Ferrihydrite Surface Research Articles

Vanadate complexation to ferrihydrite: X-ray absorption spectroscopy and CD-MUSIC modelling

Environmental contextVanadium, a metal pollutant from fossil fuels and slags, may be toxic, thereby necessitating an understanding of its environmental chemistry. One important factor that controls the mobility and bioavailability of vanadium is its binding to iron oxides. This study focuses on the characterization and modelling of vanadium adsorption onto ferrihydrite. The new model can be used to simulate the transport and bioavailability of vanadium in the environment. AbstractThe mobility of vanadium in the environment is influenced by sorption to metal (hydr)oxides, especially those containing iron. The aim of this study is to understand the adsorption behaviour of vanadium on poorly ordered (two-line) ferrihydrite (Fh). A further objective was to determine the binding mechanism of vanadate(V) to ferrihydrite surfaces in aqueous suspension to constrain the CD-MUSIC surface complexation model. Vanadium adsorption to ferrihydrite was evaluated by batch experiments which included series with different Fh-to-V ratios and pH values. Vanadate(V) adsorption was also evaluated in the presence of phosphate to compete with vanadate(V) for the available surface sites on ferrihydrite. In agreement with earlier studies, vanadate(V) was strongly adsorbed to ferrihydrite and the adsorption increased with decreasing pH. In the presence of phosphate, less vanadate(V) was adsorbed. Analysis by X-ray absorption near-edge structure spectroscopy revealed that the adsorbed vanadium was tetrahedral vanadate(V), VO4, regardless of whether vanadate(V) or vanadyl(IV) was added to the system. Spectra collected by extended X-ray absorption fine structure spectroscopy showed that vanadate(V) is bound primarily as an edge-sharing bidentate complex with V⋯Fe distances around 2.8Å. Based on this information, a surface complexation model was set up in which three bidentate vanadate(V) complexes with different degrees of protonation were included. The model provided a satisfactory description of vanadate(V) adsorption over most of the pH and concentration ranges studied, also in the presence of competing phosphate ions.

Fe(II)-induced phase transformation of ferrihydrite: The inhibition effects and stabilization of divalent metal cations

The Fe(II)-induced phase transformation of iron (hydr)oxides is an important process in the geochemical iron cycle and is one in which the coexisting metal cations inhibit the phase transformation rates. However, the underlying affecting mechanisms by metal cations and the critical property of metal cations that is responsible for the inhibition remain unclear. In this study, we focus on the cation effect of seven divalent cations (denoted as Me(II), including Mg(II), Ca(II), Ba(II), Mn(II), Co(II), Ni(II), and Zn(II)) and their influencing mechanisms on Fe(II)-catalyzed transformation processes of ferrihydrite. At initial reaction conditions (i.e. pH6.5 and 2.0mM Fe(II)), the binding ability (the affinity of cations for ferrihydrite surface) of Me(II) was found to affect the ferrihydrite transformation. Me(II) with higher binding abilities reduced the bound-Fe(II) amount on ferrihydrite and decreased the redox potentials of the Fe(II)-catalyzed system to inhibit the transformation rates of ferrihydrite. In addition to the inhibition effect, the Me(II) was partly stabilized in the formed secondary iron minerals. The binding abilities of Me(II) also affected the Fe(II)-induced transformation pathways of ferrihydrite by affecting the amount of bound-Fe(II) on ferrihydrite. Ferrihydrite was first transformed to lepidocrocite and later to goethite and magnetite with Me(II) that had lower binding ability than Fe(II), whereas it was directly transformed to goethite and magnetite when with Me(II) that had higher binding ability than Fe(II).

