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Clays and Clay Minerals, VoL 27, No. 5, pp. 313-321, 1979.

BLACK SHALE--ITS DEPOSITION AND DIAGENESIS 1

HARRY A. TOURTELOT
U.S. Geological Survey, Federal Center, Denver, Colorado 80225

Abstract--Black shale is a dark-colored mudrock containing organic matter that may have generated hy-
drocarbons in the subsurface or that may yield hydrocarbons by pyrolysis. Many black shale units are
enriched in metals severalfold above expected amounts in ordinary shale. Some black shale units have
served as host rocks for syngenetic metal deposits.
Black shales have formed throughout the Earth's history and in all parts of the world. This suggests that
geologic processes and not geologic settings are the controlling factors in the accumulation of black shale.
Geologic processes are those of deposition by which the raw materials of black shale are accumulated and
those of diagenesis in response to increasing depth of burial.
Depositional processes involve a range of relationships among such factors as organic productivity, clas-
tic sedimentation rate, and the intensity of oxidation by which organic matter is destroyed. If enough or-
ganic material is present to exhaust the oxygen in the environment, black shale results.
Diagenetic processes involve chemical reactions controlled by the nature of the components and by the
pressure and temperature regimens that continuingburial imposes. For a thickness of a few meters beneath
the surface, sulfate is reduced and sulfide minerals may be deposited. Fermentation reactions in the next
several hundred meters result in biogenic methane, followed successively at greater depths by decarbox-
ylation reactions and thermal maturation that form additional hydrocarbons. Suites of newly formed min-
erals are characteristic for each of the zones of diagenesis.
Key Words---Black shale, Deposition, Diagenesis, Organic matter, Syngenetic ores.

INTRODUCTION (1966, p. E l - E 2 ) pointed out the compositional varia-


The study of black shales has been difficult until a tions included in this definition and the ways that these
relatively few years ago. Outcrop observations have variations can be used to study black shale.
yielded relatively few kinds of data for interpreting their Most shales that immediately meet this color crite-
origin and the factors governing their formation. Re- rion contain 1% or more organic carbon; 2-10% is a
cently, however, a growing body of chemical data on common range. A few shales contain more than 20%
the organic as well as the inorganic constituents of organic carbon. Pyrolysis yields variable amounts of
black shale has widened the scope of inferences that liquid and gaseous hydrocarbons, the amount depend-
can be drawn on the genesis of such rocks. Current in- ing in part on the nature of the original organic material
vestigations of eastern black shale, particularly the and in part on subsequent burial history. Minor
Chattanooga Shale and its correlatives of Late Devo- amounts of authigenic carbonate minerals, either dis-
nian and Mississippian ages, as a source of gas (Schott persed in cements or in concretions, are characteristic
et al., 1978) are producing a new generation of data; features of many black shale units. Most black shales
and the time is appropriate to review the processes in- are marine and may have areal extents of thousands of
volved in the accumulation of black shale. Recently, square kilometers.
data from deep-sea drilling, such as the composition of Black shale units may have beds enriched in metals
pore fluids, and new methods applied to the studies of by factors greater than 50 for Ag, for example, and
organic matter and the formation of oil and gas have greater than 10 for Mo (Krauskopf, 1955, p. 417). Such
clarified many aspects of the deposition and diagenesis increased concentrations of Ag, Mo, Zn, Ni, Cu, Cr,
of organic-rich sediments. V, and less commonly Co, Se, and U are conspicuous
This paper summarizes the work of many specialists features of only some black shales (Vine and Tourtelot,
with emphasis on guides to the study and interpretation 1970, p. 270).
of black shale sequences. IMPORTANCE OF BLACK SHALE
D E F I N I T I O N OF BLACK SHALE Black shales are important to the natural fuel-re-
Black shale is a dark-colored mudrock containing source economy of the world because black shales,
organic matter and silt- and clay-size mineral grains along with their nonmarine analogue, coal, constitute
that accumulated together (Swanson, 1961, p. 69). Vine the most important accessible reservoir of organic com-
pounds in the Earth's crust. The organic matter may
1 Invited paper at 1978 Clay Minerals Conference, Bloom- have generated liquid and gaseous hydrocarbons found
ington, Indiana. in reservoir rocks in the subsurface into which they

