EPA-R 2-73-102
FEBRUARY 1973 Environmental Protection Technology Series
Oil Pollution Source Identification
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2, Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
-------
EPA-R2-73-102
February 1973
OIL POLLUTION SOURCE IDENTIFICATION
By
M. Lieberman
Contract No. 68-01-0058
Project 15080 HDL
Project Officer
Bernard Hornstein
Edison Water Quality Research Laboratory
National Environmental Research Center
Edison, New Jersey 08817
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402
Price $2.35 domestic postpaid or $2.00 GPO Bookstore
-------
EPA REVIEW NOTICE
This report has been reviewed by the Environmental Protection
Agency, and approved for publication. Approval does not signify that
the contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
ii
-------
ABSTRACT
A study was conducted to evaluate and develop a method for the
identification of sources of oil pollution. The method is based on the
comparison of certain stable chemical indices present in unweathered
suspect oil pollution sources and the weathered pollution sample.
Five different crude oils, two residual fuel oils (a Nc. 4 and
a No. 5 oil) and one distillate fuel oil (a No. 2 oil) were subjected to
simulated weathering in the laboratory. Samples were weathered for 10
and 21 days at 55 and 80°F, under high and low salt water washing rates.
"Weathered" and "unweathered" oil samples were analyzed by low voltage
mass spectroscopy (polynuclear aromatics), high voltage mass spectroscopy
(naphthenes), gas chromatograph (n-paraf fins) , emission spectroscopy
(nickel / vanadium) , X-ray total sulfur and Kjeldahl total nitrogen tech-
niques .
Several compound indices were found to be stable after lab-
oratory simulated weathering and showed the ability to help discriminate
between pairs of oils used in the study. Discriminant function analysis
was used to select the best compound indices for distinguishing among
the oils used in the study. These included:
V_ ZParaffinsl ~Z5 Ring Naphthenes "1 ~ nC20 ~
_
Ni |_ Z(P + N) J [_ Z(P + N) J
Zl+2 Ring Naphthenes
15+6 Ring Naphthenes J
These indices provided a means of clearly distinguishing among
the oils used in the study with a high degree of statistical confidence.
A procedure for applying the developed oil spill identification system
is described.
iii
-------
TABLE OF CONTENTS
1. CONCLUSIONS 1
2. RECOMMENDATIONS 3
3. INTRODUCTION 5
4. PROGRAM OBJEC1IVES 7
5. EXPERIMENTAL PROGRAM 9
5.1 Selection of Test Samples 9
5.2 Selection of Weathering Test Variables 11
5.3 Design of the Weathering Apparatus 12
5.4 Weathering Tests 16
6. SAMPLE PROCESSING AND ANALYSIS 19
6.1 Removal of Water and Light Ends 19
6.2 Removal of Insolubles ..... ..... 19
6.3 Removal of Polar Compounds - Clay Separation 21
6.4 Separation of Aromatics from Saturates -
Silica Gel Separation 21
6.5 Separation Mass Spectroscopy - Gas
Chromatography Analysis 22
6.6 Analytical Problems 23
6.7 Supplementary Analysis 23
7. OIL SPILL IDENTIFICATION SYSTEM DEVELOPMENT 27
7.1 Preliminary Selection of Fingerprint Indices 27
7.2 Development of the Final Fingerprint Indices
Using Discriminant Function Analysis 59
7.3 Estimation of the Probability of Oil Misclassification
Using the Discriminant Function 61
7.4 Estimation of Confidence Levels for Oil Classification
Using Bonferroni "t" Statistics 63
7.5 Summary of System Application 67
7.6 Discussion of Results and
System Limitations • • 68
8. GENERAL EFFECTS OF LABORATORY WEATHERING 71
8.1 General Physical Changes 71
8.2 Evaporation Effects 71
v
-------
TABLE OF CONTENTS (Cont'd.)
9. REFERENCES 81
10. ACKNOWLEDGEMENTS 83
11. APPENDICES 85
A. SAMPLE SEPARATION MATERIAL BALANCE DATA 87
B. SUMMARY OF OIL FINGERPRINT DATA 89
C. GAS CHROMATOGRAPHIC DISTILLATION DATA 157
D. GENERAL SAMPLE STATISTICS '.'.'.'.'.'.I". '. 161
E. COMPARISON OF WEATHERED AN1> UNWEATHERED OILS 171
F. SAMPLE CALCULATIONS FOR GAS CHROMATOGRAM 175
VI
-------
LIST OF FIGURES
No. -Page
1 Environmental Simulation Test Facility 13
2 Environmental Simulation Test Facility Schematic 14
3 Sample Analysis Schematic 20
4 n-Paraffin Distribution of Unweathered Samples 42
5 n-Paraffin Distribution Tia Juana Medium Crude 43
6 n-Paraffin Distribution Lago Crude Oil 44
7 n-Paraffin Distribution Grand Isle Mix Crude Oil 45
8 n-Paraffin Distribution Nigerian Crude Oil 46
9 n-Paraffin Distribution Zuitina Crude Oil 47
10 n-Paraffin Distribution No. 4 Fuel Oil 48
11 n-Paraffin Distribution No. 5 Fuel Oil 49
12 Polynuclear Aromatic Compound Distribution
Tia Juana Medium Crude. 50
13 Polynuclear Aromatic Compound Distribution
Unweathered Oils 51
14 Polynuclear Aromatic Compound Distribution
Lago Crude Oil 52
15 Polynuclear Aromatic Compound Distribution
Grand Isle Mix Crude Oil 53
16 Polynuclear Aromatic Compound Distribution
Nigerian Crude Oil 54
17 Polynuclear Aromatic Compound Distribution
Zuitina Crude Oil 55
18 Polynuclear Aromatic Compound Dis tribution
No. 2 Fuel Oil 56
19 Polynuclear Aromatic Compound Distribution
No. 4 Fuel Oil 57
Vll
-------
LIST OF FIGURES (Cont'd.)
No^ Page
20 Polynuclear Aromatic Compound Distribution
No. 5 Fuel Oil 58
21 Crude Oil Before and After Simulated Weathering 72
22 No. 5 Fuel Oil Before Weathering 73
23 No. 5 Fuel Oil After Weathering 74
24 No. 2 Heating Oil Before Weathering 75
25 No. 2 Heating Oil After Weathering 76
26 Effect of Evaporation on Boiling Point
Distribution of Tia Juana Medium Crude Oil 77
27 Effect of Evaporation on Boiling Point
Distribution of a No. 4 Fuel Oil 78
28 Effect of Evaporation on Boiling Point
Distribution of a No. 5 Fuel Oil 79
viii
-------
LIST OF TABLES
No.
1 Basis of Crude Oil Sample Selection - Movement of
Crude Petroleum to the United States (1969) 10
2 Oil Samples Selected for EPA Program 11
3 Summary of Experimental Weathering Variables 12
4 Typical Material Balance Data from
Sample Separation Processing 22
5 M.S. Computer Print-Out of Aromatic Analysis 24
6 M.S. Computer Print-Out of Naphthene Analysis 25
7 Vanadium/Nickel Ratio of Weathered Oils 30
8 Sulfur/Nitrogen Ratio of Weathered Oils 31
9 Precision of Nickel-Vanadium Sulfur-Nitrogen Measurements. . 32
10 Aromatic Compound Distribution in Unweathered Crudes .... 33
11 Effect of Weathering on Polynuclear
Aromatic Distribution 34
12 Naphthene Distribution in Unweathered Crudes 36
13 Effect of Weathering on Naphthene Distribution 37
14 Precision of n-Paraffins Using Gas Chromatography 38
15 n-Paraffins in Weathered Crudes Using Gas
Chromatography (55 °F High Mix) 39
16 Preliminary Fingerprint Indices 41
17 Summary of Coefficients for Discriminant Function. 62
18 Probability of Misclassification of Pairs of Oils 64
19 IR Analysis of Weathered Oil Samples 80
IX
-------
SECTION 1
CONCLUSIONS
1. It is possible to use certain specific ratios of chemical compounds
present in the crude oils and oil products to distinguish (with very
high statistical confidence) among any possible pairs of these oils,
even after extensive simulated weathering in the laboratory.
2. The chemical fingerprint indices used to discriminate between all
pairs of the oils used in the program were unaffected by laboratory
simulated weathering.
3. The methodology and technology used to make the discrimination will
be applicable to other oils. However, the fingerprint indices used
to discriminate between pairs of oils used in the program are
specific for the present study; their general applicability to other
oils has not as yet been established.
4. Further studies are required to test the system on other oils with
different physico-chemical properties and to test the system in a
real marine environment.
- 1 -
-------
SECTION 2
RECOMMENDATIONS
Studies conducted under EPA Contract No. 68-01-0058 utilized
only laboratory simulated weathering of specific oil samples. It was
not within the scope of the program to evaluate real marine weathered
samples. It is recommended that the oil spill identification system,
developed in the present program, be applied to samples which have been
weathered in the real marine environment. The evaluation of real marine
weathered samples is required to determine the effects of two weathering
phenomena which could not be closely simulated in the laboratory:
• The huge ratio of water to oil film occurring in the ocean.
• The bacteriological effects in the ocean.
The present EPA program was also conducted with a limited
number of samples - 5 crude oils and 3 fuel oils. These oils were se-
lected: (a) to be representative of common types which are shipped in
U.S. waterways, and (b) to have one pair of oils which originate from
the same general area (Venezuela). It is recommended that the oil spill
identification system developed in this program be expanded to other
oils which are representative of all major generic chemical types so
that the feasibility of the system may be generalized.
It is also recommended that the system be applied to crudes or
products which are of very close origin, e.g., production from neighbor-
ing wells in the same field or from the same field, but differing in
time of removal from the ground.
The ability to distinguish between heavy non-blended residual
fuels and crudes will be very useful in oil spill identification. The
present EPA-sponsored program considered the generic distinction between
residual fuels and crudes, but not as a main objective. It is recom-
mended that further work be conducted to better adapt the developed oil
spill identification program to make this distinction. This would best
be done by including some n-paraffin tags below n-C^Q.
Finally, it is recommended that the system be tested with a
number of "known" real spill situations, using samples covering as wide a
range of marine salt and fresh water environments as possible.
- 3 -
-------
SECTION 3
INTRODUCTION
In recent years, this nation has become increasingly aware of
the potential harmful effects posed by the spillage of oils into salt
and fresh waters. Oil spills have, in many cases, been damaging to
property and commercial interests and may also adversely affect many
forms of aquatic life. Although many devices and techniques have been
developed to contain, control and disperse spilled oil, clearly the best
solution to the oil spill problem is to prevent them from occurring.
Legislation passed by Congress and international conventions
adopted by many countries participating in the United Nations Inter-
governmental Maritime Consultive Organization (IMCO) have provided for
harsh penalties for deliberate and negligent accidental oil spills; but
in order for these penalties to be effective deterrents against potential
violators of the law, the Federal Government must have the capability to
enforce the law—to effectively prosecute suspects. One most important
piece of evidence that is needed for effective prosecution is a method
to positively identify the^ source of the oil spillage.
To this end, the Environmental Protection Agency, Office of
Research & Monitoring, awarded the Esso Research and Engineering Company
Government Research Laboratory, Contract No. 68-01-0058, "Oil Spill
Source Identification".
The primary objective of this contract was to develop a system
to positively identify unknown sources of oil pollution. The developed
system had to be able to clearly identify an unknown spilled oil and had
to be fully effective under a wide range of environmental conditions with
minimal sensitivity to weathering. The developed system also had to have
a high detection sensitivity and had to be practical to implement.
Several previous attempts have been made to develop oil spill identifica-
tion systems. These include two general approaches—active and passive
tagging. In the "active tagging" approach, a special chemical or sub-
stance is deliberately added (in different forms) to different oils to
uniquely identify each. Such a system is extremely difficult to imple-
ment and causes potential refinery contamination problems.
The passive tagging system utilizes the inherent chemistry of
oils and does not require the addition of an external substance. Suspect
oils are compared with a spill sample utilizing certain chemical indices
present in oils and unique to each.
The Ssso system proposed and developed under EPA Contract No.
68-01-0058, is a passive tagging system (i.e., one which is based on the
inherent chemical composition of oils only and not on the addition of
some external chemical or material) which employs the techniques of mass
- 5 -
-------
spectrescopy, gas chromatography, emission spectrescopy, X-ray total
sulfur and Kjeldahl total nitrogen analyses to resolve oil spill samples
into stable "chemical fingerprints." Data for the chemical fingerprints
used in the system are derived from:
• High molecular weight n-paraffins
• Polynuclear aromatics
• Naphthenes
• Bulk V/Ni and S/N contents.
The work conducted under this EPA contract was aimed at determining which
specific "fingerprint" indices in these families of components would be
the best for positive identification. This was done through the analysis
of a set of oil samples subjected to controlled simulated weathering
experiments.
In this final report, the methodology, techniques, and results
of this EPA sponsored study on "Oil Spill Identification" are described.
In Section 5, the experimental phase of the study is described, includ-
ing the selection of test oil samples, a description of the weathering
apparatus and tests and a discussion of the weathering variables.
Sample analysis is described in Section 6 including an overall
sample separation and analysis flowsheet, a description of the analytical
unit processes involved and a discussion of some analysis problems en-
countered. Supplemental analyses, which provided background information
on weathering effects, are also described.
Section 7 describes the steps involved in the development of
the Esso oil spill identification system, including the preliminary se-
lection of fingerprint indices, final selection of preferred fingerprint
indices, the techniques used to develop the fingerprint data and a
summary of the steps required in the application of the system. General
effects of weathering are described in Section 8.
- 6 -
-------
SECTION 4
PROGRAM OBJECTIVES
Overall Objective - To develop a passive tagging system to
positively identify the source of oil spills. The system should have
the following characteristics:
A. Compatibility of tags with subsequent handling techniques
(refining, marketing, etc.) or use.
B. Stability of tags over long periods in storage and when exposed
to ambient air and water conditions.
C. Minimum effect of weathering on effectiveness of passive
analytical techniques.
D. Capacity for a large coding vocabulary such that all oil stored
or transported is unequivocally related to the persons responsible
for preventing its spillage.
E. High sensitivity to detection and negligible effect of potentially
interferring substances.
F. Low cost and operational simplicity of both the tagging operation
and analytical procedures.
The technical objectives are as follows:
A. To develop the most stable and discriminating passive tag compound
indices for a given oil spill identification situation.
B. To develop the required data treatment methodology for the system.
C. To develop the best analytical separation and processing scheme
for the system.
D. To determine any effects of weathering.
E. To identify any problem areas and limitations of the system.
- 7 -
-------
SECTION 5
EXPERIMENTAL PROGRAM
The experimental phase of the oil spill identification program
included the following components:
• Selection of test samples.
• Selection of weathering variables.
• Design of weathering apparatus.
• Weathering tests.
These are discussed and/or described in the following paragraphs.
5.1 Selection of Test Samples
Since only a limited number of samples could be used in the
present program (due to constraints of program time and cost), those oil
samples chosen for study were chosen to be representative of the most
probable sources of pollution to the United States and vicinity. The
primary criterion used for selection was, thus, volumes transported on
U.S. waterways.
Gasoline and distillate fuel oils are the petroleum products
with the largest volumes shipped on U.S. waterways (7). These products
do not persist on the sea because of their high volatility. However,
they may contain certain highly soluble components, and thus present a
potential pollution hazard. Oil products which contribute to the next
largest volume of transport are crude oils and residual fuel oils. These
are much less volatile, tend to persist much longer after spillage and
present a much greater ecoloeical threat. Shio bilge water is also a
potential large volume spill. Although we originally intended to in-
clude a bilge water sample in our test, we later found it impractical to
study, primarily because of the dilute nature of the samples obtained.
The origin of the crude oils selected for test was also based
on volume transport. Data from the April 1970 U.S. Petroleum Industry
Annual Statistical Review showed the following distribution:
- 9 -
-------
TABLE 1
BASIS OF CRUDE OIL SAMPLE SELECTION -
(7)
MOVEMENT OF CRUDE PETROLEUM TO THE UNITED STATES (1969)
Exporting Country
Venezuela
Libya
Indonesia
Nigeria
Neutral Zone
Colombia
Iran
Egypt
Saudi-Arabia
Kuwait
Other
Total
Imports to the United States
(Thousands of Barrels)
111,722
48,862
32,271
17,958
15,864
15,551
15,306
14,778
12,665
12,539
13,035
310,551*
* Excludes imports from Canada.
Crude oil samples from the four leading import countries were
selected; two different crude oil samples from Venezuela were selected
because of its particularly high level of export to the U.S. Two crudes
with a close proximity of origin were deliberately selected to test the
ability of the developed identification system to distinguish closely
related oils. A summary of the crude and refined oil products used in
this study is given below in Table 2.
- 10 -
-------
TABLE 2
OIL SAMPLES SELECTED FOR EPA PROGRAM
Sample No. Sample Type Oil Field Location
1 Crude oil Tia Juana Venezuela
2 Crude oil Lago Venezuela
3 Crude oil Grande Isle Indonesia
4 Crude oil Nigeria Nigeria
5 Crude oil Zuitina Libya
6 No. 2 Heating oil. Refined and
7 No. 4 Fuel oil ;. formulated from
8 No. 5 Fuel oil ( Venezuelan stock
5.2 Selection of Weathering Test Variables
Several environmental factors were considered for the evalua-
tion of any effects of weathering on sample chemical fingerprint indices.
These included type of water, temperature, degree of water washing of
the oil, exposure to sunlight, wind effects and contact time.
The time that an oil sample is exposed to the environment
(contact time) is important in its measure of the rate of weathering.
The effect of contact time was incorporated into the study by using a
sufficiently large sample for test such that portions could be removed
at specific intervals.
Temperature was also considered an important factor in that it
affects the rate of weathering (evaporation, oxidation, etc.) and was
thus used as an experimental variable.
The extent of water washing of the oil samples was considered
very important. A high washing level increases the leaching rate of
partially water soluble components from the oil sample and increases the
tendency of the oil sample to emulsify (which further accelerates leach-
ing) by providing a higher oil-t^O interfacial area. Water-oil contacting
may also control chemical processes which are diffusion limited. Thus,
the level of water washing was selected as the second weathering variable
for our experimental tests.
Wind speed and sunlight intensity were also considered important
environmental factors. Wind speed can greatly affect the rate of evapo-
ration of volatile components and ultraviolet light from the sun can
effect chemical oxidation changes. However, the intensity of these
weathering factors changes substantially in nature in short time intervals
and their use as experimental variables, though of interest, was
- 11 -
-------
considered to have lower practical value. It was thus decided to pro-
vide for the simulation of sunlight and wind in our experimentation
but not to use them as experimental weathering variables.
Consideration was also given to the type of water to use in
our tests. Crude oil and residual fuel oils which present the most
persistent forms of pollution, are transferred primarily by salt water
routes; fresh water routes are primarily used for refined, more volatile
oil products such as gasoline and kerosene and generally contain con-
siderably less total volumetric oil traffic than salt water. Although
it was originally planned to run a select number of samples in fresh
water in addition to a complete set of experiments in salt water, it
was found that the program schedule would not accommodate the fresh
water tests. Thus, all tests were conducted using salt water. All the
salt water used in this study was obtained from the New Jersey shore,
Manasquan Inlet (Point Pleasant side) at high tide.
The experimental variables and levels of test of the selected
variables are summarized below in Table 3.
TABLE 3
SUMMARY OF EXPERIMENTAL WEATHERING VARIABLES
Experimental Variables Levels of Test
Time 10 days, 21 days
Temperature 55°F, 80°F
Water Washing High, Low
The responses used to determine the nature and magnitude of
any effects of these variables were selected compound concentration
ratios of candidate fingerprint tags. Compound indices that showed no
or minimal change during weathering and which had the best discriminating
capability for the oils tested in this program were used to develop the
complete fingerprint functions. The data obtained from the weathering
experiment^ and the techniques used to develop the chemical fingerprint
functions are presented in Section 7 of this report. The apparatus used
to run the weathering experimnets is described in the following paragraphs,
5.3 Design of the Weathering Apparatus
The environmental simulation test facility used in our study
is depicted in Figure 1 and illustrated schematically in Figure 2. The
main function of this facility was to provide a means of simulating and
controlling the environmental (weathering) variables being tested as
well as other important environmental conditions which were fixed during
the experiments. The main components of this facility included:
- 12 -
-------
FIGURE 1
ENVIRONMENTAL SIMULATION TEST FACILITY
'zm \
- 13 -
-------
FIGURE 2
ENVIRONMENTAL SIMULATION TEST FACILITY SCHEMATIC
c
c c
out in
t 1
r
—
Lj
—
O
O
0
o
o cc
i
l
1
I
-
O
O
o
o
o
o
O 1 Q
. .-._ — 1
-R- -&- -
1
.x.
J
r~
t
•i
>
\
>
Approx. 5 Gal.
(3/4 Full)
f — ~"~ ^^ c
'
D
^
n
^ v ' '-
'•'.^
| r
V
Ri
e2
Fl
— T
n H
R
0
"r T °
"•
B - Teflon coated baffle F -
U
T
1
- Fan, F-j_ - 5 to 50 cc/min, F2 -
.3 to 60 GPM
C , C0ut - Chilled water in and out
CCn- Cooling coil (S.S.)
CV - Check valve
D - S.S. drum (55 gal.)
DD - Drum dolly
- Tangential inlet
L - Programmed on-off sunlamp
LS - Rotating magnetic stirrer
0 - Overflow
T - Thermometer stirring magnet
TA - Teflon coated tank
S - Stirring Bar
- 14 -
-------
• A continuous water recirculation system.
• A reservoir (stainless steel drum) for holding the salt
H20.
• A Teflon coated, baffled tank to hold the oil samples.
• A cooling coil refrigeration system to chill the salt
H20.
• A Teflon coated magnetic stirrer.
• An ultraviolet lamp to simulate exposure to the sun.
• A fan to simulate wind currents.
Ten separate individual rigs of the type described in Figures
1 and 2 were used in this program. Each operated independently (except
for the water chiller cooling coils which were connected in parallel to
a water chiller).
In operation, salt water was continuously pumped from the
stainless steel drum into the Teflon magnetic pump. In the Teflon coated
tank, the water continuously "washed" the test oil sample and then was
returned to the drum by gravity. An underflow baffle in the Teflon
coated tank allowed the passage of water but prevented the oil sample
(which remained on the H20 surface) from leaving the tank. A Teflon
coated bar, activated by a magnetic stirrer, provided additional mixing
in the tank. Water cooling temperature (55°F) was maintained by means
of the chilled water cooling coil immersed in the salt water reservoir
drum for low temperature levels of test. High temperature (80°F) water
was maintained by keeping the laboratory room temperature at 80°F.
A G.E. model 78 ultraviolet lamp was used to provide simulated
sunlight to the oil samples.
Mounted to shine directly on the surface of each tank, the
ultraviolet lamps were connected to a special electric timer circuit that
provided two hours a day of lamp on time. At the selected distance of
each lamp from the oil surface, this exposure time provided an ultra-
violet dosage comparable to a cloudless full summer day in the mid-
northern hemisphere.
A constant speed fan, mounted on each tank, simulated exposure
to constant wind of about 15 mph. The weathering tests were conducted
as described in the following paragraphs.
- 15 -
-------
5.4 Weathering Tests
The weathering tests were conducted by establishing steady
state conditions of salt-t^O temperature, recirculation rate and magnetic
stirrer speed and then adding a fixed quantity of the test oils to the
salt H2<3 in the Teflon coated weathering tanks. The sample size of oil
used in each case (1000 cm3) was large enough to allow tvo 50 cm3 aliquot
samples to be removed for analysis at two different times even after
considerable evaporation of oil volatile components and leaching of
soluble components had taken place. (It was later apparent that 500 cc
would have been adequate but the original 1000 cc oil sample was main-
tained throughout the testing for uniformity.) Oil samples were taken
from the same 5 gal. cans, which were thoroughly mixed before addition
to the tanks.
As indicated earlier, a chilled t^O unit provided refrigeration
through a cooling coil immersed in each 55 gal. stainless steel drum.
Salt water was maintained at 55 + 5°F for the low temperature tests. A
temperature of 80 + 7°F was maintained throughout the high, temperature
tests by means of regulation of the laboratory ambient. No noticeable
increase in surface oil temperature was detected (by a thermometer)
when the 500 watt ultraviolet lamps were turned on for as long as two
hours. Lamp heat was efficiently removed by the heat sink effect of the
recirculating H20. Ultraviolet lamps were automatically turned on and
off for two hours of each day by an electric timer.
High and low water mixing (washing of oil) conditions were
regulated by three different experimental parameters :
Total Salt HO Volume
Salt HO Recirculation Rate
Teflon Stirrer
High MIX
55 gals.
2-3 GPM
(200-500 RPM)
approx.
Low MIX
12 gals.
0.2-0-3 GPM
25-50 RPM
Flow rates and stirrer speed were adjusted daily to maintain
the desired levels.
Salt water concentration was periodically monitored by making
specific gravity measurements. Both evaporation and condensation of 1^0
took place, depending on the temperature of test and the temperature and
humidity of the laboratory ambient air — i.e., on whether the test tem-
perature was above or below the dew point of the ambient air.
- 16 -
-------
Distilled H2<3 and concentrated salt t^O were periodically
added to maintain constant volume and concentration of the salt H20
throughout the test. However, the total volume and concentration ad-
justments required were always a negligibly small fraction of the total
wash water present*.
Weathered oil samples were removed from the Teflon coated tank
at 10 and 21-day intervals. For those oil samples which were below
their pour point (55°F tests), the total sample removed for analysis was
taken from several locations on the surface of the "immobile" oil. Two
separate samples of each of the eight oil samples under test (about 25
oP each) were sent to the mass spectroscopy-gas chromatography and
emission spectroscopy laboratories, respectively. In addition to the
weathered samples, portions of unweathered oil of each type under test
were submitted for analysis. The analytical processing and separation
of the oil samples evaluated in this study are described in the follow-
ing section.
Ambient H20 vapor condensation at the onset of testing at the low
temperature (55°F condition) was a problem. However, this problem
was solved by keeping the laboratory air-conditioner on 24 hours/
day.
- 17 -
-------
SECTION 6
SAMPLE PROCESSING AND ANALYSIS
The weathered and unweathered oil samples evaluated during this
study were subjected to an analytical processing scheme to obtain the
necessary fingerprint data. Two samples were taken from each oil under
study for each set of experimental conditions discussed in Section 5.
One sample was used for nickel/vanadium analysis (emission spectroscopy),
sulfur analysis (x-ray spectroscopy) and nitrogen analysis (Kjeldahl);
the other sample was used for mass spectroscopy and gas chromatography.
The M.S.-G.C. analysis required considerable sample processing and
separation before these techniques could be applied. This processing
is best described with reference to the sample analysis schematic
depicted in Figure 3.
6.1 Removal of Water and Light Ends
Samples were first distilled in a glass still to remove any
H_0 (which was always present with weathered samples) and to remove
light ends with boiling points up to 400'*F. Light ends were not considered
reliable fingerprint indices and tended to make subsequent separation
more difficult. They were, thus, removed in this preliminary distillation
step.
6.2 Removal of Insolubles
The residue from the distillation step was then treated to
remove insolubles. This generally follows procedure A of ASTM test
D 893-69 for pentane insoluble materials. The procedure involved the
following steps:
• Weighing the distillate residue to a tenth of a milligram.
3
• Adding 50 cm of n-pentane.
• Centrifugation and decantation of the liquid.
• Repeat pentane addition, centrifugation and decantation,
combining and saving both decanted washes.
• Weighing of the insoluble dried residue.
- 19 -
-------
FIGURE 3
SAMPLE ANALYSIS SCHEMATIC
Sulfur Analysis
X-Ray
Spectroscopy
Pentane 1
Benzene + Acetone 2
Acetone 3
Pentane 1
I
to
!
it ion
F
Nickel/
i i
Vanadium
Analysis
Emission
Spectroscopy
1
Nitrogen
Analysis
Kjeldahl
Residue
Centrifugation
Insolubles^
Clay Separation
Acetone + Polars
Benzene
Pentane
Paraffins + Naphthenes
Aromatics
Aromatics
Benzene + Acetone
f
n-Paraffin
Analysis
Aromatic Analysis - Low Voltage
Naphthene Analysis (P + N fraction) - High Voltage
- 20 -
-------
6.3 Removal of Polar Compounds - Clay Separation
After the insolubles are removed, the sample dissolved in
n-pentane from the above procedure is fed to a clay separation column to
remove polar compounds. The clay column polar compound separation
follows ASTM procedure D 2007-65T which involves the following important
steps:
« Prewetting of clay (attapulgus clay 30-60 mesh containing
11-13% H?0) column with 25 cm of n-pentane.
• Adding the sample of n-pentane containing dissolved materials
(from insolubles removal).
3
• Addition of 8 separate 10 cm portions of n-pentane (which
were used to wash the sample flask) to the column. The
pentane eluted from the clay column will contain the sample
saturate compounds (paraffins + naphthenes) and aromatics.
3
• Addition of 100-125 cm of 70% benzene-30% acetone to the
clay column.
3
• Addition of 25 cm of acetone.
The eluted acetone-benzene and acetone solvents will contain
the polar fraction of the sample. The polar compounds were not
considered as candidate chemical fingerprints because of their high
solubility.
6.4 Separation of Aromatics From Saturates - Silica Gel Separation
The elution from the clay separation step (containing saturate
and aromatic fractions of the original sample) is stripped of its pentane
and is then fed to a silica gel column to separate out the aromatics.
The silica gel separation involves the following steps:
• Dissolution of the saturate-aromatic cuts (after pentane
stripping) from the clay separation in 10 cm of n-pentane.
• Prewetting the column with 10 cm of n-pentane.
9 Addition of the sample to the column followed by 8 replicate
10 cm portions of n-pentane to elute the saturate
fraction.
3
e Addition of 75-100 cm of acetone to elute the aromatics.
Typical material balance data obtained from the processing
of samples used in this study are presented in Table 4. Additional
material balance data on sample processing may be found in Appendix A.
- 21 -
-------
TABLE 4
TYPICAL MATERIAL BALANCE DATA
FROM SAMPLE SEPARATION PROCESSING
(1)
Oil Type
Tia Juana Medium
Crude Oil
Lago Crude Oil
Grande Isle Mix
Crude Oil
Nigerian Crude Oil
Zuitina Crude Oil
No. 2 Heating Oil
No. 4 Heating Oil
No. 5 Heating Oil
Replicate Tia Juana
Medium Crude Oils
Paraffins
+
Naphthenes
46.0
39.8
73.0
61.2
66.1
49.7
63.2
64.2
48.2
47.7
47.4
Aromatics
21.6
21.8
16.1
20.7
12.1
46.6
26.2
20.4
19.5
20.8
18.6
Weight
Polars
19.3
24.7
12.3
10.6
15.2
0.0
8.6
12.1
18.4
20.4
21.5
% of Sample
Pentane
Insolubles
9.0
15.5
1.2
1.0
3.1
0.2
1.0
5.8
10.9
9.4
10.9
£ Fractions
95.9
101.8
102.6
93.5
96.5
96.5
99.0
102.5
97.0
97.9
98.4
(1) Data based on unweathered samples.
material balance data.
