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1.
Arsenite sorption on troilite (FeS) and pyrite (FeS2)   总被引：4，自引：0，他引：4  
Arsenic is a toxic metalloid whose mobility and availability are largely controlled by sorption on sulfide minerals in anoxic environments. Accordingly, we investigated reactions of As(III) with iron sulfide (FeS) and pyrite (FeS2) as a function of total arsenic concentration, suspension density, sulfide concentration, pH, and ionic strength. Arsenite partitioned strongly on both FeS and FeS2 under a range of conditions and conformed to a Langmuir isotherm at low surface coverages; a calculated site density of near 2.6 and 3.7 sites/nm2 for FeS and FeS2, respectively, was obtained. Arsenite sorbed most strongly at elevated pH (>5 to 6). Although solution data suggested the formation of surface precipitates only at elevated solution concentrations, surface precipitates were identified using X-ray absorption spectroscopy (XAS) at all coverages. Sorbed As was coordinated to both sulfur [d(As-S) = 2.35 Å] and iron [d(As-Fe) = 2.40 Å], characteristic of As coordination in arsenopyrite (FeAsS). The absorption edge of sorbed As was also shifted relative to arsenite and orpiment (As2S3), revealing As(III) reduction and a complete change in As local structure. Arsenic reduction was accompanied by oxidation of both surface S and Fe(II); the FeAsS-like surface precipitate was also susceptible to oxidation, possibly influencing the stability of As sorbed to sulfide minerals in the environment. Sulfide additions inhibit sorption despite the formation of a sulfide phase, suggesting that precipitation of arsenic sulfide is not occurring. Surface precipitation of As on FeS and FeS2 supports the observed correlation of arsenic and pyrite and other iron sulfides in anoxic sediments.  相似文献   

2.
Microbial SO42− reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL−1) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L−1 synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As4S4) and As2S3(am) were undersaturated throughout the experiment. Orpiment (As2S3) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS2) and greigite (Fe3S4) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na2S4) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO42− reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.  相似文献   

3.
Element geochemistry of gold arsenic and mineralogical features of their sulfides in the Carlin-type gold depostis of the Qinling region are discussed in this paper.The initial contents of ore-forming elements such as glod and arsenic are high the ore-bearing rock series in the Qinling region.Furthermore,both the metals are concentrated mainly in the diagenetic pyrite.Study on the mineralogy of arsenic-bearing sulfide minerals in the ores demonstrated that there is a poistive correlation between gold and arsenic in the sulfide minerals.Available evidence suggests that gold in the As-bearing sulfide minerals in likely to be presented as a charge species(Au ),and it is most possible for it to replace the exxcess arsenic at the site of iron and war probably deposited together with arsenic as solid in the sulfide minerals. Pyrite is composed of(Aux^3 ,Fe1-2^2 )([AsS]x^3-[S2]1-x^2-),and arenopyrite of (Aux^3 ,Fe1-x^3 )([AsS]x^3-[AsS2]1-x^3-).The occurrence of glod in the As-sulfied minerals from the Carlin-type gold depostis in the Qinling region has been confirmed by electron probe and transmission electron microscopic studies.The results show that gold was probably depostied together with arsenicas coupled solid solutions in sulfide minerals in the early stage of mineralization.Metallogenic chemical reactions concerning gold deposition in the Carlin-type As-rich gold deposits would involve oxidation of glod and concurrent reduction of arsenic.Later,the deposited gold as solid was remobilized and redistributed as exsolutions,as a result of increasing hydrothermal alteration and crystallization,and decreasing resistance to refractoriness of the host minerals.Gold occurs as sub-microscopic grains(ranging from 0.04tp 0.16μm in diameter)of native gold along micro factures in and crystalline grains of the sulfiedes.  相似文献   

