Eos, Vol. 93, No.

2, 10 January 2012

VOLUME 93
EOS, TRANsACtIoNs, AMeRICAN GeoPHYsICAL UNIoN

NUMBER 2

10 JANUARY 2012 PaGES 1728

chondritic meteorites, thought to reect the basic composition of the early solar system, contain up to several weight percent carbon, yet estimates of Earths total carbon inventory, though poorly constrained, are much lower, ranging from 0.07 to 1.5 weight percent more than a twentyfold uncertainty. Earth appears to be signicantly depleted in highly volatile elements compared to chondrites, but uncertainty remains because of large potential reservoirs of carbon in Earths mantle and core. Polymorphs of native carbon, including graphite and diamond, exemplify sciences relative ignorance of the deep carbon cycle. These phases, though volumetrically minor, reveal a dynamic cycling of carbon from mantle to crust [Shirey and Richardson, 2011]. Preservation of unaltered diamond crystals during eruptions of kimberlite and other ultramac intrusions suggests transport of magma from mantle depths at velocities exceeding 100 kilometers per hour. However, scientists lack knowledge of how

Carbon in Earths Interior: Storage, Cycling, and Life

PAGES 1718
Carbon plays an unparalleled role in human life. It is the element of life, providing the chemical backbone for all essential biomolecules. Carbon-based fuels supply most of societys energy, while small carbon- bearing molecules in the atmosphere play a major role in Earths variable and uncertain climate. Yet in spite of carbons importance, scientists remain largely ignorant of the physical, chemical, and biological behavior of carbon- bearing systems more than a few hundred meters beneath Earths surface. Little is known about how much carbon is stored in the Earth as a whole, how deep reservoirs form and evolve, or how carbon moves from one deep repository to another. Further, scientists are largely ignorant of the nature and extent of deep microbial ecosystems, which by some estimates rival the total surface biomass. Past consideration of the global carbon cycle has focused primarily on oceans, atmosphere, and shallow surface environments, with the understanding that these reservoirs exchange carbon relatively rapidly as an essentially closed system. Earths near-surface carbon cycle undergoes transfer of carbon through biotic and abiotic reservoirs via combustion of organic matter, burial of carbonaceous sediments, exchange of carbon dioxide (CO2) between oceans and atmosphere, and the inuence of living systems [Berner, 2004]. Distributions of fossil fuels, organic-rich shale, carbonate rocks, and near-surface life have been mapped, their abundances and ages estimated, and their contributions to Earths surface carbon cycle well established. By contrast, knowledge of the deep interior, which may contain more than 90% of Earths carbon [Javoy, 1997], is limited. Carbon forms varied mineral phases in Earths interior, yet the nature and extent of these reservoirs in space and time are poorly constrained. Even less well understood are solubilities of carbon in mantle silicates and core metals, the source uids and mechanisms of carbonate volcanism, and chemical environments of carbon at extreme conditions. BY R. M. HAZEN, R. J. HEmLEY, AND A. J. MANGUm Earth materials from crust to core are in constant, albeit relatively slow, motion: Magma generated in the upper mantle brings deep-Earth carbon to the surface in the form of CO2, diamond, graphite, carbides, and perhaps hydrocarbons, while carbon-bearing seaoor sediments move by subduction from near-surface to deep-Earth reservoirs [Seto etal., 2008]. The dynamic interface between the deep and surface carbon cycles thus includes subduction zones, volcanoes, deep hydrocarbon reservoirs, and deep life.

Deep Carbon Reservoirs

The nature and extent of carbon reservoirs in Earths deep interior (Table1 and Figure 1) are poorly known. Primitive

Fig. 1. Many questions remain about the cycling, behavior, and storage of Earths carbon from crust to core. Sources of the carbon in the crust include (a) microbial community structures on mid-ocean ridge flanks (adapted from images by R. Coggon and B. Idlefonse). Other deep biosphere habitatsaffecting subsurface carbon cyclingalso exist. (b)An epifluorescence micrograph shows an iron-reducing enrichment culture from a serpentinite-hosted habitat (image courtesy of M.Schrenk). (c)Diamonds and their inclusions give scientists glimpses into Earths deeper interior (photo by U.S. Geological Survey).Theoretical and experimental studies point to carbons role even deeper in Earth. (d)Iron carbide (Fe 7 C3 ) is a potential constituent of Earths solid inner core (image courtesy of Y.Nakajima). (e)Experimental studies reveal the existence of new carbon-bearing structures similar to phaseII of magnesite at high pressures, corresponding to depths greater than 1800 kilometers (image courtesy of E.Boulard).