See Appendix A for complete
6.5 Separation Mass Spectroscopy - Gas Chromatography Analysis
The final result of the column separation is a saturate
fraction (paraffins + naphthenes) and an aromatic fraction which were
analyzed as follows:
Saturate Fraction
Mass spectroscopy*
for naphthene type analysis
Gas chromatography
for n-paraffin analysis
Aromatic Fraction
Low voltage ,
mass spectroscopy
* Hood, A., O'Neal N. J., Advances in Mass Spectroscopy,
J. D. Waldron Ed., 1959, p. 175.
+ Lumpkin, H. E. Anal. Chem. 30, 321 (1958).
- 22 -
-------
The mass spectrometer used for both naphthene type analysis
and aromatic analysis (low voltage setting) was a CEC Model 21-103.
The gas chromatograph used for the n-paraffin analysis of the saturate
cut was a Perkin Elmer Model 900. The column used with the G.C. was
a 7-1/2' x 1/8" D stainless steel unit packed with 2 weight % SE 30
on Chromasorb G. Programmed temperature operation was started at 60°C
and increased at a rate of 8°C/min. to 350°C.
The mass spectrometer was coupled to a computer which provided
aromatic and naphthene analysis, examples of which are illustrated in
Tables 5 and 6 respectively. Gas chromatographic results were hand
calculated with the aid of a planimeter.
6.6 Analytical Problems
During the course of the program, several analytical problems
were encountered and solved.
In the initial attempt to process the weathered and unweathered
oil samples, no provision was made for removal of insolubles
(asphaltenes) and polar compounds. The presence of these materials
caused erratic silica gel separations with poor material balance. The
incorporation of the insolubles and polar removal steps prior to silica
gel separation solved this problem.
The presence of salt HO with weathered oils also caused
erratic column separation performance. This problem was alleviated
by subjecting the sample to distillation (to 400°F) prior to a column
separation. Loss of volatile oil components during distillation presentee:
no problem as they did not constitute candidate fingerprint compounds.
Finally, in the originally proposed analytical scheme for
this study, the individual n-paraffins were to be analyzed by mass
spectroscopy (simultaneously with the naphthene analysis). However, it
was found that the precision of the n-paraffin analysis, as provided
by the CEC Model 21-103 mass spectrometer, was not acceptable for this
study. The gas-chromatographic analysis described earlier was found
to be more precise for the n-paraffin analysis and was thus employed
in the final analysis train.
6.7 Supplementary Analysis
The analysis scheme described in the previous paragraphs was
aimed at providing the necessary data to develop and select stable
chemical fingerprint indices. This was the objective of the program.
However, in order to evaluate some general effects of weathering (on
sample constituents not used as chemical fingerprints) some additional
analyses were conducted on a few weathered and unweathered whole oil
samples (without using any separation processing). These included:
• A gas chromatographic distillation which was used to estimate
the effects of evaporation.
- 23 -
-------
TABLE 5
M.S. COMPUTER PRINT-OUT OF AROMATIC ANALYSIS
(D(2)
N)
•e-
METHOD= 2007
1 RUN NUMBER 18106
ANALYSIS OF AROMATICS
SERIES
CARSON NO.
C 6
C 7
C 8
C 9
CIO
Cll
012
C13
Cll*
C15
C16
C17
CIS
C19
C20
C21
C22
C23
C2l*
C25
C26
C27
C28
C29
C30
C31
C32
C33
C3i*
C35
C36
TOTALS
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
21.
CNH2N-
00
09
25
35
27
11*
17
50
38
1+9
76
12
31*
36
35
28
22
12
03
05
01
95
86
75
67
59
51
1*5
40
3U
30
05
3/20/72
LOW VOLTAGF. MS METHOD
CNH2N-8 CNH2N-10
0.16
0.22
0.21
0.18
0.16
0.20
0.28
0.50
0.76
0.92
0.96
1.
1.
1.
1.
1.
1.
05
,10
16
09
,05
01
0.99
0.93
0.85
0.77
0.70
0.63
0.56
0.1*9
0.1*1*
0.33
0.32
18.20
0.02
0.07
0.10
0.11
0.11
0.13
0.22
0.37
O.U6
0.52
0-. 55
0.59
0.61
0.65
0.63
0.6«*
0.63
0.63
0.62
0.59
0.55
0.50
0.1*3
0.39
0.36
0.31
0.00
0.25
11.16
CNH2N-12
Unweathered Tia Med
0.00
0.03
0.21
0.56
0.71
,06
,78
,79
,36
,05
0.89
0.81
0.76
0.68
U.63
0.59
0.56
0.55
0.50
0.1*2
0.36
0.52
0.28
0.25
0.22
0.19
17.17
CNH2N-1U
0.01
0.07
0.28
0.62
0.81*
0.39
0.87
O.S3
0.82
0.81
0.77
C.69
0.63
O.GO-
0.58
0.55
0.51
0.<*7
O.U2
C.36
0.33
0.29
0.25
0.23
0.20
13.01*
CNH2M-16
0.01
0.03
0.11*
0.35
0.1*7
0.1*8
0.55
0.67
0.67
0.62
0.58
0.51*
0.1*9
O.U6
0.1*5
O.U3
0.42
0.39
0.3U
0.29
0.27
0.21*
0.21
0.18
0.16
9.60
CNH2N-U
0.11*
0.53
0.89
0.83
0,60
0.56
0.59
0.57
0.51
0,1*9
0.1*1*
0.1*2
0.1*1
0.1*1
0.38
0.35
0.31
0.27
0.21*
0.21
0.19
0.16
0.15
9.75
(1) Unweathered Tia Juana Medium Crude Oil used in example.
(2) Includes small amounts of aromatic sulfur compounds which are not separately
resolved by the CEC Model 21-103 Mass Spectrometer.
-------
TABLE 6
M.S. COMPUTER PRINT-OUT OF NAPHTHENE ANALYSIS *
METHOD- 2012
1 RUN NUMBER 13089 3/15/72
OIL SPILL USING FIXED C2U MATRIX
SHELL PARAFFIN-NAPHTHENE TYPE ANALYSIS
UT.PCT.
PARAFFINS 33,26
1-RING NAPHTHENES 24.29
2-RING NAPHTHENES 19.13
3-RING NAPHTHENES 11.57
ii-RING NAPHTHEMES 7.10
5-RING NAPHTHENES 2.96
G-RING NAPHTHENES 1.66
MONO-AROMATICS 0.00
TOTAL 100.00
AVERAGE CARBON NUMBER 21.85
Unweathered Tia Juan Medium Crude Oil used in example.
» An infrared scan to estimate the effects of oxidation.
The gas chromatographic distillation followed the ASTM
procedure D-2887 using a 2' x 1/4"D column containing WC-98 on
Chromasorb.
The I.R. analysis was run on the neat oil samples using no
solvent. A Beckman IR-8 unit was used with a 0.110" cell and a slow
scan setting. The results of the supplementary weathering study, using
G.C. distillation and I.R. analysis, are presented in Section 8 of this
report.
- 25 -
-------
SECTION 7
OIL SPILL IDENTIFICATION SYSTEM DEVELOPMENT
In this section of the report, the methodology used to
develop the Esso passive tagging oil spill identification system is
presented. This includes the following:
9 Preliminary Selection of Fingerprint Indices.
• Development of Final Fingerprint Indices and Functions Using
Descriminant Function Analysis.
• Estimation of the Probability of Oil Misclassification Using
the Discriminant Function.
• Estimation of Confidence Levels for Oil Classification Using
Bonferroni "t" Statistics.
• Summary of Application of System.
• Discussion of System Limitations.
These are discussed, in turn, in the following paragraphs.
7.1 Preliminary Selection of Fingerprint Indices
Data for the preliminary selection of candidate fingerprint
indices for this system were obtained from the application of the
following analytical techniques to the program test samples:
• Low voltage mass spectrometric analysis of polynuclear
aromatic hydrocarbons.
• High voltage mass spectrometric analysis of saturate fraction
naphthenes.
• Gas chromatographic analysis of saturate fraction n-paraffins.
• Emission spectroscopic analysis of Vanadium/Nickel.
• Total sulfur analysis by x-ray.
• Total nitrogen analysis by Kjeldahl.
- 27 -
-------
The data for candidate tags from the M.S.-G.C. analysis were
expressed as weight concentration ratios within rhejfr r^M-ective fractions
Paraffin A Aromatic A , . Paraffin A
i.e. T=-. , — ~-, :~~ , and not ;——. Concentration
Paraffin B ' Total aromatics Aromatic B
ratios were used to avoid numerical changes caused by dilution or
concentration of other non-tag compounds. Ratios were maintained within
each fraction to avoid errors introduced in sample separation processing
and arising from the use of different size samples for analysis.
Vanadium/Nickel and Sulfur/nitrogen were expressed as concentration
ratios.
In the n-paraffin class of compounds, only compounds with a
carbon number of 20 or greater were considered as potential tags. This
was a decision, primarily based on weathering data from the Torey Canyon
Spill which showed,that n-paraffins below €-.<, were suceptible to
weathering changes . All n-paraffin data used in our study were
normalized to weight percents in the Coo~C40 comPoun- range.
A preliminary analysis of replicate unweathered samples of
aromatic fractions indicated that the experimental variance in specific
aromatic compounds was too large (compared with differences observed
from oil to oil) to be considered useful indices. However, if the
summation of all, or a number of compounds of a particular empirical
formula (i.e. in a particular family) were used, the measured variances
were small enough (compared with differences from oil to oil) to allow
them to be considered as potential tags.
Naphthene data from the high voltage mass spectrometer were
available as a summation of different compounds of specific ring size
and were used as such for tag evaluation.
The preliminary selection of potential oil spill identification
passive tags from the large array of available data was based on the
following criteria:
• Discriminating capability for the oils tested in the program.
• The precision of measuring these tags.
• Stability of tags to laboratory weathering (based on
preliminary, partially complete laboratory data)*.
• Previous experience in studying real spill situations.
The final selection of passive tags and development of the finger-
print functions includes data from the complete factorial
weathering experiment.
- 28 -
-------
V/Ni and S/N were selected as preliminary candidate tags for
this system. This selection was based both on previous company
experience (data presented in the Esso Research Proposal for this
Contract) and on data obtained during this program. Vanadium/Nickel
and Sulfur/Nitrogen ratios for the oils used in this test program
aided oil discrimination. This can be seen in Tables 7 and 8 which
give V/Ni and S/N values for the different unweathered and a few
weathered oils respectively. Table 9 shows that the analysis of these
candidate tags were measured with acceptable precision.
Several polynuclear aromatic ratios were also selected as
preliminary tags. This selection was based on the promising
discriminatory data given in Tables 10 and 11 and Figures 12 and 13.
Considering unweathered oil to oil differences, as well as the precision
of measuring specific indices, the following polynuclear aromatic
preliminary tags were selected:
A-l
Cn H
2n-6
I Aromatics
A-6
H,
2n-6
^Aromatics
C
C
20
36
A-2
ZCn
H2n-
10
Aromatics
A-7
H2n-10j
Aromatics
C
C
20
36
A-3
H,
2n-14
Aromatics
A-8
H
2n-6
iCn H,
2n-18
A-4
>n-16
EAromatics
A-9 ECnH2n-6+CnH2n-18
H,
2n-14
A-5
2n- 18
£Aromatics
- 29 -
-------
TABLE 7
VANADIUM/NICKEL RATIO OF WEATHERED OILS
Oil
Tia Juana Med.
Crude
Zuitina Crude
Lago Crude
Grande Isle Mix
Crude
Nigerian Crude
f2 Fuel Oil
#4 Fuel Oil
#5 Fuel Oil
Days
Weathered
0
10
10
21
10
0
10
10
21
0
10
10
21
10
0
10
10
21
0
10
21
10
0
10
21
10
21
10
0
10
21
21
0
10
10
21
10
Bath
Temperature, °F
„
55
80
80
80
—
55
80
80
—
55
80
80
80
—
55
80
80
—
55
55
80
__
55
55
80
80
80
—
55
55
80
— —
55
80
80
80
Kixing
Conditions
—
High
High
High
Low
—
High
High
High
—
High
High
High
Low
—
High
High
High
—
High
High
Low
—
High
High
High
High
Low
—
High
Low
Low
—
High
High
High
Low
V/Ni
7.4
7.4
7.8
7.6
7.8
0.3
0.1
0.2
0.3
5.6
7.2
7.0
5.4
6.2
0.2
0.2
0.3
0.1
0.2
0.1
0.3
-10(1)
-10(1)
-10(1)
-10(1)
-10(1)
-10(1)
5.3
6.8
5.7
5.4
8.3
7.7
7.9
7.8
8.8
(1) -10 used to signify ratio of very small members, e.g.
- 30 -
-------
TABLE 8
Oil
Tia Juana Med.
Crude
Zuitina Crude
Nigerian Crude
Lago Crude
Grande Isle Mix
Crude
#4 Fuel Oil
#5 Fuel Oil
#2 Fuel Oil
'NITROGEN RATIO
Days
Weathered
0
10
21
10
21
10
0
10
10
0
10
10
0
10
21
10
21
10
0
10
21
10
0
10
21
10
0
10
10
21
0
10
10
10
OF WEATHEREI
Bath
Temperature ,
°F
__
55
55
80
80
80
__
55
80
__
55
80
__
55
55
80
80
80
_»
55
80
80
_ —
55
55
80
55
80
80
_«.
55
80
50
Mixing
Conditions
High
High
High
High
Low
High
High
High
High
6.3
5.6
6.3
2.9
2.2
1.2
1.3
1.5
—
High
High
High
High
High
__
High
High
Low
__
High
Low
High
—
High
High
High
— —
High
High
Low
6.4
6.3
6.6
6.1
6.8
6.9
3.9
3.8
4.1
3.6
3.6
3.8
3.5
3.2
3.9
4.2
4.3
3.9
11.3
14.8
13.5
10.0
- 31 -
-------
TABLE 9
oo
to
PRECISION OF NICKEL- VANADIUM SULFUR-NITROGEN
Analysis
Nickel
Vanadium
Sulfur
Nitrogen
No. of Samples
11
11
19
11
Mean
Value (ppm)
23.3
173
1.61wt.%
0.26
Average
Range
0.6
6.4
0.010
0.016
MEASUREMENTS^1'
Standard
Deviation
0.53
5.67
0.009
0.0124
Coefficient
of Variation
2.3
3.3
0.56
4.8
(1) Tia Juana Crude (unweathered).
-------
TABLE 10
U>
u>
Crude EC H
n 2n-6
Benzenes
Replicate Tia Meds
Tia Med (Replicate 1) 20.8
Tia Med (Replicate 2) 20.8
Tia Med (Replicate 3) 20.8
Tia Med (Replicate 4) 21.6
Tia Med (Replicate 5) 21.1
Tia Med (Replicate 6) 21.4
Range 0.8
Range/2 0.4
Mid Range 21.2
Zuitina 16.5
Lago 18.9
Nigerian 14.9
Grande Isle Mix 18.1
No. 5 Fuel 17.9
No. 4 Fuel Oil 19.7
No. 2 Heating Oil 10.7
.OMATIC COMPOUND DISTRIBUTION IN UNWEATHERED CRUDES
Aromatic Distribution
wt.% of
°n 2n-8
Tndans
20.7
20.6
19.8
19.0
20.6
20.7
1.7
0.85
19.9
19.9
20.3
20.7
20.2
22.8
27.4
10.4
Compound
ECnH2n-10
Indenes
13.2
13.2
12.2
12.7
12.7
12.6
1.0
0.5
12.7
14.1
13.9
14.6
13.9
16.1
15.0
4.6
Type in Aromatic
ECnV-12
Naphthalenes
17.0
16.9
18.2
18.3
18.1
18.1
1.4
0.7
17.6
18.3
16.0
18.4
19.3
12.7
13.2
36.9
Fraction
ZCnH2n-14
Ac enaph th ene s
11.6
11.7
11.8
11.4
10.7
11.7
1.0
.5
11.2
12.6
12.5
14.2
11.7
12.7
11.0
18.5
ZCnH2n-16
Acenaphthalenes
8.1
8.2
8.1
7.9
8.2
8.1
0.3
0.15
8.1
9.2
8.9
9.5
8.5
10.1
7 .9
8.1
ZCnH2n-18
Phenanthrenes
8.6
8.7
9.0
9.0
8.7
8.7
0.4
0.2
8.8
9 .4
9.4
7.7
8.3
7.7
5.7
10.8
-------
TABLE 11
EFFECT OF WEATHERING ON POLYNUCLEAR AROMATIC DISTRIBUTION
Crude
Tia Med
Zuitina
Lago
Nigerian
Grande Isle Mix
No. 5 Fuel
No. 4 Fuel Oil
No. 2 Fuel Oil
Weathering
Time
Days
0
10
18
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
0
10
21
wt.% of
EC H,
ti 2n-6
20.8
21.0
24.5
3.7
16.5
16.9
16.9
0.4
18.9
19.0
18.7
0.3
14.9
15.9
14.6
1.3
18.0
17.2
17.5
0.8
17.9
18..]
1.8.1
0,2
19.7
19.0
19.6
10.7
10.2
1^.5
(55-60° F) High Mix
Compound Type in Aromatic Fraction
ICnH2n-8
20. 7
18.5
22.2
3.7
19.9
19.0
18.8
1.1
20.3
20.0
19.9
0.4
20. 7
19.1
19.1
1.6
20.2
19.4
19.6
0.8
22.8
21.8
21.9
1.0
27.4
29.8
29 . 7
10.4
9.1
°.4
rCuH2n-10
13.2
12.2
14.9
2.7
14.1
15.1
14.7
1.0
13.9
13.9
14.0
0.1
14.6
14.2
14.6
0.4
13.9
15.0
14.1
1.1
16.1
16.2
16.5
0.4
15.0
15.7
15.6
4.6
4.2
4,^
EC H, .,
n 2n-12
17.0
19.9
16.1
3.8
18.3
15.0
15.3
3.3
16.0
15.9
15.8
0.2
18.4
15.1
17.3
3.3
19.3
17.6
17.6
1.7
12.7
12.4
12.3
0.4
13.2
10.7
11.5
36.9
36.4
3A.A
EC H
n 2n-14
11.6
13.2
12.1
1.6
12.6
13.2
12.8
0.6
12.5
12.6
12.6
0.1
14.2
15.1
15.5
1.3
11.7
12.6
12.5
0.9
12.7
12.9
1.3.1
0.4
11.0
11.9
11.5
18.5
19.5
1" . 1
EC H0
n 2n-16
8.1
8.5
6.6
1.5
9.2
10.2
10.5
1.3
8.9
9.1
9.3
0.4
9.5
10.5
10.3
1.0
8.5
9.4
8.6
0.9
10.1
10.4
10.6
0.5
7.9
8.7
8.2
8.1
8.3
8.3
1C H0 -18
n 2n
8.6
6.7
3.6
5.0
9.4
10.5
11.1
1. 7
9.4
9.4
9. 7
0.3
7.7
9.9
8.5
2.2
8.3
8.8
8.8
0.5
7.7
8.1
7.6
0.5
5.7
5.8
5. 7
10.8
12.1
12 . 7
-------
Polynuclear Aromatic tags A-l thru A-6 were based on their
promising discriminating character. Tags A-6 and A-7 are similar to
A-l and A-2 respectively except that they include only compounds above
C7n. Though the results of the first few (low temperature) weathering
experiments indicated that there was apparently no disadvantage in
including the entire molecular weight range of polynuclear compounds
in ratios A-l and A-2 (B.P > 400°F) it was felt that some differences
might be seen under more severe weathering. Thus, indices A-6 and
A-7 were included to test this hypothesis, using all the weathering data
in the final tag selection. Tags A-8 and A-9 were included to accentuate
any distribution differences in tags A-l, A-3, and A-5.
In a similar manner, the discriminating capability, precision
of measurement and stability to weathering of potential naphthene
compound indices were considered. The selection of specific naphthene
indices was also based on data obtained from unweathered and some
weathered crudes. This data is given in Tables 12 and 13. The naphthenes
selected as preliminary tags included*:
N-l £ Paraffins N-4 £ 5 Ring Naphthenes
E Paraffins-)- Naphthenes ^Paraff ins -f Naphthenes
N-2 £ 3 Ring Naphthenes N-5 Zl + 2 Ring Naphthenes
^Paraffin -I- Naphthenes Z5 + 6 Ring Naphthenes
N-3 £4 Ring Naphthenes
IParaffin + Naphthenes
Tags N-3 and N-4 showed the best combined preliminary
discriminating capability and precision of measurement of the naphthene
groups. Tags N-l, and N-2 were less discriminating but showed sufficient
potential to be included. Selection of index N-5 as a preliminary tag
could not be completely justified on the basis of the preliminary data
at hand. However, it was included to determine whether an effective
tag would result by accentuating the general naphthene distribution
seen in all samples - i.e. richer in low number ring compounds - leaner
in higher number ring compounds.
The preliminary selection of n-paraffin candidate tags were
based on comparative G.C. analysis of unweathered and a few weathered
samples. Data used in the n-paraffin selection are presented in Tables 14
and 15 and Figures 4 and 5. As indicated earlier, only n-paraffin
compounds with a carbon number of 20 or greater were considered. Results
All naphthene and aromatic tags contain no compounds with a boiling
point <400°F.
- 35 -
-------
TABLE 12
NAPHTHENE DISTRIBUTION IN UNWEATHERED CRUDES
wt.% of Compound Type in Paraffin + Naphthene Fraction
Crude
Replicate Tia Meds
Tia Med
Med
Med
Med
Med
Tia Med
wt.% Parafins
in P-W Fraction
Range/2
Mid Range
Zuitina(R)
Zuitina(R')
Mid Range
La8°
Nigerian
Grande Isle Mix
No. 4 Fuel Oil
No. 5 Fuel Oil
No. 2 Fuel Oil
.2
.3
.2
.5
3. 42
34.9
31.
32.
32
39.
8.3
4.2
35.4
46.2
46.5
46.4
16.6
40.7
29.9
34.9
28.4
51.2
Il-Ring
Naphthenes
E2-Ring
Naphthenea
22.8
22.9
25.7
25.8
25.6
20.1
5.7
2.8
23.9
20.6
21.1
21.4
25.4
15.7
22.7
26.4
25.5
17.4
18.1
18.5
19.7
20.2
19.9
17.0
3.2
1.6
18.6
14.0
14.2
14.1
24.0
16.3
17.9
20.4
20.2
14.7
I3-Ring
Naphthenes
£4-Ring
Naphthenes
E5-Ring
Naphthenes
Z6-Ring
Naphthenes
11.2
11.2
11.9
11.3
11.1
10.5
1.4
.7
11.2
8.2
8.2
8.2
16.6
13.1
12.3
11.2
12.9
9.4
7.4
6.9
6.8
6.1
6.2
6.9
1.3
.7
6.8
5.7
5.6
5.6
10.5
8.3
9.7
5.5
6.8
5.2
3.6
3.3
2.9
2.5
2.9
3.4
1.1
.6
3.1
2.9
2.6
2.8
4.5
3-5
4.5
1.5
3.6
2.0
2.3
1.9
1.7
1.2
1.7
2.2
1.1
.6
1.8
2.0
1.5
1.8
2.3
2.0
2.3
0.16
2.1
o
-------
I
CO
Crude
Tia Med
Zuitina
Lago
Nigerian
Grande Isle Mix
No. 5 Fuel Oil
No. 4 Fuel Oil
TABLE 13
EFFECT OF WEATHERING ON NAPHTHENE DISTRIBUTION
(55-60°F) High Mix
Wt. % of Compound Type
Days
% P
Weathered P+N
0
10
21
0
10
21
0
10
21
0
10
21
0
10
21
0
10
21
0
10
21
35.4
36.2
36.2
46.4
46.5
47.1
16.6
23.8
22.2
40.7
39.8
40.7
29.9
31.9
30.0
28.4
33-5
31.2
34.9
35.1
35.0
£1 Ring
Naphthenes
23.9
22.5
22.2
21.4
20.4
20.4
25.4
22.5
23.0
15.7
15.9
17.8
22.7
23.2
22.9
25.5
22.5
23.4
26.4
26.2
26.2
12 Ring
Naphth_enes_
18.6
19.2
19.0
14.1
14.2
14.2
24.0
23.1
23.1
16.3
14.2
14.2
17.9
18.6
18.0
20.2
10.8
19.1
20.4
19.9
19.9
13 Ring
Naphthenes
11.2
11.7
11.8
8.2
8.5
8.4
16.6
16.5
16.1
13.1
13.9
12.9
12.3
12.1
12.2
12.9
12.1
12.6
11.2
11.5
11.2
14 Ring
Naphthenes
6.8
6.6
6.8
5.6
6.4
6.2
10.5
9.2
10.0
8.3
10.1
8.9
9.7
9.0
9.5
6.8
7.9
8.4
5.5
5.7
5.5
15 Ring
Naphthenes
3.1
2.5
2.6
2.8
2.5
2.4
4.5
3.6
3.9
3.5
4.3
3.6
4.5
3.4
4.0
3.9
3.4
3.6
1.5
1.5
1.5
16 Ring
Naphthenes
1.8
1.2
1.3
1.8
1.2
1.0
2.3
1.3
1.7
2.0
1.8
1.7
2.3
0.9
1.0
2.1
1.6
1.8
0.16
0.00
0.00
-------
TABLE 14
PRECISION OF n-PARAFFINS USING GAS CHROMATOGRAPHY
Weight % in C2Q - CAO
Crude C20 C21 C22 C23 C24 C25 C26 C27 °28 C29 C3Q
Replicate Tia Juana Meds
A 14.8 11.7 10.2 8.7 7.9 8.4 6.5 6.1 A.3 3.8 3.2
C-l 14.4 11.7 9.8 8.5 8.0 7.7 6.1 5.9 5.1 3.7 3.2
D-2 15.0 11.9 10.4 8.8 8.8 8.4 6.4 5.7 4.9 4.0 3.4
S 14.6 11.5 10.4 8.6 8.0 8.4 6.1 5.7 5.0 4.0 3.6
U 14.3 11.1 10.2 8.9 8.2 8.1 6.6 5.9 4.8 3.9 3.2
Av. 14.6 11.6 10.2 8.7 8.2 8.2 6.4 5.9 4.8 3.9 3.3
Range 0.7 0.8 0.6 0.4 0.9 0.7 0.5 0.4 0.8 0.3 0.4
Mid Range 14.7 11.5 10.1 8.7 8.4 8.1 6.4 5.9 4.7 3.9 3.4
Lago Q 11.3 8.8 8.8 8.3 7.5 8.9 6.2 6.9 4.8 3.9 2.9
Grande Isle Mix 19.2 13.2 10.0 7.3 7.4 7.7 5.5 4.7 3.3 2.8 2.8
Zuitina (R) 13.7 11.7 10.4 9.0 8.1 7.3 6.1 5.4 4.7 4.3 3.7
No, 2 Fuel Oil 47.0 28.2 13.8 6.4 2.4 1.0 0.5 0.3 0.3 0.2 0
No. 4 Fuel Oil 19.3 12.0 8.9 8.1 7.0 7.0 6.5 5.7 4.5 3.7 3.4
No. 5 Fuel Oil 12.0 10.5 9.6 8.8 8.4 9.9 7.2 7.1 5.7 4.5 3.7
- 38 -
-------
TABLE 15
Crude
Tia Medium
La go
Zuitina
Grande Isle Mix
No. 2 Fuel Oil
No. 4 Fuel Oil
No. 5 Fuel Oil
n-PARAFFINS IN WEATHERED CRUDES USING
GAS CHROMATOGRAPHY (55° F HIGH MIX)
Weight %
Weathering
Time (Days) 20
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
0
10
21
Range
14.6
14.9
15.9
1.3
11.3
12.5
11.7
1.2
13.7
14.5
13.3
1.2
19.2
19.7
19.5
0.8
47.0
46.6
48.5
1.5
19.3
17.4
17.6
1.7
12.0
11.2
10.9
1.1
C21
11.6
11.9
13.2
1.6
8.8
10.5
9.0
1.7
11.7
12.1
11.8
0.4
13.2
13.3
13.2
0.1
28.2
28.2
27.2
1.0
12.0
11.4
11.4
0.6
10.5
10.0
10.2
0.5
in C20 - C40
C22
10.2
10.6
11.2
1.0
8.8
9.3
8.9
0.5
10.4
10.7
10.5
0.3
10.0
10.7
10.6
0.7
13.8
13.9
15.2
1.4
8.9
7.9
8.0
1.0
9.6
9.7
9.2
0.5
C23
8.7
9.0
9.5
0.8
8.3
8.2
8.2
0.1
9.0
9.8
9.4
0.8
7.3
8.3
7.7
1.0
6.4
6.1
5.7
0.7
8.1
7.1
7.2
1.0
8.8
8.7
8.3
0.5
C24
8.2
8.2
8.6
0.4
7.5
7.3
7.3
0.2
8.1
8.8
8.6
0.5
7.4
7.8
7.6
0.4
2.4
2.6
2.3
0.3
7.0
6.6
6.7
0.4
8.4
8.4
7.8
0.6
C25
8.2
8.2
8.4
0.2
8.9
8.7
8.8
0.2
7.3
7.1
8.2
0.9
7.7
8.8
7,9
1.1
1.0
1.1
0.8
0.3
7.0
7.1
7.1
0.1
9.9
9.1
8.3
0.8
C26
6.4
6.0
5.9
0.5
6.2
5.5
5.6
0.7
6.1
6.5
6.5
0.4
5.5
6.0
5.7
0.5
0.5
0.5
0.2
0.3
6.5
6.6
6.5
0.1
7.2
7,5
6.8
0.7
c2?
5.9
5.8
5.9
0
6.9
6.2
6.7
0.7
5.4
5.8
5.7
0.4
4.7
4.6
4.6
0.1
0.3
0.3
0.1
0.2
5.7
6.1
6.1
0.4
7.1
7.2
7.1
0.1
C28
4.8
4.7
4.5
0.3
4,8
4.0
4.4
0.8
4.7
4.6
4.8
0.2
3.3
2.7
2.8
0.5
0.2
0.2
0
0.2
4.5
4.2
4.3
0.2
5.7
5.3
5.7
0.4
c29
3.9
3.8
3.9
0
3.9
3.0
3.5
0.9
4.3
4.1
4.3
0.2
2.8
2.7
2.7
0.1
0
0.1
0
0.1
3.7
4.2
4.2
0.5
4.5
4.4
4.8
0.3
^30
3.3
3.2
3.1
0.2
2.9
2.2
2.7
0.7
3.7
3.4
3.7
0.3
2.8
2.3
2.5
0.5
3.4
3.7
3.5
0.3
3.7
3.9
3.9
0.2
- 39 -
-------
of previous studies from real spill situations precluded inclusion of
lower molecular weight n-paraffins . N-paraffin indices selected
for further evaluation in the final selection of tags included.
