Chemical Geology 206 (2004) 167 – 176

www.elsevier.com/locate/chemgeo

Organic carbon proxies in black shales: molybdenum

Pat Wilde a,*, Timothy W. Lyons b, Mary S. Quinby-Hunt c
a
Pangloss Foundation, 1735 Highland Place, Berkeley, CA 94709, USA
b
Department of Geological Sciences, University of Missouri, Columbia, MO 65211, USA
c
Lawrence Berkeley Laboratory, Berkeley, CA 94720, USA

Abstract

Isotopic and elemental proxies are useful for discerning the original compositions of ancient rocks subject to later diagenetic/
thermal alteration, low-rank metamorphism, outcrop weathering, etc. Recent work in the Cariaco Basin [Chem. Geol. 195
(2003) 131] has shown a high correlation between total organic carbon (TOC) content and Mo normalized to Al in these modern
euxinic sediments: microlaminated, dark olive gray, silty clay (0 – 11.6 kyr BP), %TOC = 1486*(Mo/Al) + 2.8, n = 13, r2 = 0.52,
mean rate of deposition = 36 cm/kyr; distinctly microlaminated, dark olive gray, clayey mud (11.6 – 14.5 kyr BP),
%TOC = 1622*(Mo/Al) + 0.22, n = 15, r2 = 0.89, mean rate of deposition = 79 cm/kyr.
Here, we use these relationships to estimate the original TOC contents of ancient black shales with overall characteristics
similar to those of the modern Cariaco sediments. These ‘‘Group IV’’ black shales as defined by Quinby-Hunt and Wilde [Econ.
Geol. 91 (1996) 4] are characterized by relatively high concentrations of V, Mo and Co but low Mn contents. The Cariaco
regressions and those from the Carboniferous of Iowa and the Devonian of New York were used to estimate the ‘original’ TOC
contents for Lower Ordovician black shales of the Baltica and Avalonia plates, where Corg values were not taken. For individual
samples, the Carboniferous regression produced TOC values approximately double that derived from the regression equation of
the Cariaco Basin lower anoxic zone. Such variations among the results from the four regressions suggest that there is no
universal proxy for TOC using Mo/Al.
These calculated TOC values, however, are consistent with the higher levels of primary production predicted from the
paleogeographic settings of these intervals. In general, the Mo proxy for original TOC content, while approximate, works for
oxygen-deficient sites of deposition where other proxies for C loss, such as Corg/Spy ratios in normal (oxic) marine shales, do
not apply. Estimates of original TOC from Mo content in samples spanning the geologic record, combined with paleogeography
and paleoecology, should be useful in estimating pathways of C synthesis and remineralization in ancient oceans and initial
hydrocarbon potential of petroleum source rocks.
Published by Elsevier B.V.

Keywords: Black shales; Chemical proxies; Organic carbon; Molybdenum; Baltica; Avalonia

1. Introduction ing increasingly valuable in the interpretation of early

With the growing number of whole-rock geochem-
ical data now available, elemental proxies are becom-
* Corresponding author. Tel.: +1-510-841-4721.
E-mail address: pat.wilde.td.57@aya.yale.edu (P. Wilde).
depositional histories of ancient rocks. With time, the
original composition of rocks will change due to
weathering; pore-fluid exchange and associated
rock – water interactions; secondary mineral over-
prints; thermal processes, including metamorphism;
and in general with the varying chemical conditions

0009-2541/$ - see front matter. Published by Elsevier B.V.