Eos, Vol. 93, No. 2, 10 January 2012

diamonds nucleate and grow in the mantle, how they incorporate inclusions, and the sources of their sometimes isotopically light carbon. Equally enigmatic are the formation and modes of transport of natural carbide minerals often found in association with diamond. Further, seismic wave velocities reveal that both outer and inner cores are less dense than pure iron. Is carbon the missing light element in Earths core [Wood, 1993] that helps to decrease this density? Analyses must integrate theory and experiment to assess the cores carbon content by determining melting relations in iron-carbon systems and more complex carbon-bearing systems, as well as effects of carbon on density and seismic velocity of metal-carbon alloys under core conditions. A signicant uncertainty relates to possible trace amounts of carbon in presumably non carbon aceous mantle oxide, silicate, and sulde minerals. Just as presumed anhydrous mantle phases have been found to incorporate many times the known surface reservoirs of water, Earths known carbon content would increase by an order of magnitude if major mantle minerals were found to incorporate just a few parts per million carbon. One promising opportunity to learn more about this potential carbon store is to analyze carbon in tiny oxide, silicate, and sulde mineral inclusions from deep-mantle diamonds. Such analyses must be complemented by experimental studies of carbon solubility and solution mechanisms in mantle minerals and magma as a function of bulk compositions, temperature, pressure, and oxidation-reduction conditions. Carbon cycling to and from Earths deep interior is dependent on speciation in fluids rich in carbon, oxygen, hydrogen, nitrogen, and sulfur. For example, recent studies reveal significant shifts in the ratio of CO2 to methane in mantle fluids as a function of depth [Litasov etal., 2011]. However, scientists do not know the viscosity of carbon-bearing fluids in Earths deep interior, nor do they know how these fluids move through rocks under mantle conditions. Equally important are efforts to understand processes and rates by which carbon transfers between near-surface and deep reservoirs [Dasgupta etal., 2007]. Subduction and volcanism are primary ux mechanisms, but do subduction and burial result in a net sequestration of carbon, or is most deep carbon remobilized and returned to the surface? And what are the rates, sources, and species of carbon degasing? These questions are the focus of much discussion and debate in the deep-carbon research community. Table 1. Possible Deep Carbon Reservoirsa Reservoir Diamond Graphite Carbides Carbonates Metal Silicates Oxides Suldes Silicate melts CHON uids Methane Methane clathrate Hydrocarbons Organic species Deep life
a Elements

Composition C C (Ca,Mg,Fe)CO3 Fe, Ni Mg-Si-O Mg-Fe-O Fe-S Mg-Si-O C-H-O-N CH4 [H2O + CH4] CnH2n+2 C-H-O-N C-H-O-N-P-S

Structure diamond graphite unknown kamecite/awaurite various various various clathrate

Atom (% C) 100 100 50 20 minor? trace? trace? trace? trace? variable 20 variable variable variable variable

Depth (km) >150 <150 ? 0 to ? ? ? ? ? ? ? ? ? ? ? <15

Abundance (%) <<1 <<1 ? ? ? ? ? ? ? ? ? ? ? ? ?

SiC, FeC, Fe3C moissanite, cohenite

listed are carbon (C), silicon (Si), iron (Fe), calcium (Ca), magnesium (Mg), oxygen (O), nickel (Ni), hydrogen (H), nitrogen (N), phosphorous (P), and sulfur (S).

Deep Organic Synthesis and Deep Life

Recent experiments demonstrate the possibility of reactions of mantle rocks bearing reduced ferrous iron (Fe2+) with CO2 or other oxidized carbon-bearing species to produce methane and higher hydrocarbons [McCollum and Simoneit, 1999; Scott etal., 2004]. However, it is not yet clear if deep-Earth processes generate signicant amounts of hydrocarbons or other organic species. If so, to what extent do these species migrate to shallow crustal zones, for example, into methane hydrates or petroleum reservoirs? And if deep organic synthesis is a widespread process, what role has it played in the origins of life and the sustenance of the subsurface biosphere [Hazen, 2005]? Surprising discoveries of deep microbial life in terrestrial and oceanic environments point to a rich subsurface biota that may rival all surface life in total biomass [Gold, 1999; DHondt etal., 2004; Roussel etal., 2008], yet little is known of how life adapts to deep environments, what novel biochemical pathways sustain life at high pressures and temperatures, and the extreme limits of life. Living organisms hold only a small fraction of Earths carbon, yet biological cycling of carbon is relatively rapid. How does this active pool of biological carbon link to the slower deep cycle, and is biologically processed carbon represented in deep-Earth reservoirs?

