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G. Galindo C. Sainato C. Dapea J.L. Fernndez-Turiel D. Gimeno M.C. Pomposiello H.O. Panarello 《Journal of South American Earth Sciences》2007,23(4):336-345
This work studies the water quality of the Pergamino–Arrecifes River zone in the Rolling Pampa, northeast Buenos Aires Province, Argentina. Temperature, pH, specific conductivity, Na, K, Mg, Ca, , Cl−, , , Si, Ag, Al, As, B, Ba, Be, Br, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, P, Pb, Se, Tl, U, V, Zn, and the environmental stable δ18O and δ2H isotope ratios were determined in 18 sampling stations. Natural and anthropogenic features influence surface and groundwater quality. Point pollution sources (septic wells and other domestic and farming effluents) increase the nitrate concentration. The values of pH, , Al, As, B, Fe, and Mn exceed the respective Argentine reference thresholds in different sampling stations for human drinking water; B, Mo, U, and V for irrigation; and V and Zn for cattle consumption. 相似文献
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Recent experimental determinations of the solubility products of common rare earth minerals such as monazite and xenotime and stability constants for chloride, sulfate, carbonate and hydroxide complexes provide a basis to model quantitatively the solubility, and therefore the mobility, of rare earth elements (REE) at near surface conditions. Data on the mobility of REE and stabilities of REE complexes at near-neutral conditions are of importance to safe nuclear waste disposal, and environmental monitoring. The aim of this study is to understand REE speciation and solubility of a given REE in natural environments. In this study, a series of formation constants for La aqueous complexes are recommended by using the specific interaction theory (SIT) for extrapolation to infinite dilution. Then, a thermodynamic model has been employed for calculation of the solubility and speciation of La in soil solutions reacted with the La end-member of mineral monazite (LaPO4), and other La-bearing solid phases including amorphous lanthanum hydroxide (La(OH)3, am) and different La carbonates, as a function of various inorganic and organic ligand concentrations. Calculations were carried out at near-neutral pH (pH 5.5–8.5) and 25 °C at atmospheric CO2 partial pressure. The model takes account of the species: La3+, LaCl2+, , , , , , , , , La(OH)2+, LaOx+, , LaAc2+ and (where Ox2− = oxalate and Ac− = acetate).The calculations indicate that the La species that dominate at pH 5.5–8.5 in the baseline model soil solution (BMSS) include La3+, LaOx+, , and in order of increasing importance as pH rises. The solubility of monazite in the BMSS remains less than 3 × 10−9 M, exhibiting a minimum of 2 × 10−12 M at pH 7.5. The calculations quantitatively demonstrate that the concentrations of La controlled by the solubility of other La-bearing solid phases are many orders of magnitude higher than those controlled by monazite in the pH range from 5.5 to 8.5, suggesting that monazite is likely to be the solubility-controlling phase at this pH range. The calculations also suggest that significant mobility of La (and other REE) is unlikely because high water–rock ratios on the order of at least 104 (mass ratio) are required to move 50% of the La from a soil. An increase in concentration of oxalate by one order of magnitude from that of the baseline model solution results in the dominance of LaOx+ at pH 5.5–7.5. Similarly, the increase in concentration of by one order of magnitude makes the dominant species at pH 5.5–7.5. Above pH 7.5, carbonate complexes are important. The increase in oxalate or concentrations by one order of magnitude can enhance the solubility of monazite by a factor of up to about 6 below neutral pH, in comparison with that in the baseline model soil solution. From pH 7.0 to 8.5, the solubility of monazite in the soil solutions with higher concentrations of oxalate or is similar, or almost identical, to that in the BMSS. 相似文献
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Environmental isotopes (N, S, C, O, D) to determine natural attenuation processes in nitrate contaminated waters: Example of Osona (NE Spain) 总被引：1，自引：0，他引：1