doi:10.1016/j.chemgeo.2003.12.005
168 P. Wilde et al. / Chemical Geology 206 (2004) 167–176
seen by sediments as they lithify and become deeply
buried. Even black shales, which because of their low
porosities and permeabilities after early diagenesis
should be impervious to compositional alteration over
the short term, are relatively open systems over
geologic timeframes.
Berner and Raiswell (1983) noted the unsuitability
of weathered rocks for C and S analyses, a conclusion
corroborated by the recent work of Petsch et al. (2000,
2001). Zaback et al. (1993) and many others have
shown that processes such as sulfate reduction can
occur in sediments long after burial, thus modifying
the primary (water-column) geochemical signals and
even the records of early diagenesis (e.g., Lyons et al.,
2003). Canfield (1994) discussed the general problem
of C preservation in marine rocks and the degree to
which it can vary as a function of depositional redox
and sedimentation rate. Most recently, Kennedy et al.
(2002), based on a study of two black shale locations
of Cretaceous age, suggested that organic carbon
(Corg) absorption onto clay mineral surfaces is a major
controlling factor in its burial and preservation.
Peucker-Ehrenbrink and Hannigan (2000) and Jaffe
et al. (2002) investigated mobility of platinum group
elements and Corg during weathering of black shales
and found a large (77%) decrease in TOC near the
surface (Jaffe et al., 2002), supporting the contentions
of Berner and Raiswell (1983), Petsch et al. (2000,
2001) and others. The thermal loss of Corg is well
known (e.g., Raiswell and Berner, 1987). Therefore,
despite our robust, integrated models for black shale
deposition (e.g., Stow et al., 2001; Sageman and
Lyons, in press), paleoenvironmental reconstructions
are often limited by our ability to discern primary
geochemical compositions.
2. The Mo proxy
Lyons et al. (2003) reported on results from Ocean
Drilling Program Site 1002 in the Cariaco Basin, a
modern anoxic-sulfidic (euxinic) pull-apart basin off
the coast of Venezuela (Dean et al., 1999; Muller-
Karger et al., 2000; Peterson et al., 2000; Yarincik et
al., 2000; Scranton et al., 2001). Lyons et al. (2003)
reported surface sediments dating back to approxi-
mately 15 kyr before present. Earlier, Wilde et al.
(2001) recognized correlations between Corg and Mo
in these data (Fig. 1) and used the resultant regression
equations to estimate the original minimum Corg
contents of a suite of Lower Paleozoic black shales.
Such a correlation is not unexpected in anoxic sedi-
ments. For example, Brumsack (1986) reported a high
correlation between Corg and V, Mo and Zn for
Cretaceous black shales from Cape Verde Basin drill
cores, and Werne et al. (2002) showed striking co-
variance between Corg and Mo/Al ratios in Devonian
euxinic shales from western New York. Nijenhuis et
al. (1999) discussed the general Corg – trace metal
relationship using Pliocene examples. The present
paper is an expansion on our earlier abstract and a
further exploration of the relationship between Corg
and Mo in fine-grained sediments deposited beneath
oxygen-deficient waters.
The positive correlation observed between concen-
trations of Corg and Mo in many black shales and
sediments of modern, oxygen-deficient marine basins
is well known. In some instances this covariation may
be partially or entirely an artifact of dilution by high
but variable fluxes of biogenic sediment (opal or
calcium carbonate). For example, Corg and Mo con-
tents in Unit 1 in the modern Black Sea rise and fall
sympathetically with varying CaCO3 dilution (Lyons,
preliminary unpublished results), but the correlation
breaks down when Mo is normalized to Al content to
remove spurious enrichment trends. By contrast, Mo/
Al ratios and Mo mass accumulation rates (mass Mo
area 1 time 1) at many other sites suggest a true
mechanistic linkage between the delivery/burial of
Corg and Mo. This coupled accumulation of Corg and
Mo, where observed, is generally coherent over the
Phanerozoic, but it is clear that no universal linear
relationship exists. In ancient sediments, shifts in the
slope and scatter in the data can reflect selective loss
of Corg or remobilization of Mo during burial and
weathering. However, the results of the present study
reveal that primary differences can occur over com-
paratively short time intervals even within a single
anoxic basin.
Ultimately, we agree with past workers that the
availability of dissolved sulfide is a critical control in
Mo sequestration (Helz et al., 1996), and parallel
accumulation of Corg may simply drive the system
capacity to generate hydrogen sulfide on both local
and basin scales. A number of workers have sug-
gested, however, that the requisite high levels of
 P. Wilde et al. / Chemical Geology 206 (2004) 167–176 169