Copyright 9 1979,The Clay MineralsSociety 313


314 Tourtelot Clays and Clay Minerals

have migrated. Recently, however, the potential of MILLION I


YEARS
PERIOD NORTH SOUTH
AMERICA AMERICA EUROPE
SIBERIA &
CENTRAL AFRICA
AUSTRALIA
ASIA g ASIA
black shale itself as a reservoir for gaseous hydrocar- QUATERNARY
Oe 9149 00
bons has been recognized, and this potential is being g TERTIARY

explored intensively. Estimates of the gas content of CRETACEOUS ~ 0 9 9 ~ I 9149


the Chattanooga Shale, for instance, range from tens --135-
el@
to thousands of trillion cubic feet (U.S. Dept. of Ener- JURASSIC 9 US
--19a-
gy, 1977, p. 99; Brown, 1976, p. 94). TRIASSIC 9149

Hydrocarbons also can be obtained by pyrolysis


PERMIAN 9
from thermally immature black shale. Increasing atten- --280-
'ENNSYLVANIAN QelO 9 ~9
tion will be given to this possibility as demands increase
--320- MISSISSIPP[AN
and supplies from conventional sources dwindle. - - 345 -
DBVONIAN
eeoeeo
OO
coo 9149149 9

Black shale units also are important as syngenetic --395-


SILURIAN N ~ 9
hosts for metal deposits. The Kupferschiefer of Perm- --435-
ian age in central Europe is a spectacular example of ORDOVICIAN 9149 9 9 9

a metal-enriched black shale, containing a few percent --5oo-

Cu and Pb. Recent lead-isotope data clearly indicate CAMBRIAN @ Qe 9

that the metals in the Kupferschiefer were incorporated


syngenetically in the shale (Wedepohl et al., 1978). The
L
lead-zinc deposits at Rammelsberg in West Germany
?--___? . . . . . . .
are in organic-rich rocks of Devonian age and have a
similar origin. The Nonesuch Shale of Proterozoic age Figure 1. Distribution of black shale units in time and space.
has been mined for copper in Michigan (Ensign et al., Filled circles indicate occurrences. Compiled from Tourtelot
(1970) and Fulton (1977). Occurrences differ greatly in areal
1968, p. 464), and at least part of the copper is synge- extent, thickness, and other characteristics.
netic. Oklo, the natural nuclear reactor and uranium
deposit in Africa, may represent a maximum concen- gets such wholesale returns of conjecture out of such
tration of uranium in which the black shale involved a trifling investment of fact" (Clemens, 1874, p. 136).
may have played an important role in localizing the de-
posit and in retaining fission products (Brookins, 1976). DISTRIBUTION OF BLACK S H A L E IN
In Sweden, alum shales of Cambrian age containing TIME AND SPACE
about 14% organic carbon have been used as a source Figure 1 was compiled chiefly from the bibliography
of pyrolytic oil and uranium (Armands, 1972). on black shale prepared by Tourtelot (1970), but the
Only a few metal deposits have been found in black record of some occurrences was taken from Fulton
shale units in the United States, but others have not yet (1977). The symbols do not have equal significance: for
been sought systematically. The rich deposits of Ram- instance, the Chattanooga Shale in the Appalachian re-
melsberg occupy less than a square kilometer (Anger gion and the Houy Formation in Texas are each count-
et al., 1%6). It is still possible that the rocks in a similar ed as a single occurrence among black shales of Late
small area of the Chattanooga Shale, for instance, are Devonian and Mississippian ages in North America de-
rich enough in metals to constitute an ore deposit. Oth- spite the great disparity between their areal extent and
er metal-rich black shales may eventually serve as thickness. The figure indicates that black shale units
metal sources whenever normal sources are depleted have formed commonly throughout most of the history
(Davidson and Lakin, 1961, 1962; Vine and Tourtelot, of the Earth and in many places. Black shale units are
1970). being found also in the ocean basins now being explored
Metals concentrated syngenetically in a black shale by drilling (e.g., Gardner et al., 1977; Dean et al., 1977;
unit either survive metamorphic processes to be re- Hallam, 1977; Kerr, 1978). This wide geographic dis-
tained in graphitic schists (Gammon, 1966; Peltola, tribution of black shale occurrences in itself suggests
1%8) or are released by metamorphic processes to be that a range of geologic settings must be suitable for the
concentrated elsewhere (Boyle, 1968, p. 838). Con- accumulation of black shale.
versely, black shale units might be receptor beds for The organic material that gives black shale its dis-
metals released in hydrothermal or metamorphic sys- tinctive characteristics is derived from living things.
tems. Exploration strategies in the search for metal de- Since black shale has accumulated throughout the en-
posits are beginning to be based on these concepts (Cox tire evolution of life on the Earth, the composition of
and Curtis, 1977; Gulson, 1977). the organic matter in a black shale should reflect evo-
Lastly, black shale units seem to excite greatly the lutionary development of living things at the time the
intellectual curiosity and imagination of the people in- shale was deposited. The importance of biochemical
vestigating them. There is something fascinating about studies of different stages of evolving life, particularly
black shale: as Mark Twain said about science, "One plant material as preserved in black shale, was pointed
Vol. 27, No. 5, 1979 Black shale--its deposition and diagenesis 315