Nitrate-contaminated groundwater from an aquifer in the Osona region (NE Spain) was chemically and isotopically (δ15NNO3,δ18ONO3,δ34SSO4,δ18OSO4, δD, δ18OH2O and δ13CDIC) characterized. Diffuse- contamination reached values of 366 mg/L. Nearly 75% of the 37 sampled sites had higher concentrations than the 50 mg/L in limit for drinking water. To identify the source of pollution δ15NNO3 and δ18ONO3 were used with results, for most samples, in the range of pig manure . Nitrification processes were evaluated by means of the δ18O of and water. Isotopic data suggested that natural attenuation of was taking place. This process was confirmed using the δ18ONO3 coupled with the ratio, avoiding the influence of continuous inputs. A further insight on denitrification processes was obtained by analyzing the ions involved in denitrification reactions. Although the role of organic matter oxidation could neither be confirmed nor discarded, this approach showed a link between denitrification and pyrite oxidation. Therefore, in areas with no adequate infrastructure (e.g. multipiezometers), such as the one studied, this approach could be useful for implementing better water management. 相似文献
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Various isotope studies require accurate fractionation factors (α’s) between different chemical compounds in thermodynamic equilibrium. Although numerous isotope systems involve aqueous solutions, the conventional theory is formulated for the gas-phase and predicts incorrect α’s for many compounds dissolved in water. Here I show that quantum-chemistry calculations, which take into account solute–water interactions, accurately predict, for instance, oxygen isotope fractionation between dissolved and H2O (hereafter ). Simple force field and quantum-chemistry calculations for the ‘gas-phase’ ion predict (15‰) at 25 °C. However, based on -clusters with up to 22 H2O molecules, I calculate a value of 25‰, which agrees with the experimental value of 24.5 ± 0.5‰. Effects of geometry and anharmonicity on the calculated α were also examined. The calculations reveal the critical role of hydration in solution, which is ignored in the gas-phase theory. The approach presented provides an adequate framework for calculating fractionation factors involving dissolved compounds; it may also be used to predict α’s that cannot (or have not yet been) determined experimentally. 相似文献
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Maatouk E. Samrani A. El Sawan R. Salameh R. Bou Ghosn Kazpard V. Matar Z. 《Aquatic Geochemistry》2022,28(2):111-133
This work focuses on the characterization of a typical coastal karst watershed by addressing its physico-chemical parameters. The concentrations of the main ions clearly indicate the dominance of Ca2+ and HCO3? with a carbonate weathering rate equivalent to 230t/Km2/year; that is a typical weathering of karst watersheds. The spatio-temporal variability of dissolved organic matter (DOM) is also assessed in the watershed. Many samples were collected under different hydrological conditions from three representative sites. The evolution of OM composition along an urbanization gradient from upstream to downstream Kadisha watershed reveals the very strong impact of urban discharges on the receiving waters. Substantial differences in DOC results are highlighted in relation to the urban or natural origin of the DOM. Upstream OM flux is quantified and compared to downstream OM flux showing that, during the low flow period, the downstream flux is 29 times higher than the upstream. Also, a large fraction of non-humic substances, including hydrophilic organic matter HPI, is detected in the downstream section impacted by urban discharges. The higher values of SUVA noticed for DOM at upstream compared to downstream, reflects the low aromaticity and non-humic character of DOM in downstream. These outcomes show the impact of the Tripoli urban discharges on the quality and quantity of OM in the receiving waters downstream of the Kadisha catchment. This is typical at low water period when the dilution factor of urban discharges in the receiving waters is the least.
