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OCR for page 17
Chemical Composition of
Petroleum Hydrocarbon Sources
INTRODUCTION
Sources of hydrocarbons enter ing the mar ine environment are numerous,
and the number of individual hydrocarbon components are quite large.
Thus, the analytical chemist faces a challenge in der iving detailed
compositional data on a given environmental sample as does the bio-
geochemist in associating a given complex hydrocarbon a~s~mblaa" with
one or more sources. The interpretive dilemma becomes further aggra-
vated by chemical and microbial alterations that occur after intro-
duction of a particular set of hydrocarbon compounds to the mar ine
environment, a set originally attributable to a source but subsequently
modif led. This section bight ights the main compositional character-
istics of the hydrocarbon sources to the mar ine environment and
distinguishes features of each source.
~7
CRUDE OILS
Petroleum formation and composition have been discussed in detail
recently by Tissot and Welte (1979) and Hunt (1980), and unless
otherwise noted, those texts are the sources for the following
information. The chemical composition of crude oils from different
producing regions, and even from within a particular formation, can
vary tremendously. Crude oils contain thousands of different chemical
compounds owing to processes dur ing petroleum formation resulting in
"molecular scrambling. " Hydrocarbons are the most abundant compounds
in crude oils, accounting for 50-989 of the total composition (R.C .
Clark and Brown , 1977 I, although the major ity of crude oils contain the
higher relative amounts of hydrocarbons. While carbon (80-879~) and
hydrogen (10-15~) are the main elements in petroleum, sulfur (0-10%)
nitrogen (0-1%), and oxygen (0-5%) are important minor constituents
present as elemental sulfur or as heterocyclic constituents and
functional groups. Compounds containing N. S. O as constituents are
often collectively referred to as NSO compounds. Crude oils contain
widely varying concentrations of trace metals such as V, Ni, Fe, Al,
Na, Ca, Cu. and U (Posthuma, 1977~.
17
OCR for page 18
18
Table 1-1 presents examples of the composition of crude oils and
fuel oils. Petroleum hydrocarbons (Figure 1-1) consist of alkanes,
cycloalkanes, and aromatic compounds containing at least one benzene
ring. The alkanes, or aliphatic hydrocarbons, consist of the fully
saturated normal alkanes (also called paraffins) and branched alkanes
of the gener al molecular formula (CnH2n+2 ), with n r ang ing f rom 1 to
usually around 40, although compounds with 60 carbons have been
reported. Above C13, the most important group of branched compounds
is the isoprenoid hydrocarbons consisting of isoprene building blocks.
Pristane (Cl") and phytane (C20) are usually the most abundant
isoprenoids, and while the C10-C20 isoprenoids are often ma jor
petroleum constituents, extended ser. ies of isoprenoids (C20-C40)
have been repor ted (Albaiges, 1980 ~ .
Many of the cycloalkanes or saturated r ing structures, also called
cycloparaff ins or naphthenes, consist of important minor constituents
that, 1 ike the isoprenoids, have specif ic animal or plant precursors
~ e . g ., ster anes , d iterpanes , tr iterpanes ~ and that serve as impor ten t
molecular markers in of' spill and geochemical studies (Albaiges and
Albrecht, 1979; Dastillung and Albrecht, 1976 ~ .
Aromatic hydrocarbons, usually less abundant than the saturated
hydrocarbons, contain one or more aromatic (benzene) r ings connected as
fused rings (e.g., naphthalene) or lined rings (e.g., biphenyl).
Petroleum contains many homologous ser ies of aromatic hydrocarbons
consisting of unsubstituted or parent aromatic structures (e.g.,
phenanthrene) and like structures with alkyl side chains that replace
hydrogen atoms. Alkyl substitution is most prevalent in 1-, 2-, and
3-r inged aromatics, although the higher polynuclear aromatic compounds
(>3 r ings) do contain alkylated (1-3 carbons) side groups. The
polycyclic aromatics with more than 3 r ings consist mainly of pyrene,
chrysene, benzanthracene, benzopyrene, benzofluorene, benzof l uor anthene,
and perylene structures. The naphthenoaromatic compounds consist of
mixed structures of aromatic and saturated cyclic rings. This series
increases in importance in the higher boiling fractions along with the
saturated naphthenic series. The naphthenoaromatics appear related to
resins, kerogen, and sterols. Petroleum generation usually involves
the formation of some naphthenoaromatic structures.
