Reevaluating carbon fluxes in subduction zones, what goes down, mostly comes up.

Carbon fluxes in subduction zones can be better constrained by including new estimates of carbon concentration in subducting mantle peridotites, consideration of carbonate solubility in aqueous fluid along subduction geotherms, and diapirism of carbon-bearing metasediments. Whereas previous studies concluded that about half the subducting carbon is returned to the convecting mantle, we find that relatively little carbon may be recycled. If so, input from subduction zones into the overlying plate is larger than output from arc volcanoes plus diffuse venting, and substantial quantities of carbon are stored in the mantle lithosphere and crust. Also, if the subduction zone carbon cycle is nearly closed on time scales of 5-10 Ma, then the carbon content of the mantle lithosphere + crust + ocean + atmosphere must be increasing. Such an increase is consistent with inferences from noble gas data. Carbon in diamonds, which may have been recycled into the convecting mantle, is a small fraction of the global carbon inventory.

Stable Heterometallic Cluster Ions based on Werner's Hexol.

Large aqueous ions are interesting because they are useful in materials science (for example to generate thin films) but also because they serve as molecular models for the oxide-aqueous mineral interface where spectroscopy is difficult. Here we show that new clusters of the type M[(µ-OH)2 Co(NH3 )4 ]3 (NO3 )6 (M=Al, Ga) can be synthesized using Werner's century-old cluster as a substitutable framework. We substituted Group 13 metals into the hexol Co[(µ-OH)2 Co(NH3 )4 ]36+ ion to make diamagnetic heterometallic ions. The solid-state structure of the hexol-type derivatives were determined by single-crystal XRD and NMR spectroscopy and confirmed that the solid-state structure persists in solution after dissolution into either D2 O or [D6 ]DMSO. Other compositions besides these diamagnetic ions can undoubtedly be made using a similar approach, which considerably expands the number of stable aqueous heteronuclear ions.

Standard operating procedure for the analysis of major ions in hydrothermal fluids by ion chromatography.

This standard operating procedure (SOP) describes an ion chromatography (IC) procedure for the major cations and anions in hydrothermal fluids. Hydrothermal fluids are aqueous solutions with a wide range of temperature, salinity, pH and ion species that can be used by microbial metabolism as electron donors and electron acceptors. Due to the high variability of the environmental physical-chemical parameters in these samples, we have developed this protocol taking into account the special features of the matrices analyzed. An Eco IC Metrohm system equipped with a conductivity detector was used. Calibration curves are linear in the 0.1 to 10 mg/L concentration range for cations Ca 2+, Na +, K +, Mg 2+, NH 4 + and anions Cl -, Br -, NO 3 -, NO 2 -, SO 4 2- , PO 4 3-.

This manuscript details the standard operating procedure used for the determination of major cations and anions in hydrothermal fluids, which are characterized by a high variability of physico-chemical parameters. Due to the high variability of our samples, we customized the method to compensate for the variability on the physico-chemical parameters. The results are useful to interpret the geochemical processes and for understanding how these processes influence microbial diversity in geothermal systems.

Standard Operating Procedure for the determination of trace elements in hydrothermal fluids by Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

This standard operating procedure (SOP) validates an inductively coupled plasma mass spectrometry (ICP-MS) procedure for the determination of trace elements in hydrothermal fluids. Hydrothermal fluids are aqueous solutions with a wide range of temperature, salinity, pH and trace elements that can be used by a set of microbial proteins containing redox-sensitive transition metals as their catalytic core. Due to the high variability of these samples, we have developed this protocol taking into account the special features of the matrices analyzed. An ICP-MS 7900 Agilent system was used. Calibration curves are linear in the 0.01 to 100 µg/L concentration range.

This manuscript outlines the standard operating procedure used to determine trace elements in hydrothermal fluids, which are characterized by a high variability of physical-chemical parameters. Due to the high variability of our samples, we customized the method to compensate for the variability on the physico-chemical parameters. The obtained data on the distribution and abundance of trace elements in sediments and fluids can be used to track geochemical processes mobilizing the metals as well as their influence on the microbial diversity in geothermal systems.

Hydrogen Variability in the Murray Formation, Gale Crater, Mars.