out by Woodring (1954), but systematic studies still RESTRICTED CIRCULATION MODEL
0 2 CONTENT OF WATER NOT RENEWED BY CfRCULATION
have not been made, and the significance of the evo- 0 2
DEPTH CONCENTRATION WATER C O L U M N DEPTH CHARACTERISTICS
lutionary stage of life available to provide organic ma- (METERS) ,e...___. IN CIREASES
~%N% X% ~ ~NNN ~ PHOTIC ZONE
terial to a black shale has been largely overlooked. F o r / SOME ~NPUT
FROM LAND ~
ORGANIC MATTER
LARGELYRECYCLED
pHOtOSyNTHESIS AND PeODUCTION
PROOUCTIO
OF ORGANICMATTER)
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
example, land plants did not evolve until the Late Si- 80 . . . . ~.~-- ~ 02 COMPLETELY EUMtNATED BY DISPHOII C AND APHOTIC ZONES
OX~t~,~ON C~ SEdatiNG
lurian (Arnold, 1969, p. 129). The organic matter in ORGANIC MATTER (OXIDATIONAND DEGRADATION
OF ORGANICMATTER)
black shales older than that must therefore be derived
from aquatic plants and simpler life forms. The param- e\
\
eters widely used to indicate the " m a r i n e n e s s " or \ ~ H2S DIFFUSESI N T O WATERFROM
"nonmarineness" of depositional environments, such >~00
\ \. \ \ x \ \ \ \~, ZONE OF DIAGENESiS
. . . . . . . . . . . . . . j
~INCIREASESH.~ J= __ -- ZONE OF DtAGEN$1S
as the hydrogen content of kerogen (Breger and Brown, H2S
CONCENTRATION
1962) or carbon isotopic composition, may be mislead-
ALL O R G A N I C MATTER SETTLING PAST LEVEL OF ZERO 0 2
ing or invalid if the interpretation is based primarily on CONCENTRATION ACCUMULATES O N THE BOTTOM

analogies with the present. The assumption that geo- Figure 2. Restricted circulation model for accumulation of
chemical effects of metabolic processes have been the organic-rich sediments. Modified from Didyk et aL (1978).
same from the beginning as they are now probably is
not wholly correct.
In geosynclinal settings, the shales of Paleozoic age
GEOLOGIC SETTINGS OF BLACK SHALE form thick deposits the paleogeography of which is not
DEPOSITION easy to reconstruct because of complex later tectonic
The geologic settings of typical black shales were history. Black shale in the Phosphoria Formation is the
classified by Vine and colleagues in very broad terms only one of the geosynclinal shales that is enriched in
(Vine and Tourtelot, 1970) that can be further gener- metals (Vine and Tourtelot, 1970). The Phosphoria For-
alized into geosyncline, cratonic basin, and shelf, as mation itself is unusual among sedimentary rocks be-
shown in the following table (asterisks indicate metal- cause of its enrichment in P. The paleogeography of the
rich units): cratonic basin shales also is difficult to reconstruct.
Geosyncline Permian Western Rocky None of those studied by Vine and Tourtelot (1970) are
Mountains (Phos- enriched in metals. The black, carbonate-rich shale in
phoria Forma- the Paradox Formation is unusual because of its asso-
tion*)
ciation with evaporites.
Upper Paleozoic SW Midcontinent
Classification of a shale as having been deposited in
Lower Paleozoic SW Midcontinent
a shelf setting probably would vary from one person to
Cratonic Basin Pennsylvanian Colorado another. All the deposits included here, however, can
Utah (Paradox For-
mation evapo- be viewed broadly as being transgressive. One group
rites) includes those deposited in settings in which marine
Pennsylvanian- Montana and nonmarine deposition alternated. The other group
Mississippian includes shales that seem to be entirely marine in their
Upper Missis- Wyoming associations.
sippian More examples of metal-enriched shales are found
Shelf Pennsylvanian Midcontinent (Mec- among those deposited in the shelf setting than in other
(Alternating ca Quarry Shale settings, but there still is a puzzling variability between
Marine and Member* of
Nonmarine) some of the shales in the shelf setting. F o r instance, the
Linton Forma-
tion) (Zangerl and Pennsylvanian Mecca Quarry Shale Member (Zangerl
Richardson, 1963) and Richardson, 1%3) of the Linton Formation is the
Midcontinent (other only one in the Midcontinent region that is enriched in
similar shales) metals. Other marine shales of the same age and lith-
Proterozoic Michigan (None- ologic associations in the Midcontinent region are not
such Shale*)
(Entirely Marine) enriched in metals. Other metal-enriched shelf shales
Cretaceous Western Interior are the Nonesuch Shale of Proterozoic age and shales
Texas of Devonian and Mississippian ages.
Pennsylvanian Kansas (Tacket The interesting metal content of enriched shales is
Formation) (Jew- clearly related to the amount of organic matter in the
ett et al., 1965) shales. Trace metal adsorption, sulfate reduction, and
Devonian- Appalachian sulfide precipitation are the chief processes involved
Mississippian Region*
Midcontinent* (Swanson, 1961; Tourtelot, 1964; Vine and Tourtelot,
Texas* 1970). A large content of organic matter does not nec-
Rocky Mountains* essarily identify a metal-rich shale. Other factors to be
316 Tourtelot Clays and Clay Minerals

