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Osmium isotope evidence for the regulation of atmospheric CO2

by continental weathering
Anthony S. Cohen* 
Angela L. Coe  Department of Earth Sciences, The Open University, Milton Keynes MK7 6AA, UK
Stephen M. Harding 
Lorenz Schwark Geologisches Institut, Universität zu Köln, Zülpicher Strasse 49a, D-50674 Köln, Germany

ABSTRACT sedimentary facies, stratigraphic context, and


The long-term stability of Earth’s climate throughout the Phanerozoic stands in paleogeographic position of these exposures
marked contrast to the dramatic fluctuations that have taken place on time scales as all provide evidence that the mudrocks were
short as a few years, reflecting the high efficiency of longer-term climate regulation deposited under open-marine conditions (Hes-
through negative feedbacks. A fundamental mechanism is thought to involve control of selbo and Jenkyns, 1995; Howarth, 1962,
CO2 in the ocean-atmosphere system through continental weathering, although un- 1992).
ambiguous, high-resolution data supporting this hypothesis have hitherto not been avail- Our new Re and Os abundance data, and C
able. Organic-rich mudrocks from Yorkshire, England, which were deposited during the isotope results, are shown in Figure 1 and re-
Toarcian oceanic anoxic event (ca. 181 Ma, Early Jurassic), contain evidence of an excep- ported in Tables DR1 and DR21. Suites of
tionally large excursion in the 187Os/188Os ratio of contemporaneous seawater, from ;0.4 mudrock samples from the exaratum and fal-
to ;1.0. The most likely explanation for this excursion is that it resulted from a transient ciferum Subzones define Re-Os isochron ages
increase in global continental weathering rates of ;400%–800%. The Os isotope excursion of 181 6 13 Ma (Cohen et al., 1999) and 178
coincided with a well-documented global d13C excursion of 26‰ that affected all the 6 5 Ma (this study, Fig. 2), respectively, thus
major biospheric reservoirs of the time. Higher mean global temperatures caused global confirming that the Re-Os isotope system in
chemical weathering rates to increase substantially, while, in turn, chemical weathering these successions has not been disturbed since
was very effective in reducing the elevated levels of atmospheric CO2 and the high tem- deposition and that the initial Os isotope com-
peratures to preexcursion levels. position is primary (Cohen et al., 1999). There
is a major, transient increase in the calculated
187Os/188Os ratio of seawater from ;0.4 to
Keywords: osmium, weathering, Toarcian, oceanic anoxic event, strontium, methane hydrate.
;1.0 (Fig. 1) that occurred mostly during de-
INTRODUCTION sponse to changes in the balance between the position of the exaratum Subzone. Despite its
Although rapid oscillations in Earth’s cli- major inputs to the oceans—primarily from relative brevity, with an apparent duration of
mate have occurred frequently in the past (Al- continental weathering, the hydrothermal alter- ;100 k.y., the magnitude of the Os isotope
ley et al., 2003), climate-control processes ation of juvenile oceanic crust, and meteoritic excursion exceeded the total variation in the
187Os/188Os ratio of seawater over the past
have operated during the Phanerozoic to keep sources (Cohen et al., 1999; Pegram et al.,
Earth’s climate within the relatively narrow 1992; Peucker-Ehrenbrink and Ravizza, 2000). ;35 m.y. (Pegram et al., 1992).
bounds required for the continuing success of Because the hydrothermal input of unradiogen-
life on the planet. Interaction between CO2 in ic Os to the oceans can be assumed to remain DISCUSSION
the ocean-atmosphere system and the silicates constant over relatively short intervals, rapid The magnitude of the Os isotope excursion
in the continental crust is thought to be a fun- and transient increases in the seawater 187Os/ reported here would have demanded an in-
damental mechanism in the regulation of 188Os ratio can be caused only by a sudden crease of ;800% in the continental weather-
Earth’s climate, involving the release of Ca increase in the flux or isotopic composition of ing flux, if present-day isotopic ratios for the
and Mg by chemical weathering and, ulti- radiogenic Os from continental weathering. end-member components are used (Peucker-
mately, the deposition of (Ca,Mg)CO3 in the Ehrenbrink and Ravizza, 2000). This excur-
oceans (Berner et al., 1983; Broecker and San- SAMPLES AND RESULTS sion could, in theory, have involved a very
yal, 1998; Kump et al., 2000; Walker et al., The samples that we selected for study are abrupt and transient increase in the 187Os/
Toarcian organic-rich mudrocks from expo- 188Os ratio of the global continental weather-
1981). However, one of the major obstacles in
demonstrating the precise role of chemical sures at Saltwick Bay, Port Mulgrave, and ing component, rather than in its flux. How-
weathering as a regulator of climate has been Hawsker Bottoms, Yorkshire, England (Hes- ever, we consider such an eventuality to be
the difficulty in finding a distinctive chemical selbo and Jenkyns, 1995; Howarth, 1962, very remote because large-scale changes in
proxy that responds with sufficient rapidity 1992). The widespread deposition of marine the worldwide balance of rocks that are avail-
and magnitude to changes in global weather- organic-rich mudrocks across the exaratum able for weathering at Earth’s surface require
ing. The relatively short seawater resi- Biosubzone of the lower falciferum Biozone the action of long-term (millions of years) tec-
dence time for Os of ;10–40 k.y. (Peucker- (Toarcian, Early Jurassic, ca. 183–178 Ma [Palfy tonic processes. Such processes could not
Ehrenbrink and Ravizza, 2000) makes it an et al., 2000]), with as much as 15% organic have operated on the much shorter (thousands
ideal isotopic tracer for the purpose, as long carbon, is a primary feature of the Toarcian
as the recovered signal is primary and global oceanic anoxic event (Jenkyns, 1988; Jenkyns 1GSA Data Repository item 2004019, Tables

