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

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 \ub0C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni\u2013NiO\u2013H2O (\u394FMQ = 12\u20090.21 to 12\u20091.01), employing a double-capsule setting. Fluids, binary H2O\u2013CO2 mixtures at the P, T, and fO2 conditions investigated, were generated from graphite, oxalic acid anhydrous (H2C2O4) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO2-bearing fluids. The experimental data show that forsterite\u2009+\u2009enstatite solubility in H2O\u2013CO2 fluids is higher compared to pure water, both in terms of dissolved silica (mSiO2\u2009=\u20091.24 mol/kgH2O versus mSiO2\u2009=\u20090.22 mol/kgH2O at P\u2009=\u20091 GPa, T\u2009=\u2009800 \ub0C) and magnesia (mMgO\u2009=\u20091.08 mol/kgH2O versus mMgO\u2009=\u20090.28 mol/kgH2O) probably due to the formation of organic C\u2013Mg\u2013Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H2O\u2013CO2 fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO2 ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO2 ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P\u2013T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle

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

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

Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

The early Earth was characterized by the absence of oxygen in the ocean–atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5–2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen

Submarine groundwater discharge to Tampa Bay : nutrient fluxes and biogeochemistry of the coastal aquifer

This paper is not subject to U.S. copyright. The definitive version was published in Marine Chemistry 104 (2007): 85-97, doi:10.1016/j.marchem.2006.10.012.To separately quantify the roles of fresh and saline submarine groundwater discharge (SGD), relative to that of rivers, in transporting nutrients to Tampa Bay, Florida, we used three approaches (Darcy's Law calculations, a watershed water budget, and a 222Rn mass-balance) to estimate rate of SGD from the Pinellas peninsula. Groundwater samples were collected in 69 locations in the coastal aquifer to examine biogeochemical conditions, nutrient concentrations and stoichiometry, and salinity structure. Salinity structure was also examined using stationary electrical resistivity measurements. The coastal aquifer along the Pinellas peninsula was chemically reducing in all locations sampled, and that condition influences nitrogen (N) form and mobility of N and PO43−. Concentrations of NH4+, PO43− and ratio of dissolved inorganic N (DIN) to PO43− were all related to measured oxidation/reduction potential (pε) of the groundwater. Ratio of DIN: PO43− was below Redfield ratio in both fresh and saline groundwater. Nitrogen occurred almost exclusively in reduced forms, NH4+ and dissolved organic nitrogen (DON), suggesting that anthropogenic N is exported from the watershed in those forms. In comparison to other SGD studies, rate of PO43− flux in the seepage zone (μM m− 2 d− 1) in Tampa Bay was higher than previous estimates, likely due to 1) high watershed population density, 2) chemically reducing conditions, and 3) high ion concentrations in fresh groundwater. Estimates of freshwater groundwater flux indicate that the ratio of groundwater discharge to stream flow is not, vert, similar 20 to 50%, and that the magnitudes of both the total dissolved nitrogen and PO43− loads due to fresh SGD are not, vert, similar 40 to 100% of loads carried by streams. Estimates of SGD based on radon inventories in near-shore waters were 2 to 5 times greater than the estimates of freshwater groundwater discharge, suggesting that brackish and saline SGD is also an important process in Tampa Bay and results in flux of regenerated N and P from sediment to surface water.This work was supported by a USGS Mendenhall Postdoctoral Fellowship to K.D.K. and by the USGS Coastal and Marine Geology Program's (CMGP) Tampa Bay Project

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