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At least 235 records · Page 13

Evolution of Size and Chemical Composition of Copper Concentrate Particles Oxidized Under Simulated Flash Smelting Conditions

An experimental study was conducted to elucidate the evolution of size and chemical composition of La Caridad copper concentrate particles during oxidation under simulated flash smelting conditions. Input variables tested included particle size and oxygen concentration in the process gas. The response variables included the size distributions, chemical composition, and morphology of the reacted particles at seven locations along a laboratory reactor. Particles with initial size < 45 µm contained mostly chalcopyrite, they increased their mean size and decreased the amount of dust in the population during oxidation. This was explained by a reaction path involving rapid melting followed by collision and coalescence of reacting droplets during flight. Particles with sizes > 45 µm contained varying amounts of chalcopyrite and pyrite, and tended to either maintain or decrease their mean size upon oxidation. When size reduction was observed, dust was produced because of fragmentation, and the particles showed no evidence of collisions during flight. The main oxidation products detected in the particles consisted of matte, cuprospinel, and magnetite. A plot of the mean size divided by the mean size in the feed against the fraction of sulfur eliminated generalized the experimental data so far reported in the literature, and helped identify the reaction path followed by the particles.

36 MATERIALS SCIENCE↗

Physical and microstructural aspects of iron sulfide degradation in concrete

The microstructural aspects of iron sulfide degradation in dam concrete were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in both dam concrete samples and laboratory concrete. The results show that iron sulfide inclusions with a diameter of a few micrometers in the aggregates are reactive and appear to generate expansion first in the aggregates and consequently in the cement paste. The expansion from the iron sulfides is a consequence of the increase in volume of the reaction products formed. The types of iron sulfide present in the aggregate, mainly pyrrhotite (FeS) and pyrite (FeS{sub 2}), show similar reaction behavior in the aggregates. The released sulfate can lead to a secondary ettringite formation in the concrete matrix, but the degradation associated with this appears to be minor. The reaction of the iron sulfides was found to be very slow even when laboratory samples were exposed to elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Managing Chemistry Underground: Is Co-Sequestration an Option in Selected Formations?

Geochemical simulations indicate that, although co-injection of CO2 and SO2 in glauconitic sandstone may not result in the permanent sequestration of SO2, other formations are more favorable. In a predominantly dolomite formation, dissolution of calcite, and to a lesser extent, dolomite will provide Ca in solution to promote the precipitation of anhydrite, thus removing the SO2 from solution. In basalt, dissolution of basaltic glass under acidic conditions provides Ca and Fe in solution which promote the sequestration of SO2 as anhydrite and eventually, pyrite.

58 GEOSCIENCES↗

Weathering of chlorite from grain to watershed: The role and distribution of oxidation reactions in the subsurface

The reaction mechanism of weathering of chlorite, an important rock-forming phyllosilicate, is not well understood in natural settings. Here, in this work we investigated the weathering of Fe-rich chlorite from deep protolith to saprock to soil across a small shale-underlain watershed in the Appalachian Mountains, USA (Shale Hills). We found that oxidation of Fe(II) in chlorite always occurs prior to dissolution of the interlayers of the mineral. The oxidation of pyrite and chlorite commence near the water table across narrow depth intervals under the upper-catchment ridges, but well below the water table across wide depth intervals under the valley. We hypothesize that these patterns can be explained by hydrological and geochemical differences between the ridge and the valley: oxygenated water descends sub-vertically (1D flow) under the ridge, while under the valley, oxygen-depleted water moves upward to the stream and laterally out of the watershed in the subsurface (3D flow). Geochemical and mineralogical characterization indicates that the transformation of Fe-rich chlorite at Shale Hills is initiated by the oxidation of Fe(II). Next, the interlayer hydroxide sheet dissolves to form hydroxy-interlayered vermiculite and then vermiculite. During the transformation, Mg and Fe are released into solution and Fe is reprecipitated as goethite in pore space. Delivery of oxygen to the deep subsurface by infiltration of meteoric water is thought to control the initial transformation of chlorite at Shale Hills. It is possible that weathering of many Fe(II)-rich minerals is initiated by oxidation as mediated by rates of subsurface oxygen delivery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of raw and burnt oil shale from Dotternhausen: Petrographical and mineralogical evolution with temperature

The Toarcian Posidonia shale from Dotternhausen, Germany, is quarried and burnt in a fluidized bed reactor to produce electricity. The combustion residue, namely burnt oil shale (BOS), is used in the adjacent cement work as an additive in blended cements. The starting material is a typical laminated oil shale with an organic matter content ranging from 6 to 18%. Mineral matter consists principally of quartz, feldspar, pyrite and clays. After calcination in the range, the resulting product, burnt oil shale, keeps the macroscopic layered texture however with different mineralogy (anhydrite, lime, iron oxides) and the formation of an amorphous phase. This one, studied under STEM, reveals a typical texture of incipient partial melting due to a long retention time (ca. 30 min) and quenching. An in-situ high temperature X-ray diffraction (HTXRD) allowed studying precisely the mineralogical changes associated with the temperature increase. - Highlights: • We present oil shale/burnt oil shale characterization. • The Posidonia Shale is burnt in a fluidized bed. • Mineralogical evolution with temperature is complex. • The burnt oil shale is used in composite cements.

