ferrihydrite and arsenic-acid

Accurate detection and analysis of arsenic pollutants are an important means to enhance the ability to manage arsenic pollution. Infrared (IR) spectroscopy technology has the advantages of fast analysis speed, high resolution, and high sensitivity and can be monitored by real-time in situ analysis. This paper reviews the application of IR spectroscopy in the qualitative and quantitative analysis of inorganic and organic arsenic acid adsorbed by major minerals such as ferrihydrite (FH), hematite, goethite, and titanium dioxide. The IR spectroscopy technique cannot only identify different arsenic contaminants but also obtain the content and adsorption rate of arsenic contaminants in the solid phase. The reaction equilibrium constants and the degree of reaction conversion can be determined by constructing adsorption isotherms or combining them with modeling techniques. Theoretical calculations of IR spectra of mineral adsorbed arsenic pollutant systems based on density functional theory (DFT) and analysis and comparison of the measured and theoretically calculated characteristic peaks of IR spectra can reveal the microscopic mechanism and surface chemical morphology of the arsenic adsorption process. This paper systematically summarizes the qualitative and quantitative studies and theoretical calculations of IR spectroscopy in inorganic and organic arsenic pollutant adsorption systems, which provides new insights for accurate detection and analysis of arsenic pollutants and arsenic pollution control. PRACTITIONER POINTS: This paper reviews the application of infrared spectroscopy in the qualitative and quantitative analyses of inorganic and organic arsenic acid adsorbed by major minerals such as ferrihydrite, hematite, goethite, and titanium dioxide, which can help identify and evaluate the type and concentration of arsenic pollutants in water bodies. In this paper, theoretical calculations of infrared spectra of mineral adsorbed arsenic pollutant systems based on density functional theory reveal the adsorption mechanism of arsenic pollutants in water at the solid-liquid interface and help to develop targeted arsenic pollution control technologies. This paper provides a new and reliable analytical detection technique for the study of arsenic contaminants in water bodies.

Topics: Adsorption; Arsenic; Arsenicals; Ferric Compounds; Minerals; Organic Chemicals; Spectrophotometry, Infrared; Spectroscopy, Fourier Transform Infrared; Water; Water Pollutants, Chemical

Sea level rise (SLR) is estimated to impact 25% of the world's population along coastal areas leading to an increase in saltwater intrusion. Consequently, changes in the soil biogeochemistry of currently non-saline and/or well-drained soils due to saltwater intrusion are of major concern. Saltwater intrusion is expected to affect farmland across large broiler producer regions, where large amounts of manure containing organic arsenicals were applied over the past decades. To determine how SLR may impact the speciation and mobility of adsorbed inorganic and organic As, we used in situ real-time attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to determine the adsorption and desorption mechanisms of As(V) and 4-aminophenylarsonic (p-ASA, a poultry feed additive) on ferrihydrite (Fh) in the presence of sulfate at varying pH. The adsorption of As(V) and p-ASA increased at lower pH, with As(V) showing IR features consistent with the formation of inner-sphere of As-Fh surface complexes, while p-ASA also formed others structures as H-bonded As-surface complexes, likely mediated by outer-sphere complexes, based on our FTIR and batch experiments data. No observable As(V) or p-ASA desorption from the Fh surface was promoted by sulfate, however sulfate adsorption on the Fh surface was remarkably larger for p-ASA than for As(V). Complimentary, we carried out batch studies of As(V) and p-ASA desorption by Fh, using artificial seawater (ASW) at varying concentrations. The 1% ASW desorbed ∼10% of initially sorbed p-ASA, while at 100% ASW desorbed ∼40%. However, <1% of As(V) was desorbed by 1% ASW solution and only ∼7.9% were desorbed at 100% ASW. The spectroscopic data support the more extensive desorption of p-ASA compared to As(V) observed in batch experiments, suggesting that organoarsenicals may be easily desorbed and, after conversion to inorganic forms, pose a risk to water supplies.

