SIDERITE CONCRETIONS: INDICATORS OFF EARLY DIAGENESIS IN THE

GAMMON SHALE (CRETACEOUS) j

DONALD L. GAUTIER
U.S. Geological Survey
Box 25046, MS 940
Denver. Colorado 80225

ABSTRACr: The Upper Cretaceous Gammon Shale in the nor'them Great Plains contains abundant siderite
concretions that formed during the early compactional history of the fine-grained, marine sediments. The
relative depth of siderite precipitation can be estimated on the basis of textural, mineralogical, and isotopic
evidence. Siderite concretions that formed at shallow depths in the sediment column contain a large volume
percent carbonate (75-85%), preserve uncompacted sediment textures, and have oxygen isotope ratios sim-
ilar to those of carbonates precipitated in equilibrium with seawater (8~*O = 0 to -2%c, PDB}. In contrast,
lower volume percent carbonate values (55-75%), and relative decreases in ~80/160 values characterize
concretions that formed longer after deposition and {or) at greater depths in the accumulating sediments.
Both volume percent carbonate and 81sO values are strongly correlated with independently determined
sediment accumulation rates. Concretions in rapidly deposited sediments formed at shallow depths (<10
m), whereas siderite concretions in sediments that accumulated slowly formed at greater depths (>200 m),
later in the burial history.
The Gammon served as both source rock and reservoir for accumulations of biogenic methane and, like
the siderite concretions, the methane was generated during early diagenesis. Both siderite precipitation and
methane accumulation require interstitial pore waters that have sufficiently high bicarbonate activities and
that are depleted in dissolved sulfur and free oxygen. Because of chemical requirements, siderite did not
precipitate until after the onset of methane generation. Therefore, if the depth of siderite formation is
known, the minimum depth for the onset of methane accumulation can be inferred.
The presence of abundant pyrite in slowly accumulated Gammon sediments suggests, by analogy to data
from recent sediments, that the depth of siderite precipitation and methane accumulation was controlled
by the sedimentation rate. In slowly accumulating sediments, most organic matter was probably consumed
by aerobic organisms and sulfate-reducing anaerobic bacteria, whereas in areas of more rapid deposition
large quantities of organic matter were available for methane generation.

INTRODUCTION genic pyrite. The detrital minerals included

The Upper Cretaceous (late Santonian-early
Campanian) Gammon Shale or Gammon
Member of the Pierre Shale of the northern
Great Plains is a sequence of marine mudrock
and minor sandstone that accumulated far from
shore during a major regression of the epeiric
sea (Gill and Cobban, 1973). On outcrop (Fig.
1), the Gammon is characterized by the weath-
ering products of abundant siderite (Rubey,
1931).
Siderite in the Gammon Shale occurs mainly,
but not exclusively, as simple, sharply bounded
oblate spheroids 10 to 50 cm in diameter and
10 to 40 cm thick (Fig. 2). Some spheroids are
septarian and others may be concentrically
zoned and contain interior calcite nodules
(Fig. 2). The concretions consist mainly of
microcrystalline siderite which cements var-
ious amounts of detfital minerals and authi-
~Manuscript received August 24, 1981; revised January
28, 1982.
within the concretions are compositionally
similar to those of adjacent sedimentary rocks
that enclose the concretions. At shallow depths
(<1,200 m) in the subsurface, the Gammon
contains marginally economic accumulations
of natural gas that consist mainly of isotopi-
cally light methane (C l/C~_ 5 > 0.99; 813C1 =
- 6 0 to-70%0, PDB). This methane is inter-
preted to be biogenic and to have formed
during early diagenesis (Rice and Claypool,
1981).
Biogenic methane results from reduction of
dissolved CO 2 (Claypool and Kaplan, 1974)
by methanogenic archaebacteria (Balch and
others, 1979). The respiration of this unique
biological group (Wolfe, 1980) causes the
largest known kinetic fractionation of stable
carbon isotopes (Rosenfeld and Silverman,
1959). Methane is a by-product of the last in
a series of depth-zoned microbial ecosystems
(aerobic respiration, nitrate reduction, sulfate
reduction, and carbonate reduction) that se-

JOURNAL OF SEDIMENTARYPETROLOGY, VOL. 52, NO 3, SEPTEMBEa, 1982, P. 0859-0871

Copyright © 1982. The Society of Economic Paleontologists and Mineralogists 0022-4472/82/0052-0859/$03.00
860 DONALD L. GAUTIER

107 ° 106 ° 105 ° 104 ° 103 o

I I /,
,oO
47 °

~ . PORCUPINE

\\
AASEN 1-9
Forsyth

46 ° MADISON NORTH DAKOTA

/NO.2 S O U T H DAKOTA

/
OWL CREEK
/ /
MONTANA LOWER OWL
45 ° I--
WYOMING / GAMMON / CREEK
Sheridan
' PRONG
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o I Belle
o

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Fourche
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\ Gillette

