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1.
We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.  相似文献   

2.
Photoinduced oxidation of arsenite to arsenate in the presence of goethite   总被引:2,自引:0,他引:2  
The photochemistry of an aqueous suspension of goethite in the presence of arsenite (As(III)) was investigated with X-ray absorption near edge structure (XANES) spectroscopy and solution-phase analysis. Irradiation of the arsenite/goethite under conditions where dissolved oxygen was present in solution led to the presence of arsenate (As(V)) product adsorbed on goethite and in solution. Under anoxic conditions (absence of dissolved oxygen), As(III) oxidation occurred, but the As(V) product was largely restricted to the goethite surface. In this circumstance, however, there was a significant amount of ferrous iron release, in stark contrast to the As(III) oxidation reaction in the presence of dissolved oxygen. Results suggested that in the oxic environment ferrous iron, which formed via the photoinduced oxidation of As(III) in the presence of goethite, was heterogeneously oxidized to ferric iron by dissolved oxygen. It is likely that aqueous reactive oxygen species formed during this process led to the further oxidation of As(III) in solution. Results from the current study for As(III)/goethite also were compared to results from a prior study of the photochemistry of As(III) in the presence of another iron oxyhydroxide, ferrihydrite. The comparison showed that at pH 5 and 2 h of light exposure the instantaneous rate of aqueous-phase As(V) formation in the presence of goethite (12.4 × 10(-5) M s(-1) m(-2)) was significantly faster than in the presence of ferrihydrite (6.73 × 10(-6) M s(-1) m(-2)). It was proposed that this increased rate of ferrous iron oxidation in the presence of goethite and dissolved oxygen was the primary reason for the higher As(III) oxidation rate when compared to the As(III)/ferrihydrite system. The surface area-normalized pseudo-first-order rate constant, for example, associated with the heterogeneous oxidation of Fe(II) by dissolved oxygen in the presence of goethite (1.9 × 10(-6) L s(-1) m(-2)) was experimentally determined to be considerably higher than if ferrihydrite was present (2.0 × 10(-7) L s(-1) m(-2)) at a solution pH of 5.  相似文献   

3.
Phosphate sorption on Fe- and Al-oxide minerals helps regulate the solubility and mobility of P in the environment. The objective of this study was to characterize phosphate adsorption and precipitation in single and binary systems of Fe- and Al-oxide minerals. Varying concentrations of phosphate were reacted for 42 h in aqueous suspensions containing goethite, ferrihydrite, boehmite, or noncrystalline (non-xl) Al-hydroxide, and in 1:1 (by mass) mixed-mineral suspensions of goethite/boehmite and ferrihydrite/ non-xl Al-hydroxide at pH 6 and 22 degrees C. X-ray absorption near edge structure (XANES) spectroscopy was used to detect precipitated phosphate and distinguish PO4 associated with Fe(III) versus Al(III) in mixed-mineral systems. Changes in the full width at half-maximum height (fwhm) in the white-line peak in P K-XANES spectra provided evidence for precipitation in Al-oxide single-mineral systems, but not in goethite or ferrihydrite systems. Similarly, adsorption isotherms and XANES data showed evidence for precipitation in goethite/boehmite mixtures, suggesting that mineral interactive effects on PO4 sorption were minimal. However, sorption in ferrihydrite/non-xl Al-hydroxide systems and a lack of XANES evidence for precipitation indicated that mineral interactions inhibited precipitation in these binary mixtures.  相似文献   

4.
Reduction of arsenate As(V) and As-bearing Fe (hydr)- oxides have been proposed as dominant pathways of As release within soils and aquifers. Here we examine As elution from columns loaded with ferrihydrite-coated sand presorbed with As(V) or As(III) at circumneutral pH upon Fe and/or As reduction; biotic stimulated reduction is then compared to abiotic elution. Columns were inoculated with Shewanella putrefaciens strain CN-32 or Sulfurospirillum barnesii strain SES-3, organisms capable of As (V) and Fe (III) reduction, or Bacillus benzoevorans strain HT-1, an organism capable of As(V) but not Fe(III) reduction. On the basis of equal surface coverages, As(III) elution from abiotic columns exceeded As(V) elution by a factor of 2; thus, As(III) is more readily released from ferrihydrite under the imposed reaction conditions. Biologically mediated Asreduction induced by B. benzoevorans enhances the release of total As relative to As (V) under abiotic conditions. However, under Fe reducing conditions invoked by either S. barnesii or S. putrefaciens, approximately three times more As (V or III) was retained within column solids relative to the abiotic experiments, despite appreciable decreases in surface area due to biotransformation of solid phases. Enhanced As sequestration upon ferrihydrite reduction is consistent with adsorption or incorporation of As into biotransformed solids. Our observations indicate that As retention and release from Fe (hydr)oxide(s) is controlled by complex pathways of Fe biotransformation and that reductive dissolution of As-bearing ferrihydrite can promote As sequestration rather than desorption under conditions examined here.  相似文献   

