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Carbon in Earth

Carbon in Earth. Midterm Report of the Deep Carbon Observatory. Inside/Outside Cover Material DCO Mission DCO Organizational Structure Decadal Goals Map(s). Inside/Outside Text Achievements/Discoveries Quantities Movements Forms Origins Next Five Years Cameos.

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Carbon in Earth

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  1. Carbon in Earth Midterm Report of the Deep Carbon Observatory Inside/Outside Cover Material DCO Mission DCO Organizational Structure Decadal Goals Map(s) Inside/Outside Text Achievements/Discoveries Quantities Movements Forms Origins Next Five Years Cameos FUTURE VOLUMES

  2. DCO Midterm Report OVERVIEW Carbon in Earth QUANTITITES, MOVEMENTS, FORMS, ORIGINS The Deep Carbon Observatory is laying the groundwork for a new science of one of nature’s key elements. As such, the Observatory seeks to determine thequantities, movements, forms, and origins of carbon in our planet. Each goal comes with questions that we proposed to answer during the current decade. These questions are being tackled by interdisciplinary science teams in communities spanning 50 countries. As we move into the second half of the program, we will answer our decadal questions, while at the same time expanding our purview to target significant new programs connected with carbon in Earth and in extreme environments. } Reservoirs and Fluxes Deep Life Deep Energy Extreme Physics and Chemistry 1. Quantities 2. Movements 3. Forms 4. Origins Matrix Communities and phenomena Distinguish between fully supported and leveraged DCO projects 16 page high-level summary

  3. DCO Midterm Report OVERVIEW 1. Quantities • How much carbon is in Earth? What are the relative amounts of carbon-bearing phases? What physical and chemical properties of the interior affect carbon storage in different regions? • Carbon, as it presents itself to us at the surface of our planet, exists in three different oxidation states. This variation is not well determined at depth. • Diamond in the mantle as reservoirs and indicators of mantle chemistry. • Carbon should not be considered in isolation; it is a component within complex chemical systems –fluids, melts, and solids – that comprise our planet. • Among the most significant is water. • Discoveries by DCO scientists have led to the realization that there are significant unexpected reservoirs of carbon. • Having an estimate of the extent of the deep biosphere has implications for understanding how much carbon is stored in Earth.

  4. DCO Midterm Report DISCOVERIES TO DATE • EPCSpin transition and elasticity of Mg-Fe carbonate. • RFUltradeep diamonds formed within Earth’s transition zone trap inclusions of minerals. • EPCNew deep Earth water model that permits computation of carbon transport by aqueous fluids.1 • EPCThe puzzling transition of low-density water to high-density water.2 • EPCDirect measurements of carbonate ion speciation in high-pressure aqueous fluids.3 • RFRedox state of mantle Cottrell and Kelley paper4 and Stagno et al Nature5 • EPCMagnesite as a deep carbon reservoir6 • EPCLiu et al.7spin transition Same lab ferromag as a C host8 • RFMantle Temperature at Mid-Ocean Ridges (Kelley Perspective9 in Science) • RFCarbon Dioxide Content of the Icelandic Mantle Barry et al10 • RFMantle Carbon Content Influences Plate Tectonics Sifre et al11 • RFRemarkably,Carbon Isotope fractionation in the mantle Mikhail et al12 • RFGeochem of diamonds: Review by Shirey and Shigley13 • RFEPCOlivine inclusion and mantle composition • RFDiamond formation in 2 stages, 1 billion years apart Bulanova et al14 • EPCC coordination in silicates Navrotsky et al 15 • EPCPolymeric carbon dioxide as a stable form of C in the mantle16 • EPCTwo groups solve structure of polymeric CO217, 18 • EPCGalli and Sverjenskydielectric constant of water19 • RFHirschman review20 • EPCRefractive index of water under increasing pressure21 • RFDiamondite formation in the mantle Mikhail et al22 • DLCoDL developments • DLPresence of life in crust Lever et al23 • DLGlobal estimates of subseafloor life D’Hondt PNAS24 1. Quantities

