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1.
Neutron irradiation and post-irradiation annealing under oxidising and reducing conditions have been used to investigate H incorporation in, and the optical properties of, reduced (TiO2−x ) rutile. Optical absorption in rutile is mainly due to a Ti3+ Ti4+ intervalence charge transfer effect. The main mechanism for H incorporation in rutile involves interstitial H not coupled to other defects, which has important implications for the rate of H diffusion, and possibly also on the electrical properties of rutile. Additional minor OH absorption bands in IR spectra indicate that a small amount of interstitial H is coupled to defects such as Ti3+ on the main octahedral site, and indicates that more than one H incorporation mechanism may operate. Concentration of oxygen vacancies has a controlling influence on the H affinity of rutile.  相似文献   

2.
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   

3.
Arsenic in groundwater is a serious environmental problem. The contamination of groundwater with arsenic has been of utmost concern worldwide. Steel slag is a solid waste generated from steel production. Although steel slags have been used for arsenic removal from water, this process has not been systematically or integratively researched. In this study, the arsenic removal capacity and mechanism were investigated for carbon steel slag, stainless steel slag and Fe-modified stainless steel slag based on an in-depth study. The study also evaluated the potential utilization of different steel slag for regeneration. The maximum adsorption of arsenic on carbon steel slag, stainless steel slag and Fe-modified stainless steel slag was 12.20, 3.17 and 12.82 mg g?1 at 25 °C, respectively. The modification of stainless steel slag by FeC13 can generate more pore structures and larger surface areas, and 300 °C treatment produces the best regeneration efficiency. The ΔG values were negative for all of the steel slags, indicating the spontaneous nature of the adsorption process. The solution pH was a critical parameter for the removal of arsenic for steel slags. Under highly alkaline solution conditions, the mechanism of arsenic removal by carbon steel slag and stainless steel slag can be attributed to chemisorption, including chemical precipitation and coordination reactions, and under weakly alkaline solution conditions, electrostatic interaction and specific adsorption are the arsenic removal mechanisms by Fe-modified stainless steel slag. Regeneration of the Fe-modified stainless steel slag was better achieved than that of the other steel slags in the application of high-temperature treatment.  相似文献   

4.
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   

5.
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   

6.
High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)3(PO4)2.8H2O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As during the second month is due to its reduction to the more weakly adsorbed As(III) which cannot compete against carbonate ions for sorption onto ferrihydrite. The model was also successfully applied to recent experimental results on the release of arsenic from Bengal delta sediments.  相似文献   

7.
The FeS2–Ag–Pt–As system was studied using hydrothermal thermogradient synthesis (with internal sampling) of pyrite crystals at a temperature of 500°C and pressure of 1 kbar in ammonium chloridebased solutions. The modes of occurrence of precious metals (PM) were determined using atomic absorption spectrometry (AAS) in its version of statistical selections of analytical data on single crystals (SSADSC), electron microprobe analysis (EMPA), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The concentration of Pt in its structural mode in pyrite is as high as 10–11 ppm and is practically not correlated with the As concentration. The dualistic distribution coefficient of Pt between pyrite and hydrothermal solution is 21 ± 7 for the structural mode and 210 ± 80 for the surface-related mode of this element. No inclusions of either any Pt-bearing minerals or Pt itself was detected. Platinum is an element highly compatible with hydrothermal pyrite and is different in this sense from gold, and pyrite is underestimated as a potential concentrator of platinumgroup elements (PGE). The distribution of Ag in pyrite is highly heterogeneous. The likely reason for this is that the Ag solid solution cannot be quenched, and hence, the Ag concentrations broadly vary and are very unsystematically distributed in natural pyrite crystals. Assuming this hypothesis, the limit for Ag accommodation in FeS2 can be estimated using SSADSC at 0.09 ± 0.06 wt % under the experimental parameters, and the distribution coefficient of the structural Ag mode is thereby evaluated at 1400 ± 700. When crystallizing together with FeS2 proustite (Ag3AsS3) near its melting point, forms mixtures with dervillite (Ag2AsS2), in which Ag deficit is counterbalanced by excess divalent As. The limit of As incorporation into pyrite under these conditions is ≤0.1 wt %. SEM-EDS and XPS data indicate that the surface phases are of three types. In the course of crystal growth, practically two-dimensional nonautonomous phases (NP) are aggregated into submicroscopic and micrometer-sized crystalline bodies (mesocrystals) that largely inherit their unusual minor-element composition from NP and are enriched in Ag, Pt, As, and other minor elements. NP and mesocrystals are enriched in Al, which was transferred into them from the Al-bearing Ti alloy of the reaction containers. Silver occur in the volume of the crystals and on their surface as monovalent silver sulfide. Arsenic was detected mostly in the form of di- and trivalent arsenic sulfides. Pentavalent arsenic oxide was identified only on the surface of the crystals and can be easily eliminated by ion milling.  相似文献   

