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Connections Between Sulfur Cycle Evolution, Sulfur Isotopes, Sediments, and Base Metal Sulfide Deposits. FARQUHAR Et Al, 2010.
Connections Between Sulfur Cycle Evolution, Sulfur Isotopes, Sediments, and Base Metal Sulfide Deposits. FARQUHAR Et Al, 2010.
of Geology and Earth System Science Interdisciplinary Center (ESSIC), University of Maryland,
College Park, Maryland 20740
2NordCEE
and the Institute of Biology, Syddansk Universitetet, 5020 Odense C., Denmark
Abstract
Significant links exist between the sulfur cycle, sulfur geochemistry of sedimentary systems, and ore deposits
over the course of Earth history. A picture emerges of an Archean and Paleoproterozoic stage of the sulfur cycle
that has much lower levels of sulfate (<200 M), carries a signal of mass-independent sulfur, and preserves
evidence for temporal and spatial heterogeneity that reflects lower amounts of sulfur cycling than today. A second stage of ocean chemistry in the Paleoproterozoic, with higher atmospheric oxygen and oceanic sulfate at
low millimolar levels, follows this stage. The isotopic record in sedimentary rocks and in sulfide-bearing ore
deposits suggests abundant pyrite burial and implies a missing 34S-depleted pool that may have been lost via
deep ocean deposition and possibly subduction. Proterozoic ocean chemistry appears to be quite complex. The
surface waters of the Proterozoic oceans are believed to have been oxygenated, but geologic evidence from ore
deposits and sedimentary rocks supports coexistence of significant sulfidic and nonsulfidic, anoxic, intermediate water and deep-water pools in the Mesoproterozoic. This stage in ocean chemistry ends with the second
major global oxidation event in the latest Neoproterozoic (~600 Ma). This event started the transition to more
oxygenated intermediate and deep waters, and higher but variable oceanic sulfate concentrations. The event
set the scene for the formation in the Phanerozoic of the first significant MVT deposits and possibly is reflected
in changes in other sedimentary rock-hosted base metal sulfide deposits.
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FARQUHAR ET AL.
change at 2400 Ma by identifying and calibrating a dependence on ecosystem level expression of these isotope fractionations that results from changes in sulfur transport and sulfate
reduction rates within unbioturbated sediment at low sulfate
concentrations (Canfield et al., 2000; Habicht et al., 2002).
The results of Habicht et al. (2002) suggest that sulfate transport within the sediment is correlated with sulfate concentrations in the overlying water column. This limits the preservation of the fractionations produced by sulfate-reducing
bacteria in sedimentary pyrite and in the geologic record, placing limits on oceanic sulfate concentrations at less than 200
M before ~2.4 Ga, and greater than 200 M after this time.
The record of 33S and 36S provide additional insight into
the evolution of the sulfur cycle at this time. The variations of
33S and 36S in rocks older than ~2.42 Ga have been attributed to mass-independent frationation of sulfur isotopes
(MIF-S) in atmospheric source reactions. This signal has
been interpreted to reflect atmospheric and surface weathering environments with significantly lower oxygen levels for
the principal reason that it is a prerequisite for the production, transfer, and preservation of MIF-S in surface sulfur
pools (Farquhar et al., 2000, 2007a; Kasting, 2001; Farquhar
and Wing, 2003, 2005). These observations support a model
of a pre-2.42 Ga sulfur cycle with a diminished role for biological reduction of sulfate and for diminished oxidation of
sulfide because active cycling would be a process that would
homogenize and remove the MIF-S signal (Farquhar et al.,
B.
Literature data
P yrite (avg)
S eaw ater sulfate (est)
60
450
number
= (33S/32S)sample/(33S/32S)reference-[(34S/32S)sample/(34S/32S)reference]0.515
and 36S = (36S/32S)sample/(36S/32S)reference-[(34S/32S)sample/(34S/
32S)
1.9
reference] ; see Appendix 1 for information on mass-dependent and mass-independent sulfur isotope geochemistry).
350
sulfide means
X = -16.9+/- 1.2
0-540 Ma
250
150
50
number
350
40
250
150
50
34S
20
number
250
150
50
number
250
-20
150
50
number
-40
-60
0
500
1000
1500
2000
2500
3000
3500
4000
400
200
0
-60
-30
30
34S
Age (Ma)
FIG. 1. A. Compilation of 34S vs. time gray circle symbols (Canfield, 1998; Prokoph et al., 2007; Canfield and Farquhar,
2009) with running average for sulfide (gray line) and inference about seawater sulfate (black line) that we fit using a cubic
spline to sulfate data younger than 2450 Ma and constrained by literature estimates for periods prior to 2450 Ma. The curve
is similar to previous curves for the Phanerozoic. The positive values for seawater sulfate and average sulfide indicate an imbalance in the sulfur cycle record extending for almost 2000 m.y. until ~500 Ma. B. Histograms of the frequency of observations of sulfide (gray filled bars), and sulfate from the black curve (hatched bars), for five intervals in geologic time. The
height of each histogram is normalized to the total number of samples in order to put them on a similar aspect ratio. Means
for sulfide data are also plotted. Uncertainties on the mean are determined using a monte carlo resampling technique.
