The role of carbonate ions in pyrite oxidation in aqueous systems     

Claudia L. Caldeira  Virginia S.T. Ciminelli  Kwadwo Osseo-Asare 《Geochimica et cosmochimica acta》2010,74(6):1777-1789

The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO₃⁻, FeCO₃⁰, Fe(CO₃)(OH)⁻ and FeCO₃²⁻) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O₂, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O₂ is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.  相似文献   

Diurnal Variations in the Characteristics of Cloud-to-Ground Lightning Activity in the Great Lakes Region of the United States     

Claudia K. Walters  Julie A. Winkler 《The Professional geographer》1999,51(3):349-366

Cloud-to-ground (CG) lightning observations for the warm seasons (May-September) of 1989 and 1990 were analyzed for the Great Lakes region in order to assess the diurnal variations in the lightning characteristics. Several parameters, including flash rate, the spatial extent of lightning activity, first stroke peak current, and the percentage of positive flashes, varied markedly over the course of the day. In contrast, other parameters, such as the frequency of lightning periods and the multiplicity of both negative and positive CG flashes, displayed little diurnal variation. A large degree of intraseasonal (i.e., month-to-month) variation was observed in the diurnal patterns for several of the lightning parameters.  相似文献   

Co-evolution of coarse grain structuring and bed roughness in response to episodic sediment supply in an experimental aggrading channel     

Marwan A. Hassan  Matteo Saletti  Chendi Zhang  Carles Ferrer-Boix  Joel P.L. Johnson  Tobias Müller  Claudia von Flotow 《地球表面变化过程与地形》2020,45(4):948-961

We use flume experiments to better understand how gravel-bed channels maintain bed surface stability in response to pulses of sediment supply. Bed elevations and surface imagery at high spatial resolutions were used to quantify the co-evolution of surface grain-size distribution (GSD), bed roughness statistics, and bed surface structures (clusters, cells and transverse features). Using a new semi-automated method, we identified individual stone structures over a 2 m × 1 m area throughout the experiments. After an initial coarsening, surface GSD and armouring ratio remained nearly stable as sediment pulses caused net bed aggradation. In contrast, individual grain structures continued to form, increase or decrease in size, and disappear throughout the experiments. The response of the bed to sediment pulses depended on the history of surface roughness evolution and bed surface structure development, as these factors changed much more in response to supply perturbations earlier in the experiments compared to later, even as the bed continued to aggrade. We interpret that the dynamic production and destruction of bed surface structures can act as a ‘buffer’ to sediment supply pulses, maintaining a stable bed surface during aggradation with minimal change in grain size or armouring. © 2019 John Wiley & Sons, Ltd.  相似文献   

Local groundwater balance model: stakeholders’ efforts to address groundwater monitoring and literacy     

Yolanda Lopez-Maldonado  Eduardo Batllori-Sampedro  Claudia R. Binder  Brian D. Fath 《水文科学杂志》2017,62(14):2297-2312

Understanding groundwater systems is crucial to ensure their monitoring and protection. Global groundwater models and predictive tools exist to better understand them. In view of scarce groundwater data, especially in developing countries, the question of how to model these systems and make them usable for groundwater management is crucial. Herein, we demonstrate how a transdisciplinary process can overcome the data scarcity problem and lead to the development of a local groundwater balance model (LGBM). Over 50 actors from more than 15 disciplines and groundwater-related sectors were involved for the case of Yucatan, Mexico. Results revealed high wastewater emissions to the aquifer discharged without treatment and poor recycling practices. The method can be adapted to specific regions, can be used to address methodological challenges for monitoring, and can contribute to the achievement of the 2030 Development Agenda by addressing Sustainable Development Goal 6-related Targets (6.3, 6.4, 6.5, 6.6(a, b)).  相似文献   

The Geochemical Effects of Microbial Humic Substances Reduction     

John D. Coates  Romy Chakraborty  Susan M. O&#x;Connor  Claudia Schmidt  Jürgen Thieme 《洁净——土壤、空气、水》2001,28(7):420-427

