Académique Documents
Professionnel Documents
Culture Documents
ABSTRACT
are proportional to temperature, age, and organicmatter content of the sediments. Biogenic methane is
enriched in the light isotope 12C (o 13 C1 lighter than -55
ppt) owing to kinetic isotope fractionation by
methanogens. The variations in isotopic composition of
biogenic methane are controlled primarily by o13C of the
original C0 2 substrate, which reflects the net isotopic
effect of both addition and removal of C0 2 The
methane isotopic composition also can be affected by
mixing of isotopically heavier thermogenic gas. The
possible complicating factors require that geologic,
chemical, and isotopic evidence be considered in attempts to interpret the origin of gas accumulations.
Accumulations of biogenic gas have been discovered
in Canada, Germany, Italy, Japan, Trinidad, the
United States, and USSR in Cretaceous and younger
rocks, at less than 3,350 m of burial, and in marine and
nonmarine rocks. Other gas accumulations of biogenic
origin have undoubtedly been discovered; however,
data that permit their recognition are not available.
INTRODUCTION
Biogenic Gas
HYDROCARBONS
.------.-----.-"""=G"'"'E'""N""'E~R~A,.,..,T~E.,.,D-,...._~-
amounts of hydrocarbons are present which are inherited from or produced by mild degradation of
organic tissues, biogenic methane is the only hydrocarbon actually generated in significant volumes during
this stage.
2. Mature stage (catagenesis)- With increasing
temperature and advancing geologic time, the full range
of hydrocarbons is produced from kerogen and other
nonhydrocarbon precursors by thermal degradation and
cracking reactions. Depending on the concentration and
type of organic matter, oil generation occurs during this
stage accompanied by the production of significant
amounts of natural gas. As temperatures increase,
lighter hydrocarbons are formed preferentially, owing
to breaking of carbon-carbon bonds, affecting both the
residual kerogen and the hydrocarbons previously formed.
Wet gas and condensate are the primary products of the
later part of the stage.
3. Postmature stage (incipient metamorphism)-At
the end of the mature stage, the kerogen becomes highly
polymerized, condensed in structure, and chemically
stable. The main hydrocarbon generated is methane
which results from the cracking of the existing hydrocarbons. Hydrocarbons larger than methane are destroyed
much more rapidly than they are formed.
This paper discusses the methane-rich gas generated
in accumulating sediments during the immature stage
(diagenesis) by the metabolic activity of anaerobic
bacteria. Hereafter, this gas will be referred to as
biogenic gas to emphasize that microorganisms are
responsible for its formation. We emphasize that
biogenic gas not only is generated, but has accumulated
in economically significant quantities and warrants con-
.,..,,,.,.1
G)
Biogenic Gas
several studies suggest that methane is consumed in the removed to form methane is about 70 ppt lighter than
overlying sulfate-reducing zone (Barnes and Goldberg, the &13 C of the C0 2 dissolved in the interstitial water at
1976; Reeburgh, 1976; Martens and Berner, 1977; the time of its formation, owing to a large kinetic
Reeburgh and Heggie, 1977; Kosiur and Warford, isotope effect (Rosenfeld and Silverman, 1959).
1979). Thus it is likely that the balance between producPossible isotope effects of C02 addition and removal
tion and consumption of methane is an important factor during biogenic methane production are illustrated in
controlling the distribution of methane in marine
sediments (Bernard, 1979).
Methane-producing microorganisms also are even
DISSOLVED SULFATE
more restricted than sulfate reducers with respect to
mmol/kg
a34 S(%o)
substrates utilizable for growth. Hydrogen and C0 2 are
10
20
the preferred substrates studied in pure culture, whereas
formate, methanol, and acetate can be used, but the
reactions are probably much less energy-efficient
I
0/
(Wolfe, 1971; Zeikus and Wolfe, 1972; Winfrey et al,
25
I
1977; Belyaev and Laurinavichus, 1978). C0 2 reduction
10
o I
is energetically the most favorable mechanism of
I
biogenic methane production and probably accounts for
lo
50
most of the methane produced in the marine environ- .-.
o I
I
ment, although other pathways are available.