4.
对石门4处典型不同种类的含砷尾矿进行样品采集,并采用1种氧化菌(氧化亚铁硫杆菌,Thiobacillus ferrooxidans,简称T.f)和2种还原菌(硫酸盐还原菌,sulfate reducing bacteria,简称SR;嗜酸铁还原菌,Acidiphilium cryptum JF-5,简称JF-5)分别对其进行作用,据此研究生物还原和氧化条件下原生和次生含砷矿物的释砷情况,进而确定潜在的释砷风险。ICP-OES定量分析显示,3种细菌作用后,雄黄矿和雌黄矿的砷释出浓度都不断升高。168 h氧化菌T.f作用后的砷释出顺序为雌黄矿>淋滤液次生含砷矿物>雄黄矿>含砷夹矸尾矿。LC-AFS原子荧光分析释出液砷形态结果表明:①T.f作用后,雄黄矿和雌黄矿表现出非常明显的差异;1.5 h作用后4种含砷矿物释放As(Ⅴ)的顺序为含砷夹矸尾矿>雄黄矿>淋滤液次生含砷矿物>雌黄矿;②2种还原菌作用后,SR更能促进雌黄矿释放的As(Ⅲ),其释放量是JF-5的2倍;雌黄矿释出As(Ⅲ)在168 h达到20.64 mg/L(SR)和9.54 mg/L(JF-5)。96 h SR作用后4种含砷矿物释放As(Ⅲ)的顺序为雌黄矿>淋滤液次生含砷矿物>含砷夹矸尾矿>雄黄矿。96 h JF-5作用后4种含砷矿物释放As(Ⅲ)的顺序为雄黄矿>雌黄矿>含砷夹矸尾矿>淋滤液次生含砷矿物。  相似文献   

5.
Arsenite adsorption on galena (PbS) and sphalerite (ZnS)   总被引：1，自引：0，他引：1  
Arsenite, As(III), sorption on galena (PbS) and sphalerite (ZnS) was investigated as a function of solution composition and characterized using X-ray absorption spectroscopy (XAS). Adsorption conformed to a Langmuir isotherm except at the highest surface loadings, and it was not strongly affected by changes in ionic strength. Arsenite sorbed appreciably only at pH > ∼5 for PbS and pH ∼4.5 for ZnS, behavior distinct from its adsorption on other substrates. Arsenite adsorption on PbS and ZnS resulted in the conversion from As-O to As-S coordination. Arsenite does not adsorb through ligand-exchange of surface hydroxyl or sulfhydryl groups. Rather, it forms a polynuclear arsenic sulfide complex on ZnS and PbS consistent with the As3S3(SH)3 trimer postulated by Helz et al. (1995) for sulfidic solutions. This complex was unstable in the presence of oxidizing agents and synchrotron light—it quickly converted to As(V), which was largely retained by the surface. These data illustrate the complexity of As(III) adsorption to even simple sulfide minerals.  相似文献   

6.
中国砷矿资源概述   总被引：14，自引：1，他引：13  
砷在自然界中无处不有,雄黄矿是中国著名的砷矿产。砷与人类文明生活息息相关。中国砷矿主要分高中温岩浆热液硫砷化物矿床和低温非岩浆热液单硫化物雄黄雌黄矿床,系中国东部中新生代地质多旋回构造 岩浆作用下活化的产物  相似文献   

7.
The structural diversity of arsenic sulfide molecules in compositions between As4S6 and As4 was investigated using ab initio quantum chemical calculations. The As4S6 molecule consists of four trigonal pyramid coordinations of As atoms bonding to three S atoms. In the As4S5 composition, only one type of molecular configuration corresponds to an uzonite-type molecule. In the As4S4 composition, two molecular configurations exist with realgar-type and pararealgar-type molecules. Three molecular configurations are in the As4S3 composition. The first configuration comprises trigonal pyramidal As atom coordinations of two types: bonding to two S atoms and one As atom, and bonding to one S atom and two As atoms. The second is the molecular configuration of dimorphite. The third comprises trigonal pyramidal As atom coordinations of two types: bonding to three As atoms, and bonding to one As atom and two S atoms. The As4S2 composition allows molecular configurations of two types. One is comprised of trigonal pyramidal As atom configurations of one type bonding to two As atoms and one S atom. The other comprises trigonal pyramidal As atom coordinations of three types: bonding to two S atoms and one As atoms, bonding to one S atom and two As atoms, and bonding to three As atoms. The As4S molecule has trigonal pyramidal As atom coordinations of two types: bonding to one S atom and two As atoms, and bonding to three As atoms. The As4S composition permits only one molecular configuration, which suggests that the mineral duranusite comprises the As4S molecular geometry. In all, ten molecular configurations are predicted in the molecular hierarchy of the arsenic sulfide binary system. The simulated Raman spectral profiles are helpful in searching for undiscovered arsenic sulfide minerals.  相似文献   

