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1.
Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H2SO4 leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H2SO4 on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H2SO4 solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H2SO4 on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed. 相似文献
2.
Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H2SO4) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H2SO4 from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO4-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study. 相似文献
3.
Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ18O values (−10‰ to −3‰) and a δD vs. δ18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl− concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH. 相似文献
4.
An attenuated total reflectance IR study of silicic acid adsorbed onto a ferric oxyhydroxide surface
Silicic acid (H4SiO4) can have significant effects on the properties of iron oxide surfaces in both natural and engineered aquatic systems. Understanding the reactions of H4SiO4 on these surfaces is therefore necessary to describe the aquatic chemistry of iron oxides and the elements that associate with them. This investigation uses attenuated total reflectance infrared spectroscopy (ATR-IR) to study silicic acid in aqueous solution and the products formed when silicic acid adsorbs onto the surface of a ferrihydrite film in 0.01 M NaCl at pH 4. A spectrum of 1.66 mM H4SiO4 at pH 4 (0.01 M NaCl) has an asymmetric Si-O stretch at 939 cm−1 and a weak Si-O-H deformation at 1090 cm−1. ATR-IR spectra were measured over time (for up to 7 days) for a ferrihydrite film (≈1 mg) approaching equilibrium with H4SiO4 at concentrations between 0.044 and 0.91 mM. Adsorbed H4SiO4 had a broad spectral feature between 750 and 1200 cm−1 but the shape of the spectra changed as the amount of H4SiO4 adsorbed on the ferrihydrite increased. When the solid phase Si/Fe mole ratio was less than ≈0.01 the ATR-IR spectra had a maximum intensity at 943 cm−1 and the spectral shape suggests that a monomeric silicate species was formed via a bidentate linkage. As the solid phase Si/Fe mole ratio increased to higher values a discrete oligomeric silicate species was formed which had maximum intensity in the ATR-IR spectra at 1001 cm−1. The spectrum of this species suggests that it is larger than a dimer and it was tentatively identified as a cyclic tetramer. A small amount of a polymeric silica phase with a broad spectral feature centered at ≈1110 cm−1 was also observed at high surface coverage. The surface composition was estimated from the relative contribution of each species to the area of the ATR-IR spectra using multivariate curve resolution with alternating least squares. For a ferrihydrite film approaching equilibrium with 0.044, 0.14, 0.40 and 0.91 mM H4SiO4 the area of the spectra accounted for by monomeric species were 92%, 49%, 23% and 6%, respectively. The remainder was oligomer apart from a small amount (<5%) of polymerized silica at the two higher H4SiO4 concentrations. The solid phase Si/Fe mole ratios for these samples were 0.020, 0.037, 0.071 and 0.138, respectively. 相似文献
5.
Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na2S; 1500-2000 ppm S by weight) and the other with H2O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H2O) demonstrate that H2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm−1 appears in the sulphide - H2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm−1 (on expense of the combination band of molecular H2O at 5225 cm−1) and at 3400 cm−1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S2− - H2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H2O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H2O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H2O via the reaction S2− + 4H2O = SO42− + 4H2. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only. 相似文献
6.
The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pHT was between 2.20 and 9.30 at the discharge temperature and the SO4 and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg−1, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO42−), thiosulfate (S2O32−) and polythionates (SxO62−) and titration and/or colorimetry for total dissolved sulfide (S2−). Sulfite (SO32−) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S2− were detected in all samples with concentrations of 0.02-52.7 mmol kg−1 and <1-4100 μmol kg−1, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg−1 (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg−1. Thiosulfate and SO32− were not detected in <100 °C well waters and S2O32− was observed only at low concentrations (<1-8 μmol kg−1) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S2O32− was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (STOT). In steam-heated acid-sulfate waters, S2O32− was not a significant sulfur species. The results demonstrate that S2O32− and SO32− do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O2, S2− is degassed and oxidized to SO32− and S2O32− and eventually to SO42− at pH >8. In near-neutral hydrothermal waters the oxidation of S2− and the interaction of S2− and S0 resulting in the formation of Sx2− are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO42− and the sulfur chemistry of acid-sulfate pools was dominated by SO42−, which corresponded to >99% of STOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations. 相似文献
7.
