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ABSTRACT
Natural gases can be characterized genetically using four
properties: C2+ concentration, carbon and hydrogen isotope variations in methane, and carbon isotope variation
in ethane. Three diagrams for genetic characterization of
gases have been designed in which the carbon isotopic
composition of methane is correlated with the other
parameters. In these diagrams, compositional fields have
been defined for primary gases (biogenic, thermogenic
associated, and thermogenic nonassociated) and for gases
which result from mixing of these gases. These fields are
strictly empirical and comprise compositional variations
found in about 500 natural gases. The isotopic and compositional variations in natural gases can be described in
terms of (1) processes during formation of the gases such
as bacterial fermentation or maturation of organic matter,
and (2) processes during secondary migration. Mixing of
primary gases is an important and common process.
Migration of gases predominantly affects the Cj^ concentration, whereas the isotopic properties of gaseous hydrocarbons primarily remain unchanged, allowing an
assessment of the origin of migrated gases and properties
of their source rocks. The formation of gas from humic
organic matter and coals is not yet clear from published
data.
The diagrams use data from various basins and areas.
Interstitial gases from the Gulf of California are entirely
of bacterial origin: traces of thermogenic gases are formed
only in the vicinity of dolerite sills; gases in the south German Molasse basin and in the Vienna basin are of bacterial, mixed, and thermogenic origins. Data from the north
Italian Po basin provide examples for genetic characterization of migrated gases.
INTRODUCTION
Natural gases occur in a variety of environments. Bacterial processes form gases in continental swamps or marine
sediments. Natural gases of bacterial origin are found in
Copyright 1983. The American Association of Petroieum Geologists. All
rights reserved.
''Manuscript received, Novemtier 10,1982; accepted, May 13,1983.
^Bundesanstalt fijr Qeowissenschaften und Rohstoffe, Hannover, West
Germany; present address: Chevron Oil Field Research Co., P.O. Box 448, La
Habra, California 90631.
This paper could only be written by using many samples made available by
various oil companies. I am particularly grateful to AGIP San Donato, Brigitta
Elwerath BetriebsfiJhrungsgesellschaft, Deminex, Deutsche Schachtbau und
Tiefbohrgesellschaft, Preussag AG, Deutsche Texaco, dstsrreichische
MineralSlverwaltung Wien, Rohfil Aufsuchungsgesellschaft Wien, Tenneco
Oil Co., and Wintershall AG Kassel.
The paper benefitted from many comments by M. Whiticar, G. E. Claypool,
S. Silverman, and D. D. Rice, which are gratefully acknowledged.
The AAPG Foundation supported the printing of this paper which is greatly
appreciated.
2225
2226
R Q 5 CcH,i
hydrocarbons generated
l%] [ppt]
C,.[%
30
50
0.5
1.2
2.0
3.0
1.2
2.0
3.0
FIG. 1Genetic characterization of natural gases by compositional and isotopic variations. Genetic fields for various types of gases
are defined in diagrams, allowing recognition of origin of a gas.
(a) Schematic illustration of formation of natural gas and petroleum in relation to maturity of organic matter.
(b) Relative concentration of C2+ hydrocarbons in gases in relation to '''C concentration in methane. Arrows Ms and Md indicate
compositional changes owing to shallow and deep migration,respectively(see text). Mixing of gases results in linear trends of compositional changes (see Figure 2).
(c) Variation of deuterium and '^C in methane of natural gases. Mixing in diagram results in linear changes between compositions of
respective end members.
(d> Carbon isotope variations in ethane related to carbon isotope variations in methane. Compositional changes because of mixing of
gases depend on methane and ethane concentrations. Bent mixing pathways are given schematically to indicate isotopic changes due
t', deep migration. Arrow Md would result if pure isotopically positive CH4 were to mix with a gas. Admixture of biogenic methane
results in change of 5'^C of methane only (arrow Ms).
methane in relation to the concentration of hydrocarbons
in the gas. Based on carbon isotope variations in methanes, Kartsev et al (1971), Alekseyev et al (1972), and
Alekseyev (1977) proposed a general zoning of gas formation by defining a biochemical, a transition, and a thermochemical zone, respectively. Stahl (1974) presented a
concept in which immature, mature, and overmature
gases were characterized by continuously increasing "C
concentrations in their methanes, and the C2+ concentrations were inferred to change in a continuous fashion: low
C2+ content in immature, high C2+ content in mature, and
decreasing amounts of higher hydrocarbons in overmature gases. Also, gases from terrestrial and marine source
rocks were differentiated. His model, though very useful
Martin Schoell
2227
6^^C ethane
5DcHi[ppt]
200
-150
-50
-100
-40
-30
-2 3
-70
CL
n -60
\
>j
o
O -50
\
\ \ \\
!!9^^
-
TJ
k
-40
1^
"''):%.
