Subducted organic matter buffered by marine carbonate rules the carbon isotopic signature of arc emissions

Ocean sediments consist mainly of calcium carbonate and organic matter (phytoplankton debris). Once subducted, some carbon is removed from the slab and returns to the atmo- sphere as CO2 in arc magmas. Its isotopic signature is thought to reflect the bulk fraction of inorganic (carbonate) and organic (graphitic) carbon in the sedimentary source. Here we challenge this assumption by experimentally investigating model sediments composed of 13C-CaCO3 + 12C-graphite interacting with water at pressure, temperature and redox con- ditions of an average slab–mantle interface beneath arcs. We show that oxidative dissolution of graphite is the main process controlling the production of CO2, and its isotopic compo- sition reflects the CO2/CaCO3 rather than the bulk graphite/CaCO3 (i.e., organic/inorganic carbon) fraction. We provide a mathematical model to relate the arc CO2 isotopic signature with the fluid–rock ratios and the redox state in force in its subarc source

Dissolution susceptibility of glass-like carbon versus crystalline graphite in high-pressure aqueous fluids and implications for the behavior of organic matter in subduction zones

Organic matter, showing variable degrees of crystallinity and thus of graphitization, is an important source of carbon in subducted sediments, as demonstrated by the isotopic signatures of deep and ultra-deep diamonds and volcanic emissions in arc settings. In this experimental study, we investigated the dissolution of sp2 hybridized carbon in aqueous fluids at 1 and 3 GPa, and 800\ub0C, taking as end-members i) crystalline synthetic graphite and ii) X-ray amorphous glass-like carbon. We chose glass-like carbon as an analogue of natural \u201cdisordered\u201d graphitic carbon derived from organic matter, because unlike other forms of poorly ordered carbon it does not undergo any structural modification at the investigated experimental conditions, allowing approach to thermodynamic equilibrium. Textural observations, Raman spectroscopy, synchrotron X-ray diffraction and dissolution susceptibility of char produced by thermal decomposition of glucose (representative of non-transformed organic matter) at the same experimental conditions support this assumption. The redox state of the experiments was buffered at \u394FMQ 48 \u20130.5 using double capsules and either fayalite-magnetite-quartz (FMQ) or nickel-nickel oxide (NNO) buffers. At the investigated P\u2013T\u2013fO2 conditions, the dominant aqueous dissolution product is carbon dioxide, formed by oxidation of solid carbon. At 1 GPa and 800\ub0C, oxidative dissolution of glass-like carbon produces 16\u201319 mol% more carbon dioxide than crystalline graphite. In contrast, fluids interacting with glass-like carbon at the higher pressure of 3 GPa show only a limited increase in CO2 (fH2NNO) or even a lower CO2 content (fH2FMQ) with respect to fluids interacting with crystalline graphite. The measured fluid compositions allowed retrieving the difference in Gibbs free energy (\u394G) between glass-like carbon and graphite, which is +1.7(1) kJ/mol at 1 GPa\u2013800\ub0C and +0.51(1) kJ/mol (fH2NNO) at 3 GPa\u2013800\ub0C. Thermodynamic modeling suggests that the decline in dissolution susceptibility at high pressure is related to the higher compressibility of glass-like carbon with respect to crystalline graphite, resulting in G\u2013P curves crossing at about 3.4 GPa at 800\ub0C, close to the graphite\u2013diamond transition. The new experimental data suggest that, in the presence of aqueous fluids that flush subducted sediments, the removal of poorly crystalline \u201cdisordered\u201d graphitic carbon is more efficient than that of crystalline graphite especially at shallow levels of subduction zones, where the difference in free energy is higher and the availability of poorly organized metastable carbonaceous matter and of aqueous fluids produced by devolatilization of the downgoing slab is maximized. At depths greater than 110 km, the small differences in \u394G imply that there is minimal energetic drive for transforming \u201cdisordered\u201d graphitic carbon to ordered graphite; \u201cdisordered\u201d graphitic carbon could even be energetically slightly favored in a narrow P interval

Needs and opportunities in mineral evolution research

Progress in understanding mineral evolution, Earth’s changing near-surface mineralogy through time, depends on the availability of detailed information on mineral localities of known ages and geologic settings. A comprehensive database including this information, employing the mindat.org web site as a platform, is now being implemented. This resource will incorporate software to correlate a range of mineral occurrences and properties vs. time, and it will thus facilitate studies of the chang- ing diversity, distribution, associations, and characteristics of individual minerals as well as mineral groups. The Mineral Evolution Database thus holds the prospect of revealing mineralogical records of important geophysical, geochemical, and biological events in Earth history.Organismic and Evolutionary Biolog

Mineralogical and geochemical features of sulfide chimneys from the 49°39′E hydrothermal field on the Southwest Indian Ridge and their geological inferences