The Mars Science Laboratory (MSL) Curiosity rover is exploring the Murray formation, a sequence of heterolithic mudstones and sandstones recording fluvial deltaic and lake deposits that comprise over 350 m of sedimentary strata within Gale crater. We examine >4,500 Murray formation bedrock points, employing recent laboratory calibrations for ChemCam laser-induced breakdown spectroscopy H measurements at millimeter scale. Bedrock in the Murray formation has an interquartile range of 2.3-3.1 wt.% H2O, similar to measurements using the Dynamic Albedo of Neutrons and Sample Analysis at Mars instruments. However, specific stratigraphic intervals include high H targets (6-18 wt.% H2O) correlated with Si, Mg, Ca, Mn, or Fe, indicating units with opal, hydrated Mg sulfates, hydrated Ca sulfates, Mn-enriched units, and akageneite or other iron oxyhydroxides, respectively. One stratigraphic interval with higher hydrogen is the Sutton Island unit and Blunts Point unit contact, where higher hydrogen is associated with Fe-rich, Ca-rich, and Mg-rich points. A second interval with higher hydrogen occurs in the Vera Rubin ridge portion of the Murray formation, where higher hydrogen is associated with Fe-rich, Ca-rich, and Si-rich points. We also observe trends in the H signal with grain size, separate from chemical variation, whereby coarser-grained rocks have higher hydrogen. Variability in the hydrogen content of rocks points to a history of water-rock interaction at Gale crater that included changes in lake water chemistry during Murray formation deposition and multiple subsequent groundwater episodes.

Hydro-biogeochemical impacts of fugitive methane on a shallow unconfined aquifer.

Oil and gas development can result in natural gas migration into shallow groundwater. Methane (CH4), the primary component of natural gas, can subsequently react with solutes and minerals in the aquifer to create byproducts that affect groundwater chemistry. Hydro-biogeochemical processes induced by fugitive gas from leaky oil and gas wells are currently not well understood. We monitored the hydro-biogeochemical responses of a controlled natural gas release into a well-studied Pleistocene beach sand aquifer (Canadian Forces Base Borden, Ontario, Canada). Groundwater samples were collected before, during, and up to 700 days after gas injection and analyzed for pH, major and minor ions, alkalinity, dissolved gases, stable carbon isotope ratios of CO2 and CH4, and microbial community composition. Gas injection resulted in a dispersed plume of free and dissolved phase natural gas, affecting groundwater chemistry in two distinct temporal phases. Initially (i.e. during and immediately after gas injection), pH declined and major ions and trace elements fluctuated; at times increasing above baseline concentrations. Changes in the short-term were due to invasion of deep groundwater with elevated total dissolved solids entrained with the upward migration of free phase gas and, reactions that were instigated through the introduction of constituents other than CH4 present in the injected gas (e.g. CO2). At later times, more pronounced aerobic and anaerobic CH4 oxidation led to subtle increases in major ions (e.g. Ca2+, H4SiO4) and trace elements (e.g. As, Cr). Microbial community profiling indicated a persistent perturbation to community composition with a conspicuous ingrowth of taxa implicated in aerobic CH4 oxidation as well anaerobic S, N and Fe species metabolism.

Total- and methyl-mercury concentrations and methylation rates across the freshwater to hypersaline continuum of the Great Salt Lake, Utah, USA.

We examined mercury (Hg) speciation in water and sediment of the Great Salt Lake and surrounding wetlands, a locale spanning fresh to hypersaline and oxic to anoxic conditions, in order to test the hypothesis that spatial and temporal variations in Hg concentration and methylation rates correspond to observed spatial and temporal trends in Hg burdens previously reported in biota. Water column, sediment, and pore water concentrations of methylmercury (MeHg) and total mercury (THg), as well as related aquatic chemical parameters were examined. Inorganic Hg(II)-methylation rates were determined in selected water column and sediment subsamples spiked with inorganic divalent mercury (204Hg(II)). Net production of Me204Hg was expressed as apparent first-order rate constants for methylation (kmeth), which were also expanded to MeHg production potential (MPP) rates via combination with tin reducible 'reactive' Hg(II) (Hg(II)R) as a proxy for bioavailable Hg(II). Notable findings include: 1) elevated Hg concentrations previously reported in birds and brine flies were spatially proximal to the measured highest MeHg concentrations, the latter occurring in the anoxic deep brine layer (DBL) of the Great Salt Lake; 2) timing of reduced Hg(II)-methylation rates in the DBL (according to both kmeth and MPP) coincides with reduced Hg burdens among aquatic invertebrates (brine shrimp and brine flies) that act as potential vectors of Hg propagation to the terrestrial ecosystem; 3) values of kmeth were found to fall within the range reported by other studies; and 4) MPP rates were on the lower end of the range reported in methodologically comparable studies, suggesting the possibility that elevated MeHg in the anoxic deep brine layer results from its accumulation and persistence in this quasi-isolated environment, due to the absence of light (restricting abiotic photo demethylation) and/or minimal microbiological demethylation.