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Recent studies show that ferrous iron (FeII), which is often abundant in anaerobic soil and groundwater, is capable of abiotically reducing many subsurface contaminants. However, studies also demonstrate that FeII redox reactivity in geochemical systems is heavily dependent upon metal speciation. This contribution examines the influence of hydroxamate ligands, including the trihydroxamate siderophore desferrioxamine B (DFOB), on FeII reactions with nitroaromatic groundwater contaminants (NACs). Experimental results demonstrate that ring-substituted NACs are reduced to the corresponding aniline products in aqueous solutions containing FeII complexes with DFOB and two monohydroxamate ligands (acetohydroxamic acid and salicylhydroxamic acid). Reaction rates are heavily dependent upon solution conditions and the identities of both the FeII-complexing hydroxamate ligand and the target NAC. Trends in the observed pseudo-first-order rate constants for reduction of 4-chloronitrobenzene (kobs, s−1) are quantitatively linked to the formation of FeII species with standard one-electron reduction potentials, (FeIII/FeII), below −0.3 V. Linear free energy relationships correlate reaction rates with the (FeIII/FeII) values of different electron-donating FeII complexes and with the apparent one-electron reduction potentials of different electron-accepting NACs, (ArNO2). Experiments describing a redox auto-decomposition mechanism for FeII-DFOB complexes that occurs at neutral pH and has implications for the stability of hydroxamate siderophores in anaerobic environments are also presented. Results from this study indicate that hydroxamates and other FeIII-stabilizing organic ligands can form highly redox-active FeII complexes that may contribute to the natural attenuation and remediation of subsurface contaminants. 相似文献
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We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartzwhere 10−5.13 < aHF < 101.60, −0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silicawhere 10−2.37 < aHF < 101.61, −0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e.g. + H+, F− + H+, HF + , HF + F−, or + F−, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si–O bond to form a O–H group and a Si–FH group. 相似文献
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Isotopic composition of nitrate in five German rivers discharging into the North Sea 总被引：6，自引：0，他引：6
We determined concentrations and isotopic composition of nitrate in five German rivers (Rhine, Elbe, Weser, Ems, and Eider) that discharge into the North Sea. Samples were obtained on a biweekly to monthly basis and chemical and isotopic analyses were conducted for the period January 2006 to March 2007 at sampling stations situated before estuarine mixing with North Sea water. We observed maximum nitrate loads in winter and fall, when both discharge and concentration of nitrate are highest. Mean annual isotope values in nitrate ranged from 8.2‰ to 11.3‰ for and 0.4‰ to 2.2‰ for . The ranges of isotope values suggest that nitrate in these rivers derives from soil nitrification, sewage, and/or manure. These and published data on other rivers in northern Europe and northern America reveal a correlation between agricultural land use (>60% in the catchment areas of rivers examined) and values. The rivers Rhine, Elbe, Weser and Ems show similar seasonal patterns of the isotopic fractionation of nitrate with increasing values and simultaneously decreasing concentrations during summer months, indicating that assimilation of nitrate is the main fractionation process of riverine nitrate. Isotopic signals in winter are more depleted than the mean summer isotope values, attributed to less microbial activity and assimilative processes. Load weighted nitrate δ15N of the riverine input to the German Bight Coastal Water mass before estuarine mixing and processing is between 8‰ and 12‰. The high δ15N value of river nitrate is matched by high δ15N of nitrate in surface sediments in the German Bight. 相似文献
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Diffusion of helium has been characterized in natural zircon and apatite. Polished slabs of zircon and apatite, oriented either normal or parallel to c were implanted with 100 keV 3He at a dose of 5 × 1015 3 He/cm2. Diffusion experiments on implanted zircon and apatite were run in Pt capsules in 1-atm furnaces. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For diffusion in zircon we obtain the following Arrhenius relations:Although activation energies for diffusion normal and parallel to c are comparable, there is marked diffusional anisotropy, with diffusion parallel to c nearly 2 orders of magnitude faster than transport normal to c. These diffusivities bracket the range of values determined for He diffusion in zircon in bulk-release experiments, although the role of anisotropy could not be directly evaluated in those measurements.In apatite, the following Arrhenius relation was obtained over the temperature range of 148–449 °C for diffusion normal to c:In contrast to zircon, apatite shows little evidence of anisotropy. He diffusivities obtained in this study fall about an order of magnitude lower than diffusivities measured through bulk release of He through step-heating, and within an order of magnitude of determinations where ion implantation was used to introduce helium and He distributions measured with elastic recoil detection.Since the diffusion of He in zircon exhibits such pronounced anisotropy, helium diffusional loss and closure cannot be modeled with simple spherical geometries and the assumption of isotropic diffusion. A finite-element code (CYLMOD) has recently been created to simulate diffusion in cylindrical geometry with differing radial and axial diffusion coefficients. We present some applications of the code in evaluating helium lost from zircon grains as a function of grain size and length to diameter ratios, and consider the effects of “shape anisotropy”, where diffusion is isotropic (as in the case of apatite) but shapes of crystal grains or fragments may depart significantly from spherical geometry. 相似文献
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Sphalerite oxidation is a common process under acid-mine drainage (AMD) conditions and results in the release of , Zn and potentially toxic trace metals, which can pollute rivers and oceans. However, there are only a few studies on the mechanisms of aerobic sphalerite oxidation. Oxygen and S isotope investigations of the produced may contribute to the understanding of sphalerite oxidation mechanisms so helping to interpret field data from AMD sites. Therefore, batch oxidation experiments with an Fe-rich sphalerite were performed under aerobic abiotic conditions at different initial pH values (2 and 6) for different lengths of time (2–100 days). The O and S isotope composition of the produced indicated changing oxidation pathways during the experiments. During the first 20 days of the experiments at both initial pH values, molecular O2 was the exclusive O source of . Furthermore, the lack of S isotope enrichment processes between and sphalerite indicated that O2 was the electron acceptor from sphalerite S. As the oxidation proceeded, a sufficient amount of released Fe(II) was oxidized to Fe(III) by O2. Therefore, electrons could be transferred from sphalerite S sites to adsorbed hydrous Fe(III) and O from the hydration sphere of Fe was incorporated into the produced as indicated by decreasing δ18OSO4 values which became more similar to the δ18OH2O values. The enrichment of 32S in relative to the sphalerite may also result from sphalerite oxidation by Fe(III).The incorporation of O2 into during the oxidation of sphalerite was associated with an O isotope enrichment factor εSO4–O2 of ca. −22‰. The O isotope enrichment factor εSO4–H2O was determined to be ?4.1‰. A comparison with O and S studies of other sulfides suggests that there is no general oxidation mechanism for acid-soluble sulfides. 相似文献
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Richard E. Zeebe 《Geochimica et cosmochimica acta》2010,74(3):818-7445
Although the stable oxygen isotope fractionation between dissolved sulfate ion and H2O (hereafter ) is of physico-chemical and biogeochemical significance, no experimental value has been established until present. The primary reason being that uncatalyzed oxygen exchange between and H2O is extremely slow, taking ∼105 years at room temperature. For lack of a better approach, values of 16‰ and 31‰ at 25 °C have been assumed in the past, based on theoretical ‘gas-phase’ calculations and extrapolation of laboratory results obtained at temperatures >75 °C that actually pertain to the bisulfate system. Here I use novel quantum-chemistry calculations, which take into account detailed solute-water interactions to establish a new value for of 23‰ at 25 °C. The results of the corresponding calculations for the bisulfate ion are in agreement with observations. The new theoretical values show that sediment -data, which reflect oxygen isotope equilibration between sulfate and ambient water during microbial sulfate reduction, are consistent with the abiotic equilibrium between and water. 相似文献
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Solubility of Pt in sulphide mattes: Implications for the genesis of PGE-rich horizons in layered intrusions 总被引：1，自引：0，他引：1
Raúl O.C. Fonseca Ian H. Campbell Hugh St. C. O&#x;Neill Charlotte M. Allen 《Geochimica et cosmochimica acta》2009,73(19):5764-5777
The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS2 and fO2 at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS2 and decreases weakly with increasing fO2. The increase in Pt solubility with increasing fS2 is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO2 to the diluting effect of increasing O in the melt at high fO2. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 107 and 1011, depending on fO2 and fS2, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 107 and for the Stillwater Pt-rich horizon 108. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions. 相似文献