8.
Arsenic in the Muteh gold mining district, Isfahan, Iran   总被引：1，自引：1，他引：0  
Following the appearance of symptoms of arsenic toxicity in the inhabitants of villages in the Muteh gold mining region, central Iran, the concentration of this element in various parts of biogeochemical cycle is investigated. For this purpose, rock, groundwater, soil, plant, livestock hair and wool, and human hair samples are collected and analysed. Total arsenic content ranges from 23 to 2,500?mg/kg in rock samples, 7?C1,061???g/l in water, 12?C232?mg/kg in soil, 0.5?C16?mg/kg in plant samples, 4.10?C5.69?mg/kg in livestock hair and wool, and 0.64?C5.82?mg/kg in human hair. Arsenic concentration in various parts of biogeochemical cycle near the gold deposit in a metamorphic complex, and also close to the gold-processing plant, is very high and decreases exponentially with increasing distance from them. Arsenic concentration in water from a well close to the Muteh gold mine is above 1?mg/L. Arsenic in hair samples taken from local inhabitants is above the recommended levels, and the control samples in Shahre-Kord city. Arsenic concentration is higher in male population and correlates positively with age. It is suggested that arsenic resulting from the decomposition of ore mineral such as orpiment (As2S3), realgar (As2S2) and arsenopyrite (FeAsS) is responsible for polluting natural resources and the human intake via drinking water and the food chain. Gold mining and processing has undoubtedly enhanced the release of arsenic and intensified the observed adverse effects in Muteh area.  相似文献   

9.
Formation and dissolution of secondary arsenic minerals often play significant roles in controlling arsenic mobility in contaminated environments, especially in sulfide mines. Weathering of the orpiment and realgar-bearing tailings from the Shimen realgar deposit, the largest realgar deposit in Asia, were studied. An integrated mineralogical analysis by using X-ray powder diffraction (XRD), Raman spectrum, scanning electron microscope (SEM) and transmission electron microscope (TEM) reveals four kinds of As-bearing secondary minerals including arsenic oxides, arsenates, As-gypsum, and As-Fe minerals. The precipitation of arsenates is due to interaction of As-bearing run-off waters and the underlying carbonate rocks, or the transformation of gypsum into arsenates or As-bearing gypsum through SO42-/HAsO42- substitution. Ca-arsenates are mainly weilite and pharmacolite with Ca/As atomic ratio of 1. Scanning transmission X-ray microscope (STXM) and X-ray absorption fine structure (XAFS) reveal that the valence of arsenic is mainly +3 and +5.  相似文献   

10.
Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As4S4 clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As4S4 clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic 3O2 to diamagnetic 1O2 spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O2 dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As4S4, q.m. calculations reveal that 3O2 transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the 3O2 adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O2 dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O2 alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH−. First-principles, periodic calculations of the realgar surface show that the energetics and structural changes that accompany oxidation of As4S4 clusters on the surface are similar to those involving individual As4S4 clusters. Thus, assuming that an As4S4 cluster with an adsorbed hydroxyl group is a reasonable approximation of the surface of As4S4 at high pH, the theoretically calculated oxidation rate (∼1 × 10−10 mol m−2 s−1) is of the same order as empirically-derived rates from experiments at T = 298 K, pH = 8, and similar dissolved oxygen concentrations. In addition, the co-adsorption of other anions found in alkaline waters (i.e. carbonate, bicarbonate, sulfate, and sulfite) were shown to energetically promote the oxidation of As4S4 (on the order of 5-40 kJ/mol depending on the co-adsorbed anion, OH−, , , , or , and accounting for changes in the hydration of products and reactants). The effect of the co-adsorbate on the kinetics and thermodynamics of oxidation is due to each adsorbate modifying the electronic and structural environment of the other adsorption site.Activation-energy barriers due to spin transitions are rarely discussed in the literature as key factors for controlling oxidation rates of mineral surfaces, even though the magnitude of these barriers is enough to alter the kinetics significantly. The attenuation of the activation energy by co-adsorbed anions suggests the possibility of pH− or p(co-adsorbate)-dependent activation energies that can be used to refine oxidation rate laws for sulfide minerals and other, especially semiconducting minerals, such as oxides.  相似文献   