  5. DCO Midterm Report BREAKTHROUGHS Pearson, D. G. et al., Hydrous mantle transition zone indicated by ringwoodite included within diamond, Nature 507, 221-224 (2014). Diamond Reveals Oceans of Water at Depth The discovery of water-rich ringwooditein a diamond by Pearson et al. changes our view of the water (and presumably other volatile) content of mantle. The paper raises the possibility of many oceans being stored in the transition zone. This finding may have significant implications for our understanding of the deep water/hydrogen cycle and the possible effects on the properties of the minerals in that region. This result is an example of what carbon (i.e., diamond) can tell us about the abundance of other components (i.e., water) in the deep Earth. 1. Quantities

  6. DCO Midterm Report BREAKTHROUGHS Clumped Isotope Signatures of Methane Sources The implementation of two methodologies for the analysis of clumped methane isotopes is a far-reaching development/discovery and potentially can integrate research from all DCO communities. Clumped methane isotopes can reveal otherwise inaccessible secrets regarding the source and formation mechanism of methane. Clumped methane isotope measurements are triggering new research on isotopic fractionation that will result in an improved understanding of the biogeochemistry of methane in the environment. Future extensions to larger carbon-bearing molecules is particularly relevant for the identification of unique biosynthetic signatures The quantum cascade laser to measure the isotopologues of methane to distinguish geological and biological sources of methane in the atmosphere, hydrosphere, and lithosphere is a tremendous achievement. Ono, S. et al., Measurement of a doubly-substituted methane isotopologue, 13CH3D, by tunable infrared laser direct absorption spectroscopy, Analyt. Chem. 86, 6487-6494 (2014); Young, E. et al. to be published 1. Quantities

  7. DCO Midterm Report OVERVIEW 2. Movements • What is the global carbon budget and nature of the deep carbon cycle? • The global carbon flux extends the question of carbon reservoirs, an area with major implications for human energy resources at depth. • Carbon moves in crustal fluids sequestered naturally but also it is released through multiple mechanisms. • The intake and release on the global scale constitutes the deep carbon cycle. • Owing to advances made by DCO scientists in the past five years, we are just now beginning to understand that cycle, including both large apparent discrepancies between intake and release and the nature of smaller epicycles

  8. DCO Midterm Report DISCOVERIES TO DATE 2. Movements • RFZeolites masquerading carbonititic tuffs25 • DERiMGvol edited by Navrotsky and Cole on C sequestration26 • RFMetastable graphite intermediates in crustal fluids Foustoukos27 • RFGraphite formation during subduction • RFDECADE activities: Costa Rica and Nicaragua • RFCarbon in silicate melts28 • RFMeasuring outgassing Mather29 • RFDiamond morphology suggests how they move from mantle to surface30 • DEDLMethane hydrate field movement31 • RFNew Constraints on the Deep Carbon Cycle (carbonates and CO2 degassing) • RFAgue paper movement of CO2 from subduction zone to volcanoes32 • RFClues in Chilean lavas Mather et al33 • RFEarth’s ancient carbon cycle and the first ice age34 • RFMars’ ancient carbon cycle35 • RFRajdeepDasgupta chapter in RiMG36 • RFMovements of diamonds through mantle Walter et al Science37 • RFDiamonds and the beginning of plate tectonics on Earth Shirey and Richardson38 • EPC/RFOxygen fugacity at forearcs and carbon movement in the mantle Lazar et al39

  9. DCO Midterm Report BREAKTHROUGHS Volcanic Degassing A significant achievement is the discovery of the doubling of known volcanic CO2emissions. Significant outgassing is connecting deep carbon to the air we breathe, and the numbers are only increasing.  Couple this with diffuse outgassing (e.g. from tectonic regions), and we have a long term contribution to make to climate change models, and to societies concern over carbon and tax. There is a great opportunity to consolidate our connection with NASA and look at our own planet with scrutiny with some urgency to assess carbon-based and greenhouse gases.  At a time when the hydrocarbon industry is lurching towards shale gas, etc., we need spatially-resolved and time-resolved atmospheric data all the more, to assess the before and after of regional and local energy operations in the context of the natural environment.   Burton, M. R. et al., Deep carbon emissions from volcanoes, in Reviews in Mineralogy and Geochemistry: Carbon in Earth (eds. R. Hazen, Jones, A. P. and Baross, J. A.), 75, 323-354 (2013). 2. Movements

