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, Universitat zu Koln, Zulpicher Strasse 49a, D-50674 Koln, Germany ¨ ¨ ¨ ¨
ABSTRACT The long-term stability of Earth’s climate throughout the Phanerozoic stands in marked contrast to the dramatic fluctuations that have taken place on time scales as short as a few years, reflecting the high efficiency of longer-term climate regulation through negative feedbacks. A fundamental mechanism is thought to involve control of CO2 in the ocean-atmosphere system through continental weathering, although unambiguous, high-resolution data supporting this hypothesis have hitherto not been available. Organic-rich mudrocks from Yorkshire, England, which were deposited during the Toarcian oceanic anoxic event (ca. 181 Ma, Early Jurassic), contain evidence of an exceptionally large excursion in the 187Os/188Os ratio of contemporaneous seawater, from 0.4 to 1.0. The most likely explanation for this excursion is that it resulted from a transient increase in global continental weathering rates of 400%–800%. The Os isotope excursion coincided with a well-documented global 13C excursion of 6‰ that affected all the major biospheric reservoirs of the time. Higher mean global temperatures caused global chemical weathering rates to increase substantially, while, in turn, chemical weathering was very effective in reducing the elevated levels of atmospheric CO2 and the high temperatures to preexcursion levels. Keywords: osmium, weathering, Toarcian, oceanic anoxic event, strontium, methane hydrate. INTRODUCTION Although rapid oscillations in Earth’s climate have occurred frequently in the past (Alley et al., 2003), climate-control processes have operated during the Phanerozoic to keep Earth’s climate within the relatively narrow bounds required for the continuing success of life on the planet. Interaction between CO2 in the ocean-atmosphere system and the silicates in the continental crust is thought to be a fundamental mechanism in the regulation of Earth’s climate, involving the release of Ca and Mg by chemical weathering and, ultimately, the deposition of (Ca,Mg)CO3 in the oceans (Berner et al., 1983; Broecker and Sanyal, 1998; Kump et al., 2000; Walker et al., 1981). However, one of the major obstacles in demonstrating the precise role of chemical weathering as a regulator of climate has been the difficulty in finding a distinctive chemical proxy that responds with sufficient rapidity and magnitude to changes in global weathering. The relatively short seawater residence time for Os of 10–40 k.y. (PeuckerEhrenbrink and Ravizza, 2000) makes it an ideal isotopic tracer for the purpose, as long as the recovered signal is primary and global in extent. Our approach is based on the observation that the Os isotope composition of seawater has varied over geologic time in re*E-mail: a.s.cohen@open.ac.uk.

sponse to changes in the balance between the major inputs to the oceans—primarily from continental weathering, the hydrothermal alteration of juvenile oceanic crust, and meteoritic sources (Cohen et al., 1999; Pegram et al., 1992; Peucker-Ehrenbrink and Ravizza, 2000). Because the hydrothermal input of unradiogenic Os to the oceans can be assumed to remain constant over relatively short intervals, rapid and transient increases in the seawater 187Os/ 188Os ratio can be caused only by a sudden increase in the flux or isotopic composition of radiogenic Os from continental weathering. SAMPLES AND RESULTS The samples that we selected for study are Toarcian organic-rich mudrocks from exposures at Saltwick Bay, Port Mulgrave, and Hawsker Bottoms, Yorkshire, England (Hesselbo and Jenkyns, 1995; Howarth, 1962, 1992). The widespread deposition of marine organic-rich mudrocks across the exaratum Biosubzone of the lower falciferum Biozone (Toarcian, Early Jurassic, ca. 183–178 Ma [Palfy et al., 2000]), with as much as 15% organic carbon, is a primary feature of the Toarcian oceanic anoxic event (Jenkyns, 1988; Jenkyns et al., 2002). Although the duration of the exaratum Subzone is not accurately constrained, it is estimated from annual sediment-layer couplets to have been 150 k.y. (Cope, 1998; Hesselbo et al., 2000). The rich marine fauna,