Underestimation of phosphorus fraction change in the supernatant after phosphorus adsorption onto iron oxides and iron oxide–natural organic matter complexes

The phosphorus (P) fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide–humic acid (HA) complexes were analyzed using the ultrafiltration method in this study. With an initial P concentration of 20mg/L (I=0.01mol/L and pH=7), it was shown that the colloid (1kDa–0.45μm) component of P accounted for 10.6%, 11.6%, 6.5%, and 4.0% of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite (FH), goethite (GE), ferrihydrite–humic acid complex (FH–HA), goethite–humic acid complex (GE–HA), respectively. The <1kDa component of P was still the predominant fraction in the supernatant, and underestimated colloidal P accounted for 2.2%, 55.1%, 45.5%, and 38.7% of P adsorption onto the solid surface of FH, FH–HA, GE and GE–HA, respectively. Thus, the colloid P could not be neglected. Notably, it could be interpreted that Fe3+ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant. And colloidal adsorbent particles co-existing in the supernatant were another important reason for it. Additionally, dissolve organic matter dissolved from iron oxide–HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant. Ultimately, we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P, even when considering other contaminants such as organic pollutants, heavy metal ions, and arsenate at the sediment/soil–water interface in the real environment.

X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces.

Sulfate adsorption on mineral surfaces is an important environmental chemical process, but the structures and respective contribution of different adsorption complexes under various environmental conditions are unclear. By combining sulfur K-edge XANES and EXAFS spectroscopy, quantum chemical calculations, and surface complexation modeling (SCM), we have shown that sulfate forms both outer-sphere complexes and bidentate-binuclear inner-sphere complexes on ferrihydrite surfaces. The relative fractions of the complexes vary with pH, ionic strength (I), and sample hydration degree (wet versus air-dried), but their structures remained the same. The inner-sphere complex adsorption loading decreases with increasing pH while remaining unchanged with I. At both I = 0.02 and 0.1 M, the outer-sphere complex loading reaches maximum at pH ∼5 and then decreases with pH, whereas it monotonically decreases with pH at I = 0.5 M. These observations result from a combination of the ionic-strength effect, the pH dependence of anion adsorption, and the competition between inner- and outer-sphere complexation. Air-drying drastically converts the outer-sphere complexes to the inner-sphere complexes. The respective contributions to the overall adsorption loading of the two complexes were directly modeled with the extended triple layer SCM by implementing the bidentate-binuclear inner-sphere complexation identified in the present study. These findings improve our understanding of sulfate adsorption and its effects on other environmental chemical processes and have important implications for generalizing the adsorption behavior of anions forming both inner- and outer-sphere complexes on mineral surfaces.

Ge/Si in Hamersley BIF as tracer of hydrothermal Si and Ge inputs to the Paleoproterozoic ocean

Ge/Si and Ge/Fe ratios have been measured by laser ablation ICP-MS in selected sections of the Hamersley banded iron-formation (BIF), including ‘chert-siderite’ bands (i.e. carbonate- and silicate-facies BIF). The major Ge carriers are magnetite and hematite in the oxide-facies, and the Fe-rich silicates greenalite, minnesotaite and stilpnomelane in chert-siderite bands, while quartz has the lowest Ge/Si ratios (0.15–0.7μmol/mol), in accord with discrimination against Ge in quartz. The homogeneous Si/Fe ratio of 1.25 for Dales Gorge oxide-facies BIF is consistent with Si-ferrihydrite as precursor phase. This Si concentration is sufficiently high for formation of iron-free silica clusters at the surface of ferrihydrite, so that only a minor fractionation of the Ge/Si ratio should result from preferential Ge adsorption relative to Si. Hematite-chert bands that have been minimally altered by metamorphic reactions and/or fluid metasomatism, are the preferred material to determine the sources of silica in Hamersley BIF. Variations of Fe/Si and Ge/Si ratios in chert mesobands are interpreted as the result of diagenetic mineral segregation. A consistent Ge/Si ≈3μmol/mol is then derived by extrapolation of measured Ge/Si ratios to the average Fe/Si composition of Dales Gorge BIF. Simple mass balance calculations indicate hydrothermal inputs to the ocean of the order of 25% for Si and 90% for Ge, assuming Ge/Si=10μmol/mol for high-temperature hydrothermal fluids. The high Si concentration in siderite-chert bands (Si/Fe≈4) demands only a small amount of Si-ferrihydrite precursor and some excess silica likely precipitated in pore-water oversaturated with regard to amorphous silica. The average Ge/Si=0.80±0.1μmol/mol for bulk chert-siderite samples, including some stilpnomelane-rich cherts, is within the compositional range of modern riverine and aeolian inputs, pointing to a continental Si source during their deposition.