OPEN OCEAN MODEL CONTINENTAL SHELF MODEL


0 2 CONTENT OF WATER CONTROLLED BY CIRCULATION 0 2 CONTENT OF WATER CONTROLLED BY ATMOSPHERIC EXCHANGE
02
DEPTH CONCENTRATION WATER COLUMN DEPTH CHARACTERISTICS 02 WATER COLUMN DEPTH CHARACTERISTICS
DEPTH C O N C E N T R A T I O N
(METERS/ ~ INCREASES
IMETERSI ~ INCREASES
~%
f
N~N~ SOME INPUT
~ PHOTIC ZONE
ORGANIC MATTER ,~,AO~OS,fNT~ESISAND ~RODUC31
~DUC310N
----'~..,~,~ FROMLAND ~ LARGELY RECYCLED OF ORGANIC MATTER)
ER)
80 . . . . . . . . . . . . . . . . . . . . . . . . .
O 2 MINIMUM CREATED BYOX*DATION . . . . . DISPHO~IC~Z~N~-- -- - - ~
() OF SETTLING ORGANIC MATTER DISPHOTIC ND AP~OTIC
AND AP~OTIC ZONE!
ZONES
AN~ DEGRADATIO~
(OXIDATtON AND DEGRADATION
OF ORGANIC MATTER)
I ALL ORGANIC MATTER NOT RECYCLED ACCUMULATES ON BOTTOM
I
I Figure 4. Continental shelf model for accumulation of or-
I ganic-rich sediments. Modified from Didyk et al. (1978).
I
>soo I
ZONE OF DIAGENESIS

ANY ORGANIC MATTER NOT SUSCEPTIBLETO FURTHER OXIDATION The restricted circulation model is discussed first be-
ACCUMULATES ON BOTTOM
cause it represents the classic view, and unfortunately
Figure 3. Open ocean model for accumulation of organic- often the only view, of the accumulation of organic
rich sediments. Modified from Didyk et al. (1978).
material in ancient rocks (Figure 2).