Fig. 1. Mo/Al vs. total organic carbon (wt.%) from ODP site 1002 (Cariaco Basin). Modified from Lyons et al. (2003).

sulfide can occur either in pore waters or in the water The Cariaco data discussed here (Figs. 1 and 2; Lyons
column (reviewed in Lyons et al., 2003; Sageman and et al., 2003) argue against a direct coupling between
Lyons, in press), thus limiting the utility of Mo as an Mo and pyrite accumulation (compare Huerta-Diaz
unambiguous proxy for euxinicity. Also, recognizing
that persistent availability of dissolved sulfide is a
function of bacterial production as well as H2S loss
through pyrite formation, supplies of reactive Fe
become an essential control in Mo enrichment (e.g.,
Meyers et al., in review).
In addition to sulfide production, there is likely a
more direct coupling between Corg and Mo burial
through reactions between Mo-bearing dissolved spe-
cies (e.g., thiomolybdate) and organic matter (Helz et
al., 1996). If so, the types and relative amounts of
marine and terrestrial organic matter can be critical,
giving rise to intrabasinal variation in Mo (vs. Corg) Fig. 2. Regression plots and statistics for zone I: microlaminated,
dark olive gray, organic rich silty clay (0 – 11.6 kyr BP); zone II:
distributions in, for example, Carboniferous shales distinctly microlaminated, dark olive gray, organic-rich, diatom-
(Coveney et al., 1991; Helz et al., 1996; Cruse and rich clayey mud with abundant calcareous microfossils clay (11.6 –
Lyons, this volume; see review in Lyons et al., 2003). 14.5 kyr BP).
170 P. Wilde et al. / Chemical Geology 206 (2004) 167–176

and Morse, 1992). Finally, Kao et al. (2001) reported
on the mineralogy of a mixed-layer carbon – molyb-
denum sulfide phase from Cambrian metalliferous
black shales in China. The broad relevance of this
relationship is unknown, but such phases may play a
role in hosting the C – Mo pair.
Despite these and other complications and the
potential for scatter in patterns of Mo vs. Corg burial,
ratios of Corg to Mo/Al show general similarities
among many temporally and spatially diverse organ-
ic-rich sediments (e.g., Fig. 3). Overall, the correlation
should be strongest where sulfide concentrations and/
or organic matter type are most favorable to Mo
accumulation. Interestingly, however, the data in
Fig. 3 for Paleozoic shales, which have not experi-
enced appreciable heating during burial, show Corg
enrichment rather than loss relative to the Cariaco
modern baseline. This unexpected result likely reflects
intersite differences among original Corg –Mo relation-
ships in sediments that have not experienced appre-
ciable Corg loss since deposition.
Clearly, there is no universal relationship between
Corg and Mo in oxygen-deficient settings, but there is
often at least general agreement suitable for our
purpose here (Fig. 3), which is to approximate Corg
loss in highly altered shales. Nevertheless, some
modern and ancient euxinic settings fail to show
covariance between Mo/Al and Corg. These differ-
ences are beyond the scope of this paper but likely
reflect a complex combination of multiple primary
and secondary controls, such as (1) the magnitude of
sulfide availability, including water-column H2S con-
centrations that may have been less intense and less
persistent than traditional interpretations for black
shale paleoenvironments (Murphy et al., 2000; Sage-
man and Lyons, in press); (2) the relative roles of
pore-water versus water-column sulfide availability;
(3) the amount and type of organic matter present,
including relative terrestrial versus marine inputs; (4)
Mo remobilization during weathering and higher-
temperature burial alteration; (5) local and global
differences in seawater Mo chemistry; (6) Corg con-