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
511
TABLE 1. Observations and Implications from the Multiple Sulfur Isotope Record
Older than ~2.42 Ga
The presence of Archean MIF-S implies processes (photochemical) in addition to microbial sulfate reduction played an important role in the sulfur
cycle
Covariation between 34S, 33S, and 36S tells us that sulfur cycle processes were not efficient enough to homogenize MIF-S once it was present
Grain scale to thin section scale heterogeneity for 33S (e.g., Ono et al., 2003; Kamber and Whitehouse, 2007) implies mixing of sulfur with different
MIF-S compositions, suggesting more than one sulfur pool (e.g., sulfate and sulfide-polysulfides-sulfur) or short residence times (low concentrations) for
sulfur
Coherent relationships between 36S and 33S at the formation level (Fig. 4) (e.g., Farquhar et al., 2007; Kaufman et al., 2007) imply gross changes in
MIF-S source reactions and/or ecology that vary in time and possibly with geography
Observation of MIF-S signals in hydrothermal VMS systems (Farquhar and Wing, 2005; Jamieson et al., 2006) and in marine sediments subject to diagenetic processes implies the existence of multiple MIF-S sulfur cycle pools
A fractionation of ~20 is observed for 34S of the most 34S-depleted sulfides and seawater sulfate (Fig. 1)
~2.42 Ga to ~600 Ma
Samples of the ~2.42 Ga Duitschland Fm. capture the transition from a MIF-S world to a MDF-S world (Bekker et al., 2004; Guo et al., 2009)
The transition from a MIF-S world to a MDF-S world appears to be correlated with one of the Early Proterozoic carbon isotope excursions
The average 34S of Proterozoic sedimentary pyrite appears to be near zero, (if not slightly positive) and implies high fractions of pyrite burial and a
missing 34S-depleted sulfur pool
Studies of basins have shown more negative 34S is observed in deeper parts of sedimentary basins (Shen et al., 2002) implying the missing 34S-depleted
sulfur pool may have formed and been buried in deeper water settings (Logan et al., 1995), possibly subducted (Canfield, 2004)
Deep- to shallow-water variation in the 34S of the pyrite pool may reflect distillation of sulfur by sulfate reduction in Proterozoic oceans, reflecting low
sulfate concentrations (Johnston et al., 2006)
A relationship between 34S and 33S is seen in some sections that implies an isotopic reservoir (Rayleigh) effect (Johnston et al., 2005, 2006)
Significant (short time scale, high frequency) variations of 34S for carbonate associated sulfate (a proxy for seawater sulfate) have been interpreted to indicate low (mM) sulfate concentrations (Kah et al., 2004; Lyons et al., 2004)
The 33S of seawater sulfate rose during the middle Proterozoic (between ~1.6 and ~1.3 Ga) (Johnston et al., 2005a) and this observation is interpreted
to be related to a change in the ecology of the ocean-sediment system to favor expression of fractionations of sulfur disproportionators
A fractionation of ~40 is observed for 34S of the most 34S-depleted sulfides and seawater sulfate (Fig. 1)
Since ~600 Ma
The variability with time of 34S for seawater sulfate generally diminishes (e.g., Kampschulte and Strauss, 2004; Claypool et al. 1980), but some evidence
for higher frequency oscillations are still present (e.g., Paytan et al., 1998, 2004; Kurtz et al., 2003; Lyons et al., 2004); this has been interpreted to reflect growth of the oceanic sulfate pool to a size large enough to dampen, but not completely eliminate, the variability in 34S caused by changes in the
rate of or fractionations associated with pyrite burial
A fractionation of ~60 is observed for 34S between the most 34S-depleted sulfides and seawater sulfate (Fig. 1)
The magnitude of the fractionation between buried pyrite and sulfate appear to have changed from ~25 before ~550 Ma to ~35 between ~550 and
~300 Ma before increasing to ~43 by about 250 Ma (Wu et al., 2010)
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FARQUHAR ET AL.
12
0.15
0.1
10
33S
0.05
0
-0.05
-0.1
33 S
-0.15
0
500
1000
1500
2000
Age (Mya)
4
2
0
-2
Neo
Meso
Paleo
Eo
-4
0
1000
2000
3000
4000
Depth (m)
255
225
235
265
245
275
255
285
265
295
275
305
285
100
165
175
270
110
120
185
290
130
195
140
300
205
150
215
310
160
225
315
170
320
295
325
305
335
315
-5
10
33
15
280
-5
33
10
15
235
180
245
190
-5
33
10
15
330
-5
10
15
-5
33
FIG. 3. Plot of 33S as a function of depth in five drill cores that intersect roughly equivalent successions of the Naute
Shale (A, B, C GKP01, GKF01, and AD-5) and the Mount McRae Formation (D, E ABDP-9 and AUS 493). The upper
dark line represents the top of the formation and is taken as a time boundary. The lower dark line represents the bottom of
the formation (corresponding to its contact with a BIF horizon referred to as Brunos band). Where the lines (bands) are gray
instead of black, the position of this horizon is more uncertain. For panel C (AD-5) the top of the gray band represents the
bottom of the drill hole, and the bottom of the gray band is 78 m lower than the top of the formation which is similar to that
seen in cores GKP01 and GKF01. The data and the positions of the horizons are replotted from Ono et al. (2003, 2009b)
using information about the thickness of the Mount McRae Formation and Brunos band from Kakegawa et al. (1998) and
information about the GKP01 and GKF01 cores from Knoll and Beukes (2009) and Kaufman et al. (2007) using information
from Beukes et al. (1990) for the stratigraphy of AD-5 core.