R e s t r i c t e d circulation m o d e l
considered include the nature of the organic material
and its metal content, the nature of sediments and water The significant feature of the restricted circulation
in the source areas, volcanic ash, and submarine vol- model is that the oxygen content of the water column
canic exhalations. is not renewed by circulation so that organic-rich sed-
The abundances of some elements are related to iments can accumulate even if organic productivity is
those of other constituents of black shales. The con- relatively small. Organic material is produced by pho-
tents of Si and A1 obviously are related to the abun- tosynthesis in the photic zone, mixed with some organ-
dance of detrital minerals, and the Sr content is related ic material from land if terrestrial plant life exists, and
to the abundance of diagenetic carbonate minerals. is largely recycled in the photic zone by chemical and
Vine and Tourtelot (1970) discussed the complexities biological processes such as "bigger things eating littler
of these and other relations between elemental com- things." The oxygen content of the water may increase
positions and mineral or constituent abundance. towards the bottom of the photic zone because of pho-
The fact that black shale has accumulated in a wide tosynthesis, but at some point it is completely con-
range of geologic settings implies that geologic setting sumed by the oxidation of the settling organic material.
such as geosyncline or shelf is not of prime importance The oxygen depletion did not exist a priori, but was
in the formation of black shale deposits compared to caused by the large oxygen demand of the decomposing
what goes on in these settings. Features of depositional organic material itself. All the organic matter that set-
environments within geologic settings, such as organic tles below the level of zero oxygen content accumulates
productivity, sedimentation rates, and availability of on the bottom where it can be removed only by anaer-
oxygen, are the important factors in controlling the de- obic decomposition. Hydrogen sulfide generated in the
position of the sediments that form black shale. bottom sediments may diffuse into the overlying water
mass. Both the sedimentational environment and the
DEPOSITIONAL ENVIRONMENTS sediments are anoxic.
The range of depositional environments in which This situation prevails because there is too little cir-
black shale may accumulate can be described by three culation in the water mass to supply oxygen at a rate
models shown in Figures 2, 3, and 4. The formulation fast enough to equal or exceed the oxygen demand of
of these models stems directly from similar appearing the available organic material, ff enough organic ma-
diagrams presented by Didyk et al. (1978). They placed terial is produced in the photic zone, considerable
great emphasis on the chemical characteristics of the amounts of oxygen could be supplied and organic mat-
environment per se, such as the distribution of oxygen ter still would accumulate in the bottom sediments.
and hydrogen sulfide in the water column and sedi- The restricted circulation model is represented in
ments. Here, however, the role of the amount of or- part by the Black Sea (the type euxinic setting: see
ganic material in relation to oxygen supply is empha- Goldhaber, 1978) or Norwegian and other l]ords, which
sized. An abundance of organic material depletes provide good modern examples of the chemical and
oxygen and creates the conditions under which organic- sedimentational processes outlined above. Organic-
rich sediments can accumulate. Similarly, hydrogen rich deposits will accumulate in such restricted basins,
sulfide is produced under the conditions caused by the including basins formed tectonically such as the Car-
accumulation of organic material, which favors the fur- ioco trench or those off the California coast, unless the
ther accumulation of organic material. The accumula- rate of organic productivity in the photic zone above
tion of organic material is a cause of conditions, not an them is low. However, concepts of t]ords and tectonic
effect. basins cannot be applied to the origin of widespread
Vol. 27, No. 5, 1979 Black shale--its deposition and diagenesis 317

black shale units because of the contrast in area and the son, 1961). This model, like the open ocean model, does
definite morphologic characteristics of such basins. not require any a priori conditions such as a restricted
basin, density stratification, hydrogen sulfide in the
Open ocean model
water, or other characteristics based on analogies with
In the open ocean (Figure 3), the oxygen content of the Black Sea.
the water may be controlled primarily by circulation,
but it is also strongly influenced by the amount of or- R E L A T I V I T Y O F FACTORS IN
ganic material that escapes from the photic zone and DEPOSITION
settles through the water column. The oxygen mini- Different relations between rates of clasfic sedimen-
mum, just below the photic zone, is created by the ox- tation, organic productivity, and the intensity of oxi-
idation of organic material. Some of the more resistant dation result in similar kinds and, perhaps, similar
organic material settling past the oxygen minimum may amounts of black shale being deposited. Organic pro-
undergo no further degradation en route to its accu- ductivity is controlled chiefly by the availability of nu-
mulation on the bottom. Settling rates too rapid for ox- trients, although other factors such as temperature, sa-
idation of organic particles to be complete can be linity, and water clarity also are involved. In trying to
caused by incorporation of organic material in fecal understand the reasons for the distribution of black
pellets or by aggregation with mineral particles, even shales in time and space, the fundamental concept to
if the organic compounds are susceptible to oxidation. be kept in mind is that organic-rich rocks result when
Organic-rich sediments thus can accumulate even and where organic material accumulates because it is
though the sedimentational environment is completely produced faster than it can be destroyed.
oxic. In any event, the sediments themselves will be-
come anoxic a few millimeters below the sediment sur- ZONES OF D I A G E N E S I S
face because of bacterial processes and the slow re- The characteristics of the environment in which
plenishment of dissolved oxygen by diffusion below black shales were deposited are more or less imaginary
any zone of burrowing that is present. in the sense that the characteristics have to be deduced
The balance between organic productivity and avail- from very few data of uncertain significance. In con-
able oxygen can shift because of changes in patterns of trast, the zones of diagenesis can be fairly well defined
surface currents in response to tectonic events distant on the basis of data on pore fluids and sediments from
from the depositional site. Or, the depositional site deep-sea drilling, laboratory experiment, and theoret-
might be carried by seafloor spreading (in the case of ical considerations. In addition, most of the products
younger rocks) from an area of low organic productivity of diagenetic processes remain in the rocks and provide
tO cne of high productivity and then to an area of low a record that can be deciphered. It is important to rec-
productivity again (e.g., White, 1979). The sediments ognize the products of diagenesis so that data on them
deposited beneath the area of high productivity could are not used misleadingly in the interpretation of con-
be rich in organic matter and form black shales without ditions of deposition.
there necessarily being an anoxic event in the sense of Krumbein and Garrels (1952) made clear the role of
the formation of a barred basin or the cessation of cir- pH and oxidation-reduction potentials in influencing
culation. rock compositions during diagenesis. Postdepositionat
(diagenetic) changes during the accumulation of sedi-
Continental shelf model
mentary rocks had, of course, been recognized earlier
The continental shelf model (Figure 4) contains the (Krumbein, 1942). Later, Berner (1964) explored iron
same input factors as the other models, but there is little and sulfur reactions in early diagenesis. Since then,
or no water between the photic zone and the bottom. diagenetic processes have been widely studied. The fol-
Organic material is recycled in the photic zone to a less- lowing discussion is based on four principal papers
er extent because of more rapid settling to the bottom. (Claypool and Kaplan, 1974; Curtis, 1977; Goldhaber
The concentration of oxygen in the water may remain and Kaplan, 1974; and Irwin et al., 1977) that review,
large down to the top of the accumulating sediment be- with some differences in emphasis, the processes of
cause of circulation and the production of oxygen in the diagenesis of sedimentary rocks containing organic
photic zone. In this setting also, the sediments become matter.
anoxic a very short distance beneath the surface be- Figure 5 represents a sequence of diagenetic zones
cause of bacterial processes. with depth at a particular point in time. The rocks in the
This kind of sedimentational environment has been zone of hydrocarbon formation already have passed
deduced for several transgressive black shales in North through all of the overlying zones. If sedimentation
America, such as those in cyclothems of Pennsylvanian continues, the sediments in the present zone of sulfate
age (Zangerl and Richardson, 1963) and the black shales reduction can be expected to pass sequentially in order
of Devonian and Mississippian ages (Conant and Swan- through the underlying zones. The ultimate nature of
318 Tourtelot Clays and Clay Minerals