Topics: Adsorption; Animals; Arsanilic Acid; Arsenates; Chickens; Ferric Compounds; Hydrogen-Ion Concentration; Sea Level Rise; Soil; Spectroscopy, Fourier Transform Infrared; Sulfates; Sulfur Oxides

Several studies have demonstrated that gypsum (CaSO

Topics: Arsenates; Arsenic; Arsenicals; Arsenites; Bacteria; Calcium Carbonate; Calcium Sulfate; Carbonates; Ferric Compounds; Groundwater; Iron; Molybdenum; Oxidation-Reduction; Solubility; Sulfates; Sulfides

Phosphate competes with arsenate for sorption sites on poorly crystalline iron and aluminum (hydr)oxides. The competition has implications e.g. for the management of arsenic-contaminated soil and water. Phosphate competition with arsenate on mixed phases containing both iron and aluminum (hydr)oxides has rarely been investigated. Here, the phosphate competition with arsenate on mixtures of poorly crystalline aluminum hydroxide (Alhox) and ferrihydrite (Fh), was investigated in batch experiments at pH 6.5. X-ray absorption spectroscopy (XAS) was performed on the phosphorus and arsenic K edges, which offered a unique insight in the partitioning of arsenate and phosphate on mixed Alhox-Fh sorbents. Under the studied conditions the sorption capacity of the mixed sorbents (per mol Al or Fe) increased at higher Alhox to Fh ratios. The XAS measurements provided direct evidence that phosphate competed more effectively with arsenate for sorption sites on Alhox than on Fh. For example, in a mixture with 50% of both sorbents and with similar additions of arsenate and phosphate, 71% of the oxyanions adsorbed on Fh and 46% on Alhox were arsenate. Consequently, phosphate may mobilize arsenate more easily from mixed iron-aluminum matrices that are rich in aluminum.

Topics: Adsorption; Aluminum; Aluminum Hydroxide; Arsenates; Arsenic; Ferric Compounds; Iron; Oxides; Phosphates; Water

The present study provides the starch-mediated carbothermal preparation of magnetic-responsible ferrihydrite (MFHP) based on Fe-rich precipitates which is recovered by mine drainage for immobilization of arsenate and antimonate in water. Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) represented partial transformation from ferrihydrite to magnetite in MFHP due to the carbothermal reduction process, resulting in an effective saturation magnetism (= 19.2 emu/g). As and Sb K-edge EXAFS revealed that arsenate ion combines onto the surface of MFHP as inner-sphere binuclear bidentate surface complex, and antimonate forms inner-sphere mononuclear bidentate complex. In addition, the leachability by toxicity characteristic leaching procedure (TCLP) implies the environmental friendly preparation method for preparing magnetic-responsible adsorbents using mining waste.

Topics: Adsorption; Antimony; Arsenates; Ferric Compounds; Ferrosoferric Oxide; Immobilization; Mining; Spectrum Analysis; X-Ray Absorption Spectroscopy; X-Rays

Topics: Arsenates; Benzothiazoles; Biomimetic Materials; Catalysis; Colorimetry; Drinking Water; Electrochemical Techniques; Ferric Compounds; Hydrogen Peroxide; Lakes; Limit of Detection; Nanotubes; Peroxidase; Rivers; Sulfonic Acids; Water Pollutants, Chemical

In this study, we investigated the Sb(V) adsorption on ferrihydrite (Fh) at different pH values, in the presence and absence of common competing anions in soil such as phosphate (P(V)) and arsenate (As(V)). Batch adsorption experiments, carried out at pH 4.5, 6.0, and 7.0, showed a greater affinity of Fh towards P(V) and As(V) with respect to Sb(V), especially at higher pH values, while the opposite was true at acidic pH. The capacity of Fh to accumulate greater amounts of phosphate and arsenate in the 6.0-7.0 pH range was mainly linked to the different acid properties of P(V), As(V), and Sb(V) oxyanions. The Sb(V) adsorption on Fh was highly pH-dependent and followed the following order: pH 4.5 (0.957 mmol·g

Topics: Adsorption; Arsenates; Ferric Compounds; Hydrogen-Ion Concentration; Phosphates; Soil; Spectroscopy, Fourier Transform Infrared; Sulfates

A series of model anoxic incubations were performed to understand the concurrence between arsenate and ferrihydrite reduction by Shewanella putrefaciens strain CN-32 at different concentrations of arsenate, ferrihydrite and lactate, and with given ΔG

