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Sedimentary pyrite formation: An update*

ROBERTA. BERNER
Department of Geology and Geophysics, Yale University, New Haven, Connecticut 065 I I

(Received November 7, 1983; accepted December 5, 1983)

Abstract-Sedimentary pyrite formation during early diagenesis is a major process for controlling the
oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount
of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter,
dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on
pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron
minerals are abundant. By contrast, pyrite formation in non-marine, freshwatersediments is severely limited
by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh
water shales from marine shales. Under marine euxinic conditions sufficient HIS is produced that the
dominant control on pyrite formation is the availability of reactive iron minerals.
Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average
organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High C/S ratios during
Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the
land which resulted in the formation of vast coal swamps at that time. Low C/S ratios, compared to today,
during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined
with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the
ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of
refractory terrestrialorganic matter to the marine environment due to the absence of vascular land plants
at that time.

INTRODUCT’ION some assurance, that we know something about how,

THIRTEEN YEARSago I published a paper (BERNER,
1970) entitled Sedimentary Pyrite Formation in which
I tried to summarize what was known about this pro-
cess at that time. Since then much has transpired on
the subject (e.g.-see SWEENEY,1972; GOLDHABER
and KAPLAN, 1974; ROZANOVet al., 1974; RICKARD,
1975; G~LDHABERet al.. 1977; BERRYand WILDE,
1978; RLIPEK and OWEN, 1980; HOWARTH, 1979;
BERNER,1982; LEVENTHAL,1983; WESTRICH,1983;
LORDand CHURCH,1983; RAISWELL,1982; ARTHUR,
1983; BERNERand RAISWELL,1983) and I feel that
it is time to update what we know and don’t know
about pyrite formation. Knowledge of how pyrite forms
is important to a variety of fields. For one thing it is
becoming apparent that burial of pyrite in sediments
is a major process in controlling both the oxygen level
of the atmosphere (e.g. GARREL~ and PERRY,1974)
and the sulfate concentration of seawater (HOLLAND,
1978) over geologic time. The importance of pyrit-
iferous black shales to earth history has been recognized
as evidenced by a symposium devoted to this very
subject at the current Geological Society of America
meeting. Also, it is not generally realized that most
marine sediments and sedimentary rocks contain at
least traces of pyrite (RONOV, 1976; BERNER, 1982)
because the bulk of the world’s mud is and was buried
under anoxic, sulfate-reducing conditions. Thus, pyrite
is a very widespread sedimentary mineral. It is one of
the few authigenic phases of which we can state, with
* Presidential Address to the Geochemical Society, No.
vemher 1983, Indianapolis, IN.
when, and where it forms.
In the present paper we will examine the major
controls on sedimentary pyrite formation in modem
sediments and, then, try to apply this knowledge to
the study of factors controlling pyrite formation and
organic carbon burial over Phanerozoic time; in other
words over the past 600-700 million years. It is hoped
by performing this exercise that we can demonstrate
the importance and applicability of modem sediment
studies to the study of ancient sedimentary rocks.
PYRITE FORMATION IN MODERN SEDIMENTE
The principal steps in the overall process of sedi-
mentary pyrite formation should be rather well known
to most readers. Pyrite forms during shallow burial,
via the reaction of detrital iron minerals with H$.
The HzS, in turn, is produced by the reduction of
interstitial dissolved sulfate by bacteria using sedi-
mentary organic matter as a reducing agent and energy
source. The initial product of this reaction is not, in
fact, pyrite but rather a series of metastable iron
monosulfides which during early diagenesis readily
transform to pyrite under most conditions, (but by a
process that is rather poorly understood). This is all
illustrated in Fig. 1. Note in Fig. 1 that the major
factors controlling how much pyrite can form in a
sediment are the amounts of organic matter and re-
active iron minerals deposited in a sediment, and the
availability of dissolved sulfate. In the following dis-
cussion we will examine each limiting factor in detail
and show how its relative importance changes from
one sedimentary environment to another.

