Complexation and precipitation reactions in the ternary As(V)–Fe(III)–OM (organic matter) system (original) (raw)
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XAS Study of Iron and Arsenic Speciation during Fe(II) Oxidation in the Presence of As(III)
Environmental Science & Technology, 2005
The speciation of As and Fe was studied during the oxidation of Fe(II)-As(III) solutions by combining XAS analysis at both the Fe and As K-edges. Fe(II) and As(III) were first hydrolyzed to pH 7 under anoxic conditions; the precipitate was then allowed to oxidize in ambient air for 33 h under vigorous stirring. EXAFS analysis at the As K-edge shows clear evidence of formation of innersphere complexes between As(III) and Fe(II), i.e., before any oxidation. Inner-sphere complexes were also observed when Fe became sufficiently oxidized, in the form of edgesharing and double-corner linkages between As III O 3 pyramids and Fe III O 6 octahedra. XAS analyses at the Fe K-edge reveal that the presence of As(III) in the solution limits the polymerization of Fe(II) and the formation of green rust and inhibits the formation of goethite and lepidocrocite. Indeed, As(III) accelerates the Fe(II) oxidation kinetics and leads to the formation of nanosized Fe-As subunits of amorphous aggregates. These observations, rather than a presumed weaker affinity of As(III) for iron oxyhydroxides, might explain why As(III) is more difficult to remove than As(V) by aerating reducing groundwater.
Reactivity of Fe from a natural stream water towards As(V)
Applied Geochemistry, 2015
Interactions between iron (Fe) and arsenic (As) play a vital role in aquatic and terrestrial ecosystems influencing the reactivity and transport of arsenic. A key aspect is the effect of natural organic matter (NOM) on these interactions, and previous investigations have reported the existence of ternary As-Fe-NOM species. In this study, the reactivity of Fe, from a boreal stream water, towards As(V) was investigated using Fe and As K-edge X-ray absorption spectroscopy (XAS). The native stream water was shown to contain mononuclear Fe-NOM complexes together with Fe(III) (hydr)oxides associated with the NOM. Addition of As(V) to this water at Fe to As ratios of 2.0-15.6 resulted in substantial changes in the Fe speciation; the Fe(III) (hydr)oxides were partly converted into FeAsO 4 (s) or a solid solution where As(V) was incorporated into Fe(III) (hydr)oxide structures. Under the same conditions no or only small effects of As(V) on the Fe-NOM complexes initially present were observed, and the concurrent existence of these complexes and free As(V) showed that a large fraction of the Fe-NOM complexes were non-reactive towards As(V). This study suggests that complexation of Fe by NOM in organic rich environments may lead to elevated free, aqueous arsenic levels as these complexes do not interact with As(V). Moreover, the formation of Fe-NOM complexes also reduce the tendency of Fe to form reactive Fe(III) (hydr)oxides particles and Fe(III)-arsenate precipitates.
Geochimica et Cosmochimica Acta, 2012
ABSTRACT Oxidation state is a major factor affecting the mobility of arsenic (As) and antimony (Sb) in soil and aquatic systems. Metal (hydr)oxides and clay minerals are effective sorbents, and may also promote redox reactions on their surfaces via direct or indirect facilitation of electron transfer. Iron substituted for Al in the octahedral sites of aluminosilicate clay minerals has the potential to be in variable oxidation states and is a key constituent of electron transfer reactions in clay minerals. This experimental work was conducted to determine whether structural Fe in clays can affect the oxidation state of As and Sb adsorbed at the clay surface. Another goal of our study was to compare the reactivity of clay structural Fe(II) with systems containing Fe(II) present in dissolved/adsorbed forms.The experimental systems included batch reactors with various concentrations of As(III), Sb(III), As(V), or Sb(V) equilibrated with oxidized (NAu-1) or partially reduced (NAu-1-Red) nontronite, hydrous aluminum oxide (HAO) and kaolinite (KGa-1b) suspensions under oxic and anoxic conditions. The reaction times ranged from 0.5 to 720 h, and pH was constrained at 5.5 (for As) and at 5.5 or 8.0 (for Sb). The oxidation state of As and Sb in the liquid phase was determined by liquid chromatography in line with an inductively coupled plasma mass spectrometer, and in the solid phase by X-ray absorption spectroscopy. Our findings show that structural Fe(II) in NAu-1-Red was not able to reduce As(V)/Sb(V) under the