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  1. Competitive and cooperative effects of chloride on palladium(II) adsorption to iron (oxyhydr)oxides: Implications for mobility during weathering

    Wright, Emily G. ; He, Xicheng ; Flynn, Elaine D. ; ... - Geochimica et Cosmochimica Acta
    In surface and near-surface weathering environments, the mobilization and partial loss of palladium (Pd) under oxidizing and weakly acidic conditions has been attributed to aqueous chloride complexation. However, prior work has also observed that a portion of Pd is retained by iron (oxyhydr)oxides in the weathering zone. The effect chloride has on the relative amount of Pd mobilization versus retention by iron (oxyhydr)oxides is currently unclear. We studied the effect of chloride complexation on Pd(II) adsorption to two iron (oxyhydr)oxides, hematite and 2-line ferrihydrite, at pH 4. Increasing chloride concentration suppresses Pd adsorption for both hematite and ferrihydrite, which displaymore » similar binding affinities under the conditions studied. Thermodynamic modeling of aqueous Pd speciation indicates that greater suppression of binding to iron (oxyhydr)oxides should occur than is observed because of the strength of Pd-Cl complexation, implying that additional interactions at the mineral surface are counteracting this effect. While increasing dissolved chloride concentration does not measurably impact mineral surface charging, extended X-ray absorption fine structure (EXAFS) spectra indicate that ternary Pd-Cl surface complexes form on both hematite and ferrihydrite. The number of Cl ligands in the surface species increase at greater chloride concentration. A mixture of bidentate and monodentate surface species are indicated by the EXAFS spectra, although the fitting uncertainties precludes determining whether these vary in relative abundance with chloride concentration. In order to offset the effect of strong aqueous Pd-Cl complexation and align with our EXAFS results, a surface complexation model developed for Pd adsorption to hematite involves a mixture of three ternary surface complexes containing 1, 2, and 3 chloride ligands. Our results show that Pd is mobilized as a chloride complex in platinum group element-rich weathering zones. As a result, porewater chloride concentrations are thus a dominant control on Pd retention by iron (oxyhydr)oxides in these weakly acidic environments.« less

  2. Co-treating flue gas desulfurized effluent and produced water enables novel waste management and recovery of critical minerals

    Ahmed, Mohammad Hafez ; Buzby, Karen ; Finklea, Harry ; ... - Desalination
    Herein this study reports a novel approach of resource recovery from co-managing two geographically co-located and chemically complementary wastewaters using a pilot-scale treatment process. Designed to treat flue gas desulfurized (FGD) effluent from combustion powerplants and produced water (PW) from energy industries, the process consists of soda-ash softening, nanofiltration (NF), and reverse osmosis (RO). Recovered products are barite, calcite, and low-salinity water. Using field-collected waters, the results show that softening at pH 8.5 produces calcite (yield: 30 kg/m3 treated water), a chemical used as SO₂(g) scrubbers. NF treatment under an applied pressure of 3.5 MPa yields a permeate stream ladenmore » with monovalent ions (water recovery 60%) and a concentrate stream with a sulfate concentration 1.8 times of the feedwater concentration. Mixing the NF concentrate and PW at a volumetric ratio of 1.0 precipitates a high-density barite material (4.1 g/cm3, yield: ~7.5 kg/m3 mixture) – a critical mineral commonly used as a weighting agent in drilling. The RO treatment recovers >64% water as the permeate, which can be readily used as cooling make-up water at the powerplants. The RO concentrate stream can be further processed in a thermal evaporative system for additional water recovery and brine production.« less

  3. Critical mineral source potential from oil & gas produced waters in the United States

    Smith, Kathryn H. ; Mackey, Justin E. ; Wenzlick, Madison ; ... - Science of the Total Environment
    The volume of produced water, a by-product of oil & gas operations and other energy processes, has been growing across the United States (U.S.) along with the need to manage or recycle this wastewater. Produced water contains many naturally occurring elements of varying concentrations, including critical minerals which are essential to the clean energy transition. However, the current understanding of critical mineral concentrations in produced water and the associated volumes across the U.S. is limited. This study has assessed available databases and literature to gain insight into the presence and concentration of five high priority critical minerals, namely cobalt, lithium,more » magnesium, manganese, and nickel. The U.S. Geological Survey's National Produced Waters Geochemical Database was the main data source used for determining average critical mineral concentrations in produced water from the major oil and gas reservoirs in the U.S. The volumes of produced water for these major reservoirs were coupled with these concentrations to provide insights into where critical minerals are likely to have high abundance and therefore more recovery options. The analysis indicated the highest recovery potential for lithium and magnesium from produced water in the Permian basin and the Marcellus shale region. However, these assessments should be considered conservative due to the limited availability of reliable concentration data. Finally, it is expected more critical mineral recovery options could emerge with comprehensive characterization data from more recent and representative sources of produced water.« less