,_
alo
o I
I
1- 75
ISOTOPIC INDICATORS
a..
of
Cl
lo
I
100
I
I
I
I
125
.I
I
I
d
FIG. 3-Changes with depth in concentration and sulfur
isotope ratio (c534 S) of dissolved sulfate in interstitial water of
Aves Ridge (DSDP Site 148) sediments, caused by bacterial
sulfate reduction.
o13 C(%o)
-20
-15
-10
-5
+5
CONCENTRATION (mm)
40
100
'<J...o,~TITRATION
(.)
200
ALKALINITY
li:LU
I
I
300
I
,j
/1
'
E'1oo
I
f-
200
c...
W300
0
~400
fP
b~
~D
~a
o op
o 'o
!lJ-CH4
0:0
'
~ 500
o 'o.-::&co2
O~o
Do
600
Cll
~ 700
oo
10
Biogenic Gas
500
E
;i
a:
zoe
1500
;::)
co
u..
0 2000
I
IC...
LU
2500
50
150
11
12
Biogenic Gas
IMMATURE
(d1agenes1s)
BIOGENIC
GAS .
MATURE
(catagenesis)
POST MATURE
(me1amorphism)
500
1000
E
J:
1Q.
UJ
1500
2000
13
References
-70.2 to -52
Fuex, 1977
-45
-45.8
-80.2 to -57.2
-69 to -52
-47.1
-74 to -52
-73.7 to -51.7
-72 to -63
-80
-65.5 to -58
-76.3 to -59.6
-88.7 to -47.1
Deuser et al (1973)
This report
Oana and Deevey (1960)
Ovsyannikov and Lebedev (1967)
Nissenbaum et al (1972)
Lebedev et al (1969)
Doose et al ( 1978)
Hunt and Whelan (1978)
K venvolden et a! (1979)
Bernard et al (1976)
Lyon (1973)
Claypool et al (1973)
-55.6
-65.32 to -63.94
-71 to -69.2
Nissenbaum et al ( 1972)
This report
This report
*Gases isotopically heavier than -50 Ofoo may be due to microbial oxidation.
Biogenic Gas
14
Location
Reservoir Age
Depth (m)
United States
Cook Inlet, Alaska
Offshore Gulf of
Mexico
Tertiary
Pleistocene
910-1,650
460-2,800
-63 to -56
-69 to -55
Claypool et al ( 1980)
This report
Cretaceous
and
Tertiary
120- 840
-72 to -55
This report
Pleistocene
40
-84 to -72
Wasserberg et
al (1963)
Nakai (1960)
Colombo
et al (1966)
Schoell (1977)
This report; Fuex (1977)
Rocky Mountains
(Colorado, Kansas,
Montana, Nebraska,
New Mexico,
South Dakota)
Illinois
Japan
Italy
Tertiary
Tertiary
100-1,000
400-1,830
-75 to -65
-71 to -55
Germany
Canada
USSR
North Aral
Tertiary
Cretaceous
900-1,800
300-1,000
-72 to -64
-68 to -60
Tertiary
320- 350
-72 to -64
Siberia
Cretaceous
700-1,300
-68 to -58
Stravapol
Cretaceous
and
Tertiary
Tertiary
Tertiary
200-1.200
-75 to -57
300- 500
980-3,350
-72 to -63
-71 to -64
North Priaral
Trinidad
Avrov and
Gal imov ( 1968)
Yermakov et
al (1970)
Alekseyev et
al (1972)
Galimov (1969)
B. D. Carey (personal
commun., (1980)
15
than indicated by present-day burial or that can be accounted for by the thickness of Pierre Shale (Lockridge
and Scholle, 1978).
Gases from wells along the trend reflect the increasing
depth of burial by becoming isotopically heavier (Fig.
10). We interpret the gases to be of predominantly
biogenic origin because of chemical and isotopic composition, reconstructed maximum depths of burial, and
source rocks studies by Swetland and Clayton (1976)
that indicate that older Cretaceous rocks in this region
are immature.