The nonhydrocarbon petroleum constituents, such as examples in
Figure 1-lc, can be grouped into s ix classes according to Posthuma
(1977~: sulfur compounds, nitrogen compounds, porphyrins, oxygen
compounds, asphaltenes, and trace metals. Sulfur compounds compr ise
the most important group of nonhydrocarbon constituents. Most sulfur
present is organically bound, e.g., heterocyclic. The organosulfur
compounds consist of thiols, disulfides, sulfides, cyclic sulfides
~ e . g ., th iacyclohexanes ), and th iophenes . The benzoth iophenes and
d ibenzoth iophenes are important constituents of the h igher-molecular-
weight aromatic fractions of env~.ronmental samples, with the tetramethyl
dibenzothiophenes apparently having the highest molecular weight of the
sulfur heterocyclics (Jewel!, 1980) .
Nitrogen is present in all crude oils in compounds such as pyr i-
dines, quinolines, benzoquinolines, acr idines, pyrroles, indoles,
carbazoles, and benzcarbazoles (R.C. Clark and Brown, 1977; Posthuma,
OCR for page 19
19
TABLE 1-la
Crude Oils
Physical Characteristics and Chemical Properties of Several
Characteristic
or Component
Crude Oil
Prudhoe
Baya
South
. . b
Lou~s~ana
Kuwait:
API gravity (20°C) (°API)*
Sulfur (wt %)
N itrogen (wt 9
N ickel (ppm)
Vanadium (ppm)
Naphtha fractior~ (wt %)
Par af f ins
Naphthenes
Aromatics
Benzenes
Toluene
C~ aromatics
C' aromas ics
C1O aromas ics
Cll aromatics
Indans
H igh-boil ing f ractione (wt 9e
Satur ates
e-paraffins
Cl1
C12
C13
C14
C15
C16
C17
C18
C19
c2o
C
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32 plUS
Isoparaffins
27.8
0.94
0.23
10
20
23.2
12.5
7.4
3.2
0.3d
0.6
0.5
0.06
__
76.8
14.4f
5.89
0.12
0.25
0.42
0.50
0.44
0.50
0.S1
0.47
0.43
0.37
0.32
0.24
0.21
0.20
0.17
0.15
0.10
0.09
0.08
0.08
0.08
0.07
1-ring cycloparaffins 9.9
2-ring cycloparaffins 7.7
34.5
0.25
0.69
2.2
1.9
18.6
8.8
7.7
2.1
0.2
0.4
0.7
O .5
0.2
O .1
__
81.4
56.3
5.2
0.06
0.24
0.41
0.56
0.54
0.58
0.59
0.40
0.38
0.28
0.20
0.15
0.16
0.13
0.12
O .09
0.06
O .05
O .05
0.04
0.04
o
14.0
12.4
9.4
31.4
2.44
0.14
7.7
28.
22.7
16.2
4.1
2.4
0.1
0.4
0.8
0.6
0.3
O .1
O .1
77.3
34.0
4.7
0.12
0.28
0.38
0.44
0.43
0.45
0.41
0.35
0.33
0.25
0.20
0.17
0.15
0.12
0.10
0.09
0.06
0.06
0.05
O.07
0.06
0.06
13.2
6.2
4.5
OCR for page 20
20
TABLE 1-la (continued)
Characteristic
or Component
Crude Oil
.
Prudhoe South
Baya Louisian ~Kuwaitb
3-ring cycloparaffins5.5 6.83.3
4-ring cycloparaffins5.4 4.81.8
5-ring cycloparaffins-- 3.20.4
6-ring cycloparaffins-- 1.1-
Aromatics (wt %)25.O 16.521.9
Benzenes7.0 3.94.8
Indans and tetralins-- 2.42.2
Dinaphthenobenzenes-- 2.92.0
Naphthalenes9.9 1.30.7
Acenaphthenes-- 1.40.9
Phenanthrenes3.1 0.90.3
Acenaphthalenes-- 2.81.5
Pyrenes1.5 ---
Chrysenes-- --0.2
Benzothiophenes1.7 0.55.4
Dibenzothiophenes1.3 0.43.3
Indanothiophenes-- --0.6
Polar materialsh (wt %)2.9 8.417.9
Insoluble=)1.2 0.23.5
-
NOTE: These analyses represent values for one typical crude oil from each
of the geographical regions; variations in composition can be expected for
oils produced from different formations or fields within each region.