Topics: Arsenates; Ferric Compounds; Iron; Kinetics; Oxidation-Reduction; Shewanella putrefaciens; Solubility

Microorganisms play a key role in the redox transformation of arsenic (As) in aquifers. In this study, the impact of indigenous bacteria, especially the prevailing nitrate respirers, on arsenite (As(III)) oxidation was explored during groundwater filtration using granular TiO

Topics: Arsenates; Arsenic; Arsenites; Bacteria; Ferric Compounds; Filtration; Groundwater; Iron; Iron Compounds; Minerals; Nitrates; Oxidation-Reduction; Phylogeny; Proteobacteria; Water Pollutants, Chemical; X-Ray Absorption Spectroscopy

Reactions occurring at ferric oxyhydroxide surfaces play an important role in controlling arsenic bioavailability and mobility in natural aqueous systems. However, the mechanism by which arsenite and arsenate complex with ferrihydrite (Fh) surfaces is not fully understood and although there is clear evidence for inner sphere complexation, the nature of the surface complexes is uncertain. In this work, we have used periodic density functional theory calculations to predict the relative energies, geometries and properties of arsenous acid (H3AsO3) and arsenic acid (H3AsO4), the most prevalent form of As(iii) and As(v), respectively, adsorbed on Fh(110) surface at intermediate and high pH conditions. Bidentate binuclear (BB(Fe-O)) corner-sharing complexes are shown to be energetically favoured over monodentate mononuclear complexes (MM(Fe-O)) for both arsenic species. The inclusion of solvation effects by introducing water molecules explicitly near the adsorbing H3AsO3 and H3AsO4 species was found to increase their stability on the Fh surface. The adsorption process is shown to be characterized by hybridization between the interacting surface Fe-d states and the O and As p-states of the adsorbates. Vibrational frequency assignments of the As-O and O-H stretching modes of the adsorbed arsenic species are also presented.

Topics: Adsorption; Arsenates; Arsenites; Ferric Compounds; Water Pollutants, Chemical

Coprecipitation of Fe and Al (hydr)oxides has been considered a low-cost process to remove As from wastewater. Arsenate is the most stable form of As in aerobic environments such as surface water, soils, and sediments and can be removed from water through methods based on this process. Iron/aluminum molar ratios of 100:0, 80:20, and 60:40 were used to treat water contaminated with As at concentrations of 50 and 500 mg L. Aluminum, ferrous, and ferric sulfates were used to coprecipitate Al and Fe (hydr)oxides at high pH. Maghemite, magnetite, lepidocrocite, and goethite were detected in precipitates from Fe(II), whereas hematite and ferrihydrite were identified in Fe(III) treatments. Segregation of Al (hydr)oxides as gibbsite and bayerite as well as the Al isomorphic substitution in Fe (hydr)oxides were detected in the presence of Al. The precipitates were classified as nonhazardous according to the leaching test based on Brazilian Technical Standard NBR 10005. The presence of Al increased the stability of the sludge from Fe(II) treatments but did not affect the stability of precipitates from Fe(III) treatments. High efficiencies for As removal from water were obtained for all treatments, but concentrations of soluble As were, in general, lower for Fe(III) treatments especially, in the absence of Al. Treatments were efficient in reaching the threshold to effluent discharge (0.5 mg L), but only treatments with initially 50 mg L of As reached the threshold for drinking water (10 μg L).

Topics: Adsorption; Aluminum; Arsenates; Brazil; Ferric Compounds; Hydrogen-Ion Concentration; Iron Compounds; Minerals; Organic Chemicals; Oxidation-Reduction; Waste Disposal, Fluid; Water Pollutants, Chemical

Topics: Adsorption; Arsenates; Colloids; Ferric Compounds; Humic Substances; Hydrogen-Ion Concentration; Iron Compounds; Minerals; Models, Chemical; Organic Chemicals; Oxides; Phosphorus; Soil; Ultrafiltration

Topics: Arsenates; Diffusion; Environmental Monitoring; Ferric Compounds; Metals; Molybdenum; Osmolar Concentration; Vanadates; Water; Water Pollutants, Chemical

The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.

