Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers   总被引：3，自引：0，他引：3  

Claudette Spiteri  Philippe Van Cappellen  Pierre Regnier 《Geochimica et cosmochimica acta》2008,72(14):3431-3445

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.  相似文献   

Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering     

Peter M. Morris 《Geochimica et cosmochimica acta》2008,72(8):1970-1985

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.  相似文献   

Editorial     

Peter Riches 《Proceedings of the Geologists' Association. Geologists' Association》2008,119(3-4):207

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Airports, mobility and the calculative architecture of affective control   总被引：2，自引：0，他引：2  

Peter Adey 《Geoforum》2008,39(1):438-451

Drawing on work surrounding the theorisation of concepts such as mobility, affect and emotion, the paper argues that their control is now being intertwined in places like airports which are employing a number of techniques that engineer affects. Airport affect is enacted, in one way, by planning and designing the situational affective context one inhabits - throwing up structures of ethological possibility that shape capacities for the corporeal body to move and be moved. It is shown that the engineering of airport affect is premised upon a wider discursive framework of calculation and indeterminacy, and that selective techniques summon a number of different modalities of control. The paper concludes with a series of implications for the understanding of power, and the study of mobility, emotion and affect.  相似文献   

Atmospheric mercury near Salmon Falls Creek Reservoir in southern Idaho     

Michael L. Abbott  Che-Jen Lin  Peter Martian  Jeffrey J. Einerson 《Applied Geochemistry》2008

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured over 2-week seasonal field campaigns near Salmon Falls Creek Reservoir in south-central Idaho from the summer of 2005 through the fall of 2006 and over the entire summer of 2006 using automated Tekran Hg analyzers. GEM, RGM, and particulate Hg (HgP) were also measured at a secondary site 90 km to the west in southwestern Idaho during the summer of 2006. The study was performed to characterize Hg air concentrations in the southern Idaho area for the first time, estimate Hg dry deposition rates, and investigate the source of observed elevated concentrations. High seasonal variability was observed with the highest GEM (1.91 ± 0.9 ng m⁻³) and RGM (8.1 ± 5.6 pg m⁻³) concentrations occurring in the summer and lower values in the winter (1.32 ± 0.3 ng m⁻³, 3.2 ± 2.9 pg m⁻³ for GEM, RGM, respectively). The summer-average HgP concentrations were generally below detection limit (0.6 ± 1 pg m⁻³). Seasonally averaged deposition velocities calculated using a resistance model were 0.034 ± 0.032, 0.043 ± 0.040, 0.00084 ± 0.0017 and 0.00036 ± 0.0011 cm s⁻¹ for GEM (spring, summer, fall and winter, respectively) and 0.50 ± 0.39, 0.40 ± 0.31, 0.51 ± 0.43 and 0.76 ± 0.57 cm s⁻¹ for RGM. The total annual RGM + GEM dry deposition estimate was calculated to be 11.9 ± 3.3 μg m⁻², or about 2/3 of the total (wet + dry) deposition estimate for the area. Periodic elevated short-term GEM (2.2–12 ng m⁻³) and RGM (50–150 pg m⁻³) events were observed primarily during the warm seasons. Back-trajectory modeling and PSCF analysis indicate predominant source directions to the SE (western Utah, northeastern Nevada) and SW (north-central Nevada) with fewer inputs from the NW (southeastern Oregon and southwestern Idaho).  相似文献   

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2   总被引：2，自引：1，他引：1  

Josep M. Soler  Marco Boi  Jos Luis Mogolln  Jordi Cama  Carlos Ayora  Peter S. Nico  Nobumichi Tamura  Martin Kunz 《Applied Geochemistry》2008,23(12):3579-3588

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.  相似文献   

A consistent geochemical modelling approach for the leaching and reactive transport of major and trace elements in MSWI bottom ash     

Joris J. Dijkstra  Johannes C.L. Meeussen  Hans A. Van der Sloot  Rob N.J. Comans 《Applied Geochemistry》2008

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Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review     

Geert Cornelis  C. Anette Johnson  Tom Van Gerven  Carlo Vandecasteele 《Applied Geochemistry》2008

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.  相似文献   

Controlling geological and hydrogeological processes in an arsenic contaminated aquifer on the Red River flood plain,Vietnam   总被引：1，自引：0，他引：1  

Flemming Larsen  Nhan Quy Pham  Nhan Duc Dang  Dieke Postma  Søren Jessen  Viet Hung Pham  Thao Bach Nguyen  Huy Duc Trieu  Luu Thi Tran  Hoan Nguyen  Julie Chambon  Hoan Van Nguyen  Dang Hoang Ha  Nguyen Thi Hue  Mai Thanh Duc  Jens Christian Refsgaard 《Applied Geochemistry》2008

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Weed species diversity on arable land of the dryland areas of central Tanzania: impacts of continuous application of traditional tillage practices     

Riziki S. Shemdoe  Frank M. Mbago  Idris S. Kikula  Patrick L. Van Damme 《GeoJournal》2008,71(2-3):107-115

This paper presents findings from a study that assessed influence of continuous application of a particular traditional tillage practice on weed species richness, diversity and composition and identifies weed species with positive benefits to the communities in semi-arid areas of Mpwapwa district, central Tanzania. In this area farmers apply three different traditional tillage practices which are no-till (NT), shallow tillage (ST) and Ridging System (RT). A total of 36 farm fields were surveyed in 2006/2007 cropping season where 63 weed species from 26 families were identified. Analysis of variance indicated significant differences between practices (p < 0.05), with NT practice having highest weed species richness and diversity. Among the five more prevalent weed species appearing, Bidens lineariloba was observed to exist in all the three practices. Community representatives during focus group discussions indicated 9 weed species out of 63 identified to have beneficial uses. These species are Cleome hirta, Amaranthus graecizans, Bidens lineoriloba, Bidens pilosa, Dactyloctenium aegyptium, Launaea cornuta, Heteropogon contortus, Tragus berteronianus and Trichodesma zeylanicum. Their main uses include leaf-vegetable, medicines, fodder and materials for thatching. From this study NT has highest weed species richness and diversity which therefore suggests that much more time is needed for weeding in this practice compared to other practice which was the farmers’ concern. It was also noted that although weed species have negative effects in crop production and production costs, they still play a vital role in food security and for the health of different people in marginal areas as well as for the complete ecosystem including micro and macrofauna.  相似文献