Adapted from Thompson et al. (23) and Coleman et al. (24)
~ rom Pancirov (25~.
Fraction boiling from 20° to 205°C.
epor ted for fraction boiling from 20° to 150 °C.
~Fraction boiling above 205°C.
epor ted for fraction boiling above 220°C.
~Prudhoe Bay crude oil weathered 2 weeks to duplicate fractional
distillation equivalent to approximately 205°C e-paraffin percentages from
gas chromatography over the range Cll-C32 plus for the Prudhoe Bay
crude oil sample only (R. C. Clark, Jr., unpublished manuscript, 1966~.
hPolar material: clay-gel separation according to ASTM method D-2007 (10;
.part 24) using pentane on unweathered sample.
~Insolubles: pentane-insoluble materials according to ASTM method D-893
(10; part 23~.
.
*API gravity = 141.5/ (specific gravity at 60°F or 16°C) - 131.5.
SOURCE: R.C. Clark and Brown (1977~. Numbers in parentheses in footnotes
above are reference numbers in R.C. Clark and Brown (19771.
OCR for page 21
21
TABLE 1-lb Physical Character istics and Chemical Properties of Two
Ref ined Products
Character istic No. 2 Bunker C
or Component Fuel Oila Fuel Oil
API gravity (20°C) (°API) * 31.6 7.3
Sulfur (wt 9~) 0.32 1.46
Nitrogen (wt %) 0 . 024 0 . 94
Nickel (ppm) 0.5 89
Vanadium (ppm) 1.5 73
Saturates (wt %) 61.8 21.1
e-par af f ins 8 . 0 7 1 . 73
Clo ~ C11 1.26 0
C12 0.84 0
C13 0.96 0.07
C14 1.03 0.11
C15 1.13 0.12
C16 1.05 0.14
C17 0.65 0.15
C18 0.55 0.12
C19 0.33 0.14
C20 0.18 0.12
C21 0 .09 0 .11
C22 0 0.10
C23 0 o . os
C24- 0 0.08
C25 0 0 .07
C26 0 0.05
C27 0 0.04
C28 0 0.05
C29 0 O .04
C30 0 O .04
C31 0 0.04
C32 plus O O .05
Isoparaffins 22.3 S.O
1-ring cycloparaffins 17.5 3.9
2-r ing cycloparaff ~ns 9 .4 3 . 4
3-r ing cyclopar af f ins 4 .5 2 . 9
4 -r ing cyclopar af f ins 0 2 . 7
5-r ing cyclopar af f ins 0 1.9
6-r ing cyclopar af f ins 0 0.4
Aromatics (wt % ~38 .2 34 . 2
Benzenes 10 .3 1. 9
Indans and tetralins 7.3 2.1
Dinaphthenobenzenes 4.6 2.0
Naphthalenes 0.2b
Methyloaphthalenes 2. ~2.6
Dimethylnaphthalenes 3.2b
OCR for page 22
22
Table 1-lb (continued)
Characteristic No. 2 Bunker C
or Component Fuel Oila Fuel Oil
Other naphthalenes 0.4
Acenaphthenes 3.8 3.1
Acenaphthalenes 5.4 7.0
Phenanthrenes 0 11.6
Pyrenes 0 1.7
Chrysenes 0 0
Benzothiophenes 0.9 1.5
Dibenzothiophenes 0 0.7
Polar materially (wt %) O 30.3
Insolubles (pentane)C (wt %) 0 14.4
NOTE: These analyses represent typical values for two different refined
products; variations in composition can be expected for similar
materials from different crude oil stocks and different refineries.
From Pancirov (257.
This is a high aromatic mater ial; a typical No. 2 fuel oil would have
an aromatic content closer to 20-259~. From Vaughan (26~.
tFrom Vaughan (26~.