P-l
'20
Zn-Paraffins C=20
C=40
P-7
J30
Zn-Paraffins
C=20
C=40
P-2
'21
Zn-Paraffins C=20
C=40
P-8
'31
Zn-Paraffins
C=20
C=40
P-3
'24
Zn-Paraffins C=20
C=40
P-9
EC
20
C21 + C22
C30 + C31 + C32
P-4
'25
Zn-Paraffins C=20
C=40
P-IO
21
3Q
ZC24 + C25 + C26 + C27
P-5
'26
Zn-Paraffins C= 20
C=40
P-6
'27
Zn-Paraffins C=20
C=40
Indices P-l - P-8 were selected primarily because they appeared
to discriminate fairly well among the unweathered test oils. Indices
P-9 and P-10 contain several n-paraffin compounds in the numerator
and were included to determine if such tags had less variance (from
experimental error in G.C. measurement) and were better discriminators.
Thus, a total of 26 indices were selected for further
evaluation with the complete set of weathering test data. These are
summarized in Table 16. A complete tabulation of these 26 indices for
the weathered and unweathered samples used in this study is presented
in Appendix D. This data provided the basis for developing the final
fingerprint function for the 8 different oils used in the study. The
techniques used to obtain these fingerprint functions are described in
the following sections.
40 -
-------
TABLE 16
Data Format Listing
PRELIMINARY FINGERPRINT INDICES
Index
Formula
Kumerical
-Value, r IndexL jorimila
Numerical
Value
V
Ni
ECnH2n-6
£Aromat ic
£CnH2n-6
EAromatics
£CnH2n-10
EAromat ic
£CnH2n-10 c=
EAromatic
ECnH2n-14
EAromatics
£CnH2n-16
EAromatics
£CnH2n-l 8
EAromatics
19
21
s
26
C2?
^ Paraffin
c=20
c=40
EnParaffin
.„
c=40
EnParaffin
InC30+C31+C32
£n C20+C91+C22+C3CH-C31+C32
CnH2n-6
CnH
2n-18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthenes
Paraffins
X10 £ (P + N)
£ 3 Ring Naphthenes
£(P + N)
£ 4 Ring Naphthenes
£(P + N)
£ 5 Ring Naphthenes
"13 £(P + N)
Sample History
Oil Type -
Origin -
Weathering Time, days -
Weathering Temperature, °? -
Mixing Condition -
i
18
:=20
£21 c=20
&Paraffinc=40
C24 2Q
EnParaffin .-
Q=4u
EnParaffin .„
c=40
C26 C=2Q
EnParaffin ,n
c=40
- 41 ~
-------
n-PARAFFIN DISTRIBUTION OF UNWEATHERED SAMPLES
n 111 • •; i • i
C20 C21 c22 c23 c2A c25 c26 c27 c28 c29 c30 c31 c32 c33 c34 c35 c36 c37 c38 c39
n-Paraffin Carbon Number
-------
g
-H
4J
U
n)
n
^ 16
5 ,,
a, 13
:" 1 A
o 14
6
A
3
2
1
1
-f-
H
--
i
•
FFH
;
4 X^
1
i _,±
. .
1 1
HI i. ;
FIGURE 5
n-PARAFFIN DISTRIBUTION
TIA JUANA MEDIUM CRUDE
-
1 '
V
*l
i i L
:
I-
I
i
Range of Weathered
Tla Juana Medium Samples (6 Runs)* »
^ange of Unweathered
Tla Juana Medium Samples (6 Runs)* >
1"
:
•
•
V*
. 1
i i
;
i :
-
rrn
•' I
i
i
• 1 i ,
1
'
— i — _
C21 C22 C23
C25 C26 C27 C28 C29 C30 C31 C32 C33
C35 C36
r»-Paraf£ln Carbon No.
-------
3
4J
« 18
X
I 16
o 15
ID
4> 2 «
JN CO
n 13
CM
"3 10
5 9
«j Q
4-1
•a 7
*H
5
4
3
2
1
FIGUKE
'
n-PARAFFIN DISTRIBUTION
LAGO CRUDE OIL
— MM
•
•
.
:
i
.__
!
*
^
»
I
J
•
r
•
rr
g
»
1
•
A
> f
{I
i
1
1
$
, b
i'l
>
• • unweathered samples
^" weathered range
(6 samples)
•
•
,,,.L_
1 —
4
i
-
:±
4
L-
'
»
I..1J.
[-
20
22
24
26 28 30
n-Paraffin Carbon No.
32
34
38
-40
-------
23
22
21
20
C "
5
n is
o
2 17
to
aa 16
-1 * 15
.> >w
V1 ° 14
0)
1 g> 13
n)
« 12
0
u* 11
o 10
«N
3 9
5 8
** 7
4J
§ 6
1 5
FIGURE 7
n-PARAFFIN DISTRIBUTION
GRAND ISLE MIX CRUDE OIL
•
\
•
.
"I
4^
•i
j
•
•
.
J
i
»
i
•
t
i
.
/^
\^
.
.
"I
|
:
.'
t-
i
D
1
.
1 1
"
••
(i
! ~^
•I
cud
iweathered
fathered range
i samples)
•
-
*/
i
t
i
.
*'
\
i
!
'I
1
"22
"2A
28 30
n-Paraffin Carbon No.
J38
-------
o
0)
£ 18
I 17
WH 16
o
«. 15
o 13
-*
^ 12
Sll
u 8
•a
•H 7
•
* 6
5
4
3
2
1
-
t
---
J
1
1
.I
FIGURE 8
n-PARAFFIN DISTRIBUTION
NIGERIAN CRUDE Olt
4 •»
Fffl-FFi.
'•
••
1
i
un we at he red
weathered range
(8 samples)
•
I
•
1 .
;
i
1
1
i
:
C20 C22
'24
'26 ^28 U30
n-Paraffln Carbon No.
'34
'36
'38
-40
-------
i
18
17
16
13
14
12
11
10
.
1 I
-
0
I-U
1
•T
o4/
o
n-PARAFFIN DISTRIBUTION
ZUITINA CRUDE OIL
-«t
•
H n
<*$
i
o^
1 un we at he red
unweathered
weathered range
(8 samples)
$
1-
^ -1
of ^
:20 C22 C24 °26 C28 C*> °32 ^34 C36 C38
^40
n-Paraffin Carbon No.
-------
I
p
-
I
:
;•
o
I
•
1
23
97
21
20
19
18
17
i *
J.W
15
13
12
11
10
9
,
5
1
-
.
I
:
*
t
I
-
• '
-
n-PABAf
NO.
•
-
I
'•
'I
*J
r
'*
4
t
I
'
FIN
— i — i —
!
UKJC
JLU
DISTRIBUTION
FUEL OIL
I
3±
.
.
I
I
1
1
•
1
t
-
• " unweathered
J- weathered rar
(8 samples)
.1
^u
A
i
,1
,
•«e
—t—
i
'
•
'22
'26 28 30
n-ParaffIn Carbon No.
"32
"36
'38
-------
20
19
18
3 "
tj 16
£ 15
? 14
PH
•n 13
&
01 It.
00
§ u
M
0 10
-3-
c 9
8 8
« 7
d
M 6
u 5
•a ,
•H 4
111
3
FIGURE 11
n-PARAFFIN DISTRIBUTION
NO. 5 FUEL OIL
•
>r
V
-
'I
C20 C22 C24
i
1
.
"I
4
'
- unweathered
* weathered range
(8 samples)
C26 C28 C30 °32
I =
1
C34
1
i
I i
C36
.:
C38
j
C4(
n-Paraffin Carbon No.
-------
^ _ _
25
«
§20 -u -i
•H
U
O _ij
«
M
PN
o
•H
44
§ is _ ::-:
3
*
M
. .
4J
•S, 10 .
« I". .-
3
;
5 1 \ •.
-
'EiEE1""
•— — - [• — -
1
*
i A
i —
?J
•i'
•
J |:::
. -S..n^.
1 '
FIGURE 12
POLYNUCLEAR AROMATIC COMPOUND DISTRIBUTION
TIA JUANA MEDIUM CRUDE
1
A*
> '
-
.
.
— i
1,
1 i
— ^T4-i 1 1 14-
; ttttt
4
i
.
itr
-m
red Sample
ange
t samples)
r
•
- Hfiitttt
Weathered Samples
--
ange
8 samples)
.
I «
la
-------
FIGURE 13
Ort
25
8
•H
*
M
"*• 9n
20 --
Ln
I-1
P
£
d
•*15
|
^P
£
10
5 ,
1
1
:
i
|
i
=
PQLYNUGLBAR ABMUTIC COMBOUKD DISTRIBUTION
UNWEAIHEBEIL-QILS
in
=
•
tr
1 1
x
. f
^ ^_
i k
:
. -j-j-
u i
~^" J
0^
±
"
T --
±t±t±
i
Tie Juana Medtum
Lago
Nigerian
Grand Isle Mix
Zuitina
No. 5 Fuel Oil
No. 4 Fuel Otl
No. 2 Heattag Oil
m
-4-4-4-
0
«
X
D
a
4
•
CaH2n-il
-------
t
32
« 2A
u
s
a
•H
« 16
4J
i
*
B
•:-_
-
•
*
•1
FIGURE 14
PCLYMUCLKAR AROMATIC COMPO
LAGO CRUDE
1
•
r
t
UNO DISTRIBUTION
OIL
•I
-
. J
— r — i — '
I
I
•
-
r
I
i
. • unweathered
J™ weathered range
(5 samples)
"
1
i
1
-
LO
:'
L8
-------
.
FIGURE 15
POLYNUCLEAR AROMATIC COMPOUND DISTRIBUTION
GRAND ISLE MIX CRUDE
. " unweathered
•
:
H
•
1
-
weathered range
(8 samples)
I
-------
s
32
g
U 23
16
4J
i
•H
FIGURE 16
POLYNUCLEAR AROMATIC COMPOUND DISTRIBUTION
NIGERIAN CRUDE OIL
!
I
•a
i
—
*
-
i
1
•
'
i
_.._
i-
'.i
unwea Chared
weathered range ,
(8 samples)
; T
: :
'
1
i !
:
i
f
-1
i '
T
_
i
1
|
Fffl
r-T1
- ! .1"
i
, i
.
!
1
i
1
;
i -! !
12
L6
Cn
-------
\J\
?•'.
•
.
•
•H
3 16
FIGURE 17
POLYNUCLEAR AROMATIC COMPOUND DISTRIBUTION
ZUITINA CRUDE OIL
-—
i
1
•
1
:
I
.*
I
. - unweathered
£ » weathered range
(8 samples)
.1
±
.
-4 -U
±s
. '
4J
!
I
\
_
j
.
•
\
1
LO
I'
:,
:
-------
a
>'
I
H
•a
32
24
16
8
o
t -
.i
«
I
4
FIGURE 18
POLYNUCLEAR ARfMATtG COMPOUND DISTRIBUTION
NO. 2 FUEL OIL
•
•
»
1
•
t
. • unweathered
t- weathered range
(6 samples)
.
»
-
1
i
V
It
i
I
6 8 10 12 14 16 18
C H
a Zn-l
-------
•
•
16
FIGURE 19
POLYNUCLEAR AROMATIC COMPOUND DISTRIBUTION
NO. 4 FUEL OIL
1
1
1
-
!
i-
i
4
]
-
•
f
-J_,
i
= weathered range
(8 samples)
,
-
-
C H-
n 2
-------
I 32
•
s
n
V
S 16
i
;
[
FIGU1E 20
POLTWUCLEAR AROMATIC COMPOUND
NO. 5 FUEL OIL
•
J
*
I
•
• >
i
j
T
i
i
DISTRIBUTION
•t
I-
1
unweatherad
weathered range
(6 samples)
1
i
|
=
1
I
••
I C H-
n 2n-i
-------
7.2 Development of the Final Fingerprint
Indices Using Discriminant Function Analysis
The twenty-six preliminary indices selected in Section 7.1
were then subjected to Discriminant Function Analysis to select the best
discriminators for the test oils used in this program. Discriminant
function analysis is a multivariate technique for differentiating between
two groups of populations . It is employed to estimate a function which
will combine the variables of interest (compound indices) in such a way
as to produce a function which provides the best discrimination between
the two populations. For example, for two crudes, one may write
Crude 1 Y'L = &l Xn + 9 Xg + ...... anXnl (1)
Crude 2 Y2 = ai X12 + a/X22 + anXn2 ^2)
D = Y i ~ Y2
where X '= characteristics (preliminary fingerprint indices).
i = particular measurement (specific test run).
j = group (Crude or Fuel Oil).
a = Coefficients which give proper weight to the final compound
indices in the final discriminant function.
D = the discriminant function.
The discriminant function attempts to find the value of the
coefficient that will give the maximum relative difference between the
two overall responses YI and Y2, i.e., the highest resolution between two
oils. In the process of determining the discriminant function, the
analysis technique selects the best characteristics (compound indices)
which maximize the difference in the two populations, while discarding
those characteristics (compound indices) that reduce the resolution of
the function.
In the use of the discriminant function technique to distinguish
among the oils used in this program, runs conducted at different weather-
ing conditions (as well as unweathered oils) were used to represent the
population (replicates) of a specific oil. The fact that the laboratory
simulated weathering did not notably affect the preliminary selected
indices justified their use as replicates (1). Each test oil in the pro-
gram was used as a separate group in the analysis,
(1) The effects of laboratory simulated weathering on the final compound
indices selected in the discriminant function were minimal. Weather-
ing data on all test oils (Tia Med. Crude, No. 2 oil and No. 5 oil)
are summarized in Appendix C.
- 59 -
-------
The general approach used to develop the discriminant function
in this program is summarized as follows :
• Selection of the most definitive compound indices (from
array of preliminary indices) by the application of a
step-wise multiple regression technique. This is a
statistical analysis, which, on the basis of a variable
contributing to the goodness of the fit, elects the
significant variables (compound indices) from those
considered and then fits them to the data by the method
of least squares.
• Calculation of the discriminant function to discriminate
between two groups (test oils). This involves solving
a set of simultaneous equations corresponding to the two
groups of oil samples being compared. For groups 1 and
2 (equations 1 and 2) the following simultaneous equations
must be solved:
a = "l ZX1 + W2 + 33 SX1X3 + ' ' ' < 3n ZXlXn
-------
After applying the discriminant function analysis to the oils
studied in the program, the following five variable (index) general
function was obtained for the best discrimination.
^^L^j
+ a,
EParaffins
+
EParaffins| 20
40-1
£5 Ring Naphthenes
E1 + 2 Ring Naphthenes
15 + 6 Ring Naphthenes
+ a.
(8)
Equation (8) describes a function which gives the best overall
discrimination between all pairs of oils used in the study. It provides
a means of enhancing the differences in fingerprint indices that exist.
The coefficients used in equation (8) were obtained in the analysis and
depend on which two oils are considered at a time. They are summarized
in Table 17.
7.3 Estimation of the Probability of Oil
Misclassification Usinft the_Disj^ri_mi_nant Function
The probability of misclassification in any combination of pairs
of test oils used in the program was determined using the discriminant
function data and the following relationships (6) :
P =
m
(9)
and
A R (1 - R )
n + n - p -
(10)
where P = probability of misclassification
m
= normalized probability function
s = the standard deviation as defined above
= nl n2
- 61 -
-------
TABLE 17
a\
I
SUMMARY OF COEFFICIENTS FOR DISCRIMINANT FUNCTION
Oil
Comparisons
1-2
1-3
1-4
1-5
1-6
1-7
1-8
2-3
2-4
2-5
2-6
2-7
2-8
3-4
3-5
3-6
3-7
3-8
4-5
4-6
4-7
4-8
5-6
5-7
5-8
6-7
6-8
7-8
al
V
Ni
-0.0935
0.1219
0.1315
0.1292
0.0503
0.1673
-0.2057
0.1103
0.0567
0.0569
0.0510
0.0394
-0.0454
-0.2918
-0.4824
0.1169
-0 . 1062
-0.1014
-0.1060
0.1243
-0.0662
-0.1242
0.1368
-0.0633
-0.1135
-0.0675
-0.0565
-0.0928
S2
I P
I P + N
0.0377
-0.0001
-0.0045
-0.0047
0.0002
0.0105
0.0129
0.0032
-0.0251
-0.0201
0.0003
-0.0378
-0.0682
-0.0124
-0.0311
0.0057
-0.0065
-0.0024
0.0345
0.0085
0.0228
0.0049
0.0067
0.0284
0.0043
-0.0053
-0.0018
-0.0270
a
I 5 Ring Naphthenes
E P + N
-0.3138
-0.0722
-0.0708
-0.0934
0.0202
0.0780
-0.3672
0.0956
0.0003
0.0780
0.0685
0.2135
-0.0272
-0.0516
0.0259
0.0321
0.1669
0.0479
0.3679
0.0193
0.0214
0.0218
0.0044
-0.0228
0.0234
0.0316
0.0019
-0.0278
A
C20
£ Paraffin J- 2°
0.0554
-0.0708
-0.0064
-0.0035
-0.0024
-0.1002
0.1910
-0.0423
0.0626
0.0187
0.0007
0.0088
0.1978
0.0771
0,0700
"0.0073
-0.0010
0.0198
-0.2468
0.0062
-0.0500
0.0234
0.0120
-0.0534
0.0198
0.0004
0.0085
0.1115
a
I 1 Ring + 2 Ring Naphthenes
£ 5 Ring + 6 Ring Naphthenes
-0.0186
-0.0934
-0.0138
-0.0129
0.26 x 10"11
-0.0070
-0,0248
-0.0049
0.0001
0.0084
0.70 x 10
0.0072
-0.0033
-0.0069
0.0007
-0.37 x 10
0.0028
0.0024
0.0429
-0.72 x 10
-0.0019
0.0011
-0.88 x 10"11
-0.0037
0.0012
0.9 x NT* J
0.16 x 10
-0.0017
R2
0.9352
0.9979
0.9956
0.9943
0.9990
0.8019
0.8719
0.9842
0.9893
0.9930
0.9949
0.9355
0.9263
0.9843
0.9846
0.9974
0.9788
0.9979
0.9169
0.9966
0.9855
0.9964
0.9975
0.9844
0.9969
0.9920
0.9996
0.9033
S.E.E.
0.1423
0.0264
0.0380
0.0434
0.0181
0.2553
0.2059
0.0779
0.0642
0.0541
0.0443
0.1640
0.1685
0.0755
0.0758
0.0307
0.0890
0.0275
0.1762
0.0352
0.0737
0.0361
0.0306
0.0780
0.0340
0.0548
0.0121
0.1900
R = Overall Correlation Coefficient
S.E.E. = Standard Error of Estimate
-------
n and n = number of replicates in each oil population
R = overall correlation coefficient
p = number of parameters used (5 for discriminant function)
The results of these calculations are summarized in Table 18.
All possible pairs of test oils considered are shown to be
clearly distinguishable from each other. Most pairs have a vanishingly
small probability of misclassification; a few are somewhat more difficult
to distinguish, but still have extremely low probabilities of misclassi-
fication. The discriminant function developed for this set of oils is
thus capable of discriminating between any two oil populations used in
this study, even after these oils have been weathered (in laboratory
simulators) for as long as 21 days under a variety of weathering condi-
tions .
The same general procedure was used to estimate the probability
that two oils (or populations of replicates of these oils) were the same.
This was done by taking five replicate unweathered and 5 replicate
weathered (different weathering conditions) samples of the same oil
(Tia Juana Medium, or Oil 1 in our test) and comparing them using the five
best indices (as well as all other preliminary indices) in the stepwise
multiple regression program. The results showed that the two populations
were indistinguishable. Multiple regression statistics for this compari-
son are presented in Appendix E.
7.4 Estimation of Confidence Levels for Oil
Classification Us ing J3onferroni "t" Statistics
An alternate method of estimating the probability of misclassi-
fication of two oils (confidence of correct classification) is the
Bonferroni multiple "t" equation which considers all five final compound
indices and their variances simultaneously. The Bonferroni equation may
be written in the following form (5):
with p = i - <*
Both weathered and unweathered runs were used as replicates
for comparison.
- 63 -
-------
TABLE 18
PROBABILITY OF
MISCLASSIFICATION OF PAIRS OF OILS
Oil Comparison
1-2
1-3
1-4
1-5
1-6
1-7
1-8
2-3
2-4
2-5
2-6
2-7
2-8
3-4
3-5
3-6
3-7
3-8
4-5
4-6
4-7
4-8
5-6
5-7
5-8
6-7
6-8
7-8
2
R
0.935
0.998
0.996
0.994
0.999
0.802
0.872
0.984
0.989
0.993
0.995
0.935
0.926
0.984
0.985
0.997
0.979
0.998
0.917
0.997
0.985
0.996
0.997
0.984
0.997
0.992
0.999
0.903
s
"D
0.144
0.027
0.039
0.045
0.019
0.238
0.199
0.083
0.068
0.058
0.047
0.171
0.173
0,079
0.073
0.030
0.093
0,028
0.178
0,037
0.077
0,038
0,032
0,082
0.036
0,057
0.013
0.190
y
3.46
18.26
12.71
11.10
26.50
2.10
2.51
6.05
7.32
8.58
10.58
2.92
2.89
6.36
6.30
15.52
5.39
17.31
2.81
13.56
6.48
13.24
15.51
6.09
13.96
8.70
39.03
2.63
Pm
<0.0003
Nil
Nil
Nil
Nil
0.017
0.006
Nil
Nil
Nil
Nil
0.003
0.003
Nil
Nil
Nil
Nil
Nil
<0.0025
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
<0.0043
Number
1
2
3
4
5
6
7
8
Oil Identification
Tia Juana Medium Crude
Lago Crude
Grand Isle Mix Crude
Nigerian Crude
Zuitina Crude
No. 2 Fuel Oil
No. 4 Fuel Oil
No. 5 Fuel Oil
- 64 -
-------
where a'2k = the upper -~ percentile points of the t distribution
y. = normally distributed random variables (indices)
U = means of variables
i
' v-. = degrees of freedom
s. = standard deviation of variables (indices)
Ct
a = probability, a' = reduced probability = —
k = number of variables (indices)
The upper •— percentile points of the t distribution (t . )
may be approximated by the following expression (Pearson's approxima-
tion) (5) :
where g" = upper 100a! percent point of the normal N(0,l) distribution.
The steps required in applying the Bonferroni equation to esti-
mate the confidence of distinguishing between two oils with certain
characteristic indices y^ (based on the five indices developed for the
oils in this program) are as follows:
• Select an overall probability level (a) which one would
want the comparison to pass.
ct
• Calculate the reduced probability level (a1 = -^ where k =
number of discriminators).
n'
• Obtain t either from tables or Pearson's approximation,
i.e., equation (12). For five indices, y = k - 1 = 4 (this
case).
• Obtain an estimate of the standard deviation of each index
(si) from replicate analysis.
• Calculate ta s.^^ for the five indices for the suspect oil
(Oil 2). Yi
- 65 -
-------
• Calculate the acceptance intervals for the five indices,
a'
i.e., y. + t s. for suspect (Oil 2).
• If y^L (U-) for the spill source (Oil 1, for example) lies
outside any one of the five intervals calculated alone fojr
the suspect:, the hypothesis that the oils are the same is
rejected. The probability of rejection (confidence that
are different) is the originally assumed level for the
calculation.
• By trial and error, different probability levels can be
assumed to determine the cut-off point. For example, if
a was assumed to be equal to 0.01 and all five indices for
the spill oil (Oil 1, for example) were found to be outside
each acceptance interval for the suspect oil (Oil 2, for
example), the procedure could be repeated for lower assumed
values of a (higher confidence levels) until only one index
remained outside its respective acceptance interval.
The above technique was applied to the comparison of two cases
where the oils in the program were fairly similar (as shown in Table 18
Section 7.3), Oils 1 and 7 and Oils 1 and 2. The assumed probability
level for the calculations was a = 0.01. Results are summarized as
follows :
Results of Bpnf erroni Technique
Case 1 Oil 1 vs. Oil 2
k = 5, a = 0.01 (assumed value), a' = 0.001
Ni/V
y± y± a. Yi « t^ v± - t:
Index (Oil D (Oil 2) * !i __ S_i !i.
7.79 4.6 0.77 5.37 3.83
^Paraffins 34.13 17.3 13.48 30.78 3.82
IP + N
Z5 Ring Naphthenes 2.78 4.28 1.89 6.17 2.39
IP + N
nC20 . 2Q 14.87 11.0 1.21 12.2 9.79
-n Paraffins/,Q
11+2 Ring Naphthenes 11.62 5.52 10.17 15.7 0
£5+6 Ring Naphthenes
- 66 -
-------
Case 2 Oil 1 vs. Oil 7
k = 5, a = 0.01 (assumed value), a' = 0.001
yi
.a' a*
s
S s
Index (Oil 1) (Oil 7) i i i
N1/V 7.79 6.8 0.77 6.03 7.57
^Paraffins 34>13 35<1 13.48 21.6 48.6
E5 Ring Naphthenes 2.78 i-50 1.89 3-39 0
£P '+ N
££2Q _____ 2Q 14.87 19.3 1.21 18.1 20.5
zn Paraffins//n
40
Ring Naphthenes 11.62 29.0 10.17 18.8 39.2
£5+6 Ring Naphthenes
The results of the two examples given indicate that Oils 1 and
2 and Oils 1 and 7 are significantly different at the assumed confidence
level of 99.0% (i.e., three indices for Oils 1 and 2 and two indices for
Oils 1 and 7 are outside their Bonferroni acceptance limits) . The pro-
cedure could have been repeated assuming a somewhat higher confidence
level (lower probability) until only one index was outside its respective
Bonferroni acceptance limits in each case. This would give the maximum
confidence level of the oils being different.
7.5 Summary of System Application
In the application of this system to real spill situations,
the following steps should be taken:
• Analyze replicate samples of a weathered oil spill source
and all suspect sources as described in Section 6.
Initially, we recommend at least five replicates.
• Select (about 26) preliminary compound indices that appear
to aid in the discrimination of oil pairs by inspection of
the resulting data. The application of individual "t" tests
in considering potential indices is useful*.
* It is difficult to estimate how widely applicable the 26 preliminary
and final five compound indices selected for the oils used in this
program are for other oils of different origin and character. This
would have to be evaluated with other oils. Therefore, the general
approach of preliminary, then final, index selection is recommended.
- 67 -
-------
• Obtain the best discriminating indices by the application
of discriminant function analysis as outlined in Section
7.2. (In the development of the discriminant functions,
only the spilled oil sample(s) and each suspect source
sample(s) are compared in pairs, i.e., it is not necessary
to compare the suspect oils with each other.)
• Calculate the confidence levels that suspect oil sources
are different from the spilled oil. Confidence levels for
two oils being different can be obtained by either of the
methods described in Sections 7.3 and 7.4, respectively.
However, the Bonferroni technique appears more suitable
to the oil spill identification problem.
• If any of the suspect oils does not develop a discriminant
function, it will indicate that it is the same as the spill
source. An estimate is then made of the probability of the
spilled oil and the prime suspect being the same by com-
paring their discriminant indices and variances in their
me as ure ment s *.
7.6 Discussion of Results
and System Lindtations
The results of this study indicate that certain specific (or
groups of) chemical compounds, which are present in crude oils and re-
fined oil products, can be used to distinguish between pairs of oils
even after they have undergone extensive laboratory weathering. These
chemical fingerprint indices include weight concentration ratios of V/Ni
and high molecular weight (BP >400°F) paraffins, naphthenes and poly-
nuclear aromatics. The five indices selected by discriminant function
analysis for distinguishing among the eight different oils used in this
study are specific to these oils—other specific indices may be preferred
for the comparison of another group of oils. However, the methodology
developed in this identification system should be generally applicable
and should always select the best group of tags.
Laboratory weathering can only provide a limited simulation of
the real weathering process. Thus, further studies are needed to test
the system's ability to handle oils which have been weathered in the real
marine environment. In addition, only a limited number of oils were
tested in this program. The system should thus be evaluated with other
oils of different physico-chemical nature.
Until a complete library of indices for all the World's crude oils
and refined products is available, it would be virtually impossible
to preclude the possibility of other oils having the same finger-
print as an apparent suspect.
- 68 -
-------
At the present time, several replicate analysis on spill and
suspect sources are required to make the results statistically reliable.
A minimum of five replications, using each oil involved in a spill situa-
tion is recommended. This limitation would be relaxed as more data and
experience in processing and analyzing other oils are acquired such that
analysis variances could be reliably assumed.
The system, as presently developed, does not have the cap-
ability to distinguish between weathered crude oils and weathered
residual fuels as general classes of petroleum products. However, it
may distinguish between a specific crude and a specific residual fuel
(as it does between two different crudes). Further work is required to
give the system the capability to make this distinction. This would in-
volve the inclusion of more volatile n-paraffins (<£'2Q^ in the tag
responses.
The Bonferroni technique appears to be the preferred method of
estimating statistical condifence levels that two oils are different.
- 69 -
-------
SECTION 8
GENERAL EFFECTS OF LABORATORY WEATHERING
Although the chemical fingerprint indices developed in Section
7 were shown to be virtually unaffected by laboratory simulated weather-
ing, significant changes in non-index oil components did take place. It
is instructive to review these changes for they indicate that considerable
"weathering" was affected in our laboratory simulation facility. Gen-
eral physical changes and changes resulting from the weathering processes
of evaporation and oxidation are described in the following paragraphs.
8.1 General Physical Changes
Certain physical changes in the character of weathered oil
samples were observed during the simulated weathering experiments. Crude
oils generally became more viscous, and frothy with some localized dis-
colorations. This can be seen in Figure 21 which shows the physical
appearance of a typical crude oil (Tia Juana Medium) before and after 10
days of simulated weathering in the test facility described in Section 5
of the report. These changes were generally seen to a greater or lesser
degree in the other crudes. Typical changes in a residual fuel under
test are described in Figures 22 and 23.
The No. 2 distillate fuel, on the other hand, showed a somewhat
different change in physical character during the weathering process.
As indicated in Figures 24 and 25, the No. 2 fuel oil appeared to dis-
perse at the surface in the sea water in the form of small globules after
about 10 days of weathering.