605
 R. A. FJemer
FeS2
PYRITE
FIG. 1. Diagramatic representation of the overaIl process
of sedimentary pyrite formation. (After BERNER, 1972).
Bacterial suNate reduction; organic carbon
and dissolved sulfate
The first step in the overall process of sedimentary
pyrite formation is the bacterial reduction of sulfate.
This process occurs only in the absence of oxygen, in
other words, undet anoxic conditions. As noted above,
such conditions are realized in the majority of sub-
aqueous sediments because sufficient organic matter
is deposited to act as an oxygen-consuming barrier.
Dissolved oxygen migrates into the sediment from the
overlying water via molecular diffusion, wave and cur-
rent stirring, or bioturbational irrigation (for a dis-
cussion of these processes consult ALLER, 1980 or
BERNER, 1980) but is consumed by oxic bacteria, living
near the sediment-water interface, which use the ox-
ygen to convert organic matter to CO*. Rapid con-
sumption of all O2 near the sediment-water interface
prevents it from penetrating far into the sediment,
and, as a result, anoxic conditions, necessary for bac-
terial sulfate reduction, result below a depth normally
of a few centimeters. Thus, bacterially decomposable
organic matter is needed not only as a reductant for
sulfate (Fig. 1) but also as an agent for bringing about
anoxic conditions.
Bacterial sulfate reduction is a complex process and
proceeds via a variety of individual steps involving
such things as the breakdown of biopolymeric organic
matter to simple organic molecules by fermentative
micro-organisms, the utilixation of the simple mole-
cules by sulfate-reducing bacmria themselves, and the
further oxidation of organic reaction products (e.g.-
see JORGENSEN, 1982, for a detailed discussion). How-
ever, the overall process can be shown to be adequately
represented by the simple reaction (WESTRKH, 1983):
2CHz0 + SO; - HIS + 2HCO;
where sedimentary organic matter is represented by
the idea&d formula CH*O. (Proof of this stoichi-
omen-y, which is generally assumed by other authors,
is actually given by Westrich.)
As the above reaction shows. two factors which
should affect the rate of bacterial sulfate reduction are
the availability of dissolved sulfate and of organic mat-
ter. The effect of sulfate concentration in marine scd-
iments, taken from the work of WESTRICH ( 1983). is
shown in Fig. 2. Note that rate control by sulfate is
not important at concentrations above about 5 mM.
Since most pyrite forms at depths where sulfate con-
centrations are much higher (e.g.-see KAPLAN el ul..
1963), the effect of sulfate on sulfate reduction and
pyrite formation, in most marine sediments, is rela-
tively unimportant. This can be seen by comparing
Figs. 2 and 3, (The depth designated as R = f‘(S0,) in
Fig. 3 refers to that depth where dissolved sulfate has
dropped to a level sufficiently low to appreciably affect
the rate of sulfate reduction and. therefore, pyrite for-
mation.)
The major factor controlling the rate of bacterial
sulfate reduction in normal marine sediments (in other
words, those deposited in oxygenated bottom waters)
is the amount and especially the reactivity of organic
matter deposited in the sediment. The large drop in
sulfate reduction rate over the top 20 cm, shown in
Fig. 3, is due almost entirely to the progessive con-
sumption of reactive organic compounds during dia-
genetic burial. Proof of this is shown by the experi-
mental data of J. T. Westrich summarized in Fig. 4.
Freshly killed freeze-dried plankton were added, in
varying amounts, to a sediment which had been found
to exhibit low in-situ rates of sulfate reduction. Ad-
dition of the planktonic organic matter caused sulfate
reduction rate to increase considerably, and the amount
of increase was found to be directly proportional to
the amount of fresh planktonic carbon added. Use of
oxically degraded, as opposed to fresh, plankton re-
sulted in a similar relationship but with a lesser slope
response (Fig. 4). (Similar results were obtained from
.
-_!
/
I
-j
-._(
I
!
/
-1
I I
20 25
SOi-( mM)
FIG. 2. Plot of the rate of bacterial sulfate reduction (R),
measured using ‘3 tracer, vs. sulfate concentration for a lab-
oratory experiment using Long Island Sound sediment.
(Sachem site, S&lo0 cm depth). The line drawn through the
data points represents a best fit Linweaver-Burk plot for Mi-
chaelicMenten kinetics (Data from WESTRICH, 1983).
 Sedimentary pyrite formation 607