ESee footnotes h and ~ for Table 1-2.
*API gravity = 141.5/(specific gravity at 60°F or 16°C) - 131.5.
SOURCE: R.C. Clark and Brown (19771. Numbers in parentheses in
footnotes above are reference numbers in R.C. Clark and Brown (1977~.
1977; Hunt, 1979; TisSot and Welte, 1978~. The porphyrins are nitrogen-
containing compounds derived from chlorophyll and consisting of four
1 inked pyrrole r ings . Porphyr ins occur as organometall ic complexes of
vanadium and nickel.
Oxygen compounds in crude oils (0-2%) are found pr imar fly in
distillation fractions above 400°C and consist of phenols, carboxylic
acids, ketones, esters, lactones, and ethers.
Petroleum contains a significant fraction (0-20%) of material of
h igher molecular weight ~ 1 , 000-10 , 000 ), cons isting of both hydrocarbon
and NSO compounds called asphaltenes. These compounds, consisting of
10-20 fused rings with aliphatic and naphthenic side chains, contribute
signif icantly to the properties of petroleum in geochemical formations
and in spill situations in relation to emulsification behavior.
OCR for page 23
23
TABLE 1-lc Examples of Individual Polynuclear Aromatic Hydrocarbon
Concentrations in Petroleum (10-6 gig Petroleum)
South
Louisiana Kuwait
Crude Crude
No. 2
Fuel Oil Bunker C
Pyrene 4.3 4.5 4123
Fluoranthene 6.2 2.9 37240
Benzanthracene 3.1 2.3 1.290
Chrysene 23 6.9 2.2196
Triphenylene 13 2.8 1.431
Benzo~aipyrene 1.2 2.8 0.644
Benzo~eipyrene 3.3 0.5 <0.110
SOURCE: Pancirov et al . ( 1980 ~ .
Vanadium and nickel are the most abundant metallic constituents of
crude petroleum, sometimes reaching thousands of parts per million.
They are pr imar fly present in porphyr in complexes and other organic
compounds (R.C. Clark and Brown, 1977; Yen, 1975~.
The stable isotope ratio of 13C to 12C in whole crude oils, in
oil fractions, and in the total and lipid fractions of sediments and
organisms is being used to identify sources of carbon and to charac-
terize or n fingerprint" various types of petroleum. Values in the
literature are generally expressed in terms of 613C, where 613C
(in o/oo) = ~ (l3C/l2C)sample/(l3C/l3C)standard - 131,000 and the
standard is the Chicago PDB material (Craig, 1953~. The 613C
compositions of natural crude oils range from about -18 to -35 o/oo
(Silverman and Epstein, 1958~. Relative to the composition of a given
whole crude, C, CH4 values are as negative as -40 o/oo and C values
as positive as +2 o/oo for up to C15 hydrocarbons (Silverman,
can be
1963).
REFINED PRODUCTS
Ref ined petroleum products introduced to the mar ine environment include
gasoline, kerosene, jet fuels, fuel oils (No. 2, No. 4, No. S. No. 6)
or Bunker fuel oils, and 1ubricatino oils. Figure 1-2 illustrates the
t~Pes of common uroducts obtained from crude oil distillation and
cracking. As refining processes and terminologies differ worldwide,
For
_ _
example, distillation, catalytic and thermal cracking, polymerization,
and reforming yield products that are blended together to achieve
desired chemical properties. They contain all of the hydrocarbon
classes previously mentioned, but with narrower boiling ranges than
comparisons of comDositions of refined products vary widely.
OCR for page 24
24
n-ALKANES
CH4 CH3- CH3
METHAN E ETHANE
I SOALKAN ES
CH 3 - ( C H 2 ) - CH 3 (n = 1 - 58 )
C1 13 - C H - C H2 - C H3 cH3
CH3 CH - C - CH - CH - CH
3 1 2 1 3 ISOOCTANE
ISOBUTANE CH3 CH3
CH3 CH3 CH3 CH3
CH3 - C - ( CH2 )n ~ C - ( CH2 )n ~ C ~ (CH2)n C CH3 ( n = 3 )
PR I STA N E
(an isoprenoid hydrocarbon)
CYCLOALKANES
Carbon ond Hydrogen atoms
Onot shown for example
~I I represented A
CYCLOHEXANE DECALI N CH2 CH2 by
\ /
CH2
CYCLOPENTAN E
W^'
>~
HOPANE
(general class of similar
structures are friterpanes.