As part of a study on microbial redox alteration of humic substances we investigated the potential effect of this metabolism on the fate of heavy metals and hydrocarbons as a result of conformational alteration of the humic molecular structure due to microbial reduction. Our studies indicate that the microbial reduction of humic acids (HA) results in significant morphological and geochemical alterations. X‐ray microscopy analysis indicate that the conformational structure of the humic colloids is altered as a result of the redox change. In the reduced state, the HA appeared as small dense particles, on reoxidation, large loose aggregates were formed. In addition, spectrofluorometric studies indicated that the binding capacity of the HA for naphthalene was decreased by 10% when the HA was reduced. Similarly, the reduced HA yielded higher surface tension values at all concentrations tested which is indicative of a more hydrophilic and less hydrophobic solute. On reoxidation, the surface tension values reverted back to values similar to those obtained for the untreated oxidized HA. These data indicate that the hydrophobicity of the HA is altered on biological reduction of the HA and that this alteration is reversible. In contrast the reduced HA demonstrated a 15% higher affinity for heavy metals such as divalent cobalt than the oxidized HA. In addition to increasing the binding capacity of HA for heavy metals, the reduction of the HA also decreased the bioavailability and toxicity of bound heavy metals such as chromium. When incubated in the presence of Cr(III) and HA, cells of Escherichia coli grew much more rapidly in the presence of the reduced HA suggesting that the higher metal binding capacity of the reduced humic substances resulted in a removal of the Cr(III) from solution and hence reduced its bioavailability and toxicity. These studies demonstrate that HA redox state and reduction of humic acids by microorganisms can have a significant effect on the molecular morphology and binding constants of HA for heavy metals and hydrocarbons and also directly affects the bioavailability of these compounds in the environment.  相似文献   

Development and validation of a storm surge forecasting/hindcasting modelling system for the extensive Río de la Plata Estuary and its adjacent Continental Shelf     

Dinápoli  Matías G.  Simionato  Claudia G.  Moreira  Diego 《Natural Hazards》2020,103(2):2231-2259

Natural Hazards - The Río de la Plata (RdP) Estuary is affected by significant surges several times per year. This phenomenon has historically caused catastrophic water-level enlargements of...  相似文献   

Estimation of hydraulic parameters in a heterogeneous low-lying farmland near Venice     

Ester Zancanaro  Claudia Zoccarato  Francesco Morari  Pietro Teatini 《水文研究》2023,37(1):e14791

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Twinned calcite as an indicator of high differential stresses and low shock pressure conditions during impact cratering     

Lina Seybold  Claudia A. Trepmann  Stefan Hölzl  Kilian Pollok  Falko Langenhorst  Fabian Dellefant  Melanie Kaliwoda 《Meteoritics & planetary science》2023,58(9):1287-1305

Shock-related calcite twins are characterized in calcite-bearing metagranite cataclasites within crystalline megablocks of the Ries impact structure, Germany, as well as in cores from the FBN1973 research drilling. The calcite likely originates from pre-impact veins within the Variscan metagranites and gneisses, while the cataclasis is due to the Miocene impact. Quartz in the metagranite components does not contain planar deformation features, indicating low shock pressures (<7 GPa). Calcite, however, shows a high density (>1/μm) of twins with widths <100 nm. Different types of twins (e-, f-, and r-twins) crosscutting each other can occur in one grain. Interaction of r- and f-twins results in a-type domains characterized by a misorientation relative to the host with a misorientation angle of 35°–40° and a misorientation axis parallel to an a-axis. Such a-type domains have not been recorded from deformed rocks in nature before. The high twin density and activation of different twin systems in one grain require high differential stresses (on the order of 1 GPa). Twinning of calcite at high differential stresses is consistent with deformation during impact cratering at relatively low shock pressure conditions. The twinned calcite microstructure can serve as a valuable low shock barometer.  相似文献