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
5
M t M cR ae U pper
M t M cR ae Low er
G am ohaan U pper
G am ohaan Low er
36S
-5
-10
-15
-5
10
15
S
33
33S
36S
FIG. 4. Plot of
versus
for pyrite samples from the Neoarchean
of South Africa (Gamohaan Fm.) and Western Australia (Mt McRae Fm.)
(Kaufman et al., 2007). These two successions are considered to be time
equivalent and can be correlated via marker beds. The upper and lower parts
of the two formations exhibit similar changes in the relationship between
33S and 36S. The lower parts of these successions are more linear, following 36S ~ 0.85 33S, and the upper portions of these successions show more
scatter and 36S >0.85 33S. Slopes on lines in plot are 0.85 and 1.37. This
difference has been interpreted to reflect a change in mass independent
source reactions and also an overprint by cycling of sulfur in the water column in the upper parts of these two successions (Kaufman et al., 2007). It has
recently been suggested that the upper interval of the Mount McRae Formation may reflect local sulfidic conditions (Reinhard et al., 2009). In this
context, it is possible that a significant part of the change in 33S vs. 36S may
reflect stronger expression of sulfur cycling by sulfate reducers in a sulfidic
water column. This would not require a change in sulfate concentration, but
would imply more efficient expression of fractionations associated with sulfate reduction in the water column and would also be consistent with assertions for water column sulfate reduction by Kamber and Whitehouse (2007).
grains and concentrations of pyrite in the same sections preserved near zero or even negative 33S. These variations were
interpreted to reflect different generations of pyrite and formation in a gradient, or stratified, system, including a stratified water column (Kamber and Whitehouse, 2007).
A number of models have been proposed to explain 33S
variations in the geologic record. They include suggestions
that the magnitude reflects variations in the proportion of atmospheric sulfur with a much larger initial 33S (e.g., Farquhar et al., 2000, 2001), variations in 33S of the atmospheric components and therefore directly reflect a change in
the atmospheric source reactions (Ono et al., 2003; DomagolGoldman et al., 2008; Farquhar et al., 2007a), or the nature
and residence time of the sulfur pools in early Earth environments (Farquhar and Wing, 2005; Ono et al., 2009a, b). It
would appear that components of each of these suggestions
would be required to account for the three observations
above. A hybrid model that describes controls on the sulfur
cycle is thus favored (Fig. 5).
A recurring question in the literature is whether there is an
underlying systematic variation in the magnitude of the massindependent signal with respect to locality and or time, an
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FARQUHAR ET AL.
sedimentary Py from S0
(positive 33S)
variability of 33S
phic
geogra
atmospheric sources
ity to
proxim
Oceanic sulfide
(positive 33S)
m
orphis 33 S)
metam
n of
o
ti
u
trib
(redis
Oceanic sulfate
(near zero or negative 33S)
Hydrothermal
ore deposits
hydrothermal circulation
(trapping of 33S signals from sulfur pools)
re
cy
c
(n led
eg
at alte
ive re
d
?
c
Sulfate reduction
33
dilutes S signal
sulfate from
sulfide weathering
(positive? 33S)
nts
ime
sed 33 S)
led
c
y
e?
rec
sitiv
(po
33 ru
S st
)
primitive mantle
( 33S = 0)
FIG. 5. Model that describes a possible Archean sulfur cycle. The MIF signal is of atmospheric origin and the transfer of
this signal to the sediments includes components related to atmospheric, water column, and sedimentary processes. Larger
scale (longer-term) trends for 33S are interpreted to reflect long-term variations in delivery of sulfur from the atmosphere
reflecting global and regional controls as well as reaction pathways. Smaller scale (shorter-term) variability for 33S is interpreted to reflect changes in water column and sedimentary pathways for production and preservation of pyrite.
suggest that mass-independent fractionation under such conditions may involve a magnetic isotope effect (MIE) (e.g.,
Turro, 1983; Buchachenko, 1995: see App. 1) or a surface catalyzed reaction (e.g., Lasaga et al., 2008), but further work
will be needed to resolve this. This proposal might be taken
further to suggest that atmospheric reactions are not the
source of the mass-independent signal, and that mass-independent fractionation (MIF) is a result of processes that
occur in sediments. We do not think that this is presently a
defendable suggestion because several issues need to be addressed relating to the following: (1) the nature of the signal,
such as the tight coupling of 33S and 36S in many Archean
samples (Fig. 4); (2) the production and transfer of the signal
through the wide range of Archean sedimentary, metamorphic, and igneous rocks; and (3) the apparent geographic and
temporal coherence of the signal over the course of the
Archean and its abrupt disappearance in the Paleoproterozoic. Anomalous sulfur isotope fractionation arising from such
reactions may be relevant in some natural environments
where thermochemical sulfate reduction occurs, although evidence has yet to be presented that this is the case.
