1 JOKX!
.
Ion Ic>2
AJW
X-
21
ion 200
C-5 |5.» J2,
ion 220
TillK
on
Figure A9-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of Fuel Oil No. 2
240
-------
Ion
> i?*? i? sc 3J>» 35 s* y es H s:
Ion 211
29 K iTSO 31
Inn 226
W.3C 2* W S*.$Z »:« 2?M *7 » l«.» J844 »'« JC.«? 51-09 51-50
"1 IlllL"
Figure A9-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of Fuel Oil No. 2
241
-------
I cm 166
< c.
f">M ITS? '£,55 1'J S S S€ 21W 3t Si 3j CO 23 ;t 24 53 16
K 18 W -» X
» 3! $.50 2*00
Ion
Time
55 3-W 5S59 ai.'ai ft^ «> f4.» 25'» JS's
Figure A9-5d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of Fuel Oil No. 2
242
-------
m! I ton 228
' '!
IK; ;:
f 3031.383.2 CC' 32.5-3 -J-JiW if SC: 14 59
XX
ton 242
"f| 3LK i-.HS.t«&32.5'ii3.WSvK3J % p':»S?<.%'.]iC43ft'%5:*i(»3ft'52-*3:23«-Mt\CC'ii SO
s
J 200 j
< ' Ion 256
•»
3l''«3' K 31 C« J5-M34 C9»i 5054*34 *C JW 3-T C«37.Kii:C»33«.«C:.»i»M.S?:-«-33*'.-S64ls 6&4' S>
&:I- fon 27«
S>iS »J*6 » F W,lf
Time
Figure A9-5e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of Fuel Oil No. 2
243
-------
3X5;
Ion 101
nicsel.0%
•'.jf >•»-•.
-J
86
33'i:
Diesel,22°o
32.
Figure A9-6
43 CD
44 r*
I
GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z
191) of Fuel Oil No. 2
244
-------
10 GC Chromatograms for Fuel Oil Number 5
Ion 2 i 7
si x js'o aloe 34 e 3
*i'e«" ** A3
[on 2 18
i-i DC
4ic«
Ion 218
IK.
€-"i.
C 3C 41 O3 42. OO 43.00 «* DO
J: j . .,.:... v t :.„. .-.-.,- -.-"-,! "•'. -«p*»^»™-i«™aaji^^ii-iii^--^-a«...^..^...^....i.iai....-....^i...^...ii.
"I'm ic
Figure A9-7 GC-MS chromatograms of fraction 1 (Fl) for biomarker sterane analysis (m/z
217/218) of Fuel Oil No. 2
Figure A10-1 GC-FID chromatograms of fraction 1 (Fl) for saturates of Fuel Oil No. 5
245
-------
Figure Al 0-2 GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons (TPH) of
Fuel Oil No. 5
FigureA10-3 GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of Fuel Oil
No. 5
Figure A10-4 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of Fuel Oil
No. 5
Figure A10-5 Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5 target
alkylatedPAHhomologues(m/z: 128, 142, 156, 170, 184, 178, 192,206,220,234,
198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of Fuel Oil No. 5
Figure A10-6 GC-MS chromatograms offraction 1 (Fl) forbiomarkerterpane analysis (m/z 191) of
Fuel Oil No. 5
FigureA10-7 GC-MS chromatograms of fraction 1 (Fl)forbiomarkersteraneanalysis(m/z 217/218)
of Fuel Oil No. 5
246
-------
WP
MWlfaJ*^"^
No.5 ;-iidJ)%
JM^
No-5 Fuel
Figure A10-1 GC-FID chromatograms of fraction 1 (Fl) for saturates of Fuel Oil No.5
247
-------
No.5 FtidJI'%
Jl>»*
mm
''' t*
p ' ^
No 5 Kuct. 7.25%
Figure A10-2 GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of Fuel Oil No. 5
248
-------
wosw
**>??;#
SOOC5C
Ion 85
_^.,.kjy
1.4J
2SK3
*»»
n>Sv*
:?«WiC;
*H»;*
*CW
4C-5X-
fi
> <
3a "0 «
:
:
:
:
:
I
15 OB
«
&
IOC
i
2S
00 K
u*
'cc
',*.
