Showing papers on "Silicate minerals published in 2019"

Nitrogen in the Earth: abundance and transport

Abstract: The terrestrial nitrogen budget, distribution, and evolution are governed by biological and geological recycling. The biological cycle provides the nitrogen input for the geological cycle, which, in turn, feeds some of the nitrogen into the Earth’s interior. A portion of the nitrogen also is released back to the oceans and the atmosphere via N2 degassing. Nitrogen in silicate minerals (clay minerals, mica, feldspar, garnet, wadsleyite, and bridgmanite) exists predominantly as NH4+. Nitrogen also is found in graphite and diamond where it occurs in elemental form. Nitrides are stable under extremely reducing conditions such as those that existed during early planetary formation processes and may still persist in the lower mantle. From experimentally determined nitrogen solubility in such materials, the silicate Earth is nitrogen undersaturated. The situation for the core is more uncertain, but reasonable Fe metal/silicate nitrogen partition coefficients (> 10) would yield nitrogen contents sufficient to account for the apparent nitrogen deficiency in the silicate Earth compared with other volatiles. Transport of nitrogen takes place in silicate melt (magma), water-rich fluids, and as a minor component in silicate minerals. In melts, the N solubility is greater for reduced nitrogen, whereas the opposite appears to be the case for N solubility in fluids. Reduced nitrogen species (NH3, NH2−, and NH2+) dominate in most environments of the modern Earth’s interior except the upper ~ 100 km of subduction zones where N2 is the most important species. Nitrogen in magmatic liquids in the early Earth probably was dominated by NH3 and NH2−, whereas in the modern Earth, the less reduced, NH2+ functional group is more common. N2 is common in magmatic liquids in subduction zones. Given the much lower solubility of N2 in magmatic liquids compared with other nitrogen species, nitrogen dissolved as N2 in subduction zone magmas is expected to be recycled and returned to the oceans and the atmosphere, whereas nitrogen in reduced form(s) likely would be transported to greater depths. This solubility difference, controlled primarily by variations in redox conditions, may be a factor resulting in increased nitrogen in the Earth’s mantle and decreasing abundance in its oceans and atmosphere during the Earth’s evolution. Such an abundance evolution has resulted in the decoupling of nitrogen distribution in the solid Earth and the hydrosphere and atmosphere.

Surface dissolution-assisted mineral flotation: A review

Abstract: Selective flotation of minerals is a separation method based on differences in surface properties of minerals. An auxiliary pretreatment on minerals, prior to flotation, can help to increase the selectivity of separation process. Surface dissolution is a pretreatment process modifying surface properties of minerals. This critical review attempts to present the potential of the surface dissolution as a surface modification method in the mineral flotation, including parameters and mechanisms of surface dissolution, surface properties of minerals, and effect of this pretreatment on the flotation behavior of different minerals. Understanding of the different aspects of surface dissolution affecting the flotation behavior of minerals is a physicochemical challenge. The surface dissolution of minerals is led to specific changes in crystal chemistry, surface chemistry and solution chemistry of minerals that are the characteristic features in a flotation process. In addition to the mineral processing parameters, this pretreatment dissolves the mineral surface ions and affects the surface, kinetic, and thermodynamic parameters of minerals. The application potential of this method on various categories of minerals was studied. The oxide and silicate minerals had the highest potential for applying this method. In the future studies, the focus must be on the kinetic and thermodynamic characteristics of minerals, and developing of a methodology to apply the process in industrial scale.