conditions examined, but reduction was seen when aqueous Fe(II) was present in the systems with kaolinite (KGa-1b) and nontronite (NAu-1). The ability of the structural Fe in nontronite clay NAu-1 to promote oxidation of As(III)/Sb(III) was greatly affected by its oxidation state: if all structural Fe was in the oxidized Fe(III) form, no oxidation was observed; however, when the clay was partially reduced (∼20% of structural Fe was reduced to Fe(II)), NAu-1-Red promoted the most extensive oxidation under both oxic and anoxic conditions. Electron balance considerations suggest that structural Fe(III) in the NAu-1-Red was the sole oxidant in the anoxic setup, while dissolved O2 also contributes in oxic conditions. Long-term batch experiments revealed the complex dynamics of As aqueous speciation in anoxic and oxic systems when reduced arsenic was initially added: rapid disappearance of As(III) was observed due to oxidation to As(V) followed by a slow increase of aqueous As(III). This behavior is explained by two reactions: fast initial oxidation of As(III) by structural Fe(III) (anoxic) or Fe(III) and dissolved O2 (oxic) followed by the slow reduction of As(V) by dissolved Fe(II). The resulting re-mobilization of As due to As(V) reduction by aqueous Fe(II) occurs on time scales on the order of days. These reactions are likely significant in a natural soil or aquifer environment with seasonal cycling or slightly reducing conditions with an abundance of clay minerals and dissolved Fe(II).
Arsenic(III) and Arsenic(V) Reactions with Zerovalent Iron Corrosion Products
Environmental Science & Technology, 2002
Zerovalent iron (Fe 0 ) has tremendous potential as a remediation material for removal of arsenic from groundwater and drinking water. This study investigates the speciation of arsenate (As(V)) and arsenite (As(III)) after reaction with two Fe 0 materials, their iron oxide corrosion products, and several model iron oxides. A variety of analytical techniques were used to study the reaction products including HPLC-hydride generation atomic absorption spectrometry, X-ray diffraction, scanning electron microscopyenergy-dispersive X-ray analysis, and X-ray absorption spectroscopy. The products of corrosion of Fe 0 include lepidocrocite (γ-FeOOH), magnetite (Fe 3 O 4 ), and/or maghemite (γ-Fe 2 O 3 ), all of which indicate Fe(II) oxidation as an intermediate step in the Fe 0 corrosion process. The in-situ Fe 0 corrosion reaction caused a high As(III) and As(V) uptake with both Fe 0 materials studied. Under aerobic conditions, the Fe 0 corrosion reaction did not cause As(V) reduction to As(III) but did cause As(III) oxidation to As(V). Oxidation of As(III) was also caused by maghemite and hematite minerals indicating that the formation of certain iron oxides during Fe 0 corrosion favors the As(V) species. Water reduction and the release of OHto solution on the surface of corroding Fe 0 may also promote As(III) oxidation. Analysis of As(III) and As(V) adsorption complexes in the Fe 0 corrosion products and synthetic iron oxides by extended X-ray absorption fine structure spectroscopy (EXAFS) gave predominant As-Fe interatomic distances of 3.30-3.36 Å. This was attributed to inner-sphere, bidentate As(III) and As(V) complexes. The results of this study suggest that Fe 0 can be used as a versatile and economical sorbent for in-situ treatment of groundwater containing As(III) and As(V).
Water Research, 2010
The sorption of the arsenite (AsO 3 3À) and the arsenate (AsO 4 3À) ions and their conjugate acids onto iron oxides is one of main processes controlling the distribution of arsenic in the environment. The present work intends to provide a large vibrational spectroscopic database for comparison of As(III) and As(V) speciation in aqueous solutions and at the iron oxide-solution interface. With this purpose, ferrihydrite, feroxyhyte, goethite and hematite were firstly synthesized, characterized in detail and used for adsorption experiments. Raman spectra were recorded from As(III) and As(V) aqueous solutions at various pH conditions selected in order to highlight arsenic speciation. Raman Scattering and Diffuse Reflectance Infrared Fourier Transform (DRIFT) studies were carried out to examine the respective As-bonding mechanisms. The collected data were curve-fitted and discussed according to molecular symmetry concepts. X-ray Absorption Near Edge Spectroscopy (XANES) was applied to confirm the oxidation state of the sorbed species. The comprehensive spectroscopic investigation contributes to a better understanding of arsenic complexation by iron oxides.