  4. Connecting soils to life in conservation planning, nutrient cycling, and planetary science

    Lybrand, Rebecca A. - Earth-Science Reviews
    Soil supports life by serving as a living, breathing fabric that connects the atmosphere to the Earth's crust. The study of soil science and pedology, or the study of soil in the natural environment, spans scales, disciplines, and societies worldwide. Soil science continues to grow and evolve as a field given advancements in analytical tools, capabilities, and a growing emphasis on integrating research across disciplines. A pressing need exists to more strongly incorporate the study of soil, and soil scientists, into research networks, initiatives, and collaborations. This review presents three research areas focused on questions of central interest to scientists,more » students, and government agencies alike: 1) How do the properties of soil influence the selection of habitat and survival by organisms, especially threatened and endangered species struggling in the face of climate change and habitat loss during the Anthropocene? 2) How do we disentangle the heterogeneity of abiotic and biotic processes that transform minerals and release life-supporting nutrients to soil, especially at the nano- to microscale where mineral-water-microbe interactions occur? and 3) How can soil science advance the search for life and habitable environments on Mars and beyond- from distinguishing biosignatures to better utilizing terrestrial analogs on Earth for planetary exploration? This review also highlights the tools, resources, and expertise that soil scientists bring to interdisciplinary teams focused on questions centered belowground, whether the research areas involve conservation organizations, industry, the classroom, or government agencies working to resolve global challenges and sustain a future for all.« less

  5. Reactive Transport Modeling of Mineral Precipitation and Carbon Trapping in Discrete Fracture Networks

    Steefel, Carl I. ; Hu, Mengsu - Water Resources Research
    In this study we use numerical experiments to analyze reactive flow and transport behavior in discrete intersecting fracture networks, focusing on (a) how reaction-induced changes in physical and chemical properties affect flow connectivity and (b) how fracture networks developed in the Earth's critical zone contribute to carbon sequestration via mineral weathering reactions. In the first part of the study, we used two-dimensional reactive flow and transport simulations to analyze the impacts of mixing in a natural discrete fracture network. We concluded that reaction-induced changes can substantially alter the flow connectivity, especially at fracture intersections. The second set of simulations consideredmore » the problem of natural weathering of fractured mafic and ultramafic rocks in the partially saturated Earth's critical zone as a function of infiltration rates, fracture permeability, and partially saturated flow parameters. As a model system, we considered an incongruent reaction network with dissolution of forsterite and precipitation of magnesite. The behavior is complex in terms of the rate-controlling processes because of the multicomponent nature of the system as shown by the grid Peclet number: the CO2 behavior is gas diffusion-controlled in the partially saturated zone, while the rate of water flow via the Damkӧhler number controls Mg2+ transport through the fracture network. The amounts of carbon that can be trapped are modest, but the naturally fractured domain considered here provides a useful “base case” against which various engineered solutions can be compared.« less

  6. Distribution of Lanthanides, Yttrium, and Scandium in the Pilot-Scale Beneficiation of Fly Ashes Derived from Eastern Kentucky Coals

    Hower, James C. ; Groppo, John G. ; Joshi, Prakash ; ... - Minerals
    In this study, Central Appalachian coal-derived fly ashes from two power plants were beneficiated in a pilot-scale facility in order to produce a product with a relatively consistent concentration of rare earth elements (REE). The <200-mesh final fly ash product was produced by removing the carbon- and Fe-rich particles prior to screening at 200 mesh (75 µm). The Plant D fly ash had high concentrations of CaO and SO3, which were diminished through the two months when the ash was being beneficiated, representing a consequence of the heat, humidity, and excessive rainfall in the Kentucky summer. The high CaO andmore » SO3 concentrations through the early runs likely contributed to the lower REE in the <200-mesh products of those runs. Of the non-REE minor elements, Ba, V, Mn, Zn, and As showed the greatest between-run variations within the runs for each plant. The overall REE concentrations proved to be similar, both on a between-run basis for the individual fly ash sources and on a between-plant basis. Variations in fly ash quality will occur in larger-scale operations, so on-going attention to the fly ash quality and the response of the fly ash to beneficiation is necessary. Changes in the Plant D fly ash with time imply that both the freshness of the original ash and the length and conditions of its storage at the site of beneficiation could be factors in the quality and consistency of the processed fly ash.« less
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