Isotopic record since ~2400 Ma
The sulfur cycle since ~2400 Ma is characterized by a larger
range in the signal of 34S and a lack of significant mass-independent signals in sedimentary rocks, suggesting an end to
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
where sulfate reduction rates were high and resupply by circulation was low. The average 34S of sedimentary pyrite for
Paleoproterzoic rocks remains similar to the value seen in the
Archean (i.e., 2), implying abundant pyrite burial. The average 34S of sedimentary pyrite for Mesoproterozoic and
Neoproterzoic rocks increased to higher values (~4-7; Fig.
1B), which implies that both sulfide and sulfate are 34S enriched relative to the long-term sulfur inputs. This indicates
that a pool of 34S-depleted sulfur is missing from the known
sedimentary pyrite record. Such a pool may have been an offshore pool that was lost to deeper water, sedimentary facies,
and/or sulfide deposits. It would imply that sulfur isotopic
compositions and concentrations were heterogeneous in the
Proterozoic oceans. An interesting suggestion made by Canfield (2004) is that the size of the exogenic sulfur reservoir
was affected by loss of a deep-water sulfide pool to rocks that
were ultimately subducted.
The record of four isotopes since ~600 Ma supports a stabilization in isotopic variability for seawater sulfate that is related to generally higher (430 mM) oceanic sulfate concentrations and an average 34S that declines to negative values
(Fig. 1B) for the first time, implying a less significant role for
pyrite burial. This interpretation is consistent with other direct types of evidence for higher sulfate levels that come from
fluid inclusions (e.g., Horita et al., 1991, 1996, 2002; Lowenstein et al., 2005) and suggests high sulfate concentrations at
least as early as the latest Neoproterozoic. (Horita et al., 2002;
Lowenstein et al., 2005).
It has been suggested that the rise in sulfate concentration
since the latest Neoproterozoic and the change in the fraction
of sulfur lost to pyrite burial are related to oxygenation of
shelf environments and the establishment of conditions favorable for animal radiation and bioturbation (Canfield and
Farquhar, 2009). Furthermore, changes in the magnitude of
the fractionation associated with buried pyrite in the
Phanerozoic are related to changes in oxidation pathways,
which may have similar links to the evolution of open diagenetic systems on a global scale (e.g., Wu et al., 2010). The
change in the magnitude of the fractionation between sulfate
and buried pyrite at ~540 Ma could be related to bioturbation
because of the way that it affects recycling of sulfur from sulfate reduction (Fig. 6), and also because of links between bioturbation, sulfate concentration, and the magnitude of fractionations produced by sulfate-reducing bacteria (SRB)
(Canfield and Farquhar, 2009). This presents an interesting
question related to the observed change in the range of 34S
in the Neoproterozoic (e.g., ~800 Ma in Canfield and Teske,
1996), the change in the fractionation between sulfate and
buried pyrite (Fig. 1), and the change in 33S starting at ~1.4
Ga reflective of a change in oxidation pathways and disproportionation (Johnston et al., 2005a). If we accept that the
change in 33S reflects the onset of disproportionation and
the change in the fractionation between sulfate and buried
pyrite is associated with bioturbation and the rise of oceanic
sulfate, then we are left with the question of what is the significance of the change in the range of 34S at ~800 Ma. Canfield and Teske (1996) suggested that this change is the expression of disproportionation in the sedimentary record.
This may be the case if the signal seen by Johnston et al.
(2005a) was for water column disproportionation, where the
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With bioturbation
Without bioturbation
Seawater sulfate
Seawater sulfate
Porewater sulfide
Porewater sulfide
bioturbated sediment
unbioturbated sediment
Porewater sulfate
34Spyrite burial
Porewater sulfate
larger
smaller
0
none
1
all
Fraction of return flow to
seawater sulfate
Buried Pyrite
Buried Pyrite
D
sulfate input
Seawater sulfate
evaporite sink
0 .1 5
0 .1
em
st
se
0 .0 5
Porewater sulfate
33S
e
or
Porewater sulfide
sy
clo
m
0
-0 .0 5
intermediates
-0 .1
-0 .1 5
Buried Pyrite
10
20
30
40
34S sulfate
50
60
70
80
FIG. 6. A model system (box model representation) to illustrate how bioturbation may change the degree of openness of
a diagenetic setting and alter the magnitude of the fractionation preserved between buried pyrite and seawater sulfate. B.
Schematic plot showing relationship of fractionation between sulfate and pyrite and fraction of sulfur recycled to the oceanic
pool. Another direct influence on fractionation related to bioturbation is coupled to the possibility of changes in sulfate concentration that feed back to the dependence of isotope discrimination by sulfate-reducing bacteria on sulfate concentrations
(e.g., Canfield and Farquhar, 2009). C. Similar model system that incorporates disproportionation and D. Calculated fields
for overlying sulfate pool on plot of 33S versus 34S. Calculated using fractionations for sulfate reduction from Farquhar and
Johnston (2008) from experiments with natural populations of sulfate reducers and disproportionation data from Johnston et
al. (2005b). Dark line is for sulfate reduction only. Dashed line includes reoxidation and disproportionation. Other fractionations yield different size fields, but the general shapes are preserved.
