首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
《Geochimica et cosmochimica acta》1999,63(19-20):3171-3182
The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)2+ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe3+. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe2+/Fe3+ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10−4 and 10−2 mol L−1. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): rpy=0.55 c(HAsc)−0.35 rHAsc=3.6 c(HAsc)0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.  相似文献   

2.
Oxidation of pyrite by hydrogen peroxide (H2O2) at millimolar levels has been studied from 4 to 150 °C in order to evaluate isotopic effects potentially associated with radiolytic oxidation of pyrite. Gaseous, aqueous, and solid phases were collected and measured following sealed-tube experiments that lasted from 1 to 14 days. The dominant gaseous product was molecular oxygen. No volatile sulfur species were recovered from any experiment. Sulfate was the only aqueous sulfur species detected in solution, with sulfite and thiosulfate below the detection limits. X-ray diffraction patterns and images from scanning electron microscopy reveal solid residues composed primarily of hydrated ferric iron sulfates and sporadic ferric-ferrous iron sulfates. Hematite was detected only in solid residue produced during high temperature experiments. Elemental sulfur and/or polysulfides are inferred to be form on reacting pyrite surface based on extraction with organic solvents. Pyrite oxidation by H2O2 increases in rate with increasing H2O2concentration, pyrite surface area, and temperature. Rates measured in sealed-tube experiments at 25°C, for H2O2 concentration of 2 × 10−3 M are 8.8 × 10−9 M/m2/sec, which are higher than previous estimates. A combination of reactive oxygen species from H2O2 decomposition products and reactive iron species from pyrite dissolution is inferred to aggressively oxidize the receding pyrite surface. Competing oxidants with temperature-dependent oxidation efficiencies results in multiple reaction mechanisms for different temperatures and surface conditions. Sulfur isotope values of remaining pyrite were unchanged during the experiments, but showed distinct enrichment of 34S in produced sulfate and depletion in elemental sulfur. The Δsulfate-pyrite and Δelemental sulfur-pyrite was +0.5 to +1.5‰ and was −0.2 to −1‰, respectively. Isotope data from high-temperature experiments indicate an additional 34S-depleted sulfur fraction, with up to 4‰ depletion of 34S, in the hematite. Sulfur isotope trends were not influenced by H2O2 concentration, temperature, or reaction time. Results of this study indicate that radiolytically produced oxidants, such as hydrogen peroxide and hydroxyl radicals, could efficiently oxidize pyrite in an otherwise oxygen-limited environment. Although H2O2 is generally regarded as being of minor geochemical significance on Earth, the H2O2 molecule plays a pivotal role in Martian atmospheric and soil chemistry. Additional experimental and field studies are needed to characterize sulfur and oxygen isotope systematics during radiolytical oxidation of metallic sulfides and elemental sulfur.  相似文献   

3.
《Applied Geochemistry》2004,19(11):1837-1853
Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO42−, Fe2+, Fe3+, Cl−, HCO3−, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO4 and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO42− and Fe2+, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO42−, Fe3+, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.  相似文献   

4.
A stable isotope mass-balance of dissolved inorganic carbon during a blue-green algae bloom in a softwater lake demonstrates that at low partial pressure of carbon dioxide there must be a large net negative carbon isotope fractionation between atmospheric CO2 and the CO2 absorbed by lake water at pH = 9.5. The net fractionation of CO2(g) with respect to HCO−3 was about −13%. compared with about +8%. for water at equilibrium with atmospheric CO2 at pH ≈ 7. Chemical enhancement of CO2 invasion at high pH by the reaction CO2 + OH−→ HCO−3 at large apparent film thicknesses may result in carbon isotope fractionation approaching that for a hydroxide solution. This phenomenon, coupled with a decrease in the photosynthetic fractionation, forced the surface water of a softwater lake to achieve increasingly negative δ13C values during an algal bloom, which is in the opposite sense to the trend that results from photosynthesis under less extreme conditions. This and other similar systems must operate under non-equilibrium (kinetic) conditions, causing a large kinetic fractionation during CO2 invasion at pH > 8 and relatively large film thicknesses (i.e., low wind stress).  相似文献   

