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Ocean Methane Hydrates As a Slow Tipping Point in the Global Carbon Cycle

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Ocean Methane Hydrates As a Slow Tipping Point in the Global Carbon Cycle Ocean methane hydrates as a slow tipping point in the global carbon cycle David Archera,1, Bruce Buffettb, and Victor Brovkinc aDepartment of the Geophysical Sciences, University of Chicago, Chicago, IL 60637; bDepartment of the Earth and Planetary Science, University of California, Berkeley, CA 94720; and cMax Planck Institute for Meteorology, D-20146 Hamburg, Germany Edited by Hans Joachim Schellnhuber, Potsdam Institute for Climate Impact Research, Potsdam, Germany, and approved September 9, 2008 (received for review January 29, 2008) We present a model of the global methane inventory as hydrate (following the geotherm), so that at a depth of a few hundred and bubbles below the sea floor. The model predicts the inventory meters below the sea floor the temperature exceeds the melting of CH4 in the ocean today to be Ϸ1600–2,000 Pg of C. Most of the threshold. The term ‘‘hydrate stability zone’’ generally refers to hydrate in the model is in the Pacific, in large part because lower the sediment column from the sea floor down to the melting oxygen levels enhance the preservation of organic carbon. Because depth, typically a few hundred meters below the sea floor. the oxygen concentration today may be different from the long- Climate warming primarily affects hydrate stability near the base term average, the sensitivity of the model to O2 is a source of of the stability zone, where temperatures approach the melting uncertainty in predicting hydrate inventories. Cold water column point. The sediment column provides a thermal buffer that slows temperatures in the high latitudes lead to buildup of hydrates in the response of the hydrates to climate warming by many the Arctic and Antarctic at shallower depths than is possible in low centuries. latitudes. A critical bubble volume fraction threshold has been Much of the methane in ocean hydrate deposits is held in what proposed as a critical threshold at which gas migrates all through have been called stratigraphic deposits (17), its concentration the sediment column. Our model lacks many factors that lead to determined by the slow processes of sediment accumulation, heterogeneity in the real hydrate reservoir in the ocean, such as pore fluid flow, and methanogenesis of buried organic matter. preferential hydrate formation in sandy sediments and subsurface This type of deposit is most amenable to one-dimensional gas migration, and is therefore conservative in its prediction of modeling such as we present here. In other deposits, called releasable methane, finding only 35 Pg of C released after 3 °C of structural, the methane concentrations are primarily determined uniform warming by using a 10% critical bubble volume. If 2.5% by subsurface flow of gaseous methane through faults and bubble volume is taken as critical, then 940 Pg of C might escape porous channels in the sediment column. Structural hydrate in response to 3 °C warming. This hydrate model embedded into a deposits can be more concentrated than stratigraphic, and closer global climate model predicts Ϸ0.4–0.5 °C additional warming to sea floor, making them potentially more responsive to climate from the hydrate response to fossil fuel CO2 release, initially warming. Hydrates in the Gulf of Mexico and Hydrate Ridge, because of methane, but persisting through the 10-kyr duration of for example, are heavily impacted by subsurface gas migration the simulations because of the CO2 oxidation product of methane. (18–20). Because much of the hydrate is in stratigraphic deposits, the clathrate ͉ climate characteristics of these are used to estimate the total inventory of methane in the ocean. Our estimates of methane release, arge but poorly known amounts of methane are trapped in neglecting structural methane deposits, are likely to be biased Lthe sediments beneath the sea floor, frozen into a form of severely low for societal time scales of decades to a century. water ice called methane hydrate (1–3). The hydrates could be Estimates of the inventory of methane in hydrates range from vulnerable to melting with a deep ocean warming of a few 700 to 10,000 Pg of C. Uncertainties in the average volume degrees Celsius (3–6), which is obtainable given the available fraction of hydrate accounts for most of this range. Typical values inventories of fossil fuel carbon for combustion. Methane is a for the average hydrate volume fraction depth-integrated over greenhouse gas, and it oxidizes in about a decade to CO2, the stability zone range from 1% to 10% (2, 21–23). another greenhouse gas that accumulates in the Earth’s carbon The climate impact of melting hydrates in the ocean depends cycle and continues to impact climate for many millennia (7, 8). on whether the carbon reaches the atmosphere in the form of The hydrate carbon reservoir has probably accumulated over methane. The chemical lifetime of methane in