8.
Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO3− and SO42− are relatively low, while the concentrations of DOC, NH4+, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe2O3, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.  相似文献   

9.
《Applied Geochemistry》2005,20(2):275-293
The recently developed geochemical modelling code, SULFIDOX, has been applied to simulate weathering of a waste rock dump at the Aitik mine site, Sweden. SULFIDOX models the key chemical and physical processes in the dump temporally and spatially (in two dimensions). The following processes are represented: gas and heat transport; water infiltration; aqueous speciation; mineral dissolution/oxidation and precipitation.Field observations at the site suggest that sulphide oxidation rates within the dump are variable. Although the major part of the dump is oxidising slowly, there are pockets of more highly oxidising material, particularly toward the dump edges. Using SULFIDOX, several models of the dump were investigated: (i) a dump wholly comprised of slowly oxidising material (representing a case where water flow paths are such that no rapidly oxidising regions are accessed); (ii) a dump wholly comprised of the more rapidly oxidising material (representing the opposite (and probably unlikely) extreme, where water flows only through rapidly oxidising regions in the dump); and (iii) a dump comprising a mixture of both slowly and more rapidly oxidising material, that more closely represents the mix of material in the dump.All the models studied gave O2 depth profiles consistent with those observed in probe holes at the site, and confirmed that only a minimal amount of heat production would be expected in the dump due to the role of exothermic sulphide oxidation reactions. The models suggested that a medium-term steady-state, with respect to effluent chemistry, would be achieved after 3–4 years. Based on sulphide consumption rates during this steady-state period, the time periods required to consume all the sulphide in the dump range from a few hundred to many thousands of years. Using the mixed model, and based on a mixture containing 86% slowly and 14% rapidly oxidising material, the calculated effluent chemistry was in good agreement with the observed effluent chemistry. Improvements with respect to the K concentrations were possible by including precipitation of a K-bearing secondary mineral such a K-jarosite in the model. Results from the more rapidly oxidising model suggested that gypsum precipitation might be expected in those regions of the dump containing this material.In summary, the SULFIDOX modelling code has been used successfully to reproduce observed data for the Aitik waste-rock dump. Using SULFIDOX, valuable insight was gained in relation to the temporal and spatial evolution of the dump.  相似文献   

10.
Environmental remediation technologies that involve the use of sulfate-reducing bacteria constitute a feasible alternative to the remediation of sites polluted with heavy metals and metalloids. The present study evaluates hydrogen sulfide production and arsenic removal by two microbial consortia (C1 and C2) in batch systems exposed to different arsenic concentrations and oxidation states. We identify the following three consecutive stages of arsenate removal: (1) hydrogen sulfide production/accumulation, (2) arsenate reduction to arsenite associated with the incomplete oxidation of hydrogen sulfide to elemental sulfur and (3) arsenic polysulfide precipitation as the main arsenic removal mechanism from aqueous solution. Kinetic parameters are determined in regard to the arsenic oxidation state through the fit of hydrogen sulfide production. The r max reached by C1 and C2 is increased seven- or eightfold when 250 mM As[+5] was used instead 250 mM As[+3]. Arsenic removal by extracellular precipitation of arsenic polysulfides associated with elemental sulfur precipitation detected through scanning electron microscopy coupled to energy-dispersive X-ray spectroscopy (SEM–EDS) can explain the exceptional value of r max observed at 250 mM during As[+5] exposition.  相似文献   