between sedimentation rate on the one hand, and or-

R (mM yr-‘)
0 20 40 60 00 100 ganic matter and pyrite contents on the other.
I I I I 1 The dominant control of organic matter on sulfate
SOL (mM) reduction and pyrite formation in modem marine sed-
iments is shown in Fig. 5. The positive slope between
organic carbon and pyrite sulfur with zero intercept
indicates the dependence of pyrite formation on or-
ganic matter. If a roughly constant proportion of Orig-
inally deposited organic matter is used to form pyrite,
then the remaining, unused organic matter should
correlate positively with pyrite as it does in Fig. 5.
(Incidentally, the amount of organic matter destroyed
to form pyrite is greater than that shown by the stoi-
(cm)” I__- ______ ___!T!!?04j___ chiometry of the CH20 reaction given above because
;;$(/ff .\ DEPTH I all H2S produced by bacterial sulfate reduction is not
precipitated as pyrite; up to 90% of the H2S is re-
oxidized to sulfate as shown by the work of IEIRGENSEN,
1978, and WESTRICH, 1983).
140 What has been said above concerning modem ma-
ic
rine sediments does not apply to modem freshwater
‘60- 0
SPY(pmol per gm)
500 sediments. The reason is that dissolved sulfate con-
centrations in freshwater are much less, on the average
several hundred fold less, than that found in seawater.
FIG. 3. Plots of dissolved sulfate (SO;), rate of sulfate re-
duction (R), and pyrite sulfur (!$,J (plus minor FeS and el- As a result sulfate is rapidly and totally consumed via
emental sulfur) VS.depth for sediments of Long Island Sound sulfate reduction at sediment depths of only a few
(FOAM site). The depth lab&d R = j&SO,) represents that centimeters, leaving behind little pyrite and much or-
where the level of dissolved sulfate has dropped to values low
enough to appreciably affect sulfate reduction rate-see Fig.
2. (Data from WESTRICH,1983).
450
I I I I I

0
400 - /,
studies of anoxically degraded organic matter.) This
shows that the reactivity of organic matter decreases
as the more reactive compounds are consumed and
that the less reactive compounds that survive (or are
formed during aging) bring about lower rates of sulfate
reduction.
The above results can be used to explain why bac-
terial sulfate reduction and pyrite formation are more
extensive in certain areas of the present-day ocean
than in others. Except for rare euxinic environments
(see below) practically all bottom waters contain dis-
solved oxygen; consequently, pyrite formation must
take place below the sediment-water interlace. In many
pelagic regions, sedimentation rates are very low and
organic compounds, representing the remains of ma-
rine organisms, are exposed to oxic destruction near
the sediment-water interface (and in the overlying water
column) for long periods, up to thousands of years.
As a result, only small amounts of very resistant organic
compounds support very little sulfate reduction, and
as a result, little pyrite forms. By contrast, in areas of
“OW 0
0 0.5 1.0 2.5
1
3.0
high sedimentation, especially in nutrient-rich waters OROARld’“, AD’,;“,
which bring about a high rate of organic matter pro- (mg/g)
duction and sedimentation, rapid burial enables rel- FIG. 4. Rate of sulfate reduction (R) vs. concentration of
atively reactive compounds and more organic matter added organic carbon for Long Island Sound sediment (NWC
in general to become available for bacterial sulfate site). (In the lab sulfate concentrations were maintained hi%
reduction at depth. Consequently, high levels of HIS by diffusiveexchange with overlying seawater.)Car&n added
both as fresh plankton and as the plankton-derived material
are attained and much pyrite forms. These consid- remaining after 72 days of oxic degradation. Data from Wr.s-
erations help to explain why there is a crude correlation TRICH(1983). (See also WE~TRICHand BERNER,1984).
 608 R. A. Bemer

gested (BERNER and RAISWELL.,1984) that the <‘IS

2’1-----1 method should be applicable also to other sedimentary

situations. For instance, recent unpublished work by
Paul Olsen at Yale has illustrated how C/S ratios can
be used to discern saline (high sulfate) vs. freshwater
(low sulfate) phases in ancient lake sediments. Likewise
% I5 -
the work of David Lawrence (also unpublished) has
S demonstrated the usefulness of C/S ratios in distin-
guishing freshwater from marginal marine Cretaceous
environments.