36 MATERIALS SCIENCE↗

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn{sub 2} (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb{sub 2}, and the NiAs{sub 2} types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB{sub 2} structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced thermoelectric power and electronic correlations in RuSe{sub 2}

We report the electronic structure, electric and thermal transport properties of Ru{sub 1−x}Ir{sub x}Se{sub 2} (x ≤ 0.2). RuSe{sub 2} is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe{sub 2} exceeds −200 μV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru{sub 0.8}Ir{sub 0.2}Se{sub 2} shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb{sub 2}.

36 MATERIALS SCIENCE↗

Proteomic Analysis of Methanococcus voltae Grown in the Presence of Mineral and Nonmineral Sources of Iron and Sulfur

Iron sulfur (Fe-S) proteins are essential and ubiquitous across all domains of life, yet the mechanisms underpinning assimilation of iron (Fe) and sulfur (S) and biogenesis of Fe-S clusters are poorly understood. This is particularly true for anaerobic methanogenic archaea, which are known to employ more Fe-S proteins than other prokaryotes. Here, we utilized a deep proteomics analysis of Methanococcus voltae A3 cultured in the presence of either synthetic pyrite (FeS 2 ) or aqueous forms of ferrous iron and sulfide to elucidate physiological responses to growth on mineral or nonmineral sources of Fe and S. The liquid chromatography-mass spectrometry (LCMS) shotgun proteomics analysis included 77% of the predicted proteome. Through a comparative analysis of intra- and extracellular proteomes, candidate proteins associated with FeS 2 reductive dissolution, Fe and S acquisition, and the subsequent transport, trafficking, and storage of Fe and S were identified. The proteomic response shows a large and balanced change, suggesting that M. voltae makes physiological adjustments involving a range of biochemical processes based on the available nutrient source. Among the proteins differentially regulated were members of core methanogenesis, oxidoreductases, membrane proteins putatively involved in transport, Fe-S binding ferredoxin and radical S-adenosylmethionine proteins, ribosomal proteins, and intracellular proteins involved in Fe-S cluster assembly and storage. This work improves our understanding of ancient biogeochemical processes and can support efforts in biomining of minerals. Clusters of iron and sulfur are key components of the active sites of enzymes that facilitate microbial conversion of light or electrical energy into chemical bonds. The proteins responsible for transporting iron and sulfur into cells and assembling these elements into metal clusters are not well understood. Using a microorganism that has an unusually high demand for iron and sulfur, we conducted a global investigation of cellular proteins and how they change based on the mineral forms of iron and sulfur. Understanding this process will answer questions about life on early earth and has application in biomining and sustainable sources of energy.

59 BASIC BIOLOGICAL SCIENCES↗

Structure–Composition Relationship of Platelike Ferrospheres in Calcium-Rich Power Plant Ash

The structure–composition relationship for polished sections of individual platelike ferrospheres in the–0.04 + 0.032 mm size fraction isolated from fly ash from the combustion of brown coal has been studied systematically by scanning electron microscopy and energy dispersive X-ray spectroscopy. We have identified groups of globules whose overall composition, as well as the composition of local areas on their polished sections, can be represented by general equations for component concentrations: CaO = f(FeO) and SiO{sub 2} = f(FeO). Analysis of the structure–composition relationship for the globules leads us to conclude that their structure is determined by transformations that occur in the CaO–Fe{sub x}O{sub y} system in response to an increase in its oxidation potential. It has been shown that the platelike globules containing 68–73 wt % FeO are made up of Ca{sub 2}Fe{sub 2}O{sub 5} and CaFe{sub 2}O{sub 4} crystallites resulting from the oxidative transformation of Fe, Ca, and Mg complex humates in the parent brown coal. The ferrospheres containing 79–90 wt % FeO have a fragmentary core–shell structure, where the platelike shell consists of Ca{sub 2}Fe{sub 2}O{sub 5} and CaFe{sub 2}O{sub 4} crystallites, and the core consists of Fe{sub 2}O{sub 3} and a Ca-, Mg-, and Al-promoted magnetite. Precursors for the formation of this type of globule are pyrite associates with complex humates. It has also been demonstrated that the low concentration of aluminum and silicon oxides in the composition of the globules and the viscosity of their melt have no effect on the structure of the platelike ferrospheres.