11.
The oxidation rates of natural realgar and amorphous synthetic AsS by dissolved oxygen were evaluated using mixed flow reactors at pH 7.2 to 8.8 and dissolved oxygen contents of 5.9 to 16.5 ppm over a temperature range of 25 to 40°C. The ratios of As/S are stoichiometric for all amorphous AsS oxidation experiments except for two experiments conducted at pH ∼8.8. In these experiments, stoichiometric ratios of As/S were only observed in the early stages of AsS (am) oxidation whereas lower As/S ratios were observed during steady state. For realgar oxidation experiments, the As/S ratio is less than the stoichiometric ratio of realgar, ranging between 0.61 and 0.71. This nonstoichiometric release of As and S to solution indicates that realgar oxidation is more selective for S after the rates of oxidation become constant. All measured oxidation rates at 25°C can be described within experimental uncertainties as follows: Table 1
Rate ExpressionActivation Energy (kJ/mol)
R(Realgar/As) = 10−9.63(±0.41)[DO]0.51(±0.08)[H+]−0.28(±0.05)64.2 ± 9.8
R(Realgar/S) = 10−9.74(±0.35)[DO]0.54(±0.05)[H+]−0.31(±0.04)62.2 ± 9.0
R(AsS(am)) = 10−13.65(±0.82)[DO]0.92(±0.08)[H+]−1.09(±0.10)124 ± 18.8
Full-size table
  相似文献   

12.
System As–Na–S–Cl–H–O was studied. The research was carried out in three stages: (1) selection of the most likely complexes resulting from arsenic sulfide dissolution, (2) calculation of their thermodynamic constants, and (3) comparison of calculated data with thermodynamic database obtained in tests with the solution of inverse thermodynamic problems using the Selektor program complex. The system As–Na–S–Cl–H–O included more than 230 dependent components, which were divided into two groups, base and functional. The former group includes components of the solution (NaCl, NaOH, Na2S, NaHS, HCl, H2S, H2SO4, sulfates, H2SO3, sulfites, thiosulfates, Na+, Cl−,HS−, S2−), gas phase (43 components), and solid phase (orpiment, red arsenic, arsenolite, claudetite, arsenic, sulfur, sodium salts). Thermodynamic constants of the base components are contained in the Selektor database (they were borrowed from reference-books). The latter group includes 77 complexes labile in the solution but determining the solubility of arsenic and stability of its solid phases. Physicochemical modeling was performed in H2S (≥0.01 m, pH = 1–10), Na2S, and NaHS solutions at 25–250 °C and saturated-vapor pressure. It has been established that the dissolution of arsenic sulfide mineral phases in subneutral and alkaline solutions at low oxidation potential is favored by the formation of sulfoarsenides, which are more stable than arsenides and arsenates. Thermodynamic constants of functional complexes determining the orpiment solubility were calculated within the experimental error. It is shown that in hydrothermal iron-free systems with a low oxidation potential, the concentration of As in the solution decreases on cooling and with acidity increase.  相似文献   

13.
We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.  相似文献   

14.
《Applied Geochemistry》2004,19(2):169-180
Arsenic is present in aqueous environments in +III and +V oxidation states. In oxidizing environments, the principle attenuation mechanism of As migration is its adsorption on Fe(III) oxide and hydroxides. The adsorption affinity is higher for As(V) under lower pH conditions and for As(III) under higher pH conditions. Ferric oxide and hydroxides can dissolve under low Eh and pH conditions releasing adsorbed As. Oxidation-reduction processes often involve high organic matter content in sediments and also contamination by organics such as BTEX. Arsenic may desorb under high pH conditions. Changes of pH can be related to some redox reactions, cation exchange reactions driving dissolution of carbonates, and dissolution of silicates. In very reducing environments, where SO4 reduction takes place, secondary sulfide minerals like As-bearing pyrite and orpiment, As2S3, can incorporate As. Geochemical modeling can be divided into two principal categories: (a) forward modeling and (b) inverse modeling. Forward modeling is used to predict water chemistry after completion of predetermined reactions. Inverse modeling is used to suggest which processes take place along a flowpath. Complex coupled transport and geochemistry programs, which allow for simulation of As adsorption, are becoming available. A common modeling approach is based on forward modeling with surface complexation modeling (SCM) of As adsorption, which can incorporate the effect of different adsorbent/As ratios, adsorption sites density, area available for adsorption, pH changes and competition of As for adsorption sites with other dissolved species such as phosphate. The adsorption modeling can be performed in both batch and transport modes in codes such as PHREEQC. Inverse modeling is generally used to verify hypotheses on the origin of As. Basic prerequisites of inverse modeling are the knowledge of flow pattern (sampling points used in model have to be hydraulically connected) and information about mineralogy including As mineral phases. Case studies of geochemical modeling including modeling of As adsorption are presented.  相似文献   