These general physical changes indicated that significant
weathering was effected by our test facility. Further evidence of wea-
thering changes is presented in the following paragraphs.
8.2 Evaporation Effects
The effect of evaporation on the composition of a crude oil
(Tia Juana Medium) and No. 4 and No. 5 residual fuel oils is shown in
Figures 26, 27 and 28 respectively. A considerable loss of volatile
components is indicated by the decrease in boiling point range for each
weathered oil. G.C. distillation data obtained for weathered oil samples
at 10 and 21 day intervals (No. 4 and No. 5 oils) show little difference
in boiling point composition indicating that virtually all the light ends
were lost within the 10-day weathering interval. The weathering simula-
tor thus provided for significant evaporative weathering effects.
- 71 -
-------
FIGURE 21
CRUDE OIL BEFORE AND AFTER SIMULATED WEATHERING
M
- 72 -
-------
FIGURE 22
NO. 5 FUEL OIL BEFORE WEATHERING
- 73 -
-------
FIGURE 23
NO. 5 FUEL OIL AFTER WEATHERING
- 74 -
-------
FIGURE 24
NO. 2 HEATING OIL BEFORE WEATHERING
- 75 -
-------
FIGURE 25
NO. 2 HEATING OIL AFTER WEATHERING
- 76 -
-------
FIGURE 26
EFFECT OF EVAPORATION ON BOILING POINT
DISTRIBUTION OF TIA JUANA MEDIUM CRUDE OIL
C
•H
00
C
o
PQ
1200
1100
1000 -
900-
800
700
600 -
500
400 :
300
200
100
100
Volume % Distilled
- 77 -
-------
FIGURE 27
EFFECT OF EVAPORATION ON BOILING POINT
DISTRIBUTION OF A NO. 4 FUEL OIL
1200
1100
days at 80 F
days at 80°F £
Weathered 10
Weathered 21
70
80
90
100
Volume % Distilled
- 78 -
-------
FIGURE 28
EFFECT OF EVAPORATION ON BOILING POINT
DISTRIBUTION OF A NO. 5 FUEL OIL
1200*—
1100
1000
900
-
-
a
r
•H
1
---
! ? h : i
:
Weathered 10 days at 80 F
—5?^ Weathered 21 days at 80°F
Unweathered
5001——
.
•
0 0 10 20 30 40 50 60 70
Volume % Distilled
80 90 100
- 79 -
-------
8.3 Oxidation Effects
Significant oxidation was also observed to occur in non-
fingerprint tag compounds during the oil spill identification weathering
tests. This can best be seen with reference to Table 19 which shows an
increase in concentration of oxygen bonds in weathered oil samples as
indicated by an increase in infrared absorbance at 1700 cm"1 (the
carbonyl bond) . IR absorbances at 1600 cm'1 (aromatic C-H) and 1375 cm
(-CH3) bonds for each set of samples are also presented for comparison.
TABLE 19
IR ANALYSIS OF WEATHERED OIL SAMPLES (*>+)
Tia Juana (Medium) Crude
Ab s o r b an ce (Arbitrary Units)
; IJ~^
(Days) 1700 era 1600 cm 1375 cm
s o r an
Weathering Period -- ; IJ~^ _ \
0 4.0 37.0 36.5 0.108 0.109
10 24.0 35.5 24.5 0.677 0.982
21 28.5 31.5 24.0 0.905 1.186
No. 5 Fuel Oil
0 0 48.0 41.0 0 0
10 14.0 39.0 35.5 0.394 0.466
21 20.5 39.5 35.5 0.518 0.578
* Weathered at 80CF over sea water in presence of UV lamp (on 2
hours/day).
+ IR obtained on crude, dried samples.
Infrared carbonyl absorbances are seen to increase markedly
with an increase in weathering time for Tia Juana Crude and No. 5 Fuel
Oils weathered at 80°F under high water mixing conditions. A slight con-
comitant decrease in the concentration of aromatic C-H bonds (1600 cm-1)
and CH3 bonds (1375 cm"1) after the first 10 days of weathering is also
noted. Thus, it can be concluded that the weathering test facility used
in this study provided the conditions for significant oxidation to occur
even though the selected fingerprint indices were virtually unchanged
during the test.
- 80 -
-------
SECTION 9
REFERENCES
(1) Brunnock, J. V. et al., Journal of the Institute of Petroleum,
Vol. 54, No. 539, p. 310, November 1968.
(2) Esso Research and Engineering Company Proposal to EPA on "Oil
Spill Source Identification," August, 1970.
(3) Hood, A. and O'Neal, N. J., "Advances in Mass Spectroscopy,"
J. D. Walchan, Ed., 1959.
(4) Lumpkin, H. E. , Analytical Chemistry, 30, 321 (1958).
(5) Miller, R. G., "Simultaneous Statistical Inference," McGraw-Hill
Book Company (1966) .
(6) Tippett, L. H., "The Method of Statistics," 4th Ed., Wiley Book
Co., New York, 1952.
(7) U.S. Petroleum Industry Annual Statistical Review, April 1970.
- 81
-------
SECTION 10
ACKNOWLEDGEMENTS
The support given the project by the Environmental Protection
Agency, Water Quality Office and the help provided by Mr. Bernard
Hornstein is acknowledged with sincere thanks.
The design and construction of the laboratory weathering
simulators was conducted with the help of Mr. H. C. Tsien of Esso
Research's Mechanical Engineering Department.
The samples were prepared and analyzed under the supervision
and direction of Dr. Roy Pancirov of Esso Research's Analytical ana
Information Division.
Mr. Howard Oakley and Mr. Alan Crawford of Essc- Research pro-
vided considerable help in the treatment and analysis of data.
Mr. Ralph Brown of Esso Research's Analytical and Information
Division provided valuable consultation in mass sn
Mr. Leonard Berkowitz provided valuabl
the analysis and treatment of data.
- 83 -
-------
Appendix Description
A Simple Separation Material Balance Data
B Summary of Oil Fingerprint Data
C Gas Chromatic Distillation Data
D General Sample Statistics
E Comparison of Weathered and Unweathered Oils
F Sample Calculations for Gas Chromatogram
- 85 -
-------
APPENDIX A
SAMPLE SEPARATION
MATERIAL BALANCE DATA
Composition in Weight %
Computer*
Code No.
loooooj *'
100001
100002
100003
100004
100005J
110559
121551
110801
110809
121801
121809
200000
210559
221551
210809
221809
300000
310559
321551
321809
310809
321801
400020
410559
421559
421551
410801
421801
410809
421809
500000
510559
521559
510801
521551
510809
521809
Analytical No.
524222
524240
524242
524290
248450
248423
248432
578621
584910
525317
584943
525402
578630
578607
578624
525320
525405
578646
578608
598578
581114
584911
24807
578635
578606
578623
598576
588718
248406
524236
581106
578633
578605
578622
248418
586030
524231
525403
Oil Identification
Tia Juana Medium
Crude Oil
Lago Crude Oil
Grande Isle Mix
Crude Oil
Nigerian Crude
Oil
Zuitina Crude
Paraffins
+
Napthenes
46.0
48.2
47.7
47.4
44.1
46.1
44.6
44.0
52.0
50.3
44.8
50.9
39.8
40.7
42.0
40.7
27.9
73.0
67.7
62.4
70.1
62.2
60.5
61.2
64.3
64.0
61.9
61.7
57.2
62.6
63.7
66.1
73.5
72.4
67.9
71.7
70.3
71.7
\romatics
21.6
19.5
20.8
18.6
20.5
21.4
24.4
10.1
20.2
20.3
20.3
20.4
21.8
21.8
21.2
23.7
L2.9
16.1
19.8
22.1
13.9
17.4
20.2
20.7
24.1
21.1
23.1
22.8
20.5
20.7
20.8
12.1
14.0
13.6
11.1
13.5
14.4
14.7
Polars
19.3
18.4
20.4
21.5
26.5
24.1
28.2
38.3
20.1
18.4
28.5
26.8
24.7
22.6
22.5
27.8
49.2
12.3
11.2
15.1
14.8
13.6
17.4
10. 6
10.8
11.3
14.0
13.5
20.8
14.2
14.3
15.2
11.2
10.9
17.0
14.3
12.2
12.2
Pent ane
[nsolubles
9.0
10.9
9.4
10.9
8.8
9.6
11.4
10.4
10.1
10.1
10.3
10.0
15.5
12.7
12.3
12.7
13.0
1.2
0.4
0.6
0.7
0.6
0.7
1.0
0.4
0.4
0.3
0.4
0.1
0.3
0.5
3.1
2.3
2.3
1.8
1.5
1.6
1.6
E Fraction
93.9
97.0
97.9
98.4
99.9
101.2
108.6
102.8
102.4
99.1
103.9
108.1
101.8
97.8
98.0
114.9
103.2
102.6
99.1
100.2
99.5
93.8
95.8
93.5
99.6
96.8
99.3
98.4
98.6
97.8
99.3
96.5
102.0
99.2
97.8
100.0
98.5
100.2
* Computer Code Nunber Translation .1. .10. .80.
! 1
Oil Type-
**Repllcate unveathered crudes.
Tt
""C—Mix Condition (9-High, 1-Low)
Weathering Temperature, °f
Weathering Time, Days
- 87 -
-------
Composition in Weight %
Computer
Code No.
600000
610559
621559
621559
621801
621809
610801
610809
700000
7 10559
721551
710809
721809
721801
710801
aooooo
810559
821559
821551
810801
810809
82180!
821809
Analytical No.
577727
578610
578626
578628
248416
581110
588723
525324
578650
525301
598582
525325
525410
248410
588724
578609
578626
598579
588721
524239
248110
581104
Oil Identification
No. 2. Heating
Oil
No. 4 Fuel Oil
No. 5 Fuel Oil
Paraffins
+
Napthenes
49.7
57.8
64.5
65.8
62.9
65.6
63.8
59.6
63.2
61.0
62.8
65.1
67.2
62.4
66.8
64.2
61.7
53.8
59.8
58.5
54.8
61.5
roroat ics
46.6
39.5
29.7
30.2
23.3
27.4
27.7
35.3
26.2
26.0
22.8
25.8
22.4
25.4
20.5
20.4
20.6
24.1
23.5
23.1
22.1
20.6
olars
0.0
1.3
2.6
2.6
12.3
5.6
6.9
3.6
8.6
11.6
13.4
7.7
9.2
10.6
9.6
12.1
11.9
21.3
14.0
14.4
20.7
16.4
Pentane
nsolubles
0.2
0.02
0.2
0.2
0.2
0.2
0.5
0.8
1.0
1.2
1.1
1.4
1.3
1.3
1.2
5.8
5.9
5.4
b.l
1.1
5.8
5.8
E Fraction
96.5
98.5
97.0
102.8
98.7
98.8
98.9
99.3
99.0
99.8
99.6
100.0
100.1
99.7
98.1
102.5
100.1
104.6
103.4
97.1
103.4
103.3
- 88 -
-------
APPENDIX B
Computer No. 100001
Analytical No. 526938
Computer
Index Formula
SUMMARY OF OIL FINGERPRINT DATA
Computer
Numerical
Index Formula
Numerical
Value
*1
T2
X3
TA
h
h
J7
1B
J9
'10
Jll
X12
T
~13
h*
115
X16
X17
Z18
V
Ni
S
N
ZCnH?n-6
ZAromatic
ZCnH2n-6 C=^
ZAromatics1"
ICnH2n-10
JAromatic
C=iU
Ll.nHjn-10 c-Jo
ZAromatic
ZCnH2n-14
EAromatics
ZCnH2n-16
ZAromatics
ZCnH2n-18
EArotnatics
ZnParaf fins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
I 4 Ring_Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
I(P + N)
C20 o0
ZnParaffin^=-Q
C21 c_,0
ZnParafiin^=^Q
C24 c ,0
EnParaf f in'"_2Q
C?s C_TQ
InParaffin^^
C26 c_,0
InParaf f inv"_7X
7.7
6.2
21.64
11.40
12.74
8.54
11.43
7.90
8.97
32.33
11.32
6.11
2.50
14.8
11.7
7.9
8.4
6.5
Z19
X20
X21
X22
r23
X24
X25
T26
C27 c_2Q
^Paraffinc=4Q
C30 . n0
SnParaffin1" "~"
c=iQ
C^l . TQ
ZnParaffin .„
c=40
I C?Q+C21+CT^
1 C30+C31+C32
£ C20+Coi-!-C^+e30+C3i+C32
Z C24+C25+C26+C27+C28
I CnH2n-6
- C"H2n-18
E CnH2n-6+ICnH2n-18
CnHn . /
2n-14
E-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - Crude
6.1
3.2
4.6
3.45
1.42
2.40
2.69
12.40
Origin - Tia Juana Medium
Weathering Tiine, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 89 -
-------
Computer No. 100002
Analytical No. 578640
Numerical Numerical
Index Formula Value Index Formula Value
h
12
h
\
h
h
J7
*8
J9
'10
*11
J12
*13
J14
J15
X16
'17
'18
v
i N1
s
N
ICnH2n-6
EAromatic
ECnH2n-6 C=^
EAroraatics^"
ECnH2n-10
ZAromatic
c=20
ECnH2n 10 c=36
EAroraatic
ECnH2n-14
EAroraatics
ZCnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaffins
E (P + N)
Z 3 Ring Naphthenes
I(P + N)
E 4 Ring Naphthenes
r(p + N)
£ 5 Ring Naphthenes
Z(P + N)
C20 . ,0
EnParaffin^=^
C21 r -0
EnParaffin" t"
c=AO
C24 ,„
EnParaffin" t"
c=40
C?s r ,n
r*.»ffin^
C26 ,n
InParaffin^^
7.4
6.2
20.79
12.15
13.16
9. 38
11.65
8.17
8.69
34.92
11.17
6.89
3.30
14.6
11.5
8.0
8.4
6.1
X19
^0
T21
J22
*23
J24
J25
X26
C27 „
^nParaffin"" 'X
c=40
C?0 . .nn
SnParaffin" '"
r=40
C^i ^n
Snparaffin"" '"
c-40
S C?o+C?i-l-C7?
Z C30+C31+C32
^ C20+C?i+C22-i-C30+C3i^C32
L C24+C25+C26+C27+C28
^ CnH2n-6
' CnH2n-18
E CnH2n_6+J:CnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
J-5 Ring+6 Ring Naphthenes
Sample History
5.7
3.6
4.0
3.45
1.42
2.39
2.53
8.10
Oil Tvoe - Crude
Origin - Tia Juana Medium
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 90 -
-------
Computer No. 121559
Analytical No. 578621
Numerical Numerical
Index Formula Value Index Formula Value
h
''
ho
J18
V
Ni
S
N
ECnH2n-6
E Aromatic
ECnH2n-6 C",,
EAromatics""
EAromatic _ ..
ECnH2n-10 c=36
EAromatic
EAromatics
ECnH2n-16
EAromatics
EAromatics
ErjParaff ins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P 4 N)
C20 o0
rnParaffin^"
C21 ,Q
EnParaf fin^'"
EnParaff inc_'0
?^ r 70
EnParaffin" "p
C26 c ,Q
InParaffinc4o
8.0
6.0
24.53
12.9
14.92
10.0
12.07
6.59
3.59
36.17
11.75
6.80
2.69
13.4
11.0
10.0
9.1
6.7
X19
hz
'»
C27 ,0
EnParaffin^J
Cll -,n
EnParaffin^^
E C30+C31+C32
E C2Q+Cn+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
Z CnH2n-18
1 CnH2n-6+ICnH2n-18
CnH2n-14
E-l RinE+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
5.5
4.2
4.2
3.16
1.34
6.84
2.21
10.6
Oil Type - crude
Origin - Tia Juana Medium
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - High mix
- 91 -
-------
Computer No. 110551
Analytical No. 524667
Index Formula
Numerical
Value
Index Formula
Numerical
Value
h
h
h
h
h
ls
ho
hi
Xi2
T
'13
X14
X15
X18
V
Ni
S
N
ICnH2n-6
ZAromat ic
£CnH2n-6 ^°
EAroraa tics'"
ZCnH2n-10
EAromatic _2
EAroraat i c
EAromatics
ECnH2n-16
EAromatics
EAromatics
ZnParaffins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 RinR Naphthenes
E(P + N)
E 5 Rin& Naphthenes
E(P + N)
C20 c -Q
C21 .0
EnParaffin^'
C24 ,0
EnParaffin^'"
C?s C_,Q
C26 _^Q
EnParaffin^^
8.0
6.0
21.2
13.3
13.0
9.10
12.0
9.0
8.0
34.1
11.0
6.5
3.1
16.0
12.3
8.7
9.0
6.0
X20
X21
X22
X24
X25
X26
C27
InParaffin^
EnParaf finC_^
Cn
ZnParaffinc40
Z C30+C31+C32
Z C20+Cp]+C22-t-C30+C31+C32
I c24+c25+c26+c27+c28
Z CnH2n-6
1 CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
5.0
4.0
4.0
4.1
1.60
2.4
2.5
8.0
Oil Type - crude
Origin - Tia Juana Medium
Weathering Tine, days - 10
Weathering Temperature, °F - 55
Mixing Condition - Low mix
- 92 -
-------
Computer No. 100003
Analytical No. 578643
Numerical Numerical
Index Formula Value Index Formula Value
Zl
h
Z3
\
h
h
ll
h
19
xio
Xll
Z12
X13
X14
X15
X16
Z17
X18
V
Ni
S
i N
TfnHT f,
ZAromat ic
ZCnH2n-6 C=^°
I Aroma tics
ECnH2n-10
lAromatic .„
c=20
SCnH2n-10 c"36
ZAromat ic
ZCnH2n-14
ZAromat ics
ZCnH2n-16
ZAromat ics
ICnH2n-18
ZAromat ics
ZnParaf f ins
I (P + N)
1C 3 Ring Naphthenes
I(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 „„
rnParaffin^- 'X
c=40
C21 nQ
Enparaffin1" ""
c=40
C24 ,Q
InParaffin1" tY
c=40
C?s . ,n
EnParaffin" ?X
c=40
C26 .„
ZnParaffin^ '"
c=40
7.9
6.7
21. 38
11.58
12.61
8.50
11.66
8.06
8.72
39.48
10.46
6.89
3.43
14.3
11.1
8.2
8.1
6.6
T19
J20
X21
X22
X23
X24
X25
X26
C27
ZnParaffinc=4(i
C.30 . o0
SnParaffin^" 'X
r=40
cn . ^Q
ZnParaffinc-40
E C70+C71+C77
2 C30+C31+C32
1 C20+C?i+C22+C30+C3l+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
Z CnH2n_6+ZCnH2n_18
2n-14
E-l Ring+2 Ring Napjithenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
5.9
3.2
3.9
3.53
1.36
2.45
2.57
6.55
Origin - Tia Juana Medium
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 93 -
-------
Computer No. 100004
Analytical No. 578644
Numerical Numerical
Index Formula Value Index Formula Value
h
h
**
X10
*i5
V
Ni
S
N
Z Aromatic
ZCnH?n-6 C=-,
lAromatics""
£Aromatic
ICnH2n-10 c=36
EAromatic
ICnH2n-14
lAromatics
TCnH2n-16
lAromatics
lAromatics
ZnParaf fins
1 (P + N)
I 3 Ring Naphthenes
£(P + N)
£ 4 Ring Naphthenes
Z(P + N)
£ 5 Ring Naphthenes
£(P + N)
C20
InParaffinc '
c=40
C21 ,Q
ZnParaffin1" tA
c=40
C24 ,Q
InParaffin^^
ZnParaffin^^
ZnParaffin^J
7.6
5.4
20.80
12.27
13.18
9.47
11.56
8.13
8.62
34.21
11.24
7.39
3.62
14.40
11.7
8.0
7.7
6.1
X19
X20
'22
J24
X25
T26
C27 . ,Q
C/5° c "0
ZnParaffin^ 7X
c=40
SnParaffinC tn
c-40
E C30+C31+C32
I C20+C?i+C22+C30+C3i+C32
1 C24+C25+C26+C27+C28
J CnH2n-6
1 CnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
5.9
3.2
3.7
3.45
1.42
2.41
2.53
6.87
Origin - Tia Juana Medium
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 94 -
-------
Computer No. 100005
Analytical No.
Numerical Numerical
Index Formula Value Index Formula Value
'2
'•
'lO
'»
V
Ni
1
N
ECnH2n-6
EAromatic
c — 70
ECnH2n-6 7^
EAromatics
EAromatic _
ECnH2n-10 c=36
EAromatic
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaf f ins
E (P + N)
E 3 Ring Naphthenes
E(P 4 N)
E It Ring Naphthenes
E(P + N)
Z 5 Ring Naphthenes
E(P + N)
C20 „„
EnParaffin^Q
C21 «0
EnParaffin1" ^«
EnParaffin^2?Q
Co ^
EnParaffin1" '"
c=40
C26 ,n
EnParaffin1"^^
7.6
5.8
20.82
11.10
12.20
7.97
11.81
8.05
9.04
31. IS
11.88
6.78
2.91
15.0
11.9
8.8
8.4
6.4
T20
T21
T26
Oil Tyr
C27
i-nParaffin^
EnParaffin^ '
c=40
C11 c-20
£ C?0+C2i+C?7
. T C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2u-18
iJ CnHo^ /~f"i-CnHo •* a
zn— o Zn— ID
CnH2n-14
E-l Ring+2 Ring^Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
5.7
3.4
3.7
3.77
1.38
2.30
2.53
9.80
Origin - Tia Juan a Medium
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 95 -
-------
Computer No. 110551
Analytical No. 524667
Numerical Numerical
Index Formula Value Index Formula Value
\
h
13
*«
h
h
*7
Z8
X9
X10
Xll
Z12
*13
*14
r!5
*16
J17
'IB
V
Ni
S
N
ECnH2n-6
E Aromatic
ECnH2n-6 c°^
EAromatics*"
ECnH2n-10
EAromatic c=2Q
Aromatic
£CnH2n-14
EAiximatics
TCnH2n-16
EAroraatics
ECnIl2n-18
EAromatics
EnParaffins
E (P + N)
E 3 Ring Naphthenes
Z(P + N)
Z 4 Rin£ Naphthenes
£(P + N)
I 5 Ring Naphthenes
E(P -»- N)
C20 ,0
InParaffin^^
C21 _ ,Q
EnPara£fin^=^
C24 c_,Q
InParaffin^Q
C?s OQ
EnParaffin^^
C26 _,_,0
EnParaffin^
8.0
6.0
21.2
13.3
13.0
9.10
12.0
9.0
8.0
34.1
11.0
6.5
3.1
16.0
12.3
8.7
9.0
6.0
J19
T20
X21
J22
J23
J24
X25
J26
C27
inParaffin" t"
c=40^
C30 ~
SnParaffin"" '"
r=40
Cl1 ?n
EnParaffin" "
c-40
z c?o-i-c?1+c??
£ C30-fC31+C32
S C20+Cpi+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
£ CnH2n-6
1 CnH2n-18
1 C««2n-6+5:CnH2n-18
CnH, , ,
2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring-W Ring Naphthenes
Sample History
5.0
4.0
4.0
4.1
1.60
2.4
2.5
8.0
Oil Type - crude
Origin - Tia Juana Medium
Weathering^ Time , days - 10
Weathering Temperature, °F - 55
Mixing Condition - Low mix
- 96 -
-------
Computer No. 110559
Analytical No. 578618
Index
Formula
Numerical
Value
Index Formula
Numerical
Value
h
X2
*3
\
15
X6
X7
X8
X9
ho
Jll
X12
X13
X14
X15
r!6
X17
he
V
Ni
S
N
£CnH2n-6_
EAromatic
ECnH2n-6 C=3°
EAromatics'"
ZCnH2n-10
EAromatic
EAromatic
ECnH2n-14
EAromatics
ECnH2n-16
ZAromatics
ZCnH^n-18
EAromatics
JhParaffins
1 (P + N)
E 3 Ring Naphthenes
Z(P + N)
I 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 c o0
ZnParaffin^" ^
c=4u
C21 . oQ
InFaraffin^ 7X
c=40
C2« . ,Q
ZnParaf f in^_tX
c?s C_o0
DnParaf fin*" 7X
c=AO
C26 . oQ
EnParaffin^Q
7.4
6.4
20.97
10.31
12.23
7.09
13.20
8.49
6.70
36.20
11.70
6.62
2.51
14.4
11.4
7.6
7.6
6.7
J19
12Q
I2i
X22
T23
T24
X25
X26
Oil Ty;
C27 .
EnParaffin1' '"
c=40^
CW -n
SnParaffin" ""
r=40
Cl1 r "n
EnParaffin"' '"
c~40
E C?Q+C21+C?2
Z C30+C31+C32
£ C2Q+C21+C22+C3Q+C31+C32
E C24+C25+C26+C27+C28
I CnH2n-6
E CnH2n-18
E CnH2n-6+ICnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthenes
Sample History
Origin - Tia Juana Medium
Weathering Time, days - 10
Weathering Temperature, °F - 55
Mixing Condition - High Mix
5.8
2.9
3.8
3.78
1.42
3.13
2.10
11.30
- 97 -
-------
Computer No. 121551
Analytical No. 586031
Numerical Numerical
Index Formula Value Index Formula Value
Xl
h
X3
\
15
h
17
>8
X9
J10
Zll
J12
T
"13
X14
*15
X16
J17
he
V
Mi
^
N
il-nnpjn-t)
lAromatic
ECnH2n-6 C=?°
EAromatics
r.CnH2n-10
^Aromatic c=20
£CnH2n-10 c«36
EAroniat ic
ICnH2n-14
KAromatics
£CnH2n-16
lAromatics
EC.iH?n 18
CAromatics
JiiParaffins
Z. (f + N)
£ 3 Rine Naphthenes
E(P + N)
Z 4 Ring Naphthenes
£(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 c_,0
TnParaffin^Q
C21 c_->0
ZnParaffin^_^Q
C24 c_,0
EnParaffin^0
c->«i c_,0
ZnParaffin^^
C?fi c_,Q
EnPataffin^Q
9.1
6.6
21.45
14.23
12.93
8.64
11.99
8.62
8.05
33.76
12.00
6.57
1.76
14.6
11.5
8.5
7.9
6.6
J19
X20
X21
J22
X23
Z24
X25
X26
C27 c ,0
EnParaffin^Q
cw c <,0
SnParaffin"" 7X
r=40
c^i c ,0
ZnParaffin^" t^
c~40
£ C70+C71+C77
E C30+C31+C32
I C20+C?]+C22+C30+C3]+C32
Z C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
Z CnH,^ ,+ICnH0 , B
in-6 2n-18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
5.8
4.1
3.4
3.74
1.41
2.68
2.46
24.9
Oil TVDC - Crude
Origin - Tia Juana Medium
Weathering Tine, days - 21
Weathering Temperature, °F - 55
Mixing Condition - Low
- 98 -
-------
Computer No. 110801
Analytical No. 588716
Index Formula
h
h
J3
X4
h
16
*7
h
X9
ho
hi
X12
X13
X14
X15
J16
X17
he
V
Ni
j>
N
ZCnH2n-6
Z Aromatic
ZCnH2n-6 C=?°
EAromatics1"
rCnH2n-10
^Aromatic
£CnH2n-10 c~36
lAromatic
ICnH2n-14
lAromatics
£CnH2n-16
ZAromatics
ECnH2n-18
lAromatics
SaParaffins
Z (P + N)
£ 3 Ring Naphthenes
I(P + N)
I 4 Ring Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C20 __,n
InParaffin" t"
c=40
C21 ,n
Znparaffin1- t"
c=40
C24 . ,
InParaffin1- ,.
c=40
C?-i _ ,0
ZnParaffin" ""
c=40
C26 7n
InParaffinc:^
Numerical Numerical
Value Index Formula Value
7.6
6.1
21.27
13.70
12.28
8.86
12.58
9.07
8.45
34.40
11.91
6.81
2.22
14.2
11.3
8.4
7.9
6.6
J19
'20
T21
I22
*23
X24
J25
T26
C27 . ,
^nParaffinc=;^
c-w o0
rnParaffinr=40
C^ - "0
ZnParaffin /n
c=40
S C7o+Q>i-l-C7?
Z C30+C31+C32
E C20+C71-f-C22+C30+C31+C32
S C24+C25+C26+C27+C28
Z CnH2n-6
Z CnH2n-18
Z CnH2n_6+ICnH2n_18
CnH2n_u *
E-l Ring+2 Ring_Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - Crude
Origin - Tia Juana Medium
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
6.0
4,3
3.8
3.42
1.40
2.53
2.36
16.7
- 99 -
-------
Compute! No. H0809
Analytical No. 524248
Numerical Numerical
Index Formula Value Index Formula Value
Jl
h
*3
h
h
h
17
h
19
rio
Jll
X12
*13
Z14
J15
116
hi
xie
V
i Ni
f
N
£CnH2n-6
EAromat ic
ECnH2n-6 C=^
EAroraatics
£CnH2n-10
EAromatic ^
TCnH2n 10 c"36
lAromatic
ICnHjg-u
lAromatics
it,nM2n-lo
lAromatics
ZCnH2n-18
lAromatics
Infarafflng
I (P + H)
E 3 Ring Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
E(P + N)
T 5 Ring Naphthenes
E(P + N)
C20 -n
InParaffin" '"
c=40
C21 «.
Enparaffin" '"
c=40
C24 0
InParaffin" ,"
c=40
^^ r=?n
EnParaffin" *"
c=40
C26 ,n
E*.r.ffl»^JJ
7.8
6.3
21.23
13.21
12.60
9.07
12.31
9.00
8.72
34.05
11.01
6.51
3.05
16.1
12.3
8.7
8.7
6.0
J19
X20
J21
X22
J23
X24
J25
J26
C27 c ^Q
2-nParaffin^^^
C3Q c_^0
SnParaffin^ 7n
c=40
C^1 c ".Q
EnParaffin"" 7n
C-40
E C->Q+C?-\+C??