36 MATERIALS SCIENCE↗

Prospects of radiation-thermal treatment of wastes of Novosibirsk Tin Works

The experimental test data on magnetic properties of the waste iron-containing mineral materials under radiation-thermal treatment are presented. It is found that the volume magnetic susceptibility of pyrite- and arsenopyrite-containing wastes has increased 5 times on the average. The authors demonstrate that radiation-thermal magnetization and magnetic separation allows production of KOS-3 grade tin concentrate meeting fuming process requirements from wastes of Novosibirsk Tin Works.

36 MATERIALS SCIENCE↗

Stereochemistry of silicon in oxygen-containing compounds

Specific stereochemical features of silicon in oxygen-containing compounds, including hybrid silicates with all oxygen atoms of SiO{sub n} groups ({sub n} = 4, 5, or 6) entering into the composition of organic anions or molecules, are described by characteristics of Voronoi—Dirichlet polyhedra. It is found that in rutile-like stishovite and post-stishovite phases with the structures similar to those of СаСl{sub 2}, α-PbO{sub 2}, or pyrite FeS{sub 2}, the volume of Voronoi—Dirichlet polyhedra of silicon and oxygen atoms decreases linearly with pressure increasing to 268 GPa. Based on these results, the possibility of formation of new post-stishovite phases is shown, namely, the fluorite-like structure (transition predicted at ~400 GPa) and a body-centered cubic lattice with statistical arrangement of silicon and oxygen atoms (~900 GPa).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Comparison of the Wymark CO2 Reservoir with the Midale Beds at the Weyburn CO2 Injection Project

The Devonian carbonates of the Duperow Formation on the western flank of the Williston Basin in southwest Saskatchewan contain natural accumulations of CO{sub 2}, and may have done so for as long as 50 m.y. in the views of some investigations. These carbonate sediments are characterized by a succession of carbonate cycles capped by anhydrite-rich evaporites that are thought to act as seals to fluid migration. The Weyburn CO{sub 2} injection site lies 400 km to the east in a series of Mississippian carbonates that were deposited in a similar depositional environment. That natural CO{sub 2} can be stored long-term within carbonate strata has motivated the investigation of the Duperow rocks as a potential natural analogue to storage of anthropogenic CO{sub 2} that may ultimately provide additional confidence for CO{sub 2} sequestration in carbonate lithologies. For the Duperow strata to represent a legitimate analog for Midale injection and storage, the similarity in lithofacies, whole rock compositions, mineral compositions and porosity with the Midale Beds must be established. Previous workers have demonstrated the similarity of the lithofacies at both sites. Here we compare the whole rock compositions, mineralogy and mineral compositions. The major mineral phases at both locales are calcite, dolomite and anhydrite. In addition, accessory pyrite, fluorite and celestine are also observed. The distribution of porosity in the Midale Vuggy units is virtually identical to that of the Duperow Formation, but the Marly units of the Midale have significantly higher porosity. The Duperow Formation is topped by the Dinesmore evaporite that is particularly rich in anhydrite, and often contains authigenic K-feldspar. The chemistry of dolomite and calcite from the two localities also overlaps. Silicate minerals are in low abundance within the analyzed Duperow samples, < 3 wt% on a normative basis, with quartz the only phase identifiable in x-ray diffraction patterns. The Midale Beds contain significantly higher silica/silicate concentrations, but the silicate minerals observed, K-feldspar and quartz, are unlikely to participate in carbonate mineral precipitation due to the absence of alkaline earths. Hence, physical and solution trapping are likely to be the primary trapping mechanisms at both sites. Given the similarity of mineral constituents, whole rock and mineral chemistry, reactive transport models developed for the Weyburn site should also be applicable to the Duperow lithologies.