the rocks will depend chiefly on the maximum pressure DEPTH TEMP POROSITY
(KM) (~ (%) D I A G E N E T I C ZONES A N D PRODUCTS
and temperature that they reach during their burial his- 0
tory. 0.01- -~- =0-----80 - SULFATE R E D U C T I O N
PYRITE, CARBONATES (I 2C ENRICHED)
The diagram is only a model, and the boundaries be- PHOSPHATES
tween the zones are not sharply defined. The depths, _-.- FERMENTATION
METHANE, CARBONATES (13C ENRICHED
temperature, and porosity may not be generally agreed
to. The numbers in themselves are not important com- 1- - - - - - 3 0 - - - - - 30 - -
DECARBOXYLATION
-2-_-- SIDERITE
pared to the sequence of zones downwards. In an or- -~--Z
ganic-rich sediment, a zone of oxidation at the top of 2--
the sediment column may be absent, thin, or, if present, "------70 -----20-
HYDROCARBON FORMATION
the accumulating organic material may pass through it 3-- LIQUID AND GASEOUS HYDROCARBONS
:'-..2-." PYROCATALYT{C METHANE
so rapidly as to be little affected. A zone of oxidation 4- "2-- MONTMORILLONITE ~ILLITE
is not shown on Figure 5, but its presence can be im-
5--
portant because in it any remaining free oxygen in the ? i--- - 1 9 0 - - - - - - 1 0 -
pore water is eliminated, a necessary condition before METAMORPHISM
VARIOUS MINERALS
GRAPHITE
anaerobic sulfate-reducing bacteria can live. In addi- RECRYSTALLIZAT{ON
tion, aerobic bacterial oxidation of part of the organic
Figure 5. Zones ofdiagenesis. Modified from Curtis (1977).
material may increase the abundance of compounds A zone of oxidation may or may not be present at top of sed-
that serve as a utilizable substrate for the sulfate-re- iment column: see text.
ducing bacteria. The thickness of both the zones of ox-
idation and sulfate reduction depends on the extent of
diffusion of oxygen and sulfate into the sediments from
the overlying waters. The reduction of sulfate results that could not be reduced under the milder conditions
in the formation of pyrite. of the overlying zones.
In both the zones of oxidation and sulfate reduction, The remaining organic matter presumably is different
the carbon dioxide formed is very light in carbon-iso- in composition than it was when the containing rocks
tope composition. Carbonate minerals in cements or entered the zone of decarboxylation. Such differences
concretions formed from such carbon dioxide would have not been detected, perhaps because rocks that
also be very light. have entered the zone of decarboxylation but gone no
In the zone of fermentation, methane is produced by further have not been recognized.
the bacterial reduction of carbon dioxide. This process The gradation from the lower zone of decarboxyla-
begins when all available sulfate has been reduced. The tion into the upper part of the zone of hydrocarbon for-
bacterial population must be a mixed one containing not mation is particularly broad. Pyrocatalytic formation
only methane-producing bacteria but also other bac- of methane, for example, can begin at about 50~ b u t
teria capable of producing carbon dioxide. The fermen- large amounts may not be produced until much higher
tive production of biogenic methane causes a large frac- temperatures are reached. The carbon in pyrocatalytic
tionation of the carbon isotopes although the nature of methane has a 6C '3 more positive than that in biogenic
the fractionation process is not well understood. Bio- methane. Organic composition, vitrinite reflectance,
genic methane having the expected very light carbon- and the color alteration index of conodonts are all
isotope composition is being produced commercially promising tools for defining the characteristics of this
from rocks of Cretaceous age in eastern Montana where hydrocarbon zone that has such great economic im-
the fermentation zone represents the zone of greatest portance. This is also the zone in which montmorillo-
diagenesis yet reached by the rocks (Rice, 1975). nite is converted into illite through several successive
Ferroan dolomite, ankerite, and siderite are the car- intergrades. The expelled water is a potential force for
bonate minerals likely to be deposited in concretions driving the migration of liquid hydrocarbons. Such ex-
and cements because of the depletion of sulfate and pelled water may also carry metals that can be depos-
complete reaction of sulfide. Iron carbonate does not ited in favorable sites within a black shale, e.g., Cu re-
form in the presence of dissolved sulfide except under placing Fe in pyrite (Tourtelot and Vine, 1976, p. C26).
unusual circumstances.
With increasing temperature and depth of burial as R E L A T I V I T Y O F FACTORS IN
sedimentation goes on, the rocks reach the zone o f d e - DIAGENESIS
carboxylation where the organic matter begins to de- Temperature, pressure, and time are the chief factors
compose by chemical instead of biologic processes. that control what goes on in each successively deeper
The carbonate mineral deposited is likely to be siderite, zone of diagenesis. The relations between diagenetic
perhaps with a mixed composition, because the higher factors can be viewed in the same way as the relations
temperatures promote the reduction of iron compounds of depositional factors. Diagenetic factors may vary
Vol. 27, No. 5, 1979 Black shale--its deposition and diagenesis 319