1 C30+C31+C32
E C20+C?i+C22+C3CH-C3i+C32
Z C24+C25+C26-HC274-C28
E CnH2n-6
1 ^"an-is
1 <*H2n_6+ECnH2n_18
Cnii2n-14
E-l Ring+2 RIn£_Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type — Crude
Origin - Tia Juana Medium
Weathering Time, days - 10
Weathering Temperature, °? - 80
Mixing Condition - HM
4.8
3.5
3.5
4.1
1.55
2.43
2,44
7.81
- 100 -
-------
Computer No. 121801
Analytical No. 586027
Numerical Numerical
Index Formula Value Index Formula Value
Xl
12
h
*4
X5
X6
X7
X8
*9
X10
Xll
Z12
T
'13
X14
X15
*16
<17
Z18
V
Ni
S
N
ECnH2n-6
JAromatic
ICnH2n-6 C=^
ZAroma tics'"
£CnH2n-10
lAromatic
c=iU
lAroraatic
ICnH2n-14
EAromatics
ZCnH2n-16
lAromatics
ZCnH2fi-18
lAromatics
ZiiParaffins
X (P + N)
E 3 Ring Naphthenes
£(P + N)
I A Ring Naphthenes
E(P + N)
I 5 Ring Naphthenes
I(P + N)
C20 c ^Q
TtiParaffin^g
C21 c n0
EnParaffin^ _""
C24 C_,Q
EnParaffin^=^Q
C7S c_-,0
SnParaffin _,_
C26 c ,Q
EnParaffin^=^
8.0
5.9
21.76
14.63
12.67
9.58
12.86
8.90
7.62
31.88
11.81
6.91
2.59
15.2
12.7
8.4
8.3
6.7
.^9
T20
J21
X22
J23
X24
T25
T26
C27 _ „
i-nPara£finc=40
c^o c^,0
EnPara£fin^=^
, . ._C.T1 c ,Q
EnParaffin^^
I C7n+C21+C?7
. Z C30+C31+C32
I C2Q+C?.i+C22+C30+C3i+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
1 CnH2n-6+ZCnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthenes
Sample History
Origin - xia Juana Medium
Weathering Tine, days - 21
Weathering Temperature, °F - go
Mixing Condition - Low Mix
6.2
3.5
3.5
4.12
1.42
2.86
2.29
12.50
- 101 -
-------
Computer No. 121809
Analytical No. 599393
Numerical Numerical
Index Formula Value Index Formula Value
h
12
J3
'4
h
16
X7
X8
Z9
'10
hi
X12
T13
X14
115
T16
X17
X18
V
Ni
! s
s
£CnH2n-6
EAromatic
ECnH2n-6 CI^
EAromatics""
ECnH2n-10
E Aromatic c=2Q
ECnH">n-10 c=36
EAromatic
ECnH2n-lA
EAromatics
ECnH2n-16
EAroraatics
ECnH2n-18
EAromatics
EnParaffins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
Z 5 Ring Naphthenes
E(P + N)
C20 C_o0
EnParaf£in^*Q
C21 C_^Q
EnFaraffin^^Q
C24 ._,0
EnParaf fin^=^Q
C?-; c_,0
EnParaffin^~Q
C26 c_,0
EnParaffin^-Q
7.6
5.6
21.17
11.16
11.31
6.82
13.24
9.22
8.55
33.07
11.31
6.50
2.67
16.00
11.7
8.2
8.7
6.3
T19
^0
X21
T22
Z23
J24
X25
T26
Oil Typ
C27 „.
inParaffin^
. CM ..,n
i-nParaffin^^
V Cl1 c-20
XnParaffin rr.
c-40
Z C70+C?1+C7?
1 C30+C31+C32
2 C20+C71+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
J CnH2n-6
1 CnH2n-18
I CnH2B_6+ECnH2n_18
CnH2n-14
Z-l RinR+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
e Crude
Origin - Tia Juana Medium
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
5.3
3.6
3.9
3.73
1.51
2.48
2.25
10.90
- 102 -
-------
Computer No. 200000
Analytical No. 578630
Numerical Numerical
Index Formula VnliiP Tndp-x Formula Value
Xl
12
X3
\
X5
X6
X7
X8
X9
X10
Xll
Xi2
I13
X14
X15
X16
X17
he
V
Ni
S
N
ECnH2r.-6
EAromatic
ECnH2n-6 C=?°
EAromaticE1"
ECnH2n-10
EAromatic „„
c=20
£CnH2n-10 c=36
IIAroraat ic
ICnH2n-lA
EAroraatics
ZCnH2n-16
J^romatics
ECnH7p-i8
EAromatics
IhParaff ins
£ (P + N)
I 3 Ring Naphthenes
E(P + N)
I 4 Ring^ Naphthenes
Z(P + N)
E 5 Rin& Naphthenes
E(P + N)
C20 CT.n0
rnParaffin^=~Q
C21 _ -Q
EnParaffin^=^Q
C24 c o0
EnParaffin^Q
c?s c_,0
EnParaffin-=4Q
C26 CT-"0
EnParaffin~_^Q
5.6
6.4
18.86
11.17
13.92
9-59
12.54
8.87
9.39
16.60
16.60
10.50
4.50
11.30
8.80
7.50
8.90
6.20
T19
Z20
X21
X22
X23
X24
X25
X26
C27 c ,Q
lnPata£fin^=^^
C^O r or.
InParaffin1- "
r=40
Cll . ,0
InParaffin" ,.
c=40
I C7Q+C7T+C??
1 C30+C31+C32
Z C2Q+C71+CT2+C30+C31+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
1 CnH2n-6+ECnH2n-18
CnH2n-14
1-1 Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
garople History
Oil Type - Crude
6.90
2.90
7.30
1.85
1.30
2.01
2.25
7.27
Origin - Lago
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 103 -
-------
Computer No. 210559
Analytical No. 578607
Numerical Numerical
Index Formula Value Index Formula Value
\
12
h
\
h
h
J7
Z8
Z9
T10
Xll
T12
X13
L14
'15
116
lll
X18
V
Ni
1
N
ICnH2n-6
EAromatic
ZCnH2n-6 °"^
ZAromat ics
ZCnH2n-10
lAromatic _
ZCnH2n-10 c=36
^Aromatic
ICnH2n-lA
ZAromatics
£CnH2n-16
lAromatics
ICnH2n-l 8
ZAromatics
JhParaffins
E (P + N)
I 3 Ring Naphttienes
Z(P + N)
I 4 Ring Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C20 C_,Q
rnParaffinc=40
C21 c_,0
ZnParaffin"_, _
C24 ._,Q
ZnParaffinc=AO
C7S ,-OQ
ZnParaffin" ~~
c=4U
C26 C_o0
ZnParaffin^=^
7.2
6.3
18.95
11.46
13.94
9.69
12.60
9.14
9.43
23.82
16.45
9.17
3.60
12.50
10.50
7.30
8.70
5.50
T19
X20
J21
Z22
T23
X24
X25
T26
C27 . „.
inParaffin^
C30 r_nQ
i-nParaffin ...
c=40
c^i c._,Q
ZnParaffin^^
z C?o+C2i+C72
1 C30+C31+C32
I C20+C21+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 ^^n-ie
I CnH2n_6+i:CnH2n_18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
1-5 Ring+€ Ring Naphthenes
Sample History
Oil Type - Crude
Origin - La go
Weathering Tine, days - 10
Weathering Temperature, °¥ - 55
Mixing Condition - High Mix
6.20
2.20
6.20
2.37
1.45
2.01
2.25
9.35
- 104 -
-------
Computer No. 221557
Analytical No. 598577
Numerical Numerical
Index Formula Value Index Formula Value
h
12
13
\
15
h
*7
*8
X9
xio
Xll
h2
X13
X14
X15
X16
r!7
X18
V
Ni
S
N
rPn Ho f.
EAromat ic
ECnH2n-6 ^°
EAromatics'"
ZCnH2n-10
EAromatic =2Q
ECnH2n-10 c=36
EAromatic
ECnH2n-U
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
SaParaffins
E (P + N)
E 3 RinR Naphthenes
E(P + N)
E 4 Ring Naphthenes
£(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 £_^0
EnParaffin^Q
C21 c n0
EnParaffin^Q
C2A c_.0
EnParaffin^=^
C7S C_OQ
EnParaffinc=40
C26 C_o0
EnParaffin^^
7.3
6.5
19.70
12.69
14.07
10.32
12.10
8.68
8.86
18.31
16.57
9.64
3.17
11.1
9.9
8.9
8.1
7.1
Z19
r20
X21
r22
:23
X24
X25
X26
C27 . „„
2nParaffin^=^
C^Q OQ
EnParaffin ", A
r-=40
C?l . OQ
SnParaffin^" t«
c"40
I. C7o+C?1+C7?
1 C30+C31+C32
£ C2Q+C71+C22+C30+C31+C32
Z C24+C25+C26+C27-fC28
S CnH2n-6
1 CnH2n-18
E CnH2n_6+ECnH2n_18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Type — Crude
Origin - Lago
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - Low Mix
5.9
5.5
5.1
2.21
1.26
2.22
2.37
14.8
- 105 -
-------
Computer No. 210809
Analytical No. 525320
Numerical Numerical
Index Formula Value Index Formula Value
Xl
:2
X3
\
X5
h
17
h
X9
X10
Zll
X12
X13
'14
X15
X16
J17
T18
V
Ni
£
N
ICnH2n-6
EAromatic
ECnH2n-6 C=^
EAromatics1"
£CnH2n-10
lAromatic ^^
ICnH2n-10 c=36
ZAromatic
TCnH2n-14
EAroroatics
ECnH2n-16
lAromatics
TCnH*?n i fi
ZAromatics
JiiParaffins
I (P + N)
T 3 Ring Naphthenes
I(P + N)
I 4 Ring Naphthenes
Z(P + N)
I 5 Ring Naphthenes
Z(P + N)
C20 ... ,n
rnParaffin^^J
C21 .. ,Q
InParaffin ,r
c=40
C2<. r ,n
InParaffin^^
c?s ^OQ
EnParaffin1" "
c=40
C26 rlc7n
ZnParaffin" t"
c-40
7.00
6.10
20.06
11.85
13.38
9.41
12.17
8.97
9.62
20.09
15.14
9.69
4.39
12.40
10.40
8.40
9.50
6.80
T19
^0
T21
J22
X23
J24
J25
T26
C27 . ,Q
inParaffinc4q.
C-,0 ,Q
EnParaffin ";:
c=40
C^T
JnParaffin1" '"
c-AO
Z C^o+Cpi+C??
1 C30+C31+C32
Z C20+C?]+C22+C30+C3l+C32
1 C24+C25+C26+C27+C28
£ CnH2n-6
Z ^'^n-lS
1 Cn«2n-6-|-ZCnli2n-l8
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Lago
Weathering Time , days - 10
Weathering Temperature, °F - go
Mixing Condition - Hieh Mix
5.20
2.57
4.73
3.08
1.33
2.09
2.45
8.00
- 106 -
-------
Computer No. 221809
Analytical No. 525405
Numerical Numerical
Index Formula Value Index Formula Value
.
Tl
Z2
*3
h
X5
X6
X7
'8
X9
T10
ril
J12
T13
Z14
X15
Z16
*17
X18
V
Ni
£
N
EAromatic
ECnH2n-6 C=^°
EAroraatics1"
ECnH2n-lQ
EAromatic _
ECnHjn-lO c-36
LAromat ic
ECnH2n-lA
EAroraatics
ECnH2n-16
EAromatics
ECnH2n-i8
EAromatics
InParaff ins
Z (P + N)
E 3 Ring Naphthenes
E(P + N)
E A Ring Naphthenes
E(P + N)
E 5 RitiK Naphthenes
E(P + N)
C20 c_-,0
rnParaf£in^=AO
C21 ..c_,0
EnParaffinc=40
C24 c ,0
EnParaffinc=40
C?"i -c-2fl
InParaffinc=40
C?6 C_o0
SnParaffin~=40
4.6
5.4
19.13
14.50
15.64
12.50
13.28
8.95
5.82
17. 3u
16.73
11.18
4.28
11.0
9.0
8.0
9.0
6.0
Z19
r20
X21
X22
X23
X24
^5
X26
C27 . ,Q
^nParaffin^=^
C30 ^0
5-nParaffin , .
c=4Q
C^T __oQ
InParaff in .n
c-40
I C70+C71+C7?
1 C30+C31+C32
I C20+C?i+C22+C30+C3l+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
E CnH2n_6+ZCnH2tl_18
CnH2n-14
1-1 Rinp+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Lag°
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
7,0
3.0
7.0
1.90
1.30
3.3
1,90
5.52
- 107 -
-------
Computer No. 3-00-00-0
Analytical No. 578646
Index
Xl
12
X3
l«
15
h
17
18
J9
X10
Tll
J12
T13
*14
J15
*16
hi
hB
Numerical Numerical
Formula Value Index Formula Value
! v
; Ni
S
N
£CnH2n 6
EAromatic
ECnH2n-6 c*2°
EAromaticsC
ECnH2n-10
EAromatic c=20
ECnH2n-10 c=36
EAromatic
£CnH2n-14
EAroroatics
ICnH^n-ie
EAromatics
ECnH2n-18
EAromatics
ZnParaffins
E CF + N)
J! 3 Ring Naphthenes
I(P + N)
E A Rin& Naphthenes
E(P + N)
I 5 Ring Naphthenes
E(P + N)
C20 7n
InParaffin"-"^
c=AO
C21 >.
EnParaffin" ,.
c=40
C24 2fl
EnParaffin" '"
c=40
Cjs ^?n
EnParaffir?- '"
c=40
C26 ,n
ZnParaffin1- ,„
c»40
0.25
3.90
18.06
7.51
13.92
6.85
11.70
8.54
8.25
29.94
12.34
9.70
4.51
19.23
13.24
7.40
7.72
5.52
X19
Z20
X21
X22
:23
L24
X25
!26
i
Oil Tvp
C27
^nParafiin1- '"
c=40^
ClO ,n
^nParaffin^ ^
_ r-uO
v C^ c 20
InParaffin ,n
c-40
Z C70+C71+C77
r C30+C31+C32
2 C20+C?i+C22+C30-t-C3i+C32
> C24+C25+C26+C27+C28
S CnH2n-6
E CnH2n-18
E CnH2n_6+ICnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
e - Crude
4.67
2.83
4.25
4.29
1.83
2.19
2.25
5.96
Origin - Grande Isle Mix
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
_ 108 -
-------
Computer No. 310801
Analytical No. 588720
Index
Formula
Numerical
Index Formula
Numerical
Value
J
X8
X10
T12
T13
X17
'IB
V
Ni
S
N
ECnH2n-6
VAromat ic
ECnH2n-6 '^
EAromat ics
ECnH2n-lQ
EAroraatic
L CnH2n-10 c = J o
EAromatic
ECnH2n-14
EAromatics
ECnH2n~16
EAromat ics
ECnH2n-18
EAromatics
ZiiParaf fins
E (P + N)
Z 3 Ring Naphthenes
E(P + N)
I 4 Ring Naphthenes
I(P + N)
I 5 Ring Naphthenes
E(P + N)
C20 ,0
EnParaffin^=^
C21 . ,Q
EnParaffin
c=40
EnParaffin^ t.
c=40
EnParaffin^
C26 ,Q
2nParaf£inc=40
0.61
3.63
18.01
10.98
14.72
9.45
13.20
10.12
8.74
27.25
12.89
10.81
4.06
22.0
11.0
9.0
12.0
7.0
X20
T23
'„
Oil Tyj
C27 _ OQ
EnParaffin 7n
0=40^
C30 c n0
EnParaffin^Q
c,,
E C70+C?i+C?2
2 C30+C31+C32
E C20+C?i^C22+C30+C3l+C32
1 C24+C25+C26+C27+C28
E CnH?n_6
Z CnH2n-18
CnH2n-14
E-l Rinfi+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Origin - Grand Isle Mix
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
4.0
3.0
4.0
5.30
1.60
2.07
2.03
9.14
- 109 -
-------
Computer No. 331551
Analytical No. 598578
Numerical
Index Formula Value Index Formula
h
h
*3
J4
J5
J6
J7
J8
X9
X10
lu
X12
T
"13
Tl«
J15
X16
'17
hs
V
Si
S
N
ICnH2ri-6
S Aromatic
ICnH2n-6 C=3°
£Aroroatics^"
_£CnH2n-10
EAromatic .,
c"20
rCnH2n-10 c"36
lAroraatic
rCnH2n-14
I^Aromatics
ICnH2n-16
EAromatics
ICiiH^n-lS
lAromatics
JiiParaffins
1 (P + N)
Z 3 RlnR Naphthenes
E(P + N)
I 4 Ring Naphthenes
E(P + N)
I 5 Rin^ Naphthenes
E(P + N)
C20 c_,0
rnParaffin~=-Q
C21 c-,-»o
InParaffin-^Q
C24 c_,Q
v;nParaffin^=^0
C7s C_o0
EnPara£fin-=40
C26 c_^0
InParaffin^Q
0.50
4.70
18.08
10.97
14.91
9.53
12.71
9.71
8.66
27.53
12.60
10.13
3.95
19.5
12.8
7.8
8.7
6.7
X19
X20
X21
J22
X23
!24
J25
X26
C27 ._,„
i-nParaffin^^Q
c^o ,0
EnParaffin^=-g
C^l c ,Q
EnParaf fin"" 7ri
C~MO
I C7o+C7i+C??
1 C30+C31-fC32
I C2Q+C71+C22+C30+C31+C32
r c,.+c,"+c ,+c +c.,
24 25 26 27 /.o
I CnH2n-6
1 a^n-is
1 CnH2n-6+£CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthanes
Sample History
Oil Type - Crude
Origin - Grand Isle Mix
Weathering Time, days - 21
Weathering Temperature, °F - 55
MixinR Condition - Low Mix
Numerical
Value
4.0
3.2
3,2
5.1
1.70
2.08
2.10
9.13
- 110 -
-------
Computer No. 321559
Analytical No. 578625
Numerical
Index Formula Value Index Formula
Xl
X2
X3
\
X5
16
X7
Z8
J9
ho
Zll
X12
T13
J14
X15
X16
X17
he
V
Ni
S
N
ICnH2n-6
lAromatic
ZCnH2n-6 C=?°
ZAromatics
£CnH2n-10
ZAromatic
5;CnH2r.-10 c-36
lAromatic
ZCnH2n-14
EAroraatics
ECnH2n-16
EAroraatics
ICnH^n-18
IAromati.cs
EnParaf f ins
1 (P + N)
Z 3 Ring Naphthenes
T(P + N)
I 4 Rine Naphthenes
I(P + N)
Z 5 Ring Naphthenes
E(P + N)
C20 ,0
InParaffin^Q
C21 . ,n
InPara£fin^;J
C24 _c,Q
InParaffin;40
C" c-"0
Ztfaraffln^-0
C26 r=20
ZnParaffin^^
0.43
4.69
17.48
11.17
15.28
10. 39
12.68
10.21
9.92
25.59
12.32
10.67
4.51
19.9
15.9
8.1
8.3
5.8
X19
^0
T21
T22
X23
X24
T25
T26
C27 c ,Q
EnPaiaffin^^
CM c n0
InParaffin^^
c?i c ,0
InParaffin^g
£ C7Q+C2T+C72
. E C30+C31+C32
g C2Q+C21+C22+C30+C31+C32
E C24+C25+C26+C27H-C28
2 CnH2n-6
E CnH2n-18
E CnH2n_6+ZCnH2n_lg
2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Grand Isle Mix
Weathering Time, days - 21
Weathering Temperature, °F - ^
Mixing Condition - Hl8h Mlx
Numerical
Value
4.0
1.9
2.8
6.4
1.83
1.76
2.16
7.25
- Ill -
-------
Computer No. 310809
Analytical No. 525321
Numerical
Tndpx Formula Value Index Formula
h
I5
'10
hi
Z13
he
V
Hi
S
N
ECnH2n-6._
EAromat ic
ECnH2n-6 °~,,
: c= Jo
EAromatics
E,CnH2n-10
EAromat ic _._
ECnH2n-10 c=36
EAromat ic
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaffins
E (P + N)
T 3 Ring Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
Z(P + N)
E 5 Rinj» Naphthenes
E(P + N)
C20 c ,Q
EnParaf fin^_7X
C21 . ,0
EnParaf fin^_"
C24 c ,Q
C7S c_og
C26 c=,0
EnParaffin _^Q
0.24
4.4
17.06
8.42
14.12
7.05
13.10
9.47
9.22
33.34
11.15
9.01
4.03
21.4
15.7
6.9
9.8
5.1
X20
X22
126
C27 ,Q
nParaffinc=40^
£nParaffinC _t0
Cv\
EnParaffinc_40
1 C30+C31+C32
E C20+C7i+C22+C3_Q+C3i+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
1 CnH2n-6+ECnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Numerical
Value
4.6
1.8
3.7
5.6
1.96
1.85
2.01
6.92
Oil Type - Crude
Origin - Grande Isle Mix
Weathering Tine, days - 10
Weathering Temperature, "F - ttO
Mixing Condition - Hi8h Mix
- 112 -
-------
Computer No. 321801
Analytical No. 586003
Numerical Numerical
Index Formula Value Index Formula Value
h
'<
X10
"13
'»
V
Ni
N'
ECnH2n-6
ZAromat ic
ZCnH2n-6 C"0(.
ZAromat ics^
EAromatic
e=20
EAroraat ic
£CnH2n-14
EAromat ics
ECnH2n-16
EAromat ics
ECnHin ig
EAromat ics
JhParaf f ins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 _ on
EnParalrin ...
c=40
C21 . -,0
EnParaffin^" t"
c=40
EnParaffin'"_2X
EnParaffin ~.
C26 c n0
EnParaf f in^_7Q
0.605
4.07
17.45
11.00
15.75
10.14
13.78
10.07
7.38
26.34
12.72
11.00
4.42
21.6
10.8
8.9
11.8
6.5
'20
'„
T26
Oil Tyi
C27 ^Q
*
C30 ._oQ
EnParaffin ,n
r=40
c,,
EnParaffin"" 7X
c=40
^ C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
CnH2n-U
_E-1 Ring+2 Ring Naphthenes
i-5 Ring+6 Ring Naphthenes
Sample History
Origin - Grand Isle Mix
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
3.6
2. 7
3.6
5.24
1.57
2.37
1.80
7.86
- 113 -
-------
Computer No. 321809
Analytical No. 525406
Numerical
Index Formula Value Index Formula
T
h
h
ho
hi
h2
'14
he
ln
X18
V
Ni
S
N
ECnH2n-6
E Aromatic
ECnH2n-6 C~-j£
EAromatics*"
ZCnH2n-10
ZAromatic _Q
ECnH2n-10 c=36 '
EAroraatic
ECnH2n-14
EAroraatics
EAromatics
EAromatics
EnParaffins
Z (P + N)
Z 3 Ring Naphthenes
Z(P -1- N)
E 4 Ring Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C20 ,Q
ZnParaf fln"~_"
C21 ,Q
EnParaffin '.
C2b *in
EnParaffin ...
ZnParaffin /n
C26 CC,Q
ZnParaffin^-
0.33
4.1
17.73
10.17
13.83
8.03
13.55
10.79
9.82
31.39
11.62
9.65
4.11
21.4
12.2
8.4
9.8
6.0
'20
•a
•»
C27 c ,0
l-nparaffinc,4(i
EnParaffinc *~. n
c=40
C^l c 1Q
£ c?n+c71+c72
E C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
E CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Numerical
Value
4.4
2.9
3.8
5.4
1.65
1.81
2.04
7.10
Oil Tvoe - Crude
Origin - Grand Isle Miy
Weathering Tiae , days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
- 114 -
-------
Computer No. 310559
Analytical No. 578608
Numerical Numerical
Index Formula Value Index Formula Value
Zl
12
J3
X4
X5
Z6
J7
J8
X9
ho
*11
Z12
X13
X14
Z15
X16
Z17
X18
V
; si
s^
N
jgnH2r, 6
EAromatic
ECnH2n-6 C~2°
EAromatics""
ECnH2n-10
HAromatic
c=20
ECnH2n-10 c=36
EAroraatic
ECnH2n-lA
EAromatics
ECnH2n-16
EArotnatics
ECnH2n-i8
ZAromatics
EnParaf f ins
E (P + N)
I 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P H- N)
C20 „„
EnParaffin1" '"
c=40
C21 . ,n
EnParaffin" '„
c=40
C24 _. „
EnParaffin1- ""
c=40
c?ti r -n
ZnParaffin1" 'X
c=40
C26 _ ,n
EnParaffin" t"
c=40
0.20
3.80
17.20
8.92
15.04
8.48
12.59
9.39
8.79
31.91
12.11
8.98
3.35
19.80
13.30
7.80
8.80
6.00
T19
Z20
Z21
X22
Z23
X24
X25
J26
Oil Typ
C27
inParaffine=4o
C.W . -,n
InParaffin"" '"
r=40
C^i _.
^nParaffin" '„
c-40
E C2fl+C21+C22
1 C30+C31+C32
Z C20+C?i-t-C22+C30+C3i+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
2 CnH2n-18
E CnH2n_6+ECnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
e Crude
Origin - Grand Isle Mix
Weathering Time, davs - 10
Weathering Temperature, °F - 55
Mixing Condition - High Mix
4.60
2.30
3.73
5.00
1.76
1.96
2.07
9.75
- 115 -
-------
Computer No. 400000
Analytical No. 578635
Numerical
Index Formula Value Index Formula
X2
;>
X10
xll
X15
X16
X17
h*
V
Ni
S
N
£CnH2n-6
EAromatic
ECnH2n-6 C~36
EAromatics1"
ECnH2n-10
EAromatic -n
ECnH?n-10 c-36
EAromatic
ZCnH2n-14
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaffins
Z (P + N>
Z 3 Rin^ Naphthenes
Z(P + N)
E 4 RinR Naphthenes
Z(P + N)
Z 5 RinK Naphthenes
Z(P + N)
cjo c,?0
C21 C_o0
C24 CT,0
EnParaffin^jj
C26 c ,0
ZnParaffin;,--
0.07
1.2
14.93
8.04
14.62
7.51
14.20
9.50
7.65
40.66
13.13
8.28
3.45
10.20
9.50
8.80
8.20
7.40
X20
21
'»
C27 OQ
*
C™ c "0
lnc=40
ZnParaffin0"'
c— *»u
Z C^f^C^ 1 "^"C^^
E C30+C31+C32
Z C20+C? 1+C2 2+C30+C31+C32
r C24+C25+C26+C27+C28
I CnH2n-6
Z CnH- . o
£.tl~ iO
2n— 6 2n~18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Numerical
Value
6.90
4.10
5.60
2.10
1.16
1.96
1.59
5.90
Origin - Nigerian
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 116 -
-------
Computer No. 410559
Analytical No. 578606
Numerical Numerical
Index Formula Value Index Formula Value
\
12
J3
T4
*5
h
17
ls
J9
Z10
Tll
X12
Z13
'14
hi
X16
X17
J1B
V
Ni
S
: N
ECnH2n-6
EAromatic
ECnH2n-6 C=^
JAromat ics
ECnH2n-10
^Aromatic c=2Q
FCnHin 10 c~36
^Aromatic
ECnH2n-14
EAromatics
EAromatics
ECnH2n-18
EAromatics
ZnParaf f ins
£ (P + N)
E 3 Ring Naphthenes
Z(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 _ OQ
EnParaffin^^
C21 . ,Q
EnParaffin^ 7X
c=40
C24 ,Q
EnParaf f inv'_'"
C7S c_^0
EnParaffinv'_""
C26 . ,0
EnParaffin"" ?„
c=4u
0.22
1.30
15.94
9.43
14.22
8.87
15.12
10.51
9.94
39.82
13.93
10.10
4.30
10.30
9.10
8.30
8.40
7.10
X19
Z20
X21
X22
J23
X24
X25
T26
C27
i-'nParaffin^ ^"
0=40,
C^O ,n
EnParaffin"- '"
r=40
V C^ c-20
ZnParaffin^J
E C70+C71+C7?
Z C30+C31+C32
E C20+C?]+C22+C30+C3]+C32
L C24+C25+C26+C27+C28
E CnH2-i-6
1 CnH2n-18
E CnH2n_6+ECnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
Z-5 .Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 10
Weathering^ Temperature , °F - 55
Mixing Condition - High Mix
7.10
4.10
6.00
1.93
1.16
1.61
1.72
6.30
- 117 -
-------
Computer No. 421559
Analytical No. 578623
Numerical Numerical
Index Formula Value Index Formula Value
Xl
X2
X3
'«
:5
X6
X7
X8
X9
X10
Xll
X12
J13
X14
'15
J16
X17
X18
! v
Ni
£
N
£CnH2n-6
E Aromatic
£CnlI2n-6 C=*£
EAromatics^"
£CnH2n-lQ
Aromatic
ICnH2n-10 c=36
^Aromatic
ZCnH2n-lA
S^romatics
ICnH2n-16
EAromatics
JTCnH2n-18
EAromatics
EnParaffins
1 (P + N)
£ 3 Ring Naphthenes
E(P + N)
£ 4 Ring Naphthenes
£(P + N)
£ 5 Ring Naphthenes
£(P + N)
020 c-"0
TnParaffin^--
C21 C_^Q
EnParaffin^^
C24 c--0
EnParaffin^Q
C?S j-^Q
EnParaffin-,--
C26 C^o0
EnParaffin^'Q
0.08
1.2
14.62
8.05
14.61
7.65
15.50
10.33
8.47
40.71
12.87
8,90
3.60
9.90
10.60
8.10
8.10
6.80
T19
J20
J21
X22
J23
T24
T25
T26
C27 „
EnParaffin1" "
c=bQf
C30 . on
InParaffin" ""
r=40
Cn „„
£nParaffin" t"
c-AO
I C7(rK:2i+C7?
1 C30+C31+C32
£ C20+CTi+C22-*-C30+C^i-t-C32
1 C24+C25+C26+C27+C28
I CnH2n-6
E ^n-lB
I CnH2n_6+ICnH2n_18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthenes
Sample History
6.90
4.10
5.60
2.11
1.22
1,73
1.49
6,00
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - High Mix
1
- 118 -
-------
Computer No. 421551
Analytical No. 598576
Index
Formula
Numerical
Value
Index Formula
Numerical
Value
h
h
13
*4
h
X6
J7
X8
*9
T10
Xll
X12
T13
X14
Xi5
Z16
hi
X18
V
Ni
S
N
ZCnH?n-6
lAroraat ic
ECnH2n-6 C=?°
EAroinat ics
ECnH2n-10
EAromatic
c=2u
£CnH2n-10 c=36
EAromatic
ICnH2n-lA
EAromat ics
iLnH2n-16
EAromatics
ZCriH^p-lg
EAromat ics
ZiiParaffins
I (P + N)
£ 3 Ring Naphthenes
E(P + N)
£ 4 Ring Naphthenes
£(P + N)
£ 5 Ring Naphthenes
£(P + N)
C20 C_o0
InParaf f in1"_tg
C21 ,0
Znparaffin" "
c=40
C2^ ._,0
EnParaffin^=40
Co1! c ^Q
EnParaffin^-Q
C26 c o0
EnParaf f in""_TQ
0.08
1.3
15.84
9.07
13.91
7.50
15.16
10.27
8.12
39.96
13.27
7.61
2.53
10.6
12.1
8.6
8.6
7.4
J19
J20
Z21
Z22
X23
12U
T25
J26
C27 . „
^'nParaffin^ ""
0=40^
C30 . on
InParaffin"-";"
c=40
C^T ^ OQ
InParaffin ,.-,
c™40
£ C?o+C?i+C72
1 C30+C31+C32
£ C20+C?l+C22+C30+C3l+C32
E C24+C25+C26+C27+C28
£ CnH2n-6
S CnH2n-18
E CnH2n_6+ECnH2n_18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 21
Weathe
Mixing Condition - Low Mix
7.1
4,4
3.8
3.16
1.12
1.95
1.57
11.6
- 119 -
-------
Computer No. 421801
Analytical No. 586005
Numerical
Index Formula Value Index Formula
h
h
1B
X13
X17
'18
V
Ni
S.