Limited reduction of ferrihydrite encrusted by goethite infreshwater sediment.

Many physical and chemical processes control the extent of Fe(III) oxyhydroxide reduction by dissimilatory Fe(III)-reducing bacteria. The surface precipitation of secondary Fe minerals on Fe(III) oxyhydroxides limits the extent of microbial Fe(III) reduction, but this phenomenon has not yet been observed in nature. This paper reports the observation of secondary Fe-mineral (goethite) encrustation on ferrihydrite surface within freshwater sediment up to 10cm deep. The sediment surface was characterized by the predominance of ferrihydrites with biogenic stalks and sheaths. An Fe(II)-oxidizing bacterium (Gallionellaceae) was detected by 16S rRNA gene analysis at sediment depths of 1 and 2cm. Fe(2+) concentration in the sediment pore water was relatively higher at 2-4cm depths. The 16S rRNA genes affiliated with dissimilatory Fe(III)-reducing bacteria were detected at 1, 2, and 4cm depths. The results of the Fe K-edge extended X-ray absorption fine structure (EXAFS) analysis suggested the presence of goethite and siderite at depths below 3cm. However, the change in the Fe-mineral composition was restricted to sediment depths between 3 and 4cm, despite the presence of abundant ferrihydrite at depths below 4cm. An increase in CH4 concentration was observed at deeper than 6cm. Stable isotopic analysis of CH4 in the pore water indicated that acetoclastic CH4 occurred at depths below 7cm. Transmission electron microscope observations suggested the presence of goethite and siderite on stalks and sheaths at depths below 3cm. Results from conversion electron yield EXAFS analysis suggested that goethite dominated at 10cm depth, thereby indicating that ferrihydrite was encrusted by goethite at this depth. Moreover, the incomplete reduction of ferrihydrite below depths of 4cm was not due to the lack of organic carbon, but was possibly due to the surface encrustation of goethite on ferrihydrite.

Phosphate effects on cadmium(II) sorption to ferrihydrite

HypothesisPhosphate influences the sorption of metals to iron (hydr)oxides. An enhanced formation of inner-sphere complexes on the (hydr)oxide surface can be attributed to electrostatic interactions and/or to changes in metal coordination on the iron (hydr)oxide surface. Phosphate was expected to increase cadmium(II) sorption on ferrihydrite. It should be possible to identify changes in cadmium(II) coordination upon phosphate addition by Extended X-ray absorption fine structure (EXAFS) spectroscopy and implement the identified complexes in a surface complexation model (SCM). ExperimentsThe effect of phosphate addition on cadmium(II) sorption to ferrihydrite was studied by a series of batch experiments covering the pH range from 4 to 8. EXAFS spectroscopy was performed on ferrihydrite from the batch experiments at the cadmium K edge. The identified surface complexes were incorporated in the Charge distribution multisite complexation (CD-MUSIC) model, and new surface complexation constants were optimized. FindingsWithout phosphate addition cadmium(II) formed inner-sphere bidentate complexes on the ferrihydrite surface. With phosphate there was an increased cadmium(II) sorption that could not be explained by electrostatic interactions alone. The enhancement was best explained by the formation of a ternary complex including cadmium(II), phosphate and ferrihydrite surface groups.