sedimentary facies, stratigraphic context, and paleogeographic position of these exposures all provide evidence that the mudrocks were deposited under open-marine conditions (Hesselbo and Jenkyns, 1995; Howarth, 1962, 1992). Our new Re and Os abundance data, and C isotope results, are shown in Figure 1 and reported in Tables DR1 and DR21. Suites of mudrock samples from the exaratum and falciferum Subzones define Re-Os isochron ages of 181 13 Ma (Cohen et al., 1999) and 178 5 Ma (this study, Fig. 2), respectively, thus confirming that the Re-Os isotope system in these successions has not been disturbed since deposition and that the initial Os isotope composition is primary (Cohen et al., 1999). There is a major, transient increase in the calculated 187Os/188Os ratio of seawater from 0.4 to 1.0 (Fig. 1) that occurred mostly during deposition of the exaratum Subzone. Despite its relative brevity, with an apparent duration of 100 k.y., the magnitude of the Os isotope excursion exceeded the total variation in the 187Os/188Os ratio of seawater over the past 35 m.y. (Pegram et al., 1992). DISCUSSION The magnitude of the Os isotope excursion reported here would have demanded an increase of 800% in the continental weathering flux, if present-day isotopic ratios for the end-member components are used (PeuckerEhrenbrink and Ravizza, 2000). This excursion could, in theory, have involved a very abrupt and transient increase in the 187Os/ 188Os ratio of the global continental weathering component, rather than in its flux. However, we consider such an eventuality to be very remote because large-scale changes in the worldwide balance of rocks that are available for weathering at Earth’s surface require the action of long-term (millions of years) tectonic processes. Such processes could not have operated on the much shorter (thousands
1GSA Data Repository item 2004019, Tables DR1 and DR2 (sample locations, stratigraphic positions, Re and Os abundances, Os isotope and 13C data), is available online at www.geosociety.org/ pubs/ft2004.htm, or on request from editing@ geosociety.org or Documents Secretary, GSA, P.O. Box 9140, Boulder, CO 80301-9140, USA.

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.

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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), 13C 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. Protogrammoceras, D. Dactylioceras, cl. clevelandicum, ten. 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).

Figure 2. Re-Os isochron diagram for all six mudrock samples from falciferum Subzone. Regression age is 178.2 5.6 Ma (mean square of weighted deviates 3.0). Initial 187 Os/188Os ratio (0.4 0.15) reflects that of contemporaneous seawater (Cohen et al., 1999; Peucker-Ehrenbrink and Ravizza, 2000).

of years) time scale over which the global seawater Os isotope excursion in the exaratum Subzone was established. Nevertheless, if we consider an extreme event in which the 187Os/ 188Os ratio of the global weathering flux suddenly increased by 50% to 2 (compared with its present-day value of 1.4), then the observed Os isotope shift would have still required an additional increase in weathering flux of 400%. Thus, the magnitude of the transient excursion in the Os isotope composition of seawater during deposition of the exaratum Subzone was so large that it would have involved a relatively brief interval of greatly enhanced continental weathering, on a global scale, for any realistic Os isotope composition of the weathering flux. The Os isotope excursion coincided with a global 13C shift of 6‰ (Fig. 1) that was one of the largest of the Phanerozoic, affecting

all the major biospheric carbon reservoirs at that time, i.e., bulk marine organic matter (Hesselbo et al., 2000; Kuspert, 1982; Schouten et al., 2000), primary organic production biomarkers (Schouten et al., 2000), marine carbonate (Kuspert, 1982; Schouten et al., 2000), and terrestrial carbon (Hesselbo et al., 2000). Hesselbo et al. (2000) demonstrated that the only geologic process consistent with a global C isotope excursion of this magnitude would have been the dissociation of very large amounts of methane hydrate, an immediate consequence of which would have been its rapid oxidation to CO2 and a threefold increase in atmospheric CO2 levels (Beerling et al., 2002). A crucial point is that the precise interval over which the levels of atmospheric CO2 were high is clearly defined by the highly distinctive light C isotope composition imparted by the dissociated and oxidized meth-