Topics: Arsenates; Arsenic; Ferric Compounds; Ferrous Compounds; Groundwater; Iron; Oxidation-Reduction; Phosphates; Shewanella; X-Ray Absorption Spectroscopy

A novel hyperthermophilic, anaerobic, archaeon was isolated from a terrestrial hot spring at Uzon Caldera, Kronotsky Nature Reserve, Kamchatka, Russia. The isolate, strain 1860(T), grew optimally at 90-95 °C and pH 6.0-7.0. The cells were non-motile straight rods, 1.5-5.0 µm in length, covered with surface-layer lattice. Strain 1860(T) utilized complex proteinaceous compounds as electron donors and ferrihydrite, Fe(III) citrate, nitrate, thiosulfate, selenite, selenate and arsenate as electron acceptors for growth. The sequence of the 16S rRNA gene of strain 1860(T) had 97.9-98.7 % similarity with those of members of the genus Pyrobaculum. On the basis of its physiological properties and phylogenetic analyses including in silico genome to genome hybridization, the isolate is considered to represent a novel species, for which the name Pyrobaculum ferrireducens sp. nov. is proposed. The type strain is 1860(T) ( = DSM 28942(T) = VKM B-2856(T)).

Topics: Arsenates; DNA, Bacterial; Ferric Compounds; Hot Springs; Molecular Sequence Data; Nucleic Acid Hybridization; Phylogeny; Pyrobaculum; RNA, Ribosomal, 16S; Russia; Selenic Acid; Sequence Analysis, DNA; Water Microbiology

Sorption by ferrihydrite is an important control on As(V) concentrations in many oxic aquatic systems. There are significant discrepancies in reported sorption constants (log(KAs)), which presents a problem for quantifying and understanding this important system. A review of reported ferrihydrite-As(V) sorption studies indicated a positive correlation between reaction time used in the experiments and the log(KAs) values derived from the data. In this paper, we study the kinetics of As(V) sorption over ≈3000 h in nine systems with varying pH and As(V)/Fe. Ferrihydrite was stable in all systems containing As(V), and the [As(V)] in solution decreased linearly as a function of log(t) (termed Elovich kinetics) over the full 3000 h in most systems. A stable [As(V)] was only observed in systems with low As(V)/Fe and low pH. Apparent As(V) sorption constants were derived from the data at specific time intervals using the diffuse layer model and equations describing log(KAs) values as a function of time provide a way to describe this elusive equilibrium. IR spectra support the hypothesis that slow interparticle diffusion is responsible for the slow approach to equilibrium. This work resolves discrepancies in previous studies of As(V)-ferrihydrite and provides equations to allow for system appropriate log(KAs) values to be used.

Topics: Adsorption; Arsenates; Ferric Compounds; Kinetics; Models, Theoretical; Solutions; Spectrophotometry, Infrared

In this study, a method is proposed for the selective retention of As(V) using diffusive gradient in thin film (DGT) samplers containing a strongly basic anion exchange resin (Amberlite IRA 910) supported on a polyacrylamide gel. In addition, the total arsenic content is determined by ferrihydrite gel discs. Subsequently, the concentration of As(III) was obtained by determining the difference between the total As and As(V). DGT experiments showed linear accumulation of As(V) (up to 280 ng) until a deployment time of 8 h deployment (R(2) > 0.99). The retention of As(V) was appropriate (97.9-112.3%) between pH 5 and 9. For a solution with an ionic strength ranging from 0.001 to 0.05 mol L(-1), the As(V) uptake ranged from 90-120%. The proposed method was applied for the speciation of arsenic in river water. For the analysis of spiked samples collected at the Furnas stream, the recoveries of total arsenic content ranged between 103.9% and 118.8%. However, the recoveries of As(III) and As(V) were 43.3-75.2% and 147.3-153.4%, respectively. These differences were probably because of the oxidation of As(III) to As(V) during deployments. For spiked samples collected at the Ribeirão Claro, the recoveries of dissolved As(III), As(V) and As(T) were 103.1%, 108.0% and 106.3%, respectively. Thus, the DGT technique with Amberlite IRA 910 resin as the binding phase can be employed for the in situ redox speciation of inorganic arsenic.