Mechanisms of Chromate, Selenate, and Sulfate Adsorption on Al-Substituted Ferrihydrite: Implications for Ferrihydrite Surface Structure and Reactivity

Ferrihydrite is a nanocrystalline Fe (hydr)oxide and important sink for environmental contaminants. Although Fe (hydr)oxides are rarely pure in natural systems, little is known about the effects of structural impurities such as Al on the surface properties and reactivity of ferrihydrite. In this study, we characterized the adsorption mechanisms of chromate, selenate, and sulfate on Al-substituted ferrihydrite (0, 6, 12, 18, and 24 mol % Al) using in situ attenuated total reflection Fourier transform infrared spectroscopy. Spectral data sets recorded as a function of pH were processed using a multivariate curve resolution technique to identify which types of surface species form and to generate their concentration profiles as a function of pH and Al content. Results show a significant increase in relative fraction of outer-sphere complexes for all three oxyanions with increasing Al substitution. In addition, the effect of Al substitution is found to be mechanism-specific in the case of chromate, with bidentate complexes disproportionately suppressed over monodentate complexes at higher Al contents. Overall, our findings have important implications for the fate of chromate, selenate, and sulfate in subsurface environments and offer new insight into the surface reactivity of Al-ferrihydrite.

Desorption mechanisms of phosphate from ferrihydrite and goethite surfaces

The fate of phosphate in the environment is governed by reactions at particle surfaces. These adsorption and desorption reactions display biphasic kinetics involving an initial rapid reaction followed by a substantially slower one extending over long time periods. In this study we have investigated the molecular mechanisms of desorption kinetics of phosphate from ferrihydrite and goethite nanoparticles in the absence of competing ligands. Desorption was studied by means of in-situ infrared (IR) spectroscopy over a wide pH range and a time period of 24h. The spectroscopic data sets were subjected to multivariate curve resolution alternating least squares (MCR-ALS), which enabled the resolution of surface species characterized by unique IR spectra together with their corresponding kinetic profiles. The desorption results showed the typical biphasic behavior and that increasing positive surface charge of ferrihydrite and goethite slowed down desorption of the negatively charged phosphate ions. Moreover, diprotonated phosphate desorbed faster than monoprotonated phosphate at a given pH. At circumneutral pH values desorption from ferrihydrite was substantially faster as compared to goethite, and this could be ascribed to electrostatic effects and differences in charging between ferrihydrite and goethite. The collective desorption results were explained by a model, consisting of a series monodentate phosphate surface complexes in different protonation states, in conjunction with a description that accounts for the electrostatic effects on desorption kinetics at charged mineral-water interfaces. The fast and slow desorption followed directly from this model and indicated that biphasic kinetics can be caused by a single phosphate surface complex as a result of decreasing surface coverage along with the lateral repulsive interactions between adsorbed phosphate groups. Hence, in contrast to previous models our study has shown that biphasic desorption kinetics do not have to involve several different structural complexes related to either weak and strong sites or a distribution of phosphate between external surfaces and mineral pores.

Exploring the critical dependence of the adsorption of various dyes on the degradation rate using a ferrihydrite surface under visible light

The strength of the affinity between dyes and ferrihydrite has an important influence on their degradation rate in a Fenton-like system.

Arsenic retention and transport behavior in the presence of typical anionic and nonionic surfactants

The massive production and wide use of surfactants have resulted in a large amount of surfactant residuals being discharged into the environment, which could have an impact on arsenic behavior. In the present study, the influence of the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) and nonionic surfactant polyethylene glycol octylphenyl ether (Triton X-100) on arsenic behavior was investigated in batch and column tests. The presence of SDBS and Triton X-100 reduced arsenic retention onto ferrihydrite (FH), enhanced arsenic transport through FH coated sand (FH-sand) columns and promoted arsenic release from the FH surface. With coexisting surfactants in solution, the equilibrium adsorbed amount of arsenic on FH decreased by up to 29.7% and the adsorption rate decreased by up to 52.3%. Pre-coating with surfactants caused a decrease in the adsorbed amount and adsorption rate of arsenic by up to 15.1% and 58.3%, respectively. Because of the adsorption attenuation caused by surfactants, breakthrough of As(V) and As(III) with SDBS in columns packed with FH-sand was 23.8% and 14.3% faster than that in those without SDBS, respectively. In columns packed with SDBS-coated FH-sand, transport of arsenic was enhanced to a greater extent. Breakthrough of As(V) and As(III) was 52.4% and 43.8% faster and the cumulative retention amount was 44.5% and 57.3% less than that in pure FH-sand column systems, respectively. Mobilization of arsenic by surfactants increased with the increase of the initial adsorbed amount of arsenic. The cumulative release amount of As(V) and As(III) from the packed column reached 10.8% and 36.0%, respectively.