Geochemical characteristics of waters in mineralised area of Peloritani Mountains (Sicily,Italy) 总被引：1，自引：0，他引：1
This paper presents the results of a study on the geochemistry of waters circulating in the mineralised area of the south-eastern sector of Mt. Peloritani (north-eastern Sicily, Italy), aimed at basic understanding of the geochemical processes influencing their chemical composition. Chemico-physical parameters and data on 26 major and minor chemical elements are reported for 103 water samples. Water chemistry is mainly dominated by dissolution of carbonates and hydrolysis of aluminosilicate minerals. Total dissolved salts (TDS) range from 80 to 1398 mg/L. All the waters exhibit EH characteristic of an oxygenated environment. Excluding two samples, which show very high H+ activity (pH = 3.0 and 2.7), all the waters have pH values in the range 6.2–8.6. Cluster analysis based on major ion contents defined three main chemical water types, reflecting different hydrochemical processes. The first, group I, has low salinity (average TDS = 118 ± 30 mg/L) and abundance orders (meq/L) Na > Ca ≈ Mg > K and Cl ≈ HCO3 > SO4. With increased water–rock interaction, waters in groups II and III become more saline, changing composition towards SO4–Cl-alkaline earth and HCO3-alkaline earth types. Weathering of carbonate minerals causes waters to become saturated with respect to calcite and dolomite, whereas the incongruent dissolution of aluminosilicate minerals causes the solution to reach equilibrium with kaolinite and to form smectites. Trace element geochemistry in the analysed waters reflects interactions between waters and existing mineralisation, with elemental concentrations showing highly variable values, and higher concentrations of As, Pb, Sb and Zn near known mineralisation. Lead–Zn and As–Sb statistical associations, probably distinguishing interactions with different mineralogical phase paragenesis, were revealed by factor analysis. The main aqueous chemical forms of trace elements predicted by chemical speciation calculations are also reported. As most of the analysed spring waters provide the main source of freshwater for domestic purposes, attention should be given to As and Sb, whose concentrations exceed the recommended limits. 相似文献
8.
A. Aiuppa S. Inguaggiato M. O’Dwyer M.J. Padgett M. Valenza 《Geochimica et cosmochimica acta》2005,69(7):1861-1871
We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO2/H2S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H2S flux of 6 to 9 t · d−1 for the summit crater. For Mt. Etna and Stromboli, we found SO2/H2S molar ratios of ≈20 and ≈15, respectively, which combined with SO2 flux measurements, suggest H2S emission rates of 50 to 113 t · d−1 and 4 to 8 t · d−1, respectively. We observe that “source” and plume SO2/H2S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H2S emission. 相似文献
9.
Claire Chaïrat Eric H. Oelkers Jacques Schott 《Geochimica et cosmochimica acta》2007,71(24):5888-5900
The surface chemistry of fluorapatite in aqueous solution was investigated using electrokinetic techniques, potentiometric titrations, solubility measurements, and attenuated total reflection infrared spectroscopy. All methods indicate the formation of Ca/F depleted, P enriched altered layer via exchange reactions between H+ and Ca2+, and OH− and F− at the fluorapatite (FAP) surface. Observations suggest that this leached layer has a di-calcium phosphate (CaHPO4) composition and that it controls the apparent solubility of FAP. Electrokinetic measurements yield an iso-electric point value of 1 ± 0.5 consistent with a negatively charged FAP surface at pH > 1. In contrast, surface titrations give an apparent pH of point of zero charge of ∼7.7, consistent with a positively charged surface at pH < 7.7. These differences are shown to stem from proton consumption by both proton exchange and dissolution reactions at the FAP surface. After taking account for these effects, FAP surface charge is shown to be negative to at least pH 4 by surface titration analysis. 相似文献
10.
Ellen P.M.J. Fest Erwin J.M. Temminghoff Jasper Griffioen Bas Van Der Grift Willem H. Van Riemsdijk 《Applied Geochemistry》2007
Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)3 and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L−1 at pH > 7 to 1941 μmol L−1 at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al3+ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)3 minerals (e.g. gibbsite or amorphous Al(OH)3), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater. 相似文献
11.
