ferrihydrite and ferric-hydroxide

The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log K

Topics: Adsorption; Binding Sites; Environmental Pollutants; Ferric Compounds; Fractionation, Field Flow; France; Hydrogen-Ion Concentration; Kinetics; Lead; Models, Theoretical; Nanoparticles; Plastics; Surface Properties; 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

The redox chemistry of chromate (Cr(VI)) and arsenite (As(III)) on the iron oxyhydroxide, ferrihydrite (Fh), was investigated. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS) were used to determine the composition of the adsorbed layer on Fh during and after exposure to solution-phase Cr(VI) and As(III). The individual exposure of Cr(VI) or As(III) on Fh resulted in the adsorption of the respective species, and there was no change in the oxidation state of either species. In contrast, exposure of Fh simultaneously to Cr(VI) and As(III) led to an adsorbed layer that was primarily Cr(III) and As(V). This redox transformation occurred over various experimental conditions at pH 3, 5, and 7 and in the presence or absence of O2, as demonstrated by in situ ATR-FTIR results. A similar redox transformation was not observed at a solution of pH 9, due to minimal Cr(VI) adsorption. Postreaction XPS showed that the majority of adsorbed arsenic existed as As(V) at pH 3, 5, and 7, while As(III) was the main species detected at pH 9. At pH 3 the redox chemistry between Cr(VI) and As(III) led to a As(V) product surface loading of ∼600 mmol/kg. Experiments performed in the absence of dissolved O2 resulted in less As(V) on the surface compared to experiments in which O2 was present for equivalent reaction times.

Topics: Adsorption; Arsenites; Chromates; Ferric Compounds; Oxidation-Reduction; Photoelectron Spectroscopy; Spectroscopy, Fourier Transform Infrared; X-Ray Absorption Spectroscopy

Inspired by a nanometric iron-based oxide material of bacterial origin, silicon (Si)-doped iron oxyhydroxide nanoparticles or 2-line ferrihydrites (2Fhs) were prepared and their lithium (Li) storage properties were investigated. The structures of the Si-doped 2Fhs strongly depended on the Si molar ratio [x = Si/(Fe + Si)] whose long-range atomic ordering gradually vanished as the Si molar ratio increased, with a structural change from nanocrystalline to amorphous at x = 0.30. The most striking properties were observed for the sample with x = 0.30. Over the voltage range of 1.5-4.0 V at a current rate of 500 mA/g, this material exhibited a relatively high reversible capacity of ∼100 mAh/g, which was four times greater than that of the Si-free 2Fh and indicated a good rate capability and cyclability. The large capacity and good rate and cycle performances are presumably because of the amorphous structure and the strong and stabilizing covalent Si-O bonds, respectively. The minor amount of Si(4+) in the structure of the iron oxyhydroxides is considered to improve the electrochemical properties. Use of more appropriate doping elements and fabrication of more appropriate nanostructures could drastically improve the Li storage properties of the developed bioinspired material.

Topics: Biomimetics; Electric Conductivity; Electric Power Supplies; Electrodes; Ferric Compounds; Lithium; Nanoparticles; Particle Size; Silicon

Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

Topics: Adsorption; Colorado; Ferric Compounds; Geologic Sediments; Iron; Oxidation-Reduction; Uranium; X-Ray Absorption Spectroscopy; X-Ray Diffraction

Arsenic is a toxic trace element, which commonly occurs as contaminant in riverine floodplains and associated wetlands affected by mining and ore processing. In this study, we investigated the solid-phase speciation of As in river floodplain soils characterized by circumneutral pH (5.7-7.1) and As concentrations of up to 40.3 g/kg caused by former mining of arsenopyrite-rich ores. Soil samples collected in the floodplain of Ogosta River (Bulgaria) were size-fractionated and subsequently analyzed using a combination of X-ray fluorescence (XRF) spectrometry, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and selective chemical extraction of poorly crystalline mineral phases. Arsenic and Fe were found to be spatially correlated and both elements were strongly enriched in the fine soil particle size fractions (<2 μm and 2-50 μm). Between 14 and 82% of the total As was citrate-ascorbate extractable. Molar As/Fe ratios were as high as 0.34 in the bulk soil extracts and increased up to 0.48 in extracts of the fine particle size fractions. Arsenic K-edge XAS spectra showed the predominance of As(V) and were well fitted with a reference spectrum of As(V) adsorbed to ferrihydrite. Whereas no As(III) was detected, considerable amounts of As(-I) were present and identified as arsenopyrite originating from the mining waste. Iron K-edge XAS revealed that in addition to As(V) adsorbed to ferrihydrite, X-ray amorphous As(V)-rich hydrous ferric oxides ("As-HFO") with a reduced number of corner-sharing FeO6 octahedra relative to ferrihydrite were the dominating secondary As species in the soils. The extremely high concentrations of As in the fine particle size fractions (up to 214 g/kg) and its association with poorly crystalline Fe(III) oxyhydroxides and As-HFO phases suggest a high As mobilization potential under both oxic and anoxic conditions, as well as a high bioaccessibility of As upon ingestion, dermal contact, or inhalation by humans or animals.