,~
CH OLESTA NE
genera I class of simi lar
structures are steranes.)
FIGURE 1-la Chemical structure of petroleum hydrocarbons. Isooctane
was formed in cracking process for gasoline production.
OCR for page 25
25
Benzene
I ndane
tOlOJ
2-Methyl
Phenanthrene
3,4-Benzopyrene and
3,4-Benzo [a] pyrene
Hi,
Naphthalene 1-Methyl
Naphthalene 2,5-Dimethyl
Naphthalene
F luorene
Fl uoranth rene
Phenanthrene
Benzanth racene
Pyrene
FIGURE 1-lb Chemical structure of petroleum hydrocarbons.
corresponding crude oils. In addition, cracking operations generate
olefins (alkenes and cycloalkenes), which occur in concentrations as
high as 30% in gasoline and about 1% in jet fuel. Olefins are not
present in crude petroleum and are present only in minor amounts in
other refined products. Alkylation processes yield many branched
compounds such as isooctane (Figure 1-la). An excellent discussion of
the chemical properties of refined products pertinent to fate and
effects in the environment is found in R.C. Clark and Brown (19771.
OIL SEEPS AND ANCIENT SEDIMENTS
The composition of seep oil is similar in many respects to crude oil
pumped from wells, but can be influenced by a variety of physical,
chemical, and biological processes to be discussed in a later section.
OCR for page 26
26
SULFUR COMPOUNDS
CH3- CH2 - SH
Ethanethio I
CH3- CH2 - S - S - C H - CH
3~4 Dithia hexane
Thiacyclohexane Thiophene
NITROGEN COMPOUNDS
Dibenzothiophene
H H
Pyridine Quinoline Indoline Carbazole
OXYGEN COMPOU N D S
[ - ~OH
o
Fluorenone Phenol
Dibenzofuran
FIGURE 1-lc Nonhydrocarbon petroleum constituents: NSO compounds.
Hydrocarbons and other compounds associated with ancient sediments
range in composition from that of many crude oils to that of biogenic
and early diagenetic compounds found in recent nonpolluted sediments.
8IOGENIC HYDROCARBONS
Hydrocarbons are synthesized by most mar ine plants and animals, includ-
ing microbiota (Han and Calvin, 1969; J.B. Davis, 1968), phytoplankton
(Blumer et al., 1971; Clark and Blumer, 1967), zooplankton (Blumer et
al. , 1969 ; Blumer and Thomas, 1965a,b; Avignan and Blumer , 1968),
benthic algae (Youngblood et al., 1971; Youngblood and Blumer, ~ 973;
Clark and Blumer, 1967), and fishes (Blumer et al., 1969; Blumer and
Thomas, 1965b) . Organisms can both produce their own hydrocarbons and
acquire them from food sources.
Species of marine organisms synthesize limited numbers of hydro-
carbon constituents over relatively narrow boiling ranges. For example,
odd-numbered carbon chains predominate in mar ine biotic systems (C15-C2 1
normal alkanes in phytoplankton) , although the biogenic production of
even-numbered carbon chains has been observed (R.C . Clark, unpubl ished
manuscript, 19661. Pristane (C19) is a major component of calanoid
copepods and, consequently, of some f ishes (Blumer et al . , 1963 ; Blumer ,
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27
FRACTIONAL D ISTI LLATION DISTR I BUTION
STRAIGHT-RUN MIDDLE DISTILLATES WIDE-CUT RESIDUAL
GASO L I N E GAS Ol LS Ol LS
O1 1
200
r,
400
By
CC
z
o
m
600
800
1000
GASOLINE
FR ACTI ONS
my_
KEROSINE
HEATI NG
| /
DIESEL
FU EL
JET
FU EL
LIGHT
LUBES
I
HEAVY
' LUBES
FIGURE 1-2 Boil ing point range of fractions of crude petroleum.
o
-1 00
-200 o
UJ
CO
Z
a:
a:
-300 ~
By
_
-
o
400 m
500
600
NOTE: Bunker oil (not shown) is an oil of high viscosity used as a
fuel oil. A given Bunker oil may be a mixture of two or more of the
distillate cuts shown in the f igure or it may be a residual oil from a
distillation run.
