Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

Effect of phosphate, silicate, and Ca on Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water studied by X-ray absorption spectroscopy

We studied the local coordination and structure of Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water (buffered to pH 7 by 8 mM bicarbonate) using synchrotron-based X-ray absorption spectroscopy (XAS) at the K-edges of Fe, P, Ca, and As. Dissolved phosphate, silicate, and Ca at different ratios relative to each other and to Fe affect the forming Fe(III)-phases in a complex manner. The high affinity of phosphate for Fe(III) results in the predominant precipitation of Fe(III)-phosphate as long as dissolved phosphate is present, with Fe(III) polymerization limited to small oligomers. In Ca-containing solution, Ca uptake by Fe(III)-Ca-phosphate involves the linkage and coagulation of negatively charged Fe(III)-phosphate oligomers via Ca-O-P bonds. In the absence of phosphate, dissolved silicate at Si/Fe ratios above ∼0.5 results in the formation of hydrous ferric oxide (HFO) with mainly edge-sharing Fe-Fe linkage. At lower Si/Fe ratios of ∼0.5-0.1, mainly 2-line ferrihydrite (2L-Fh) with both edge- and corner-sharing Fe-Fe linkage forms. Only in the absence of phosphate at low Si/Fe ratio, lepidocrocite (Lp) forms. In solutions containing sufficient Fe(II), aeration results in the sequential precipitation of Fe(III)-(Ca-)phosphate, HFO or 2L-Fh (depending on solution Si/Fe), and finally Lp. The amount and oxidation state of As co-precipitated with Fe(III) are controlled by the co-oxidation of As(III) with Fe(II), which increases with initial Fe/As ratio, and the competitive uptake of phosphate, As(V) and less strongly sorbing silicate and As(III). This study demonstrates that the diversity and sequence of short-range-ordered Fe(III)-precipitates forming by Fe(II) oxidation in near-neutral natural waters depend on water chemistry. Because differences in the colloidal stability and biogeochemical reactivity of these phases will affect the fate of associated major and trace elements, the different Fe(III)-precipitates and their specific biogeochemical properties must be taken into account when addressing nutrient and contaminant dynamics at redox boundaries in natural and engineered systems.     

江汉平原浅层含水层中土著硫酸盐还原菌对砷迁移释放的影响

硫酸盐还原菌是厌氧环境中参与砷形态转化的重要微生物种群,其介导的生物地球化学循环过程对铁氧化物表面吸附态砷迁移转化的影响亟待深入研究.选取江汉平原典型高砷含水层原位沉积物分离纯化出一株严格厌氧硫酸盐还原菌Desulfovibrio JH-S1,对其进行砷和铁还原能力鉴定,并通过模拟培养实验探究硫酸盐还原菌参与下的铁矿物相转化对吸附态砷迁移的影响.Desulfovibrio JH-S1具有Fe(III)还原能力,无硫和有硫体系中Fe(III)均能被还原,但在硫酸盐充足条件下铁还原量显著增加;该菌株不具备As(V)还原能力,但添加硫酸盐的培养体系中As(V)去除率可达96%以上.Desulfovibrio JH-S1能够还原硫酸盐从而促进载砷的水铁矿还原转化为纤铁矿,并导致吸附的砷释放.江汉平原高砷含水层土著硫酸盐还原菌兼具硫酸盐/铁还原功能,参与了高砷含水层系统中砷-铁-硫耦合循环,对高砷地下水的形成具有重要作用.      

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.     

Effect of phosphate, silicate, and Ca on the morphology, structure and elemental composition of Fe(III)-precipitates formed in aerated Fe(II) and As(III) containing water

We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (∼0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (<0.1). Results from this study show that the size of the polymeric units increased along the same sequence and that the aggregation of these polymeric units resulted in spherical particles with characteristic surface textures changing from smooth to coarse. The diameter of the spherical particles increased from 15 to 380 nm as the molar ratio (P + Si + As)/Fe(II) in the starting solution decreased and larger spherical particles precipitated from Ca-containing than from Ca-free solutions. These trends suggested that the size of the spherical particles was controlled by the charge of the polymeric units. Spherical particles coagulated into flocs whose size was larger in the presence than in the absence of Ca. Further observations pointed to the importance of Fe(II) oxidation and polymerization versus polymer aggregation and floc formation kinetics in controlling the spatial arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic.     

Size, density and composition of cell-mineral aggregates formed during anoxygenic phototrophic Fe(II) oxidation: Impact on modern and ancient environments

Cell-Fe(III) mineral aggregates produced by anoxygenic Fe(II)-oxidizing photoautotrophic microorganisms (photoferrotrophs) may be influential in the modern Fe cycle and were likely an integral part of ancient biogeochemical cycles on early Earth. While studies have focused on the environmental conditions under which modern photoferrotrophs grow and the kinetics, physiology and mechanism of Fe(II) oxidation, no systematic analyses of the physico-chemical characteristics of those aggregates, such as shape, size, density and chemical composition, have as yet been conducted. Herein, experimental results show most aggregates are bulbous or ragged in shape, with an average particle size of 10-40 μm, and densities that typically range between 2.0 and 2.4 g/cm³; the cell fraction of the aggregates increased and their density decreased with initial Fe(II) concentration. The mineralogy of the ferric iron phase depended on the composition of the medium: goethite formed in cultures grown by oxidation of dissolved Fe(II) medium in the presence of low phosphate concentrations, while poorly ordered ferrihydrite (or Fe(III) phosphates) formed when amorphous Fe(II) minerals (Fe(II)-phosphates) and high concentrations of phosphate were initially present. Importantly, in all experiments, a fraction of the photoautotrophic cells remained planktonic, demonstrating a constant stoichiometric excess of Fe(III) compared to the autotrophically fixed carbon in the biogenic precipitate. These results not only have an important bearing on nutrient and trace element cycling in the modern water column, but the size, shape and composition of the aggregates can be used to estimate aggregate reactivity during sediment diagenesis over short and geologic time scales.     