[nim].
kl ^^"'^
^e^^H
-30
TT(h)Migration i MHHH
-20
1
@
F I G . 1 Continued
Two stages of thermogenic gas formation may be differentiated: (1) during or immediately following oil formation, which results in gases associated with crude oils (T),
PREREQUISITES AND DEnNITIONS
and (2) following the principal stage of oil formation,
which
resuhs in dry or deep dry gases (TT).
Primary Gases
The use of terms "associated" and "nonassociated" in
This paper follows the classification of types of natural this paper is different from the standard petroleum geogases used by Schoell (1980) (Fig. la). Primary gases origi- logic usage, which has no genetic connotation. Levorsen
nate from the two principal processes of gas formation- and Berry (1967) defined associated gases as those probacterial respiration (biogenic) and thermal alteration of duced when oil exists as a separate phase in the reservoir; if
only gas is present, it is termed nonassociated. If these defliquid or solid organic precursors (thermogenic).
Biogenic gases (B)' originate in immature regimes from initions are to be used when discussing the origin of gases,
bacterially mediated anaerobic mineralization of organic the usage becomes slightly different. If, for example, a gas
matter in sediments. There is convincing evidence that the from a gas cap migrates off its primary reservoir it may
same bacterial processes observed in recent sediments become a nonassociated gas in standard usage but it still
account for gas accumulations in young sedimentary has the isotopic composition of an associated gas. Subsebasins (Schoell, 1977; Claypool, 1979; Rice and Claypool, quently, it may become a nonassociated, extremely dry gas
in a shallow reservoir, yet it still would be recognized iso1981; MattaveUietal, 1983).
topically as a formerly associated gas. In genetic terms,
this gas is a migrated associated gas. Examples are given
below.
' ^ h e following abbreviations are used in this paper
The problem of the precursor of associated and nonassoB = Biogenic gas; B(m) and B(t) denote marine and terrestrial (or continental) environments, respectively; T = associated gases; TQ/T,. = gases associciated thermogenic gases has not yet been addressed in the
ated witti petroleum and condensates respectively; TT(m) = nonassociated
literature, particularly to what extent cracking of either oil
dry gases from sapropelic liptinitic organic matter; TT(h) = nonassociated
gases from humic organic matter; M = mixed gas.
or kerogen contributes to the formation of gas. The sim(2) compositional changes after their formation.
2228
plest assumption is that associated gas originates predominantly from cracking of petroleum, and deep dry gas
originates from cracking reactions in kerogens. However,
if petroleum becomes deeply buried, thermal alteration in
overmature environments would also lead eventually to
the formation of dry gases, and both kerogen and petroleum may form gas.
Dry gases and associated gases may be differentiated by
their C2+ compositions. In this context, it should be
emphasized that the C2+ content of a gas is sensitive to
many secondary processes. Primarily, it is controlled by
the present-day temperature and pressure conditions in the
reservoir as well as the composition of the reservoir system. The use of C2+ concentration as a genetically controlled property is based primarily on the fact that C2+
concentration in gases is high at peak oil generation levels
and it decreases with increasing maturity (Evans et al,
1971). A value (level of organic matter maturity) > 1.2%
on the vitrinite reflectance scale is commonly agreed to be
the deadline for oil occurrence and the onset of dry gas
formation (TeichmuUer, 1971; Dow, 1977; Robert, 1980).
2229
Martin Schoell
C2. = 1
EC
X 100
(pph)
The plot of the carbon and hydrogen isotopic composition of methane makes use of genetically relevant properwhere C is the sum of all hydrocarbons C, through C5 and ties which are independent of the compositional changes
C, denotes relative methane content. The carbon and in a gas. The diagram in Figure Ic is an improved version
hydrogen isotope concentrations of methane and ethane of an earlier plot of the carbon versus hydrogen isotopic
are expressed in the usual 5-notation,
composition of methanes (Schoell 1980, 1981). Again,
Rsample
fields are defined for the three primary genetic types of
6 =
1 X 1000 (ppt)
gasesbiogenic, associated, and nonassociated.