11.
To predict the long-term behavior of arsenic(As) in soil profiles,the solid-solution partitioning of As was studied in four paddy soil profiles obtained from agricultural areas in Chengdu Plain,Southwest China.Paddy soil profile samples were collected and soil solution samples were extracted.Total As contents in soil solution and soil solid were analyzed,along with the soil solid phase properties.The As in soil solution was significantly higher in the upper layer(0—20 cm) and had a definite tendency to decrease towards 40 cm regardless of the sampling locations.When the concentration of arsenic in soil solution decreased,its content in solid phase increased.Field-based partition coefficient(K_d) for As was determined by calculating the ratio of the amount of As in the soil solid phase to the As concentration in the soil solution.K_d values varied widely in vertical samples and correlated well with soil pH,total organic carbon(TOC) and total As. The results of this study would be useful for evaluating the accumulation trends of arsenic in soil profiles and in improving the management of the agricultural soils.  相似文献   

12.
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   

13.
A low-salinity, mixed aqueous-carbonic fluid is common to all Archæan lode-gold deposits throughout the range of mineralising conditions from sub-greenschist to lower-granulite facies temperatures. Alteration assemblages and fluid-inclusion data give constraints on the fluid composition. Fluid XCO 2 is 0.1–0.3 in typical greenschist-facies (mesothermal) deposits. At higher temperatures, the assemblages are consistent with formation from a fluid of similar composition, but slightly higher or lower XCO 2 cannot be ruled out, and fluid-inclusion data indicate that CH4 may be an important component in ore fluids at these temperatures. Fluid pH is neutral or weakly alkaline at all conditions. A range of relative oxidation states of four orders of magnitude fO 2 is indicated at any temperature, with deposits more oxidising relative to QFM at lower temperature. Sulphur contents of the fluids vary from ≈ 10 to 10?3.5m∑S, with a trend towards lower sulphur contents at lower temperatures. The relative concentrations of major cations in solution are similar at all conditions with Na ? K ≥ Ca, although Ca may be less abundant at low temperatures. The broad similarities in ore-fluid composition at all temperatures give support to ‘crustal-continuum’ models, in which Archæan lode-gold mineralisation involved either a single fluid moving through the middle and upper crust, or derivation of ore fluids by similar processes at different crustal levels. Many of the compositional differences between high- and lowtemperature ore-fluids may be attributed to evolution of deep-sourced hydrothermal solutions as they rise along structurally-controlled conduits. The constancy of major ore-fluid component concentration (e.g. CO2, Cl, ± K) suggests fluid-buffering and high fluid-rock ratios along fluid pathways. Fluid-buffered conditions can also explain the ore-fluid fO 2-temperature relations; with equilibria between oxidised and reduced aqueous carbon or sulphur species controlling the oxidation state. In contrast, the concentrations of components present in lesser abundance in Archæan gold ore-fluids (e.g. S, Ca, H+) were probably controlled either by saturation of one or more mineral phases brought on by decreasing temperature, or were rock-buffered through fluid-rock reactions. Extrapolation to high temperatures of the K, Na and Ca contents of the gold-bearing fluids indicates that their composition is consistent with derivation from, or final equilibration with, rocks of intermediate-granitic composition, thus giving support to isotopic and geological arguments for ore-fluid source regions external to the greenstone belts. The fluid oxidation states are characteristic of a wide range of potential source rocks, including mantle-derived igneous rocks, calc-alkaline granitoids and magmas, and seaflooraltered metabasalts. Strongly oxidised magmatic sources or unusually oxidising source processes (e.g. CO2-streaming during granulitisation of the lower crust) are therefore not required in the genesis of Arch?an lode-gold deposits.  相似文献   