A structure hierarchy for silicate minerals: sheet silicates

Abstract: The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerisation of coordination polyhedra of higher bond-valence. A hierarchical structural classification is developed for sheet-silicate minerals based on the connectedness of the two-dimensional polymerisations of (TO4) tetrahedra, where T = Si4+ plus As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Two-dimensional nets and oikodomeic operations are used to generate the silicate (sensu lato) structural units of single-layer, double-layer and higher-layer sheet-silicate minerals, and the interstitial complexes (cation identity, coordination number and ligancy, and the types and amounts of interstitial (H2O) groups) are recorded. Key aspects of the silicate structural unit include: (1) the type of plane net on which the sheet (or parent sheet) is based; (2) the u (up) and d (down) directions of the constituent tetrahedra relative to the plane of the sheet; (3) the planar or folded nature of the sheet; (4) the layer multiplicity of the sheet (single, double or higher); and (5) the details of the oikodomeic operations for multiple-layer sheets. Simple 3-connected plane nets (such as 63, 4.82 and 4.6.12) have the stoichiometry (T2O5)n (Si:O = 1:2.5) and are the basis of most of the common rock-forming sheet-silicate minerals as well as many less-common species. Oikodomeic operations, e.g. insertion of 2- or 4-connected vertices into 3-connected plane nets, formation of double-layer sheet-structures by (topological) reflection or rotation operations, affect the connectedness of the resulting sheets and lead to both positive and negative deviations from Si:O = 1:2.5 stoichiometry. Following description of the structural units in all sheet-silicate minerals, the minerals are arranged into decreasing Si:O ratio from 3.0 to 2.0, an arrangement that reflects their increasing structural connectivity. Considering the silicate component of minerals, the range of composition of the sheet silicates completely overlaps the compositional ranges of framework silicates and most of the chain-ribbon-tube silicates.

The novel and efficient method for isolating potassium solubilizing bacteria from rhizosphere soil

Abstract: Potassium (K) is the third major essential macronutrient for plant growth and more than 90% of potassium in the soil exists in the form of insoluble rocks and silicate minerals. 150 potassi...

Reviews and syntheses: Weathering of silicate minerals in soils and watersheds: Parameterization of the weathering kinetics module in the PROFILE and ForSAFE models

Abstract: . The PROFILE model, now incorporated in the ForSAFE model can accurately reproduce the chemical and mineralogical evolution of the soil unsaturated zone. However, in deeper soil layers and in groundwater systems, it appears to overestimate weathering rates. This overestimation has been corrected by improving the kinetic expression describing mineral dissolution by adding or upgrading breaking functions . The base cation and aluminium brakes have been strengthened, and an additional silicate brake has been developed, improving the ability to describe mineral-water reactions in deeper soils. These brakes are developed from a molecular-level model of the dissolution mechanisms. Equations, parameters and constants describing mineral dissolution kinetics have now been obtained for 102 different minerals from 12 major structural groups, comprising all types of minerals encountered in most soils. The PROFILE and ForSAFE weathering sub-model was extended to cover two-dimensional catchments, both in the vertical and the horizontal direction, including the hydrology. Comparisons between this improved model and field observations is available in Erlandsson Lampa et al. (2019, This special issue). The results showed that the incorporation of a braking effect of silica concentrations was necessary and helps obtain more accurate descriptions of soil evolution rates at greater depths and within the saturated zone.

Atmospheric Carbon Capture Performance of Legacy Iron and Steel Waste.

Abstract: Legacy iron (Fe) and steel wastes have been identified as a significant source of silicate minerals, which can undergo carbonation reactions and thus sequester carbon dioxide (CO2). In reactor experiments, i.e., at elevated temperatures, pressures, or CO2 concentrations, these wastes have high silicate to carbonate conversion rates. However, what is less understood is whether a more “passive” approach to carbonation can work, i.e., whether a traditional slag emplacement method (heaped and then buried) promotes or hinders CO2 sequestration. In this paper, the results of characterization of material retrieved from a first of its kind drilling program on a historical blast furnace slag heap at Consett, U.K., are reported. The mineralogy of the slag material was near uniform, consisting mainly of melilite group minerals with only minor amounts of carbonate minerals detected. Further analysis established that total carbon levels were on average only 0.4% while average calcium (Ca) levels exceeded 30%. It was calculated that only ∼3% of the CO2 sequestration potential of the >30 Mt slag heap has been utilized. It is suggested that limited water and gas interaction and the mineralogy and particle size of the slag are the main factors that have hindered carbonation reactions in the slag heap.