Fig. 3. Summary of Mo/Al vs. Corg for euxinic sediments of the Cariaco Basin (Lyons et al., 2003, this study) and euxinic black shales within the
Devonian Oatka Creek Formation, New York, northern Appalachian Basin (Werne et al., 2002), and the Carboniferous Hushpuckney Shale
Member of the Swope Limestone, Iowa (Cruse and Lyons, 2003, submitted).
 P. Wilde et al. / Chemical Geology 206 (2004) 167–176
tributions via in situ production of microbial biomass;
and (7) secondary Mo overprints related to hydrother-
mal processes.
3. The C –S analog
In an effort to quantify the loss of Corg during
thermal maturation, Raiswell and Berner (1987)
exploited the commonly observed covariation be-
tween Corg and pyrite sulfur (Spy) observed in many
modern and ancient normal (oxic) marine sediments.
Because pyrite formation beneath oxic bottom waters
in restricted to the sediments (i.e., is purely diagenet-
ic), and because H2S production is thus controlled by
the local availability of metabolizable Corg, Spy con-
centrations are frequently limited by the concentration
of Corg if adequate reactive Fe is present (Berner,
1984; compare Raiswell and Canfield, 1998). Such a
coupling between Corg and Spy is expressed as the
well-known covariation between the abundances of
the two components in normal marine sediments, with
a zero sulfur intercept (modern C/S ratio of f 2.8;
Berner, 1984; Morse and Berner, 1995). Raiswell and
Berner (1986) explored the principal controls on this
ratio over time and later concluded (Raiswell and
Berner, 1987) that dramatic deviance from the pre-
dicted temporal trends could be attributed to selective
Corg loss during thermal maturation of the organic
matter. In short, this was a tool for assessing Corg loss
much like that proposed here.
One complicating consideration for the C –S meth-
od is that the positive linear relationship between Corg
and Spy exploited by Raiswell and Berner (1987)
breaks down under the oxygen-deficient conditions
that prevail in the Cariaco Basin, the Black Sea
(Lyons and Berner, 1992; Lyons, 1997), and during
deposition of many black shales (Raiswell and Berner,
1985). Under such conditions, iron limitation, rather
than Corg supplies, becomes the dominant control on
pyrite formation. We suggest, therefore, that the C/S
and Corg –Mo/Al approaches are complementary rath-
er than overlapping, and each has unique paleoenvir-
onmental relevance. It is also important to note that,
like the Corg –Mo relationship, the strength of the C – S
method is limited by the appreciable scatter surround-
ing the modern mean C/S ratio of 2.8 and the mean
ratios spanning geologic time. Many of the caveats
171
outlined here for the Corg – Mo relationship, such as
the importance of terrestrial versus marine organic
inputs, also apply to the C – S system and have been
addressed in detail in past studies of sedimentary
pyrite formation (Raiswell and Berner, 1986). How-
ever, the fruits of two decades of research centered on
C– S relationships far exceed our nascent understand-
ing of coupled Corg –Mo burial.
4. Results
Fig. 1 is a composite profile of the material
sampled in the Cariaco Basin (see Lyons et al., 2003
for details). As shown, the correlations between Corg
and Mo/Al ratios divide into two, sedimentologically
and geochemically distinct intervals in the core: (1)
microlaminated dark olive gray silty clay spanning the
upper f 420 cm (0– 11.6 kyr BP), with a mean rate of
sedimentation of f 36 cm/kyr, underlain by (2)
distinctly microlaminated dark olive gray clayey
mud about 230 cm thick (11.6 –14.5 kyr BP), with a
mean sedimentation rate of f 79 cm/kyr. Below these
zones, the sediment are bioturbated, indicating oxic
overlying bottom waters, and the correlation does not
hold (see Lyons et al., 2003 and references therein for
sedimentological, geochemical and paleoceano-
graphic details). The Mo values on the graph are
normalized to aluminum as a proxy for detrital clay
content. This way, the time-varying effects of dilution
by calcium carbonate and biogenic opal are removed.
Van der Weijden (2002) discussed the potential prob-
lems associated with data normalization, but because
we are simply looking for Mo enrichment beyond the
detrital flux, and our Mo/Al trends are generally
consistent with the Mo accumulation rates calculated
by Dean et al. (1999), we feel justified in using this
procedure.
Fig. 2 shows the linear regressions with the ac-
companying statistics for the two anoxic zones iden-
tified in the post-glacial Cariaco Basin. It should be
noted that the lower anoxic zone with the higher rate
of sedimentation has a higher r2 value than the upper
zone (0.9 vs. 0.5). One possibility for the two different
trends in the Cariaco sediments is the relationship
between the deeper zone and the high primary pro-
ductivity inferred over this interval (Peterson et al.,
1991; Werne et al., 2000; Lyons et al., 2003). Among
172 P. Wilde et al. / Chemical Geology 206 (2004) 167–176