44 °

50 100 KILOMETERS
! I

loo Isopach contours in feet

Precambrian rocks
~.-~ Outcrop of Gammon Shale and equivalent rocks
FIG. l.---Study area, outcrops, and isopach of the Gammon Shale (locally a member of the Pierre Shale), and
sample collection localities discussed in the text and listed in Table 1. Isopach contours (in feet) of Gammon Shale
are from Gill and Cobban (1961).
 SIDERITE CONCRETIONS
PD-1
I 1963), abundant siderite in a marine sediment
D E F i G
I i/
a
~~ OD Loc-.
Oxidation
b
0C-3
FIG. 2.--Cross-sectional views, looking parallel to
bedding, of selected siderite concretions showing sample
distribution (analytical data are listed in Table 1): a) sim-
ple concretion from Porcupine Dome locality (PD-1); b)
septarian concretion, with calcite-filled septaria, from
lower Owl Creek locality (LOC-11); c) zoned concretion
with an interior nodule of calcite and a main body of sid-
erite from Owl Creek locality (OC-3).
quentially dominate interstitial water chemis-
try in organic-rich marine sediments (Curtis
and others, 1972; Claypool, 1974; Claypool
and Kaplan, 1974). The quantity of methane
accumulated in the sediment depends, in part,
upon the amount of metabolizable organic
matter that survives previous aerobic and an-
aerobic oxidation. Gas accumulation is thus
controlled by the original organic matter con-
tent of the sediment and by the sedimentation
rate.
The biochemical requirements for biogenic
methane accumulation include the presence of
dissolved CO, and the absence of dissolved
sulfate and free oxygen (Claypool and Kaplan,
1974). Siderite precipitation is favored by sim-
ilar chemical conditions, being restricted to
waters of high bicarbonate activity, low oxi-
dation potential, and extremely low concentra-
tions of dissolved sulfide (Garrels and Christ,
861
1965; Curtis, 1967). Inasmuch as seawater
contains about 2,700 mg/l 5 0 4 2 - (Goldberg,
such as the Gammon Shale is evidence for the
reduction of pore-water sulfate and complete
reaction of the resulting aqueous sulfide during
early diagenesis. In recent marine sediments,
sulfate reduction is bacterially mediated (see,
e.g., Kaplan and others, 1963; Ostroumov and
others, 1961). Methane may be consumed
(and perhaps also produced?) during bacterial
sulfate reduction (Reeburgh and Heggie, 1977;
Barnes and Goldberg, 1976) but does not ac-
cumulate until more than 90 percent of the
dissolved sulfate has been reduced (Martens
and Berner, 1974). Because of the thermody-
namic constraints on iron carbonate precipita-
tion (Garrels and Christ, 1965; Curtis, 1967),
siderite concretions in the Gammon probably
began forming just subsequent to the onset of
methane accumulation. Therefore, if the depth
of siderite precipitation is known, the m i n i -
m u m depth for the onset of methane accumu-
lation can be inferred.
Owing to the probable early diagenetic ori-
gin of natural gas in the Gammon, knowledge
of the timing and rate of siderite formation is
significant for understanding the conditions of
gas accumulation, for interpreting early geo-
chemical history, and for estimating gas re-
sources. The volume percent carbonate, oxy-
gen isotope composition, and sulfide sulfur
content of siderite concretions in the Gammon
Shale are significantly correlated to one an-
other and to sediment accumulation rates.
These relationships suggest that the relative
depth and (or) time of siderite formation can
be estimated on the basis of mineralogic and
isotopic data.
SAMPLING AND ANALYSIS
Fresh siderite concretions were collected
from outcrops and cores of the Gammon Shale
or Gammon Member of the Pierre Shale in the
vicinity of the Black Hills and at Porcupine
Dome, Montana (Fig. 1). Collection localities
included sections of Gammon deposited to
various thicknesses (Fig. 1) and at differing
rates (to be discussed in a later section). Each
concretion was sawed normal to bedding such
that a slice was removed from the concretion
center. The slice was then subdivided into ra-
dial samples for analysis in a manner similar
to that described by Raiswell (1971) (Fig. 2).
 862 DONALD L. G A U T 1 E R

TABLE 1 .--Analytical data from siderite concretions ~f the Gammon Shale and equivalent rocks for selected localities in the
Northern Great Plains.
[N.D.~No Determination]

Uncorrected Siderite X-ray data

Concretion Sub- MeCO 3 S2 sed. rate Carbonate
No. sample (Vol. %) 81SO 8nC (wt. %) 834S (m/m.y.) mineral dl041A) a0121a)

A a s e n N o . 1-9, C o r e s
Paine a n d A s s o c i a t e s , A a s e n N o . 1-9 w e l l , sec. 9, T . 129 N , , R. 106 W . ,
Bowman Co., North Dakota

AA-1190 A 81.8 -2.44 10,38 0.31 -13.20 40 Siderite 2.808 3.616

AA-1211 A 79,7 0.14 6.46 N.D. N.D. ----do . . . . . . . . do .... 2.804 3.614

Alkali Creek, Outcrop

S e c . 8, T. 4 N . , R. 8 E , M e a d C o . , S o u t h D a k o t a

AC-14 A 68.1 -5.06 -8.59 N.D. N.D. 18 Siderite 2.812 3.613

Do ....... B 66,4 -5.13 -9,02 N,D. N.D. ----do . . . . . . . . do .... 2.810 3.611
Do ....... C 70.0 -4.90 -8.67 2.49 14.52 .... do ........ do .... 2.813 3.610
DO . . . . . . . D 71.6 -4.37 -9.03 3.08 10.43 .... do ........ do .... 2.810 3.616
Do ....... E 70.1 -4.76 -9.46 N.D. N.D. ----do . . . . . . . . do .... N.D. N.D.
Do ....... F 65.6 -4.84 -9.43 N.D. ND ----do . . . . . . . . do .... N.D. ND.
Do- . . . . . . G 64,5 -4.78 -9.48 2.50 16.40 .... do ........ do .... N.D. N.D.