Topics: Arsenic; Arsenicals; Bulgaria; Ferric Compounds; Iron; Iron Compounds; Minerals; Mining; Particle Size; Rivers; Soil; Soil Pollutants; Spatial Analysis; Spectrometry, X-Ray Emission; Sulfides; X-Ray Absorption Spectroscopy; X-Ray Diffraction

Floodplain soils are frequently contaminated with metal(loid)s due to present or historic mining, but data on the bioaccessibility (BA) of contaminants in these periodically flooded soils are scarce. Therefore, we studied the speciation of As and Fe in eight As-contaminated circumneutral floodplain soils (≤ 21600 mg As/kg) and their size fractions using X-ray absorption spectroscopy (XAS) and examined the BA of As in the solids by in-vitro gastrointestinal (IVG) extractions. Arsenopyrite and As(V)-adsorbed ferrihydrite were identified by XAS as the predominant As species. The latter was the major source for bioaccessible As, which accounted for 5-35% of the total As. The amount of bioaccessible As increased with decreasing particle size and was controlled by the slow dissolution kinetics of ferrihydrite in the gastric environment (pH 1.8). The relative BA of As (% of total) decreased with decreasing particle size only in a highly As-contaminated soil--which supported by Fe XAS--suggests the formation of As-rich hydrous ferric oxides in the gastric extracts. Multiple linear regression analyses identified Al, total As, C(org), and P as main predictors for the absolute BA of As (adjusted R(2) ≤ 0.977). Health risk assessments for residential adults showed that (i) nearly half of the bulk soils may cause adverse health effects and (ii) particles <5 μm pose the highest absolute health threat upon incidental soil ingestion. Owing to their low abundance, however, health risks were primarily associated with particles in the 5-50 and 100-200 μm size ranges. These particles are easily mobilized from riverbanks during flooding events and dispersed within the floodplain or transported downstream.

Topics: Arsenic; Arsenicals; Environmental Pollution; Ferric Compounds; Iron Compounds; Minerals; Mining; Rivers; Soil; Soil Pollutants; Sulfides; X-Ray Absorption Spectroscopy

It has recently been reported that the Fe(II)-catalyzed crystallization of 2-line ferrihydrite to goethite and magnetite can result in the immobilization of uranium. Although it might be expected that interference of the crystallization process (for example, by the presence of silicate) would prevent uranium immobilization, this has not yet been demonstrated. Here we present results of an X-ray absorption spectroscopy study on the fate of hexavalent uranium (U(VI)) during the Fe(II)-catalyzed transformations of 2-line ferrihydrite and ferrihydrite coprecipitated with silicate (silicate-ferrihydrite). Two-line ferrihydrite transformed monotonically to goethite, whereas silicate-ferrihydrite transformed into a form similar to ferrihydrite synthesized in the absence of silicate. Modeling of U L(III)-edge EXAFS data indicated that both coprecipitated and adsorbed U(VI) were initially associated with ferrihydrite and silicate-ferrihydrite as a mononuclear bidentate surface complex. During the Fe(II)-catalyzed transformation process, U(VI) associated with 2-line ferrihydrite was reduced and partially incorporated into the newly formed goethite mineral structure, most likely as U(V), whereas U(VI) associated with silicate-ferrihydrite was not reduced and remained in a form similar to its initially adsorbed state. Uranium(VI) that was initially adsorbed to silicate-ferrihydrite did, however, become more resistant to reductive dissolution indicating at least a partial reduction in mobility. These results suggest that when the Fe(II)-catalyzed transformation of ferrihydrite-like iron oxyhydroxides is inhibited, at least under conditions similar to those used in these experiments, uranium reduction will not occur.