N
ECnH2n-6
EAromat ic
ECnH2n-6 °=2°
EAromat ics""
ECnH2n-10
EAromat ic .-
ECnH2n-10 c=36
EAromat ic
EAromat ics
EAromat ics
EAroitatics
EnParaffins
E (P + N)
1 3 Ring Naphthenes
I(P + N)
I 4 Ring Naphthenes
I(P + N)
E 5 Ring Naphthenes
£(P + N)
C2° c-"0
C21 c ,Q
C?4 Cr--0
C26 c^^0
InParaffin^--
0.25
1.1
13.73
7.39
15.50
7.06
16.71
9.98
6.17
39.59
13.46
7.97
2.57
10.8
9.9
8.8
8.8
7.2
X20
I22
*»
C27 c ,Q
CM n0
2nParaffin^_^
C?1 c "0
1 C30+C31+C32
E c24+c25+c26+c27+c28
E CnH2n-6
1 0nH2n-18
£ CnH2n-6+ICnH2n-18
CnH2n-14
Z-l Rine+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 21
Weathering Temperature, F - 80
Mixing Condition - Low Mix
Numerical
Value
6.8
4.6
4.8
2.49
1.13
2.22
1.19
11.0
- 120 -
-------
Computer No. 410801
Analytical No. 588718
Numerical Numerical
Index Formula Value Index Formula Value
H
12
X3
X9
X10
Hi
X12
X13
Hs
X16
X17
V
Ni
S
N
ECnH2n-6
EAromatic
ECnH?n-6 C=^
EAromatics1"
ECnH2n-lQ
EAromatic
EAromatic
ECnH2n-14
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaf fins
E (P + N)
£ 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 _ -,Q
EnParaffin^"
C21 _,0
Q= q. 0
EnParaffmc=40
EnParaffin^" 7X
c=40
C26 ,Q
EnParaffin^Q
0.29
1.37
11.90
7.26
19.18
5.39
14.84
11.48
7.80
42.70
14.10
8.61
2.14
10.1
9.7
8.8
8.6
7.5
X20
X21
X23
X25
C27
J-nParaffin^^
C30 _ ,Q
ara lnc=ijQ
EnParaf finC_'
. l C30+C31+C32
1 C24+C25+C264C27+C28
E CnH2n-6
Z CnH2n-18
CnH2n-14
E-l RinR+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthanes
Sample History
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
7.1
4.9
4.3
2.52
1.07
1.53
1.33
15.0
- 121 -
-------
Computer No. 410809
Analytical No. 525319
Numerical
Index Formula Value Index Formula
h
h
19
ho
hi
h2
t
"13
hs
hi
hB
V
Ni
S
N
ICnH2n-6
EAromatic
ECnH2n-6 C=3°
EAromatics""
ECnH2n-10
EAroraatic
ECnH2n-10 c=36
EAromatic
ECnH2n-14
EAromatics
ECnH2n-16
EArowatics
ECnH2n 18
EAromatics
EnParaffins
E (P + N)
E 3 Ring Naphthenes
I(P + N)
£ 4 Ring Naphthenes
Z(P + N)
I 5 Rin& Naphthenes
E(P + N)
C20 _ ,Q
C21 . ,0
EnParaffin^o
EnParaffinc=40
C26 ,Q
EnParaffin^-
.14
1.5
15.08
7.97
14.01
6.39
15.59
10.17
7.78
44.19
13.57
8.18
1.59
10.60
10.32
8.43
8.33
7.10
'19
'22
Z25
C27 c__0
nParaffinc=4Cl
InParaffin^=~0
C,i
InParaffinC_^°
1 C30+C31+C32
Z C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-6+ICnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthanes
Sample History
Numerical
Value
6.68
4.07
5.26
2.31
1.40
1.94
1.47
19.9
Oil Type - Crude
Origin - Nigerian
Weathering Time, days - 10
Weathering Temperature. °F - 80
Mixing Condition - High Mix
- 122 -
-------
Computer No. 421809
Analytical No. 525404
Numerical Numerical
Index Formula Value Index Formula Value
^
X6
h
1B
'11
X15
X16
Z17
V
Ni
S
N
ZCnH?
ZAromatic
ZCnH?.n-6 °=3°
ZAromatics
ZCr>H2n-10
lAromatic
yTnHon— 1 n r- 36
lAromatic
ZCnH2n-14
ZAromatics
ZCnH2n-16
ZAromatics
ZCnH2n-18
ZAromatics
ZnParaffins
E (P + N)
£ 3 Ring Naphthenes
S(P + N)
£ 4 Ring Naphthenes
£(P + N)
Z 5 Ring Naphthenes
£(P + N)
C20 _ ,0
C21 -,Q
C24 _
Erfaraffin^J
C" --o
ZnParaf finu_^"
C26 ._,Q
InParaffin^-
0. 33
0.77
15.32
9.06
14.21
7.47
16.00
10.53
8.34
43.96
12.66
8.10
3.16
10.30
9.9
9.1
9.4
7.8
J19
X20
X23
X24
Oil '£yi
C27 ,Q
nParaffin^
ZnParaffin^^
£31 c- 2 0
. Z C30+C31+C32
Z C24+C25+C26+C27+C28
Z CnH2n-6
1 CnH2n-18
Z CnH2n.6+ZCnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Origin - Nigerian
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
7.1
4.0
5.1
2.48
1.05
1.83
1.48
6.30
- 123 -
-------
Computer No. 500000
Analytical No. 578633
Numerical Numerical
Index Formula Value Index Formula Value
h
*2
X3
X4
JS
l€
17
1B
19
ho
hi
h2
hi
X14
J15
J16
hi
J18
V
Ni
S
I N
ECnH2n-6
EAromatic
ECnH2n-6 C"*°
EAronatics""
£CnH2n-10
EAromatic c_20
rCnH">«-1fi r«*lA
EAromatic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
EAromatics
EnParaffins
E (P + N)
I 3 Ring Naphthenes
E(P + N)
E 4 Rlng^ Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + »)
C20 ,n
InParaffin1" '"
c-40
C21 ___„.
EnParaffin ,n
c"40
026 -.= -0
EnParaffin^J
C">* r-->0
EnParaffin^;J
C26 r«JO
EnParaffin ."
c-40
0.30
2.5
16.51
8.67
14.10
7.87
12.63
9.21
9.37
49.54
8.25
5.80
2.32
13.70
11.40
8.10
7.30
6.10
J19
Z20
X21
X22
T23
X24
^5
X26
Oil Tyj
C27 ,Q
i-nParaffin^^
c-?o _ .n
SnParaffin" 'X
c=40
C-,! _ ,Q
InParaffin^^
I C50+C7T+C??
1 C30+C31+C32
S C20+CV1+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 ^^n-lS
I CnH2n^+ICnH2n_18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring-l-6 Ring Naphthenes
Sample History
5.40
3.70
3.60
3.62
1.45
1.77
2.05
9.19
Origin - Zuitina
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 124 -
-------
Computer No. 521809
Analytical No. 525403
Index Formula
h
'«
ho
hi
T
"13
'»
V
Ni
S
N
rr-nNi c
EAromatic
c=20
ECnH2n-6 C ^
EArotnatics1"
ECnH2n-lQ
JArcmatic
c=^0
EAromatic
EAromatics
EAromatics
EAromatics
EnParaf fins
Z (P + N)
Z 3 Ring Naphthenes
E(P + N)
E 4 Ring Saphthenes
E(P + N)
L 5 Ring Naphthenes
Z(P + N)
C20 £ n0
TnParaffin^o
C21 ^0
EnParaf fin , .
c=4U
C24 . o0
EnParaffin^^
EnParaf finc_"
C26 . ,0
EnParaffin"" 7n
c=40
Numerical Numerical
Value Index Formula Value
0.26
2.05
17.40
10.68
13.66
8.22
14.49
10.69
9.72
48.23
7.84
6.03
2.63
14.6
12.5
8.8
8.2
6.3
'»
21
'»
C27 ,Q
^Paraffinc=40
ZnParaffin^"2°
• "^ (• 20
1 C30+C31+C32
Z C2Q+C71+C22+C3Q+C31+C32
1 C24+C25+C26+C27+C28
Z CnH2n-6
Z CnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthanes
Sample History
5.3
3.5
3.1
4.42
1.42
1.79
1.87
7.70
Oil Type - Crude
Origin - Zuitina
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
- 125 -
-------
Computer No. 510559
Analytical No. 578605
Numerical Numerical
Index Formula Value Index Formula Value
\
h
h
\
h
16
17
1B
J9
X10
Xll
X12
X13
r!4
X15
X16
117
h*
V
Ni
S
N
ECnH2n-6
lAromatic
ICnH2n-6 C=^°
ZAromatics""
ZCnH2n-10
JAromatic
ICnH2n-10 c-36
lAromatic
ICnH2n-14
rAromatics
ICnH2n-16
ZAroroatics
ZCnH2n-18
Wromatics
SaParaffins
E (P + N)
£ 3 Ring Naphthenes
E(P + N)
I 4 Rine Naphthenes
Z(P + N)
I 5 Ring Naphthenes
E(P + N)
020 c-"0
InParaffin^Q
C21 _,Q
EnParaffin;^
C24 f"0
EnParaffin^-~
C?-; ^^Q
EnParaffin^--
C26 c^-0
EnParaffin^-Q
0.10
2.90
16.94
10.83
15.10
10.20
13.21
10.24
10.51
46.53
8.53
6.35
2.53
14.50
12.10
8.80
8.10
6.50
X19
X20
J21
J22
J23
:24
Z25
X26
Oil Tvi
C27 ...,Q
inparaffinc=40.
C30 oc
EnParaffin^^
C^n _ ,Q
EnParaffin1" ?»
c~40
I ^)0+C2T+C;j
1 C30+C31+C32
£ C20+C?i+C22+C30+C3i+C32
Z G24+C25+C26+C27+C28
S CnH2i-6
1 ^^n-lB
1 CnH2n-6+l:CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Origin - Zuitina
Weathering Time, days - 10
Weathering Temperature, °F - 55
Mixing Condition - High Mix
5,80
3.40
3.30
4.34
1.36
1.61
2.09
9.21
- 126 -
-------
Computer No. 521559
Analytical No. 578622
Numerical Numerical
Index Formula Value Index Formula Value
h
X2
Z3
X6
X7
X8
X9
xio
X12
X13
X15
X16
X17
X18
V
Ni
N
ECnH2n-6
EAromat ic
£CnH2n-6 °~3C
EAromatics""
£CnH2n-10
EAromatic
c=2(J
ECnH2n-10 c=36
EAromat ic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
ECnH2n-l 8
EAromatics
EnParaf fins
E (P + N)
£ 3 Ring Naphthenes
E(P + N)
E A Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 C_,Q
C21 C_o0
Enparaf f in"_, ,.
CP5 C_2Q
C26 C_o0
0.2
2.8
16.92
9.52
14.70
8.77
12. 77
10.49
11.08
47.06
8.40
6.22
2.40
13.30
11.80
8.60
8.20
6.50
X20
I22
T23
X25
C27 ,,Q
^nParaf finC_^Q
C30 HQ
SnParaffin '
c=AO
C^l
EnParaffinc_40
. l C30+C31+C32
E C2(H-C?i+C22+C30+C3i+C32
Z C24+C25+C26+C27+C28
I CnH2n-6
S CnH2n-18
I CnH2n_6+ECnH2n_18
^rt 1 A
E-l Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample History
5.70
3.70
3.29
3.87
1.33
1.53
2.17
Oil Tvpe - Crude
Origin - Zuitina
Weathering Time, days - 21
Veathering Temperature, °F - 55
Mixing Condition - High Mix
- 127 -
-------
Computer No. 510801
Analytical No. 588717
Numerical Numerical
Index Formula Value Jndex Formula Value
Xl
h
*3
*4
h
lo
17
X8
Z9
'10
hi
lu
T
~13
X14
X15
X16
Z17
X18
V
Ni
S
K
ECnHjn 6
E Aromatic
ECnH2n-6 C=^
JAromatics1"
ICnH2n-10
Aromatic ^^
ICnH2n-10 c=36
Aromatic
ECnH2n--14
Wroraatics
ECnH2n-16
EAromatics
ZCnH2n-18
EAromatics
EnParaffins
E (P + N)
I 3 Ring Naphthenes
Z(P + N)
£ 4 Ring Naphthenes
I(P + N)
I 5 Ring Naphthenes
Z(P + N)
C20 „,„
InParaffin^;"
C21 r .n
EnParaffin" '"
c=40
C2« ,n
EnParaffin1-"'"
c=40
C?S r ,n
EnParaffin ,.
c=40
C26 ^-20
EnParaffin" 'X
c*40
0.15
2.92
16.70
10.30
12.70
7.62
13.20
9.80
9.90
48.64
8.76
5.96
0.00
14.7
12.9
8.9
8.1
6.3
T19
X20
X21
X22
J23
J24
X25
X26
C27
i-nParaffin" ,„
c=40^
u C
-------
Computer No. 521551
Analytical No. 586030
Index
Formula
Numerical
Index , Formula
Numerical
Value
J
'•
X12
hi
V
Ni
S
N
EAromat ic
ECnH2n-6 C~&
EAromat ics
ECnH2n-10
EAromat ic
EAromat ic
ECnH2n-14
EAromat ics
ECnH2n-16
EAromat ics
ECnH2n-18
EAromat ics
ZnParaffins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
£(P + N)
E 5 Rinf> Naphthenes
E(P + N)
C20 ,Q
EnParaf f in1" '"
c=40
C21 ._„„
EnParaffin^-
EnParaf finc_'
C26 «Q
EnParaf fin1" t«
0.19
2.8
17.61
9.89
13.92
8.01
13.02
9.49
8.65
48.27
8.81
5.95
1.92
14.6
12.5
8.9
7.9
6.4
'»
'22
'„
C27 . ,Q
inParaffin^=^
C30 _ ^0
EnFaraffinc=^o
CT1 . 7ri
EnParaffin-.^
E C30+C31+C32
£ C20+C71+C22+C3Q+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
I CnH2n_6+ECnH2n_lfi
CnH, . .
2n-14
E-l RinR+2 Rin^ Naphthenes
Z-5 Ring+6 Ring Naphthanes
Sample History
Oil Type - Crude
Origin - Zuitina
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - Low Mix
5.5
3.4
2.9
4.6
1.39
2.03
2.01
14.70
- 129 -
-------
Computer No. 510009
Analytical No. 525318
Numerical Numerical
Index Formula Value Index Formula Value
h
J2
J3
'«
J5
J6
J7
J8
*9
ho
lll
h2
X13
Jl«
315
T16
X17
J18
V
Ni
_S
N
ECnH2n-6
I Aromatic
ECnH2n-6 £=3°
EAromatics""
ECnH2n-10
EAromatlc
c"20
5"CnH->n in 0=^6
ZAromatic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
ECnH2n-18
LAromatics
liiParaffins
I (P + N)
I 3 Ring Naphthenes
I(P + N)
£ 4 Ring Naphthenes
Z(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 ,_
rnParaffin" 'X
c=40
C21 _-
EnFaraffin" '°
c=40
C24
rnParaffin1-"'"
c=40
Cjc* f -n
EnParaffin" '"
c>=40
C26 ,„
EnParaffirT1-"^
c«40
0.24
2.2
17.25
10.76
14.32
9.40
13.40
10.35
10.68
47.18
7.88
6.09
3.03
14.3
12.5
9.2
8.3
6.4
X19
^0
X21
122
X23
X24
J25
126
C27 „
i-"nParaf£in" '"
c=40,
CM . -n
EnParaffin" ""
c=40
Cii c OQ
ZnParaffin^^o
Z C70+C71-I-C7?
E C30+C31+C32
I C20+C?i+C22+C30-*-C3i+C32
L C24+C25+C26+C27+C28
Z CnH2n-6
1 ^n-lS
E CnH, ,+ECnH, ia
2n-6 2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
£-5 Ring+6 Ring Naphthenes
Sample History
5.7
3.4
3.0
4.26
1.31
1.61
2.08
5.92
Oil Type - Crude
Origin - Zuicina
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - High Mix
- 130 -
-------
Computer No. 600000
Analytical No. 577727
Numerical
Index
Formula
Formula
Numerical
Value
- — — - •• -
h
h
X9
X10
X12
T
X17
X18
V
Ni
N
ECnH2^— 6
EAromatic
ECnH2n-6 C~^6
EAromatics1"'
ECnH2n-10
EAromatic
ECnH2n-10 c-36
EAromatic
EAroraat ics
ECnH2n-16
EAromatics
£CviH2n 18
EAromatics
EnParaf fins
E (P H- N)
E 3 Ring Naphthenes
£(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 c o0
EnParaf f in^TX
C21 C_o0
EnParaffinc=40
EnParaffinC_^0
C26 _ o0
EnParaffin\^Q
-10
11.30
10.65
0.63
4.58
0.36
18.47
8.12
10.83
51.18
9.35
5.17
1.95
47.00
28.20
2.40
1.00
0.45
X20
X21
X25
C27 _Q
lnc=40.
C-,0 ~Q
EnParaffin'" tX
r=4.Q
C^i
2nParaffinL ^
c=40
I C7Q+C?1+C?7
. E C30+C31+C32
Z C2Q+C?]+C22+C30+C3i+C32
1 C24+C25+C26+C27+C28
Z CnH2n-6
1 CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
0.25
0.00
0.00
20.50
0.99
1.16
16.50
Oil Type - Xo . 2 Fuel Oil
Origin -
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
V
Note: Ni index for No. 2 fuel oil w
ratios of very small values i
assigned to represent this coi
as always
e. ,
*as arbitrarily
idition
- 131 -
-------
Computer No. 610551
Analytical No. 573078
Index
Formula
Numerical
Value
Index Formula
Numerical
Value
*1
T2
J3
X4
J5
h
X7
ls
19
T10
Xll
X12
X13
J14
X15
T16
h7
he
V
Ni
S
N
ZCnH2n-6
£ Aromatic
£CnH2n-6 c"*°
ZAromatics'"
£CnH2n-lQ
ZAromatic
ECnHjn-lO c=36
EAromatic
ECnH2n-14
EAromatics
ECnH2n-16
£Aromatics
ICnH2n-18
EAroicatics
^Paraffins
Z (P + N)
£ 3 Rlnfi Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C2° f^a
InParaffin'" '"
c=40
C21 _ ,n
ZnParaffin1" "
c=40
C24 . ,n
ZnParaffin" .„
c=40
C^S ?n
ZnParaffin" "
c=40
C26 »?n
ZnParaffin"- "
c-40
-10
15.0
10.2
.5
4.20
0.20
t
20.0
8.40
12.10
62.0
4.0
3.3
0.20
47.0
28.2
2.6
1.2
0.5
X19
X20
Z21
Z22
T23
J24
J25
126
C27 ?n
2-nParaffin1- '"
c=40.
Cw on
SnParaffin" ^
cr=40
C-^T „
SnParaffin""^
c"40
£ C70+C?1+C77
E C30+C31+C32
^ C20+C9j+C22+C30<-C3i+C32
1 C24+C25+C26+C27+C28
S CnH2n-6
' ^^n-lS
E CnH2n-6+ICnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
Z-5 Ring-Hi Ring Naphthenes ,
Sample History
0.3
0.1
0.1
34.0
19.0
0.8
1.2
17.0
Oil Type -
Origin -
Weathering Time, days -
Weathering Temperature, °F -
Mixing Condition -
- 132 -
-------
Computer No. 6L0559
Analytical No. 578610
Index
Formula
Numerical
Value
Formula
Numerical
Value
h
h
ho
h.
V
Ni
S
N
ECnH2n-6
EAromat ic
£CnH2n-6 C~,£
EAromat ics1"
lAromatic _
£CnH2n-10 c=36
EAromat ic
EAromat ics
ECnH2n-16
EAromatics
FCnH?n i ft
EArotr.atics
EnParaf fins
1 (P + N)
£ 3 Ring Naphthenes
£(P + N)
I 4 Ring^ Naphthenes
I(P + N)
I 5 Ring Naphthenes
Z(P + N)
C20 c OQ
C21 ._,„
ZnParaffin" ""
C— ** U
C24 c__0
5.nParatfinc=40
C26 c ,Q
ZnParafflnc=40
-10
14.80
10.21
0.47
4.21
0.14
19.51
8.38
12.09
62.20
3.90
3.30
0.20
46.60
28.20
2.60
1.13
0.52
h*
hi
Z22
X25
C27 ,Q
^-nParaf f in1" tX
0=40,
InParaffin^=2°
c,,
ZnParaffinC ^ n
c=40
. l C30+C31+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
CnH2n-14
l-l Rlng+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
0.30
0.13
0.13
3.42
18.9
0.84
1.15
Oil Type No • 2 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, °F - 55
Mixing Condition - High Mix
- 133 -
-------
Computer No. 621559
Analytical No.
578628
Index
Formula
Numerical
Value
Index Formula
Numerical
Value
h
12
h
l*
h
*6
17
h
h
ho
hi
hz
X13
*14
'IS
'16
ln
ht
V
Ni
S
N
ZA-nH2n-o
£ Aromatic
£CnH2n-6 C=^
lAromatics'"
ZCnH2n-10
EAromatic _
^Aromatic
rCnH2n-14
lAromatics
ZCnH2n-16
lAromatics
j;CnH2n-i8
lAromatics
EaParaffins
E (P + N)
£ 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C2° r»-n
InParaffin— J
C21 r ,n
EnParaffin^
C24 ,0
EnParaffin;=;J
C'^ ro"0
EnParaffinc40
C26 r=-0
ErtParaffin^^
-10
14.0
10.44
.53
4132
.U
20.03
8.39
13.61
60.70
4.00
3.10
0.00
48.50
27.20
2.. 30
0.80
0.22
ho
ho
hi
h2
hi
J24
X25
J26
C27 ,-
J-'nParaffin" ^
0=40,
C30 r *n
EnParaffin" t"
c=40
Cn ,.
EnParaffin"" '"
c~40
Z C7o+C2i+C22
Z C30+C31+C32
I C20+C?l+C22+C30+C31-l-C32
1 C24^C25+C26+C27+C28
I CnH2n-6
1 ™2n-18
E CnH2n_6+ECnH2n_18
CnH2n-H
E-l Ring+2 Ring Naphthenes
E-5 Ring-^ Ring Naphthenes
Sample History
Oil Type - No. 2 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - High Mix
0.11
0.00
0.00
26.70
0.77
1.21
- 134 -
-------
Computer No. 61( 80',»
Analytical No. 525324
Numerical Numerical
Index Formula Value Index Formula Value
h
12
19
ho
T
'13
T15
X18
V
Ni
S
N
ZCnH2n-6
Z Aromatic
ECnH2n-6 C=^°
EAromatics1"
ZCnH2n-10
ZAromatic _..
ECnH2n-10 c=36
EAroraatic
ECnH2n-14
EAromatics
ECnH2n-16
EAroraatics
ECnH?n-l 8
EAromatics
ZnParaff ins
Z (P + N)
Z 3 Ring Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
Z(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C20 c_,-,0
C21 c_^0
C24 C_o0
ZnParaffin _~.Q
C26 C_o0
rnParaffinc=40
-10
13.50
11.60
0.72
4.82
0.38
20.48
7.47
9.54
60.70
2.50
3.80
0.00
49.80
28.40
1.90
0.60
0.00
'20
-»
<„
C27 ,
InP.raffln^
ZnParaffinC "
c=40
!nParaffinc-40
. Z C30+C31+C32
2 C20+C?_i+C22+C30+C3l+C32
Z CnH2n-6
^ CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - No. 2 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - High Mix
0.00
0.00
0.00
36.70
1.22
1.03
- 135 -
-------
Computer No. 621801
Analytical No. 525409
Numerical Numerical
Index Formula Value Index Formula Value
'l
X2
J3
\
J5
16
J7
X8
19
ho
Jll
X12
X13
Z1A
'is
J16
J17
X18
V
Ni
S
N
ECnH2n 6
EAromatic
£CnH2n-6 C=^°
EAromatics""
£CnH2n-10
EAromatic c_2Q
£CnH2n-10 c=36
EAroraatic
ECnH2n-14
EAromatics
£CnH2n-16
EAroraatics
ECnH2n-18
EAromatics
EnParaffins
E (P + N)
Z 3 Ring Naphthenes
Z(P + H)
Z 4 Ring Naphthenes
Z(P + H)
I 5 Ring Naphthenes
Z(P + N)
C20 c OQ
rnParaffin^g
C23 C_n0
rnParaffin"=~Q
C24 C_,Q
EnParaffin^Q
C?s c_^0
EnParaffin^=~Q
C26 c_^0
EnParaffin^p
-10
28.5
10.99
0.88
4.36
0.32
22.35
9.15
13.31
63.6
3.1
2.4
0.0
51.8
26.8
2.1
0.7
0.2
X19
I20
X21
122
X23
X24
*25
X26
C27 „_
i-'nParaffin^ '"
c=AO,
c^o ..20
ZnParaffin^^
V C^ c 20
inParaffin .„
c-40
I C7o+C7l+C?7
Z C30+C31+C32
Z C20+C?1+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
Z CnH2n-6
1 ^"an-is
1 Cn»2n-6+ZCnH2n-18
CnH2n-l4
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthanes
Sample History
Oil Type - No . 2 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature, °F - 8U
Mixing Condition - High Mix
0.0
0.0
0.0
30.5
0.83
1.10
- 136 -
-------
Computer No. 621809
Analytical No. 598591
Numerical Numerical
Index Formula Valnp Index Formula Value
12
*>
h2
J16
X17
X18
V
Ni
N
ZCnH2n-6
ZAromatic
ICnH2n-6 °~3e
ZAromat ics
ZCnH2n-10
lAromatic _..
£CnH2n-10 c=36
ZAromatic
ZCnH2n-14
ZAromat ics
ZCnH2n-16
ZAromat ics
ZCnH2n-18
ZAromat ics
ZnParaffins
1 (P + N)
Z 3 Ring Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
£(P + N)
Z 5 Ring Naphthenes
Z(P + N)
C20 c ->0
C21 __,0
ZnParaffinC_^0
C2fi c^0
ZnParaffin^=-
-10
31.6
14.11
0.62
5.69
0.28
18.38
6.00
7.32
51.1
9.25
3.65
0.33
45.3
27.5
4.1
2.0
0.0
X19
X22
X23
:;:
C27 ^Q
nParaffinc=4(l
ZnParaffin ". n
c=40
c,,
ZnParaffin^^0
1 C30+C31+C32
1 C24+C25+C26+C2/'C28
Z CnH2n-6
Z CnH2n-18
CnH2n-14
Z-l Ring+2 Ring Narjhthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - NO. 2 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature, F - SL)
Mixing Condition - High Mix
0.0
0.0
0.0
10/10
14.3
1.92
1.17
-
- 137 -
-------
Computer No. 621801
Analytical No. 586050
Index Formula
Numerical
Value Index Formula
Numerical
Value
h
1
L2
13
A
5
X6
I?
-
8
Z9
xio
T
11
12
T
13
14
15
16
17
T18
N'i
S
N
ICnH? 6
lAromatic
ICnH2n-6 C"^
EAromatic a1"
EAromatic
5"CnH2n-10 c=^6
EAromat ic
ECnH2n-l^
ZArotrsat ics
iCnH2n-16
TAromatics
ICnH2n-18
EAromat ics
JilParaffins
E (P + K)
Z 3 Ring Kaphthenes
T(v> + K}
T. A Ring XaDhthenes
I(P + N)
-, _
I(P + N)
C20 ,Q
TnParaffin^^
C21 oQ
tnParaffin T_
c=40
EnParatfin^_^
EnParaf f inv_'
C26 ,Q
InParaffin^-
-10
8.0
1 .00
- . _
- 33
2 1 . 9 ">
60 . /O
3 .80
0 00
30 00
-" 6 00
; .90
0 . oO
0 . 20
T20
I
21
Z22
,
23
24
j
25
X26
Origin
Weather
Weather
Mixing
C27 ,Q
^•nParaf f in"" f«
c=40
«
En?araffinL 7,-,
c= 40
: C.ll - ?Q
. InParaffin _~Q
S C30+C31+C32
- C20~*~C^i+r^2+C30~H'3^~^32
E C2i+C25+C26+C27+C28
•- CnH-,,-6
" CnH2n-18
I CuH2n.6+ICnH2n_lg
r"nH
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample Historv
inp Time, davs - 21
ing Temperature. °F - 80
Condition - Low Mix
0.10
o
0
10/10
27 .00
1 .95
091
- 138 -
-------
Computer No. 610801
Analytical No. 533723
Index
Formula
Numerical
Value , Index , Formula
Numerical
Value
h
''
h2
h3
hs
he
h7
hs
V
Ni
s
N
ii^nn2 ji~~o
EAromatic
ECnH2n-6 C~ '
EAromat ics
ECnH2n-10
EAromatic _
EAromatic
ECnH2n-14
EAromat ics
ECnH2n-16
EAromat ics
ECnH2n-18
EAromat ics
ZnParaf f ins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E It Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 _ ,Q
InParaffin^" 'X
c=40
C21 ._,Q
C24 . ^
EnParaf f inv_4"
EnParaffin^ "
c=40
C26 __,Q
InParaffin^-
-10
13.5
10.62
0.69
4.54
0.22
22.80
7.12
8.20
51.40
9.40
3.60
0.00
48.0
28.4
2.1
0.3
0.0
T20
Z21
T23
X»
Oil Ty
C27 . ,0
lnc=40t
SnParaf f in^'tf.
c,.