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
assembly of Pangea
alpine laramide
assimilation
Pangea
(assimilation)
30
Count
6
20
5
4
3
10
Sulfate (mMolar)
2
1
00
600
100
500
200
400
300
300
400
200
500
100
600
Age (Ma)
FIG. 7. Comparison between histogram of frequency of MVT mineralization events (using data in Leach et al., 2001) and models of the evolution of
seawater sulfate concentrations from Lowenstein et al. (2005) (thick black
line) and Horita et al. (2002) (thick gray line with estimates of uncertainty
given by thin gray lines). The figure shows a correspondence between the
frequency of MVT deposit forming events and tectonic processes, rather
than a direct relationship with sulfate concentrations. It is not clear whether
sulfate lags mineralization events or vice versa.
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FARQUHAR ET AL.
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A.
80
60
34S
40
20
0
-20
-40
-60
-80
0
500
1000
1500
2000
2500
3000
3500
4000
2500
3000
3500
4000
Age (Ma)
60
B.
50
40
34S
100
30
20
10
0
0
500
1000
1500
2000
Age (Ma)
FIG. 8. A. Compilation of 34S vs time for base metal sulfides filled gray
circle symbols and for sulfate (barite, anhydrite, gypsum) unfilled diamond
symbols. Unfilled gray circle symbols are same as those plotted in Figure 1
for sedimentary pyrites. Black line is seawater sulfate curve from Figure 1. B.
Expanded plot with data for sulfate from ore deposits and seawater sulfate
curve presented in Figure 1. Note that we do not include data for the ~2.7
Ga Hemlo deposit, because of the inference that much of this variation reflects later redistribution of sulfur isotopes during amphibolite facies metamorphism (Thode et al., 1991). (DeChow, 1966; Tupper, 1960; Buschendorf
et al., 1963; Anger et al., 1966; Ryznar et al., 1967; Sasaki and Krouse, 1969;
Solomon et al., 1969, 1988; Guha, 1971; Kajiwara, 1971; Lusk, 1972; Arnold
et al., 1977; Carr and Smith, 1977; Campbell et al., 1978, 1980; Smith et al.,
1978; Green et al., 1981; Rye and Williams, 1981; Sverjensky, 1981; Walker
et al., 1983; Willan and Coleman, 1983; Akande and Zentilli, 1984; Goodfellow and Jonasson, 1984; Olson, 1984; Gardner and Hutcheon, 1985; Scott et
al., 1985; Taylor and South, 1985; Deloule et al., 1986; Shanks et al., 1987;
Eastoe and Nelson, 1988; Andrew et al., 1989; Crocetti and Holland, 1989;
Kase et al., 1990; Whelan et al., 1990; Pandalai et al., 1991; Davidson and
Dixon, 1992; Eldridge et al., 1993; Nakai et al., 1993; Cagatay and Eastoe,
1995; Frietsch et al., 1995; Bechtel et al., 1996; Dixon and Davidson, 1996;
Jones et al., 1996; Perkins, 1996; Cook and Hoefs, 1997; Kesler et al., 1997;
I.K. Anderson et al., 1998; Broadbent et al., 1998; Velasco et al., 1998, 2003;
Painter et al., 1999; Ding and Jiang, 2000; Gaboury et al., 2000; Lyons et al.,
2000; Melezhik et al., 2000; St. Marie and Kesler, 2000; Sharpe and Gemmell, 2000; B.R. Anderson et al., 2001; Luepke and Lyons, 2001; Blakeman
et al., 2002; Wagner et al., 2002; Peevler et al., 2003; Ma et al., 2004, 2007;
Wilkinson et al., 2005; Gilg et al., 2006; Huizenga et al., 2006; Jamieson et al.,
2006; Kesler and Reich, 2006; Leach et al., 2006; Decre et al., 2008; Tornos
et al., 2008; Johnson et al., 2009).
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
_
sulfide: X= 7.6 8.0
_
sulfate: X= 28.8 7.7
Number
500
400
40
35
30
25
300
20
200
15
10
100
5
0
0
-50
-30
-20
-10
10
20
30
40
50
60
70
20
30
40
50
60
70
20
30
40
50
60
70
34S
45
_
sulfide: X= 4.1 6.6
40
Number
-40
35
30
25
20
15
10
5
0
-50
-40
-30
-20
-10
10
34S
C
90
_
sulfide: X= 1.6 1.4
Number
80
70
60
50
40
30
20
10
0
-50
-40
-30
-20
-10
10
34S
FIG. 9. Histograms of the frequency of observations of sulfide (gray filled bars), and sulfate (hatched bars), for Phanerozoic (A), Proterozoic (B), and Archean (C) VMS deposit intervals in geologic time. The heights of each histogram are normalized to the total number of samples in order to put them on a similar aspect ratio. Mean and standard deviation given on
plots. Data sources listed in Figure 8.