The biogenic gas probably was generated in situ
Field
Producing Unit 1
Depth (m)
I3CI(o/oo)
CdCJ.j
Colorado
Armel
Beecher Island
Republican
San Luis basin
Vernon
Whisper
Wildcat
Bell Creek
Black Coulee
Bowdoin
Niobrara Fm.
Niobrara Fm.
Niobrara Fm.
Alamosa Fm.
Niobrara Fm.
Niobrara Fm.
Niobrara Fm.'
Muddy Ss.
Eagle Ss.
Bowdoin and
Phillips ss. 2
Eagle Ss.
Eagle Ss.
Eagle Ss.
Frontier Fm.
Eagle Ss.
Shannon Ss. Mbr.
of Gammon Shale
Eagle Ss.
Eagle Ss.
Niobrara Fm.
and Dakota Ss.
Dakota Ss.
Shannon Ss. Mbr.
of Gammon Shale
482
491-518
691
300
647
842
328
I ,387
349
224-445
-62.5
-60.8 to -60.1
-59.7
-70.2 to -69.7
-58.8
-54.7
-65.4
-65.1
-66
-72.3 to -68.6
0.981
0.982 to .981
0.981
0.999 to .998
0.98
0.976
0.993
0.98
0.996
0.997 to .995
385
517
171
253
470
829
-70
-69.7
-65.2
-65.9
-68.7
-64.8
0.998
0.996
0.987
0.989
0.996
0.992
318
347-432
394-655
-68.1
-65.5 to -63.5
-66.5 to -62.8
0.997
0.997 to .991
0.956 to .998
119-134
417-605
-59.8 to -55.3
-70.0 to -69.7
0.999
0.996 to .998
Kansas
Montana
Cassady
Cedar Creek
Guinn
Hardin
Leroy
Liscom Creek
Nebraska
New Mexico
South Dakota
Lohman
Tiger Ridge
Wildcats
Wagon Mound
West Short
Pine Hills
334
338
350
416
433
436
471
563
564
566
643
758
783
831
Producing unit
Milk River Fm. equivalent
Milk River Fm. equivalent
Milk River Fm. equivalent
Medicine Hat Ss.
Medicine Hat Ss.
Medicine Hat Ss.
Medicine Hat Ss.
Second White Specks ss.
Second White Specks ss.
Second White Specks ss.
Second White Specks ss.
Bow Island Formation
Bow Island Formation
Basal Colorado Ss.
-68
-67.5
-68.3
-67.8
-68
-68
-67.1
-65.7
-65.3
-65.4
-65.4
-66
-66
-60.2
0.997
0.997
0.993
0.997
0.997
0.997
0.996
0.995
0.995
0.9950
0.996
0.994
0.995
0.963
16
Biogenic Gas
Table 5. Biogenic Gas Fields of Pleistocene Age in Offshore Gulf of Mexico
Field
Depth (m)
o'"C I
I ,818- 1,876
458- 983
2,224 - 2,312
917
2,498- 2,573
I ,355 - I ,562
I ,414- I ,512
1,391-1,399
2,721 - 2,786
I ,390 - 2,208
I ,456 - 2,430
1,829- 1,916
I ,270 - 2,393
~59.9
c,;c,_j
/oo)
to
~69.4 to
- 57.2 to
~56.9
~65.9
~56.9
~64.3
~58
~56.7
~58.7
~58.!
to
to
~63.2 to
~55.4 to
~65.1 to
~ 61.5 to
~66.5 to
~67
to
~65.3 to
~57.9
~55.3
~61.7
~57
.4
~64.5
~66.8
~60.6
0.989
0.999
0.997
0.999
0.98
0.981
0.996
0.974
0.999
0.986
0.997
0.999
0.998
to .987
to .972
to .978
to .985
to .997
to .982
to .998
to .96
reservoirs and traps as exemplified by productive intervals in the Bearpaw Mountains and Bowdoin Dome. In
the Bearpaw Mountains, the primary trapping
mechanism is gravity-induced faulting and the reservoirs are porous and permeable marine sandstones
enclosed by offshore marine shales (Rice, 1980).