5.
Coprecipitation of arsenic with iron or aluminum occurs in natural environments and is a remediation technology used to remove this toxic metalloid from drinking water and hydrometallurgical solutions. In this work, we studied the nature, mineralogy, and reactivity toward phosphate of iron-arsenate coprecipitates formed at As(V)/Fe(III) molar ratios (R) of 0, 0.01, or 0.1 and at pH 4.0, 7.0, and 10.0 aged for 30 or 210 days at 50 degrees C and studied the desorption of arsenate. At R = 0, goethite and hematite (with ferrihydrite at pH 4.0 and 7.0) crystallized, whereas at R = 0.01, the formation of ferrihydrite increased and hematite crystallization was favored over goethite. In some samples, the morphology of hematite changed from rounded platy crystals to ellipsoids. At R = 0.1, ferrihydrite formed in all the coprecipitates and remained unchanged even after 210 days of aging. The surface area and chemical composition of the precipitates were affected by pH, R, and aging. Chemical dissolution of the samples showed that arsenate was present mainly in ferrihydrite, but at R = 0.01, it was partially incorporated into the structures of crystalline Fe oxides. The sorption of phosphate on to the coprecipitates was affected not only by the mineralogy and surface area of the samples but also by the amounts of arsenate present in the oxides. The samples formed at pH 4.0 and 7.0 and at R = 0.1 sorbed lower amounts of phosphate than the precipitates obtained at R = 0 or 0.01, despite the former having a larger surface area and showing only a presence of short-range ordered materials. This is mainly due to the fact that in the coprecipitates at R = 0.1 arsenate occupied many sorption sites, thus preventing phosphate sorption. Less than 20% of the arsenate present in the coprecipitates formed at R = 0.1 was removed by phosphate and more from the samples synthesized at pH 7.0 or 10.0 than at pH 4.0. Moreover, we found that more arsenate was desorbed by phosphate from a ferrihydrite on which arsenate was added than from an iron-arsenate coprecipitate, attributed to the partial occlusion of some arsenate anions into the framework of the coprecipitate. XPS analyses confirmed these findings.  相似文献   

6.
This study examined the potential impact of microbially mediated reduction of Fe in the Fe(III)-(hydr)oxide mineral ferrihydrite on the mobility of As in natural waters. In microcosm experiments, the obligately anaerobic bacterium Geobacter metallireducens reduced on average 10% of the Fe(III) in ferrihydrite with varying sorbed As(V) surface coverages, which resulted in deflocculation of initially micron-sized As-bearing ferrihydrite aggregates to nanometersized colloids. No reduction of As(V) to As(III) was observed in microcosm samples. Measurement of Fe and As within operationally defined particulate, colloidal, and dissolved fractions of microcosm slurry samples revealed that little Fe or As was released from ferrihydrite as dissolved species. Microbially induced deflocculation of ferrihydrite in the presence of G. metallireducens was correlated with more negative zeta potential of ferrihydrite nanoparticles suggesting that G. metallireducens mediated As mobilization through alteration of ferrihydrite surface charge. TEM analysis and solution chemistry conditions suggested formation of a magnetite surface layer through topotactic recrystallization of ferrihydrite (2LFH) driven by sorbed Fe(II). The formation of nanometer-sized As-bearing colloids through microbially mediated reduction of Fe-(hydr)oxides has the potential to increase human As exposure by enhancing As mobility in natural waters and hindering As removal during subsequent drinking water treatment.  相似文献   