regionally within a black shale of great areal extent. The parameters must be taken into account in interpreting
eastern extent of a black shale unit, as a general ex- data on the chemical and mineralogic composition of
ample, may reach a more advanced zone of diagenesis black shales.
than the western extent because of greater burial from
thicker overlying rocks, tectonism, or igneous intru- CONCLUSIONS
sions. Variation of this kind is indicated by the distri- In any depositional setting, rates of clastic sedimen-
bution of conodont color alteration indices shown by tation and organic productivity and the intensity of ox-
Harris et al. (1978). The relations of diagenetic factors idation are the primary controls for the accumulation
can vary between shales, also. A shale of Tertiary age of organic material.
at a depth of 3-5 km in a region of large thermal gradient In zones of progessive diagenesis, the mixture of or-
may have had most of its original montmorillonite ganic matter and clastic sediment is operated on in rath-
transformed to illite. Another shale of Cretaceous age er predictable ways by biologic and chemical processes
in a region of small geothermal gradient may still retain controlled chiefly by temperature, pressure, and time.
its original montmorillonitic composition even though The separate products of the processes operating in
at some time during its history it has been buried to a the depositional environment and in the zones of dia-
depth of 10 km. Given equal burial depths and thermal genesis should be clearly distinguished to avoid mis-
gradients, mineral transformations may have gone fur- leading interpretations of either setting.
ther in a shale of Paleozoic age than in one of Mesozoic The factors influencing both the amount and com-
age, simply because of more time having passed. It thus position of organic matter in a black shale can be ex-
seems likely that a moderate range of relations between pressed in an equation of the form sometimes derisively
pressure, temperature, and time can yield the charac- stated as " s o m e of it plus the rest of it equals all of it,"
teristics of a given diagenetic zone. This relativity of as follows:

BLACK DEPOSITIONAL ZONE OF DIAGENESIS


SHALE ENVIRONMENT
[Oxidation )
Organic ~Organic ~ ]Sulfate reduction ~Migration]
matter = [productivity - Oxidation) - ] F e r m e n t a t i o n + of
| Decarboxylation - l productsl
[Pyrocatalytic reactions