Buffalo Gap, Outcrop

Sec. 2 l , T . 4 0 N . , R. 7 E , Fall R i v e r C o . . S o u t h D a k o t a

BG-17 A 71,7 -3.47 -3,17 N.D. N.D N.D. Siderite N.D. N.D.
Do- . . . . . . B 69.9 -3.75 -3.86 2.57 -29.12 N.D. ----do .... N.D. N.D.
Do- ...... C 66.4 -4.62 -5.33 1.30 -21.91 N.D. ----do .... N.D. N.D.
BG-22 A 75.5 -3.17 -2.39 N.D. N.D. N.D. ----do .... N.D. N.D.
Do- . . . . . . B 76.5 -3.66 -2.19 N.D. ND. N.D. ----do .... 2.813 3.613
Do- . . . . . . C 77,3 -3.68 -2.27 N.D. N.D N.D. ----do .... 2.813 3.617
Do- - D 75.6 -3.84 -2.37 0,70 -15.43 N.D. d o --- 2.809 3.604

Gammon Prong, Outcrop

Sec. 19. T. 5 7 N . , R. 6 7 W . , C r o o k C o . , W y o m i n g

GM-6 A 72.5 -2.68 -4.98 N.D. N.D N.D. Siderite 2.800 3.603
Do ....... B 72.2 -2.55 -3.23 0.81 -24.10 N.D. ----do .... 2.804 3.610
Do- ...... C 69.5 -3.04 -5,13 N.D. N.D N.D. ----do .... N.D. N.D.

Lower Owl Creek, Outcrops

Sec. 24, T. 11 N . , R. l E , , a n d sec. 20, T . 11 N . , R . 2E.,
Butte C o . , S o u t h D a k o t a

LOC-7-1 A 82.5 -0.98 +0,35 0.07 ND. 80 Siderite 2,811 3.616

LOC-7-3 A 82.3 -0.96 -0.01 0.37 -29.76 80 .... do .... 2.809 3.613
LOC-8-1 A 81.0 -2.31 -5.91 0,12 -8,31 >52 .... do .... N.D. N.D.
Do- ...... B 82.5 -2.11 -5.62 N.D. ND. >52 .... do .... N.D. N.D.

LOC-8-2 A 85.5 -2.10 -5.29 0,50 -15,42 >52 .... do .... 2.803 3.606
Do- ...... B 86.4 -2,30 -5.41 N.D, ND, >52 .... do .... 2,805 3.607
Do- ...... C 82.8 -2.39 -5.97 0.04 N.D. >52 .... do .... 2.805 3.613
LOC-I1 C 85.0 -0.64 -18.50 0.13 -32.08 50 .... do .... N.D. N.D.
DO . . . . . . . D 85.2 -0.32 - 19.52 N.D. N.D. 50 .... do .... N.D. N.D.

Madison #2, Core

U S G S M a d i s o n T e s t W e l l N o . 2, sec. 18, T, 1 N . , R . 5 4 E . ,
Custer Co., Montana

MAD-1994 B 68.34 ~ -0.05 -8.83 0.13 -18.10 N.D. Siderite N.D. N.D.

Owl Creek, Outcrop

Sec. 13, T. 9 S . , R. 61 E . , C a r t e r C o . , M o n t a n a

OC-3 A 82.0 -2.53 -20.59 N.D. ND. >52 Calcite N.D. N.D.
Do ....... B 81.9 -2.57 -20.71 0.82 -27,00 .... do .... Calcite N.D. N.D.
Do- ...... C 87.0 -0.77 -5.34 0.61 -21.98 .... do .... Siderite 2.812 3.613
Do ....... D 81.9 -0.66 -3.83 N.D. ND. ----do . . . . Siderite 2.811 3.608

OC-6 A 83.1 -1.72 -20.73 0.90 -22.51 .... do .... Calcite N.D. N.D.
Do ....... B 84.7 O. 14 N.D. N.D. ND. ----do . . . . Siderite N.D. N.D.
Do ....... C 82.2 -2.54 -20.73 1.24 -24.52 .... do .... Calcite N.D. N.D.
Do ....... D 82.6 -2.67 -20.27 N.D. N.D. ----do .... Calcite N.D. ND.
 SIDERITE CONCRETIONS 863

TABLE 1.---Continued

Do- . . . . . . E 86.3 -2.06 -5.53 0.39 -18.46 . . . . do . . . . Siderite 2.812 3.608

Do- . . . . . . F 82.4 -2.20 -5.33 N.D. N.D. ----do . . . . . . . . do . . . . 2.811 3.613

Porcupine D o m e , Outcrop
Sec. 10, R. 8 N . , R. 39 E . , R o s e b u d C o . , M o n t a n a

PD-I A 77.9 -2.59 -4.57 N.D. N.D. >47 Siderite N.D. N.D.
Do . . . . . . . B 79.3 -2.91 -4.76 N.D. N.D. ----do . . . . . . . . do . . . . N.D. N.D.
Do . . . . . . . C 80.4 -2.80 -4.67 N.D. N.D. ----do . . . . . . . . do . . . . N.D. N.D.
Do- . . . . . . D 82.5 -2.16 -4.38 N.D. ND. ----do . . . . . . . . do . . . . 2.804 3.613
Do ....... E 81.2 -2.31 -4.33 N.D. ND. ----do . . . . . . . . do . . . . N.D. N.D.
Do . . . . . . . F 78.3 -2.50 -4.53 N.D. N.D. ----do . . . . . . . . do . . . . N.D. N.D.
PD-2 D 88.6 -2.53 -4.46 N.D. N.D. ----do . . . . . . . . do . . . . N.D. ND.
Do- . . . . . . E 86.5 -2.77 -5.12 N.D. N.D. ----do . . . . . . . . do . . . . N.D. N.D.