Polymineralic Inclusions in Megacrysts as Proxies for Kimberlite Melt Evolution—A Review

Abstract: Polymineralic inclusions in megacrysts have been reported to occur in kimberlites worldwide. The inclusions are likely the products of early kimberlite melt(s) which invaded the pre-existing megacryst minerals at mantle depths (i.e., at pressures ranging from 4 to 6 GPa) and crystallized or quenched upon emplacement of the host kimberlite. The abundance of carbonate minerals (e.g., calcite, dolomite) and hydrous silicate minerals (e.g., phlogopite, serpentine, chlorite) within polymineralic inclusions suggests that the trapped melt was more volatile-rich than the host kimberlite now emplaced in the crust. However, the exact composition of this presumed early kimberlite melt, including the inventory of trace elements and volatiles, remains to be more narrowly constrained. For instance, one major question concerns the role of accessory alkali-halogen-phases in polymineralic inclusions, i.e., whether such phases constitute a common primary feature of kimberlite melt(s), or whether they become enriched in late-stage differentiation processes. Recent studies have shown that polymineralic inclusions react with their host minerals during ascent of the kimberlite, while being largely shielded from processes that affect the host kimberlite, e.g., the assimilation of xenoliths (mantle and crustal), degassing of volatiles, and secondary alteration. Importantly, some polymineralic inclusions within different megacryst minerals were shown to preserve fresh glass. A major conclusion of this review is that the abundance and mineralogy of polymineralic inclusions are directly influenced by the physical and chemical properties of their host minerals. When taking the different interactions with their host minerals into account, polymineralic inclusions in megacrysts can serve as useful proxies for the multi-stage origin and evolution of kimberlite melt/magma, because they can (i) reveal information about primary characteristics of the kimberlite melt, and (ii) trace the evolution of kimberlite magma on its way from the upper mantle to the crust.

Silicon Isotope Geochemistry: Fractionation Linked to Silicon Complexations and Its Geological Applications.

Abstract: The fundamental advances in silicon isotope geochemistry have been systematically demonstrated in this work. Firstly, the continuous modifications in analytical approaches and the silicon isotope variations in major reservoirs and geological processes have been briefly introduced. Secondly, the silicon isotope fractionation linked to silicon complexation/coordination and thermodynamic conditions have been extensively stressed, including silicate minerals with variable structures and chemical compositions, silica precipitation and diagenesis, chemical weathering of crustal surface silicate rocks, biological uptake, global oceanic Si cycle, etc. Finally, the relevant geological implications for meteorites and planetary core formation, ore deposits formation, hydrothermal fluids activities, and silicon cycling in hydrosphere have been summarized. Compared to the thermodynamic isotope fractionation of silicon associated with high-temperature processes, that in low-temperature geological processes is much more significant (e.g., chemical weathering, biogenic/non-biogenic precipitation, biological uptake, adsorption, etc.). The equilibrium silicon isotope fractionation during the mantle-core differentiation resulted in the observed heavy isotope composition of the bulk silicate Earth (BSE). The equilibrium fractionation of silicon isotopes among silicate minerals are sensitive to the Si–O bond length, Si coordination numbers (CN), the polymerization degrees of silicate unites, and the electronegativity of cations in minerals. The preferential enrichment of different speciation of dissoluble Si (DSi) (e.g., silicic acid H4SiO40 (H4) and H3SiO4− (H3)) in silica precipitation and diagenesis, and chemical weathering, lead to predominately positive Si isotope signatures in continental surface waters, in which the dynamic fractionation of silicon isotope could be well described by the Rayleigh fractionation model. The role of complexation in biological fractionations of silicon isotopes is more complicated, likely involving several enzymatic processes and active transport proteins. The integrated understanding greatly strengthens the potential of δ30Si proxy for reconstructing the paleo terrestrial and oceanic environments, and exploring the meteorites and planetary core formation, as well as constraining ore deposits and hydrothermal fluid activity.