R.,
'^C in Methane and Ethane
The diagrams and their genetic fields have been developed from variations found in the specific types of gases
2230
QQ.
X
o
m
oO
70 -
Mixing
70
;^SI -
Mixing
- SUN
. ^
^JNS\^
-20 "
10
50
20
;
-300
v^s2;
100
6DcH,[ppt]^
-6%,Helpptl
FIG. 2Various processes and resulting compositional variations in natural gases. C = chromatograpliic effect; O = oxidation; SI/
S2 = end members of mixed gases. Note various possibilities owing to migration. Daslied arrows indicate mixing owing to migration.
Horizontal arrows result from a change of the C2+ concentrations only. Mixing in 5"C-methane/6"C-ethane diagrams may result in
bciil mixing pathways if gases with different C, and C24 concentrations are mixed.
analyzed, so there is no inference to the fields. The design and - 190 ppt in 6"C and 5D values, respectively. Interstiand statistical reliability of such diagrams will improve tial gases are isotopically similar to methanes from gases
with an increasing number of analyses. The fields may of Tertiary basins (Schoell, 1977; Mattavelli et al, 1983),
change slightly with inclusion of new analytical data. Jus- which suggests that essentially similar processes are operatification of the fields shown is discussed briefly below.
tive in marine sediments and Tertiary basins (Schoell,
1982).
The second group of biogenic gases, B(t), are derived
Biogenic Gases (B)
from continental environments. Examples include various
Biogenic gases, denoted as B(m) in Figure 1, are derived swamp gases and gases from glacial deposits in Illinois
from Holocene to sub-Holocene marine sediments from (glacial drift gases) described by Coleman (1976). The difDSDP drilling sites at the Cape Verde Rise (Baker et al, ferent deuterium concentrations in continental methane
1977), the Cariaco Trench (Lyon, 1974), and the Gulf of compared to marine methane results from the different
California (Schoell, 1982). The isotope compositions in deuterium concentrations in the respective environmental
interstitial gases from localities worldwide are surprisingly waters (Schoell, 1980). Recent findings by Wohemate et al
uniform; they range between - 60 and - 75 ppt and -170 (in press) indicate that active freshwater environments
Martin Schoell
2231
2232
the respective end members (Fig. 2). Both isotope concentrations change in strict proportion to the mixing ratios;
mixing of various proportions of two gases results in a linear change in their isotopic composition. This may be used
to estimate the end members if some intermediate values
of different mixing proportions are known. Gases which
fall into field M have been found in abundance at the base
of Tertiary basins where thermogenic gases from below
become mixed with indigenous bacteriogenic gases
(Schoell, 1977; Mattavelli et al, 1983). Also, gases from
immature marine sediments adjacent to magmatic bodies
fall into this field (Baker et al, 1977; Schoell, 1982). Mixing of gases results also in a linear relationship on the 6'^C/
C2+ diagram (Fig. 2).
Mixing of two gases of different origins means that the
constituents of a gas are not cogenetic. For cogenetic
methane-ethane pairs in thermogenic gases, it is observed
generally that ethane is enriched in "C between 5 and 10
ppt compared to the methane (Silverman, 1971; Deines,
1980). This relationship can, with some exceptions, be
used to differentiate gases of mixed origins. Figure Id
genetically defines natural gases by their "C concentrations in methane and ethane. A good correlation is found
for associated gases and for nonassociated gases. This
relation changes for coal gases and for nonassociated
gases from high-rank sources (fields TT(m) and TT(h) in
Figure Id). The fields of the primary gases are defined by
the '^C variations of cogenetic methane-ethane pairs. If
bacterial methane is added to a thermogenic gas, the S'^C
value of the methane changes accordingly and the 5'^C
value of the ethane remains constant (arrow Ms in Figure
Id). Mixing a deep dry gas (i.e., predominantly methane
with 6'^C values of - 30 ppt) with an associated gas would
change the S'^C/S^Cj relationship accordingly (arrow Md
in Figure Id).
Migration
The genetically controlled isotope variations in gases
indicate that the isotopic composition of methane is not
significantly changed after its generation. Appreciable isotopic changes in gases during migration are to be expected
when the gas becomes mixed with another gas during
migration. The C2+ concentrations in associated gases,
however, may change during migration, as has been noted.