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A. MVT (Phanerozoic)
350
120
C. CD-Pb-Zn (Phanerozoic)
450
20
400
100
350
_
sulfide: X= 6.4 16.4
_
sulfate: X= 25.3 10.3
250
200
15
Number
Number
300
10
150
_
sulfide: X= 12.2 10.7
_
sulfate: X= 25.1 7.2
300
250
80
60
200
40
150
100
100
50
20
50
0
0
-50
-40
-30
-20
-10
10
20
30
40
50
60
0
-50
70
-40
-30
-20
-10
10
34S
30
40
50
60
70
34S
B. MVT ((Proterozoic)
80
20
D. CD-Pb-Zn (Proterozoic)
500
50
400
_
sulfide: X= 15.3 11.3
_
sulfate: X= 23.7 0.5
60
50
Number
Number
70
40
30
20
40
_
sulfide: X= 7.9 9.9
_
sulfate: X= 23.6 10.4
300
30
200
20
100
10
10
0
0
-50
-40
-30
-20
-10
10
20
30
40
50
60
0
-50
70
34S
-40
-30
-20
-10
10
20
30
40
50
60
70
34S
FIG. 10. Histograms of the frequency of observations of sulfide (gray filled bars), and sulfate (hatched bars), for Phanerozoic MVT (A), Proterozoic MVT (B), Phanerozoic CD-Pb-Zn (C), and Proterozoic CD-Pb-Zn (D) deposits. The heights of
each histogram are normalized to the total number of samples in order to put them on a similar aspect ratio. Mean and standard deviation given on plots. Data sources listed in Figure 8.
520
SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
521
(~38) and thus the isotopic composition of seawater sulfate was not strongly fractionated by global-scale burial of
pyrite. Second, Foriel et al. (2004) use the Cl/Br of fluid inclusions from the quartz-carbonate pods of the 3.49 Ga
Dresser Formation, a shallow-water facies that is slightly
older than the Kangaroo Caves and Sulphur Springs depositional environments, to argue for mixing of Ba-rich hydrothermal fluids with low sulfate seawater that had been
subject to evaporative concentration, consistent with other
constraints on the nature of the local depositional environment. The fluid inclusion data support an upper limit of 8
mM for seawater sulfide. This is not as low as the estimates
made using other lines of evidence; it is also the upper detection limit of the analytical technique.
A number of Neoarchean VMS deposits do not appear to
contain similar barite mineralization. This reflects lower sulfate concentrations or the nature of the hydrothermal circulation systems such that the size of the events in the
Neoarchean may have been unusually large and that they may
have influenced the chemistry of the overlying water, thus
making barite precipitation unlikely. Both of these suggestions are difficult to test, and each may carry consequences
for the sulfur cycle. For the first suggestion of lower global
seawater sulfate concentrations, the reasoning is that during
the Neoarchean there was a return to more anoxic conditions
from an earlier Archean, more oxygenated environment. As
described above, we do not believe that the evidence for an
oxygenated Paleoarchean is compelling and another reason
for a change in sulfate concentrations would be required. It is
possible, but not proven, that oceanic sulfate concentrations
may have declined in the Neoarchean because of the establishment of more effective sinks for sulfate, perhaps associated with the establishment of a niche for sulfate reducers.
This is difficult to test, but evidence for the hypothesis should
be present in the 34S of seawater sulfate. Some isotopic data
for pyrite in carbonates, sulfide from marine sediments, and
sulfides and rare barite in VMS deposits suggest that the 34S
of Neoarchean sulfate had higher values (~1015; Thode
et al., 1991; Ono et al., 2003; Farquhar and Wing, 2005; Kaufman et al., 2007). This may signal the onset of bacterial sulfate reduction in the oceanic sulfur cycle and would imply a
growing sink of pyrite burial and larger fractionations associated with this sink.
Cameron and Hattori (1987) report 34S analyses of pyrite
and sulfate (barite and anhydrite) from Hemlo and related
gold-rich possible VMS deposits in the Superior province that
provide an exception to these more general observations of a
lack of sulfate and a lack of significant sulfur isotope fractionation in Neoarchean deposits. They interpret these deposits
to be the result of metal deposition in an environment with locally high sulfate concentrations that indicate an Archean
ocean with isolated sulfate-rich basins, despite a relatively sulfate poor overall concentration. The range of variability for
34S approaches 30 per mil and is interpreted to be a result of
abiological processes. Thode et al. (1991) note that the fractionation of 34S/32S between coexisting barite and pyrite is uniform, despite compositions that vary from sample to sample.
They also note the observed fractionations are remarkably
similar to the predicted fractionation on the basis of equilibrium isotope exchange at postdepositional metamorphic
521
522
FARQUHAR ET AL.
