The influence of Fe-rich coatings on the dissolution of anorthite at pH 2.6

Surface coatings are very common on mineral grains in soils but most laboratory dissolution experiments are carried out on pristine, uncoated mineral grains. An experiment designed to unambiguously isolate the effect of surface coatings on mineral dissolution from any influence of solution saturation state is reported. Two aliquots of 53 to 63 mum anorthite feldspar powder were used. One was dissolved in pH 2.6 HCl, the other in pH 2.6 FeCl3 solution, both for similar to6000 h in flow-through reactors. An amorphous Fe-rich, Al-, Ca- and Si-free orange precipitate coated the anorthite dissolved in the FeCl3 solution. BET surface area of the anorthite increased from 0.16 to 1.65 m(2) g(-1) in the HCl experiment and to 3.89 m(2) g(-1) in the FeCl3 experiment. The increase in surface area in the HCl experiment was due to the formation of etch pits on the anorthite grain surface whilst the additional increase in the FeCl3 experiment was due to the micro- and meso-porous nature of the orange precipitate. This precipitate did not inhibit or slow the dissolution of the anorthite. Steady state dissolution rates for the anorthite dissolved in the HCl and FeCl3 were similar to2.5 and 3.2 X 10(-10) mol(feldspar) m(-2) s(-1) respectively. These rates are not significantly different after the cumulative uncertainty of 17% in their value due to uncertainty in the inputs parameters used in their calculation is taken into account. Results from this experiment support previous theoretical and inference-based conclusions that porous coatings should not inhibit mineral dissolution. Copyright (C) 2003 Elsevier Ltd.

Fe-sulphate-rich evaporative mineral precipitates from the Rio Tinto, southwest Spain

The soluble metal sulphate salts melanterite, rozenite, rhomboclase, szornolnokite, copiapite, coquimbite, hexahydrite and halotrichite, together with gypsum, have been identified, some for the first time oil the banks of the Rio Tinto, SW Spain. Secondary Fe-sulphate minerals call form directly from evaporating acid, sulphate-rich Solutions as a result of pyrite oxidation. Chemical analyses of mixtures of these salt minerals indicate concentrations of Fe (up to 31 wt.%), Mg (up to 4 wt.%), Cu (up to 2 wt.%) and Zn (up to wt.%). These minerals are shown to act as transient storage Cor metals and can store on average up to 10% (9.5 - 11%) and 22% (20-23%) Zn and Cu respectively, of the total discharge of the Rio Tinto during the summer period. Melanterite and rozenite precipitates at Rio Tinto are only found in association with very acidic drainage waters (pH <1.0) draining directly from pyritic waste piles. Copiapite precipitates abundantly oil the banks of the Rio Tinto by (1) direct evaporation of the river water; or (2) as part of a paragenetic sequence with the inclusion of minor halotrichite, indicating natural dehydration and decomposition. The natural occurrences are comparable with the process of paragenesis from the evaporation of Rio Tinto river water under laboratory experiments resulting in the formation of aluminocopiapite, halotrichite, coquimbite, voltaite and gypsum.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

The influence of viscous and latent heating on crystal-rich magma flow in a conduit

The flow dynamics of crystal-rich high-viscosity magma is likely to be strongly influenced by viscous and latent heat release. Viscous heating is observed to play an important role in the dynamics of fluids with temperature-dependent viscosities. The growth of microlite crystals and the accompanying release of latent heat should play a similar role in raising fluid temperatures. Earlier models of viscous heating in magmas have shown the potential for unstable (thermal runaway) flow as described by a Gruntfest number, using an Arrhenius temperature dependence for the viscosity, but have not considered crystal growth or latent heating. We present a theoretical model for magma flow in an axisymmetric conduit and consider both heating effects using Finite Element Method techniques. We consider a constant mass flux in a 1-D infinitesimal conduit segment with isothermal and adiabatic boundary conditions and Newtonian and non-Newtonian magma flow properties. We find that the growth of crystals acts to stabilize the flow field and make the magma less likely to experience a thermal runaway. The additional heating influences crystal growth and can counteract supercooling from degassing-induced crystallization and drive the residual melt composition back towards the liquidus temperature. We illustrate the models with results generated using parameters appropriate for the andesite lava dome-forming eruption at Soufriere Hills Volcano, Montserrat. These results emphasize the radial variability of the magma. Both viscous and latent heating effects are shown to be capable of playing a significant role in the eruption dynamics of Soufriere Hills Volcano. Latent heating is a factor in the top two kilometres of the conduit and may be responsible for relatively short-term (days) transients. Viscous heating is less restricted spatially, but because thermal runaway requires periods of hundreds of days to be achieved, the process is likely to be interrupted. Our models show that thermal evolution of the conduit walls could lead to an increase in the effective diameter of flow and an increase in flux at constant magma pressure.