EnParaffin1" '
c-40
I C7Q+C2i+C?7
y f +r +r
. " ^30 31 32
E C2Q+C?i+C22+C30+C3l+C32
E C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
1 Cn«2n-6+ECnH2n-18
CTlH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Origin -
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
0.0
0.0
0.0
31.8
1.29
0.83
- 139 -
-------
Computer No. 700000
Analytical No. 578650
Numerical
Index Formula Value Index Formula
H
H
X5
16
19
Ho
Hi
X12
H«
X15
He
H7
He
V
Ni
ij
EAromat ic
ECnH2n-6 C~^
EAromatics1"
lCnH2n-10
ZAromatic 20
ECnH2n-10 c=36
EAromat ic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
EAromatics
JjjParaffins
Z (P + N)
I 3 Ring Naphthenes
E(P + N)
i 4 RinK Naphthenes
E(P •«- N)
I 5 Ring Naphthenes
E(P + N)
C2° CT--O
C21 C_,Q
C24 .,.,„
C26 c-'O
5.3
3.6
19.67
8.31
15.03
7.45
11.03
7.88
5.73
34.93
11.16
5.46
1.49
20.3
11.8
7.5
7.5
6.9
X19
Hi
>25
C27 ,Q
InParaffin^
CIT fn
EnParaffin" t"
c~40
1 C30+C31+C32
1 C244C25+C26+C27+C28
I CnH2n-6
1 CnH2n-6+5:CnH2n-18
CnH2n-14
Z-l Rlng+2 Ring Naphthenes
Z-5 Rlng+6 Ring Naphthenes
Sample History
Oil Type - No, 4 Fuel Oil
Numerical
Value
6.8
4.3
3.1
4.54
1.52
3.46
2.31
Origin -
Weathering Time, days - Unweathered
Weathering Temperature, °F -
Mixing Condition -
- 140 -
-------
Computer No. 710559
Analytical No. 525301
Numerical Numerical
Tnrlpx Formula Vil'j" TnH..L Formula Value
h
X2
X8
X10
:13
he
V
Ni
S
N
ECnH2n-6
£Aromat ic
£CnH2n-6 C",c
JAromat ics
E Aromatic ,
c=20
ECnH2n-10 c-36
EAromat ic
ICnH2n-14
EAromat ics
ECnH2n-16
EAromatics
£,v>n n2j^ — ,1-, 8
EAromatics
InParaf f ins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 . o0
C21 __OQ
EnParaffin
c=40
EnParaffin _,„
C26 c ,Q
EnParaf f in^"_^Q
6.8
3.8
18.98
9.11
15.66
8.05
11.93
8.76
5 . 84
35.11
11.45
5.72
1.50
19.3
12.0
7.0
7.0
6.5
Z20
X23
'25
C27 c _0
^nParaffin ", n
c=»0t
ZnParaffin ". .
c=40
Cv
I C7Q+C21+C?2
E C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
E CnH2n-18
£ CrxH2n_6^CnH2n_18
CnH2n-14
E-l Rin?+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
5.7
3.4
5.5
3.53
1.68
3.25
2.09
29.0
Oil Type - No. 4 Fuel Oil
Origin -
Weathering Tine, days - 10
Weathering Temperature, °F - 55
Mixing Condition - High Mix
- 141 -
-------
Computer No. 721551
Analytical No. 598582
Index Formula
Xl
12
X3
X4
X5
X6
17
1B
19
J10
Tll
J12
*13
Z14
X15
ri6
X17
h*
V
Ni
S
N
ICnH2n-6
EAromatic
£CnH2n-6 C"j°
ZAromatics*"
ICnH2n-10
EAromatic ^^
ECnH2n-10 c=36
lAromat i c
ICnH2n-U
JAromatics
rCnH2n-16
lAroroatics
SCnH2n 18
ZAromatics
foParaffins
I (P + N)
E 3 Ring Naphthenes
E(P + N)
I 4 Ring^Naphthenes
l(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 7n
rnParaffin^J
C21 ,0
ZnParaffin1- '„
c-40
C24 ..
EnParaffiiT- '"
c-40
C's ^«-n
EnParaffin" "
c»40
C26 ,n
EnParaffin^ '"
c»40
Numerical Numerical
Value Index Formula Value
5.7
3.5
24.07
11.98
19.65
11.68
7.75
4.85
3.16
35.90
10.97
5.61
1.45
16.9
10.7
7.6
7.3
6.8
X19
I20
I2l
122
T23
T24
^5
J26
., C27 „
^nParaffin" '"
0=40^
ClO r -,n
i-nParaffin" '"
c=40
C^l ,n
ZnParaffin^ '„
c-40
1 C7{rl-C71+C77
1 C30+C31+C32
1 C20+C51+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
I CnH2n_6-HCnH2n_lg
CnH2n-14
E-l Rlng+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
6.2
4.7
4.1
3.28
1.45
7.64
3.51
31.4
Oil Type - No. 4 Fuel Oil
Origin -
Weathering Time, davs - 21
Weathering Temperature, °F - 55
Mixing Condition - Low Mix
- 142 -
-------
Computer No. 710809
Analytical No. 525325
Numerical
Index Formula Valiie Index Formula
'>
'*
Z10
X12
Z16
hi
V
Ni
S
N
ECnH2n-6
EAromat ic
£CnH2n-6 C~-,^
EAromat ics
ECnH2n-10
EAromatic
ECnH2n-10 c=36
EAroraatic
£CnH2n-14
EAromatics
ECnH2n-16
EAromatics
ICnHjr 1 8
EAromatics
EnParaffins
E (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Rii\£ Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 C_o0
C21 c_,0
C24 c_,0
^" pj-OQ
EnParaffin^--
8.2
3.3
18.76
9.75
16.24
8.95
11.97
9.31
7.23
34.35
11.05
6.31
2.81
17.4
11.4
6.6
7.1
6.1
'»
I22
T24
J26
C27 c--0
c=40
M
CIO c n0
InParaffin^^o
Cn
EnParaffin'' 7o
c-40
1 C30+C31+C32
2 C20+C?1+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
2 CnH2n-6+ECnH2n-18
CnH2n-14
E-l Rlng+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthanes
gamplc History
Oil Type - No . 4 Fuel Oil
Chrigin -
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - High Mix
Numerical
Value
6.1
3.7
5.3
2.83
1.66
2.60
2.17
29.1
- 143 -
-------
Computer No. 721801
Analytical No. 586049
Numerical
Index Formula Value Index Formula
T2
h
Ho
J17
He
V
Ni
S
N
ECnH?n-6
EAromatic
ECnH2n-6 C~ ,
EAromatics*"
ECnH2n-10
EAromatic _„„
£CnH2n-10 c=36
EAromatic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
ECnH2n 18
EAromatics
EnParaff ins
1 (P + N)
Z 3 Ring Naphthenes
Z(P + N)
I 4 Ring Naphthenes
Z(P + N)
I 5 Ring Naphthenes
Z(P + N)
C20 . oQ
C21 ._,Q
— c^^O
C26 -c-0
EnParaffin^-
5.42
2.67
18.24
10.05
17.36
10.09
12.73
9.09
5.74
33.57
12.13
6.76
1.43
18.6
11.5
7.1
8.0
6.5
'19
I22
Z23
126
C27 ,Q
nParafflnc=40.
EnParaffin0 . .
c=40
EnParaffinC ,_
E C30+C31+C32
1 C24+C25-fC26+C27+C28
I CnH2n-6
1 Cn«2n-6+J:CnH2n-18
CnH2n-14
Z-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Numerical
Value
5.6
4.9
4.6
3.15
1.62
3.18
1.89
31.7
Oil Type - No. 4 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature, °F - 80
Mixing Condition - Low Mix
- 144 -
-------
Computer No. 721809
Analytical No. 523410
Numerical Numerical
Index Formula Value Index Formula Value
h
12
h
\
h
h
h
h
h
ho
hi
h2
hi
X14
X15
^6
Z17
h*
V
Ni
S
N
ECnH2n 6
E Aromatic
ECnH2n-6 C=?°
EAromatics^"
£CnH2n-10
EAromatic „„
c=20
ECnH2n 10 c~36
EAromatic
ICnH2n-14
SAroraatics
SCnH2n-16
EAromatics
ECnH2n-18
ZAromatics
JiiParaf f ins
1 (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring_ Naphthenes
E(P + N)
C20 c -,0
EnParaffin^=^
C21 . ^0
EnParaf f in^_7Q
C24 ._,0
EnParaf fin"_~Q
C?"i c_og
EnParaf fin"_7Q
C26 C_o0
EnParaf f in^_7X
5.0
3.6
19.13
8.89
16.24
7.79
12.67
9.26
5.87
35.92
10.80
5.79
2.17
20.1
11.2
6.8
7.6
6.3
J19
^0
hi
h2
X23
X24
X25
he
C27
inParaffin^^
C-50 _ ,n
InParaffin;=^
r Cl1 c 20
EnParaffin ,n
c-40
1 C70+C7T+C??
. E C30+C31+C32
1 C20+C?i+C22+C30+C3l+C32
Z C24+C25+C26+C27+C28
E CnH2n-6
1 CnH2n-18
E CnH2n_6+ECnH2n_18
CnU2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type - No. 4 Fuel Oil
Origin
We a the)
-ine Time , days - 21
Weathering Temperature, °F - 80
Mixing Condition - High Mix
5.7
4.7
5.0
3.13
1.69
3.25
1.97
13.40
- 145 -
-------
Computer No. 710801
Analytical No. 588724
Numerical
Index Formula Value Index Formula
h
12
h
1B
J10
Xll
X13
J15
J17
J18
V
Ni
S
N
ZCnH2n-6
EAromat ic
ICnH?n-6 °~,,
JAromatics
lAromatic
ICnH2n-10 c=36
EAroroatic
ECnH2n-14
£Aromatics
ECnH2n-16
EAroraatics
lAromatics
EnParaf fins
E (P + N)
I 3 Ring Naphthenes
I(P + N)
I 4 Ring Naphthenes
I(P + S)
I 5 Ring Naphthenes
Z(P + N)
C20 cc,0
TnParaf finv'_2X
C21 ...,Q
Z;nParaffxnc=40
ZnParaf f in^"_'"
C26 C,Q
EnParaffin^ '"
5.60
3.23
18.30
9.12
16.41
8.27
12.90
9.26
5.98
37.25
11.40
6.29
2.10
18.2
12.7
6.8
7.3
5.8
J20
I22
24
C27 ,Q
2-nParaffin ,n
0=40^
SnParaffirT" ^
Cn
inParaffin*" .„
C"40
^ C20+C?i+C22+C3Q+C3l+C32
1 C24+C25+C26+C27+C28
Z CnK2a-6
1 CnH. , „
2n-i8
1 CnH2n-6+ZCnH2n-18
CnH2n-14
E-l Ring+2 Ring Napjithenes
1-5 Ring+6 Ring Naphthenes
Sample History
Numerical
Value
6.00
3.9
4.8
3.16
1.65
3.06
1.88
16.70
Oil Type - No. 4 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature , "F - 80
Mixing Condition - Low Mix
- 146 -
-------
Computer No. 800000
Analytical No. 578639
Numerical Numerical
Index Formula Value Index Formula Value
'l
16
T
1 o
hi
V
Ni
S
N
ZCiH
ZAromatic
ZCnH2n-6 °=^
£CnH2n-10
ZAromatic _ „
ZCnH2n-10 c-36
ZAromatic
ZAromatics
ZAromatics
ZAromat ics
EnParaf f ins
I (P + N)
I 3 Ring Naphthenes
I(P + N)
£ 4 Rin& Naphthenes
E(P + N)
I 5 Ring Naphthenes
£(P + N)
C20 __oQ
ZnPara£fin^0
C21 ._,Q
C24 .0
ZnParaf fin"" trt
c=tO
EnParaffin 7^
c=40
C26 c_oQ
8.3
3 . Q
17.90
9.79
16.06
9.23
12.67
10.09
7.73
28.38
12.93
6.83
3.57
12.00
10 . 30
8.40
9.90
7 .20
'»
'22
'23
C27 c ^Q
^nParaffin^ 7n
0=40,
c_-?o c^,0
EnParaffin1" 7X
C-4U
SnParaffin . n
c-AO
. Z C30""L31+C32
1 C24+C25+C26+C27"C28
I CnH^-fi
1 CnH2n-18
Z-l Ring+2 Rin£_Na£hthenes
1-5 Ring+6 Ring Naphthenes
Sample Historv
7.10
3.70
1.00
5.36
1.00
2.31
2.03
8.05
Oil Tv'De -No. 5 Fuel Oil
Origin -
Weathering Tine, days - Urweathered
Weathering Teir.re rature , °F -
Mixing Condition -
- 147 -
-------
Computer No. 810559
Analytical No. 578609
Numerical
Truteir Formula Value Index Formula
h
h
17
ho
X12
Z17
V
Ni
S
N
ICnH2n-6
I Aromatic
ZCnH2n-6 -jg
EAromatics
ECnH2n-lQ
EArotDatic ...
ECnH?n-10 c»36
EAroraatic
ECnH2n-14
EAromatics
ECnH2n-16
EAromatics
EAromatics
InParaffins
E (P + N)
E 3 RinR Naphthenes
E(P + N)
E 4 Rinp Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 .„(,
C21 r -0
EnParaffin" ""
c«40
C24 c ,Q
EnParaffinc=40
EnParaffin^°
C26 7Q
Erf>araffinc-40
7.70
4.20
18.11
10.50
16.23
9.78
12.90
10.36
8.14
33.53
12.19
7.92
3.43
11.20
10.00
8.40
9.10
7.50
J19
'22
<25
C27 C_o0
nPara£f:mc=AO
EnParaffin^0
C,i
EnParaffinC ".n
Cm 4U
£ C20+C7]+C22+C30+C31+C32
E C24+C25+C26+C27-fC28
E CnH2n-6
1 CnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type — «0 5 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, "F - 55
Mixing Condition - High Mix
Numerical
Value
7.20
3.87
4.68
2.67
1.13
2.23
2.04
8.20
- 148 -
-------
Computer No. 810551
Analytical No. 235620
Numerical Numerical
Index Formula Value Index Formula Value
'l
X3
X9
T10
X13
X17
X18
y
Ni
N
E Aromatic
ZCnH2n-6 £=^°
SAroraatics1"
rCnH2n-10
EAromatic _,,
L"CnH2n-10 c=36
EAromat ic
ICnH2n-14
lAromatics
ICnH2n-16
EAromatics
7CnH?n i ft
EAromatics
JiiParaffins
Z (P + N)
E 3 Ring Naphthenes
E(P + N)
E 4 Ring Naphthenes
E(P + N)
E 5 Ring Naphthenes
E(P 4- N)
C20 c n0
C21 c^,0
EnParaffmc=40
EnParaffin _'
C26 c ,0
EnParaffin ._
c=4Q
8.0
4.2
18.0
11.0
16.0
10.0
13.0
10.3
8.1
33.5
12.0
8.0
3.4
11.2
10.0
8.0
9.2
7.5
'»
'23
'25
C27 _0
C30 ._,0
SnParaffin^=^
Cn
ZnParafflnc»AO
. E C30+C31+C32
E C2Q+C71+C22+C.30+C3.1+C.3.2
I CnH2n-6
1 CnH2n-18
CnH2n-14
E-l Ring+2 RingJJa^hthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Type -
Origin -
Weathering Tirae , days -
Weathering Temperature, r
Mixing Condition -
7.3
3.9
4. 7
2.70
1.10
2.30
2.00
8.0
- 149 -
-------
Computer No. 821559
Analytical No. 578626
Numerical Numerical
Index Formula Value Index Formula Value
h
h
13
h
J5
h
ll
h
X9
ho
hi
h2
hi
*i*
X15
X16
hi
h*
| V
Ni
S
N
£CnH2n-6
EAromatic
£CnH2n-6 C~™
EAromatics1"
ECnH2n-lQ
EAromatic c=2Q
rCnKOn — 1 n r-= "^ft
ZAroraatic
rCnH2n-14
EAromatics
ICnH2n-16
ZAroraatics
ECnH2n-18
lAromatics
EaParaffins
E (P + N)
£ 3 Ring Naphthenes
Z(P + N)
Z 4 Ring Naphthenes
E(P + N)
£ 5 Ring Naphthenes
£(P + N)
C2° c-"0
rnParaffinc=i40
C21 c.,0
ZnTaraffin^;-
C2A r,Q
InParaffin^-
C7S ^IQ
InParaffin^'-
C26 ^->o
EnParaffin;.^
18.07
10.45
16.45
9.87
13.12
10.56
7.56
31.18
12.58
8.38
3.56
10.90
10.20
7.80
8.30
6.80
X19
J20
T21
X22
T23
J24
X25
X26
Oil Tyr
C27
LnParaffinL ^"
c=40,
Cw on
EnParaffin" '"
r=40
C^i
EnParaffin" '"
c"40
E C7o+C?i+C??
E C30+C31+C32
E C20+C?i+C22+C30+C3i+C32
1 C24+C25+C26+C27+C28
E CnH2n-6
E ^n-lB
Z CnH2n_6+ECnH2n_18
CnH2n-lA
Z-l Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthenes
Sample Historv
Origin -
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - High Mix
7.10
3.90
5.00
2.49
1.19
2.39
1.95
7.87
- 150 -
-------
Computer No. 821551
Analytical No. 598579
Index
Xl
h
X3
\
X5
X6
T7
X8
X9
T10
Xll
X12
:13
lu
:15
X16
X17
He
Numerical Numerical
Formula Value Index Formula Value
V
; Ni
1 S
: N
ICnH2n-6
lAromat ic
ZCnH2n-6 C=^°
EAromat ics
£CnH2n-10
TAromatic
c=^U
ZCnH2n-10 e~36
EAromatic
ZCnH2n-14
SAromatics
ECnH2n-16
EAroraatics
ECnH2n 1 8
I^romatics
EnParaf f ins
£ (P + N)
E 3 Ring Naphthenes
E(P + N)
I 4 Ring Naphthenes
£(P + N)
I 5 Ring Naphthenes
I(P + N)
C20 c o0
EnParaffin^^
C21 . ,Q
InParaffin^ 7^
c=4u
C24 . ^0
ZnParaffin^=^Q
C7S C_o0
InParaffin^=^
C26 . o0
ZnParaffin^Q
8.4
4.4
18.05
10.39
16.97
10.45
13.09
9.47
5.81
30.43
12.47
7.54
2.82
11.3
9.7
8.8
8.3
7.1
X19
^0
X21
^2
Z23
J24
X25
^6
, C27 -n
i-nParaffin" "
c=4C;
Cw >-
^nParaffin"- 7"
r=40
v Cl1 c 20
EnParaffin '"
c"40
E C90+C?TfC99
Z C30+C31+C32
S C20+C?l+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
I CnH2n-6
1 CnH2n-18
I CnH2n_6+ECnH2n_lg
CnH2n-14
E-l Ring+2 Ring Naphthenes
1-5 Ring+6 Ring Naphthanes
Sample History
Oil Type -No. 5 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature, °F - 55
Mixing Condition - ]_„„ M;x
6.5
4.9
4.3
2.56
1.19
3.10
1.82
12.70
- 151 -
-------
Computer No. 810801
Analytical No. 588721
Numerical
Indey Formula VA! UP Index Formula
h
h
h
h
h
h
h
h
h
ho
hi
h2
Jn
X14
J15
X16
L17
He
V
Ni
S
N
ICnH2n-6
lAromatic
c=20
ECnH2n-6 3£
EAromatics1"
£CnH2n-10
Aromatic ^^
ECnH2n--10 c=36
EAroraatic
ECnH2n-14
J^roraatics
ECnH2n-16
EAromatics
ECnH2n-lS_
EAroF.atics
JiiParaffins
E (P + N)
I 3 Ring Naphthenes
Z(P + N)
£ 4 RinR Naphthenes
E(P + N)
E 5 Ring Naphthenes
I(P + N)
C20 C_,Q
rnParaffin^=~Q
C21 c ,0
InParaf fin"_~Q
C24 c_,Q
InParaffin^=^
C?s C_o0
EnParaf fin"_^Q
C26 c_,0
EnParaf f in^_^Q
7.8
3.9
18.53
11.44
16.17
10.37
12.94
10.40
7.64
32.24
13.08
7.43
1.12
11.9
10.1
8.6
9.1
6.8
Z19
X20
hi
122
hi
T24
X25
r26
C27 ,Q
J-nParaffln^
cw c .0
EnParaffin^ 7X
c=40
C^l _ OQ
EnParaffin^ t^
c«40
Z C7n+C?i+C??
Z C30+C31+C32
- C20+C71+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
S CnH2n-6
1 CnH2n-18
1 CnH2n-6+ECnH2n-18
CnH2n-14
E-l Ring+2 Ring Naphthenes
E-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - No. 5 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, °F - #>
Mixing Condition - Low Mix
Numerical
Value
6.5
3.6
4.7
2.75
1.18
2.42
1.48
40.8
- 152 -
-------
Computer No. 810809
Analytical No. 525320
Numerical Numerical
Index Formula Value Index Formula Value
h
h
X9
X10
X14
X15
X16
'18
V
Ni
N
EAromat ic
ECnll2n-6 C=^
EAromat ics
ECnH2n-10
EAromat ic
c~ 2 0
EAromat ic
ECnH2n-14
EAromat ics
ECnH2n-16
EAromat ics
EAromat ics
EnParaffins
E (P + N)
I 3 RinE Naphthenes
E(P + N)
E 4 Ring Naphthenes
Z(P + N)
E 5 Ring Naphthenes
E(P + N)
C20 . -,Q
EnParaffin _'
C21 ._„„
EnParaf f in^_"^
ZnParaffinc=40
EnParaffin1" '"
c=40
C26 . ,Q
ErtParaffinc-40
7.9
4.3
18.25
10.95
16.71
7.65
12.60
10.01
7.79
31.17
11.95
7.22
2.95
11.70
9.80
8.50
10.10
6.90
X20
21
'»
C27
^nParaffin" ,„
0=40,
EnParaffin1""^
c=40
C^n ^
InParaffin^^
. Z C30+C31+C32
I C20+C71+C22+C30+C31+C32
1 C24+C25+C26+C27+C28
Z CnH2n-6
1 CnH2n-18
1 CnH2n-6+ICnH2n-18
Cnli2n-14
Z-l Ring+2 Ring Naphthenes
Z-5 Ring+6 Ring Naphthenes
Sample History
Oil Tvpe - No . 5 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, °F - 80
Mixing Condition - High Mix
5.80
4.20
4.50
2.69
1.20
2.35
2.07
10.30
- 153 -
-------
Computer No. 821801
Analytical No. 586002
Numerical
Index P^i-m,,1a Ual,,^ Tndex Formula .
Zl
Z2
h
X4
*5
J6
X7
X8
J9
Jio
Jll
X12
T
'13
Xl«
X15
X16
X17
he
V
Ni
S
N
ECnH2n-6
EAromatic
ECnH2n-6 C"L
EAromatics
ECnH2n-10
J^roraatic =^
ECnH?n-iO c=36
EAromatic
ECnH2n-14
EAromat ics
ZCnH2n-16
ZAromatics
ICr>H2n-18
EAromat ics
JilParaffins
1 (P + N)
I 3 Ring Naphthenes
E(P + N)
£ 4 Ring Naphthenes
E(P -1- N)
£ 5 Ring Naphthenes
E(P •- N)
C20 C_.Q
InParaffin^^
C21 c_,0
Enparaffin^^Q
C24 ._,0
EnParaf fin^_~Q
C7S C_i0
EnParaf fin'_^p
C26 c_^0
EnParaf f in^_7X
8.12
3.61
18.15
10.70
18.26
11.51
12.86
9.08
5.31
30.41
13.03
7.74
0.93
11.40
9.90
8.50
9.10
7.20
X19
X20
T21
X22
X23
X24
X25
T26
C27 ,0
'•nParaffin /n
0=40^
ClO r i0
SnParaffin ,n
_ _ r=40 _
C^T . ,0
ZnParaffin^^
E C7n+C?i+C?2
E C30+C31+C32
E C2Q+C?i+C22+C30-l-C31+C32
S C24+C25+C26+C27+C28
£ CnH2n-6
E CnH2n-18
I CnH2n_6+ICnH2n_18
CnH2n-14
£-1 Ring+2 Ring Nap>thenes
E-5 Ring+6 Ring Naphthenes
Sample History
Numerical
Value
6.50
5.00
5.00
2.29
1.24
3.42
1.83
50.5
Oil Tvpe - No. 5 Fuel Oil
Origin -
Weathering Time, days - 10
Weathering Temperature, "F - OU
Mixing Condition - j ow ^^x
- 154 -
-------
Computer No. 821809
Analytical No. 525407
Numerical Numerical
Index Formula yaj,^ Tndpx Formula Value
Xl
h
X3
J4
X5
X6
17
h
X9
X10
Xll
I12
X13
X14
Z15
X16
X17
X18
V
Hi
S
N
ICiiH2n-6
ZAromatic
ECnH2n-6 °=^
ZAroma tics'"
ZCnH2r-10
EAromatic
c=20
ICnH?n-10 c-36
EAromatic
ECnH2n-14
EAromatics
ECnH2u-16
EAromatics
ELnHjn 18
EAroir.atics
JiiParaf f ins
E (P + N)
I 3 Ring Naphthenes
E(P + N)
E 4 Ring Saphthenes
E(P + N)
E 5 Ring Naphthenes
Z(P + N)
C2fl__.. c o0
rnParaffin^Q
C21 . o0
EnParaffin^ 7X
c=AU
C2-4 ^_.0
EnParaff in^=^
C?5 C_OQ
EnParaffin" 7n
C=AU
C26 . OQ
EnParaffin^=^Q
7.82
3.89
19.97
9.55
16.24
9.03
12.62
9.72
6.82
33.12
11.79
7.48
3.23
11.70
9.80
8.50
10.10
6.90
X19
ho
Z21
Z22
X23
X24
X25
X26
C27
J-nParaffln^
C30 r ^n
ZnParaffin ,.
c=40
c^i ,0
InParaffin" t^
c-40
g C?Q+C21+C22
. Z C30+C31+C32
I C20+C?]+C22+C30+C3i+C32
Z C24+C25+C26+C27+C28
2 CnH2n-6
S CnH2n-18
S CnH2n_6+SCnH2n_18
CnH2n-14
£-1 Ring+2 Ring Naphthenes
E-5 Ring-Hi Ring Naphthenes
Sample History
5.80
4.20
4.50
2.69
1.20
2.93
2.12
8.64
Oil Type - No . 5 Fuel Oil
Origin -
Weathering Time, days - 21
Weathering Temperature^, °F - «U
Mixing Condition - High Mix
- 155 -
-------
APPENDIX C
GAS CHROMATOGRAPHIC DISTILLATION DATA
No. 5 Fuel Oil
% Boiled Off Unweathered 10 Days at 80 °F 21 Days at 80 °F
Initial B.P. Below 250 550 450
1 285 582 565
2 325 600 585
3 347 612 600
5 380 627 615
7 400 640 630
10 425 657 648
15 465 682 673
20 500 705 696
25 537 725 717
30 580 744 740
35 623 763 760
40 661 782 782
45 695 801 802
50 727 820 823
55 757 838 842
60 786 860 862
65 815 882 885
70 847 907 910
75 880 935 935
80 915 965 965
85 958 1005 1003
90 1013 1007 1070
- 157 -
-------
GAS CHROMATQGRAPHIC DISTILLATION DATA
No. 4 Fuel Oil
Temperature, °F
% Boiled Off Unweathered 10 Days at 80°F 21 Days at 80 F
Initial B.P. Below 250 325 500
1 315 495 522
2 355 528 532
3 380 542 540
5 412 550 552
7 435 562 563
10 560 575 575
15 491 595 592
20 515 615 608
25 535 636 623
30 553 659 641
35 572 684 664
40 590 711 690
45 608 742 720
50 631 771 752
55 660 798 783
60 698 823 813
65 744 847 840
70 790 873 867
75 832 900 895
80 872 932 925
85 915 968 960
90 965 1018 10Q5
1056
- 158 -
-------
GAS CHROMATOGRAPHIC DISTILLATION DATA
Tia Juana Medium Crude
Temperature, °F
% Boiled Off Unveathered 21 Days at 55°F
Initial B.P. TT°° 430
1 Ll&ht 465
2 M to 485
3 Measure 49g
5 520
7 540
10 250 563
15 345 598
20 415 631
25 475 665
30 532 700
35 585 735
40 637 771
45 690 808
50 743 845
55 798 882
60 855 922
65 917 964
70 983 1011
75 1060 1070
- 159 -
-------
APPENDIX D
GENERAL STATISTICS
L'irsL!5FA.\ -"sower i
NU" BE:? VARIABLES
r.LK"E<
GEI.ESAL
;x'"<3E
l" ~
2
3
4
" ~""~ "" " "5 "
6
7
a
10
IT""
12
14
15
16
17
18
" 19"
20
21
22
23
24
26
OHSt'^VA i
' - 1
u.JS
•"'" " "TOL"
PPC
?6
11" "' •"
riPE'E
JG^A'1
STATISTICS
R SUN'
"OV8"5"£9~E 02"
0.6719E 02
0. 2332E
0.1357E
"'7T.T3T5T"
0 . 9 3 9 1 E
0.9360E
0.3754E
0.7397E
C.1635E
C.1287E
O.Q069E
0.9009E
0.7059E
0.3349E
0.4179E
0.4053E
0.2802E
0.127BE
03
03
'13
02
03
02
03
02
03
03
02
02
02
02
02
02
r, ~>
02
03
AVERAGE
C.6i0909E 01
0.123399E
0.125372^
C.B53B1SE
•"~cr.-irzuBi"r
0.850999E
0.341345E
0.672545E
" "CV2"77Bl"8r
0.14S727E
O.B24545E
O.S1909CE
0.641G1J5E
C.574545E
0«3^*9^^^E
n - 3 *?~Q ^ o o F"
0 t^fo^S^S^
->.2 5481 BE
0.1162 09E
02
02
Cl
-or""
01
Ul
02
--02-
01
02
02
01
01
Cl
31
01
ii
01
01
Cl
02
•™>«™-
-A::,I
DEVIATION'
""G"."?.5CT£"0"r""0"j "'
C.3S4836E 00
0. 13475 8 E
C.f75565E
•••ti".5'37r54Tr""
0.454132E
C.217177E
""C~.'4^WA"5F"
C.309144E
0.623904E
0 . 3420P9E
0. 360440E
0.244273E
0.375046F
0.3E8470E
6. 3 104 24 E
0.241712E
T).52"l9l6F-
0.23632SE
0.&06911E
01
--, r-
00
Cl
00
00
00
00
CO
"50"
00
00
01
CO
mr """•
01
YST5~"
'•'AX
0 . 6 7 0 0 0 0 E
0. 146300E
tr.T3"r?"rKJF"
0. 95800 CE
r . 1 3 Z"4"
0.9220
0.3945
0.7390
o'.ieio
0.1270
c . s 6 o o
0.6700
0.4300
o!4?20;
0.3130
0.2490
OCE
OOE
;;OE
JOL
OCE
OOE
-OE
OOE
~01TF~~
OOE
H A :•; o f:
01 0.540000E
02
"02
01
01
02
01
02
J2
01
01
01
01
01
02
0. 2079'JJb
0.1 031 COE
0. 113100fc
0.6R20COE
0. 114300L
0.790000E
O.SllSOCf
. 0.6110001
0.142000E
0. Ill 0 OOE
0. 7600COE
0 . 7 6 C •"> 0 0 E
0 .600 0 0 0 E
0 . 4 8 0 o 0 0 E
0. 29000 ".E
0.3400 OOE
0.342^00E
0.136000C
0,2300'iOE
""" "" 0".210T50^
0.655000E
^
01
02
02
02
01
01
Ul
02
Cl
"in;
02
C2
01
01
Cl
01
01
01
01
01
0 1
~~CTi
01
-------
PROGRAM REG
to
I
NUMBER VARIABLES
NUW.BEK UHShKVATTO'nS'
GENERAL
5W72 -
26
- 5
,
STATISTICS
VARIABLE
\UVBER SUt-'
2
3
6
- ~" T"
e
10
"~ " ' ' n ~
12
""• ' ' "13
14
15
16
17 -
18
20
21
22
\l
26
0.3069E
0.9669E
0.6166E
blsisoE
Q.4460E
0.4311E
0.9611E
Ot50l7E
0.5330E
C.4859E
0.4Q09E
'C.4420E"
0.3160E
0.3I19E
C.1617E
0.3C33E"
C.1140E
0.6639E"
0.1163E
0.4494E
02
02
02
02
02
02
02
02
02
02
02
02
02
02
02
02
01
02
02
C2
AVERAGE
0.613999E 01
0.193399E
0.123339E
C.103019E
•uvi25~379r
0.892200E
'O.B62399E
Qil92239E
0.100359E
' 0.398799E
0.116600E
0.601999E
C.631999E
"O". 6 2 39 9 9 P
C.3234COE
0.606600E
0.228199E
0.132799E
0.232599E
Oii J4399E
02
02
02
02
or
Cl
01
02
02
02
01
02
01
01
01
01
01
01
01
01
.. 5 .........