Red Bird, Outcrop

Sec. 18, T. 38 N . , R. 61 W . , N i o b r a r a C o . , W y o m i n g

RB-4 A 59.4 -6.96 -4.32 N.D. N.D. 4 Siderite ND. ND.

Do- . . . . . . B 59.2 -7.26 -4.30 2.11 -27.48 . . . . do . . . . . . . . do . . . . N.D. ND.
Do- . . . . . . C 59.0 -7.45 -4.50 2.27 -28.18 . . . . do . . . . . . . . do . . . . N.D. N.D.
Do- . . . . . . D 57.3 -7.40 -5.02 N.D. N D. ----do . . . . . . . . do . . . . N.D. ND

a-oxidized s a m p l e - - v o l , percent F e C O 3 is p r o b a b l y too low.

Textural relationships and bulk mineralogy isotope ratios were approximately corrected
were determined petrographically and by X- back to 25 ° C by subtracting 0.68%o from the
ray powder diffraction, respectively. Weight 40 ° C value. Inasmuch as the equilibrium iso-
percent carbonate in each sample was calcu- topic fractionation factors for siderite-water
lated from weight difference after dissolution and siderite-phosphoric acid are not known,
of crushed and milled material in cold HCI. samples were analyzed using standard tech-
This treatment was conducted according to the niques for calcite (Craig, 1957) except for the
methods of Ostrom (1961) and Pollastro (1977) elevated reaction temperature. Carbon and ox-
so as to minimize dissolution of noncarbonate ygen isotope data are reported with reference
constituents. In order to determine that disso- to the PDB University of Chicago standard.
lution of the siderite was complete, insoluble Isotopic data are listed in Table 1. For the ben-
residues were analyzed by X-ray powder dif- efit of the reader ~13C data are included al-
fraction. Following washing with distilled water, though their interpretation will be reported
the residues were dried and weighed, and py- elsewhere.
rite was oxidized and dissolved in bromine/ Replicate analyses conducted by Global
aqua-regia. The percent sulfide sulfur (entirely Geochemistry Corporation indicate reproduc-
from pyrite) was then determined by weight ibility of oxygen isotopic analyses to be
as BaSO 4 precipitate (Table 1). ±0.2%0 or better, and of carbon to be
Isotopic analyses were conducted under con- -+0.1%o or better. As a further check on
tract by Global Geochemistry Corporation. reproducibility and effectiveness of laboratory
The isotopic composition of pyrite sulfur was preparation techniques, seven duplicate sam-
determined from SO 2 gas obtained from the ples were selected which included the entire
BaSO 4 precipitates (Kaplan and others, 1963). range of oxygen isotopic compositional vari-
Sulfur isotope data are reported in standard g- ation in the siderite sample set. These dupli-
notation relative to troilite from the Canyon cates were analyzed in the stable isotope lab-
Diablo Meteorite (CDT). Carbon and oxygen oratory of the U.S. Geological Survey, Denver,
isotopic compositions were measured with a Colorado. Approximately 50 mg of crushed
double-collecting, isotope-ratio mass spec- sample were reacted at 25 ° C with 100 percent
trometer on CO 2 generated by reacting about phosphoric acid for seven days. To ensure
50 mg of each crushed sample with about 3 complete reaction, the sample residues were
ml of 100 percent phosphoric acid (McCrea, tested for siderite by X-ray powder diffraction.
1950). Siderite-phosphoric acid reactions were The CO 2 was extracted, purified, and analyzed
conducted at 40 ° C for 16 hours, following re- on a triple-collecting mass spectrometer, and
moval of organic matter with chlorox. Oxygen the resulting data were plotted against corre-
864
sponding data from Global Geochemistry Cor-
poration. This test showed a correlation coef-
ficient of 0.984 for 6~80 and 0.997 for 6'3C.
These correlations are statistically significant
at the 99.5 percent confidence level. Analyti-
cal results and statistical information from rep-
licate analyses are available on request from
the author.
The chemical composition of the siderite
cements was not a principal concern of this
investigation. However, it was important to
determine if chemical composition bears a sig-
nificant relationship to the isotopic composi-
tion or volume percent carbonate in the con-
cretion samples. The great sensitivity of the
crystal lattice dimensions of rhombohedral car-
bonates to compositional variation as mea-
sured by X-ray diffraction (e.g., Graf, 1961;
Morelli, 1966) provides a useful index by
which relative composition can be compared
to other variables. Twenty-one splits from the
original sample set were selected, and the sid-
erite 012 and 104 peak positions were mea-
sured with respect to a quartz standard (Table
I). The resulting d-spacings were then com-
pared with the isotopic and volume percent
carbonate data. These comparisons, which
showed no statistically significant correlations,
argue convincingly that the chemical compo-
sition of the siderite concretions has little or
no effect on isotopic composition or volume
percent carbonate measurements.
00- ~. " dence does indicate that the Gammon concre-
~ " CORRELATION
CCEFRCIENT = 0.89
-20 - -, • burial depth.
60
-4O I • of a microcrystalline siderite mosaic that com-
-6O
I I
80 7O 60
SIDERITE, VOLUME PERCENT
FIG. 3.---.Volume percent siderite and 51SO, relative to
PDB, for siderite samplesdiscussed in the text and listed
in Table 1. Line represents best fit linear equation.
DONALD L. GAUTIER
RELATIVE DEPTH OF SIDERITE FORMATION
Three types of criteria were used to estimate
the timing of concretion development: 1) the
relationship of textural features preserved in
concretions to textures in adjacent sediments;
2) volume percent carbonate of the concre-
tions; and 3) oxygen isotope composition of
concretionary siderite.
The siderite ~lSO becomes significantly more
negative as the volume percent of siderite de-