in extent. Our approach is based on the ob- et al., 2002). Although the duration of the ex- DR1 and DR2 (sample locations, stratigraphic po-
servation that the Os isotope composition of aratum Subzone is not accurately constrained, sitions, Re and Os abundances, Os isotope and d13C
data), is available online at www.geosociety.org/
seawater has varied over geologic time in re- it is estimated from annual sediment-layer pubs/ft2004.htm, or on request from editing@
couplets to have been ;150 k.y. (Cope, 1998; geosociety.org or Documents Secretary, GSA, P.O.
*E-mail: a.s.cohen@open.ac.uk. Hesselbo et al., 2000). The rich marine fauna, Box 9140, Boulder, CO 80301-9140, USA.

q 2004 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.
Geology; February 2004; v. 32; no. 2; p. 157–160; DOI 10.1130/G20158.1; 3 figures; Data Repository item 2004019. 157
Figure 1. Os, C, and Sr isotope variations in seawater for part of Toarcian (Lower Jurassic); plots display large, concurrent
changes in seawater 187Os/188Os ratios (Table DR1; see footnote 1), d13C values for bulk organic matter (this study, Table
DR2; see footnote 1; VPDB is Vienna Peedee belemnite), and seawater 87Sr/86Sr ratios (McArthur et al., 2000) that took place
during deposition of exaratum Subzone; gray band across isotope curves indicates exaratum Subzone. Sample positions
relate to composite stratigraphic section from three localities in Yorkshire, England, shown here as summary graphic log
(for details see Table DR1; see footnote 1). Lithostratigraphy and biostratigraphy are from Hesselbo and Jenkyns (1995) and
Howarth (1962, 1992). P. 5 Protogrammoceras, D. 5 Dactylioceras, cl. 5 clevelandicum, ten. 5 tenuicostatum. Lithologies
include dark gray mudrocks (dark gray tone), medium gray mudrocks (gray tone), and carbonate bands and nodules (white).
Early Jurassic seawater Os isotope compositions were calculated from present-day Re and Os abundances and Os isotope
compositions of mudrock samples by assuming closed-system behavior (as indicated by isochron relationships, this study,
and Cohen et al. [1999]) and using depositional ages indicated by isochrons (Table DR1; see footnote 1).