A combined BIE-FE method for the Stokes equations

A numerical algorithm for the biharmonic equation in domains with piecewise smooth boundaries is presented. It is intended for problems describing the Stokes flow in the situations where one has corners or cusps formed by parts of the domain boundary and, due to the nature of the boundary conditions on these parts of the boundary, these regions have a global effect on the shape of the whole domain and hence have to be resolved with sufficient accuracy. The algorithm combines the boundary integral equation method for the main part of the flow domain and the finite-element method which is used to resolve the corner/cusp regions. Two parts of the solution are matched along a numerical ‘internal interface’ or, as a variant, two interfaces, and they are determined simultaneously by inverting a combined matrix in the course of iterations. The algorithm is illustrated by considering the flow configuration of ‘curtain coating’, a flow where a sheet of liquid impinges onto a moving solid substrate, which is particularly sensitive to what happens in the corner region formed, physically, by the free surface and the solid boundary. The ‘moving contact line problem’ is addressed in the framework of an earlier developed interface formation model which treats the dynamic contact angle as part of the solution, as opposed to it being a prescribed function of the contact line speed, as in the so-called ‘slip models’. Keywords: Dynamic contact angle; finite elements; free surface flows; hybrid numerical technique; Stokes equations.

Trace element partitioning and soil particle characterisation around mining and smelting areas at Tharsis, Riotinto and Huelva, SW Spain

Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling trace element distribution in soils around ancient and modem mining and smelting areas are not always clear. Tharsis, Riotinto and Huelva are located in the Iberian Pyrite Belt in SW Spain. Tharsis and Riotinto mines have been exploited since 2500 B.C., with intensive smelting taking place. Huelva, established in 1970 and using the Flash Furnace Outokumpu process, is currently one of the largest smelter in the world. Pyrite and chalcopyrite ore have been intensively smelted for Cu. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters, being found up to a maximum of 2 kin from the mines and smelters at Tharsis, Riotinto and Huelva. Trace element partitioning (over 2/3 of trace elements found in the residual immobile fraction of soils at Tharsis) and soil particles examination by SEM-EDX showed that trace elements were not adsorbed onto soil particles, but were included within the matrix of large trace element-rich Fe silicate slag particles (i.e. 1 min circle divide at least 1 wt.% As, Cu and Zn, and 2 wt.% Pb). Slag particle large size (I mm 0) was found to control the geographically restricted trace element distribution in soils at Tharsis, Riotinto and Huelva, since large heavy particles could not have been transported long distances. Distribution and partitioning indicated that impacts to the environment as a result of mining and smelting should remain minimal in the region. (c) 2006 Elsevier B.V. All rights reserved.

Sequential extraction and single-step cold-acid extraction: A feasibility study for use with freshwater-canal sediments

This investigation examines metal release from freshwater sediment using sequential extraction and single-step cold-acid leaching. The concentrations of Cd, Cr, Cu, Fe, Ni, Pb and Zn released using a standard 3-step sequential extraction (Rauret et al., 1999) are compared to those released using a 0.5 M HCl; leach. The results show that the three sediments behave in very different ways when subject to the same leaching experiments: the cold-acid extraction appears to remove higher relative concentrations of metals from the iron-rich sediment than from the other two sediments. Cold-acid extraction appears to be more effective at removing metals from sediments with crystalline iron oxides than the "reducible" step of the sequential extraction. The results show that a single-step acid leach can be just as effective as sequential extractions at removing metals from sediment and are a great deal less time-consuming.

Weathering microenvironments on feldspar surfaces: implications for understanding fluid-mineral reactions in soils

The mechanisms by which coatings develop on weathered grain surfaces, and their potential impact on rates of fluid-mineral interaction, have been investigated by examining feldspars from a 1.1 ky old soil in the Glen Feshie chronosequence, Scottish highlands. Using the focused ion beam technique, electron-transparent, foils for characterization by transmission electron microscopy were cut from selected parts of grain surfaces. Some parts were bare whereas others had accumulations, a few micrometres thick, of Weathering products, often mixed with mineral and microbial debris. Feldspar exposed at bare grain surfaces is crystalline throughout and so there is no evidence for the presence of the amorphous 'leached layers' that typically form in acid-dissolution experiments and have been described from some natural Weathering contexts. The weathering products comprise sub-mu m thick crystallites of an Fe-K aluminosilicate, probably smectite, that have grown within an amorphous and probably organic-rich matrix. There is also evidence for crystallization of clays having been mediated by fungal hyphae. Coatings formed within Glen Feshie soils after similar to 1.1 ky are insufficiently continuous or impermeable to slow rates Of fluid-feldspar reactions, but provide valuable insights into the complex Weathering microenvironments oil debris and microbe-covered mineral surfaces.