creases (0.88 correlation coefficient, signifi-
cant at the 99.5 percent confidence level) (Fig.
3). This correlation is inferred to result from
dependence of both volume percent siderite
and ~ 8 0 values upon a third variable: depth
of siderite formation. The inferred relationship
of precipitation depth to oxygen isotope com-
position and volume percent siderite is con-
sistent with the textural evidence.
Textural Evidence
Numerous authors have discussed textural
relationships useful in timing concretion for-
mation (Tomkeieff, 1927; Weeks, 1957;
Lippmann, 1955; Pantin, 1958; Woodland,
1964; Hallam, 1969; Raiswell, 1971; Oertel
and Curtis, 1972). Because of the high degree
of bioturbation in the Gammon and the scar-
city of fossils in the concretions, many methods
suggested by previous workers, such as tracing
continuous bedding laminae through concre-
tions (Tomkeieff, 1927; Raiswell, 1971) or
examining the degree of fossil compaction
(Weeks, 1957), are of little use in estimating
the time and depth of siderite formation in the
Gammon Shale. However, the textural evi-
tions are postdepositional and that they formed
before the sediments attained their maximum
Many Gammon siderites preserve delicate
sedimentologic features such as burrow struc-
tures or fecal pellets. The concretions consist
monly reflects the prevailing pore size and
pore network geometry of the original sedi-
ment. For example, crystals of siderite cement
in siltstone are coarser than siderite crystals in
5O adjacent claystone. Concretions which pre-
serve such sedimentary structures and textures
must have formed mainly as pore-filling ce-
ment, subsequent to sediment deposition. The
concretions are enclosed by mudstones, the
 SIDERITE CONCRETIONS
bedding planes of which curve around the con-
cretions, indicating that the siderite formed
prior to at least some compaction and before
maximum sediment burial. Further, many con-
cretions preserve undeforrned cylindrical bur-
rows and uncompacted fecal pellets and glau-
conite grains all of which display evidence of
compaction in adjacent sediments outside the
concretions. Such concretions must have formed
early in the burial history of the sediment. Sep-
taria, which evidently form only in uncom-
pacted, water-laden sediment (Lippman, 1955;
Raiswell, 1971), are present in a few concre-
tions (Fig. 2). Septarian concretions are among
those in which the least amount of compaction
is recognized.
Volume Percent Carbonate
Lippmann (1955), Raiswell (1971, 1976),
Seibold (1962), Oertel and Curtis (1972), and
others have developed a model of concretion
growth whereby precipitating carbonate pas-
sively occupies effective porosity. If their
interpretation is correct, the volume percent
carbonate in a concretion closely approximates
the porosity of enclosing sediments at the time
the concretion grew. Sediment porosity, in
turn, is directly related to depth of burial,
overburden pressure, sedimentation rate, and
sediment type (see, e.g., Hamilton, 1976).
Volume percent carbonate values reported
in Table 1 were derived from weight percent
determinations, assuming siderite density to be
3.96 g/cm 3 and detrital grain density to be 2.6
g/cm 3. Analytical error due to weighing is
probably less than 2 percent.
In addition to analytical error, four major
effects can complicate the relationship be-
tween volume percent carbonate and original
sediment porosity: 1) Carbonate crystals could
have displaced the host sediment during con-
cretion growth. 2) Porosity may not have been
completely filled by siderite precipitation. 3)
Detrital grains may have been replaced by car-
bonate during concretion formation. 4) Detrital
or biogenic carbonate grains could have been
dissolved during acid treatment, and thus in-
creased the apparent volume percent authi-
genic carbonate measured.
Several lines of evidence substantiate the
findings of previous workers that these effects
are unimportant and suggest that volumetric
carbonate contents are within 10 percent of
original porosity. The delicate preservation of
865
sediment textures is evidence that significant
displacement of the original sediment did not
occur during concretion growth. The presence
of septaria, as discussed by Lippmann (1955)
and Raiswell (1971), suggests that porosity
was not quite filled during concretion forma-
tion, but the small volume of porosity attrib-
uted to septaria (<3%) indicates that cemen-
tation was so nearly complete that unfilled
porosity is insignificant for the purposes of this
investigation. The preservation of sediment
textures and the absence of microscopic evi-
dence for replacement of detrital grains sug-
gests that replacement has been minimal. De-
trital carbonate grains account for about 5
percent of the original sediment and approxi-
mately 2 percent of the concretions. Dissolu-
tion of detrital carbonate, therefore, could not
seriously affect calculations of volume percent
authigenic carbonate.
Siderite in concretions analyzed during this
study ranges from 57 to 87 percent by volume
(Fig. 3). These measurements suggest that
concretions with the highest carbonate volume
(that is from 80-87%) began forming at shal-
low depths in the sediment column. In modern
muds, high initial porosities (+ =
fractional porosity = 0.7-0.9) decrease rap-
idly with burial (see, e.g., Engelhardt, 1977,
p. 262-293; Rieke and Chilingarian, 1974,
p. 31-86) and generally are not present at
depths greater than 10 m below the sediment-
water interface. Siderite concretions with the
lowest volume percent carbonate, those from
Red Bird, Wyoming, in contrast, developed
after considerable sediment compaction. Po-
rosities of 50 to 60 percent, such as those in-
ferred from the Red Bird samples, are com-