of years) time scale over which the global sea- all the major biospheric carbon reservoirs at
water Os isotope excursion in the exaratum that time, i.e., bulk marine organic matter
Subzone was established. Nevertheless, if we (Hesselbo et al., 2000; Kuspert, 1982; Schou-
consider an extreme event in which the 187Os/ ten et al., 2000), primary organic production
188Os ratio of the global weathering flux sud- biomarkers (Schouten et al., 2000), marine
denly increased by ;50% to 2 (compared carbonate (Kuspert, 1982; Schouten et al.,
with its present-day value of 1.4), then the ob- 2000), and terrestrial carbon (Hesselbo et al.,
served Os isotope shift would have still re- 2000). Hesselbo et al. (2000) demonstrated
quired an additional increase in weathering that the only geologic process consistent with
flux of 400%. Thus, the magnitude of the tran- a global C isotope excursion of this magnitude
sient excursion in the Os isotope composition would have been the dissociation of very large
of seawater during deposition of the exaratum amounts of methane hydrate, an immediate
Subzone was so large that it would have in- consequence of which would have been its
volved a relatively brief interval of greatly en- rapid oxidation to CO2 and a threefold in-
Figure 2. Re-Os isochron diagram for all six
mudrock samples from falciferum Subzone. hanced continental weathering, on a global crease in atmospheric CO2 levels (Beerling et
Regression age is 178.2 6 5.6 Ma (mean scale, for any realistic Os isotope composition al., 2002). A crucial point is that the precise
square of weighted deviates 5 3.0). Initial of the weathering flux. interval over which the levels of atmospheric
187
Os/188Os ratio (0.4 6 0.15) reflects that of
The Os isotope excursion coincided with a CO2 were high is clearly defined by the highly
contemporaneous seawater (Cohen et al.,
1999; Peucker-Ehrenbrink and Ravizza, global d13C shift of 26‰ (Fig. 1) that was distinctive light C isotope composition im-
2000). one of the largest of the Phanerozoic, affecting parted by the dissociated and oxidized meth-

158 GEOLOGY, February 2004


et al., 2002; McArthur et al., 2000) and Mg/ the oxidation of methane hydrate during the
Ca ratios (McArthur et al., 2000) from bel- exaratum Subzone would have been con-
emnites, some of which were used to define sumed in ;37–123 k.y. This result is fully
the contemporaneous seawater Sr isotope consistent with the other estimates for the du-
curve. The d18O values suddenly decreased by ration of the Os and C isotope excursions.
;3‰ at the same point that marked the start The dramatic rise in the 87Sr/86Sr ratio of
of the Os and C isotope excursions, while Mg/ seawater during deposition of the exaratum
Ca ratios approximately doubled, from 0.2 to Subzone represented one of the fastest rates of
0.4. Both data sets independently suggest that increase of the Phanerozoic. It was superim-
average seawater surface temperatures during posed on a longer-term increase (Fig. 3) that
deposition of the exaratum Subzone were as extended from the late Pliensbachian to the
much as 10 8C higher than those before and early Bajocian. The singular change in slope
after (Jenkyns et al., 2002; McArthur et al., of the seawater Sr isotope curve in the late
2000). Pliensbachian coincided with the main erup-
Although the precise relationship between tive phase of the Karoo-Ferrar igneous prov-
continental weathering rates and mean global ince at 183 6 1 Ma, according to the dates of
temperature in the Toarcian would have de- Duncan et al. (1997). Under the assumption
pended on the highly complex interplay be- that the contribution of unradiogenic Sr from
tween vegetation and hydrology as well as on seafloor spreading remained essentially con-
atmospheric CO2, the 400%–800% increase in stant over this interval (Rowley, 2002), we
weathering rates in the exaratum Subzone of suggest that the eruption of the Karoo-Ferrar
the Toarcian is nevertheless fully consistent igneous province caused both the initial rise
with estimates of the temperature dependence in seawater 87Sr/86Sr ratio in the late Pliens-
of current chemical weathering rates (Gaillar- bachian and its longer-term increase. This oc-
det et al., 1999; Kump et al., 2000). An anal- curred through volcanic CO2 outgassing,
ysis of the dissolved loads carried by the which led in turn to higher mean global tem-
world’s rivers shows that a 500% increase in peratures and enhanced continental weather-
Figure 3. Variations in Jurassic seawater weathering rate occurs for every 5 8C rise in ing. We further suggest that the transient and
87
Sr/86Sr ratio. A: High-resolution profile for temperature where weathering rate is not con- exceptionally high rate of increase in seawater
upper Pliensbachian–lower Toarcian (Mc- trolled by water supply (Gaillardet et al., 87Sr/86Sr ratio during deposition of the exar-
Arthur et al., 2000), showing variations with
stratigraphic height. B: Variations in 87Sr/ 1999). The sudden and large increase in con- atum Subzone was caused by the acceleration
86
Sr ratio of Jurassic seawater, based on in- tinental weathering rates in the greenhouse of weathering rates resulting from higher at-
tegrated data set (Jones et al., 1994a, world of the Toarcian is commensurate with mospheric CO2 and mean global temperatures
1994b). Bold arrow indicates approximate highly efficient hydrologic and weathering following methane hydrate destabilization
duration of eruption of Karoo-Ferrar igneous
province (Duncan et al., 1997).
systems where groundwater flow predominat- (Beerling et al., 2002; Hesselbo et al., 2000).
ed, as was the case in the Late Cretaceous After the deposition of the exaratum Subzone,
when groundwater flow exceeded runoff by a the seawater Os isotope composition and the
ane hydrate (Fig. 1). The concurrent Os and factor of six (Floegel et al., 2003). For com- rate of increase of the seawater 87Sr/86Sr ratio
C isotope excursions in the Toarcian also co- parison, during the present-day icehouse con- returned rapidly to levels similar to those be-
incide with an exceptionally sharp increase in ditions, global runoff exceeds groundwater fore the methane hydrate destabilization, in-
the seawater Sr isotope composition (Figs. 1 flow by a factor of three. dicating a relaxation in continental weathering
and 3) (Jones et al., 1994b; McArthur et al., The transient increase in continental weath- rates.
2000). Because these synchronous C and Sr ering rates in the exaratum Subzone resulted An alternative explanation for the steep rise
isotope shifts were demonstrably global in ex- in an increased flux of Ca and Mg to the in the seawater 87Sr/86Sr ratio across the ex-
tent (Hesselbo et al., 2000; Jenkyns et al., oceans, which would have served to balance aratum Subzone, proposed by McArthur et al.
2002; Jones et al., 1994b), they provide ad- the higher levels of CO2 in the oceans and (2000), is that it is an artifact of unusually
ditional compelling evidence that the seawater atmosphere. The approximate time scale of the slow sedimentation rates in the exaratum Sub-
Os isotope excursion, which occurred over the C (and Os) isotope excursions may be esti- zone alone. These authors make the explicit
same short interval, also represented a global mated from global sedimentation and CO2 assumption that the rate of increase of sea-
signal. consumption rates; this calculation also pro- water 87Sr/86Sr ratio in the early Toarcian was
One of the main factors governing rates of vides an independent check of the feasibility constant. They conclude that the exaratum
chemical weathering is temperature (Kump et of enhanced continental weathering having Subzone is greatly condensed compared with
al., 2000). Beerling et al. (2002) calculated acted as the negative feedback that regulated the strata above and below, and that it was
that the global d13C isotope excursion of atmospheric CO2. Sediment supply to the deposited over an interval of ;1 m.y. How-
26‰ in the Toarcian would have required the oceans was relatively low in the Early Jurassic ever, the assumption upon which this approach
dissociation of ;5000 Gt of methane hydrate and, outside the exaratum Subzone, may have is based—that the rate of increase in seawater
been as little as 12%–20% of its current level 87Sr/86Sr ratio was constant—is hard to justify
and that average global temperatures would
have increased by at least 3 8C as a conse- (Floegel et al., 2000). Present-day chemical in view of the dramatic reversal of slope of
quence of the threefold increase in atmospher- weathering of Ca- and Mg-bearing silicates the seawater Sr isotope curve in the latest
ic CO2. Direct evidence for a sudden, large consumes 0.085 Gt of C annually (Gaillardet Pliensbachian, perhaps no more than ;1 m.y.
increase in seawater temperatures at that time et al., 1999); thus, depending on the exact earlier (Fig. 3).
also comes from O isotope analyses (Jenkyns choice of values, the excess CO2 derived from The transient geochemical and climatic