5.
《Geochimica et cosmochimica acta》1999,63(19-20):3417-3427
In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [FeII1−xFeIIIx(OH)2]+x· [x/z A−z]−x, where compensating interlayer anions, A−, can be Cl−, SO42−, CO32− or OH−, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fet, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log Ksp = 28.2 ± 0.8 for the reaction Fe3(OH)7 + e− + 7 H+ = 3 Fe2+ + 7 H2O; log Ksp = 25.4 ± 0.7 for the reaction Fe2(OH)5 + e− + 5 H+ = 2 Fe2+ + 5 H2O; log Ksp = 45.8 ± 0.9 for the reaction Fe3(OH)8 + 2e− + 8 H+ = 3 Fe2+ + 8 H2O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: ΔfG° (Fe3(OH)7, cr, 282.15 K) = −1799.7 ± 6 kJ mol−1, ΔfG° (Fe2(OH)5, cr, 282.15 K) = −1244.1 ± 6 kJ mol−1 and ΔfG° (Fe3(OH)8, cr, 282.15 K) = −1944.3 ± 6 kJ mol−1.  相似文献   

6.
《Geochimica et cosmochimica acta》1999,63(13-14):2001-2007
Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ18O of the foraminiferal calcite decreases with increasing CO32− concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H2CO3] + [HCO3−] + [CO32−] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO3 also decreases with increasing pH. The slope of shell δ18O vs. [CO32−] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg−1)−1 (Spero et al., 1997), whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg−1)−. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed.  相似文献   

7.
The acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, plays a part in the pyrite oxidation process and has been widely studied in order to determine the kinetics of the reactions and the isotopic composition of dissolved product sulphates, but the details of the oxidation processes at the surface of pyrite are still poorly known. In this study, oxygen and sulphur isotopic compositions (δ18O and δ34S) were analyzed for dissolved sulphates and water from experimental aerobic acidic (pH < 2) pyrite oxidation by A. ferrooxidans. The oxidation products attached to the pyrite surfaces were studied for their morphology (SEM), their chemistry (Raman spectroscopy) and for their δ18O (ion microprobe). They were compared to abiotically (Fe3+, H2O2, O2) oxidized pyrite surface compounds in order to constrain the oxidation pathways and to look for the existence of potential biosignatures for this system.The pyrite dissolution evolved from non-stoichiometric (during the first days) to stoichiometric (with increasing time) resulting in dissolved sulphates having distinct δ18O (e.g. +11.0‰ and −2.0‰, respectively) and δ34S (+4.5‰ and +2.8‰, respectively) values. The “oxidation layer” at the surface of pyrite is complex and made of iron oxides, sulphate, polysulphide, elemental sulphur and polythionates. Bio- and Fe3+-oxidation favour the development of monophased micrometric bumps made of hematite or sulphate while other abiotic oxidation processes result in more variable oxidation products. The δ18O of these oxidation products at the surface of oxidized pyrites are strongly variable (from ≈−40‰ to ≈+30‰) for all experiments.Isotopic fractionation between sulphates and pyrite, Δ34SSO4-pyrite, is equal to −1.3‰ and +0.4‰ for sulphates formed by stoichiometric and non-stoichiometric processes, respectively. These two values likely reflect either a S-S or a Fe-S bond breaking process. The Δ18OSO4-H2O and Δ18OSO4-O2 are estimated to be ≈+16‰ and ≈−25‰, respectively. These values are higher than previously published data and may reflect biological effects. The large δ18O heterogeneity measured at the surfaces of oxidized pyrites, whatever the oxidant, may be related (i) to the existence of local surface environments isolated from the solution in which the oxidation processes are different and (ii) to the stabilization at the pyrite surface of reaction intermediates that are not in isotopic equilibrium with the solution. Though the oxygen isotopic composition of surface oxidation products cannot be taken as a direct biosignature, the combined morphological, chemical and isotopic characterization of the surfaces of oxidized pyrites may furnish clues about a biological activity on a mineral surface.  相似文献   