This has been demonstrated by Coleman et al (1977), who
showed that migrated gases may be completely stripped of
C2+ hydrocarbons, whereas the '^C concentration in the
methane remained unchanged. In this situation, migration
should result (Fig. lb) as a change parallel to the C2+ axis
or along mixing lines accordingly. Because migration can
be monitored only if this results in changes of one of the
investigated parameters, migrated gases can be recognized
close to boundaries of maturity regimes or in very deep
basins.
The writer believes that methane plays an important role
in migration, as outlined by Sokolov et al (1964), Hedberg
(1979, 1981), and Neglia (1980). Depending on depth,
migration of methane may have two effects.
I. Deep migration (arrows Md in Figures 1, 2).Deep
dry methane which has been formed or is forming in overmature zones below zones of oil formation could migrate
Martin Schoell
2233
6 DcH, [ppt]
C.Jpph]
10
-|
r-
20
I
30
1
50
-300
-250
-200
-150
-100
^V-r
70
-70
Gulf of California
-1.2
-20
FIG. 3Compositional variations of interstitial gases from Gulf of California. Data from Schoell (1982).
through these areas and thereby act as "carrier" for C2+
hydrocarbons by means of gas-liquid phase equilibria
(Sokolov et al, 1964). Such gases would increase compositionally in wetness (horizontal arrow Md in Figures 1, 2).
Bray and Foster (1980) have proposed CO2 as a principal
extraction medium during primary migration. Methane
could be an adequate carrier, probably more important
during secondary migration (Sokolov et al, 1964; Hedberg, 1979, 1981). Evidence for this type migration has
been found recently in the Mahakam delta (Durand and
Oudin, 1979) and may be important in rapidly subsiding
areas (Niger delta, Mississippi delta, etc).
2. Shallow migration (arrows Ms in Figures 1, 2).
Here migration results in depletion of the C2+ hydrocarbons because higher hydrocarbons are segregated or are
stripped off during passage of the gas through less permeable, possibly unconsolidated, sediments. Part of the C2+
depletion may result from the process described by Silverman (1971) as "separation migration" (i.e., retrograde
condensation of C5 hydrocarbons in reservoirs of lower
pressure). Shallow migration may result eventually in dry
gases with '^C isotopic compositions of methanes around
- 40 to - 50 ppt, whereas deep migration may give rise to
wet gases with relatively positive 5' C values in their methane ( - 4 0 to - 3 5 ppt).
APPLICATIONS
Examples of applications of the genetic diagrams are
2234
6DcH, [ppt]
20
10
1
30
50
^^
-300
-250
-200
-150
-100
1
70
^ 3
-70 r
y
Q.
Q.-50
L_ m
Q.
^
-60
X
CI
lO
"O -50
40
^^
---""'
"
'
/
/
/
-50
/
~1.2^\
-40
\W
\-2.o\
-30 -
-30
Ostmolasse
-20
20
'
\r.4..P
H^ "
^
FIG. 4Compositional variations of natural gases from soutli German Molasse basin. 3 = Miocene; 2 = Oligocene; and 1 =
Eocene reservoirs. Data from Schoell (1977).
the reservoir. Gases from Miocene reservoirs at an approx- is a migrated thermogenic gas. Another gas, which plots in
imate depth of 2,000 m (6,500 ft) are lowest in "C and field M (2 in Figure 5) is also derived from a Tertiary reseralmost devoid of C2+ hydrocarbons, whereas Oligocene voir. Here bacterial and deep thermogenic gases were
reservoirs at an approximate depth of 3,000 m (9,800 ft) mixed.
are more enriched in C2+ and ' C in the methane. Both
Po Basin
groups can be characterized as early and late bacterial
gases, respectively. Typical mixed gases are found in the
A last example is from a study of natural gases in the Po
Eocene Lithothamnia limestone (depth of 3,500 to 4,000 basin (Mattavelli et al, 1983). A compilation of these
m, 11,500 to 13,000 ft), where thermogenic gases are results is given in Figure 6 as an example of a basin with
mixed with bacterial gases.