Matthew B.J. Lindsay David W. BlowesPeter D. Condon Carol J. Ptacek 《Applied Geochemistry》2011,26(7):1169-1183
A field-scale experiment was conducted to evaluate various organic C sources as amendments for passive treatment of tailings pore water. Varied mixtures of peat, spent-brewing grain (SBG) and municipal biosolids (MB) were assessed for the potential to promote dissimilatory sulfate reduction (DSR) and metal-sulfide precipitation. Five amended cells and one control were constructed in the vadose zone of a sulfide- and carbonate-rich tailings deposit, and the geochemistry, microbiology and mineralogy were monitored for 4 a. Increases in pore-water concentrations of dissolved organic C (DOC) and decreases in aqueous SO4 concentrations of >2500 mg L−1 were observed in cells amended with peat + SBG and peat + SBG + MB. Removal of SO4 was accompanied by shifts in δ34S-SO4 values of >+30‰, undersaturation of pore water with respect to gypsum [CaSO4·2H2O], and increased populations of SO4-reducing bacteria (SRB). Decreases in aqueous concentrations of Zn, Mn, Ni, Sb and Tl were observed for these cells relative to the control. Organic C introduction also supported growth of Fe-reducing bacteria (IRB) and increases in Fe and As concentrations. Enhanced Fe and As mobility occurred in all cells; however, maximum concentrations were observed in cells amended with MB. Subsequent decreases in Fe and As concentrations were attributed to DSR and metal-sulfide precipitation. The common presence of secondary Zn-S and Fe-S phases was observed by field emission-scanning electron microscopy (FE-SEM) and energy dispersive X-ray (EDS) spectroscopy. Selective extractions indicated that large decreases in water-soluble SO4 occurred in cells that supported DSR. Furthermore, amendments that supported DSR generally were characterized by slight decreases in solid-phase concentrations of extractable metal(loid)s. Amendment of tailings with organic C amendments that supported ongoing DOC production and DSR was essential for sustained treatment. 相似文献
12.
Forward dissolution rates of Na-Montmorillonite (Wyoming) SWy-2 smectite (Ca0.06Na0.56)[Al3.08Fe(III)0.38Mg0.54] [Si7.93 Al0.07]O20(OH)4 were measured at 25 °C in a mixed-flow reactor equipped with interior dialysis compartment (6-8 kDa membrane) as a function of pH (1-12), dissolved carbonate (0.5-10 mM), phosphate (10−5 to 0.03 M), and nine organic ligands (acetate, oxalate, citrate, EDTA, alginate, glucuronic acid, 3,4-dihydroxybenzoic acid, gluconate, and glucosamine) in the concentration range from 10−5 to 0.03 M. In organic-free solutions, the Si-based rates decrease with increasing pH at 1 ? pH ? 8 with a slope close to −0.2. At 9 ? pH ? 12, the Si-based rates increase with a slope of ∼0.3. In contrast, non-stoichiometric Mg release weakly depends on pH at 1 ? pH ? 12 and decreases with increasing pH. The empirical expression describing Si-release rates [R, mol/cm2/s] obtained in the present study at 25 °C, I = 0.01 M is given by
13.