The role I$ iron in pyrite jormation

% organic C
FIG. 5. Plot of w&ht percent organic carbon (dry wt.) VS. seems to be the case in many normal marine sediments
weight percent pyrite sulfur for modem normal marine (non-
euxinic) sediments. Data points from BERNER (1982).Dashed-
line encloSeS many additional points summarized by LEV-
ENTHAL (1983) from the compilation of SWEENEY (1972)
and GOLDHABER and KAPLAN (1974). (Afier BERNER and
RAISWELL, 1983).
ganic matter. Thus (in contrast to marine sediments)
sulfate is the principal factor controlling pyrite for-
mation in freshwater sediments. This results in a rel-
ative lack of correlation of pyrite sulfur with organic
carbon, and high carbon to sulfur (C/S) ratios in such
sediments. This is shown for modem lake muds in
Fig. 6 and the results are probably also representative
of the sediments of fresh-water swamps.
The large difference in C/S ratios of organic-rich
modem marine and freshwater sediments suggests that
this ratio, measured on ancient shales, might serve as
a useful paleosalinity indicator. Data taken from pub-
lished results for Carboniferous shales, are shown in
Fig. 7 and it is clear that the C/S ratio is indeed a
useful parameter for distinguishing original deposition
under freshwater vs. marine conditions. We have sug-
In the above discussion it has been implied that
greater production of H2S, via bacterial sulfate reduc-
tion, simply means more pyrite formation, and this
where pyrite sulfur correlates positively with organic
carbon. However, pyrite formation is also limited by
the amount and reactivity of detrital iron minerals
added to the sediment. Apparently, in terrigenous ma-
rine sediments deposited under normal oxygenated
conditions, the iron minerals are sufficiently abundant
and reactive that they don’t pose a serious problem.
However, this is not the case for highly calcareous
sediments. In localities far removed from sources of
terrigenous clays or silts and where the sediments in-
stead consist almost entirely of calcium carbonate de-
rived from the skeletal debris of marine organisms,
there is insufficient iron to bring about appreciable
pyrite formation. (Calcareous skeletal debris is much
lower in iron than terrigenous material.) Even in the
presence of high organic matter concentrations and
abundant H2S, if the sediment is dominated by CaCO,,
the pyrite concentration is low. This is shown in Table
1 for the highly calcareous sediments of Florida Bay,
Florida, which are decidedly lower in pyrite sulfur
than those from a terrigenous locality in Long Island
Sound containing similar levels of organic matter
and H$i.