the atmosphere millions of years (9, 10), with the gradual cooling of the ocean at present concentrations is about a decade, so an abrupt pulse over geologic time, but a release of carbon from the hydrate pool of methane released to the atmosphere would generate a tran- because of melting could take place on a time scale of millennia sient spike of high methane concentrations, which would subside (11, 12). Human release of CO2 from fossil fuel combustion has in about a decade. If methane is released on a time scale that is the potential to make the oceans warmer than they have been in long relative to its atmospheric lifetime, the result would be an millions of years (13, 14), thus, potentially releasing more increase in the steady-state concentration of methane in the methane than the apparently small releases through the repeated atmosphere; a doubling of the total source flux would lead to a glacial-interglacial cycles (15). The methane hydrate reservoir bit more than a doubling of the steady-state concentration. The can be considered a slow but, for societal purposes, irreversible oxidation product of methane is CO2, another greenhouse gas tipping point in the Earth’s carbon cycle (16). although a weaker one (per molecule, by a factor of Ϸ30). In The melting temperature of hydrate increases with pressure, whereas temperature in the ocean water column decreases with pressure (depth), so in the presence of sufficient concentrations Author contributions: D.A., B.B., and V.B. designed research, performed research, and of dissolved methane, hydrate would become increasingly stable wrote the paper. with depth in the ocean. However, methane concentrations in The authors declare no conflict of interest. the open ocean are too low to support hydrate formation, This article is a PNAS Direct Submission. restricting hydrates to the sediments below the sea floor. Within 1To whom correspondence should be addressed. E-mail: [email protected]. the sediment column, the temperature increases with depth © 2008 by The National Academy of Sciences of the USA 20596–20601 ͉ PNAS ͉ December 8, 2009 ͉ vol. 106 ͉ no. 49 www.pnas.org͞cgi͞doi͞10.1073͞pnas.0800885105 contrast to methane, a transient chemical species, CO2 accumu- lates in the atmosphere, ultimately taking hundreds of thousands SPECIAL FEATURE of years to be consumed by weathering reactions with igneous rocks. Methane that dissolves in the deep ocean would be oxidized to CO2 (24), in which form it would ultimately equili- brate with the atmosphere, releasing some 15–25% of the carbon to the air. The bottom-line question is whether the methane released from melting hydrates in the sediment column is likely to escape to the ocean or the atmosphere or to remain in place below the sea floor. The production of bubbles associated with melting may act to destabilize the sediment column to landslides (25). How- ever, even the largest known submarine landslide, the Storrega slide off Norway, did not release a climatically significant amount of methane to the atmosphere (11). The most likely impact of a melting hydrate reservoir is therefore a long-term, chronic methane source, thus, elevating atmospheric methane and contributing to the total CO2 load on the atmosphere from combustion of fossil fuels. In the absence of sediment slumping, the sediment column overlying the melting hydrate acts as a physical cap through which the released methane must travel to escape to the ocean or the atmosphere. Assuming that the surface sediment remains colder than the melting temperature, released bubbles or dis- solved methane would have to migrate through the cold trap of the stability zone. There is also a chemical trap of oxidation by sulfate. Several authors (10, 26) suggest that the probability of Fig. 1. Maps from the bathymetric model. (A) Active (red) versus passive SCIENCE methane escape increases when bubbles make up a large fraction (purple) margin classification. (B) Column-integrated inventory of methane in SUSTAINABILITY of the pore fluid. High bubble volume would encourage bubbles hydrates. (C) Column-integrated methane in bubbles. (D) Area average bub- to migrate through the sediment column by creating a pressure ble fraction of the pore volume. (E) Area average bubble fraction upon differential between the bubble and the water at the tops and the melting of the hydrate at the base of the stability zone. (F) Column inventory bottoms of the bubbles. High salinities from freezing hydrate or of releasable methane, defined as in text. dissolving evaporates might also create channels of hydrate instability through the nominal stability zone (27–29). Simple ϫ kinetics might also allow the methane to escape if it passes methane with an efficiency of 25% and a time constant of 3 Ϫ13 Ϫ1 GEOPHYSICS through the stability and oxidized zones quickly (30). These 10 yr . Sediment surface organic carbon concentrations mechanisms are motivated, in part, by evidence for free gas come from the Muds model of the early diagenesis reaction zone moving through the stability zone (31).
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