C
Pyrolusite
St
ab
20 FeCl+
2
Bixbyite
ilit
iel
log a O 2 (aq)
Goethite
++
Ferrite-Mg
40
FeCl
df
or
Mn
Hausmannite
Mn
20
yf
Rhodochrosite
Go
eth
ite
ox with / Fe
y-h ou rri
teyd t
Mg
rox
,M
ide
ag
s
n
40
eti
te,
60
60
Mn(OH) 2 (am)
Magnetite
Pyrite
80
80
Alabandite
25C
100
pH
10
12
25C
0
pH
10
12
25C
14
10
pH
FIG. 11. Plots of oxygen activity in a seawater model system for Fe-O2-Mn-H2O as a function of pH at 25C, showing the
stability fields of Fe phases (A) Mn phases (B), and overlap (C) for goethite (-FeOOH) with pKsp = 44.1, where amorphous
Mn(OH)2 are not stable. Assuming total dissolved sulfate equals 1mM 10 mM at aqueous-solid boundaries. Magnetite
(Fe3O4) and pyrite (FeS2) are metasable, implying that other metastable Fe-S and Mn-S species can occur chiefly in sulfate
seawater complexes. The solubility calculation of goethite (-FeOOH) in seawater composition was estimated using the
Stumm and Morgan (1981) equation: Log Ksp = log Ksp + s (S/2.303RT), where S is the surface area of mole of fine-grained
to well crystalline goethite material (m2/mol), s is an assumed particle size correction term (cal/m2), T is temperature, and
R is 1.9872 cal/molK. Precipitation of goethite and metastable Fe-O and Fe-S mineral is due to amphoteric behavior of oxyhydroxides. In seawater solutions high in chloride and sulfate, initial precipitation ferrihydrite/hydrous ferric oxide HFO
Fe(OH)3 from rapid hydrolysis of Fe(III) or oxidation of Fe(II) leads to the formation of goethite at cold temperature and
hematite at high-temperature conditions. At 1 mM sulfate concentrations, chloride anions substitute for hydroxyl radicals,
forming metastable solids such as Fe(OH)(Cl) and FeCl3 complexes at low pH conditions.
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12
100
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
523
523
524
FARQUHAR ET AL.
TABLE 2. Observations Relevant to Proterozoic Ocean Chemistry
Type of evidence
Age
Setting
Reference
1740 Ma,
Since 1.85 Ga
Oxygenated water
Deep water
(>1,000 m)
1, 2
1740 Ma
Low oxygen,
limited formation
of Fe,- Mn-oxide
Whole ocean
1.8 Ga 1.0 Ga
Low oxygen/
Limited formation
of Fe,- Mn-oxide
Whole ocean
3, 4
Late
Mesoproterozoic
~1430 Ma
Low sulfate
Sulfidic waters or
other Sulfidic sinks
Whole ocean
~1.64 Ga
Sulfidic waters
Photic zone/
possible restricted
marine basin
8, 9, 10
~1.85 Ga
Shelf below
wave base
11
~1.6 Ga
Below wave
base, possible
restricted basin
6, 12
1.8 Ga 1.0 Ga
Whole ocean
Figures 1,
810 and
see 12, 13,
14, 15
(1) Slack et al. (2007), (2) Slack and Cannon (2009), (3) Anbar and Knoll (2002), (4) Arnold et al. (2004), (5) Holland (2005), (6) Cooke et al. (2000), (7)
Scott et al. (2008), (8) Brocks et al. (2004), (9) Brocks et al. (2005), (10) Brocks and Schaeffer (2008), (11) Poulton et al. (2004), (12) Lyons et al. (2004), (13)
Logan et al. (1995), (14) Canfield (2004), (15) Johnston et al. (2007)
524
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SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
Atmosphere
cause, but it would appear that further studies of ore deposits and sedimentary sulfur in combination with biogeochemical models are needed to provide an answer to why
these changes have been suggested.
Synthesis
Evidence from ore deposits and the sedimentary rock
record yield several important observations on the connections between the sulfur cycle and the secular evolution of
ocean chemistry. The most significant of these are summarized below and are used to develop an evolutionary model
for the principal features of the oceans (Fig. 12).
The presence of Superior-type banded iron formations
(Cloud, 1973) is evidence for significant solubility of ferrous
iron (Fe2+) in the oceans that limited oxygen and free sulfide.
On the basis of trace metal and sulfur isotope data, it has been
suggested that local, or spatially constrained oxygenated
(Wille et al., 2006; Anbar et al., 2007; Kaufman et al., 2007),
or sulfidic pools (Reinhard et al., 2009; Poulton et al., 2009)
developed in the Neoarchean ocean that reflected the appearance of oxygenic photosynthesizers. These suggestions
indicate that the oceans of early Earth evolved from a Paleoarchean and Mesoarchean state with ferruginous deep waters and relatively small amounts of cycling to a Neoarchean
state with ferruginous deep waters and surface waters with
production of oxygen and local competition between iron,
oxygen, and sulfur. Nevertheless, oceanic sulfate levels likely
remained below 200 M during the entire Archean (Habicht
et al., 2002), and there is no conclusive evidence for spikes in
sulfate concentration. This is consistent with the lack of significant variability for 34S and the preservation of MIF-S in
the sedimentary record.
Anoxic
Oxic
low
Oxic
Ferruginous
Sulfidic
Ferruginous
Surface
Ocean
high
OAEs
Oxic
Ferruginous
Oceanic
sulfate
concentration
nonsulfidic
anoxic
3.8
2.8
2.42
1.8
1.4
0.8
0.55
0.3
Today
Time (Ga)
FIG. 12. Inferred evolution of atmosphere, surface ocean, and deep ocean and oceanic sulfate concentration. Note that
the representation does not imply depth or geographic distribution of pools in the deep ocean.
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FARQUHAR ET AL.
et al., 2008), and the existence of shallow-water euxinia is indicated by a biomarker (Olcott et al., 2005). The reasons for
the re-establishment of iron-rich conditions are debated, but
include hypotheses related to the size of the exogenic sulfur
pool (Canfield, 2004; Canfield et al., 2008) or the change in
the supply of hydrothermal ferrous iron.