Halogen diffusion in a basaltic melt 总被引：2，自引：0，他引：2
The diffusion of the halogens fluorine, chlorine and bromine was measured in a hawaiitic melt from Mt. Etna at 500 MPa and 1.0 GPa, 1250 to 1450 °C at anhydrous conditions; the diffusion of F and Cl in the melt was also studied with about 3 wt% of dissolved water. Experiments were performed using the diffusion-couple technique in a piston cylinder. Most experiments were performed with only one halogen diffusing between the halogen-enriched and halogen-poor halves of the diffusion couple, but a few experiments with a mixture of halogens (F, Cl and Br) were also performed in order to investigate the possibility of interactions between the halogens during diffusion. Fluorine and chlorine diffusivity show a very similar behavior, slightly diverging at low temperature. Bromine diffusion is a factor of about 2-5 lower than the other halogens in this study. Diffusion coefficients for fluorine range between 2.3 × 10−11 and 1.4 × 10−10 m2 s−1, for chlorine between 1.1 × 10−11 and 1.3 × 10−10 and for bromine between 9.4 × 10−12 and 6.8 × 10−11 m2 s−1. No pressure effect was detected at the conditions investigated. In experiments involving mixed halogens, the diffusivities appear to decrease slightly (by a factor of ∼3), and are more uniform among the three elements. However, activation energies for diffusion do not appear to differ between experiments with individual halogens or when they are all mixed together. The effect of water increases the diffusion coefficients of F and Cl by no more than a factor of 3 compared to the anhydrous melt (DF = 4.0 × 10−11 to 1.6 × 10−10 m2 s−1; DCl = 3.0 × 10−11 to 1.9 × 10−10 m2 s−1). Comparing our results to the diffusion coefficients of other volatiles in nominally dry basaltic melts, halogen diffusivities are about one order of magnitude lower than H2O, similar to CO2, and a factor of ∼5 higher than S. The contrasting volatile diffusivities may affect the variable extent of volatile degassing upon melt depressurization and vesiculation, and can help our understanding of the compositions of rapidly grown magmatic bubbles. 相似文献
14.
Teresa Roncal-Herrero 《Geochimica et cosmochimica acta》2011,75(2):416-426
The dissolution rates of natural, well crystallized variscite (AlPO4·2H2O) were determined from the evolution of aqueous Al and P concentrations in closed and open-system mixed-flow reactors at 25 °C and pH from 1.5 to 9.0. Measured dissolution rates decrease with increasing pH, from 6 × 10−16 mol/cm2/s at pH 1.5 to 5 × 10−17 mol/cm2/s at pH 5.89, and then increase with increasing pH to 4 × 10−16 mol/cm2/s at pH 9.0. Geochemical modeling calculations, performed using measured dissolution rates, indicate that it would take no more than a few weeks or months to equilibrate a mildly acidic, Al and P-free solution with variscite. Hence, variscite can buffer aqueous phosphate concentrations in mildly acidic near surface environments. This conclusion is confirmed by consideration of the compositions of natural waters. 相似文献
15.
Anthropogenic S emissions in the Athabasca oil sands region (AOSR) in Alberta, Canada, affect SO4 deposition in close vicinity of industrial emitters. Between May 2008 and May 2009, SO4-S deposition was monitored using open field bulk collectors at 15 sites and throughfall collectors at 14 sites at distances between 3 and 113 km from one of the major emission stacks in the AOSR. At forested plots >90 km from the operations, SO4 deposition was ∼1.4 kg SO4-S ha−1 yr−1 for bulk deposition and ∼3.3 kg SO4-S ha−1 yr−1 for throughfall deposition. Throughfall SO4 deposition rates in the AOSR exceeded bulk deposition rates at all sites by a factor of 2–3, indicating significant inputs of dry deposition especially under forest canopies. Both bulk and throughfall SO4 deposition rates were elevated within 29 km distance of the industrial operations with deposition rates as high as 11.7 kg SO4-S ha−1 yr−1 for bulk deposition and 39.2 kg SO4-S ha−1 yr−1 for throughfall at industrial sites. Sulfur isotope ratio measurements of atmospheric SO4 deposited in the AOSR revealed that at a few selected locations 34S-depleted SO4, likely derived from H2S emissions from tailing ponds contributes to local atmospheric SO4 deposition. In general, however, δ34S values of SO4 deposition at distant forested plots (>74 km) with low deposition rates were not isotopically different from δ34S values at sites with high deposition rates in the AOSR and are, therefore, not suitable to determine industrial S contributions. However, O isotope ratios of atmospheric SO4 in bulk and throughfall deposition in the AOSR showed a distinct trend of decreasing δ18O-SO4 values with increasing SO4 deposition rates allowing quantification of industrial contributions to atmospheric SO4 deposition. Two-end-member mixing calculations revealed that open field bulk SO4 deposition especially at industrial sites in close proximity (<29 km) to the operations is significantly (17–59%) affected by industrial S emissions and that throughfall generally contained 49–100% SO4 of industrial origin. Hence, it is suggested that δ18O values of SO4 may constitute a suitable tracer for quantifying industrial contributions to atmospheric SO4 deposition in the AOSR. 相似文献
16.