GEOLOGY, February 2004 159


changes that occurred as a result of methane provided by S.P. Hesselbo and an anonymous Palaeontological Society [London] Mono-
reviewer. graph, v. 145, p. 1–200.
hydrate destabilization during the Toarcian are Jenkyns, H.C., 1988, The early Toarcian (Jurassic)
among the largest that have been reported for anoxic event: Stratigraphic, sedimentary, and
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ACKNOWLEDGMENTS event: Nature, v. 406, p. 392–395. temperature: Journal of Geophysical Research,
We thank K.W. Burton, N.B.W. Harris, N.W. Howarth, M.K., 1962, The Jet Rock Series and the v. 86, p. 9776–9782.
Rogers, R.A. Spicer, N. Vigier, and three anony- Alum Shale Series of the Yorkshire coast:
Manuscript received 5 September 2003
mous reviewers for comments on an earlier version Yorkshire Geological Society Proceedings, Revised manuscript received 24 October 2003
of this manuscript, and the Natural Environment Re- v. 33, p. 381–422. Manuscript accepted 27 October 2003
search Council and the Open University for finan- Howarth, M.K., 1992, The ammonite family Hil-
cial support. We are grateful for journal reviews doceratidae in the Lower Jurassic of Britain: Printed in USA

160 GEOLOGY, February 2004

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