58 GEOSCIENCES↗

Evolution of Chemical Conditions and Estimated Plutonium Solubility in the Residual Waste Layer During Post-Closure Aging of Tank 18

This document updates the Eh-pH transitions from grout aging simulations and the plutonium waste release model of Denham (2007, Rev. 1) based on new data. New thermodynamic data for cementitious minerals are used for the grout simulations. Newer thermodynamic data, recommended by plutonium experts (Plutonium Solubility Peer Review Report, LA-UR-12-00079), are used to estimate solubilities of plutonium at various pore water compositions expected during grout aging. In addition, a new grout formula is used in the grout aging simulations and apparent solubilities of coprecipitated plutonium are estimated using data from analysis of Tank 18 residual waste. The conceptual model of waste release and the grout aging simulations are done in a manner similar to that of Denham (2007, Rev. 1). It is assumed that the pore fluid composition passing from the tank grout into the residual waste layer controls the solubility, and hence the waste release concentration of plutonium. Pore volumes of infiltrating fluid of an assumed composition are reacted with a hypothetical grout block using The Geochemist's Workbench{reg_sign} and changes in pore fluid chemistry correspond to the number of pore fluid volumes reacted. As in the earlier document, this results in three states of grout pore fluid composition throughout the simulation period that are termed Reduced Region II, Oxidized Region II, and Oxidized Region III. The one major difference from the earlier document is that pyrite is used to account for reducing capacity of the tank grout rather than pyrrhotite. This poises Eh at -0.47 volts during Reduced Region II. The major transitions in pore fluid composition are shown. Plutonium solubilities are estimated for discrete PuO2(am,hyd) particles and for plutonium coprecipitated with iron phases in the residual waste. Thermodynamic data for plutonium from the Nuclear Energy Agency are used to estimate the solubilities of the discrete particles for the three stages of pore fluid evolution. In Denham (2007, Rev. 1), the solubilities in the oxidized regions were estimated at Eh values in equilibrium with dissolved oxygen. Here, these are considered to be maximum possible solubilities because Eh values are unlikely to be in equilibrium with dissolved oxygen. More realistic Eh values are estimated here and plutonium solubilities calculated at these are considered more realistic. Apparent solubilities of plutonium that coprecipitated with iron phases are estimated from Pu:Fe ratios in Tank 18 residual waste and the solubilities of the host iron phases. The estimated plutonium solubilities are shown. Uncertainties in the grout simulations and plutonium solubility estimates are discussed. The primary uncertainty in the grout simulations is that little is known about the physical state of the grout as it ages. The simulations done here are pertinent to a porous medium, which may or may not be applicable to fractured grout, depending on the degree and nature of the fractures. Other uncertainties that are considered are the assumptions about the reducing capacity imparted by blast furnace slag, the effects of varying dissolved carbon dioxide and oxygen concentrations, and the treatment of silica in the simulations. The primary uncertainty in the estimates of plutonium solubility is that little is known about the exact form of plutonium in the residual waste. Other uncertainties include those inherent in the thermodynamic data, pH variations from those estimated in the grout simulations, the effects of the treatment of silica in the grout simulations, and the effect of varying total dissolved carbonate concentrations. The objective of this document is to update the model for solubility controls on release of plutonium from residual waste in closed F-Area waste tanks. The update is based on new information including a new proposed grout formulation, chemical analysis of Tank 18 samples and more current thermodynamic data for plutonium and grout minerals. In addition, minor changes to the modeling of the grout chemical evolution have been made. It should be noted that the intent is to provide bounding solubilities for plutonium to be used in Performance Assessment modeling rather than trying to identify an exact concentration of plutonium in pore fluids released from a tank at any given time. This document also considers suggestions and opportunities for improvement regarding the plutonium modeling assumptions from the Plutonium Solubility Peer Review Report, LA-UR-12-00079.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Iodine adsorption on ion-exchange resins and activated carbons: batch testing

Iodine sorption onto seven resins and six carbon materials was evaluated using water from well 299-W19-36 on the Hanford Site. These materials were tested using a range of solution-to-solid ratios. The test results are as follows. The efficacy of the resin and granular activated carbon materials was less than predicted based on manufacturers’ performance data. It is hypothesized that this is due to the differences in speciation previously determined for Hanford groundwater. The sorption of iodine is affected by the iodine species in the source water. Iodine loading on resins using source water ranged from 1.47 to 1.70 µg/g with the corresponding K d values from 189.9 to 227.0 mL/g. The sorption values when the iodine is converted to iodide ranged from 2.75 to 5.90 µg/g with the corresponding K d values from 536.3 to 2979.6 mL/g. It is recommended that methods to convert iodine to iodide be investigated in fiscal year (FY) 2015. The chemicals used to convert iodine to iodate adversely affected the sorption of iodine onto the carbon materials. Using as-received source water, loading and K d values ranged from 1.47 to 1.70 µg/g and 189.8 to 226.3 mL/g respectively. After treatment, loading and K d values could not be calculated because there was little change between the initial and final iodine concentration. It is recommended the cause of the decrease in iodine sorption be investigated in FY15. In direct support of CH2M HILL Plateau Remediation Company, Pacific Northwest National Laboratory has evaluated samples from within the 200W pump and treat bioreactors. As part of this analysis, pictures taken within the bioreactor reveal a precipitate that, based on physical properties and known aqueous chemistry, is hypothesized to be iron pyrite or chalcopyrite, which could affect iodine adsorption. It is recommended these materials be tested at different solution-to-solid ratios in FY15 to determine their effect on iodine sorption.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling of fate and transport of co-injection of H2S with CO2 in deep saline formations