™™T
»X
»
4
No 5 [=i
No.5 Pud, 7.25°,,
+JCC« *l CC
me
Figure A10-3 GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of Fuel Oil
No. 5
249
-------
No 5 Ktif!
J-JO5Q
5.06
u
ttl'l-Tl
•its
i i
BOWW
j
4-SMKW
SdajO
XMMKB
" ~"*J"*W
sees*
'
j
•^ * - 4- - ^ -J-^-sl.-J-.L ".V..*
J
B =.:. J%
i
1
is I
|t
[
1:
Jj
J
I
i j
i I '
1 I I
: 1 ; III
i^ ' B 1 J i^;iWl
: fat:
rim v
H *
i • *
me
Figure A10-4 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of Fuel
Oil No. 5
250
-------
I
Ion 128
MW 23.03 24 3
Ion 142
1O.K1
ji 330C03-
on
I:«" I7t)
ft,
is to
2<,90
Ion 184
/-
if!'-:*: lira i?co ^395 iso 'aac irca' i.ja zj-cc 2i'«- a 5*' ?««*
Time
Figure A 10-5 a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of Fuel Oil No. 5
251
-------
Ion 178
1X1-33
SfSff 29- !W 3C-sX
15. 09 5309
1 !!
Ion 192
5'5lC J ftS
KC« 3'i«
pea
Ion 206
ss-cc
-
13 '30 *•*,!»
Time
Ion 220
Ion 234
Figure A 10-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of Fuel Oil No. 5
252
-------
98
ft'' S3
Si W i
.»1« Si €
kin 21 2
22.50 S-':K ;j
K ;?
is ac a. 10 2100 .je :o x.» at-Kf
"C-JK
i. »
Ion 220
Jtte tiie i*&C ?t/30 2T.sc K.
Figure A 1 0-5 c Extracted ion GC-MS chromatograms of fraction 1 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 166, 180, 194) of Fuel Oil No. 5
253
-------
J'X'Xi
ion 166
'55e -?c
-------
IROSG-
.T105S1.W3?:
f€?ft»
t
1»«K,
Ion 228
Q S8 38 ST.DC 3T.S1 33 «,S}
Ion 242
J1.K31
Jl
T^Vaftfai'5' .
-<^*"
!
!
COJI »3
Ion 256
T -m ^t t-«
Ion 2 'II
Jl€»}Jl,5a32,CaK,t<}-3iS,S333 SS^i »-»»-
Time
Figure A10-5e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of Fuel Oil No. 5
255
-------
330CC-
ISMS
No.5 hicl.0%
'».»' '32 SO" "*:«'
Jfj
2«H
44.00 5*0-3
CC W
Time
Figure A10-6 GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z 191) of
Fuel Oil No. 5
256
-------
11 GC Chromatograms for HFO 6303
Figure Al 1-1 GC-FID chromatograms of fraction 1(F1) for saturates of FIFO 6303
Ion2l?
j No 5 hud
o... - - ..
vi •» ?«*o a .&
«see
JSM Ion218
sine*
ej
•-j
•JQ S?CC
IS SB i? 3*
•' Of
oo * J ffl Ji ce
No 5 Kiel 7,25%
j?-j; 3* ;«? ,^3
««,«
-------
HFO 6303
Figure A11 -3 GC-MS chromatograms of fraction 1 (F1) for n-alkane distribution (m/z 85) of HFO 63 03
Figure Al 1 -4 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of FIFO
6303
Figure A11 -5 Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5 target
alkylated PAH homologues (m/z: 128, 142, 156, 170, 184, 178, 192, 206, 220, 234,
198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of HFO 6303
Figure Al 1-6 GC-MS chromatograms offraction 1 (Fl) forbiomarkerterpane analysis (m/z 191) of
HFO 6303
Figure Al 1 -7 GC-MS chromatograms offraction 1 (F 1) for biomarker sterane analysis (m/z 217/218)
of HFO 6303
258
-------
U-X).0%
HFCX2.5%
Figure Al 1-1 GC-FID chromatograms of fraction 1 (Fl) for saturates of HFO 6303
259
-------
I IK"). 0%
tW
IN
HKX 2.5%
Figure Al 1-2 GC-FID chromatograms of fraction 3 (F3) for total petroleum hydrocarbons
(TPH) of HFO 6303
260
-------
•?*:"»*;>'
iFO,0%
I
14XOC-
1MCOC-
i
3f 1 > f
! :
,y
u
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c
.