Parental magma composition of the Main Zone of the Bushveld Complex : evidence from in situ LA-ICP-MS trace element analysis of silicate minerals in the cumulate rocks

Abstract: In situ trace element analysis of cumulus minerals may provide a clue to the parental magma from which the minerals crystallized. However, this is hampered by effects of the trapped liquid shift (TLS). In the Main Zone (MZ) of the Bushveld Complex, the Ti content in plagioclase grains shows a clear increase from core to rim, whereas most other elements [e.g. rare earth elements (REE), Zr, Hf, Pb] do not. This is different from the prominent intra-grain variation of all trace elements in silicate minerals in mafic dikes, which have a faster cooling rate. We suggest that crystal fractionation of trapped liquid occurred in the MZ of Bushveld and the TLS may have modified the original composition of the cumulus minerals for most trace elements except Ti during slow cooling. Quantitative model calculations suggest that the influence of the TLS depends on the bulk partition coefficient of the element. The effect on highly incompatible elements is clearly more prominent than that on moderately incompatible and compatible elements because of different concentration gradients between cores and rims of cumulate minerals. This is supported by the following observations in the MZ of Bushveld: (1) positive correlation between Cr, Ni and Mg# of clinopyroxene and orthopyroxene; (2) negative correlation between moderately incompatible elements (e.g. Mn and Sc in clinopyroxene and orthopyroxene; Sr, Ba and Eu in plagioclase); but (3) poor correlation between highly incompatible elements and Mg# of clinopyroxene and orthopyroxene or An# of plagioclase. Modeling suggests that the extent of the TLS for a trace element is also dependent on the initial fraction of the primary trapped liquid, with strong TLS occurring if the primary trapped liquid fraction is high. This is supported by the positive correlation between highly incompatible trace element abundances in cumulus minerals and whole-rock Zr contents. We have calculated the composition of the parental magma of the MZ of the Bushveld Complex. The compatible and moderately incompatible element contents of the calculated parental liquid are generally similar to those of the B3 marginal rocks, but different from those of the B1 and B2 marginal rocks. For the highly incompatible elements, we suggest that the use of the sample with the lowest whole-rock Zr content and the least degree of TLS is the best approach to obtain the parental magma composition. The heavy REE contents of the magma calculated from orthopyroxene are similar to those of B3 rocks and lower than those of B2 rocks. The calculated REE contents from clinopyroxene are generally significantly higher than for B2 or B3 rocks, and those from plagioclase are in the lower level of B2, but slightly higher than for B3. However, the calculated REE patterns for both clinopyroxene and plagioclase show strong negative Eu anomalies, which are at the lower level of the B2 field and within the B3 field, respectively. We suggest that Eu may be less affected by TLS than other REE owing to its higher bulk compatibility. Based on this and the fact that the calculated REE contents of the parental magma should be higher than the real magma composition owing to some degree of crystal fractionation and TLS, even for the sample with the lowest amount of trapped liquid, we propose that a B3 type liquid is the most likely parental magma to the MZ of the Bushveld Complex. In the lowermost part of the MZ, there is involvement of the Upper Critical Zone (UCZ) magma.

Experimental Studies of Reactivity and Transformations of Rocks and Minerals in Water-Bearing Supercritical CO2