15.
We present an approach for determining source terms for modeling trace element release from minerals, using arsenic (As) as an example. The source term function uses laboratory-measured mineral dissolution rates to predict the time rate of change of As concentrations (mol/L s) released to water by the dissolving mineral. Application of this function to As-bearing minerals (realgar, orpiment, arsenopyrite, scorodite, pyrite, and jarosite) in air saturated water at 25 °C shows that mineralogy, grain size and pH are important factors affecting the As source term while DO concentration and temperature are relatively unimportant for conditions found in typical aquifers. The derived function shows that the source term decreases as a function of (1 − t/tL)2, where tL is the grain lifetime, due to the shrinkage of the mineral grains as they dissolve. For some models, either a constant or an instantaneous term might be used, provided that certain time constraints are met. The methods outlined in this paper are intended to help bridge the gap between laboratory measurements and field-based models. Although this paper uses As as an example, the methods are general and can be used to predict source terms for other mineral-derived trace elements to groundwater.  相似文献   

16.
We have evaluated the potential application of sulfur gas analysis to exploration for buried sulfide mineral deposits by: (1) calculating by use of equilibrium thermodynamics, the relative abundances of gases that should be given off by decomposing sulfide minerals; and (2) determining experimentally the abundances of gases that are actually given off. The calculations indicate that the gases that should be given off by decomposing sulfide minerals are (in order of decreasing abundance) H2S, COS, CS2, CH3SH, (CH3)2S2 or SO2 or S2 (depending on Eh and pH). In contrast, our experiments show that decomposing sulfide minerals evolve only CS2 and COS, in order of decreasing abundance. Pyrite produces the largest amounts of sulfur gas. Moist (rather than saturated) and non-sterile (rather than sterile) conditions enhance gas generation from pyrite, although no large difference appeared between sterile and non-sterile experiments for other sulfide minerals. These experiments indicate that the sulfur gases CS2 and COS could be useful indicators of buried metal sulfide deposits.  相似文献   

17.
Changes in the UV spectra of As(OH)3 solutions with variations in pH and temperature have recently been used to determine the temperature dependence of the pKa of the acid. In previous studies I used quantum mechanical techniques to study changes in structure and vibrational spectra as a function of pH for arsenites and thioarsenites. I previously calculated UV spectra for ``molecular' minerals, like realgar As4S4. Here I use a number of different quantum mechanical methods, both Hartree-Fock and density functional theory based, to calculate the UV spectra for both a related simple well-characterized gas-phase molecule PF3 and for As(OH)3 and As(SH)3 and their conjugate anions and some neutral and anionic oligomers in aqueous solution. For the monomeric species small numbers of water molecules have been explicitly included, in a supermolecule or microsolvation approach. I find that UV absorption energies accurate to a few tenths of an eV can be obtained both for gas- phase PF3 and for neutral arsenious acid in aqueous solution, for which the UV absorption maximum is calculated to occur around 6.5 eV, consistent with experiment. Accurate calculation of the UV energies for arsenite anions in aqueous solution is much more difficult, since basis set size and solvation effects are considerably larger than for the neutral molecules, but fairly reliable results can still be obtained. Deprotonation is found to reduce the lowest calculated UV transition energy by about half an eV. Oligomerization also reduces the lowest calculated UV energy by at least half an eV. Replacement of one or all the –OH groups by –SH groups reduces the lowest calculated UV energies by about 2 eV. UV excitation energies have been calculated for oligomeric species as large as As3E3(EH)3 and As4E6, where E = O, S, and may be useful for identifying such species in solution.  相似文献   