SOUPBONE: Adapted from Bureau of Naval Personnel by R.C. Clark and Brown
(1977 ~ .
1967~. Although normal and branched alkanes are biosynthesized, alkenes
are the most abundant biosynthetic compounds in all trophic levels.
Terrestrial plants (and sargassum) produce C21-C33 odd-chain
n-alkanes, with the C21-C29 compounds dominating in marsh grasses
and the C27-C33 alkanes associated with the waxy coatings of grasses
and leaves. These are major hydrocarbon components of most "cleans
coastal sediments (Wakeham and Farrington, 1980; Simoneit, 19781.
Other compounds that have been detected in mar ine organisms include
certain of the tr iterprenoid (hopane) hydrocarbons in mar ine bacter ia
(Our isson et al ., 1979 ~ and naphthenes containing 1-3 r ings in land
herbs and plants (Blumer, 1969 ~ . Although there have been reports of
the synthes is of polycyclic aromatic hydrocarbons by algae and higher
plants (e.g., Borneff et al., 1968a,b), these contentions are disputed
(Gr immer and Duval , 1970 ; Hase and H ites , 1976 I, and at present the
issue remains unresolved.
OCR for page 32
32
4. Petroleum contains several homologous series of compounds
(e.g., normal alkanes; branched alkanes; cycloalkanes; isoprenoid
alkanes, including branched cyclohexanes, steranes, and triterpanes).
5. Petroleum contains homologous series of alkylated aromatics
(e.g., mono-, di-, trim, and tetra-methyl benzenes; naphthalenes;
fluorenes; dibenzothiophenes; phenanthrenes).
6. Petroleum contains numerous naphthenic and naphthenoaromatic
compounds.
7. Petroleum contains numerous heterocyclic compounds containing
S. N. and 0.
8. Petroleum contains trace metals, with Ni and V often present in
ng/g quant it ies .
9. Hydrocarbons of a petroleum or igin should have little 14C
activity.
10. Stable carbon isotope ratios are isotopicall-y heavier than
b iogen ic inputs .
- All character istics are attr ibutable to petroleum and ref ined
products, although the composition of distillate cuts is narrower in
boiling range than the corresponding crude oil. Light distillate cuts
may contain olef inic mater ial and little, if any, trace metal content
unless added.
However, one caveat pertains to carbon-number ratios. Smooth
distributions of alkanes (CPI or 0EP = 1) within the crude oil
nonvolatile molecular weight range have been reported for marine
bacteria (Han and Calvin, 1969) and have been detected in marine fish
(Whittle et al., 1977a,b; Boehm, 1980~. ThUS, paraffinic tar and
biogenic alkanes may be very similar in the C20-C30 range.
Furthermore, smooth n-alkane distributions have been noted in urban air
(Heuser and Pattison, 1972) and in laboratory dust (Gelpi et al., 1970)
samples. Thus, n-alkane distributions alone, in environmental samples
and especially in marine fish, cannot be attributable to oil pollution
without corroboration by other petroleum compositional features.
Characteristics of Petroleum Altered by Physical, Chemical,
and Biological Processes
Most often, except for recent spill studies, environmental samples
contain altered, rather than "fresh, n petroleum. Thus, some diagnostic
features associated with petroleum may be reduced in importance, and
other or new diagnostic parameters become more important. The
compos ition can be altered on time scales varying from days to years
past the point where of] can be easily attributed to a particular
source. Certain chemical marker compounds survive longer than others,
and the time course and degree of change in composition vary with each
spill or source of input, sample type, and environmental conditions.
An example of a time series for fresh petroleum and samples subjected
to alteration by natural processes is shown in Figure 1-5. The
following changes in composition occur:
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Representative terms from entire chapter:
mar ine
33
1. Loss of low boiling (
34
A R EF ERENCE MOUSSE
1
C ~ CD ~ . - Cat ~ a, O - ~ ~ ~
- - - .L - - -A,- ~- ~ Cad ~ ~ Cad
UCM ~
C "ONE YEAR EXPOSURE
l
c
|> UCM
NAAI
~1
_~
FIGURE 1-5 Glass capillary gas chromatograms of time series for fresh
petroleum and petroleum subjected to alteration by natural processes in
sediments.