Table 1 water-column pyrite formation throughout the section

Organic carbon regression values for Tremadoc black shales (Lyons et al., 2003; Werne et al., 2003). The discor-
Regressions dant trends may also stem from differences in rates of
Cariaco I Upper Anoxic zone %TOC = 1486(Mo/Al) + 2.8 sedimentation and other variations in depositional
Cariaco II Lower Anoxic zone %TOC = 1622(Mo/Al) + 0.22 history, including relative amounts of turbiditic sedi-
New York Devonian %TOC = 2024(Mo/Al) + 3.9
ment, temporal variation in the types of dominant
Iowa Carboniferous %TOC = 2479(Mo/Al) + 5.5
organic material produced and deposited in the basin
Mo/Al values calculated from data in Quinby-Hunt et al. (1989) and
Fyffe and Pickerall (1993).
(Werne et al., 2000), and overall persistence of a given
set of environmental conditions in the water column.

other things, such an interval might have had higher

associated hydrogen sulfide concentrations in the
water column and in the sediments, facilitating
more-effective scavenging of Mo. The S and Fe
expressions of such differences in H2S conditions
would be muted by the persistent record of Fe-limited,
5. Application to ancient sediments
Based on the black shale database of Quinby-Hunt
et al. (1989), Quinby-Hunt and Wilde (1991, 1994,
1996) postulated four geochemical groups for black

Fig. 4. Paleographic reconstruction for Lower Ordovician 490 Ma. South Polar Mollewiede Projection. Modified from Wilde et al. (1997) and
updated with Plate Tracker v.2 by Eldridge et al. (2000) with permission. The samples are from the Tremadoc and Arenig so the reconstruction
time is approximately medial thus the actual map positions would vary with plate motions. Group IV, Baltica samples: D = Denmark,
E = Estonia, S = Sweden, O = Norway (Oslo district). Avalonia samples: NB = New Brunswick. Group III: Bel = Belgium, Bol = Bolivia,
Q = Quebec (Levis).
 P. Wilde et al. / Chemical Geology 206 (2004) 167–176 173