Topics: Adsorption; Ferric Compounds; Ferrosoferric Oxide; Ferrous Compounds; Iron Compounds; Minerals; Oxidation-Reduction; Uranium

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

Lead (Pb) bioaccessibility was assessed using 2 in vitro methods in 12 Pb-contaminated soils and compared to relative Pb bioavailability using an in vivo mouse model. In vitro Pb bioaccessibility, determined using the intestinal phase of the Solubility Bioaccessibility Research Consortium (SBRC) assay, strongly correlated with in vivo relative Pb bioavailability (R(2) = 0.88) following adjustment of Pb dissolution in the intestinal phase with the solubility of Pb acetate at pH 6.5 (i.e., relative Pb bioaccessibility). A strong correlation (R(2) = 0.78) was also observed for the relative bioaccessibility leaching procedure (RBALP), although the method overpredicted in vivo relative Pb bioavailability for soils where values were <40%. Statistical analysis of fit results from X-ray absorption near-edge structure (XANES) data for selected soils (n = 3) showed that Pb was strongly associated with Fe oxyhydroxide minerals or the soil organic fraction prior to in vitro analysis. XANES analysis of Pb speciation during the in vitro procedure demonstrated that Pb associated with Fe minerals and the organic fraction was predominantly solubilized in the gastric phase. However, during the intestinal phase of the in vitro procedure, Pb was strongly associated with formation of ferrihydrite which precipitated due to the pH (6.5) of the SBRC intestinal phase. Soils where Fe dissolution was limited had markedly higher concentrations of Pb in solution and hence exhibited greater relative bioavailability in the mouse model. This data suggests that coexistence of Fe in the intestinal phase plays an important role in reducing Pb bioaccessibility and relative bioavailability.

Topics: Animals; Biological Availability; Cities; Environmental Monitoring; Ferric Compounds; In Vitro Techniques; Lead; Mice; Soil Pollutants; X-Ray Absorption Spectroscopy

The photodissolution of the iron oxyhydroxide, ferrihydrite, in the presence of oxalic acid was investigated with vibrational spectroscopy, density functional theory (DFT) calculations, and batch geochemical techniques that determined the composition of the solution phase during the dissolution process. Specifically, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR- FTIR) was used to determine the structure of the adsorbed layer during the dissolution process at a solution pH of 4.5. DFT based computations were used to interpret the vibrational data associated with the surface monolayer in order to help determine the structure of the adsorbed complexes. Results showed that at pH 4.5, oxalate adsorbed on ferrihydrite adopted a mononuclear bidentate (MNBD) binding geometry. Photodissolution at pH 4.5 exhibited an induction period where the rate of Fe(II) release was limited by a low concentration of adsorbed oxalate due to the site-blocking of carbonate that was intrinsic to the surface of the ferrihydrite starting material. Oxalate displaced this initial carbonate over time, and the dissolution rate showed a corresponding increase. Irradiation of oxalate/ferrihydrite at pH 4.5 also ultimately led to the appearance of carbonate reaction product (distinct from carbonate intrinsic to the starting material) on the surface.

Topics: Adsorption; Ferric Compounds; Oxalic Acid; Photochemistry; Quantum Theory; Spectroscopy, Fourier Transform Infrared; Surface Properties; Vibration

Dihydrogenarsenate [H(2)AsO(4)(-), As(V)] or dichromate [Cr(2)O(7)(2-), Cr(VI)] at pH=4.0 showed to be sorbed on a Fe(OH)(x)-polymerin complex and ferrihydrite to a greater extent than on polymerin, the organic polymeric fraction of olive oil mill wastewater (OMW). In particular, the maximum amount (x(m)) of arsenate sorbed on Fe(OH)(x)-polymerin complex was similar to that on ferrihydrite (880.26 and 743.02 mmol kg(-1), respectively), and was much greater than that sorbed on polymerin (384.25 mmol kg(-1)). The sorption of dichromate was to a comparable extent on Fe(OH)(x)-polymerin complex and ferrihydrite (205.90 and 254.88 mmol kg(-1), respectively). Cr(III), a less toxic chromium form, mainly, and Cr(V) were indeed the effective forms sorbed on polymerin (200 mmol kg(-1)), as a consequence of the redox reaction of the strongly toxic Cr(VI) with the CH(2)OH groups of the polysaccharide moiety of this bio-sorbent, according to the data deriving from XPS and DRIFT analyses. The potential exploitation of the selected sorbents for the removal of As(V) or Cr(VI) from aqueous effluents is briefly discussed.

Topics: Adsorption; Anions; Arsenates; Chromates; Ferric Compounds; Industrial Waste; Oxidation-Reduction; Polymers; Water Pollutants, Chemical