Abstract: Geologic storage of carbon dioxide is a promising strategy for reducing CO2 concentrations in the atmosphere. In this process, silicate minerals in the host rock can react to permanently trap CO2 as precipitated carbonates. In addition, expandable clays in caprocks can swell or shrink and impact the integrity of the caprock seal. While the reactivity of minerals in CO2-rich aqueous fluids has been well studied, much less is known about mineral transformations in supercritical CO2 (scCO2) containing dissolved water. This chapter focuses on experimental investigations of mineral reactivity and transformations in variably hydrated scCO2. We summarize research regarding reservoir rocks, including carbonates, sandstone, granite, basalt, and peridotite. We also cover studies on several mineral systems, including phyllosilicate (montmorillonite), olivine (forsterite), serpentine (antigorite), pyroxene (enstatite), and feldspars (albite, anorthite, and microcline). For expandable phyllosilicate clay minerals, it is shown that volume changes are induced by both H2O and CO2 intercalation. For metal silicate minerals, a common observation is the adsorption of angstrom- to nanometer-thick H2O films, which facilitate mineral dissolution, ion transport, and nucleation of metal carbonate precipitates. Many silicates exhibit a threshold concentration of adsorbed H2O, before which carbonation is limited to possibly amorphous phase precipitation or surface complexation, but beyond which carbonation is continuous and crystalline carbonates can form.

Stability of Organic Carbon Components in Shale: Implications for Carbon Cycle

Abstract: Stability and mobility of organic matter in shale is significant from the perspective of carbon cycle. Shale can only be an effective sink provided that the organic carbon present is stable and immobile from the host sites and, not released easily during geological processes such as low pressure-temperature burial diagenesis and higher pressure-temperature subduction. To examine this, three Jurassic shale samples of known mineralogy and total organic carbon content, with dominantly continental source of organic matter, belonging to the Haynesville-Bossier Formation were combusted by incremental heating from temperature of 200 to 1400°C. The samples were analyzed for their carbon and nitrogen release profiles, bulk δ13C composition and C/N atomic ratio, based on which, at least four organic carbon components are identified associated with different minerals such as clay, carbonate, and silicate. They have different stability depending on their host sites and occurrences relative to the mineral phases and consequently, released at different temperature during combustion. The components identified are denoted as, C-1 (organic carbon occurring as free accumulates at the edge or mouth of pore spaces), C-2 (associated with clay minerals, adsorbed or as organomineral nanocomposites; with carbonate minerals, biomineralized and/or occluded), C-3(a) (occurring with silicate minerals, biomineralized and/or occluded) and C-3(b) (graphitized carbon). They show an increasing stability and decreasing mobility from C-1 to C-3(b). Based on the stability of the different OC components, shale is clearly an efficient sink for the long term C cycle as, except for C-1 which forms a very small fraction of the total and is released at temperature of ∼200°C, OC can be efficiently locked in shale surviving conditions of burial diagenesis and, subduction at fore arc regions in absence of infiltrating fluids. Under low fluid flux, C-3(b) can be efficiently retained as a refractory phase in the mantle when subducted. It is evident that the association and interaction of the organic matter with the different minerals play an important role in its retention in the shale.

Mg and Li Stable Isotope Ratios of Rocks, Minerals, and Water in an Outlet Glacier of the Greenland Ice Sheet

Abstract: Magnesium and lithium stable isotope ratios (dMg and dLi) have shown promise as tools to elucidate biogeochemical processes both at catchment scales and in deciphering global climate processes. Nevertheless the controls on riverine Mg and Li isotope ratios are often difficult to determine as a myriad of factors can cause fractionation from bulk rock values such as secondary mineral formation and preferential weathering of isotopically distinct mineral phases. Quantifying the relative contribution from carbonate and silicate minerals to the dissolved load of glaciated catchments is particularly crucial for determining the role of chemical weathering in modulating the carbon cycle over glacial-interglacial periods. In this study we report Mg and Li isotope data for water, river sediment, rock and mineral separates from the Leverett Glacier catchment, West Greenland. We assess whether the silicate mineral contributions to the dissolved load, previously determined using radiogenic Sr, Ca, Nd and Hf isotopes, are consistent with dissolved Mg and Li isotope data, or whether a carbonate contribution is required as inferred previously for this region. For dLi, the average dissolved river water value (+19.2±2.5‰, 2SD) was higher than bedrock, river sediment and mineral dLi values, implying a fractionation process. For dMg, the average dissolved river water value (-0.30±0.14‰, 2SD) was within error of bedrock and river sediment and within the range of mineral dMg values (-1.63 to +0.06‰). The river dMg values are consistent with the mixing of Mg derived from the same mineral phases previously identified from radiogenic isotope measurements as controlling the dissolved load chemistry. Glacier fed rivers previously measured in this region had dMg values approximately 0.80‰ lower than those measured in the Leverett River and could potentially be caused by a larger contribution from garnet (-1.63‰) dissolution compared to Leverett. This study highlights that dissolved Mg and Li isotope ratios in the Leverett River are affected by different processes (mixing and fractionation), and that since variations in silicate mineral dMg values exist, preferential weathering of individual silicate minerals in addition to carbonate should be considered when interpreting dissolved dMg values.