Table 2
MSG Tremadoc Group IV Regressions
Cariaco I Cariaco II New York Devonian Iowa Carboniferous
Sample # Baltica Mo/Al %TOC %TOC %TOC %TOC
9480070 Oslo, Toyen 0.000795 3.982 1.510 5.573 7.494
9770340 Oslo, Sjostrand (Oslo-Asker) 0.000884 4.114 1.654 5.753 7.714
9770110 Scania (SE), Flagabro core 0.008116 14.860 13.384 20.391 25.642
9480050 Oslo, Vaekkero 0.001289 4.716 2.311 6.572 8.718
9480080 Oslo, Stensberggaten 0.000131 2.994 0.432 4.228 5.846
9480100 Norway (Oslo ?) 0.004182 9.015 7.004 12.429 15.890
9770160 Scania (SE), Flagabro core 0.001628 5.220 2.861 7.259 9.559
9360220 Oslo 0.000619 3.720 1.224 5.216 7.057
9360300 Sjostrand 0.000213 3.116 0.565 4.393 6.049
9480160 Baltischport 0.002744 6.877 4.671 9.517 12.324
9480150 Scania, Sandby 0.005992 11.704 9.939 16.091 20.376
9770070 Fagelsang core, Scania 0.004049 8.817 6.788 12.160 15.561
9480170 Estonia 0.003619 8.178 6.091 11.289 14.195
9770060 Fagelsang core, Scania 0.002227 6.109 3.832 8.471 11.043
9480060 Oslo, Vaekkero 0.002799 6.959 4.760 9.629 12.461
9480090 Oslo, Killingen, Bygdo 0.001285 4.709 2.304 6.563 8.707
9770040 Fagelsang core, Scania 0.000904 4.143 1.686 5.792 7.762
9770180 Scania (SE), Flagabro core 0.001534 5.080 2.708 7.068 9.325
9770090 Fagelsang core, Scania 0.000307 3.256 0.718 4.585 6.283
9480030 Oslo, Hammersborg 0.002886 7.089 4.902 9.806 12.678
9770320 Oslo, Toyen 0.000279 3.214 0.672 4.527 6.213
9770330 Oslo, near Eternite Factory 0.000171 3.054 0.497 4.309 5.946
9480040 Oslo, Hammersborg 0.001951 5.700 3.385 7.913 10.360
9770210 Scania (SE), Flagabro core 0.000871 4.095 1.633 5.727 7.682
9770190 Scania (SE), Flagabro core 0.003878 8.563 6.510 11.813 15.136
9480120 Denmark Bornholm, Laesaa 0.001737 5.381 3.037 7.479 9.828
9770080 Fagelsang core, Scania 0.001453 4.959 2.577 6.904 9.124
9480110 Oslo, Toyen 0.001134 4.485 2.059 6.258 8.333
9480010 Oslo, Toyen 0.004172 8.999 6.987 12.407 15.864
9361540 Oslo, Sars Gate 0.002518 6.542 4.304 9.060 11.765
9360230 Oslo 0.000793 3.978 1.506 5.568 7.488
9770050 Fagelsang core, Scania 0.00198 5.742 3.431 7.970 10.429
9480020 Oslo, Roken 0.000897 4.132 1.674 5.778 7.745
9770170 Scania (SE), Flagabro core 0.001091 4.421 1.989 6.171 8.226
9480130 Scania, Flagabro 0.000733 3.890 1.409 5.447 7.340
Average 5.766 3.458 8.003 10.470
Maximum 14.860 13.384 20.391 25.642
Minimum 2.994 0.432 4.228 5.846