To date, the various transformation products have not been used as
markers for particular sources of inputs, although useful indicator
compounds may emerge with further research.
Characteristics that have proven useful are the following:
35
D STAG E 3 WEATH E R I NG (Saturated Hydrocarbons)
In
PCA=Polycycl ic Al iphatics
UCM
PCA
it_
1 _`
E STAGE 4 WEATHERING (Saturated Hydrocarbons)
O ,
At'
1.~
In
_
~ ~'
UCM
PCA
l
i..
.)
my_
Aim_ _ .. . /. . .
F BACKGROUND (Saturated Hydrocarbons)
i t~ ~ ~1~ L4,
. . ~
. -
C~
~ g
Cal
~1~i
FIGURE 1-5 (continued).
1. An unresolved complex mixture is characteristic of weathered
oils (see Chapter 3, Gas Chromatography section).
2. The normal alkane-to-isoprenoid ratio, which in fresh oils is
much greater than 1, decreases as biodegradation proceeds (Boehm et
al., 1981; Atlas et al., 1981~. That is, pristane, phytane, and
farnesane become dominant saturated hydrocarbon components of weathered
oils until they, too, are degraded.
36
3. Extended series of isoprenoids (C20-C40) become useful
indicators of petroleum in weathered samples (Albaiges, 1980~.
4. C27+ pentacyclic triterpanes (e.g., hopanes; Figure 1-6),
being relatively resistant to degradation, become prominent marker
compounds (Dastillung and Albrecht, 1976; Albaiges and Albrecht, 1979;
Boehm et al., 1981) as the presence of paired peaks (22R and S
diastereomers) of the Cal, C32, and C33 17H,21H-hopanes is unique
to petroleum (see Figure 1-61.
5. Alkylated phenanthrenes and alkylated dibenzothiophenes
sometimes are the prominent aromatic components of weathered petroleum
(Teal et al., 1978; Ber thou et al., 1981; Boehm et al., 1981; Overton
et al., 1981~.
6. The relative amount of polar (N. S. O) material increases as
degradation proceeds due to oxidation reactions (J.R. Payne et al.,
1980a,b).
7. Stable isotope ratios of carbon, hydrogen, and sulfur do not
vary greatly with weathering, and thus may be useful to identify
weathered oils (Sweeney et al., 1980; Sweeney and Kaplan, 1978~.
Character istics of Combustion-Related Hydrocarbons
Little is known about the saturated hydrocarbon composition of the
combustion products of fossil fuels. Most compositional information is
based on polynuclear aromatic hydrocarbons.
1. PAH compounds generally occur in the 2- to 6-ring range.
2. Fluoranthrene and pyrene are often the most abundant PAH in
pyrolysis-related samples together with phenanthrene, benzanthracene,
chrysene, and the benzopyrenes.
3. Unsubstituted (nonalkylated parent) compounds are much more
abundant than alkylated members of any homologous series. ThiS
important difference from weathered petroleum is often most striking
for the phenanthrene series. Alkylated phenanthrene members are often
the most abundant aromatic constituents of weathered oils.
4. Dibenzothiophene is relatively far less abundant than in oils.
37
REFERENCE MOUSSE
91 .0
T]
91 .a
T]
In"
~ Hopane
Norhopane _
Low Homohopanes
Trisnorhopanes ~
1 |4 61 yes
~s"'.~"'~s"'L'i'lllli'l~ll~l6'llll~l `~'6i'i~`'lLl~`r
BAY OF MORLAIX SEDIMENT
November t978
~__ _ ~=~__
1)~
t.~1
111. 11~4
I..
t
_
101111
2. 2 ~He ~ - ca CA en '^ ~ - ~__
FIGURE 1-6 Gas chromatographic mass spectrometry selected ion searches
for pentacyclic tr iterpanes (hopanes) in Amoco Cadiz reference oil and
November 1978 weathered oil in sediments.
38
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