monly observed m pelagic clays and terrigenous
sediments at burial depths of 500 m or less
(Hamilton, 1976). Within the range of 0 to
1,500 m, the depths to which the Gammon
Shale sediments were buried (Gautier, 1981),
most compaction occurs above a depth of 500
m (see, e.g., Rieke and Chilingarian, 1974, p.
41-50). Porosity decreases slowly below 500
m, and small errors in carbonate volume per-
cent determinations would have a great effect
on estimates of siderite precipitation depth.
Within the range of error of these data, the
concretions with the lowest volumetric siderite
are inferred to have formed at burial depths
greater than 200 to 300 m and possibly at
depths approaching maximum burial.
866 DONALD L, GAUTIER
O©'gen Isotopes
The equilibrium isotopic composition of ox-
ygen in carbonate minerals is determined mainly
by temperature and by the isotope composition
of the water from which the carbonate precip-
itates (Urey, 1947; McCrea, 1950; Epstein and
others, 1951; Epstein and others, 1953). Sid-
erite cannot, as yet, be used as an absolute
paleothermometer because the equilibrium
fractionation factors (a) for siderite-water and
for siderite-phosphoric acid have not been de-
termined. Nevertheless, the linear relationship
of relative fractionation among divalent metal
carbonates and water at low temperature
(O'Neil, Clayton, and Mayeda, 1969) permits
the confident use of siderite as a relative in-
dicator of temperature and (or) isotopic com-
position. Further, the similarity of fractiona-
tion factors of the divalent metal carbonates
and their dependence on atomic weight (O'Neil,
Clayton, and Mayeda, 1969) suggest that 8180
values for siderite are within one or two per
mil of those fl)r calcite precipitated from water
of the same isotopic composition and temper-
ature.
Siderite concretions from the Gammon have
oxygen isotope compositions that range from
8180 = 0.14 to-7.45%0 (Fig. 3; Table 1). A
principal interpretation of this study is that this
range in 8~80 values reflects mainly the tem-
perature and, to a lesser degree, the possible
progressive diagenetic depletion of pore waters
in 13C as described by Hudson (1978). There-
fore, the oxygen isotopic composition indi-
cates depth of siderite precipitation and may
also suggest the amount of time elapsed since
sediment deposition. The concretions with the
heaviest (least negative 8180) isotopic com-
position contain the largest volume percent
siderite, as noted above (Fig. 3). For example,
siderite concretions from the lower Owl Creek
locality (Fig. 1) are interpreted to have formed
at very shallow depths on the basis of septarian
structures and uncompacted sediment textures.
Siderite constitutes 80 to 85 percent of the sep-
tarian concretions from lower Owl Creek, by
volume, indicating formation in essentially un-
compacted sediment at depths of less than 10
m in the sediment column. The 3t80 of these
same siderites is between 0 and -2%0, con-
sistent with siderite precipitated from waters
with temperature and isotopic composition
similar to seawater.
The most negative 81SO values were mea-
sured in the Gammon siderites from the Red
Bird, Wyoming and Alkali Creek, South Da-
kota localities (Table 1). Assuming equilib-
rium fractionation of siderite to be similar to
that of calcite (probably not a good assump-
tion), and allowing for the ice-storage effect
(Shackleton and Kennett, 1975), one can de-
termine that concretions from the Red Bird lo-
cality would have formed from water of sea-
water isotopic composition at a temperature of
about 48 ° C. This temperature approaches the
maximum interpreted burial temperature
(-~60° C) for Gammon sediments cored in the
Aasen 1-9 well (Fig. 1) (Gautier, 1981). In-
asmuch as the isotopic composition of siderite
in equilibrium with water may be one or more
per mil heavier than that of calcite (John D.
Hudson and Harry A. Tourtelot, oral comm.,
1981), an even higher temperature of precip-
itation may be indicated, one that is possibly
inconsistent with the interpreted thermal his-
tory of the Gammon Shale. However, in the
absence of knowledge about siderite fraction-
ation factors further speculation is unwar-
ranted. For a discussion of several mecha-
nisms proposed to explain anomalously light
oxygen isotope compositions in concretions,
including closed-system reactions with detrital
minerals, ultrafiltration by shales, and the in-
cursion of meteoric waters, see Hudson and
Friedman (1976) and Hudson, (1978).
RELATION OF CONCRETION DATA TO SEDIMENT
ACCUMULATION RATE
In the vicinity of the Black Hills, the Gam-
mon Shale and equivalent rocks were depos-
ited during a time interval comprising seven
of the ammonite range zones established for
the Cretaceous in the Western Interior (Gill
and Cobban, 1973). In Montana, the Gammon
is overlain by the Claggett Shale and, in much
of South Dakota, by its equivalent, the Sharon
Springs Member of the Pierre Shale. The up-
per Gammon contact is a time line marked by
the Ardmore Bentonite Beds. These bentonites
are in the lower part of the Baculites obtusus
range zone (Gill and Cobban, 1966) and have
been dated by the K/Ar method at approxi-
mately 80 m.y. (Obradovich and Cobban,
1975; Lanphere and Jones, 1978). The Gam-
mon overlies and, to a limited extent, inter-
tongues with the Niobrara Formation (Gill and
Cobban, 1961). The base of the Gammon rises
stratigraphically and transgresses time from
 SIDERITE CONCRETIONS
west to east. To the west, the oldest Gammon
Shale is in the range zone of Desmoscaphites
bassleri (Gill and Cobban, 1973), dated by the
K/Ar method at about 84.5 m.y. (Obradovich
and Cobban, 1975; Lanphere and Jones, 1978),
whereas in the vicinity of Alkali Creek, on the
northeast flank of the Black Hills (Fig. 1), the