Co-adsorption of phosphate and zinc(II) on the surface of ferrihydrite.

Ferrihydrite (Fh) is of great importance in affecting the migration and transformation of heavy-metal cations and oxyanions. To advance the understanding of co-adsorption reactions on Fh surface, the co-adsorption of phosphate and Zn(II) from aqueous solution to a synthesized Fh was determined. The batch experiments demonstrated a synergistic adsorption of phosphate and Zn(II) on Fh. In the pH range of 3.5-6, the adsorption of the two contaminants showed strong pH dependence in the single solute adsorption systems, but the dependence alleviated in the simultaneous adsorption system. X-ray photoelectron spectroscopy (XPS) revealed that the chemical shifts of Zn 2p1/2 and Zn 2p3/2 binding energies were more significant than that of P 2p in the single and simultaneous adsorption systems. On the other side, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) observed increased formation of outer- and inner-sphere complexes of phosphate in the simultaneous system. Thus, the synergistic adsorption of the two contaminants could be attributed to the formation of ternary complexes as well as electrostatic interactions, while surface precipitation could not be completely ruled out. On the basis of the results from both the batch adsorption experiments and structural characterization, these two contaminants were likely to form phosphate-bridged ternary complexes (≡Fe-P-Zn) in the simultaneous adsorption system.

Characterization of the Adsorption of Nucleic Acid Bases onto Ferrihydrite via Fourier Transform Infrared and Surface-Enhanced Raman Spectroscopy and X-ray Diffractometry.

Minerals could have played an important role in concentration, protection, and polymerization of biomolecules. Although iron is the fourth most abundant element in Earth's crust, there are few works in the literature that describe the use of iron oxide-hydroxide in prebiotic chemistry experiments. In the present work, the interaction of adenine, thymine, and uracil with ferrihydrite was studied under conditions that resemble those of prebiotic Earth. At acidic pH, anions in artificial seawater decreased the pH at the point of zero charge (pHpzc) of ferrihydrite; and at basic pH, cations increased the pHpzc. The adsorption of nucleic acid bases onto ferrihydrite followed the order adenine >> uracil > thymine. Adenine adsorption peaked at neutral pH; however, for thymine and uracil, adsorption increased with increasing pH. Electrostatic interactions did not appear to play an important role on the adsorption of nucleic acid bases onto ferrihydrite. Adenine adsorption onto ferrihydrite was higher in distilled water compared to artificial seawater. After ferrihydrite was mixed with artificial seawaters or nucleic acid bases, X-ray diffractograms and Fourier transform infrared spectra did not show any change. Surface-enhanced Raman spectroscopy showed that the interaction of adenine with ferrihydrite was not pH-dependent. In contrast, the interactions of thymine and uracil with ferrihydrite were pH-dependent such that, at basic pH, thymine and uracil lay flat on the surface of ferrihydrite, and at acidic pH, thymine and uracil were perpendicular to the surface. Ferrihydrite adsorbed much more adenine than thymine; thus adenine would have been better protected against degradation by hydrolysis or UV radiation on prebiotic Earth.

Removal of arsenate by ferrihydrite via surface complexation and surface precipitation

In this study, macroscopic and spectroscopic experimental methods accurately modeled the sorption process of arsenate on ferrihydrite. EXAFS, X-ray diffraction and infrared (IR) spectroscopy indicated that the behavior of As(V) adsorption onto ferrihydrite took place mainly via surface complexation and surface precipitation at acidic pH (3.0–6.0), while the surface precipitation was dominated at longer time intervals and higher Fe3+ concentration. The macroscopic competitive adsorption experiment between arsenate with phosphate indicated two types of adsorption sites existing on the surface of ferrihydrite, i.e., non-exchangeable sites, which are responsible for a rapid surface complex formation; and exchangeable sites for a slow build-up of surface precipitates. In the slow build-up precipitates, the As(V) surface coverage (mmol/g) exhibited a good linear relationship (R2=0.952) with the amount of dissolved Fe3+. Three steps are involved during the process of surface precipitation, i.e., (1) an initial uptake of As(V) via surface complexation; (2) re-adsorption of Fe3+ leaching from ferrihydrite on the surface complex; and (3) As(V) adsorption via surface complexation again and finally forming the surface precipitate.