Sample # Avalonia Mo/Al Cariaco I Cariaco II New York Devonian Iowa Carboniferous
9770010 Chesley Dr., St. John, NB 0.000165 3.046 0.488 4.298 5.932
B9481080 St. John, NB 0.000097 2.944 0.378 4.160 5.763
9480210 St. John, Navy Island, NB 0.000472 3.501 0.985 4.918 6.692
B9481190 St. John, NB 0.000567 3.643 1.140 5.112 6.929
B9481160 St. John, Navy Island, NB 0.000126 2.987 0.424 4.218 5.834
bb1-3 Canada Appalachian 0.000554 3.623 1.118 5.084 6.895
bb4-6 Canada Appalachian 0.00031 3.260 0.722 4.590 6.289
Average 3.288 0.753 4.626 6.333
Maximum 3.643 1.140 5.112 6.929
Minimum 2.944 0.378 4.160 5.763
174 P. Wilde et al. / Chemical Geology 206 (2004) 167–176
shales varying as a function of pH and redox con-
ditions and identified by characteristic elemental
abundances. Only two of the four groups had signif-
icant Mo content. These groups are characterized by
relatively low Mn and Fe contents, relatively high V,
Mo and Co, and were considered the more anoxic of
the black shale facies. Based on their overall geo-
chemical characteristics, we group the microlaminated
Cariaco Basin samples with as borderline Group IV on
a carbonate-free basis. The two separate regressions
identified for the two facies seen in Fig. 1 demonstrate
that Mo in black shales is expressed by more than one
simple relationship with TOC content, which is not
surprising given the multiple controlling factors on
Mo accumulation in marine systems (Morford and
Emerson, 1999; Meyers et al., in review).
Table 1 shows the predicted values of Corg for
samples in a black shale database from the Lower
Ordovician of the Baltica and Avalonia terranes of the
Iapaetus Ocean, calculated from the regressions
shown in Fig. 3. Paleogeographic reconstructions
(Fig. 4) of these terranes place the Baltica samples
at approximately 30j off a western coast and the
Avalonia samples at 60j south, importantly both in
regions of predicted high primary productivity (Wilde
et al., 1989, 1990). The Laurentia samples from
Quebec (Levis) are on the same latitude as the Baltica
samples but are not from a coastal region of paleo-
upwelling. Samples from the same continental masses
but off the productivity highs do not show Group IV
characteristics and are therefore excluded from the
calculations.
The highest calculated TOC values are from Swed-
ish core material, thus re-enforcing the Berner and
Raiswell (1983) dictum on the difference in preserva-
tion between core and potentially weathered outcrop
samples. In this case, because we are calculating TOC
from Mo content, the calculations appear to be com-
promised by the weathering effects on Mo. Thus,
while our method permits estimates of original TOC
contents, it may be best applied to Corg loss through
burial processes less extreme to metal remobilization
than surficial weathering. Which regression is most
applicable to these Ordovician rocks is not clear.
However, the use of all in Table 2 allows us to bracket
the range of possible original Corg contents. The wide
range of Corg (reported as %TOC) values certainly
indicate that we have not achieved a method for
universal application to any black shale without some
additional regression criteria.
6. Summary
A proxy for original Corg content in black shales
based on an extrapolation of Mo/Al trends seen in
modern material from the Cariaco Basin and from two
Paleozoic locales has been applied to black shales
from the Lower Ordovician. The significant variation
in Corg (calculated values using different regressions)
indicates that more work is needed in classifying
black shales to match any proxy regression with a
particular shale. However, this technique, once re-
fined, has the potential to ‘‘rescue’’ many older data
sets for which TOC data were not generated, but
where metals such as Mo were analyzed, and for
which the C – S normal marine proxy does not apply.
Such approaches are useful in evaluating petroleum
potential of reservoir shales by comparing present
TOC values with the proxy estimates, thus constrain-
ing thermal Corg loss. Gelinas et al. (2001) reaffirmed
the view that anaerobic sediments, such as examined
here, ‘‘were essential for the generation of petroleum
source rocks’’. This technique for assessing potential
hydrocarbon yield may be used best for core material,
which will not have experienced weathering and thus
recent surficial oxidation of Corg. Also, metal remo-
bilization associated with surficial processes will not
be a factor (see Morford and Emerson, 1999). Finally,
proxy values for TOC when viewed in an integrated
geochemical, paleoceanographic and paleogeographic
context could aid in reconstructions of areas of high
productivity as well as other paleoecologic processes.
For example, Ganeshram et al. (1999) found Corg
burial in the modern environment off NW Mexico
was governed mainly by productivity rather than
overlying oxygen content in the water column, as
has been suggested for many other settings, including
the Holocene Black Sea (Calvert and Karlin, 1998). In
future papers, we will investigate other proxies such
as vanadium, which are also characteristically
enriched in Type IV black shales. We also recognize
that this technique can result, at best, in a minimal
approximation of the TOC values without a more
comprehensive mechanistic understanding of the re-
lationship between Corg accumulation and Mo enrich-
 P. Wilde et al. / Chemical Geology 206 (2004) 167–176
ment, including the primary controls on any temporal
and spatial variability in the Corg –Mo correlation. In
the short term, we would do well to explore this
correlation in a variety of other settings, modern and
ancient, with the hope of finding consistencies of
broad temporal and spatial relevance.
Acknowledgements
The authors thank Prof. Dr. Hans Brumsack for
sharing his data and two external reviewers for their
time and useful comments. TWL acknowledges
support from NSF grants EAR-9875961 and EAR-
9725326 and from JOI-USSSP. This is Contribution
03-01 of the Pangloss Foundation. [LW]
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