Bioleaching of silicon in electrolytic manganese residue using single and mixed silicate bacteria.

Abstract: Electrolytic manganese residue (EMR) is a type of industrial solid waste with a high silicon content. The silicon in EMR can be used as an essential nutrient for plant growth, but most of the silicon is found in silicate minerals with very low water solubility, that is, it is inactive silicon and cannot be absorbed and used by plants directly. Thus, developing a highly effective and environmentally friendly process for the activation of silicon in EMR is important both for reusing solid waste and environmental sustainability. The aim of this study was to investigate the desilication of EMR using cultures of Paenibacillus mucilaginosus (PM) and Bacillus circulans (BC). The results showed that the two types of silicate bacteria and a mixed strain of them were all able to extract silicon from EMR with a high efficiency, but the desilication performance of the mixed PM and BC was the best. Fourier transform infrared spectroscopy indicated that silicate bacteria can induce a suitable micro-environment near the EMR particles and release Si into the solution through their metabolism. X-ray diffraction analysis confirmed that layered crystal minerals, such as muscovite and diopside, were more likely to be destroyed by the bacterial action than quartz, which has a frame structure. Scanning electron microscopy–energy dispersive spectrometry proved that the silicate structures were destroyed and that Si in the residue was decreased, indicating the dissolution of silicon under the action of these microorganisms. This study suggests that bioleaching may be a promising method for the activation of silicon in EMR.

Effect of Beam Current and Diameter on Electron Probe Microanalysis of Carbonate Minerals

Abstract: The effect of operating conditions on the time-dependent X-ray intensity variation is of great importance for the optimal EPMA conditions for accurate determinations of various elements in carbonate minerals. Beam diameters of 0, 1, 2, 5, 10, 15, and 20 μm, and beam currents of 3, 5, 10, 20, and 50 nA were tested. Ca, Mg, Zn, and Sr were found to be more sensitive to electron beam irradiation as compared to other elements, and small currents and large beam diameters minimized the time-dependent X-ray intensity variations. We determined the optimal EPMA operating conditions for elements in carbonate: 10 μm and 5 nA for calcite; 10 μm and 10 nA for dolomite; 5 μm and 10 nA or 10 μm and 20 nA for strontianite; and 20 nA and 5 μm for other carbonate. Elements sensitive to electron beam irradiation should be determined first. In addition, silicate minerals are preferred as standards rather than carbonate minerals.

Isotope Drift Characteristics in Ordovician Limestone Karst Water Caused by Coal Mining in Northern China

Abstract: Samples from different areas near the Fengfeng Mine in northern China were analyzed for 2H and 18O isotopes. In the southern areas, the 2H and 18O isotopes exhibited no significant drift off the background. However, in the eastern area, the 2H isotope drifted remarkably, although 2H and 18O both drifted in some samples. In the northern area, the 2H and 18O both obviously drifted. The 2H drift is attributed to deuterium equilibrium due to water–rock interactions between the Ordovician limestone (OL) karst water and silicate minerals. The 18O drift probably came from water–rock reactions between OL water and carbonate minerals, along with the 18O equilibrium reaction. It was demonstrated that the dual drift were connected to water–rock reactions between the OL water, carbonate, and silicate minerals. Therefore, the drift was actually due to equilibrium exchange of OL water–rock interactions during the water level descent and ascent, which was closely related to the mining activities.