8.
This work focuses on sulfide mineral oxidation rates under oxic conditions in freshly processed pyrite-rich tailings from the ore concentrator in Boliden, northern Sweden. Freshly processed tailings are chemically treated in the plant to kill bacteria and to obtain increased metal yields, resulting in a high pH level of 10–12 in the process water. Different oxidation experiments (abiotic oxidation in untreated tailings, acid abiotic oxidation and acid microbial oxidation), containing the Boliden tailings, were performed at room temperature with dissolved oxygen (0.21 atm O2) for 3 months. The different pyrite oxidation rates given from the study were 2.4×10−10 mol m−2 s−1 for the microbial, 5.9×10−11 mol m−2 s−1 for the acidic abiotic and 3.6×10−11 mol m−2 s−1 for the untreated experiments. Because of the potential precipitation of gypsum in the batch solutions, these oxidation rates are considered minimum values. The release rates for copper and zinc from chalcopyrite and sphalerite in the acid experiments were also investigated. These rates were normalized to the metal concentration in the tailings, and then compared to the release rate for iron from pyrite. These normalized results indicated that metal release decreased in the order Cu>Zn>Fe, demonstrating that pyrite is more resistant to oxidation than sphalerite and chalcopyrite. Pyrite was also more resistant to acidic dissolution than to microbial dissolution, while a significant fraction of sphalerite and chalcopyrite dissolved in the acid abiotic solutions.  相似文献   

9.
《Chemical Geology》2006,225(1-2):16-29
Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10− 10 mol m− 2 s− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.  相似文献   

10.
The Gibbs free energies of formation of RuO 2, OsO 2 and IrO 2 have been determined by measuring the chemical potentials of oxygen (μO 2) defined by the reactions M +O 2 = MO 2,whereM =Ru, Os. or Ir, using an electrochemical method with calcia-stabilized zirconia (CSZ) solid electrolytes. Measurements were attempted in the temperature ranges from ∼870 K to 1620, 1270, and 1415 K for the Ru, Os, and Ir equilibria, respectively, but inspection of the results reveals that equilibrium could not be established below ∼930 K for all three reactions. For Ru + RuO 2, the highest temperature data (above 1520 K) may be systematically affected by the onset of significant electronic conduction in the CSZ electrolyte, while the attempted measurements of the Os + OsO 2 equilibrium above 1190 K are obscured by the disproportionation of OsO 2 to gaseous Os oxides.The high temperature heat capacities at constant pressure (Cp) of RuO 2 and IrO 2 were determined from 370 to 1070 K by differential scanning calorimetry. These data were combined with heat content measurements and low-temperature heat capacities from the literature, and fitted to an extended Maier-Kelley equation. The calorimetric data for RuO 2 and IrO 2, together with assessed data for Ru, Os, and Ir metals and estimated data for OsO 2, were used in a third law analysis of the electrochemical measurements.The values of μO 2 of the three equilibria were smoothed and filtered by the third-law analysis to yield the following equations which can be extrapolated to lower and higher temperatures as indicated: μO 2 (Ru + RuO 2) = −324563 + 344.151 T−22.1155 TlnT (700 ⩽ T ⩽ 1800) μO 2 (Os + OsO 2) = −300399 + 307.639 T−17.4819 TlnT (700 ⩽ T ⩽ 1500) μO 2 (Ir + IrO 2) = −256518 + 295.854 T−15.2368 TlnT (700 ⩽ T ⩽ 1500) where μO 2 is in J mol −1, T is in K, the reference pressure for O 2 is 1 bar (10 5 Pa), and estimated accuracies are approximately 200 to 400 J mol −1. For Ru + RuO 2, the drift in the measurements relative to the calorimetric data deduced from the third-law evaluation is 0.7 J K −1 mol −1, and for Ir + IrO 2 is 1.6 J K −1 mol −1. The analogous third-law evaluation of the Os + OsO 2 data gives S° 298K = 54.8 ± 0.7J K −1mol −1 and Δ /tfH° 298K = −291.8 ± 0.6 kJ mol −1 for OsO 2.  相似文献   