Topics: Acrylic Resins; Arsenates; Arsenic; Arsenites; Diffusion; Environmental Monitoring; Ferric Compounds; Osmolar Concentration; Oxidation-Reduction; Resins, Synthetic; Rivers; Water Pollutants, Chemical

Batch experiments were conducted in order to investigate the competitive interaction of arsenite (As(III)) and arsenate (As(V)) onto ferrihydrite as a function of initial pH, adsorbent dosage, concentration of coexisting ligands, and order of addition. The pH generally had a great impact on adsorption under both single ion and competitive conditions. However, the amount of As(V) in solution was the controlling factor of adsorption behavior, and As(III) more or less outcompeted As(V) across the pH scale from 4 to 10. Under competitive conditions, i.e., both species were present at the same time, As(III) and As(V) were adsorbed almost equally up to a pH of 5 at an adsorbent dosage of 0.5 g/L and up to a pH of 6 at an adsorbent dosage of 1 g/L. This was contrary to the theoretical prediction that As(V) should adsorb more strongly than As(III) at pH values below the point of zero charge (pzc) of ferrihydrite of about 7 to 8. At low pH, As(V) impedes the adsorption of As(III) but to lesser degree than As(III) impedes As(V) adsorption at a pH above 6. The effect of As(III) on the adsorption of As(V) increased with an increase in pH, and the adsorption of As(V) was almost absent at pH 9 at an adsorbent dosage of 1 g/L and at pH 8 at an adsorbent dosage of 0.5 g/L. In the range of ferrihydrite dosages from 0.2 to 1.6 g/L, As(III) was adsorbed preferentially over As(V) under the availability of less adsorbent. The order of anion addition also had significant effects on their competitive adsorption behavior: the first species was always more favored to compete for the adsorbing sites than when the two species were added to the suspensions simultaneously.

Topics: Adsorption; Arsenates; Arsenites; Ferric Compounds; Hydrogen-Ion Concentration; Surface Properties

Short-range ordered ferric arsenate (FeAsO4 · xH2O) is a secondary As precipitate frequently encountered in acid mine waste environments. Two distinct structural models have recently been proposed for this phase. The first model is based on the structure of scorodite (FeAsO4 · 2H2O) where isolated FeO6 octahedra share corners with four adjacent arsenate (AsO4) tetrahedra in a three-dimensional framework (framework model). The second model consists of single chains of corner-sharing FeO6 octahedra being bridged by AsO4 bound in a monodentate binuclear (2)C complex (chain model). In order to rigorously test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their local (<6 Å) structure by As and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO6 octahedra being bridged by AsO4 tetrahedra (RFe-As = 3.33 ± 0.01 Å). Our shell-fit results further indicated a lack of evidence for single corner-sharing FeO6 linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of ∼5.3 Å, consistent with crystallographic data of scorodite and in disagreement with the chain model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments.

Topics: Arsenates; Arsenic; Ferric Compounds; Fourier Analysis; Iron; Minerals; Synchrotrons; X-Ray Absorption Spectroscopy; X-Ray Diffraction

Sorption to iron (Fe) minerals determines the fate of the toxic metalloid arsenic (As) in many subsurface environments. Recently, thiolated As species have been shown to dominate aqueous As speciation under a range of environmentally relevant conditions, thus highlighting the need for a quantitative understanding of their sorption behavior. We conducted batch experiments to measure the time-dependent sorption of two S-substituted arsenate species, mono- and tetrathioarsenate, and compared it to the sorption of arsenite and arsenate, in suspensions containing 2-line ferrihydrite, goethite, mackinawite, or pyrite. All four As species strongly sorbed to ferrihydrite. For the other sorbents, binding of the thiolated As species was generally lower compared to arsenate and arsenite, with the exception of the near instantaneous and complete sorption of monothioarsenate to pyrite. Analysis of the X-ray absorption spectroscopy (XAS) spectra of sorbed complexes implied that monothioarsenate binds to Fe oxides as a monodentate, inner-sphere complex. In the presence of Fe sulfides, mono- and tetrathioarsenate were both unstable and partially reduced to arsenite. Adsorption of the thiolated As species to the Fe sulfide minerals also caused the substitution of surface sulfur (S) atoms by As and the formation of As-Fe bonds.