7.
The modes of As(III) sorption onto two-line ferrihydrite (Fh), hematite (Hm), goethite (Gt), and lepidocrocite (Lp) have been investigated under anoxic condition using X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure spectroscopy (XANES) indicates that the absence of oxygen minimized As(III) oxidation due to Fenton reactions. Extended X-ray absorption fine structure spectroscopy (EXAFS) indicates thatAs(III)forms similar inner-sphere surface complexes on two-line ferrihydrite and hematite that differ from those formed on goethite and lepidocrocite. At high surface coverage, the dominant complex types on Fh and Hm are bidentate mononuclear edge-sharing (2E) and bidentate binuclear corner-sharing (2C), with As-Fe distances of 2.90 +/- 0.05 and 3.35 +/- 0.05 A, respectively. The same surface complexes are observed for ferrihydrite at low surface coverage. In contrast, As(III) forms dominantly bidentate binuclear corner-sharing (2C) sorption complexes on Gt and Lp [d(As-Fe) = 3.3-3.4 A], with a minor amount of monodentate mononuclear corner-sharing (1V) complexes [d(As-Fe) = 3.5-3.6 A]. Bidentate mononuclear edge-sharing (2E) complexes are virtually absent in Gt and Lp at the high surface coverages that were investigated in the present study. These results are compared with available literature data and discussed in terms of the reactivity of iron(III) (oxyhydr)oxide surface sites.  相似文献   

8.
Microbial reduction of structural Fe(III) in nontronite (NAu-2) was studied in batch cultures under non-growth condition using Shewanella putrefaciens strain CN32. The rate and extent of structural Fe(III) reduction was examined as a function of electron acceptor [Fe(III)] and bacterial concentration. Fe(ll) sorption onto NAu-2 and CN32 surfaces was independently measured and described by the Langmuir expression with the affinity constant (log K) of 3.21 and 3.30 for NAu-2 and bacteria, respectively. The Fe(II) sorption capacity of NAu-2 decreased with increasing NAu-2 concentration, suggesting a particle aggregation effect. An empirical equation for maximum sorption capacity was derived from the sorption isotherms as a function of NAu-2 concentration. The total reactive surface concentration of Fe(III) was proposed as a proxy for the "effective" or bioaccessible Fe(III) concentration. The initial rate of microbial reduction was first-order with respect to the effective Fe-(III) concentration. A kinetic biogeochemical model was assembled that incorporated the first-order rate expression with respect to the effective Fe(III) concentration, Fe(II) sorption to cell and NAu-2 surfaces, and the empirical equation for maximum sorption capacity. The model successfully described the experimental results with variable NAu-2 concentration. The initial rate of microbial reduction of Fe(III) in NAu-2 increased with increasing cell concentration from 10(2) up to approximately 10(8) cells/mL, and then leveled off with further increase. A saturation-type kinetics with respect to cell concentration was required to describe microbial reduction of Fe(III) in NAu-2 as a function of cell concentration. Overall, our results indicated that the kinetics of microbial reduction of Fe(III) in NAu-2 can be modeled at variable concentration of key variables (clay and cell concentration) by considering the surface saturation, Fe(II) production, and its sorption to NAu-2 and cell surfaces.  相似文献   

9.
The sorption of uranium on mineral surfaces can significantly influence the fate and transport of uranium contamination in soils and groundwater. The rates of uranium adsorption and desorption on a synthetic goethite have been evaluated in batch experiments conducted at constant pH of 6 and ionic strength of 0.1 M. Adsorption and desorption reactions following the perturbation of initial states were complete within minutes to hours. Surface-solution exchange rates as measured by an isotope exchange method occur on an even shorter time scale. Although the uranium desorption rate was unaffected by the aging of uranium-goethite suspensions, the aging process appears to remove a portion of adsorbed uranium from a readily exchangeable pool. The distinction between sorption control and precipitation control of the dissolved uranium concentration was also investigated. In heterogeneous nucleation experiments, the dissolved uranium concentration was ultimately controlled by the solubility of a precipitated uranyl oxide hydrate. The X-ray diffraction pattern of the precipitate is characteristic of the mineral schoepite. Precipitation is kinetically hindered at low degrees of supersaturation. In one experiment, metastable sorption controlled dissolved uranium concentrations in excess of the solubility limit for more than 30 d.  相似文献   