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Vol. 27, No. 5, 1979 Black shale--its deposition and diagenesis 321

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Resfimee---Schwarzschieferist ein dunkler Schieferton, der organische Substanz enth~ilt, die durch Uber-
lagerung oder dutch Pyrolyse Kohlenwasserstoffebilden kann. Vide Schwarzschieferschichtenzeigen eine
Anreicherung an Metallen, sodal3 ihre Metallgehalte um einiges h6her liegen als die der fiblichen Schiefer.
Einige Schwarzschieferschichten dienten als Muttergestein ffir syngenetische Metallablagerungen.
Schwarzschiefer wurden w~ihrend der ganzen Erdgeschichte und/iberall auf der Erde gebildet. Daraus
folgt, dab geologische Prozesse, nicht geologische Gegebenheiten die ausschlaggebenden Faktoren f/Jr die
Ablagerung yon Schwarzschiefer sind. Diese geologischen Prozesse sind die Ablagerung, dutch die das
Ausgangsmaterial f/Jr den Schwarzschiefer sedimentiert wurde und die Diagenese infolge der zunehmenden
Uberlagerung.
Ablagerungsprozesse werden durch die Einwirkung mehrerer Faktoren beeinfluBt, wie z.B. organische
t~itigkeit, Absatzgeschwindigkeit klastischer Sedimente, und Intensit~it der Oxidation, dutch die organ-
isches Material zerst6rt wird. Schwarzschiefer entsteht, wenn genfigend organisches Material vorhanden
ist, um den Sauerstoff der Umgebung zu verbrauchen.
Diagenetische Prozesse beinhalten chemische Reaktionen, die durch die Art der Komponenten sowie
dutch die herrschenden Druck- und Temperaturverhiiltnisse kontrolliert werden, die durch zunehmende
Uberlagerung entstehen. Denn unter einer Uberlagerung yon einigen Metern wird Sulfur reduziert, und
Sulfidminerale k6nnen abgelagert werden. Fermentationsreaktionen in den n~ichsten hundert Metern fiihr-
en zur Bildung von biogenem Methan. Ihnen folgen mit zunehmender Tiefe nach und nach Decarboxyli-
erungsreaktionen und thermische Alterung, die weitere Kohlenwasserstoffe bilden. Abfolgen von neu ge-
bildeten Mineralen sind charakteristisch ffir jede der Diagenesezonen.

R6snm&--L'argile shisteuse noire est une roche argileuse fonc6e contenant de la mati~re organique
qui peut avoir g6n6r6 des hydrocarbones dans le sous-sol ou qui peut donner des hydrocarbones par
pyrolyse. Beaucoup d'unites d'argile shisteuse noire sont enrichies de quantit6s de m6taux plusieurs
fois plus importantes que celles aux quelles on s'attendrait dans l'argile shisteuse ordinaire. Certaines
unitds d'argile shisteuse noire ont servi de roches h6tes pour des d6p6ts de m6tal syng6n6tique.
Les argiles shisteuses noires ont 6t6 form6es tout au long de l'histoire terrestre et dans routes les
parties du monde. Ceci sugg~re que ce sont des proc6des g6ologiques et non des lieux gdologiques
qui sont les facteurs controUants duns l'accumulation de l'argile shisteuse noire. Les proced6s geologiques
sont: la deposition par laquelle les mati&es premieres d'argile shisteuse sont accumul6es et la
diag6n~se r~pondant a une profondeur d'enterrement croissante.
Les proced6s de deposition comprennent une 6tendue de relations entre des facteurs tels la productivit6
organique, la vitesse de s6dimentation clastique et l'intensit6 d'oxidation par laquelle la mati~re organique
est d6truite. S'il ya assez de matibre organique pour epuiser l'oxygbne de Fenvironnement, il en r6sulte
une argile shisteuse noire.
Les proc6d6s diagen6tiques comprennent des r6actions chimiques contr61ds par la nature des
composants et par les r6gimes de pression et de temp6rature impos6s par l'enterrement continuel.
A une bpaisseur de quelques m~tres sous la surface, la sulphate est reduite et des min6raux sulphides
peuvent ~tre d6pos6s. Les r6actions de fermentation duns les prochaines centaines de m~tres resultent
en de la m~thane biog6nique, suivie successivement ~ de plus grandes profondeurs de r6actions d e
d6carboxylation et de maturation thermale qui forment d'avantage d'hydrocarbones. Des suites de
min~raux nouvellement form6s sont caractbristiques de chacune des zones de diag6n6se.