base of the Gammon is in the range zone of
Scaphites hippocrepis III (Cobban, 1969),
herein assigned an age of 82.25 m.y.
For the purpose of estimating relative sedi-
ment accumulation rates, in the absence of
data to the contrary, continuous, steady-state
deposition is assumed for all localities, and the
4.5 m.y. time interval including the range
zones from D. bassleri through B. obtusus was
subdivided equally (0.75 m.y./zone) as fol-
lows:
assignedt or
ammonite range zone measured* age (m.y.)
Baculites obmsus 80.0*
B. sp. (weak flank ribs) 80.75i"
B. sp. (smooth) 81.5"t
Scaphites hippocrepis III 82.25t
S. hippocrepis II 83.0t
S. hippocrepis I 83.751"
Desmoscaphites
bassleri 84.5*
Rates were calculated from measured sections
with ammonite control (Fig. 1; Table 1) by
dividing the thickness of Gammon Shale at-
tributed to each range zone by the time inter-
vals assigned to the zones. These uncorrected
relative sediment accumulation rates (Table 1)
probably represent less than 50 percent of the
actual accumulation rate when adjusted for
compaction.
Across the Black Hills region, the Gammon
displays large variations in total thickness (Gill
and Cobban, 1961), ranging from a maximum
of more than 300 m north and west of the
Black Hills to a minimum of about 10 m near
Red Bird, Wyoming (Fig. 1). As expected,
calculated sediment accumulation rates for the
region show similar variation; highest rates
during specific ammonite range zones gener-
ally correspond to greatest total thickness.
Both volume percent siderite values and ox-
ygen isotope data correlate significantly with
the inferred sedimentation rates and fit closely
(coefficient of determination = 0.92) to curves
of the form: y = ae bx (Fig. 4). Such exponen-
867
\
~O~ER OWL CREEK
COEFFICIENT OF DETERMINATION = O 92
i SO
g
4O AASEN I~
g
c~ ~e E
'-----4gz-~L____
FIG. 4.--Interpreted sedimentation rate and average
volume percent siderite for samples from localities with
measured sections for which ammonite control is avail-
able. Curve represents best fit for equations of the form:
y = aeb', Sources of stratigraphic and fossil data are as
follows: Aasen 1-9--bentonite marker correlations by the
author, based, in part, on subsurface and outcrop studies
by Shurr (1975); Alkali Creek>--unpublished measured
section by J. R. Gill with fossil identifications by W. A.
Cobban, with position of Scaphites hippocrepis Ili zone
in Gammon from Cobban (1969); lower Owl Creek--
unpublished measured section and fossil identifications by
W. A. Cobban; Owl Creek--unpublished measured sec-
tion and fossil identifications by W. A. Cobban; Porcu-
pine Dome--Gill, Cobban, and Schultz (1972); Red
Bird--Gill and Cobban (1966).
tial curves also describe compaction of fine-
grained siliciclastic sediments and other early
diagenetic phenomena (see, e.g., Berner, 1980).
Concretions from sections with highest sedi-
ment accumulation rates display large volume
percent carbonate values and oxygen isotope
compositions similar to those expected for car-
bonate in equilibrium with marine waters of
normal salinity and reasonable surface tem-
peratures. Conversely, concretions collected
from measured sections with lowest sediment
accumulation rates contain less siderite by vol-
ume and isotopically lighter oxygen. Evi-
dently, siderite concretions formed at shal-
lower depths and (or) earlier in the burial
history of rapidly accumulating sediments than
did siderites in sediments that were accumu-
lating more slowly.
Within individual concretions, trends of de-
creasing volumetric siderite and decreasing
~lSo values are present from center to outside
edges (Fig. 5). Such trends are common fea-
tures of concretions and have been described
by several authors (e.g., Oertel and Curtis,
868 DONALD L. GAUTIER
9O r-
PO-1
i CENTER
/ ALL VALUES A R E
ee / ~ ~lao
,~ a4
D
EDGE EDGE
FIG. 5.--Weight percent acid-soluble carbonate (sid-
erite) and siderite ~ O across diameter, parallel to bed-
ding, of concretion (PD-1) from Porcupine Dome, Mon-
tana (Fig. 2). See Table 1 for analytical data.
1972; Raiswell, 1971). Like most previous
workers I attribute these trends to sediment
compaction and increasing temperature (or iso-
topic evolution of pore waters) during concre-
tion growth. However, it is emphasized that
lateral variation within any single concretion
is small compared to that observed between
concretions from various localities (Table 1).
SULFIDE SULFUR
The thermodynamic instability of siderite
relative to pyrite in the presence of aqueous
sulfide (Garrels and Christ, 1965; Curtis,
1967) is the basis for the conclusion that sid-
erite in the Gammon Shale did not form until
nearly all dissolved sulfur had been reduced
and precipitated. The existence of siderite in
these sediments indicates that sulfide precipi-
tation was not limited by the availability of
reactive iron (see Berner, 1970). Because of
this genetic relationship between pyrite and
siderite in the Gammon concretions, correla-
tions are to be expected between the volume
percent and ~]So of siderite and the abundance
of pyrite. Although considerable scatter exists,
linear trends, statistically significant at the
99.5 percent confidence level, are apparent if
sulfide sulfur abundance data are plotted against
either volume percent or 3~sO of siderite (Fig.
6). Concretions containing the most siderite
and the least negative oxygen isotope ratios
also contain the lowest percentage of sulfide
sulfur in their insoluble residues, whereas con-
cretions with the least volume percent siderite
and lightest oxygen contain the most sulfide
in their insoluble fractions.
Except for samples from the Alkali Creek
locality (Fig. 1; Table 1), pyrite in the con-
cretions occurs mainly as framboids that are