%
S

% organic C
FIG. 6. Plot of weight percent organic carbon vs. weight perocnt reduced sulfur for modem fresh water
lake sediments. Also, shown are data for normal marine sediments taken from Fig. 5. (After BERNER and
RAISWELL, 1983).
 Sedimentary pyrite formation
20
CARBON I FEROUS
,,T
MARINE
NON-MARINE
FIG. 7. Frequency distribution of C/S weight ratio for British Carboniferous marine and non-marine
sediments. Data from HIR~Tand KAYE(1971), PEARSON (1979) AMIN(1979), and SPEARS
(1981) (After BERNER and RUSWELL, 1984).
The amount and reactivity of iron minerals also
plays a major role in pyrite formation under euxinic
conditions. The word euxinic (derived from the Black
Sea whose ancient Latin name was Pontus Euxinus)
refers to sediments deposited in bottom waters which
are anoxic and contain HIS in place of Or. The anoxic
bottom waters result from strong density stratification
and the long-term isolation of these waters (stagnation)
from contact with the atmosphere (see the compilation
by DEGENS and Ross, 1974, for a further discussion
of Black Sea water chemistry). Under such conditions
relatively fresh planktonicallyderived organic material
becomes available for bacterial sulfate reduction. (This
contrasts with the extensive loss of more rapidly re-
active organic compounds under oxic conditions which
occurs in normal marine sediments.) As a result organic
accumulations are high, bacterial sulfate reduction is
extensive, and HIS builds up in the bottom water as
well as in the underlying sediments (e.g.-see SWEENEY
and KAPLAN, 1980).
Under euxinic conditions the reaction of HIS with
iron-minerals can occur both before and after burial,
even during sedimentation itself (e.g.-see LEVEN-
THAL, 1983). Thus, the amount of pyrite formed de-
pends more on the amount and reactivity of detrital
iron minerals, and less on the amount of locally de-
posited organic matter. Because of advection of sulfidic
bottom water, pyrite may form from HrS transported
laterally from organic-rich source localities and, thus,
there is no need for sulfate reduction and organic mat-
609
and AMIN
ter deposition to occur at the same exact place where
the detrital iron-minerals are deposited. In this way
appreciable pyrite can build up in euxinic sediments
in the presence of locally low concentrations of organic
matter. Also, in contrast to normal marine sediments,
appreciable pyrite can form where deposition rates are
very low. There is no problem with the long-term t-e-
moval of organic matter during slow deposition, which
inhibits pyrite formation in normal pelagic sediments,
because the oxic bottom water conditions which bring
this about are not present. In fact, very slow deposition
under euxinic conditions maximizes the amount of
pyrite formed, because slowly reacting iron compounds
are given more time for reaction with H#. In most
normal marine sediments slowly reacting iron minerals
are given insufficient time to react with HIS because
the source of the HrS, interstitial dissolved sulfate, is
rapidly exhausted with depth (for instance see Fig. 3).
These considerations suggest that pyrite sulfur in
euxinic marine sediments should exhibit a weaker cor-
relation with organic carbon contents, and, at low or-
ganic carbon concentrations, should be present in
higher concentrations, than those found in normal
marine sediments. These predictions are borne out by
actual observations as shown in Figs. 8 and 9. Present
day sediments of the deep portions of the Black Sea,
as well as many ancient euxinic shales, exhibit pyrite
sulfur concentrations which are relatively independent
of organic carbon concentrations and, which at low
organic carbon levels, are distinctly higher than those
found in normal marine sediments. (In some euxinic
sediments reactive iron positively correlates with or-
ganic matter and this gives an apparent correlation
between pyrite and organic matter-see below).
Regardless of the environment of deposition the
amount of pyrite formed in a sediment, except in highIy
calcareous ones, is almost never limited by the amount
of total iron deposited. Instead, pyrite content is con-
trolled by the reactivity of detrital iron minerals. The
most reactive fraction is made up of fine-grained hy-
drous ferric oxides formed via continental weathering,
 610
I I I I
I.0 2.0 3.0 4.0 5.0
% ORGANIC C
FIG. 8. EOt Of Weightpercent OrganicC&On vs. weight
percent pyrite sulfur for deep water (> 1500 m) cuxinic s#l-
iments of the Black Sea. For comparison the normal marine
regression line, taken from Fig. 1, is also shown. Black Sea
data from ROZANOV et al. (I 974). (Modified from BERNER
and RAIsWELL, 1983).
which normally occur as rust-colored coatings on other
mineral grains. Other less reactive sources of iron in-
clude that contained within clay minerals and that
present in unweathered primary minerals such as bio-
tite, pyroxenes, amphiboles, magnetite, and ilmenite
(for example see ROZANOV et al., 1974). Under euxinic
conditions a greater proportion of the less reactive iron
minerals are converted to pyrite, as discussed above,
but even here there is excess iron which does not react.
In studies of thousands of sediments and ancient rock
samples we and other workers have encountered very
few instances where all iron in the sediment has been
converted to pyrite. Instead, depending upon H2S lev-
els, iron mineral reactivity, and time for reaction, the
degree of pyritization of iron attains levels which are
distinctly less than 100%.
Chzcasionally normal marine and euxinic sediments
are encountered which exhibit positive correlations of
o Le Riche
A Raiswell
0 A
2 0
IT
1 I I I
0 I 2 3
FIG. 9. Plot of 96organic carbon vs. 7%total sulfur (mainly pyrite) for euxinic lower Lias (JurpFsic)Black
Ven Marls of England. (Apparently dilkrent values for the two sets of analyses due probably to different
analytical methods.) Euxinicity deduced on the basis of fine laminations and a lack of benthic fauna. Note
the lack of a positive correlation between pyrite and organic matter. (Data fmm LERICHE. 1959; and UIS-
WELL, unpublish~),
R. A. Bemer
pyrite sulfur content both with organic carbon and
with total iron. This comes about, most likely. because
of a correlation between organic carbon and reactive
iron at the time of deposition. Sediments of finer grain
size have greater specific surface areas for the adsorp-
tion of both colloidal hydrous ferric oxides and organic
compounds. Thus, where there is a greater deposition
of finer detritus, one may find more iron and more
organic carbon and, consequently, more pyrite. In this