10.
The risk posed from incidental ingestion to humans of arsenic-contaminated soil may depend on sorption of arsenate (As(V)) to oxide surfaces in soil. Arsenate sorbed to ferrihydrite, a model soil mineral, was used to simulate possible effects on ingestion of soil contaminated with As-(V) sorbed to Fe oxide surfaces. Arsenate sorbed to ferrihydrite was placed in a simulated gastrointestinal tract (in vitro) to ascertain the bioaccessibility of As(V) and changes in As(V) surface speciation caused by the gastrointestinal system. The speciation of As was determined using extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge spectroscopy (XANES). The As(V) adsorption maximum was found to be 93 mmol kg(-1). The bioaccessible As(V) ranged from 0 to 5%, and surface speciation was determined to be binuclear bidentate with no changes in speciation observed post in vitro. Arsenate concentration in the intestine was not constant and varied from 0.001 to 0.53 mM for the 177 mmol kg(-1) As(V) treated sample. These results suggest that the bioaccessibility of As(V) is related to the As(V) concentration, the As(V) adsorption maximum, and that multiple measurements of dissolved As(V) in the intestinal phase may be needed to calculate the bioaccessibility of As(V) adsorbed to ferrihydrite.  相似文献   

11.
Antimony is an element of growing interest for a variety of industrial applications, even though Sb compounds are classified as priority pollutants by the Environmental Protection Agency of the United States. Iron (Fe) hydroxides appear to be important sorbents for Sb in soils and sediments, but mineral surfaces can also catalyze oxidation processes and may thus mobilize Sb. The aim of this study was to investigate whether goethite immobilizes Sb by sorption or whether Sb(III) adsorbed on goethite is oxidized and then released. The sorption of both Sb(III) and Sb(V) on goethite was studied in 0.01 and 0.1 M KClO4 M solutions as a function of pH and Sb concentration. To monitor oxidation processes Sb species were measured in solution and in the solid phase. The results show that both Sb(III) and Sb(V) form inner-sphere surface complexes at the goethite surface. Antimony(III) strongly adsorbs on goethite over a wide pH range (3-12), whereas maximum Sb(V) adsorption is found below pH 7. At higher ionic strength, the desorption of Sb(V) is shifted to lower pH values, most likely due to the formation of ion pairs KSb(OH)6 degrees. The sorption data of Sb(V) can be fitted by the modified triple-layer surface complexation model. Within 7 days, Sb(III) adsorbed on goethite is partly oxidized at pH 3, 5.9 and 9.7. The weak pH-dependence of the rate coefficients suggests that adsorbed Sb(III) is oxidized by 02 and that the coordination of Sb(III) to the surface increases the electron density of the Sb atom, which enhances the oxidation process. At pH values below pH 7, the oxidation of Sb(III) did not mobilize Sb within 35 days, while 30% of adsorbed Sb(III) was released into the solution at pH 9.9 within the same time. The adsorption of Sb(III) on Fe hydroxides over a wide pH range may be a major pathway for the oxidation and release of Sb(V).  相似文献   

12.
Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5-6, whereas, above pH 7-8, As(II) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate that, under most of the chemical conditions investigated in this study, reduction of As(V) in the presence of HFO or goethite would have only minor effects on or even decrease its mobility in the environment at near-neutral pH conditions. As(V) and As(III) sorption isotherms indicate similar surface site densities on the three oxides. Intrinsic surface complexation constants for As(V) are higher for goethite than HFO, whereas As(III) binding is similar for both of these oxides and also for magnetite. However, decrease in specific surface area and hence sorption site density that accompanies transformation of amorphous iron oxides to more crystalline phases could increase arsenic mobility.  相似文献   

13.
Shewanella putrefaciens, a heterotrophic member of the gamma-proteobacteria is capable of respiring anaerobically on Fe(III) as the sole terminal electron acceptor (TEA). Recent genetic and biochemical studies have indicated that anaerobic Fe(III) respiration by S. putrefaciens requires outer-membrane targeted secretion of respiration-linked Fe(III) reductases. Thus, the availability of Fe(III) to S. putrefaciens may be governed by equilibrium chemical speciation both in the solution phase and at the bacterial cell-aqueous or cell-mineral interface. In the present study, effects of Fe(III) speciation on rates of bacterial Fe(III) reduction have been systematically examined by cultivating S. putrefaciens anaerobically on a suite of Fe(III)-organic complexes as the sole TEA. The suite of Fe(III)-organic complexes spans the range of stability constants normally encountered in natural water systems and includes Fe(III) complexed to citrate, 5-sulfosalicylate, NTA, salicylate, tiron, and EDTA. Rates of bacterial Fe(III) reduction in the presence of dissolved chelating agents correlate with the thermodynamic stability constants of the Fe(III)-organic complexes, implying that chemical speciation governs Fe(III) bioavailability. Equilibrium Fe(III) sorption experiments measured the reversible coordination of Fe(III) with S. putrefaciens as a function of cell/Fe(III) concentration, time, and activity of competing chelating agents. Results show that S. putrefaciens readily sorbs dissolved Fe(III) but that adsorption is restricted by the presence of strong Fe(III)-chelating agents. Our results indicate that dissimilatory Fe(III) reduction by S. putrefaciens is controlled by equilibrium competition for Fe(III) between dissolved organic ligands and strongly sorbing functional groups on the cell surface.  相似文献   