  10. DCO Midterm Report BREAKTHROUGHS Volcanic Degassing (cont’d) The summer school in Yellowstone captured a facet of volcanic degassing similarly under appreciated on the planet, namely that active carbon emission through a nominally "inactive" system rivals the most "active" volcano, and the interaction between fluids in the crust and degassing carbon directly connects, again,  the biosphere to  deep earth volatiles requiring multidisciplinary science to untangle (and a new generation of carbon scientists we are truly helping to educate and transform).   Capturing young scientists' minds and enabling pathways for their early careers in DCO are tremendous legacy goals we are already starting to achieve.  They will also need the valuable databases, which DCO is creating. 2. Movements

  11. DCO Midterm Report BREAKTHROUGHS Carbon-soaked upper mantle melts The upper mantle is pervasively soaked in a carbonate-rich melt. This melt is the precursor to all magmatism, and also lubricates the plates. DCO has helped revolutionized understanding of the mantle melting beneath mid-ocean ridges. It is very likely that precursors to Earth’s most important magmatic system, mid-ocean ridges, are carbonate-rich melts of low melt fraction. These react progressively with the mantle as they rise, eventually becoming MORB. If true, all CO2 degassed at ridges originated carbonate rich magma. This explains recent evidence for deeper melting beneath ridges. Dasgupta, R., A. Mallik, K. Tsuno, A. C. Withers, G. Hirth, and M. M. Hirschmann, Carbon-dioxide-rich silicate melt in the Earth's upper mantle, Nature 493, 211-215 (2013). 2. Movements

  12. DCO Midterm Report OVERVIEW 3. Forms • What forms and structures of carbon and carbon-bearing phases exist and prevail in Earth? • Novel carbon structures and chemical reactionsare being documented, observationally, experimentally and theoretically. • Structurally, electronically, and chemically, carbon can behave mimic other elements in the Periodic Table (e.g., silicon, which is cosmochemically abundant). • Novel carbon phases are leading to new physics, and to carbon-based devices with potential implications for materials science and technology. • The questions of diversity of carbon forms also touches on biological diversity. Observations over the past five years have led to remarkable findings, and surprising correlations are emerging.

  13. DCO Midterm Report DISCOVERIES TO DATE 3. Forms • EPCSpanu et al43 • EPCStruzhkin et al49defects in synthetic diamond for quantum computing • EPCExtreme Conditions and the Periodic Table Bini et al47 • EPCCarbon substitution for Si in ceramics Navrotsky et al40 • EPCMethane forms heavy hydrocarbons not just diamond and H2Lobanov et al41 • EPCNovel Carbon structure various authors (not sure DCO contrib) • EPCCarbon storage in the mantle Wu and Buseck42 • RFFormation of carbonados Ishibashi et al44 • EPC“Amorphous” carbon forms crystalline material at high P Mao et al45 • EPCHigh pressure crystals of methane clathrates Tulk et al46 • EPCMore from Wu and Buseck48 • EPCSuperconducting C polymers at high P Dias et al50 • EPCUsing moissanite to compress methane51 • DLThe deep virosphereBaross et al52 • DLSubseafloor microbial populations 2 publications53, 54 • DLDistribution of similar microbes around the world Moser55 • DLReview of deep life Colwell et al56 • DLDirected evolution at high pressure Vanlint et al (not sure DCO contrib)57 • DLDeep nematode worms TC Onstott et al58 • DLVisualizing diversity Pham et al59

  14. DCO Midterm Report BREAKTHROUGHS Nature of Water at Depth One of the greatest discovery of DCO to date is the calculation of the dielectric constant of water under extreme conditions of pressure and temperature. This has opened the possibility of understanding deep fluids, thanks to the DEW model and to a series of experiments. This advance has deeply changed our understanding of the chemistry of deep fluids that are a major agent of transport of carbon. Whilst carbon in deep fluids has mostly been considered previously as oxidized, DCO has changed the view-- with potentially a lot more reduced carbon in the deep Earth.  The model is a fundamental and lasting contribution with the promise of revolutionizing our understanding mantle fluid geochemistry. Pan, D. et al., Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth, Proc. Nat. Acad. Sci. 110, 6646-6650 (2013). 3. Forms

  15. DCO Midterm Report BREAKTHROUGHS Dense Polymeric SiO2-CO2 The detailed determination of the crystal structure of ‘polymeric’, silica-like CO2 , together with the determination of their stability range, open vast new possibilities for carbon storage at high pressure. This is now even more viable with demonstration of CO2-SiO2 solid solution, forming a cristobalite-type mixed polymeric structures. Santoro, M. et al., Carbon enters silica forming a cristobalite-type CO2-SiO2 solid solution, Nature Comm. 5, 3761 (2014). 3. Forms