i
£
i
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^iLWW'-1^*1^^'-
-IJ-O.2.5
"> 48.
12,'fc if- 'JC- 45 2t
Time
Figure All-3 GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of FIFO
6303
261
-------
i*€m'
I-BC5&"
IK-i-SC
15 es
IMI
s-oe AIM
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.' I*. tf > 7. # 4
Time
Figure Al 1-4 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of
HFO 6303
*.€.*
* *i*is'w
'
262
-------
lon 128
1i. as
'400
k»n 142
Jg-
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it.W 12
-------
3KT-J
Jon 178
£?'C£> Sic*
1SSC 33
Ion J 92
Ion 2116
'
km 220
54.C=;
26C5
I
2JCO
JJCt-
Ion 231
Figure Al l-5b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of HFO 6303
264
-------
Ion 198
WC
?> 50 JSJK) !»<»: ;Sf* ,"rf
Ion 212
M K 2§ Of, i/i)
Ion 226
•;»;•;€;
' ^
4 c»: a i;s js<«o 25.50 29.oc a-so 2,* :•»,?? » IP *a ^oo 29 a *3«> B f:-. .11 -,» 3i'&3
Time
Figure All-5c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of HFO 6303
265
-------
?{;frfs
* 1
"
SJK 17.CO 17.se '8.
-------
ton 228
«• I Ion 2-12
C«-5*^3:JS.5«*l§.?M-l§W't9 »4l
Ion 256
3": »Si:» 32,»M«33 00 W 95 SB 9"? K3? S3» SJ «P 4UXH1
[on 270
SQCCS.
•«-' i* 3' .SO IS m 1J f-5.J "<9 'JA.iK 41 ».5? 1C 3? §3 J8 » Si 50 «C M 41 OC 41 S
1'itne
Figure All-5e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of HFO 6303
267
-------
1EBC!
i ;»*- i
.t/ SWA** :
* i *9T*is :
Ion 191
!FO. 0%
I ;
32. w *<»s
2.5%
c ^ice *4,ao *js?c
Time
Figure Al 1-6 GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z 191) of
HFO 6303
268
-------
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1C3C !
.
1S3C!
I on pi 8
< I
Ion 21
HFO,2.5%
.
.
.i* ] |on£|j{
f*f«, >>:'X 3'.SC 38 S '*fr.OC it.33 4I4.6J
Time
Figure Al 1-7 GC-MS chromatograms of fraction 1 (Fl) for biomarker sterane analysis (m/z
217/218)ofHFO6303
269
-------
12 GC Chromatograms for Orimulsion-400
Figure A12-1 GC-FID chromatograms of fraction 1 (F1) for saturates and of fraction 3 (F3) for total
petroleum hydrocarbons (TPH) of Orimulsion-400
Figure A12-2 GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
Orimulsion-400
Figure A12-3 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of
Orimulsion-400
Figure A12-4 Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5 target
alkylatedPAHhomologues(m/z: 128, 142, 156, 170, 184, 178, 192, 206, 220, 234,
198, 212, 226, 166, 180, 194, 228, 242, 256, and 270) of Orimulsion-400
Figure A12-5 GC-MS chromatograms offraction 1 (Fl) forbiomarkerterpane analysis (m/z 191) of
Orimulsion-400
Figure A12-6 GC-MS chromatograms offraction 1 (Fl) for biomarkersterane analysis (m/z 217/218)
of Orimulsion-400
270
-------
Orfmiilston-400
Fl
F3
Figure A12-1 GC-FID chromatograms of fraction 1 (Fl) for saturates and of fraction 3 (F3)
for total petroleum hydrocarbons (TPH) Orimulsion-400
271
-------
Son 85
I*1
*»». T
Figure A12-2 GC-MS chromatograms of fraction 1 (Fl) for n-alkane distribution (m/z 85) of
Orimulsion-400
272
-------
Oritviitlsbri-KM)
ik lit*
JL;v^''
Jw
;
ttW' --'V'
Figure A12-3 Total ion GC-MS chromatograms of fraction 2 (F2) for determination of PAHs of
Orimulsion-400
273
-------
25-JO
},,,..„ ,vv :_....:: ,:,, -.L,..,...