Topics: Adsorption; Arsenates; Arsenites; Ferric Compounds; Ferrous Compounds; Iron; Iron Compounds; Kinetics; Minerals; Models, Chemical; Sulfides; X-Ray Absorption Spectroscopy

In this study, mobilization and re-adsorption of arsenate on 2-line ferrihydrite and hematite in the presence of oxalate was investigated. Our results showed that arsenate could be mobilized during the dissolution of ferrihydrite and hematite. After reaching the maximum values, the released arsenate could re-adsorb on the residual ferrihydrite, whereas such an observation was not significant in hematite system. More reactive sites exposed during the dissolution of ferrihydrite could contribute to the re-adsorption of the released arsenate at pH 3.0, while the insignificant re-adsorption of arsenate on hematite could be explained by the inhibitory adsorption effect of oxalate on arsenate. Although dissolution rates of iron oxides decreased with the increase of arsenate on both ferrihydrite and hematite, dissolution rate was mainly determined by the reactivity of iron oxides, and ferrihydrite showed a higher reactivity than hematite in the presence of oxalate. Mathematic model proposed in our study further indicated that arsenate loading showed a more significant effect on arsenate mobilization in hematite system, while it was more effective in arsenate re-adsorption in ferrihydrite system.

Topics: Adsorption; Arsenates; Ferric Compounds; Hydrogen-Ion Concentration; Models, Theoretical; Oxalates; Solubility; Water Pollutants, Chemical

Arsenic Crystallization Technology (ACT) is a potentially eco-friendly, effective technology for stabilization of arsenic-bearing solid residuals (ABSRs). The strategy is to convert ABSRs generated by water treatment facilities into minerals with a high arsenic capacity and long-term stability in mature, municipal solid waste landfills. Candidate minerals considered in this study include scorodite, arsenate hydroxyapatites, ferrous arsenates (symplesite-type minerals), tooeleite, and arsenated-schwertmannite. These minerals were evaluated as to ease of synthesis, applicability to use of iron-based ABSRs as a starting material, and arsenic leachability. The Toxicity Characteristic Leaching Procedure (TCLP) was used for preliminary assessment of candidate mineral leaching. Minerals that passed the TCLP and whose synthesis route was promising were subjected to a more aggressive leaching test using a simulated landfill leachate (SLL) solution. Scorodite and arsenate hydroxyapatites were not considered further because their synthesis conditions were not found to be favorable for general application. Tooeleite and silica-amended tooeleite showed high TCLP arsenic leaching and were also not investigated further. The synthesis process and leaching of ferrous arsenate and arsenated-schwertmannite were promising and of these, arsenated-schwertmannite was most stable during SLL testing. The latter two candidate minerals warrant synthesis optimization and more extensive testing.

Topics: Arsenates; Arsenic; Crystallization; Environmental Restoration and Remediation; Ferric Compounds; Hydrogen-Ion Concentration; Iron; Iron Compounds; Materials Testing; Refuse Disposal; Soil Pollutants; Temperature; Waste Disposal Facilities; Water Pollutants, Chemical; Water Purification; X-Ray Diffraction

Addition of iron oxide to arsenic-contaminated soil has been proposed as a means of reducing the mobility of arsenic in the soil. Arsenic and zinc are common coexisting contaminants in soils. The presence of zinc therefore may affect the adsorption properties of arsenic on iron oxide, and may thus affect its mobility in the soil. The influence of Zn(II) on the adsorption of arsenate ions on iron oxide was studied. Batch adsorption experiments indicated that Zn(II) increased the arsenate removal from a solution by ferrihydrite at pH 8. However, ATR-FTIR spectroscopy showed that no adsorption of arsenate on a ferrihydrite film occurred at pD 8 in the presence of Zn(II). Precipitation of zinc hydroxide carbonate followed by arsenate adorption onto the precipitate was found to be a plausible mechanism explaining the arsenate removal from a solution in the presence of Zn(II) at pH/pD 8. The previously suggested mechanisms attributing the enhanced removal of arsenate from solution in the presence of Zn(II) to additional adsorption on iron oxides could not be verified under the experimental conditions studied. It was also shown that at pH/pD 4, the presence of Zn(II) in the system did not significantly affect the adsorption of arsenate on ferrihydrite.