Laboratory simulation of terrestrial meteorite weathering using the Bensour (LL6) ordinary chondrite

Laboratory dissolution experiments using the LL6 ordinary chondrite Bensour demonstrate that meteoritic minerals readily react with distilled water at low temperatures, liberating ions into solution and forming reaction products. Three experiments were performed, all for 68 days and at atmospheric fO(2) but using a range of water/rock ratios and different ternperatures. Experiments I and 2 were batch experiments and undertaken at room temperature, whereas in experiment 3, condensed boiling water was dripped onto meteorite subsamples within a Soxhlet extractor. Solutions from experiment 1 were chemically analyzed at the end of the experiment, whereas aliquots were extracted from experiments 2 and 3 for analysis at regular intervals. In all three experiments, a very significant proportion of the Na, Cl, and K within the Bensour subsamples entered solution, demonstrating that chlorapatite and feldspar were especially susceptible to dissolution. Concentrations of Mg, Al, Si, Ca, and Fe in solution were strongly affected by the precipitation of reaction products and Mg and Ca may also have been removed by sorption. Calculations predict saturation of experimental solutions with respect to Al hydroxides, Fe oxides, and Fe (oxy)hydroxides, which would have frequently been accompanied by hydrous aluminosilicates. Some reaction products were identified and include silica, a Mg-rich silicate, Fe oxides, and Fe (oxy)hydroxides. The implications of these results are that even very short periods of subaerial exposure of ordinary chondrites will lead to dissolution of primary minerals and crystallization of weathering products that are likely to include aluminosilicates and silicates, Mg-Ca carbonates, and sulfates in addition to the ubiquitous Fe oxides and (oxy)hydroxides.

Hydrological controls on soil redox dynamics in a peat-based, restored wetland

Increasing areas of altered wetland are being restored by re-flooding the soil. Evidence in the literature indicates that this practice can induce the redox-mediated release of soil nutrients, thereby increasing the risk of diffuse water pollution. However, for the sake of improving wedand management decisions, there is a need for more detailed studies of the underlying relationship between the hydrological and redox dynamics that explain this risk; this is particularly the case in agricultural peatlands that are commonly targeted for the creation of lowland wet grassland. A 12-month field study was conducted to evaluate the relationship between hydrological fluctuations and soil redox potential (Eh) in a nutrient-rich peat field (32 g N kg(-1) and 1100 mg P kg(-1) in the surface 0-30 cm soil) that had been restored as lowland wet grassland from intensive arable production. Field tensiometers were installed at the 30-, 60- and 90-cm soil depths, and Pt electrodes at the 10-, 30-, 60- and 90-cm depths, for daily logging of soil water tension and Eh, respectively. The values for soil water tension displayed a strong negative relationship (P < 0.001) with monthly dip well observations of water table height. Calculations of soil water potential from the logged tension values were used, therefore, to provide a detailed profile of field water level and, together with precipitation data, explained some of the variation in Eh. For example, during the summer, alternating periods of aerobism (Eh > 330 mV) in the surface, 0-10 cm layer of peat coincided with intense precipitation events. Redox potential throughout the 30-100 cm profile also fluctuated seasonally; indeed, at all depths Eh displayed a strong, negative relationship (P < 0.001) with water table height over the 12-month study period. However, Eh throughout the 30-100 cm profile remained relatively low (< 230 mV), indicating permanently reduced conditions that are associated with denitrification and reductive dissolution of Fe-bound P. The implications of these processes in the N- and P-rich peat for wetland plant diversity and water quality are discussed. (c) 2006 Elsevier B.V. All rights reserved.

Inorganic synthesis of Fe-Ca-Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 degrees C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 degrees C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite-siderite and dolomite solid solutions. A calcite-siderite solid solution precipitated at 25 degrees C, with the percentage of CaCO3 in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 degrees C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature. (C) 2009 Elsevier Ltd. All rights reserved.

Triacylglycerol-rich lipoprotein-gene interactions in endothelial cells

Lipoproteins such as LDL (low-density lipoprotein) and oxidized LDL have potentially adverse effects on endothelial cells due to their ability to activate pro-inflammatory pathways regulated via the transcription factor NF-kappaB (nuclear factor kappaB). Triacylglycerol-rich lipoproteins (the chylomicrons, very-low-density lipoprotein and their respective remnant particles) have also been implicated in the induction of a pro-inflammatory phenotype and up-regulation of adhesion molecule expression. Although early studies supported the proposal that LPL (lipoprotein lipase)-mediated hydrolysis of TRLs (triglyceride-rich lipoproteins) at the endothelium could activate the NFkappaB pathway, more recent studies provide evidence of pro-and anti-inflammatory responses when cells are exposed to fatty acids of TRL particles. A large number of genes are up- and down-regulated when cells are exposed to TRL, with the net effect reflecting receptor- and nonreceptor-mediated pathways that are activated or inhibited depending on fatty acid type, the lipid and apolipoprotein composition of the TRL and the presence or absence of LPL. Early concepts of TRL particles as essentially pro-inflammatory stimuli to the endothelium provide an overly simplistic view of their impact on the vascular compartment.