© The Author(s), 2011. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Chinese Science Bulletin 56 (2011): 2828-2838, doi:10.1007/s11434-011-4619-4.During January–May in 2007, the Chinese research cruise DY115-19 discovered an active hydrothermal field at 49°39′E/37°47′S on the ultraslow spreading Southwest Indian Ridge (SWIR). This was also the first active hydrothermal field found along an ultraslow-spreading ridge. We analyzed mineralogical, textural and geochemical compositions of the sulfide chimneys obtained from the 49°39′E field. Chimney samples show a concentric mineral zone around the fluid channel. The mineral assemblages of the interiors consist mainly of chalcopyrite, with pyrite and sphalerite as minor constitunets. In the intermediate portion, pyrite becomes the dominant mineral, with chalcopyrite and sphalerite as minor constitunets. For the outer wall, the majority of minerals are pyrite and sphalerite, with few chalcopyrite. Towards the outer margin of the chimney wall, the mineral grains become small and irregular in shape gradually, while minerals within interstices are abundant. These features are similar to those chimney edifices found on the East Pacific Rise and Mid-Atlantic Ridge. The average contents of Cu, Fe and Zn in our chimney samples were 2.83 wt%, 45.6 wt% and 3.28 wt%, respectively. The average Au and Ag contents were up to 2.0 ppm and 70.2 ppm respectively, higher than the massive sulfides from most hydrothermal fields along mid-ocean ridge. The rare earth elements geochemistry of the sulfide chimneys show a pattern distinctive from the sulfides recovered from typical hydrothermal fields along sediment-starved mid-ocean ridge, with the enrichment of light rare earth elements but the weak, mostly negative, Eu anomaly. This is attributed to the distinct mineralization environment or fluid compositions in this area.This work was supported by the China Ocean Mineral Resources Research and Development Association Program (DY115- 02-1-01) and the State Oceanic Administration Youth Science Fund (2010318)

Field, Experimental, and Modeling Study of Arsenic Partitioning across a Redox Transition in a Bangladesh Aquifer

To understand redox-dependent arsenic partitioning, we performed batch sorption and desorption experiments using aquifer sands subjected to chemical and mineralogical characterization. Sands collected from the redox transition zone between reducing groundwater and oxic river water at the Meghna riverbank with HCl extractable Fe(III)/Fe ratio ranging from 0.32 to 0.74 are representative of the redox conditions of aquifers common in nature. One brown suboxic sediment displayed a partitioning coefficient (K_d) of 7-8 L kg^-1 at equilibrium with 100 μg L^-1 As(III), while two gray reducing sediments showed K_d of 1-2 L kg^-1. Lactate amendment to aquifer sands containing 91 mg kg^-1 P-extractable As resulted in the reduction of As and Fe with sediment Fe(III)/Fe decreasing from 0.54 to 0.44, and mobilized an equivalent of 64 mg kg^-1 As over a month. Desorption of As from nonlactate-amended sediment was negligible with little change in sediment Fe(III)/Fe. This release of As is consistent with microbial reduction of Fe(III) oxyhydroxides and the resulting decrease in the number of surface sites on Fe(III) oxyhydroxides. Arsenic partitioning (K_d) in iron-rich, sulfur-poor aquifers with circumneutral pH is redox-dependent and can be estimated by HCl leachable sediment Fe(III)/Fe ratio with typical Fe concentrations

Phase Behavior of Aqueous Na-K-Mg-Ca-CI-NO3 Mixtures: Isopiestic Measurements and Thermodynamic Modeling

A comprehensive model has been established for calculating thermodynamic properties of multicomponent aqueous systems containing the Na{sup +}, K{sup +}, Mg{sup 2+}, Ca{sup 2+}, Cl{sup -}, and NO{sub 3}{sup -} ions. The thermodynamic framework is based on a previously developed model for mixed-solvent electrolyte solutions. The framework has been designed to reproduce the properties of salt solutions at temperatures ranging from the freezing point to 300 C and concentrations ranging from infinite dilution to the fused salt limit. The model has been parameterized using a combination of an extensive literature database and new isopiestic measurements for thirteen salt mixtures at 140 C. The measurements have been performed using Oak Ridge National Laboratory's (ORNL) previously designed gravimetric isopiestic apparatus, which makes it possible to detect solid phase precipitation. Water activities are reported for mixtures with a fixed ratio of salts as a function of the total apparent salt mole fraction. The isopiestic measurements reported here simultaneously reflect two fundamental properties of the system, i.e., the activity of water as a function of solution concentration and the occurrence of solid-liquid transitions. The thermodynamic model accurately reproduces the new isopiestic data as well as literature data for binary, ternary and higher-order subsystems. Because of its high accuracy in calculating vapor-liquid and solid-liquid equilibria, the model is suitable for studying deliquescence behavior of multicomponent salt systems

Subduction hides high-pressure sources of energy that may feed the deep subsurface biosphere

Geological sources of H2 and abiotic CH4 have had a critical role in the evolution of life and sustainability of the deep subsurface biosphere, yet the origins of these sources remain largely unconstrained. Here the authors show that deep serpentinization (40–80 km) during subduction generates significant amounts of H2 and abiotic CH4, potentially providing energy to the overlying subsurface biosphere

Subduction hides high-pressure sources of energy that may feed the deep subsurface biosphere

Geological sources of H2 and abiotic CH4 have had a critical role in the evolution of our planet and the development of life and sustainability of the deep subsurface biosphere. Yet the origins of these sources are largely unconstrained. Hydration of mantle rocks, or serpentinization, is widely recognized to produce H2 and favour the abiotic genesis of CH4 in shallow settings. However, deeper sources of H2 and abiotic CH4 are missing from current models, which mainly invoke more oxidized fluids at convergent margins. Here we combine data from exhumed subduction zone high-pressure rocks and thermodynamic modelling to show that deep serpentinization (40–80 km) generates significant amounts of H2 and abiotic CH4, as well as H2S and NH3. Our results suggest that subduction, worldwide, hosts large sources of deep H2 and abiotic CH4, potentially providing energy to the overlying subsurface biosphere in the forearc regions of convergent margins