If scientists are to determine whether life exists or once existed on other planets, they need be able to distinguish biotic from abiotic carbon, for example, by identifying chemical and isotopic biosignatures. Thus, many in this research community are calling for a census of deep microbes and viruses, including their extent, metabolic strategies, and biological limits, as well as the nature of evolutionary relationships between deep subsurface and surface life forms.

A Subterranean Scientific Puzzle

Given these many recent tantalizing discoveries, coupled with a host of intriguing unanswered questions, research on carbon throughout Earths interior represents an exciting frontier for planetary science. The research also complements studies of carbon in the atmosphere, oceans, and other near-surface environments. As a result, a focused interdisciplinary effort on deep carbon, linking experimental, eld, and theoretical approaches, is warranted. With the combined efforts of the international research community, transformational understanding of carbons chemical and biological roles in Earth can be attained.

Acknowledgments
The authors thank the AlfredP. Sloan Foundation and the Carnegie Institution of

Eos, Vol. 93, No. 2, 10 January 2011

Washington for support of the Deep Carbon Observatory. For more information, see http://dco.ciw.edu.
and fate, Geophys. Res. Lett., 24, 177180, doi:10.1029/96GL03931. Litasov, K. D., A. F. Goncharov, and R.J. Hemley (2011), Crossover from melting to dissociation of CO2 under pressure: Implications for the lower mantle, Earth Planet. Sci. Lett., 309, 318323, doi:10.1016/j.epsl.2011.07.006. McCollum, T. M., and B. R. Simoneit (1999), Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate, Origins Life Evol. Biosphere, 29, 167186, doi: 10.1023/A:1006556315895 Roussel, E. G., M.-A. Cambon Bonavita, J.Querellou, B. A. Cragg, G. Webster, D. Prieur, and R.J. Parkes (2008), Extending the sub-sea-oor biosphere, Science, 320, 1046, doi:10.1126/ science.1154545. Scott, H. P., R. J. Hemley, H. Mao, D. R. Hershbach, L. E. Fried, W. M. Howard, and S. Bastea (2004), Generation of methane in Earths mantle: In situ high pressure-temperature measurements of carbon reduction, Proc. Natl. Acad. Sci. U. S. A., 101, 14,02314,026, doi:10.1073/ pnas.0405930101. Seto, Y., D. Hamane, T. Nagai, and F. Fujino (2008), Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation, Phys. Chem. Miner., 35, 223229, doi:10.1007/ s 00269-0080215-9. Shirey, S. B., and S. H. Richardson (2011), Start of the Wilson cycle at 3 Ga shown by diamonds from subcontinental mantle, Science, 333, 434 436, doi:10.1126/science.1206275. Wood, B. J. (1993), Carbon in the core, Earth Planet. Sci. Lett., 117, 593607, doi:10.1016/ 0 012 -821X(93)90105-I.

References
Berner, R. A. (2004), The Phanerozoic Carbon Cycle, Oxford Univ. Press, Oxford, U.K. Dasgupta, R., M. M. Hirschmann, and N.D. Smith (2007), Water follows carbon: CO2 incites deep silicate melting and dehydration beneath midocean ridges, Geology, 35, 135138, doi:10.1130/ G22856A.1. DHondt, S., etal. (2004), Distributions of microbial activities in deep subseaoor sediments, Science, 306, 22162221, doi:10.1126/ science.1101155. Gold, T. (1999), The Deep Hot Biosphere, Copernicus, New York. Hazen, R. M. (2005), Genesis: The Scientic Quest for Lifes Origin, Joseph Henry, Washington, D.C. Javoy, M. (1997), The major volatile elements of the Earth: Their origin, behavior,

Author Information
Robert M. Hazen, Russell J. Hemley, and AndreaJ. Mangum, Deep Carbon Observatory, Geophysical Laboratory, Carnegie Institution of Washington, Washington, D.C.; E-mail: rhazen@ciw.edu