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Figure 3. Variations in Jurassic seawater 87 Sr/86Sr ratio. A: High-resolution profile for upper Pliensbachian–lower Toarcian (McArthur et al., 2000), showing variations with stratigraphic height. B: Variations in 87Sr/ 86 Sr ratio of Jurassic seawater, based on integrated data set (Jones et al., 1994a, 1994b). Bold arrow indicates approximate duration of eruption of Karoo-Ferrar igneous province (Duncan et al., 1997).

ane hydrate (Fig. 1). The concurrent Os and C isotope excursions in the Toarcian also coincide with an exceptionally sharp increase in the seawater Sr isotope composition (Figs. 1 and 3) (Jones et al., 1994b; McArthur et al., 2000). Because these synchronous C and Sr isotope shifts were demonstrably global in extent (Hesselbo et al., 2000; Jenkyns et al., 2002; Jones et al., 1994b), they provide additional compelling evidence that the seawater Os isotope excursion, which occurred over the same short interval, also represented a global signal. One of the main factors governing rates of chemical weathering is temperature (Kump et al., 2000). Beerling et al. (2002) calculated that the global 13C isotope excursion of 6‰ in the Toarcian would have required the dissociation of 5000 Gt of methane hydrate and that average global temperatures would have increased by at least 3 C as a consequence of the threefold increase in atmospheric CO2. Direct evidence for a sudden, large increase in seawater temperatures at that time also comes from O isotope analyses (Jenkyns

et al., 2002; McArthur et al., 2000) and Mg/ Ca ratios (McArthur et al., 2000) from belemnites, some of which were used to define the contemporaneous seawater Sr isotope curve. The 18O values suddenly decreased by 3‰ at the same point that marked the start of the Os and C isotope excursions, while Mg/ Ca ratios approximately doubled, from 0.2 to 0.4. Both data sets independently suggest that average seawater surface temperatures during deposition of the exaratum Subzone were as much as 10 C higher than those before and after (Jenkyns et al., 2002; McArthur et al., 2000). Although the precise relationship between continental weathering rates and mean global temperature in the Toarcian would have depended on the highly complex interplay between vegetation and hydrology as well as on atmospheric CO2, the 400%–800% increase in weathering rates in the exaratum Subzone of the Toarcian is nevertheless fully consistent with estimates of the temperature dependence of current chemical weathering rates (Gaillardet et al., 1999; Kump et al., 2000). An analysis of the dissolved loads carried by the world’s rivers shows that a 500% increase in weathering rate occurs for every 5 C rise in temperature where weathering rate is not controlled by water supply (Gaillardet et al., 1999). The sudden and large increase in continental weathering rates in the greenhouse world of the Toarcian is commensurate with highly efficient hydrologic and weathering systems where groundwater flow predominated, as was the case in the Late Cretaceous when groundwater flow exceeded runoff by a factor of six (Floegel et al., 2003). For comparison, during the present-day icehouse conditions, global runoff exceeds groundwater flow by a factor of three. The transient increase in continental weathering rates in the exaratum Subzone resulted in an increased flux of Ca and Mg to the oceans, which would have served to balance the higher levels of CO2 in the oceans and atmosphere. The approximate time scale of the C (and Os) isotope excursions may be estimated from global sedimentation and CO2 consumption rates; this calculation also provides an independent check of the feasibility of enhanced continental weathering having acted as the negative feedback that regulated atmospheric CO2. Sediment supply to the oceans was relatively low in the Early Jurassic and, outside the exaratum Subzone, may have been as little as 12%–20% of its current level (Floegel et al., 2000). Present-day chemical weathering of Ca- and Mg-bearing silicates consumes 0.085 Gt of C annually (Gaillardet et al., 1999); thus, depending on the exact choice of values, the excess CO2 derived from

