Kinetics of pyrite to pyrrhotite reduction by hydrogen in calcite buffered solutions between 90 and 180 °C: Implications for nuclear waste disposal

The kinetics of abiotic redox reactions induced by hydrogen are poorly documented although it represents a growing area of interest in terms of both nuclear waste storage assessment and the comprehensive study of hydrogen-rich fluid in mid-ocean ridge hydrothermal systems. We present an experimental kinetics study of pyrite reduction into pyrrhotite under significant H₂ pressure and mid-hydrothermal conditions. We describe the mechanism and kinetic behavior of this reaction by combining textural and solution analyses under various conditions of temperature, pyrite particles size, H₂ pressure and pH. When pH is controlled by calcite, the reaction presents all the characteristics of a coupled dissolution-precipitation mechanism occurring at the pyrite-pyrrhotite interface. By considering the chemical affinity of the coupled reaction as a function of reaction extent, we demonstrate that the spatial coupling is induced both by pyrite as a substrate for pyrrhotite nucleation and by the role of fluid chemistry at the reaction front. Far from equilibrium with respect to pyrite, the kinetics of sulfide production associated with the reaction are linearly related to the square root of time with an activation energy of 53 kJ/mol. This value is higher than what is expected for a diffusion-controlled kinetic regime. We suggest that the reaction rate is controlled both by pyrite reductive dissolution and by sulfide diffusion through the porous pyrrhotite microstructure. We provide a simple sulfide production-rate expression on the basis of our measured rate constants that can be used in geochemical modeling to further evaluate the impact of hydrogen on pyrite under nuclear waste disposal conditions.     

The role of sea ice formation in cycling of aluminium in northern Marguerite Bay,Antarctica

The use of dissolved Al as a tracer for oceanic water masses and atmospheric dust deposition of biologically important elements, such as iron, requires the quantitative assessment of its sources and sinks in seawater. Here, we address the relative importance of oceanic versus atmospheric inputs of Al, and the relationship with nutrient cycling, in a region of high biological productivity in coastal Antarctica. We investigate the concentrations of dissolved Al in seawater, sea ice, meteoric water and sediments collected from northern Marguerite Bay, off the West Antarctic Peninsula, from 2005 to 2006. Dissolved Al concentrations at 15 m water depth varied between 2 and 27 nM, showing a peak between two phytoplankton blooms. We find that, in this coastal setting, upwelling and incorporation of waters from below the surface mixed layer are responsible for this peak in dissolved Al as well as renewal of nutrients. This means that changes in the intensity and frequency of upwelling events may result in changes in biological production and carbon uptake. The waters below the mixed layer are most likely enriched in Al as a result of sea ice formation, either causing the injection of Al-rich brines or the resuspension of sediments and entrainment of pore fluids by brine cascades. Glacial, snow and sea ice melt contribute secondarily to the supply of Al to surface waters. Total particulate Al ranges from 93 to 2057 mg/g, and increases with meteoric water input towards the end of the summer, indicating glacial runoff is an important source of particulate Al. The (Al/Si)_opal of sediment core top material is considerably higher than water column opal collected by sediment traps, indicative of a diagenetic overprint and incorporation of Al at the sediment–water interface. Opal that remains buried in the sediment could represent a significant sink of Al from seawater.     

On the small-scale fractal geometrical structure of a living coral reef barrier

The topographical complexity of coral reefs is of primary importance for a number of hydrodynamical and ecological processes. The present study is based on a series of high-resolution seabottom elevation measurements along the Maupiti Barrier Reef, French Polynesia. Several statistical metrics and spectral analysis are used to characterize the spatial evolution of the coral geometrical structure from the reef crest to the backreef. A consistent fractal-like power law exists in the spectral density of bottom elevation for length scales between 0.1 and 7 m, while at larger scale, the reef structure shows a different pattern. Such a fine characterization of the reef geometrical structure provides key elements to reconstruct the reef history, to improve the representation of reef roughness in hydrodynamical models and to monitor the evolution of coral reef systems in the context of global change. © 2020 John Wiley & Sons, Ltd.     

Ontologies to interpret remote sensing images: why do we need them?

The development of new sensors and easier access to remote sensing data are significantly transforming both the theory and practice of remote sensing. Although data-driven approaches based on innovative algorithms and enhanced computing capacities are gaining importance to process big Earth Observation data, the development of knowledge-driven approaches is still considered by the remote sensing community to be one of the most important directions of their research. In this context, the future of remote sensing science should be supported by knowledge representation techniques such as ontologies. However, ontology-based remote sensing applications still have difficulty capturing the attention of remote sensing experts. This is mainly because of the gap between remote sensing experts’ expectations of ontologies and their real possible contribution to remote sensing. This paper provides insights to help reduce this gap. To this end, the conceptual limitations of the knowledge-driven approaches currently used in remote sensing science are clarified first. Then, the different modes of definition of geographic concepts, their duality, vagueness and ambiguity, and the sensory and semantic gaps are discussed in order to explain why ontologies can help address these limitations. In particular, this paper focuses on the capacity of ontologies to represent both symbolic and numeric knowledge, to reason based on cognitive semantics and to share knowledge on the interpretation of remote sensing images. Finally, a few recommendations are provided for remote sensing experts to comprehend the advantages of ontologies in interpreting satellite images.     

Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine‐grained matrix (ICM), clast‐laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just‐saturated near neutral (6 < pH<10), H₂S‐HS‐rich fluids at minimum log fO₂ of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400–500 °C, during or shortly after a short‐duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.     

A Rapid Method for Determining Boron Concentration (ID‐ICP‐MS) and δ11B (MC‐ICP‐MS) in Vegetation Samples after Microwave Digestion and Cation Exchange Chemical Purification

We present in this article a rapid method for B extraction, purification and accurate B concentration and δ¹¹B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ¹¹B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g^?1 of total salts or 25 μg g^?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ¹¹B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).     

Insights into estuarine benthic dissolved organic carbon (DOC) dynamics using δC-DOC values, phospholipid fatty acids and dissolved organic nutrient fluxes

Benthic dissolved organic carbon (DOC) flux rates and changes in DOC isotope ratios, along with nutrient fluxes, phospholipid fatty acids concentration and carbon isotope ratios were measured in productive estuarine sediments over a diel cycle to determine the mechanisms driving benthic-pelagic coupling of DOC. There was uptake of DOC during the dark and efflux during the light at all sites. DOC uptake rates were related to benthic respiration (dark O₂ uptake) and effluxes were coupled to the trophic status (ratio of production to respiration) of the sediments. Highest uptake and efflux rates were observed at two high nutrient concentration sites. The DOC:DON ratio of water column dissolved organic matter (DOM) decreased during the dark and increased during the light indicating preferential uptake and release of carbon rich dissolved organic matter. The calculated carbon isotope ratio of the DOC taken up by the benthos was significantly more depleted than the bulk water column DOC pool, suggesting preferential uptake of selected components of the water column DOC pool. Generally the isotope ratio of the DOC released during the light was more enriched than that taken up during the dark, which suggests that the benthos has the potential to significantly alter the estuarine DOC pool. Uptake and efflux were coupled to respiration and algal grazing/mineralization, therefore increased nutrient loading may shift the composition of the estuarine DOC pool through changes in the magnitude of benthic DOC fluxes. A combination of biological (diel shifts in DOC production and consumption) and abiotic processes (flocculation) appear to be driving the observed benthic DOC dynamics at the study sites. This study was the first to measure carbon isotopic changes in the water column DOC pool due to benthic processes, and shows that the benthos can alter the estuarine DOC pool through diel differences in DOC uptake and efflux.