18.
Gold mineralisation at Zarshuran, northwestern Iran, is hosted by Precambrian carbonate and black shale formations which have been intruded by a weakly mineralised granitoid. Granitoid intrusion fractured the sedimentary rocks, thereby improving conditions for hydrothermal alteration and mineralisation. Silicification is the principal hydrothermal alteration along with decalcification and argillisation. Three hydrothermal sulphide mineral assemblages have been identified: an early assemblage of pyrrhotite, pyrite and chalcopyrite; then widespread base metal sulphides, lead-sulphosalts and zoned euhedral arsenical pyrite; and finally late network arsenical pyrite, massive and colloform arsenical pyrite, colloform sphalerite, coloradoite, and arsenic–antimony–mercury–thallium-bearing sulphides including orpiment, realgar, stibnite, getchellite, cinnabar, lorandite and a Tl-mineral, probably christite. Most of the gold at Zarshuran is detectable only by quantitative electron microprobe and bulk chemical analyses. Gold occurs mainly in arsenical pyrite and colloform sphalerite as solid solution or as nanometre-sized native gold. Metallic gold is found rarely in hydrothermal quartz and orpiment. Pure microcrystalline orpiment, carbon-rich shale, silicified shale with visible pyrite grains and arsenic minerals contain the highest concentrations of gold. In many ways Zarshuran appears to be similar to the classic Carlin-type sediment-hosted disseminated gold deposits. However, relatively high concentrations of tellurium at Zarshuran, evidenced by the occurrence of coloradoite (HgTe), imply a greater magmatic contribution in the mineralising hydrothermal solutions than is typical of Carlin-type gold deposits. Received: 13 May 1999 / Accepted: 2 February 2000  相似文献   

19.
Generation of dust particles from the Owens Lake playa creates a severe air pollution hazard in the western United States. Much of the dust produced from the dry lakebed is derived from salts formed by evaporation of saline groundwater that often contains high concentrations of dissolved arsenic (As). The objectives of this research were to study the spatial distribution of dissolved arsenic in the shallow groundwater, and to examine factors affecting arsenic solubility and speciation. Evapoconcentration, redox potential, pH, and mineral solubility were examined as factors regulating arsenic biogeochemistry. Dissolved arsenic concentrations ranged from 0.1 to 96 mg L−1 and showed a general increase from the shoreline to the center of the lakebed. Arsenic concentrations were strongly correlated to electrical conductivity (EC) and δD suggesting that evapoconcentration is an important process regulating total As concentrations. Arsenite [As(III)] was the dominant form of inorganic arsenic at Eh values less than about −170 mV while arsenate [As(V)] was predominant at higher Eh values. Organic arsenic was negligible (<0.21%) in all shallow groundwater samples. Dissolved arsenic concentrations do not appear to be strongly regulated by solid-phase reactions. Solid-phase arsenic concentrations generally ranged between 4.0 and 42.6 mg kg−1 and a maximum concentration range (20 to 40 mg kg−1) was reached as solution concentration increased up to 80 mg L−1, indicating minimal sorption and/or precipitation of arsenic. Chemical equilibrium modeling indicated that orpiment (As2S3) was the only solid phase with a positive saturation index (indicating over-saturation), but only at high arsenic and sulfide concentrations. The findings of this research are important for assessing the potential environmental impacts of elevated arsenic concentrations on dust mitigation efforts taking place at Owens Dry Lake.  相似文献   

20.
The results of X-ray induced photoelectron spectroscopy (XPS) experiments on several phases of the ternary system Tl-Sb-S are reported. The binding energies of the inner S, Sb and Tl electrons increase with increasing quantities of Sb and decreasing amounts of Tl in these compounds. This is explained by the influences of the proportions of the bonded metals on the effective electron affinity of S. The higher proportions of the more electronegative element bonded to S cause the increase of its effective electron affinity. The results for Tl2S (carlinite), Tl3SbS3, TlSbS2 (weissbergite), TlAsS2 (lorandite) and Sb2S3 (antimonite) can be interpreted in this way. The results for Tl4S3 suggest a predominantly covalent character of bonding for both Tl(III) and Tl(I), which are present in this sulfide. From comparison with Tl3SbS4 it could be supposed that Tl(III)-S bond has a more covalent character than Sb(V)-S bond. The results for Tl3SbS4 are in agreement with crystal structure data and the results of Moessbauer spectroscopy. For AsS (realgar) the binding energies of the inner electrons of As and S significantly increase, showing that the electrons in molecular orbitals are less strongly bonded to individual atoms, as compared to pure elements. The results for the amorphous TlSb5S8 (corresponding in composition to parapierrotite) suggest that in amorphous compound the Tl-S bonding is stronger and the coordination of Tl more regular than in a crystalline one.  相似文献   

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