Petrographic studies indicate that extensive early
mineral diagenesis in the reservoirs has taken place as a
result of migrating waters (Gautier, in press). This interpretation suggests that the gas was held in solution in
formation waters of the surrounding shales during
diagenesis. Subsequent exsolution of the gas during
uplift and erosion resulted in a free-gas phase that
migrated to and accumulated in the sandstone because
of capillary pressure differentials between the shale and
sandstone beds.
In the Bowdoin Dome area, biogenic gas is
stratigraphically entrapped over a large area (1,500 sq
km) in thin (commonly less than 3 em), discontinuous
sandstone and siltstone laminae (Nydegger et al, 1979).
Here, laminae are enclosed by organic-rich shales, containing numerous bentonite beds, that served as both a
source and a seal for the gas. Because the reservoirs
typically exhibit low permeability, stimulation is required to provide flow rates sufficient for economic
development. However, this type of reservoir is
developed over large areas of the northern Great Plains
and structure is not required for trapping the gas.
17
95'
105'
'
-~-
1:).1
SASKATCHEWAN
i
I
__ C A N1A DA
:.
2 ~}:j;r---U N i1T-- --i- ------,---.f \
-~~~-
~~--
3~5
'
ED
7 <t
~-., .......
STAT E'.S
\.'
\.
45'
ONTARIO
MANITOBA
NORn DAKOTA
B--:
S<t
L______
~
\. ___ __,~------ ---.?-:)~10 ----------(i
104
Ho
-~-
WYOMING
~-J
40'
I'
;
11~
- - - - L ___ l
/ WISCONSIN!!~ ~
'
-.....
'\ .
~
'-14
COLORADo
l
15~
KANSAS
-~
'.
'1
I,
ILLINOIS
\-.
MiSSOURI
1'
35'
ARtzoNA
~---
-~---
TN
(_ ___ .,ARKANSAS
/
........
'
..........
..,_,. ......,.,..,
~-------1:
MS
AL
---- ----.:__
! J----:------.._J
M ._
+>.
'
TEXAS
(')
'-,..- . '
. r: K v
'-(
''\...,,
'""~ ............
i_ -...-.J
..
:~
OKLAHOMA
NEW MEXICO
IN
l-- -- --- - - )
~------
161:).
~
J
-......
'
'
-- _/
--------
,..-J
13'i--------------~-
'\:
IOWA
NEBRASKA
' 12
- -- -- ___ j
MICHIGAN
----~\r:/
----;-------
UTAH
souTH DAKOTA
MINNESOTA
.
;
...-- -
.,..._
o\
(----
'.
/
:' __ .. ..,
',
I ;-
fc~
0
500 KILOMETERS \
250
~----~------~
--17
'
\
\ ............ ~ ..
FIG. 9-Map showing location of biogenic gas fields in United States and Canada: (1) Suffield Block; (2) Tiger Ridge, Lohman,
Black Coulee, and Cassady; (3) Leroy; (4) Bowdoin; (5) Guinn; (6) Hardin; (7) Liscom Creek; (8) Cedar Creek; (9) Bell Creek;
(10) West Short Pine Hills; (11) Wildcat, Sec. 22, T19N, R39W; (12) Wildcat, Sec. 14, T16N, R33W; (13) Armel, Beecher Island,
Republican, Vernon, and Whisper; (14) Wildcat, Sec. 10, T95N, R40W; (15) San Luis basin; (16) Wagon Mound; (17) Offshore
Gulf of Mexico. Fields are listed in Table 5.
18
Biogenic Gas
013C1(%o)
-62
-66
-64
-60
-58
-54
-56
-52
300~~--"----,----,----,----,----,---~
'
Q.
UJ
600
''
'
'
'
''
''
'
2 '
'3.,
'
4.
''
''
'
''
''
'
''
5
'''
''
'~
''
'
''
''
''
''
7 '
'
''
'
'
19
106'
104
42~--------r-----------~----------~----------.-------------------------------.