  16. DCO Midterm Report OVERVIEW 4. Origins • What is the origin of various forms of carbon? What can deep carbon tell us about the origins of life, Earth, and the Solar System? How do conditions of the deep Earth affect life and what does this tell us about the origins of life? • Carbon and carbon-bearing materials includes prebiotic systems and life itself. • Carbon atoms are born in exploding supernova, but what has been their subsequent trajectory otthe present? • Thus, we use carbon as historical tracer, a recorder of events into the depths of not only space but also time. • We have the opportunity to study carbon in meteorites, planetary surfaces, and planetary atmospheres. • Serpentinization and geologic hydrogen production fuels deep ecosystems. • New discoveries made in mineralogy provide fossil evidence for early life. • New measurements are allowing us to distinguish between abiotic and biotic sources of hydrocarbons

  17. DCO Midterm Report DISCOVERIES TO DATE 4. Origins • DLMicrohydrogarnets that may have constituted a prebiotic environment of prime interest for studying the emergence of the first microbial cells on earth. • EPCZnS cleanly catalyzes a fundamental chemical reaction – the making and breaking of a C-H bond.63 • DEAncient water and implications for origins of life here and on other planets.67 • DE Continental Lithosphere doubles global hydrogen flux estimates for the deep biosphere • DEDLAluminum catalysis of serpentinization60 • DEDLLow-temperature serpentinizationMcCollom et al61 • DEDLSerpentinization in subseafloor mantle and origins of life Menez et al62 • DEDLSphalerite catalyzes hydrothermal reactions Shipp, Shock et al63 • DEDLMinerals present on Earth at birth of life Hazen64 • RFDLEarth’s atmosphere at the birth of life Marty et al65 and Pujol, Marty, Burgess et al34 • DLFossils of ancient ecosystem (oldest maybe?) found in Australia Noffke and Hazen66 • DLMethane as a source of food Boetiuspaper68 • DLPiezophillic organisms in nature and the lab (review) Picard and Daniel69 • DEDLGeochemical constraints on deep life Pockalny, D’Hondt et al70 • DLSulfate starvation in deep ecosystems Bowles, Hinrichs et al71

  18. DCO Midterm Report BREAKTHROUGHS Hydrocarbon Generation at Mineral Surfaces The generation of hydrocarbons by mineral reactions, and in particular, the catalysis of organic reactions by sulfide minerals, in the laboratory represent a major advance This discovery bridges the gap between organic and inorganic chemistry, which is in itself a scientific game-changer, and places the generation of DNA-type molecules and eventually life within the mineral world.  The most favorable systems for eventful interactions between organic and inorganic compounds, i.e. hydrothermal systems, have been identified/confirmed. Shipp, J. A. et al., Sphaleriteis a geochemical catalyst for carbon−hydrogen bond activation, Proc. Nat. Acad. Sci. 111, 11642-11645 (2014). 4. Origins

  19. DCO Midterm Report BREAKTHROUGHS 3 Billion Year Old Water The discovery of very old waters in the Canadian shield by Holland et al. has important implications for very ancient deep biosphere. Noble gas dataare used to determine the protozeroic age of the waters. The existence of very old and deep pockets of water, isolated from the surface for almost the last 3 billions of years, has potential to host  (more recent) microbial life sustained by hydrogen. This feature, as the result of the interaction between rocks and water, may be the most important one through the history of the Earth and other planets in the Solar System and is closely related to the origin of life. Holland, G. et al., Deep fracture fluids isolated in the crust since the Precambrian era, Nature 497, 357-360 (2013). 4. Origins

  20. DCO Midterm Report BREAKTHROUGHS Kallmeyer et al., Global distribution of microbial abundance and biomass in subsea floor sediment, Proc. Natl. Acad. Sci. 109 16213-16216 (2012). Subsurface Microbial Biomass Research from the DCO has reduced estimates of microbes in the subseafloor by one order of magnitude relative to Barney Whitman’s classic PNAS paper on the number of microbes in different environmental contexts. The influential work by Kallmeyer et al. provides to date most accurate estimate of the microbial biomass in the global subseafloor; it improves the mechanistic understanding of the distribution of microbial life in the subsea floor. 4. Origins