case, no simple statement can be made concerning the
chief limiting factor in pyrite formation. An example
of this situation is given in Fig. 10.
I I
6.0 Summary
Pyrite fo~ation resuhs from the reaction of H2S,
from bacterial sulfate reduction, with reactive detrital
iron minerals. In freshwater sediments this process is
limited by low concentrations of dissolved sulfate. As
a result, little pyrite is formed and there is no simple
correlation between organic carbon and pyrite sulfur.
In normal marine sediments (those deposited in ox-
ygen-containing bottom waters), pyrite formation is
limited mainly by the amount and reactivity of organic
matter buried in the sediment, and as a result pyrite
sulfur and organic carbon correlate positively with one
another. This correlation may be due partly to a pas-
itive correlation between (fine-grained) reactive iron
and organic carbon at the time of deposition. In euxinic
marine sediments (those deposited in anoxic, Hz.9
confining bottom waters), a plentiful supply of both
organic matter and hydrogen sulfide brings about the
formation of high concentrations of pyrite which are
limited only by the reactivity of the iron-minerals
brought to the site of deposition. More pyrite is formed.
compared to normal marine conditions, because more
time is available for the reaction of high concentrations
of H2S with less reactive iron minerals. In normal
marine sediments rapid sedimentation can bring about
the production also of high concentrations of HIS due
( 1959)
(unpublished)
a
!
I
0
AA A -1
A
liA A I
A
A
-I
I I I t I I I
4 5 6 7 8 9 IO
% ORGANIC c
 Sedimentary pyrite formation
RG. 10. Plots of 96organic carbon, ‘51pyrite sulfur, and %
HCl-soluble iron vs. depth for a sediment (LIS site) in Long
Island Sound. HCI-soluble iron representsexcess detrital iron
minerals that have not reacted to form pyrite (pyrite is in-
soluble in HCI). (After BERNER,1970).
to the rapid burial of reactive organic compounds into
the zone of bacterial sulfate reduction. However, this
results also in the rapid depletion of sulfate (and even-
tually HrS) with depth which limits the time during
which the less reactive iron minerals are exposed
to H2S.
PYRITE FORMATION OVER
PHANEROZOIC TIME
The observations, discussed above, made on modem
sediments prove to be useful in helping to interpret
the formation and distribution of pyrite over geologic
time. Sedimentary pyrite formation has been a major
process in the past for controlling the amount and
isotopic composition of sulfate in the oceans and the
level of oxygen in the atmosphere, and this becomes
apparent when incorporating sedimentary pyrite for-
mation in models for explaining possible changes in
these parameters over Phanerozoic time (HOLSER and
KAPLAN, 1966; REES,1970; HOLLAND, 1973; !SCHID
LOWSKI et al., 1977; ARTHUR and KELTS, 1979;
CLAYFOOLet al., 1980; VEIZER ef al., 1980; GARREL~
and LERMAN,198 1). One such model, that of G-I-s
and LERMAN (198 1) will be discussed here and its
predictions interpreted in terms of what is known about
pyrite formation in modem sediments.
According to the Garrels and Lerman model,
changes in the isotopic composition of seawater sulfate
(as recorded by evaporite minerals) are due mainly to
changes in the relative rates of removal of CaSO, and
pyrite from the oceans. Like other models, the Garrels
and Lerman mode1 considers weathering inputs to the
oceans from sedimentary pyrite and CaSO,, and out-
puts from the ocean to form the same minerals. Unlike
some other models, Garrels and Lerman assume that
the level of sulfate in the ocean remains essentially
constant; only its isotopic composition changes. Rough
constancy of sulfate concentration is a very reasonable
611
assumption, as pointed out by H. D. Holland in his
Geochemical Society presidential address of several
years ago (HOLLAND, 1972), based on what is known
about marine evaporite minerals. Constancy of sulfur
content in the oceans means that any imbalances be-
tween weathering and oceanic deposition must result
in the growth of sedimentary pyrite at the expense of
&SO, or vice versa. In other words, it is assumed that
total sedimentary sulfur (CaS04 + pyrite) remains
constant.
Another basic assumption of the Garrels and Ler-
man model, previously used by others, is that any
redox imbalance resulting from a net shift of sulfur
between the CaSO., and pyrite reservoirs is taken care
of by concurrent shifts between the organic carbon
and calcium carbonate reservoirs. In other words, in
order to maintain essentially constant Or levels over
Phanerozoic time, redox balance is maintained by
complementary shifts in the sedimentary carbon and
sulfur reservoirs. This can be expressed in terms of
the overall chemical reaction:
15CHrO + 8CaS04 + 2Fe203 + 7MgSiOJ P
4FeSr + 8CaC03 + 7MgCOs + 7SiOz + 15H20.
Thus, to make more pyrite at the expense of CaSO,,
we must oxidize some organic carbon to calcium car-
bonate. This coupled reaction allows one to make links
between rates of sulfur transfer, to and from the ocean,
and rates of carbon transfer. One can actually calculate
such rates using known values of oceanic sulfur isotopic
composition and the assumptions of the Garrels and
Lerman model. (Values of 6’%J for the oceans over
time, calculated by Garrels and Let-man, agree well
with actual values recorded by marine carbonates. This
provides strong backing for the use of the above carbon-
sulfur coupling reaction and for ignoring other possible
processes of oceanic sulfate reduction, such as basalt-
seawater reaction.)
Robert Raiswell and I (BERNER and RAISWELL,
1983) have used the Garrels and Lerman model to
calcuiate (using a different technique than that used
by Garrels and Lerman) rates of pyrite sulfur burial
and organic carbon burial over Phanerozoic time and
results are shown in Fig. 11. Note that percentage
changes in pyrite burial are much greater than cor-
responding changes in organic carbon burial and this
results in large calculated worldwide changes in C/S
ratios of sediments over Phanerozoic time. This is
shown in Fig. 12. Are these changes real? Can they be
explained in terms of known geologic processes? Also,
how can pyrite burial rate decrease while organic car-
bon burial rate increases if in normal marine sediments
there should be a positive correlation between the two
as shown in Fig. 5. These and other questions can be
answered by applying what we know about pyrite for-
mation in recent sediments.
A major way that worldwide C/S ratios could change
is to change the locus of organic carbon burial. Burying
more carbon on land and less in the oceans should
 R. A. Bemer