Hydration of rhyolitic glass during weathering as characterized by IR microspectroscopy 总被引：1，自引：0，他引：1
Tadashi Yokoyama Satoshi Okumura Satoru Nakashima 《Geochimica et cosmochimica acta》2008,72(1):117-125
The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H2O (H2Om), OH species (OH) and total water (H2Ot) were determined. The diffusion profile of H2Om in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H2Om in the hydrated region is much higher than that of OH species. Thus, the reaction from H2Om to OH appears to be little and H2Om is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H2Om(DH2Om) and H2Ot(DH2Ot) were determined to be 2.8 × 10−10 and 3.4 × 10−10 μm2 s−1 for Ohsawa lava, and 5.2 × 10−11 and 4.1 × 10−11 μm2 s−1 for Awanomikoto lava, respectively. The obtained DH2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C. 相似文献
17.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates. 相似文献
18.
Claire Chaïrat Jacques Schott Jean-Eric Lartigue 《Geochimica et cosmochimica acta》2007,71(24):5901-5912
The dissolution rates of natural fluorapatite (FAP), Ca10(PO4)6F2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ? pH ? 7, FAP dissolution rates are pH independent at 7 ? pH ? 10, and FAP dissolution rates again decrease with increasing pH at pH ? 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10.Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using
19.
Lurdes Fernández-Díaz Ángeles Fernández-González 《Geochimica et cosmochimica acta》2010,74(21):6064-6076
The nucleation and growth of CaCO3 phases from aqueous solutions with SO42−:CO32− ratios from 0 to 1.62 and a pH of ∼10.9 were studied experimentally in batch reactors at 25 °C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO42−:CO32− ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO42−:CO32− ? 1. For SO42−:CO32− > 1, vaterite persisted as a major phase for a longer time (>250 h for SO42−:CO32− = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior. 相似文献
20.
Dissolution experiments on a serpentinite were performed at 70 °C, 0.1 MPa, in H2SO4 solution, in open and closed systems, in order to evaluate the overall dissolution rate of mineral components over different times (4, 9 and 24 h). In addition, the serpentinite powder was reacted with a NaCl-bearing aqueous solution and supercritical CO2 for 24 h at higher pressures (9-30 MPa) and temperatures (250-300 °C) either in a stirred reactor or in an externally-heated pressure vessel to assess both the dissolution rate of serpentinite minerals and the progress of the carbonation reaction. Results show that, at 0.1 MPa, MgO extraction from serpentinite ranges from 82% to 98% and dissolution rate varies from 8.5 × 10−10 mole m−2 s−1 to 4.2 × 10−9 mole m−2 s−1. Attempts to obtain carbonates from the Mg-rich solutions by increasing their pH failed since Mg- and NH4- bearing sulfates promptly precipitated. On the other hand, at higher pressures, significant crystallization (5.0-10.4 wt%) of Ca- and Fe-bearing magnesite was accomplished at 30 MPa and 300 °C using 100 g L−1 NaCl aqueous solutions. The corresponding amount of CO2 sequestered by crystallization of carbonates is 9.4-15.9 mole%. Dissolution rate (from 6.3 × 10−11 mole m−2 s−1 to 1.3 × 10−10 mole m−2 s−1) is lower than that obtained at 0.1 MPa and 70 °C but it is related to pH values much higher (3.3-4.4) than that (−0.65) calculated for the H2SO4 solution.Through a thorough review of previous experimental investigations on the dissolution kinetics of serpentine minerals the authors propose adopting: (i) the log rate [mole m−2 s−1] value of −12.08 ± 0.16 (1σ), as representative of the neutral dissolution mechanism at 25 °C and (ii) the following relationship for the acidic dissolution mechanism at 25 °C:
log rate=-0.45(±0.09)×pH-10.01(±0.30). 相似文献