14.
The efficiency of Australian laterites in arsenic adsorption has been examined using three laterite samples collected from different locations in South Australia. The characteristics such as electrical conductivity, pH, mineral compositions, and isoelectric point of laterite samples have been measured. The laterite samples are mainly composed of iron and aluminum oxides, and rutile (TiO2). Two batch experiments have been performed to compare the efficiencies of different laterites to remove AS (III) from water at two different doses, and to examine whether pH influences arsenic adsorption. For 50 mg/l arsenic solution, at doses 1,000 g (laterite)/l (arsenic solution) and 200 g/l, the laterites removed more than 97% and 87–97%, respectively. At the dose of 200 g/l, adsorption capacity has been found to be 200–243 mg/kg. Out of the laterite samples from three localities, the Kangaroo Island laterite performed the best. This is probably related to its high content of gibbsite. It has been found that arsenic adsorption by laterite is not significantly affected at the examined pH ranges of 4.7–10.0.  相似文献   

15.
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   

16.
The mobility and availability of arsenite, As(III), in anoxic environments is largely controlled by adsorption onto iron sulfides and/or precipitation of arsenic in solid phases. The interaction of As(III) with synthetic mackinawite (FeSm) in pH 5 and 9 suspensions was investigated using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), STEM elemental mapping, high resolution TEM, and X-ray photoelectron spectroscopy (XPS). At pH 5, arsenic sulfide phases precipitate among the FeSm particles as discrete particles that are an amorphous hydrous phase of arsenic sulfide. The oxidation state of As in the surface layers of the arsenic sulfide precipitates is ‘realgar-like’ based on XPS results showing that > 75% of the As 3d peak area is due to As with oxidation states between 0 and 2+. Discrete, arsenic sulfide precipitates are absent at pH 9, but elemental mapping in STEM-EDX mode shows that arsenic is uniformly distributed on the FeSm, suggesting that uptake is caused by the sorption of As(III) oxyanions and/or the precipitation of highly dispersed arsenic sulfides on FeSm. XPS also revealed that the FeSm that equilibrated without As(III) has a more oxidized surface composition than the sample at pH 9, as indicated by the higher concentration of O ( three times greater than that at pH 9) and the larger fraction of Fe(III) species making up the total Fe (2p3/2) peak. These findings provide a better understanding of redox processes and phase transitions upon As(III) adsorption on iron sulfide substrates.  相似文献   

17.
Reductive dissolution of arsenic-bearing ferrihydrite   总被引：2，自引：0，他引：2  
Ferrihydrites were prepared by coprecipitation (COP) or adsorption (ADS) of arsenate, and the products were characterized using solid-state methods. In addition, the kinetics of reductive dissolution by hydroquinone of these well-characterized materials were quantified. Characterization and magnetism results indicate that the 10 wt% As COP ferrihydrite is less crystalline and possibly has smaller crystallite size than the other ferrihydrites, which all have similar crystallinity and particle size. The results from reductive dissolution experiments show similar reaction rates, reaction mechanism, and activation energy for ferrihydrite precipitated with or without added arsenate. However, a marked decrease in reactivity was observed for 10 wt% As ADS ferrihydrite. The decrease is not attributed to differences in activation energy but rather the preferential blocking of active sites on the ferrihydrite surface. Results demonstrate that arsenic may be released by the reductive dissolution of arsenic-bearing ferrihydrite regardless of whether the arsenic is coprecipitated with or adsorbed onto the ferrihydrite. However, under these reaction conditions, release from materials with adsorbed arsenate greatly exceeds that from materials with coprecipitated arsenate. In fact, a considerable amount of arsenic was released from the 10 wt% ADS ferrihydrite before reductive dissolution was initiated. Therefore, the characterization of arsenate-bearing iron oxide materials to determine the method of arsenate incorporation into structures—perhaps by quantification of Fe-Fe coordination with EXAFS spectroscopy—may lead to improved predictions of the large-scale release of arsenic within aquifer systems under reducing conditions.  相似文献   