01
01
01
5T Art CARD
DEVIATION
0.392937E 00
0.463594^
0.11976CE
0.114C93E
0.149586E
0.258053E
0.714215E
0 .5 154 95 E
0.652993E
0.702566E
0.58446&E
0.454312E
0.570613E
0.116714E
0.101352E
0.443233E
o'.493?15l
6.1880CCE"
0.315600E
00
01
00
01
00
00
01
01
00"
CO
co-
co
00
00
00
00
cc
01
01
oc
00
on
01
0.
0.
0.
r
o^
0.
V f
c.
0 •
c.
V *
0".
c •
c.
c.
0.
V •
0 •
V •
c.
c.
0.
c.
0»
VAX
Tycircro'E'
650000E
203600E
145000E
125000E
914000E
962000E
238200E
1118COE
125000E
105000E
890000E
71COOOE
55COOOE
730000E
30800CE
145000E
330000E
245COOE
148000E
RANGE
WIN
01
02
02
02
02
01
01
02
02
02
C2
01
01
01
ul
01
01
01
01
02
0.540000E
0.111700E
0.133800E'
0.9410COE
Ot868000E
0.5E2000t
0.166000E
' ~C7T5T4TMDT"
0.91700CE
0.110000E
0.860000E
0.730000E
0.550000E
0.220000E
0.473000E
0.185000E
6. 126000E
0.201000E
0.190000E
0.552000E
— -
m~ • - - -
01
02
02
U2
01
02
01
01
02
"OTi
01
02
01
01
~ci~"
01
01
01
01
01
01
01
01
-------
-— -— - MULTIPLE REGRESSION' 'ANALYSIS' ~ ~"
PROGRAM REG
LIEBERN'A'N""'
NUMBER
VTJVBER'
- SOURCE 3 "-
VARIABLES
OBSERVATIONS
15MAY72
= 26
= 8
GENERAL STATISTICS
VARIABLE
NUMBER SUV
• - 1- • Q.3164E 01
2
3
4
5
6
7
8
IT™
10
11
12
13
14
T5
16
17
18
19
2 C
21
22
23
24
25
X A
0.3328E
0.1410E
0.7913E
0.1175E
0.6991E
0.1033E
0.7P.29E
0.7C77E
0 . 2 3 3 2 1
C.9774E
0.7994E
0.3293E
0.164fiE
0.1049E
0.6429E
0.7691E
0 . 5 C 6 2 E
0.3387F
0.2062 E
0.29C7E
0.4232E
C . 1 3 3 9 E
0 . 1 6 0 8 E
r , 1645E
0.631CE
02
03
02
03
02
03
02
03
02
02
02
03
03
02
/"i O1
02
02
0 ?
^ <-
02
02
02
02
02
AVERAGE
0.395624E 00
0.416124F,
C.176337F
0 «9R924-9E
C.146962F
0»fi739990I
C.129137E
G.978749E
"0 • 8~~?T4~7 4 9TT
0.2 >1599E
O.U2187E
C.999374E
0.411749E
0.206037E
C'.131l74F
C.803749E
0 , 9 6 1 4 9 9 E
0.632750E
G.423375E
L .257374E
C.363499E
0 . 5 2 9 1 2 4 E
0.173749E
0 . 2 C ] 1 2 4 E
0.20 5749 E
0.788874E
01
02
01
02
01
02
01
01
02
02
01
01
02
02
01
01
01
01
01
01
01
01
01
01
01
^J 1 f\ 1 \ p ft
DEVIAT]
0.154058C
0.374146E
0.371665ET
0.132615E
0 t"6423l8E'
0.126543E
0.606S35E
C.631956E
0.77422IE
0.268537E
0.545972E
0.737782E
0.358425E
0, 1C2615E
0.177683E
0.672565E
0. 147277E
0.111592E
C.362592E
0.485963E
0.424205E
0.554S74E
0. 124071E
0. 193999 E
0. 122040E
0. 123794E
!0.'4
0"0
00
CO
01
00
01
00
00
CO
01
00
00
00
^ j
w ^
CO
01
01
CO
oc
CO
n n
0 0
CO
CO
01
' 0
o
<^
0
0
'\J
0
r<
^
:w
Q
C
r
C
r-
V
C
Q
o
fy
C
w'
C
f\
C
C
o
MAX
.610000E
•470000E
.1808GOE
.111700E
. 157560E
.103900E
.13780CF
•1079QOE
.992000P1
. 3 3 3 4 0 0 E
.12890CE
.ll^COCE
.451COOE
. 2 2 0 0 C 0 E
.1590CCE
. 9 0 0 " 0 0 E
.1200COE
. 9 C 0 0 0 0 E.
.467COOE
. 3 2 0 0 C 0 E
• 4 2 5 0 0 0 F
. 64C^CGE
. 1 9 6 0 C 0 E
. 2. 3 7 0 0 0 £
•225000E
.97500CE
RANGE
WIN
00 "0". 2 00 CO OE"'
01
02
02
02
02
02
02
Cl
32
02
02
01
02
02
01
02
01
01
01
01
01
01
01
01
01
0.3630CJOE
0.170600E
0.751000E
0/1 38 3 6 OT
0.685000E
O.inO'OOE'
C.854000E
0 . 7 3 8 0 0 0 E
0.255800E
0.1115COF
0 . 8 9 8 iJ 0 0 E
0.3350(,OE
0. 192300E
0.108000 E
0.69COOOE
0.77POOOE
0 . 5 1 U 0 0 0 E
0, 360 00 OE
0 . 1 8 0 0 0 0 E
0.2800GOE
0.429000E
0.157UOOE
0. 17600GE
0, leOGOOE
C, 596nOOE
oo *
01
02
01
02
01
02 " -
01
01
02
02
01
01
02
02
01
01
01
01
01
01
01
01
01
01
01
-------
MULT IPLE REGRESS ION ANALYSIS
PROGRAM REG
Li E3ERXAN •
NUMBER
• SOURCE" 4 ""-
VARIABLES
NIJ>.BE& OBSERVATION*
GENERAL STATISTICS
VARIABLE
MT'SER SUV
1 O.U59E 01
2 C.9BOOE 01
3
A
6
7
8
9
10
11
12
13
14
16
17
18
19
20
21
22
23
25
26
0.1173E
0.6626E
OtlJjO'ZE
0.57B3E
0.123 IE
0.8276E
0.3315E
0.1069E
C.6774E
C.2333E
0.8279E
0.6892E
0.6842E
C.5829E
0.5567E
0.3426E
0.1910E
C.9309E
0.1476E
0.1183E
C.?199E
03
02
03
02
03
02
02
03
03
02
02
02
02
02
02
02
02
02
02
02
01
02
02
02
15MAY72
• ... 26
. * fl
AVERAGE
0.1225COE 01
0.828374E
0. 15C324E
0.722999E
0.414487F
0. 13 3737 C
0.846874F
0" .1G1399E
0.855374E
0.728749E
Q.695999E
0.505749E
0.238750E
C.184624H
0.147999E
0.102499E
02
01
02
01
C2
02
01
02
01
01
02
02
01
01
01
01
01
01
01
01
01
01
02
" " STANDARD
DEVIATION
"C'.96663GE-01
0.203836E OC
0.123465E
0.757791E
0. 163596E
0.94P353E
0,70807BE
Qt528368£
0.176346E
0.463167E
0.716596E
O.P18317E
0.276388E
0.857729E
0.303477E
0.384997E
0.284769E
Oil5394SE
0.300164E
0.683844E
0.355026E
0.102339E"
0.206696E
0.151904E
0.482519E
01
00
01
CO
CO
CO
00
01
00
00
DC
00
00
00
00
00
00
OC
00
00
00 "
00
00
01
- -
f-'AX
OV33COOOE'
0.150000E
0.159400E
0.943000E
0,T918QbE
0.887COOE
0.167 10 O'E
0.114800E
0.994'JOOt
C.44190QE
C.101000E
0.108000E
0.910000E
0. 9400 0^0 E
0.780000E
0.710000E
0.490CCOE
0.600000E
C.316000E
0.140000E
0.222000E
0.172000E
0.199000E
RANGE
00 0.
01 0.
02
01
"02"
01
02
01
02
32
02
O'l
02
02
01
01 "
01
01
01
01
01
01
01
01
02
0,
c.
"0."
0.
"CY
0.
c.
0.
0.
c.
0.
0.
0.
0.
" 0 .
0.
Ot
0.
0.
0.
0.
Oi
0.
0.
M I n
70'00'WE-Ol
770000E 00
119000E
726000E
139100T
539000E
950000E
617000E
395900E
1266"O^E
7610COE
159000E
990000E
910000E"
810000E
8 100 00 E'
680000E
668000E
400000E
380000E
193000E
105000E
153000E
119000E
590000E
02
01
"02"""
01
01
Cl
02
"C2"'"
01
01
01
01
01
"01 " " '
01
"01
01
01
.0_1. .._
01
01
01
-------
.MULTIPLE REGRESSION ^ANALYSIS"
PROGRAM REG
AN'"- SOURCE ""5 "-" 15MAY72 '~
i\U'/BER VARIABLES = 26 _ _ _
XU^HliK U«5tT«VATIO!\iS = 7
GENERAL STATISTICS _ ___
VARIABLESTANDARDRANGE
NUMBER SUM AVERAGE DEVIATION ^AX MIM
Ui
I
"OVU"39E"OT
0.1816E 02
0.1193E
4
5
6
'"7
8
Q.7065E
03
02
0.6008E 02
0."92 7 IE 02T
0.7026E 02
C.6990E 02
0.259571E
Oil70471E
Otl00928E
0.140'714T
0.858423E
OV132457E
Oil00385E
01
02
02
"02"
01
02
02
"0 . 6
0.3261S3E 00
00
0.292000E
0,176i66E"
01
02
0.733868E 00
0.108300E 02
0.2050QOE 01
0, 1651 00 E 02
0.867000E 01
10
11
12
13
0.3354E
0. 5846E
0.4239E
0.1482E
C.9969E
15
16
17
18
19
20
0.6129E
0.5609E
21
22
23
24
25
26
0".'3899E
0.2429E
0.2218E
0.2985E
0.9899E"
0.1202E
"OVi427E"
0.8871E
03
02
02
02
02
02
02
02
02
02
_02_
02
02
'oi
02
02
02
Ot4792l4E 02
0.835285E 01
0.605714E 01
0.211857E 01
0.142428E 02
0.862966E 00
0.564645E" 00
0.508511E 00
"0.774183E 00
0.969586E 00
0.359671E 00
0.169513E 00
0.918779E CO
0.495284E CO
0.122428E 02
0.875714E 01
0.801428E 01
0.635714E 01
"O'.'E i7l42E 01
0.3-47142E 01
0.471645E 00
0.315581E 00
0, 3i3635E'"bO
0.129362E 00
0. 166598E 00
0.166598E 00
0.102000E 02
0 • 144^9 0~OE 02
Oil06900E 02
C.110800E 02
0.495400E 02
O'.'8'S'I'OOO'E' O'l
C.635000E 01
0.303000E" O'l'
0.147000E 02
Oil29000E 02
0. 920000E 01
'0".'8"3000"OE~"01"
0. 65000 OE 01
0."58000"0~E"~0""1"
0.370000E 01
0.762000E 01
0.921QOOE 01
0.865000E 01
0.465300E 02
0. 580COOE_ 0_1
0".'OOCO"OOF~0"0"
0.133000E 02
0.114000E 02
0.810000E 01
0«7306"60E"~Ol"
0. 610000E _01
0. 530000E"" 01~
0.320000E 01
0.316999E 01
0.426571E 01
Otl41428E 01
0.171857E 01
0.203999E 01
0.126742E 02
0.224181E 00
0.368233E 00
0.102658E 00
Oi_15_3383E 00
"0. 860232E-01"
0.819864E 01
0.360000E 01
0.475000E 01
0. 164000E 01
0.290000E 01
0,362000E_01
"Ot"1310"00l" 01
p.l5_3pOOE01
"' ~
__
OV217000E 01
0.318000E 02
0.592000E 01
-------
PROGRAM REG
_NyMBER_ VARIABLES
26
GENERAL STATIST
ICS
VAKIAHLE
NUM9ER SUM
2
3
4
6
7
8
9
10
11 "
12
- 13
15
16
~~ IT
18
" 19
20
21
22
23
24
25
26
"-(r.BWOF
0.1528E
0.9168E-
_0.5539E
0.2189E
0.1639E
0.6063E
0.8157E
0.2881E
0.*Z479E
0.3870E
0.2226E
0.1939E
" 0.7629E
C.1589E
0.759"9E
0.13COE
0.13COE
0.7000E
0.2063E
0.2735E
0.8559E
0.6000E
~i3r
03
o 0(0 o
*~* M; »-• M
03
02
02
03
02"
02
01
03
03
02
01
01
00
OC
00
11
03
02
01
11
AVERAGE
0.191124E 02
0*114612E 02
0.6 >2499E 00
074758T5P "01
0.273749E 00
~~1T.^4"9T4T"0?
0.757999E 01
0.101974E 02
0.576974E 02
0.360249E 01
' 0.309999E" 00
0.483750E 02
0.278374E 02
0.242499E 01
0. 95 3?49 E 00
0.198749E 00
Ot949999E-01
0.162500E-01
0.16250GE-01
0.875000E 10
0.257999E 02
0.341999E 01
0.106999E 01
0.750000E 10
0.
0.
o!
0.
0.
0.
Ot
0 .
0.
0.
0.
0.
0.
0.
0.
0.
0.
Ot
0.
"0".
0.
STANDARD
DEVIATION
914213E 01
131432E 01
164145E 00
849908E-01
T$5T5*r~0'l
107456E 01
25097IE 01
509681E 01
735471E OC
630T3TE" T>0
197C24E Cl
561109E 00
672216E 00
431536E 00
188841E OC
113137E 00
429934E-01
429934E-01
330718E 1C
6956T1E 01
6C8774E 01
127377E OC
433012E 10
0.
0,
C.
"" OT
0.
- ----- n~
v •
Ot
c.
Ot
- 0".
Ct
Ot
Ot
Ot
0.
0.
Ot
Ot
C t
Ot
Ct
Ot
0 t
c.
0.
VAX
317000E
141100E
100000E
380000E
915000E
136100E
636000E
9400"OOE
517000E
195000E
518000E
284000E
410000E
20000CE"
520000E
300COOE"
130000E
130000E
1COOOOE
367000E
195UOOE
121000E
100000E
ITA'NCE"
02
02
02
01
"01
00
01
02
02
01
01
02
'J
-------
PROGRAM REG
NUVBER
DUMBER
VARIABLES
OHSE^VATT
GENERAL STATISTI
ONS
cs
VARIABLE
NUMBER SUV
2
4
6
8
9
10
1T-
12
IT"
15
16
18
IT"
20
21
22
23
24
25
26
0.2369E
0 • 1 3 fit
0.6721E
0.6227E
02
03
02
02
0.8097E U2
0.5840E 02
0.2470E
tr;7W5F~
0.4193E
0.1308E
0.6130E
Ot4940E
OT5T79F"
0.4489E
0.4209E
0.2959E
0.3240E
Ot2361E
0.1126E
0.2643E
OV1581E
0.1413E
03
02
03
02
02
02
T52~
02
02
02
02
02
02
03
26
• 7
AVERAGE
0.338571E
0.960142E
0.889714E
Ot834428F
0.352900E
---0,11280"OE
0.599142E
"0."I84:'285E '
0.186857E
0.705714E
0.641428E
0.422857E
0.462S57E
0.337428E
0.160999E
Ot377714E
Oi201928E
01
uz
01
01
01
0 1
02
01
m
02
02
01
01
01
01
01
01
01
01
02
DEVIAT
"~""CTiTC3B?TE
00342338E
Ut lOB'Jfcilt
0.110376E
0.139391E
0.15C067E
0.110934E
0.434821E
0.119931E
0.5890'15E
0.345820E
"OV311677F
0.356284E
0.531075E
0.755588E:
0.513276E
"TJT8T5J&5E
0.159618E
0't530148E
0.940943E
I ON
00
Oi
01
01
-01 -
01
u 1
01
00
01
00
00
00
CO
00
00
00
01
or
01
— • -•
-'•"AX
0.3800COE
U§^4'J f'JVt
0.119800E
Oill6800E
"OV129000E'
0.931000E
0.372500E
0.676000E
0.203000E
0.127000E
0.760000E
0(690000E
0.490000E
0.55000CE
Ot454000E
0.169000E
Ci764000E
0.317000E
KAHGt
01
y<£
02
0"2~"
02
02
01
u i
02
01
02
U2
01
01
01
01
01
01
01
"OT~
02
" "0.
0.
0.
0.
c.
U t
0.
0.
0.
w •
0.
0.
0,
0.
0.
0.
P: I M
2670COE
831000E
745000E
775UGOE
485000E
3 IfaUUUt
335700E
546000E
169000E
107000E
660000E
7 OOOOTTE
5 80000E
560000E
340000E
310000E
283000t
260000E
915000E
—
01
01
01
01
01
U 1
02
01
02
or
01
01
01
01
01
01
01
01
-------
00
I
PROGRA
MJ-.3ER V
sower ir~-"
15MA
26
M REG
i~A?J7
SUYSTS
GE'MEHAL
^S-KVA 1
"°
*
H
STATISTICS
^U'-'BE^ SUM
1
2
3
4
5
6
~" '" " " 7"
8
V
10
12
~ 13
15
16
17 ~
18
20
21
22
24
26
0.3239E
0.1470E
0.8376E
TTniTOF
0.7788E
0.7968E
0.56 f9i
C.2504E
•CrnTTOUE'
C.6053E
C.0209E
C t7999E
0.6750E
•Q". 7T99T
0.5639E
C.3337E
C.3368E
0.2349E
0.2114E
0.1470E
02
02
03
02
w 2
02
02
02
03
UT
02
02
02
02
01"
02
02
02
02
02
03
0,
0,
Oi
0.
— ^...
0.
Oi
0.
0.
o!
0.
0.
0.
0.
c»
0,
0,
.... -g.._
0,
AVERAGE
4C4999E
183787E
104712E
973624E
996124E
313C74E
756749E
999999F
643750E
704999E
417125E
421000E
293749E
264374E
Ui
01
U2
02
01
01
Ul
02
01
02
01
01
or
01
01
01
01
01
19l749T~0~l
183824E 02
S! AMDAHL)
DEVIATION
""O.Z15T5T5F
0.248545E
0.563547E
0.676349E
0.107148E
""""OiTTnOBTST
0.475011E
0.155222E
0.433899E
0.351559E
0, 244949E
0.268967E
0.229128E
0.491463E
0.123438E
0.925996E
0.414726E
0.r94l48E
0.159983E
"cru •
00
00
00
00
01
00
00
01
00
CO
00
00
00
•w
00
01
00
00
02
.^AX
KAKL
G.8430COE 01
C.44000CE 01
0.199700E
0.1144COE
C.192603E
0 . 1 1 5 1 0 0 E
0.105600E
O.S14000E
0.335300E
0.838UOOE
0.120000E
0 * 1 3 5 0 0 0 E
C.68CCOOE
0.750000E
"0 t'7TDT"C"0~E~
0.5COOOOE
0.500000E
0.536000E
0.124000E
0.342000E
0.212000E
0.505000E
02
02
T2
02
02
01
02
01
02
02
01
01
77T~
01
01
01
01
01
01 ~
02
E
N I N
C.77CCOOE'
0.361CCOE
flt 179000E
C.955COOE
C.1606COE
0.7650COE
C.126000E
0.908000E
0.531000E
0.283800E
0.68300CE
C.930000E
0. 109000E
Ot9700COE
0.780000E
0.680000E."
0.360000E
o*idooco£
0.229000E
0.100000E
0.223COOE
0. 148000E
C.78700CE
"OT"
01
01
"0"2
01
02
01
01
02
01
ITC" " ~ ~ ~ -
02
01
01
01
01
01
01
01
01
01
01
-------
VD
I
MULTIPLE REGRESSION ANALYSIS
PROGRAM REG
LlEtttKYAN - KtPL.IC.AT
NUMBER VARIABLES
NUFTVETTi:
GENERAL
TKSTRVSTT
t5 FOR SOURCE 1
26
ONS «
' ~5—
STATISTICS
VARIABLE
NUMBER SUM
2
4
5
6
7
8
" - "" -9
10
11 '
12
13
14
"1-5
16
17
Ifl
- 19
20
" "" ""2T
22
23
24
25 -
26
0.3029E
0.5849E
U • b '.•) H M E
0..4386E
0.5BIOE
0.4030E
0.1721E
0.1576E
0.7310E
a.57H9F
0.4090E
0.4C99E
0.3169E
"0.2929E
0.1660E
""OVITO9E""
0.1764E
0. 700UE
0.1194E
0.1Z84E
0.4371E
02
02
02
02
02
02
02""
03
02
02
02
02
02
02
02
02
02
02
02" "
02
01' '
02
02 "
02
AVERAGE
~OTT5y99~9T-
0«606000E
0.116999E
U« 1 2779Ut
0.877199E
011T62T9E""
0.806199E
CYRJnTSOTTE"
0.344239E
0.11Z139E
0.681199E
0.315199E
0.146200E
OYH5799E
0.817999F
U.819999L
0.633999E
0.5B5999E
0.331999E
Oi352999E
0.238999E
0.874399E
01
"02"
02
01
02
01
-or
02
01
-01
02
"0"2
01
01
01
01
01
Ul
01
"O"!"
01
DEVIAT
Oil62480E
0.436348E
TT.T5"5"9""5"5r
0.445376E
A7?D
ION
UO^""
00
00
0.570592E 00
0.923912E-01
0.265528E 01
0.409897E
0.256124E
~ 0.271293E
0.324961E
0.205912E
O.T49"e6"6T
0. 160000E
0.123935E
UU
00
" 0 0
00
0"0
00
uo
00
'"00
00
00
0.493963E-01
0.215507E 01
MAX
0«790000E
0.670000E
0.122700E
U. 1318UUL
0.947000E
""o.iTsraoT
0.817000E
Oi394800E
U.1188UOL
0.739000E
0.362COOE
0.150000E
-0'.H"9"OOOE
0.880000E
U.840UOOE
0.6600COE
0-,610"OCOE"
0.360000E
0.377000E
U.142000E
01245000E
0.269000E"
0.124000E
-or ~
01
02
02
02
01
01
"Oi"""
02
U2
01
GT
02
01
01
01
01
01
01
01
01 "
01
"oi --"
02
,,..,.
U
0
WIN
r7400~0~OT
.540000E
'&• 207900E
0.111000E
0
0
0
0
U
0
0
0
"0
0
0
0
0
0
0
0
U
0
0
0
» 122000L
.797000E
.790000E
.311800E
,l'D46"OOr
.611000E
.2500CDE
.143000E
.111000E
.79000QE
» 770000 1
.610000E
.570000E
•320000E
.370000E
.345000E
i 136000L
•230000E
.253000E
.655000E
0 1
01
OT"" ~" "
02
02
01
"OT "
01
02
02
01
01
02
02
01
01
01
01
01
01
01
01
01
01
-------
APPENDIX E
C7EBERMAN - SOURCE 1 WEATHERED VS UNWEATHERED - 17MAY72
STEPWISE REGRESSION CASE. 1
DEPENDENT VARIABLE""TTJ—IS X 27 F-LEVtL TO ENTER =0.100"
STA
NDARD
1 \UtHt
1
1
b
M5
t
^
16
ERROR OF Y = 0.49792959E 00 F-LEVtL TU KEMUVt * 0*010
Ml ^VAKIABLE NUMBt-KS
• " T- 4 5 6 7 " 8 9 10 11 12 13 14
~17 IE" --19 20 21 22 23 24 25 26
F-LEVEL 0.447
T-LEvEL C.669
STANDARD ERROR OF ESTIMATE 0.51C91526E 00
F RATIO FOR THE REGRESSION D.44794339E 00
FRACTIOiNI OF EXPLAINED VARIAMCE (RSQD) 0.04267
DETERMINANT OF THE CORRELATION MATRIX 1.00000 P = 0.48
RESIDUAL DEGREES OF FREEDOM (N-K-1) 10
CONSTANT TER^ C.OOOOOOOOE 00
VARIABLE ESTIMATED COVARIA?*
26 -C.B1320E-02 0.12150E-01 0.669 0.447 _°VOOC
STEP NO
VARIABLE ENTERED
- 171 -
-------
ro
I
ESTIMATED
)!->(• R I EN'
T-RATTCT
COVARIANCE
T=RATIO~"RATTb (R SCD"
01 0.13408E 01
1 COMPLFT?D
'LICATES FOR SOURCE 1
1.005
1.C11
o«occo
-------
CALCULATED AND OBSERVED VALUES
OJ
I
MUM NUMHEH
1000.01000
1000.02000
1000.03000
lOOO.OfOO'O
1000.05000
1218.0'9000
1108.09000
1105.59000'
1218.0100C
1 lOt! .0 1 UUU
1215.51000
CHRONOLOGICAL ORDER
OBSERVED CALCULATED OBS-CALC WT
0.
0.
0.
u,
0.
-0.
-0.
-0.
-0.
-0 .
-0.
545500E
545500E
545500E
i> 45 5u 0 1
545500E
454500E
454500E
45450CE
454500E
4 ^ ^ 5 (J U t
454500E
00
00
00
u u
00
00
00
00
00
uu
00
0.541663E
0.418135E
0.592347E
u.svu&lot
0.497377E
-0.572624E
-0.300400E
-0.327559E
-0.515923E
-0.526441L
-0.392134E
00
00
00
uu
00
00
00
00
00
uu
00
0.3B3670E-02
0.127364E 00
-0.468471E-01
-0.451105E-01
0.481221E-01
0.118124'E 00
-0.154099E CO
-0.126940E 00
0.614233E-01
0.71941BE-01
-0.623653E-01
ERROR
RUN NUMBER
1108.09000
" 1105.59000
1215.51000
1000. 03000
1000.04000
1000.01000
1000.05000
1218.01000
1108.01000
121B.090CO
1000.02000
MAGNITUDE
ORDER
OBSERVED
-0 .4541.0 E
"-0".4545T)E
-0.45450E
0.54550E
0.54550E
0.54550E
0.54550E
-0.45450E
-0.45450E
-0.45450E
0.54550E
00
"00
00
0 0
00
00
00
00
00
00
00
OBS-CALC
-0
-0
-0
•"0
-0
0
0
0
0
n
0
•15409E 00
VI 2 6 94 E" 00
.62365E-01
•46847E-01
.45110E-01
.38367E-02
•48122E-01
.61423E-01
.71941E-01
.11812E 00
.12736E 00
-------
APPENDIX F
SAMPLE CALCULATIONS FOR GAS CHROMATOGRAM
The calculation procedure used to determine the n-paraffin
concentrations in a sample by means of the gas chromatogram involves
the following steps.
• Location of n-paraffin peaks by means of a standard run.
• Ascertaining peak areas by peak height x width at half
height.*
• Normalization of areas to obtain > C_n n-paraffins.
* Peak height measured from crest of peak to valley.
e.g.
- 175 -
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
/. Rep ttfo.
w
4. Title
OIL SPILL SOURCE IDENTIFICATION,
7. A uthor(s)
Lieberman, M.
Esso Research and Engineering Company
Government Research Division
Florham Park, New Jersey
.?. K irtD
£
S. PrrfoTtnir > Qtgar.
o.
15080 HDL
68-01-0058
13 Type Repo ,nd
Period Co
1?..
Environmental Protection Agency report
number, EPA-R2-73-102, February 1973.
A b sir set
Five different crude oils, two residual fuel oils (No. 4 and No. 5) and one
distillate fuel oil (No. 2) were subjected to simulated weathering in the labora-
tory. Samples were weathered for 10 and 21 days at 55 and 80°F, under high and
low salt water washing rates. "Weathered" and "unweathered" oil samples were
analyzed by low voltage mass spectroscopy (polynuclear aromatics), high voltage
mass spectroscopy (naphthenes), gas chromatograph (n-paraffins), emission spec-
troscopy (nickel/vanadium), X-ray total sulfur and Kjeldahl total nitrogen tech-
niques.
Several compound indices were adequately stable toward simulated weathering to
discriminate between like and unlike pairs of oils. Discriminant function analysis
was used to select the best compound indices for the oils used.
Using these indices, weathered and unweathered samples were correctly paired
with high statistical confidence.
17a. Descriptors
*0il Spills, *Pollutant Identification, *Chemical Analysis, Correlation Analysis,
*Weathering, Gas Chromatography, Mass Spectrometry, Tagging
7 7b. Identifiers
Passive Tagging, n-Paraffins, Polynuclear Aromatics, Naphthenes, Nickel, Vanadium,
Nitrogen, Sulfur
l~c. COWRR Field & Group 05A
IS. tl<.:-iil.it;iUty
19. S vrity *" ,:ss.
20, Secure jf Class,
21. j'^_-. 'of
n: ;??/«
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 20240
. Lieberman
Esso Research and Engineering
»U.S. GOVERNMENT PRINTING OFFICE: 1973 514-153/ao L-S
------- |