isotopically light (g34S -- - 3 2 to -8%0) (Ta-
ble 1). In many samples, sulfide sulfur is pres-
ent in quantities that exceed the amount which
could have been produced from the seawater
sulfate originally contained in pore waters at
the time of deposition (=28 mmoles/1). This
excess suggests that most pyrite sulfur was
added by processes, such as biogenic mixing
by macrofauna or diffusion, which are capable
of providing sulfate in addition to that trapped
in pore waters (Goldhaber and Kaplan, 1974,
1980). During the Campanian Stage, seawater
sulfate probably had a 834S of about 18%o
(Claypool and others, 1979). Assuming pyrite
that formed in the zone of mixing (which al-
lows extensive communication of pore waters
with the "infinite" seawater sulfate reservoir)
was depleted in 34S by about 54%0 relative to
seawater sulfate (Goldhaber and Kaplan, 1980),
one can determine that the earliest-formed py-
rite would have had a g34S of about -36%0.
Because most observed values are heavier than
this, at least some pyrite in the insoluble res-
idues is inferred to have formed outside the
zone of rapid interchange with seawater by the
closed-system reduction of trapped sulfate and
(or) from sulfate that diffused downward into
o o
i
8
: ," ." .
8O
o.
i,o
60
I I I I
1 2 3 4
SULFIDE SULFUR, WEIGHT PERCENT
FIG. 6,--Volume percent siderite and percent sulfide
sulfur in the insoluble residues of samples discussed in
the text and listed in Table 1. Line represents best fit lin-
ear equation.
 SIDERITE CONCRETIONS
the sediment beneath the near-surface mixing
zone.
Insoluble residues of concretions from the
Alkali Creek locality contain anomalously
large quantities (2.5 to 3%) of sulfide sulfur,
mainly in subhedral to euhedral crystals of
pyrite. Sulfur in this pyrite is isotopically
heavy, with ~34S values of + 10.4 to + 16.4%o.
The abundance and isotopic composition sug-
gest that most of this sulfide precipitated rel-
atively late in sulfur diagenesis (near the base
of the sulfate reduction zone), probably from
waters that were previously depleted in 345 to
a large degree by bacterial sulfate reduction.
The depth at which siderite precipitation be-
gan is inferred to have been controlled by the
depth in the sediment column to which dis-
solved sulfide was present. This inference is
not inconsistent with the apparent shallow
depth of pyrite formation in most Gammon
concretions, since dissolved sulfide in recent
sediments is commonly transported by diffu-
sion to depths well below the zone of maxi-
mum pyrite precipitation (Goldhaber and Ka-
plan, 1980). The depth to which dissolved
sulfide persists in a sediment column is the
result of complex relationships between sedi-
mentation rate, the amount of available or-
ganic matter, and the rate of molecular diffu-
sion. For detailed and quantitative treatment
of the movement of sulfur in recent marine
sediments, the reader is referred to Berner
(1980) and to Goldhaber and Kaplan (1980).
In recent marine sediments dissolved sulfate
is generally only present to depths as great as
hundreds of meters in slowly accumulating
sediments that are low in organic carbon
(Goldhaber and Kaplan, 1974). Aqueous sul-
fate is depleted at shallow depths in organic-
rich, rapidly accumulating sediments. Thus the
inference that siderite precipitation occurred
soon after deposition and at shallow depths in
areas of high sedimentation rate but was pro-
hibited except at considerable depths in slowly
accumulated sediments of the Gammon Shale
is consistent with known trends of sulfur dia-
genesis.
CONCLUSIONS
Important aspects of the early diagenetic
history of the Gammon Shale can be inter-
preted from mineralogic, textural, and isotopic
data. The consistent relationships between vol-
ume percent siderite and ~18O in the siderite
869
concretions suggest that the relative depth and
(or) time and, in some cases, the approximate
actual depth of concretion formation can be
estimated. These estimates indicate the mini-
mum depth for the depletion of dissolved pore-
water sulfur and the minimum depth for the
onset of methanogenesis. The minimum depths
were largely determined by sedimentation rate
and therefore varied from place to place and
with time during Gammon deposition.
In contrast to calculations of integrated sed-
iment accumulation rate based on rock thick-
ness and biostratigraphic zonation, the siderite
concretions of the Gammon evidently record
information about the instantaneous sedimen-
tation rate during concretion growth. In re-
gions of relatively rapid sediment accumula-
tion, large quantities of reactive, metabolizable
organic matter passed quickly through zones
of aerobic oxidation and sulfate reduction and
became available for methane generation. In
contrast, where sediments accumulated slowly,
siderite precipitation and methane generation
did not begin until long after deposition and
after significant sediment compaction. Siderite
precipitation and methane generation were in-
hibited by the persistence of dissolved sulfide
and sulfate respectively in the interstitial waters.
The long residence time of the slowly accu-
mulating sediments in the sulfate reduction
zone resulted in the precipitation of relatively
large quantities of iron sulfide, suggesting that
much, if not most, available metabolizable
organic matter was consumed by sulfate-re-
ducing bacteria, and was thus not available for
methane generation.
ACKNOWLEDGMENTS
Special thanks go to H. A. Tourtelot for
sharing his knowledge of shale in the Western
Interior and to W. A. Cobban for permission
to use unpublished data. This work was funded
by the U.S. Department of Energy through the
Western Tight Gas Sands Program of the U.S.
Geological Survey.
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