Iron-Modification of Pyroclastic Material from PCCVC Eruption (Chile): Characterization and Application to Remove Arsenic from Groundwater

Pyroclastic material from the PCCVC eruption (Chile) was modified with iron (III) solutions leading to the formation of ferrihydrite surface deposits. The aim of the chemical treatment was to prepare an adsorbent to remove arsenic from water by using low-cost mineral wastes. Physicochemical characterization of original and modified materials was carried out by XRD, BET-N2 adsorption, SEM-EDS microscopy and ICP-AES chemical analysis. The modified ash revealed that the increase of bulk iron content was close to 5% (expressed as Fe2O3) whereas surface values were 20.6% Fe2O3. Surface properties showed an increase of BET specific surface with prevalence of mesopores and an increase of total pore volume attributed to presence of nanoscopic iron phase. Kinetic and equilibrium studies were directed to optimize the operative conditions related to the material adsorptive capacity for removing arsenate species. Hence, the adsorbent dose, contact time, pH, stirring and sedimentation were evaluated in batch process. The optimal adsorption dose was 40 g ·L-1 and the solid-liquid contact time was stirring (1 h) and sedimentation (23 h), enough to ensure an adequate turbidity value valid for a pH range between 3.77 and 8.95. The analysis of the isotherm equilibrium by using the Langmuir linear method showed a R2 = 0.995 value. The performance of the treatment to remove arsenic by using a cost-effective adsorbent prepared from volcanic material is a promising technology to apply in the environmental field.

Parametrization of a classical force field for iron oxyhydroxide/water interfaces based on Density Functional Theory calculations

We perform a study of the bulk and surface properties of FeOx(OH)y phases in contact with water by means of electronic structure calculations based on Density Functional Theory (DFT), and develop a classical potential to study FeOx(OH)y/water interfaces in combination with standard biomolecular force fields. We identify the optimal position of the H atoms in the bulk unit cell of ferrihydrite and confirm an experimental prediction suggesting an antiferromagnetic ordering of the Fe(III) ions in the ground state. Surface free energy calculations reveal that the most stable (0001) ferrihydrite surface in equilibrium with bulk water and dissolved oxygen is a fully hydroxylated plane terminating octahedrally-coordinated Fe atoms. DFT potential energy profiles of small molecules (water, ammonia, formic acid) adsorbing at hydrated goethite and ferrihydrite surfaces are used as a basis to optimize and validate the parameters of the classical potential. The identified set of parameters is able to reproduce the DFT energy values at the surface/molecule equilibrium adsorption position, and predicts the heat of immersion of goethite and ferrihydrite surfaces in good agreement with experimental measurements for FeOOH particles. However, as a general tendency the equilibrium surface–molecules Fe–O bond distances are slightly underestimated, motivating future analyses of the adsorption free energy and adhesion forces of small peptides on ferrihydrite and goethite surfaces to further evaluate the predictive power of the developed force field.

Effect of solution and solid-phase conditions on the Fe(II)-accelerated transformation of ferrihydrite to lepidocrocite and goethite.