Environmental Science & Technology, 2007
Arsenic mobilization in soils is mainly controlled by sorption/desorption processes, but arsenic also may be coprecipitated with aluminum and/or iron in natural environments. Although coprecipitation of arsenic with aluminum and iron oxides is an effective treatment process for arsenic removal from drinking water, the nature and reactivity of aluminum-or iron-arsenic coprecipitates has received little attention. We studied the mineralogy, chemical composition, and surface properties of aluminumarsenate coprecipitates, as well as the sorption of phosphate on and the loss of arsenate from these precipitates. Aluminum-arsenate coprecipitates were synthesized at pH 4.0, 7.0, or 10.0 and As/Al molar ratio (R) of 0, 0.01, or 0.1 and were aged 30 or 210 d at 50°C. In the absence of arsenate, gibbsite (pH 4.0 or 7.0) and bayerite (pH 10.0) formed, whereas in the presence of arsenate, very poorly crystalline precipitates formed. Shortrange ordered materials (mainly poorly crystalline boehmite) formed at pH 4.0 (R ) 0.01 and 0.1), 7.0, and 10.0 (R ) 0.1) and did not transform into Al(OH) 3 polymorphs even after prolonged aging. The surface properties and chemical composition of the aluminum precipitates were affected by the initial pH, R, and aging. Chemical dissolution of the samples by 6 mol L -1 HCl and 0.2 mol L -1 oxalic acid/ oxalate solution indicated that arsenate was present mainly in the short-range ordered precipitates. The sorption of phosphate onto the precipitates was influenced by the nature of the samples and the amounts of arsenate present in the precipitates. Large amounts of phosphate partially replaced arsenate only from the samples formed at R ) 0.1. The quantities of arsenate desorbed from these coprecipitates by phosphate increased with increasing phosphate concentration, reaction time, and precipitate age but were always less than 30% of the amounts of arsenate present in the materials and were particularly low (<4%) from the sample prepared at pH 4.0. Arsenate appeared to be occluded within the network of shortrange ordered materials and/or sorbed onto the external surfaces of the precipitates, but sorption on the external surfaces seemed to increase by increasing pH of sample preparation and aging. Furthermore, at pH 4.0 more than in neutral or alkaline systems the formation of aluminum arsenate precipitates seemed to be favored. Finally, we have observed that greater amounts of phosphate were sorbed on an aluminum-arsenate coprecipitate than on a preformed aluminum oxide equilibrated with arsenate under the same conditions (R ) 0.1, pH 7.0). In contrast, the opposite occurred for arsenate desorption, which was attributed to the larger amounts of arsenate occluded in the coprecipitate.
Geochimica et Cosmochimica Acta, 2010
In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, '2-line' Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH) 6 octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å ) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear ( 2 C) As(V) surface complexes and (ii) combinations of 2 C, monodentate mononuclear ( 1 V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing 1 V/ 2 C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I $0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios P25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.
Chemical reactions between arsenic and zero-valent iron in water
Water Research, 2005
Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen. r
Does As(III) interact with Fe(II), Fe(III) and organic matter through ternary complexes?
Journal of colloid and interface science, 2016
Up until now, only a small number of studies have been dedicated to the binding processes of As(III) with organic matter (OM) via ionic Fe(III) bridges; none was interested in Fe (II). Complexation isotherms were carried out with As(III), Fe(II) or Fe(III) and Leonardite humic acid (HA). Although PHREEQC/Model VI, implemented with OM thiol groups, reproduced the experimental datasets with Fe(III), the poor fit between the experimental and modeled Fe(II) data suggested another binding mechanism for As(III) to OM. PHREEQC/Model VI was modified to take various possible As(III)-Fe(II)-OM ternary complex conformations into account. The complexation of As(III) as a mononuclear bidentate complex to a bidentate Fe(II)-HA complex was evidenced. However, the model needed to be improved since the distribution of the bidentate sites appeared to be unrealistic with regards to the published XAS data. In the presence of Fe(III), As(III) was bound to thiol groups which are more competitive with reg...