WYOMING
EXPLANATION
40
o./
38
L.
coLORADO
- - - - N E W MEXIC_O_____
;t - - - - - ..J:
100 KILOMETERS
~A~~-OKLAHOMA
~----;-'ExAs ___ _
'
36
FIG. 11-Map showing location of Niobrara gas wells (Fig. 10), reconstructed thickness of Pierre Shale, and limit of immature
oU source roc:ks.
Estimated Reserves
I 0 12 m 3 (Tcf)
Arkticheskoye
Gubkinskoye
Komsomolskoye
Medvezhye
Severo-Stavropolskoye
Urengoiskoye
Vyngapurskoye
Zapolyamoye
Total
0.18 (6.4)
0.35 (12.5)
0.46 (16.2)
1.55 (54.7)
0.23 (8.1)
5.04 (177 .8)
0.29 (10.3)
2.66 (94.1)
10.8 (380.1)
Depth of
Production (m)
C1/C;.s
-61.7
-61.1
-64.7
-58.3
-68.7 to -66.5
-59.2 to -59
-60
-60.3
0.999
0.999
0.998
0.999
0.999
0.998
0.998
0.999
2,500
780
985
I ,207
I ,050
3,160
I ,091
1,300
*Data from Alekseyev et al (1972); McCaslin (1977); Yermakov eta! (1970). All fields except Severo-Stavropolskoye are in
northwest Siberia.
20
Biogenic Gas
YAJSKOYE
(_)3~
,..,_..
67'
iilinois
URENG~O..I.SKO~~o. y
~'ct;
Biogenic gas is present both in a free state and in solution in Pleistocene glacial drift of Illinois. Although free
gas accumulations are not of commercial significance,
many produce sufficient gas for domestic use (Meents,
1960, 1968). Local accumulations are composed
primarily of methane, are at an average depth of 40 m,
and have &13 C1 values in the range of - 84 to -72 ppt
(Wasserburg et al, 1963). Radiocarbon dating of several
gas samples indicates that the gas resulted from the
microbial degradation of organic matter in the Robein
Silt, which dates from 22,000 to 28,000 radiocarbon
years B.P. (Coleman, 1976). The sands and gravels just
above and below provide the reservoir, and the overlying till serves as the seal.
Coleman et al (1977) analyzed many gas samples in an
effort to distinguish gas leaking from underground
storage reservoirs from indigenous shallow biogenic gas
in solution. They found that migration of gas resulted in
chemical fractionation by removal of the heavier
hydrocarbons from the gas that leaked out of the injected storage reservoir so that it became methane
enriched in a manner similar to biogenic gas. This
migration did not significantly affect the isotopic composition. They concluded that the two types of gases can
be distinguished by isotopic composition: storage reservoir gas has &13C 1 values in the range of - 46 to - 40 ppt
whereas biogenic gas in solution is isotopically lighter
(& 13 C 1 = -90 to -64 ppt).
80'
75'
MEDVEZHYE
.,YUMEtv
.. L
. .
..
--..z
ARNOYE
~--~e
-----
...
Urengoi
(!p
GUBKINSKOYE
KOMSOMOCSK QV
VYNGAYAKHINSKOYE0
200 KILOMETERS
EXPLANATION
0
:l
GAS FIELDS
WATER
21
Area
Cook Inlet. Alaska
Reserve'
Initial
In-Place
Blasko (1974);
Alaska Div. Oil
and Gas (1976)
0.34 (12) 2
0.13 ( 4. 7)
2.83 (100)
USSR
Reference
0.21 (7.5) 1
Gulf of Mexico
Japan
Undiscovered
Volumes
0.42 (15)
13.0 (460) 3
*Total discovered estimate 21.3%; total discovered plus undiscovered estimate 25.5%.
1
lncludes cumulative production of 0.28 X l0 12 m'l (I Tcf).
2 75% of total estimated volumes because approximately 25% of gas is of thermal origin and has migrated from deeper, mature
source rocks.
22
Biogenic Gas
23
24
Biogenic Gas
25
relations (abs.): Geol. Soc. America Abs. with Programs, v. 11, p. 522.