Fcfg-c 4o - PRESENT WLLUE

ORGANK: CARBON _

0.25

TIME (my BP)

FIG. 11. Burial rate F, of organic carbon and pyrite sulfur as a function of time recalculated according
to the model OfGARRELs and LERMAN (198 I). For details ofthe calculation consult BERNERand RAISWELL
(1983) (After BERNERand RAISWELL, 1983).

resuit in less pyrite burial worldwide. As seen from
Fig. 6 and our discussion of pyrite formation under
freshwater conditions, organic carbon burial in fresh-
water involves less pyrite burial than in seawater be-
cause of the low con~nt~tion of sulfate in freshwater.
We beiieve the very high predicted C/S ratio shown
in Fig. I2 for the late Carboniferous and early Permian
is due to a shift to much greater organic deposition
on the continents in freshwater at that time and pro-
pronely tower burial at sea.
There is good geologic evidence to back up our
explanation of the Permo-Carboniferous C/S maxi-
mum. This is a period when large quantities of organic
matter were deposited on land in vast swamps to form
many present-day coal deposits. The abundance of
minable coal as a function of time is plotted in Fig.
13 and one can note a distinct ~~llelisrn with the
C/S plot of Fig. 12. Thus, qualitatively, the high C/S
ratio can be explained in terms of a major shift in the
locus of organic carbon burial from marine to non-
marine sediments during Permo-Carboniferous time.
Ap~~ntIy at that time, nutrients such as pho~ho~s
were removed from sluggish streams as they flowed
through swamps on the continents, and as a result,

201 I I I 1 I I 1 6.0 I I I I
;

PRESENT
--- W _--___.

8 -EOSDCP-kJK T
I I I I I
600 500 400 3co 200 n)o C
TIME (my BP) TIME (my BP)
FIG. 12. Weight ratio of organic carbon 10 pyrite sulfur FIG. 13. Mass per unit time of potentially recoverable coal
(C/S) buried in sediments over Phancrozoie time. Data derived as a function of geological age. Note similarity to Fig. 12.
from fluxes e;iven in Fig. 11.(After BERNER and RAISWELL, Data fmm BE~T~UGEFF (1980). (After BERNER and RAIS-
1983). WELL,1983).
 Sedimentary pyrite formation 613

less nutrients should have been delivered by the rivers
to the oceans resulting in a lower overall oceanic Pro-
ductivity of organic matter.
A quantitative check on our qualitative explanation
and of the model prediction of high Permo-Carbon-
iferous C/S ratio is provided by the data of RONOV
(1976). In Table 2 I have combined his data for the
mass of coal-measure rocks and total rocks laid down
at that time (320-250 my BP), suitably corrected for
subsequent erosion using the data of GREGOR (1984),
with his average %C for all rocks of this age and my
independent estimate of the percentage of organic car-
bon in coal measures. My estimate (see legend to Table
2 for references) is based on the average thickness
percentage of coals from various coal basins along
with estimates of ratios of both non-exploitable coal
and ~~rninat~~~n-in-~iat~-~~~ to ex-
p~oi~b~e coal and of the proper conversion factors for
transforming coal thickness percent to weight percent
organic carbon. Note that there is good agreement
between model-predicted (see Fig. 11) and measured
estimates for the average rate of Permo-Carboniferous
total organic carbon burial and that the amount of
carbon buried on land is, as predicted from the high
C/S ratios, a high proportion of the total carbon burial.
Considering the many possible errors in both the model
predictions and burial rate estimates, I find this agree-
ment highly gratifying.
Another feature of the curve of Fig. 12 is the low
predicted C/S ratio for Cambrian through Silurian
times. Is this reasonable? Recent unpublished data of
Robert Raisweil and myself suggests that it is. We have
analyzed a number of late Proterozoic, Cambrian and
Ordovician shales and have found distinctly lower C/
S ratios than in rocks deposited at later times. A simple
explanation for this observation, which we have already
offered (BERNER and RAISWELL, 1983) is that euxinic
basins (which produce sediments with low C/S ratios-
see above) were much more widespread at that time
than they are today, a suggestion in keeping with the
findings of others (e.g.-BERRY and WILDE, 1978). In
this way more pyrite could have been buried per unit
of organic carbon. However, carbon-sulfur plots for
euxinic shales should show a positive intercept on the
sulfur axis and some of our early Paleozoic data, do
not. An example is given in Fig. 14. Since we made
an attempt to analyze as many early Paleozoic shales
as possible which were not obviously euxinic (some
showed evidence of bottom fauna which could not
live in sulfidic bottom water), we believe the decreased
C/S ratio represents something in addition to wide-
spread euxinicity.
If the sediments shown in Fig. 14 represent “normal
marine” sediments, then we can offer two possible
explanations for the low C/S ratios. First, the sediments
are all finely laminated, even when they include evi-
dence of bottom-dwelling fauna, and this indicates an
absence ofdeep bioturbation, whether or not dissolved
oxygen was present in bottom waters. Absence of ap-
preciable sediment disturbance by bioturbation is ap
parently typical of the early Paleozoic in general (e.g.
LARWN and RHOADS,1983); at this time benthic fauna
ha+ not yet evolved the ability to undergo deep sed-
iment burrowing. Perhaps this represents a response
to lower (but not zero) oxygen concentrations in early
Paleozoic seawater, which might have helped to bring
about greater pyrite formation (per unit of carbon) by
bringing about higher sulfate Yukon rates at slow
sedimentation rates. In this way pyrite formation would
still be dependent on accompanying organic burial at
the same place (in contrast to euxinic conditions), but
more pyrite could form because there would be less
destruction of highly reactive (toward sulfate reduction)
organic compounds due to both less re-oxygenation
of anoxic sediments by bioturbation and lower oxygen
concentrations in the bottom waters.
The alternative explanation is that, because of the
absence of vascular iand plants in the early Paleozoic,
only marine or terrestrial algal-derived organic carbon
was delivered to the sediments. At present large quan-
tities of terrestrial organic matter derived from vascular
plants are added to the oceans by rivers, (e.g.-see