Starting in the latest Neoproterozoic (~600 Ma), a second
oxidation of the Earths surface is indicated by the colonization of the oceans by animal life (e.g., Logan et al., 1995). It
has also been suggested this change corresponded to a rise of
sulfate above Proterozoic levels that is attributable to the
onset of bioturbation (Canfield and Farquhar, 2009). Evidence for this rise is indirectly tied to a change in the range of
variation for 34S. Direct evidence for episodes of high sulfate
concentrations is present in rocks as old as latest Neoproterozoic (Lowenstein et al., 2005) and in other parts of the geologic record in the Phanerozoic (Horita et al., 1991, 1996,
2002; Lyons et al., 2004; Lowenstein et al., 2005; Fig. 7).
However, data do not provide clear evidence that sulfate levels exceeded terminal Proterozoic values for all of the
Phanerozoic. We suggest that sulfate concentrations were,
however, generally higher in the Phanerozoic, which allowed
for increased formation of evaporates that provided favorable
conditions for generation of MVT deposits. The main control
on the temporal distribution of MVT deposits is the tectonic
remobilization of sulfate-rich evaporative concentrated seawater, rather than a maximum in oceanic sulfate concentration (see also Leach et al., 2010). It is unclear, however, how
the absence of continental rift- and sag-related CD Pb-Zn deposits are related to changing ocean chemistry (Leach et al.,
2010). This may reflect slightly higher oxygen levels in the
water column that inhibited formation of sulfidic conditions
in the sediments and in the deeper parts of these basins.
Some CD Pb-Zn deposits from this time suggest development of euxinic conditions in certain basins (Goodfellow and
Jonasson, 1984).
The picture that has emerged is not simple, but it is consistent with observations from a number of sources. Oceans
with a single, well-mixed surface pool and a well-mixed
deep-water pool were not present throughout most of the
geologic history. Rather, variations in the geographic and
temporal distribution of oxic, ferruginous, and sulfidic pools
occurred. The view that emerges is more intricate than described by the existing models, but we do not believe that
we have added unnecessary complexity. Rather, we argue
that the combination of geochemically distinct pools is a
general feature of the oceans state during significant periods in Earth history, which is required by the contrasting observations of sulfidic, iron-rich, and oxygenic signals extending from the Neoarchean until the present. The balance
between these pools has varied considerably. Prior studies
have sought to understand ocean chemistry and its evolution
in geologic time in terms of the underlying controls on and
responses of the oceans to changes in the supply and sinks
of elements such as iron, oxygen, and sulfur. Future research will be needed to understand the mechanisms that
drove large scale changes in ocean chemistry and to understand the ways that feedbacks between elements of the sulfur cycle and responses of sulfur pools may have been
recorded in sediments and sulfide ore deposits.
526
SULFUR CYCLE EVOLUTION, SULFUR ISOTOPES, SEDIMENTS, AND BASE METAL SULFIDE DEPOSITS
Acknowledgments
JF acknowledges support from the Guggenheim Foundation, The NASA Exobiology Program, NORDCEE, and the
Danish National Science foundation. Funding from the NSF
(EAR0918382) supported Nanping Wu during the final
stages of this project. Thoughtful reviews by Wayne Goodfellow, Craig Johnson, Rich Goldfarb, and David Leach as well
as a separate set of comments by Dick Holland were also
greatly appreciated. Collectively, these reviews provided critical and constructive comments resulted in significant
changes to the manuscript and are gratefully acknowledged.
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APPENDIX 1.
Mass-Dependent and Mass-Independent Sulfur Isotope Geochemistry
The foundation of isotopic geochemistry is the existence of
processes that discriminate between isotopes. For sulfur
which has four stable isotopes, the host of processes that discriminate between 34S and 32S do not discriminate between
33S, 36S, and 32S in exactly the same way. This allows one to use
variations in the relative abundance of 32S, 33S, 34S, and 36S to
provide insight into changes in the way that sulfur is cycled in
geological environments. Sulfur isotope notation used here
includes 34S, 33S, and 36S. The 34S describes the deviation of a measured 34S/32S from a reference 34S/32S, and the
33S and 36S describe the deviation of a measured 33S/32S or
a measured 36S/32S from reference relationship between
34S/32S, 33S/32S, and 36S/32S. We choose these reference relationships to approximate single-step equilibrium isotope and
draw on an exponential relationship between fractionation
factors (e.g. 34 = (33)
1
33
exponential term that is related to the relative mass differences between the different sulfur isotopes). We illustrate
this principle using thermodynamics of isotope exchange involving elemental sulfur and hydrogen sulfide using an equation that describes the distribution coefficients:
a 3 kS a H 32S
G 3k _ 32 S = RT ln
a32S a H 3k S
(1)
G3k_32S is the Gibbs free energy associated with the exchange reaction involving species with 32S and 3kS (in this case
k is 3, 4, or 6), R is the natural gas constant, T is temperature
(in Kelvins), and the activities are given by aspecies. Because
isotope exchange reactions are ideal with respect to mixing
(Ono et al., 2006b; Farquhar et al., 2007b), activity equals
concentration, and we can rewrite these as:
[ S ][H S ]
,
[ S ][H S ]
3k
G3 k _ 32 S = RT ln
32
32
(2)
3k
33S
34
SH2S =
3k
S H2 S
G34 _ 32
G3 k _ 32
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