various origins of gases and their migration into shallow
traps. Three types of gases can be differentiated in the Po
Vienna Basin
basin. A quantitative assessment there revealed a predomiAs a third example, compositional variations of gases nance of biogenic gases. Gases of mixed origin could be
from the Vienna basin are shown in Figure 5. The geology identified by their carbon and hydrogen isotopic composiof the area has been described in detail by Kroell and Wes- tion of methane and ethane (Fig. 6). Mixed gases were
sely (1973). Briefly, the Vienna basin is an intramontane found predominantly in a transgressive facies that folbasin tectonically formed within the alpine system. Below lowed Miocene deposition. Thermogenic gases are suborthe Tertiary basin fillings are typical carbonate and dolo- dinate in the basin. The gas of Medesano field is
mitic alpine rocks of Triassic age (e.g., Hauptdolomit, etc) recognized as a migrated thermogenic associated gas, prowhich form the most important reservoirs in the area. duced from a shallow reservoir of Pleistocene age at an
Three principal types of gases can be differentiated in the approximate depth of 170 m (550 ft). It is dry, chemically
basin: bacterial and associated gases in Tertiary reservoirs resembling a biogenic gas, but isotopically it is recognized
(1 and 4 in Figure 5), as well as deep dry gases in pre- as an associated gas. In addition, gas from the Malossa
Tertiary reservoirs (3 in Figure 5). Two gases are notewor- deep gas and condensate field can be identified as a conthy. One gas, found in a Tertiary reservoir ("Migrated" in densate associated gas. Figure 6 demonstrates the applicaFigure 5), has an identical isotopic composition as the deep tion of genetic characterization of gas types in a basin.
dry gases from pre-Tertiary reservoirs; this suggests that it Mattavelli et al (1983) present more details on the geology
Martin Schoell
2235
C,ipph]^
20
30
6DcH, [ppt]
250
50
-200
-150
-100
FIG. 5Compositional variations of natural gases from Vienna basin. 1 = bacterial gases from Tertiary reservoirs; 2 = mixed deep
dry and bacterial gas; 3 = deep dry gases from pre-Tertiary reservoirs; and one migrated gas (Migrated) in Tertiary reservoir; 4 =
associated gases from Tertiary reservoirs. Data from Schoell (in press).
e'^Celhane
C^.N20
30
50
300
-250
-200
6DcH4 [ p p t ]
-150
-100
-50
-i.0
[ppt]
-30
-20
\ ? \
\
\
\
\
Caviaga
\
\^ \
Crennona Sud
"^
TT(m)
\
\
FIG. 6Genetic characterization of natural gases in Po basin, northern Italy, as example for application of genetic diagrams. Genetic
types of gases change with age and geologic condition of reservoir. Clear identification of shallow migration at Medeseno; the S'^C/
6D plot indicates this to be a gas that was associated with oil. Malossa is a deep condensate deposit, and Caviaga has a gas of mixed
origin. Age of reservoirs: 1 = upper middle Pliocene; 2 = lower Pliocene; 3 = Messinian; 4 = middle Miocene; 5 = pre-Tertiary.
2236
-C,.1%1
JO
20
30
6DcH,[pptl
50
-300
-250
-200
-150
-100
-70
(3}
-60
-50
Bl\
-40
f^
-30
\||H
-20
C;.I%120
30 . 50
6DcH,lpptl
-300
-250
-200
-150
-100
fT
70-
\^^^
(^^^
\^
20
30 ,. 50
-300
-250
.flr^~
x^
It , 6DcHjpptl
-C,.l%)JO
v.\
\i \..V
-200
-150
-100
-70 -
-JS-
FIG. 7Application of genetic interpretive diagrams for genetic cliaracterization of natural gases in wells. Various well sites (I, II, III)
areshownschematlcallyasawellasinferredtypesof gases encountered. Regimes: A = immature; B = mature; C = overmature. For
identifications of genetic fields in diagrams see Figure 1.
and other regional information.
Well site I is considered unprospective because an overmature area is covered by Tertiary strata. Positions II and
III are recognized as prospective sites because the gases
Application in Exploration
enter the genetic field of associated gases, indicating that
Figure 7 summarizes scenarios in exploration drilling the gases are formed together with petroleum. If paramewhere the concept of genetic characterization of gases ters for genetic characterization of natural gases were
could be applied to test gases. Several positions within a determined in a semicontinuous fashion in wells (e.g., on
hypothetical basin are given, and genetic types of gases head-space gases), the evolution pathways as indicated in
Figure 7 would result. By applying genetic characterizalikely to be encountered are portrayed.
Martin Schoell
2237
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^
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