14.
Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for  相似文献   

15.
Adsorption-desorption of arsenic is the primary factor that impacts the bioavailability and mobility of arsenic in soils. To examine the characteristics of arsenate [As(V)] adsorption-desorption, kinetic batch experiments were carried out on three soils having different properties, followed by arsenic release using successive dilutions. Adsorption of As(V) was highly nonlinear, with a Freundlich reaction order N much less than 1 for Olivier loam, Sharkey clay, and Windsor sand. Adsorption of arsenate by all soils was strongly kinetic, where the rate of As(V) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing reaction time. Freundlich distribution coefficients and Langmuir adsorption maxima exhibited continued increase with reaction time for all soils. Desorption of As(V) was hysteretic in nature and is an indication of lack of equilibrium retention and/or irreversible or slowly reversible processes. A sequential extraction procedure provided evidence that a significant amount of As(V) was irreversibly adsorbed on all soils. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption successfully described the adsorption kinetics of As(V) for Olivier loam and Windsor sand. The model was also capable of predicting As(V) desorption kinetics for both soils. However, for Sharkey clay, which exhibited strongest affinity for arsenic, an additional irreversible reaction phase was required to predict As(V) desorption or release with time.  相似文献   

16.
For the long-term performance assessment of nuclear waste repositories, knowledge about the interactions of actinide ions with mineral surfaces such as iron oxides is imperative. The mobility of released radionuclides is strongly dependent on the sorption/desorption processes at these surfaces and on their incorporation into the mineral structure. In this study the interaction of Am(III) with 6-line-ferrihydrite (6LFh) was investigated by EXAFS spectroscopy. At low pH values (pH 5.5), as well at higher pH values (pH 8.0), Am(III) sorbs as a bidentate corner-sharing species onto the surface. Investigations of the interaction of Am(III) with Fh coated silica colloids prove the sorption onto the iron coating and not onto the silica substrate. Hence, the presence of Fh, even as sediment coating, is the dominant sorption surface. Upon heating, Fh is transformed into goethite and hematite as shown by TEM and IR measurements. The results of the fit to the EXAFS data indicate the release of sorbed Am(III) at pH 5.5 during the transformation and likely a partial incorporation of Am into the Fh transformation products at pH 8.0.  相似文献   

17.
Iron cycling and the associated changes in solid phase have dramatic implications for trace element mobility and bioavailability. Here we explore the formation of secondary iron phases during microbially mediated reductive dissolution of ferrihydrite-coated sand under dynamic flow conditions. An initial period (10 d) of rapid reduction, indicated by consumption of lactate and production of acetate and Fe-(II) to the pore water in association with a darkening of the column material, is followed by much lower rate of reduction to the termination of the experiment after 48 d. Although some Fe (<25%) is lost to the effluent pore water, the majority remains within the column as ferrihydrite (20-70%) and the secondary mineral phases magnetite (0-70%) and goethite (0-25%). Ferrihydrite converts to goethite in the influent end of the column where dissolved Fe(II) concentrations are low and converts to magnetite toward the effluent end where Fe(III) concentrations are elevated. A decline in the rate of Fe(II) production occurs concurrent with the formation of goethite and magnetite; at the termination of the experiment, the rate of reduction is <5% the initial rate. Despite the dramatic decrease in the rate of reduction, greater than 80% of the residual Fe remains in the ferric state. These results highlight the importance of coupled flow and water chemistry in controlling the rate and solid-phase products of iron (hydr)oxide reduction.  相似文献   