The geological storage of CO{sub 2} in deep saline formations is increasing seen as a viable strategy to reduce the release of greenhouse gases into the atmosphere. However, costs of capture and compression of CO{sub 2} from industrial waste streams containing small quantities of sulfur and nitrogen compounds such as SO{sub 2}, H{sub 2}S and N{sub 2} are very expensive. Therefore, studies on the co-injection of CO{sub 2} containing other acid gases from industrial emissions are very important. In this paper, numerical simulations were performed to study the co-injection of H{sub 2}S with CO{sub 2} in sandstone and carbonate formations. Results indicate that the preferential dissolution of H{sub 2}S gas (compared with CO{sub 2} gas) into formation water results in the delayed breakthrough of H{sub 2}S gas. Co-injection of H{sub 2}S results in the precipitation of pyrite through interactions between the dissolved H{sub 2}S and Fe{sup 2+} from the dissolution of Fe-bearing minerals. Additional injection of H{sub 2}S reduces the capabilities for solubility and mineral trappings of CO{sub 2} compared to the CO{sub 2} only case. In comparison to the sandstone (siliciclastic) formation, the carbonate formation is less favorable to the mineral sequestration of CO{sub 2}. Different from CO{sub 2} mineral trapping, the presence of Fe-bearing siliciclastic and/or carbonate is more favorable to the H{sub 2}S mineral trapping.

54 ENVIRONMENTAL SCIENCES↗

Pre-Combustion Technique for Desulphurization of Waterberg Coalfield: Biological Treatment - 18444

The current study evaluates a microbial desulphurization of medium - sulphur type coal containing total sulphur (1.45 wt.%) and pyritic sulphur (≥ 0.51 wt. %) as a pre-combustion technique. Coal sample containing particle size in the range of - 0.85 mm was used in the experiments with bacteria isolated from nearby stockpiles of newly commissioned South African National Power Utility's (Eskom's) Medupi Power Station. After a stipulated hydraulic retention time (HRT), the coal samples were filtered, washed, dried and analyzed for total sulphur, ash content and calorific values. The calorific value of the coal significantly improved from 20.42 MJ/Kg to 24.16 MJ/Kg on the 5. day. The process removed up to 72% of the total sulphur content in the coal samples at a HRT of day 9. Furthermore, ash content reduced by 16%. This study provides a novel breakthrough of an alternative microbial desulphurization process of Waterberg steam coal as a further pre-treatment technique in order to meet stringent environmental emissions standards for SO{sub 2}. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Manganese uptake by red maples in response to mineral dissolution rates in soil

Manganese (Mn) is an essential plant micronutrient that influences photosynthesis, ecosystem productivity, and soil carbon storage. Our objective was to quantify how Mn uptake by forest vegetation relates to Mn release into soil solution through mineral dissolution. In this work, a greenhouse pot experiment was conducted to quantify Mn uptake by red maple saplings as a function of mineral solubility to test whether Mn uptake was limited by the supply of Mn to soil solution. Differences in soil microbial community composition between treatments, particularly amongst Mn cycling bacteria and fungi, were also evaluated to assess potential microbial impacts on observed Mn fluxes. Plant Mn uptake was highest in systems supplied with dissolved Mn(II) because it was not kinetically limited by mineral weathering. Mn uptake was also higher in systems supplied with a fast-weathering substrate (shale containing Mn(II)-bearing pyrite) than a slow-weathering substrate (Mn(IV)-oxide). However, vegetation accumulated a decreasing proportion of available Mn with increasing solubility, indicating that uptake was tempered relative to solubility. The presence of bacterial phyla containing known Mn-oxidizing bacteria indicates the potential for Mn-oxidizing bacteria to influence Mn solubility within Mn-oxide and dissolved Mn treatments. A relatively low abundance of these bacteria points to their limited capacity to oxidize and retain Mn in the shale treatments, consistent with substantial Mn leaching. We conclude that Mn uptake was primarily controlled by dissolution rates of Mn-bearing minerals but modified by biological processes. The quantitative framework presented here can guide understanding of how biogeochemical processes control element cycling between plants and soils.

59 BASIC BIOLOGICAL SCIENCES↗