  21. DCO Midterm Report BREAKTHROUGHS Sherwood Lollar, B., et al. Continental lithosphere doubles global hydrogen flux estimates for the deep biosphere, submitted Hydrogen Fuels the Deep Biosphere A research team using 200 borehole samples from 32 continental sites world estimated the first global estimate of H2 sources (radiolysis, serpeninization) from the Precambrian continental lithosphere. This previously neglected H2 source is on the order of in put from marine hydrothermal systems and may double the global hydrogen flux estimate for the deep biosphere 4. Origins

  22. DCO Midterm Report Cameos DCO Early Career Scientist Network Bringing People Together Panorama Mass Spectrometer Serpentine Days Workshop Kazan Workshop on Abiotic Hydrocarbons DCO Global Field Studies

  23. NEXT FIVE YEARS DCO Midterm Report Origins of Life Earth through time and the origins of life are now questions we will address in the next five years.  The natural connections with space and planetary research as a future area we may be able to enhance, which stem from the outstanding concept of mineral evolution and mineral diversity at Earths dynamic exosphere. Deep Carbon and Deep Time The deep time data Infrastructure, including new fundamental models along with vast data and modeling resources in an open-access platform could be a major breakthrough, at least in terms of its contribution to the global scientific community to do new things. This effort is building a new scientific instrument, available to everyone, that will be an engine of discovery about Earth's changing geosphere and biosphere through deep time. The statistical and visualization features we have in mind will make this "instrument" an absolutely new and transformative advance.

  24. NEXT FIVE YEARS DCO Midterm Report Earth’s Carbon Budget DCO has created a world-wide community of scientists who really work together according to a well-defined plan,  linking strands of research that complement one another and that otherwise would have been carried out out of sync. The problem of the Earth carbon budget is truly a global one and needs to be tackled at the appropriate scale. Biophysics (“EPC-B”) Systematic exploration of fundamental physico-chemical origin of biological processes in extreme environments could lead to breakthroughs in understanding form and function of organisms and ecosystems in the deep biosphere. New Carbon-based Materials New discoveries of the physics and chemistry of carbon under extreme conditions raise the possibility of creating altogether new carbon and carbon-rich materials with extraordinary properties for a range of new technologies (e.g., superconductors, sensors, thermoelectrics, high-strength components)

  25. Diamond Nanothreads [Fitzgibbons et al.,Nature Mat., 2014]

  26. NEXT FIVE YEARS DCO Midterm Report Satellite Observations of Carbon Emissions A potential new satellite would be able to be targeted with a high resolution footprint of ~500 m and would counterbalance existing global missions like OCO-2.  It could be attractive to industry and agencies for monitoring, both anthropogenic and natural emissions. and we could point at an active volcano when it erupts. The first satellite detection of CO2 in an explosive eruption plume would open the door for finally quantifying point sources of carbon into the atmosphere, needed to understand natural vs anthropogenic fluxes. This discovery from the DCO will end up affecting climate research as well.

  27. NEXT FIVE YEARS DCO Midterm Report Missions Beyond the Earth An important new opportunity is he on-going Rosetta mission which sniffs out gases released by comet 67P/CG, 500 millions km from the Earth. Resultswill certainly give strong constraints on the origin of water, carbon and other volatile elements on terrestrial planets. And this is exploration at its purest level. DCO scientists are associated with groups who built and are in charge of the mass spectrometers on board of the spacecraft. The origin of this carbon is clearly a first-order cosmological problem.

  28. NEXT FIVE YEARS DCO Midterm Report Nature of Extrasolar Carbon The recognition that planets are commonplace in the cosmos, some having variable compositions, including some that are carbon-rich, open up new prospects for the DCO where its techniques, methodologies, and expertise could be applied to the nature of carbon well beyond our Solar System (“Deep Space Carbon Observatory”). New Physics of Ultradense Carbon Materials New facilities and instruments for exploring matter and materials to P-T conditions that are orders of magnitude more extreme than current approaches. Both P and T can be independently controlled from cold, warm, and hot dense matter approaching stellar interiors. The succcess is demonstrated by the landmark highly accurate measurement of the compression of diamond to 50 Mbar at the National Ignition Facility (LLNL).

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