___ et al, 1977, Carbon isotopes in oil and gas exploration, in
Internal. Symposium on Nuclear Technology in Exploration, Extraction and Processing of Mineral Resources: Vienna, Internal.
Atomic Energy Agency, p. 73-82.
Suffield Evaluation Committee, 1974, Final report relating to evaluation of gas resources of the Suffield Block: Prepared for Province
of Alberta, Canada, 31 p.
Sugisaki, R., 1964, Genetic relation of various types of natural gas deposits in Japan: AAPG Bull., v. 48, p. 85-101.
Swetland, P. J., and J. L. Clayton, 1976, Source beds of petroleum in
the Denver basin: U.S. Geol. Survey Open-File Rept. 76-572, 23 p.
Tissot, B., et a!, 1974, Influence of nature and diagenesis of organic
matter in formation of petroleum: AAPG Bull., v. 58, p. 499-506.
Toerien, D. F., and W. H. J. Hattingh, 1969, Anaerobic digestion; I,
The microbiology of anaerobic digestion: Water Reseach, v. 3,
p.385-416.
Trofimuk, A. A., N. V. Cherskiy, and V. P. Tsarev, 1975, Thereserves of biogenic methane in the ocean: Akad. Nauk. SSSR Doklady, v. 225, p. 199-202.
Tucholke, B. E., G. M. Bryan, and J. I. Ewing, 1977, Gas-hydrate
horizons detected in seismic-profiler data from western North Atlantic: AAPG Bull., v. 61, p. 698-707.
Wasserburg, G. J., E. Mazor, and R. E. Zartman, 1963, Isotopic
and chemical composition of some terrestrial natural gases, in
J. Geiss and E. D. Goldber, eds., Earth science and meteoritics:
Amsterdam, North Holland Pub. Co., p. 219-240.
Waterman, L. S., F. L. Sayles, and F. T. Manheim, 1973, Appendix
II, Interstitial water studies on small core samples, Legs 16, 17, and
18: Initial Rept. Deep Sea Drilling Project, v. lo, p. 1001-1012.
Weber, V. V., and S. P. Maximov, 1976, Early diagenetic generation
of hydrocarbon gases and their variations dependent on initial organic composition: AAPG Bull., v. 60, p. 287-293.
Welte, D. H., 1972, Petroleum exploration and organic geochemistry:
Jour. Geochem. Exploration, v. 1, p. 117-136.
Whelan, J. K., and J. M. Hunt, 1978, C,-C, hydrocarbons in holes
378A, 380/380A and 381: Initial Rept. Deep Sea Drilling Project,
v. 42, p. 673-677.
Whelan, T., III, J. T. Ishmael, and G. B. Rainey, 1978, Gas-sediment
interactions in Mississippi delta sediments: lOth Offshore Tech.
Conf. Proc., v. 2, p. 1029-1036.
_ _ et a!, 1975, The geochemistry of recent Mississippi River delta
sediments-gas concentration and sediment stability: 7th Offshore
Tech. Conf. Proc., v. 3, p. 71-84.
Winfrey, M. R., et a!, 1977, Association of hydrogen metabolism
with methanogenesis in Lake Mendota sediments: Applied and Environ. Microbiology, v. 33, p. 312-318.
Wolfe, R. S., 1971, Microbial formation of methane: Adv. Microbial
Physiology, v. 6, p. 107-146.
Yermakov, V. 1., et al, 1970, Isotopic composition of carbon in
natural gases in the northern part of the west Siberian plain in relation to their origin: Akad. Nauk, SSSR Doklady, v. 190, p.
196-199.
Zeikus, J. G., and M. R. Winfrey, 1976, Temperature limitation of
methanogenesis in aquatic sediments: Appl. and Environ. Microbiology, v. 31, p. 99-107.
_ _ and R. S. Wolfe, 1972, Methanobacterium thermoautotrophicum sp. n., an anaerobic, autotrophic, extreme thermophile: Jour.
Bacteriology, v. 109, p. 707-713.
ZoBel!, C. E., and S. C. Rittenberg, 1948, Sulfate-reducing bacteria
in marine sediments: Jour. Marine Research, v. 7, p. 606.