11.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

12.
Geochemical and iron isotopic compositions of magnetite, ilmenite and pyrite separates from the FeTi oxide ores hosted in the Damiao anorthosite-type FeTi ore deposit were analyzed to investigate sub-solidus cooling history of the titanomagnetite. The FeTi oxides form two series of solid solutions, namely, ulvöspinel-magnetite (Usp-Mtss) and hematite-ilmenite (Hem-Ilmss) solid solutions. The magnetite separates have 14–27 mol% ulvöspinel, while the ilmenite separates have 5–8 mol% hematite. Major element compositions of the mineral separates suggest that the ilmenites were mainly exsolved from the Usp-Mtss by oxidation of ulvöspinel in the temperature range of ~820–600 °C and experienced inter-oxide re-equilibration with the magnetites. Associated with the exsolution is the substantial inter-mineral iron isotope fractionation. The magnetite separates are characterized by high δ57Fe (+0.27 − +0.65‰), whereas the ilmenite separates have lower δ57Fe (−0.65 to −0.28‰). Two types of pyrite are petrographically observed, each of which has a distinctive iron isotope fingerprint. Type I pyrite (pyriteI) with higher δ57Fe (δ57Fe = +0.63 − +0.95‰) is consistent with magmatic origin, and type II pyrite (pyriteII) with lower δ57Fe (δ57Fe = −0.90 to −0.11‰) was likely to have precipitated from fluids. Iron isotopic fingerprints of the pyriteI probably indicate variations of oxygen fugacity, whereas those of the pyriteII may result from fluid activities. The iron isotopic fractionation between the magnetite and ilmenite is the net result of sub-solidus processes (including ulvöspinel oxidation and inter-oxide re-equilibration) without needing varying oxygen fugacity albeit its presence. Although varying composition of magnetite-ilmenite pairs reflects variations of oxygen fugacity, inter-oxide iron isotopic fractionation does not.  相似文献   

13.
《Applied Geochemistry》2001,16(9-10):1215-1230
Oxidation rates of low sulphide (<0.5 wt.%) gneissic waste rock from the Cluff lake U mine, northern Saskatchewan, Canada were determined using 3 independent methods: O2 consumption rates in kinetic cells, SO4 measurements of kinetic cell effluent and humidity cell SO4 release rates. The O2 consumption measurements demonstrated that the oxidation of pyrite was strongly dependent on grain size and moderately dependent on water content, temperature and microbiology. Oxygen consumption rates were highest at water contents of 5–10 wt.% (12–25% saturation). Measured SO4 release rates (3.1–91 mg SO4 kg−1 wk−1) for the kinetic cells were comparable to rates calculated from the O2 consumption values (6.9–70 mg SO4 kg−1 wk−1). Sulphate release rates determined from humidity cells were generally higher than those obtained from the kinetic cells, ranging from 6 to 64 mg SO4 kg−1 wk−1 for the coarsest and finest fraction, respectively. These differences were attributed to sample heterogeneity.  相似文献   

14.
The abundant iron sulfide mineral pyrite has been shown to catalytically produce hydrogen peroxide (H2O2) and hydroxyl radical ( . OH) in slurries of oxygenated water. Understanding the formation and fate of these reactive oxygen species is important to biological and ecological systems as exposure can lead to deleterious health effects, but also environmental engineering during the optimization of remediation approaches for possible treatment of contaminated waste streams. This study presents the use of the amino acid phenylalanine (Phe) to monitor the kinetics of pyrite-induced . OH formation through rates of hydroxylation forming three isomers of tyrosine (Tyr) - ortho-, meta-, and para-Tyr. Results indicate that about 50% of the Phe loss results in Tyr formation, and that these products further react with . OH at rates comparable to Phe. The overall loss of Phe appeared to be pseudo first-order in [Phe] as a function of time, but for the first time it is shown that initial rates were much less than first-order as a function of initial substrate concentration, [Phe]o. These results can be rationalized by considering that the effective concentration of . OH in solution is lower at a higher level of reactant and that an increasing fraction of . OH is consumed by Phe-degradation products as a function of time. A simplified first-order model was created to describe Phe loss in pyrite slurries which incorporates the [Phe]o, a first-order dependence on pyrite surface area, the assumption that all Phe degradation products compete equally for the limited supply of highly reactive . OH, and a flux that is related to the release of H2O2 from the pyrite surface (a result of the incomplete reduction of oxygen at the pyrite surface). An empirically derived rate constant, K pyr , was introduced to describe a variable . OH-reactivity for different batches of pyrite. Both the simplified first-order kinetic model, and a more detailed numerical simulation, yielded results that compare well to the observed kinetic data describing the effects of variations in concentrations of both initial Phe and pyrite. This work supports the use of Phe as a useful probe to assess the formation of . OH in the presence of pyrite, and its possible utility for similar applications with other minerals.  相似文献   