Aqueous ferrous iron (Fe(II)) accelerates the transformation of ferrihydrite into secondary, more crystalline minerals however the factors controlling the rate and, indeed, the underlying mechanism of this transformation process remain unclear. Here, we present the first detailed study of the kinetics of the Fe(II)-accelerated transformation of ferrihydrite to goethite, via lepidocrocite, for a range of pH and Fe(II) concentrations and, from the results obtained, provide insight into the factors controlling the transformation rate and the processes responsible for transformation. A reaction scheme for the Fe(II)-accelerated secondary mineralization of ferrihydrite is developed in which an Fe(II) atom attaches to the ferrihydrite surface where it is immediately oxidized to Fe(III) with the resultant electron transferred, sequentially, to other iron oxyhydroxide Fe(III) atoms before release to solution as Fe(II). This freshly precipitated Fe(III) forms the nuclei for the formation of secondary minerals and also facilitates the ongoing uptake of Fe(II) from solution by creation of fresh surface sites. The concentration of solid-associated Fe(II) and the rate of transport of Fe(II) to the oxyhydroxide surface appear to determine which particular secondary minerals form and their rates of formation. Lepidocrocite growth is enhanced at lower solid-associated Fe(II) concentrations while conditions leading to more rapid uptake of Fe(II) from solution lead to higher goethite growth rates.

Chemical processes for the extreme enrichment of tellurium into marine ferromanganese oxides

Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation.This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as in the case of some cations. This enrichment mechanism also means that ferromanganese oxides mainly scavenge dominant Te(VI) species from seawater and do not affect its species distribution in seawater, as described in a previous model. The variation in Te abundances and the correlation of Te concentration with the growth rate of natural ferromanganese oxides are consistent with the coprecipitation mechanism.

Observations and assessment of iron oxide and green rust nanoparticles in metal-polluted mine drainage within a steep redox gradient

Environmental context Legacy contamination from mining operations is a serious and complex environmental problem. We examine a former uranium mine where groundwater leaving the site enters a stream with chemically dramatic effects resulting in a fundamental change in the way contaminant metals are transported to the surface environment. The results are important for our understanding of how these contaminants are dispersed, and how they could interact with the biosphere. Abstract In this study of iron- and silica-bearing nanoparticle and colloid aggregates in slightly acidic mine drainage, we combined bulk scale geochemistry techniques with detailed nanoscale analyses using high-resolution transmission electron microscopy (HR-TEM) to demonstrate the complexity of iron oxide formation and transformation at a steep redox gradient (groundwater outflow into a stream), and the resulting role in metal(loid) uptake. We also identified pseudohexagonal nanosheets of Zn-bearing green rust in outflowing groundwater using HR-TEM. This is only the second study where green rust was identified in groundwater, and the second to examine naturally occurring green rust with analytical TEM. In aerated downstream waters, we found aggregates of poorly crystalline iron oxide particles (20–200nm in diameter). Inductively coupled plasma–mass spectrometry (ICP-MS) analysis of water fractions shows that most elements such as Ni and Zn were found almost exclusively in the dissolved–nanoparticulate (&lt;0.1μm) fraction, whereas Cu and As were primarily associated with suspended particles. In the underlying sediments composed of deposited particles, goethite nanoneedles formed on the ferrihydrite surfaces of larger aggregated particles (100–1000nm), resulting in more reactive surface area for metal(loid) uptake. Sequential extraction of sediments showed that many metal(loid)s, particularly As and Zn, were associated with iron oxides identified as ferrihydrite, goethite and possibly schwertmannite. Amorphous silica co-precipitation with iron oxides was prevalent at all sampling sites, but its effect on metal(loid) sorption is unknown. Fine-grained iron oxide sediments are easily remobilised during turbulent flow events, adding to the mobility of the associated metals.

Structure of Sulfate Adsorption Complexes on Ferrihydrite

Sulfate adsorption on mineral surfaces is an important environmental chemical process. However, the structure of sulfate adsorption complexes has remained uncertain. In this study, we have determined the S−Fe distance of sulfate inner-sphere adsorption complexes on iron (Fe) oxyhydroxide (ferrihydrite) surfaces under air-dried conditions using sulfur K-edge extended X-ray absorption fine structure spectroscopy and differential X-ray pair distribution function analysis. Both approaches indicate that the S− Fe interatomic distance of the sulfate adsorption complexes is 3.22−3.25 A, suggesting that sulfate forms bidentate−binuclear adsorption complexes on ferrihydrite surfaces. Outer-sphere complexes are also observed using infrared spectroscopic analysis. This finding clarifies the long-standing debate over the structure of sulfate adsorption complexes and has important implications for understanding the chemistry of sulfate at environmental interfaces.