Topics: Adsorption; Arsenates; Carbonates; Chemical Precipitation; Ferric Compounds; Hydrogen-Ion Concentration; Hydroxides; Microscopy, Electron, Scanning; Solutions; Spectroscopy, Fourier Transform Infrared; X-Ray Diffraction; Zinc; Zinc Compounds

The adsorption-desorption kinetics of arsenate on a Fe(III)-modified montmorillonite (Fe-M) was studied at different arsenate concentrations, pH and stirring rates. The synthesized solid was a porous sample with Fe(III) present as a mix of monomeric and polymeric Fe(III) species in the interlayer and on the external surface. Adsorption took place in a two-step mechanism, with an initial fast binding of arsenate to Fe(III) species at the external surface (half-lives of 1 min or shorter) followed by a slower binding to less accessible Fe(III) species in pores and the interlayer (half-lives of around 1 h). Desorption kinetics also reflected the presence of externally and internally adsorbed arsenate. At pH 6 the maximum adsorbed arsenate was 52 μmol/g, a value that is low as compared to adsorption on ferrihydrite (700 μmol/g) and goethite (192-220 μmol/g). However, since the Fe(III) content of Fe-M is much lower than that of ferrihydrite and goethite, Fe(III) species in Fe-M are more efficient in binding arsenate than in ferrihydrite or goethite (one As atom is attached every 8.95 iron atoms). This high binding efficiency indicates that Fe(III) species are well spread on montmorillonite, forming small oligomeric species or surface clusters containing just a few iron atoms.

Topics: Adsorption; Algorithms; Arsenates; Bentonite; Ferric Compounds; Hydrogen-Ion Concentration; Iron Compounds; Kinetics; Minerals; Porosity; Solubility; Surface Properties; X-Ray Diffraction

The photochemistry of an aqueous suspension of the iron oxyhydroxide, ferrihydrite, in the presence of arsenite has been investigated using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption near edge structure (XANES), and solution phase analysis. Both ATR-FTIR and XANES show that the exposure of ferrihydrite to arsenite in the dark leads to no change in the As oxidation state, but the exposure of this arsenite-bearing surface, which is in contact with pH 5 water, to light leads to the conversion of the majority of the adsorbed arsenite to the As(V) bearing species, arsenate. Analysis of the solution phase shows that ferrous iron is released into solution during the oxidation of arsenite. The photochemical reaction, however, shows the characteristics of a self-terminating reaction in that there is a significant suppression of this redox chemistry before 10% of the total iron making up the ferrihydrite partitions into solution as ferrous iron. The self-terminating behavior exhibited by this photochemical arsenite/ferrihydrite system is likely due to the passivation of the ferrihydrite surface by the strongly bound arsenate product.

Topics: Arsenates; Arsenites; Carcinogens, Environmental; Ferric Compounds; Hydrogen-Ion Concentration; Oxidation-Reduction; Photochemical Processes; Spectroscopy, Fourier Transform Infrared; X-Ray Absorption Spectroscopy

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.

Topics: Adsorption; Arsenates; Arsenites; Ferric Compounds; Iron Compounds; Minerals; Polysaccharides, Bacterial; Shewanella putrefaciens; Soil Pollutants; Spectroscopy, Fourier Transform Infrared; Surface Properties

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ≪ PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).

Topics: Adsorption; Arsenates; Arsenites; Ferric Compounds; Inorganic Chemicals; Ligands; Organic Chemicals

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.

Topics: Adsorption; Arsenates; Ferric Compounds; Hydrogen-Ion Concentration; Iron Compounds; Mass Spectrometry; Minerals; Mining; Saskatchewan; Spectrum Analysis, Raman; Temperature; Time Factors; Uranium; X-Ray Diffraction

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (∼5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.