the oxidation of methane hydrate during the exaratum Subzone would have been consumed in 37–123 k.y. This result is fully consistent with the other estimates for the duration of the Os and C isotope excursions. The dramatic rise in the 87Sr/86Sr ratio of seawater during deposition of the exaratum Subzone represented one of the fastest rates of increase of the Phanerozoic. It was superimposed on a longer-term increase (Fig. 3) that extended from the late Pliensbachian to the early Bajocian. The singular change in slope of the seawater Sr isotope curve in the late Pliensbachian coincided with the main eruptive phase of the Karoo-Ferrar igneous province at 183 1 Ma, according to the dates of Duncan et al. (1997). Under the assumption that the contribution of unradiogenic Sr from seafloor spreading remained essentially constant over this interval (Rowley, 2002), we suggest that the eruption of the Karoo-Ferrar igneous province caused both the initial rise in seawater 87Sr/86Sr ratio in the late Pliensbachian and its longer-term increase. This occurred through volcanic CO2 outgassing, which led in turn to higher mean global temperatures and enhanced continental weathering. We further suggest that the transient and exceptionally high rate of increase in seawater 87Sr/86Sr ratio during deposition of the exaratum Subzone was caused by the acceleration of weathering rates resulting from higher atmospheric CO2 and mean global temperatures following methane hydrate destabilization (Beerling et al., 2002; Hesselbo et al., 2000). After the deposition of the exaratum Subzone, the seawater Os isotope composition and the rate of increase of the seawater 87Sr/86Sr ratio returned rapidly to levels similar to those before the methane hydrate destabilization, indicating a relaxation in continental weathering rates. An alternative explanation for the steep rise in the seawater 87Sr/86Sr ratio across the exaratum Subzone, proposed by McArthur et al. (2000), is that it is an artifact of unusually slow sedimentation rates in the exaratum Subzone alone. These authors make the explicit assumption that the rate of increase of seawater 87Sr/86Sr ratio in the early Toarcian was constant. They conclude that the exaratum Subzone is greatly condensed compared with the strata above and below, and that it was deposited over an interval of 1 m.y. However, the assumption upon which this approach is based—that the rate of increase in seawater 87Sr/86Sr ratio was constant—is hard to justify in view of the dramatic reversal of slope of the seawater Sr isotope curve in the latest Pliensbachian, perhaps no more than 1 m.y. earlier (Fig. 3). The transient geochemical and climatic

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changes that occurred as a result of methane hydrate destabilization during the Toarcian are among the largest that have been reported for the Phanerozoic. Lesser changes of a similar nature also occurred at the Paleocene-Eocene boundary (ca. 55 Ma) (Dickens et al., 1995), when a smaller gas hydrate release was responsible for a 13C isotope shift of 2.5‰ and an increase in mean global temperature of 2 C. Then, an 26% increase in continental weathering flux was inferred from an 10% increase in the seawater 187Os/188Os ratio (Ravizza et al., 2001). In the more recent past, seawater 187Os/188Os ratios for warmer interglacial periods were found to be 5% higher than for colder glacial periods (Oxburgh, 1998). Although the implications of these two studies are in full accord with the results presented here—that continental weathering rates increase with higher mean global temperatures—in both these cases the changes in the seawater Os isotope composition could have been caused by relatively minor changes in the Os isotope composition of the continental component, rather than in its flux. CONCLUSIONS The seawater 187Os/188Os ratio suddenly increased from 0.4 to 1.0 for a short interval during deposition of the Toarcian exaratum Subzone. The magnitude of the Os isotope excursion indicates an increase in continental weathering flux of 400%–800% and was so great that it rules out the possibility that the excursion was caused by a change in Os isotope composition of the weathering flux alone. High levels of CO2 in the oceans and atmosphere, which were the likely consequence of massive methane hydrate dissociation, led to elevated mean global temperatures and higher rates of chemical weathering. Enhanced chemical weathering resulted in higher fluxes of Ca and Mg to the oceans, which consumed CO2 and thereby caused mean global temperatures and weathering rates to fall. The large, synchronous changes in the Os, Sr, C, and O isotope ratios of Early Jurassic seawater provide very strong evidence supporting the hypothesis (Walker et al., 1981) that continental weathering rates are temperature dependent and that weathering provides a rapid and effective negative feedback that can moderate major climatic perturbations through CO2 consumption.
ACKNOWLEDGMENTS We thank K.W. Burton, N.B.W. Harris, N.W. Rogers, R.A. Spicer, N. Vigier, and three anonymous reviewers for comments on an earlier version of this manuscript, and the Natural Environment Research Council and the Open University for financial support. We are grateful for journal reviews

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