18.
The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.  相似文献   

19.
A laboratory investigation was carried out to examine the mechanism of arsenic (As) mobilization under flooded conditions (24 and 240 h) in 18 alluvial soils of Punjab, North–West India. Total dissolved As increased from a range of 3–16 μg L?1 (mean 9 μg L?1) to a range of 33–1,761 μg L?1 (mean 392 μg L?1) with the increase in flooding period from 24 to 240 h. The amount of As mobilization varied depending upon redox potential (pe) created by flooding conditions. After 24 h of flooded conditions, pe of soil water suspension ranged from ?1.75 to 0.77 (mean ?0.24). Increasing the flooding period to 240 h, pe of soil water suspension decreased in the range of ?4.49 to ?2.74 (mean ?3.29). Pourbaix diagram identified arsenate (HAsO4 2?) as predominant species in most of the alluvial soil–water suspensions under oxidized conditions, after 24 h of equilibration period, which ultimately transformed to arsenite (H3AsO3 0) after 240 h of anaerobic condition due to more reduced status. The solid phase identified was orpiment (As2S3). Identification of iron and manganese species in alluvial soil water suspension by Pourbaix diagram indicated decline in both soluble Fe2+ and SO4 2? concentration due to the formation of iron sulfide mineral phase after 240 h under anaerobic conditions. In these soils, decline in soluble Fe was also due to the precipitation of vivianite [Fe3(PO4)2·8H2O]. Elevated arsenic content and low pe value were measured in aquifers located in paddy growing fields comparative to aquifers of other sites. Large degree of variability in As concentrations was recorded in aquifers located at same sites. Thus, it is better to analyze each aquifer for their As content rather than to depends on the prediction on As content of neighbouring wells. The present investigation elucidates that flood irrigation practices in Punjab for growing paddy crop could induce the geochemical conditions favorable to mobilize arsenic from surface soils which could eventually elevate its content in the underlying shallow aquifers. Water abstracted from these aquifers by hand pumps or tube wells for drinking purposes could create hazards for local population due to loading with arsenic concentration above the safe limits. Thus, to avoid further contamination of shallow aquifers with arsenic, it is advisable to shift the flooded rice cultivation to other upland crops having lesser water requirement.  相似文献   

20.
Arsenic contaminated waters are not uncommon; indeed from naturally occurring contaminated waters through to those that are a direct consequence of human activities such as mining, all are affecting the quality of water resources worldwide. The ever increasing demands on natural water resources mean that the effective control of this toxic contaminant is paramount and this is reflected in the ever increasing global legislation.There are currently three mechanisms by which arsenic is commercially treated in effluents. These are physical separation processes such as reverse osmosis, precipitation/adsorption processes, some of which are bacterially assisted, and a whole variety of ion exchange processes, again with some bacterial enhancement. The choice of treatment is not only driven by cost but by the chemistry of the water and the water quality standard to be met.In this study a very high arsenic enriched groundwater, containing in excess of 25,000 µg/L arsenic, was treated by a typical treatment method through a continuously operated pilot plant. In the treatment, iron III salts were added to the influent in order to form precipitates with the arsenic and to form an adsorptive surface that would assist with treatment of the enriched water. This addition of iron III salts for the removal of arsenic is common practice in the water treatment industry as the resulting iron III arsenates are highly stable.However, results from the pilot plant show that the process was further enhanced by the addition of small amounts of hydrogen peroxide. Hydrogen peroxide is a powerful oxidising reagent and assists in ensuring the complete conversion of any arsenic III to arsenic V that was then effectively removed in the pilot plant. After treatment residual arsenic levels of 10 µg/L were obtained compared to 68 µg/L without oxidation reagent addition.  相似文献   

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