Table 2. Estimates of average ratm of organic carbon burial during

late-Csrboniferous through lower Permian tim (320 to 250 my
BP). Rock masses and organic carbon content of total rocks
from uonov (1976). Organic contents of coal-masure rocks
based oe average Chickmss percentages of minable coals in
coal basin rocks lScutzet I
and So&. 1940: Lawrence. 1982)
ratio. of total c&m to m%nable coal carbon <Nicholls and
briwz. 1962; Eaaar end Smars. 1966: Pearson. 1979: R.
Raisv;ll, person& cmmunicari& and the ass&p& that the
average density of associated sandstones and shnleris twice
chat of coal.

All Pem-
Carboniferous
rocks (320-
250 my BP)

Coal bearing
sands and
clays only
(320-250 my BP> 12 _ 48 3.0 1.7
* original ~8s based on 75X loss due LO subsequent erosion over 300
nly (Gregor, 1984)
614 R. A. Bemer
MOOERN NORMAL
MARINE x.x-
.H’
/y
/M
/’
I
I I
00 3 4
1
I 2 5 6
V. ORGANIC C 862.
FIG. 14. Plot of % pyrite sulfur vs. % organic carbon for
Cambrian age sediments. (Gutwoods shales, Warwickshire,
England). (RAISWELL and BERNER,unpub. data.)
MEYBECK, 1982) and it is believed that this material,
because it contains a high proportion of microbiolog-
ically resistant lignin and humic substances, is less
available for bacterial sulfate reduction than marine
or algal organic matter. In the early Paleozoic such
resistant organic matter was not present because of
the absence of land plants, and thus, efficient use was
made of the available algal or marine material. As a
result more sulfate reduction and pyrite formation per
unit of carbon burial took place. (This effect could
have been enhanced by preferential thermal degra-
dation of the less resistant, wholly marine material
during long term burial.) In addition, the more me-
tabolizable organic matter might have eliminated the
necessity of processing large volumes of sediment for
food and this could help explain why extensive bio-
turbation had not yet evolved. Further tests using
methods of distinguishing marine from terrestrial or-
ganic matter, are needed, before this idea can gain
additional credence. Personally, 1 prefer it to the first
explanation.
Ackrwwredgemrms-Research supportedby NSF GrantsOCE
81-09454, GCE 82-19580, and EAR 83-05925. The writer
has benefited from discussions with M. B. Goldhaber, D.
Canfield, D. Lawrence, P. Olsen, and R. RaisweIl, as well as
numerous Friends of Anoxic Mud, Shale and Pyrite (FGAM-
SAP). Musical inspiration provided by: H. Hanson (Symphony
No. 3), F. Poulenc (Concerto for Two Pianos), and M. Rosa,
(Spellbound Concerto).
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