Topics: Adsorption; Aluminum Hydroxide; Aluminum Oxide; Arsenates; Environmental Pollutants; Ferric Compounds; Iron Compounds; Kinetics; Minerals; Oxidation-Reduction; Shewanella putrefaciens

Dilute arsenate (As(V)) coprecipitation by ferrihydrite was investigated to determine if treatment of acid mine drainage containing dilute As(V) using coprecipitation is feasible. The sorption density obtained at pH 5 and 7 was nearly identical when As(V) was coprecipitated with ferrihydrite, while it was higher at pH 5 when As(V) was adsorbed on the ferrihydrite. The high sorption density of As(V) to ferrihydrite in coprecipitation with 1-h reaction time suggested that coprecipitation occurs via both adsorption and precipitation. Furthermore, the relationship between residual As(V) and sorption density revealed a BET-type isotherm, with a transition point from a low residual As(V) concentration to a high residual As(V) concentration being observed for all initial As(V) concentrations between 0.15 and 0.44 mmol/dm(3) when the initial molar ratio was 0.56 at pH 5 and 7. X-ray diffraction and the zeta potential revealed that the transition point from surface complexation to precipitation was obtained when the initial As/Fe ratio was 0.4 or 0.5. When dilute As(V) was coprecipitated with ferrihydrite at pH 5 and 7, it was primarily adsorbed as a surface complex when the initial molar ratio was As/Fe < 0.4, while a ferric arsenate and surface complex was formed when this ratio was >or= 0.4.

Topics: Adsorption; Arsenates; Chemical Precipitation; Ferric Compounds; Solutions; Water; Water Pollutants, Chemical; X-Ray Diffraction

In the present study, in situ ATR-FTIR spectroscopy was used for the first time to study the competitive adsorption of phosphate and arsenate on ferrihydrite. Deuterium oxide was used as solvent to facilitate the interpretations of recorded infrared spectra. It was found that arsenate and phosphate adsorbed more strongly at lower pD-values, showing similarities in the adsorption behavior as a function of pD. However, arsenate complexes were found to be more strongly adsorbed than phosphate complexes in the pD range studied. About five times higher concentration of phosphate in solution was needed to reduce the absorbance due to pre-adsorbed arsenate to the same relative level as for pre-adsorbed phosphate, which was desorbed using a solution containing equal (molar) concentrations in arsenate and phosphate. At pD 4, two phosphate complexes were adsorbed on the iron oxide, one deuterated and one de-deuterated. When phosphate was pre-adsorbed and arsenate subsequently added to the system, the deuterated phosphate complex desorbed rapidly while the de-deuterated phosphate complex was quite stable. At pD 8.5, only the de-deuterated phosphate complex was adsorbed on the iron oxide. Moreover, the arsenate adsorbed was also predominantly de-deuterated as opposite to the arsenate adsorbed at pD 4. During the substitution experiments the configuration of these complexes on the iron oxide surface did not change. To the best of our knowledge, this is the first time this difference in stability of the different phosphate complexes is reported and shows the power of employing in situ spectroscopy for this kind of studies.

Topics: Adsorption; Arsenates; Ferric Compounds; Membranes, Artificial; Particle Size; Phosphates; Spectroscopy, Fourier Transform Infrared; Surface Properties

An iron reducing bacterial strain was isolated from a paddy soil and identified as a member of the Aeromonas group by 16S rRNA gene sequence analysis. When the cells were growing with dissolved Fe(III) as electron acceptor in the presence of As(V), Fe(II) minerals (siderite and vivianite) were formed and dissolved As was removed efficiently from solution. When the cells were growing with the Fe(III) hydroxide mineral (ferrihydrite) as electron acceptor in the presence of As(V), ferrihydrite was reduced and dissolved As(V) concentrations decreased sharply. Our results demonstrated firstly that members of the Aeromonas group can reduce Fe(III) in paddy soils, and secondly that iron reduction does not necessarily lead to arsenic mobilization. However, As immobilization can occur in environments that contain significant concentrations of counter ions such as bicarbonate and phosphate.

Topics: Aeromonas; Arsenates; Arsenic; Biodegradation, Environmental; Carbonates; Ferric Compounds; Ferrous Compounds; Phosphates; RNA, Bacterial; RNA, Ribosomal, 16S; Sequence Analysis, RNA; Soil; Soil Microbiology