15.
《Applied Geochemistry》1998,13(2):177-184
Calcium carbonate is one of the most common and important scale-forming minerals in oilfield produced water, but the kinetics of CaCO3 precipitation has been ignored in most scale prediction models because of the lack of reliable precipitation rate model. There are none in the open literature for oilfield conditions (temperature > 100°C, pressure > 200 bar and salinity > 0.5 mol kg− 1). In this work the kinetics of calcite (CaCO3) precipitation from high salinity waters (up to 2 mol kg−1) have been studied by a pH-free-drift method in a closed water system. This method. is much easier to operate than the often used steady-state method. The experimental results indicate that the calcite precipitation rate is not only affected by the solution CaCO3 saturation level, but also by the solution pH, ionic strength and the concentration ratios of Ca to HCO3− ions (CCa2+/CHCO3−). When the concentration ratios of Ca to HCO3− ions are close to their chemical stoichiometric ratio of 0.5, the calcite growth from a supersaturated solution is believed to be surface reaction controlled. However, at higher CCa2+CHCO3− ratios, the transportation of the lattice ions to calcite crystal surface has to be considered.  相似文献   

16.
The enrichment of gold in arsenian pyrite is usually associated closely with the enrichment of arsenic in the mineral, generally known as As1−-pyrite [Fe(As, S)2]. Direct analyses of the valence state of Au in pyrite are, however, difficult due to generally low (∼ppm level) Au concentrations. By means of X-ray photoelectron spectroscopy (XPS), this study obtained reliable valence states of As in pyrite from the Yang-shan gold deposit, a giant “Carlin-type” Au deposit in the western Qinling orogen, central China. The arsenian pyrite specimens were sputtered with Ar+ beam in the vacuum chamber of an XPS to obtain pristine surfaces and to avoid As oxidation during sample preparation. Analyses before and after sputtering show that the As3+ peak are only present on surface that was once exposed to the air. In contrast, the peak of As−1 was essentially unchanged during continuous sputtering. The results indicated that As− is the predominant state on the pristine surface of arsenian pyrite; the peak of As3+ previously reported for Au-bearing arsenian pyrite was probably due to oxidation when exposed to air during sample preparation. It is unlikely that the coupled substitution of (Au+ + As3+) for 2Fe2+ takes place in the pyrite lattice. The so-called As3+-pyrite proposed by previous studies may occur in some special (oxidizing) geologic settings, but it is not observed in the Yang-shan gold deposit, and is unlikely to be important in typical orogenic or Carlin-type gold deposits, in which arsenian pyrite is a dominant Au carrier. Combining previous studies on Carlin-type Au deposits with our XPS experimental results, we suggest that the most likely state of Au in the Yang-shan Au deposit is lattice-bounded Au with or without nanoparticles (Au0).  相似文献   

17.
The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ13CDIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO3−-rich, SO42−-rich and Cl−-rich. The HCO3−-rich groundwater is undergoing closed system carbonate evolution from soil CO2(g) and weathering of aquifer carbonates. The SO42−-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl−-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ13CDIC of the HCO3−-rich groundwater was controlled by nearly equal contribution of carbon from soil CO2(g) and the aquifer carbonates, such that the δ13C of carbon added to the groundwater was −11.6‰. In the SO42−-rich groundwater, gypsum induced dedolomitization increased the 13C such that the δ13C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl−-rich groundwater, common ion induced precipitation of calcite depleted the 13C such that the δ13C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.  相似文献   

18.
The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ34S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ34S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ34S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ34Spyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe3+ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H2O, not O2. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.  相似文献   

19.
The rate of pyrite oxidation in moist air was determined by measuring, over time, the pressure difference between a sealed chamber containing pyrite plus oxygen and a control. The experiments carried out at 25°C, 96.7% fixed relative humidity, and oxygen partial pressures of 0.21, 0.61, and 1.00 atm showed that the rate of oxygen consumption is a function of oxygen partial pressure and time. The rates of oxygen consumption (r, mol/m2sec) fit the expression
(A)  相似文献   

20.
《Applied Geochemistry》1998,13(6):767-778
A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO3 was injected as a pulse simultaneously with a conservative tracer -Br−. During the test, which lasted 210 h, 73% of the injected Br− was recovered, as against only 47% of the NO3. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS2+14NO3−+4H+→7N2+10SO42−+5Fe2++2H2O, and in part due to subsequent iron oxidation according to the reaction: NO3−+5Fe2++6H+→1/2N2+5Fe3++3H2O. Despite the potential increase in SO4 and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO3-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO3-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号