18.
Arsenic sorption onto maghemite potentially contributes to arsenic retention in magnetite-based arsenic removal processes because maghemite is the most common oxidation product of magnetite and may form a coating on magnetite surfaces. Such a sorption reaction could also favor arsenic immobilization at redox boundaries in groundwaters. The nature of arsenic adsorption complexes on maghemite particles, at near-neutral pH under anoxic conditions, was investigated using X-ray absorption fine structure (XAFS) spectroscopy at the As K-edge. X-ray absorption near edge structure spectra indicate that As(III) does notoxidize after 24 h in any of the sorption experiments, as already observed in previous studies of As(III) sorption on ferric (oxyhydr)oxides under anoxic conditions. The absence of oxygen in our sorption experiments also limited Fenton oxidation of As(III). Extended XAFS (EXAFS) results indicate that both As(III) and As(V) form inner-sphere complexes on the surface of maghemite, under high surface coverage conditions (approximately 0.6 to 1.0 monolayer), with distinctly different sorption complexes for As(III) and As(V). For As(V), the EXAFS-derived As-Fe distance (approximately 3.35 +/- 0.03 A) indicates the predominance of single binuclear bidentate double-corner complexes (2C). For As(III), the distribution of the As-Fe distance suggests a coexistence of various types of surface complexes characterized by As-Fe distances of approximately 2.90 (+/-0.03) A and approximately 3.45 (+/-0.03) A. This distribution can be interpreted as being due to a dominant contribution from bidentate binuclear double-corner complexes (2C), with additional contributions from bidentate mononuclear edge-sharing (2E) complexes and monodentate mononuclear corner-sharing complexes (1V). The present results yield useful constraints on As(V) and As(III) adsorption on high surface-area powdered maghemite, which may help in modeling the behavior of arsenic at the maghemite-water interface.  相似文献   

19.
Owing to its high surface area and intrinsic reactivity, ferrihydrite serves as a dominant sink for numerous metals and nutrients in surface environments and is a potentially important terminal electron acceptor for microbial respiration. Introduction of Fe (II), by reductive dissolution of Fe(III) minerals, for example, converts ferrihydrite to Fe phases varying in their retention and reducing capacity. While Fe(II) concentration is the master variable dictating secondary mineralization pathways of ferrihydrite, here we reveal thatthe kinetics of conversion and ultimate mineral assemblage are a function of competing mineralization pathways influenced by pH and stabilizing ligands. Reaction of Fe(II) with ferrihydrite results in the precipitation of goethite, lepidocrocite, and magnetite. The three phases vary in their precipitation extent, rate, and residence time, all of which are primarily a function of Fe(II) concentration and ligand type (Cl, SO4, CO3). While lepidocrocite and goethite precipitate over a large Fe(II) concentration range, magnetite accumulation is only observed at surface loadings greater than 1.0 mmol Fe(II)/g ferrihydrite (in the absence of bicarbonate). Precipitation of magnetite induces the dissolution of lepidocrocite (presence of Cl) or goethite (presence of SO4), allowing for Fe(III)-dependent crystal growth. The rate of magnetite precipitation is a function of the relative proportions of goethite to lepidocrocite; the lower solubility of the former Fe (hydr)oxide slows magnetite precipitation. A one unit pH deviation from 7, however, either impedes (pH 6) or enhances (pH 8) magnetite precipitation. In the absence of magnetite nucleation, lepidocrocite and goethite continue to precipitate at the expense of ferrihydrite with near complete conversion within hours, the relative proportions of the two hydroxides dependent upon the ligand present. Goethite also continues to precipitate at the expense of lepidocrocite in the absence of chloride. In fact, the rate and extent of both goethite and magnetite precipitation are influenced by conditions conducive to the production and stability of lepidocrocite. Thus, predicting the secondary mineralization of ferrihydrite, a process having sweeping influences on contaminant/nutrient dynamics, will need to take into consideration kinetic restraints and transient precursor phases (e.g., lepidocrocite) that influence ensuing reaction pathways.  相似文献   

20.
2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic. As ferrihydrite is unstable under oxic conditions and can undergo dissolution and subsequent transformation to hematite and goethite over time, the impact of transformation on the long-term stability of EOC within tailings is of importance from an environmental standpoint. Here, studies were undertaken to assess the rate of 2-line ferrihydrite transformation at varying As/Fe ratios (0.500-0.010) to simulate tailings conditions at the Deilmann Tailings Management Facility of Cameco Corporation, Canada. Kinetics were evaluated under relevant physical (~1 °C) and chemical conditions (pH ~10). As the As/Fe ratio increased from 0.010 to 0.018, the rate of ferrihydrite transformation decreased by 2 orders of magnitude. No transformation of ferrihydrite was observed at higher As/Fe ratios (0.050, 0.100, and 0.500). Arsenic was found to retard ferrihydrite dissolution and transformation as well as goethite formation.  相似文献   

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