11.05 *ZK
ion 128
I
f
22-96 iW W
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j Ion 156
J
; if i
dV.^-^A-,-. .,.,...... • -..-^-
11JD 1S.:X> 15,90 1?"W !f.C4 1180 Z'.CC ** W S2.PC J3 P» L'4 )J
I till I 70
•1 '
:l • i
'••- ,«l • ''• ' <-•*',•'
3,,,, .,.._- .,^,-, , , , , . , , ,,,,,. .-»-:,,-..„-.,,-,,,,.»„,.„ -,,--,,,„,„,„,,-.S^jliCii.'--.---^^^^- /?V',-iv..'[--,'-i- ---- --i I....;...;,
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'*"itO€~Ti«j -jco iV« u;<»' i&so ' ir.« ric-i' 'aao 'aVx'
Time
Figure A 12-4a Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 128, 142, 156, 170, 184) of Orimulsion-400
274
-------
Ion 178
1 (MM
23. M
U>EI 192
77 »
ion 206
~;
-AssJ
***
3'.no
Ion 220
HOC
:>,;>*' ai MI '5,2.00
31'!KJ 'S« HffJ
Figure A 12-4b Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 178, 192, 206, 220, 234) of Orimulsion-400
275
-------
Ion
?? w ?j oo 2,3 SD 54 oo
?ST* js so s «o 3T'sj jf jo as as ioso 31 1» :K'*O
ION 212
S K 23 CC S3 Ml 24 C-? 15 5C 1C -3C » X' IT -30 2? » 2S C-3 IS *•" 11 fr? 25 5C ?3 IK 31 03 "JI.»
on 226
S-» 24.CO »» 2?« -fli-C *» J* C<> -J1 *0
Figure A 12-4c Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 198, 212, 226) of Orimulsion-400
276
-------
Ion
43K'
.
17.CC
21.52 2?-.
Ion
m« »oe
94
"KC
•»» lii 'ft*J 1»*3 SB « 21.W-21.SO JiM S » ;«*••
«|=j «•
1 line
Figure A 12-4d Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH hornologues (m/z: 166, 180, 194) of Orimulsion-400
277
-------
Ion 22«
jiic«3 ji 5 i? 00 s^iri«l!*ji«,tC' S* "•* » «' w
T3a' "W y* W-ft S* }->'C'3 *{ *0:-"*- W J* 5*3 3f ftOI* 0354 MI J' OC .J?-,» A».?t0* 13 -»-"*:'*3 fie X»41 H
ion 256
CO3i S8 32 0013 SC «• 03 24.CC .03 ICC Al -XJ
ou
.*! ai.se
Figure A 12-4e Extracted ion GC-MS chromatograms of fraction 2 (F2) for determination of the 5
target alkylated PAH homologues (m/z: 228, 242, 256, 270) of Orimulsion-400
278
-------
lor, 191
Figure A12-5 GC-MS chromatograms of fraction 1 (Fl) for biomarker terpane analysis (m/z 191) of
Orimulsion-400
279
-------
Ion 2 i 8
! w J» * >« "A* J> » IS. *A *}*«• X M A '-X :
hmc
;rt K. »;, sins » »; ikMt'tt ««* «f ?<:••-* »-'«« ,;i; M
Figure A12-6 GC-MS chromatograms of fraction 1 (Fl) for biomarker sterane analysis (m/z
217/218) of Orimulsion-400
280
------- |