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。     

Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.     

Intermobility of barium,strontium, and lead in chloride and sulfate leach solutions

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t_50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t_50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

     

Iron oxide incrustations in wells. Part 1: genesis,mineralogy and geochemistry

The formation of incrustations seriously affects the performance of wells, piezometers and drains. Their economic relevance must not be underestimated. Oxides of Fe(III) represent the most common incrustation type. Their formation via oxidation of dissolved Fe(II) is enhanced at zones of elevated flow velocities. The first, “amorphous” precipitates (ferrihydrite) are thermodynamically unstable and re-crystallise with time to form stable phases, mainly goethite (“ageing”). This transformation involves a decrease of surface area and a simultaneous decrease in reactivity and explains why older incrustations are harder to remove by chemical treatment. During formation, Fe oxide incrustations take up large amounts of trace elements from groundwater. Anions such as phosphate and arsenate dominate over cations. Anions are surface-bound and are mostly expelled with the decrease of surface area during ageing. Cations are probably bound in the crystal structure rather than as sorbed surface species. Only those with large ionic radius are mostly not expelled during ageing. Trace element concentrations influence the rate of transformation and the solubility of Fe oxide incrustations.     

Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using ⁵⁷Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O₂, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

Schwertmannite stability in acidified coastal environments

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.     

Influence of pH and dissolved Si on Fe isotope fractionation during dissimilatory microbial reduction of hematite

Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low ⁵⁶Fe/⁵⁴Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ⁵⁶Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ⁵⁶Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.     

Contrasting effects of Al substitution on microbial reduction of Fe(III) (hydr)oxides

Aluminum, one of the most abundant elements in soils and sediments, is commonly found co-precipitated with Fe in natural Fe(III) (hydr)oxides; yet, little is known about how Al substitution impacts bacterial Fe(III) reduction. Accordingly, we investigated the reduction of Al substituted (0-13 mol% Al) goethite, lepidocrocite, and ferrihydrite by the model dissimilatory Fe(III)-reducing bacterium (DIRB), Shewanella putrefaciens CN32. Here we reveal that the impact of Al on microbial reduction varies with Fe(III) (hydr)oxide type. No significant difference in Fe(III) reduction was observed for either goethite or lepidocrocite as a function of Al substitution. In contrast, Fe(III) reduction rates significantly decreased with increasing Al substitution of ferrihydrite, with reduction rates of 13% Al-ferrihydrite more than 50% lower than pure ferrihydrite. Although Al substitution changed the minerals’ surface area, particle size, structural disorder, and abiotic dissolution rates, we did not observe a direct correlation between any of these physiochemical properties and the trends in bacterial Fe(III) reduction. Based on projected Al-dependent Fe(III) reduction rates, reduction rates of ferrihydrite fall below those of lepidocrocite and goethite at substitution levels equal to or greater than 18 mol% Al. Given the prevalence of Al substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe (hydr)oxide bioavailability and suggest a more prominent role of natural lepidocrocite and goethite phases in impacting DIRB activity in soils and sediments.     

Ferrous phosphate surface precipitates resulting from the reduction of intragrain 6-line ferrihydrite by Shewanella oneidensis MR-1

The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO₃), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behavior with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L⁻¹ Fe(III)_T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.     

Mössbauer hyperfine parameters of iron species in the course of <Emphasis Type="Italic">Geobacter</Emphasis>-mediated magnetite mineralization

Amorphous ferric iron species (ferrihydrite or akaganeite of <5 nm in size) is the only known solid ferric iron oxide that can be reductively transformed by dissimilatory iron-reducing bacteria to magnetite completely. The lepidocrocite crystallite can be transformed into magnetite in the presence of abiotic Fe(II) at elevated pH or biogenic Fe(II) with particular growth conditions. The reduction of lepidocrocite by dissimilatory iron-reducing bacteria has been widely investigated showing varying results. Vali et al. (Proc Natl Acad Sci USA 101:16121–16126, 2004) captured a unique biologically mediated mineralization pathway where the amorphous hydrous ferric oxide transformed to lepidocrocite was followed by the complete reduction of lepidocrocite to single-domain magnetite. Here, we report the ⁵⁷Fe Mössbauer hyperfine parameters of the time-course samples reported in Vali et al. (Proc Natl Acad Sci USA 101:16121–16126, 2004). Both the quadrupole splittings and linewidths of Fe(III) ions decrease consistently with the change of aqueous Fe(II) and transformations of mineral phases, showing the Fe(II)-mediated gradual regulation of the distorted coordination polyhedrons of Fe³⁺ during the biomineralization process. The aqueous Fe(II) catalyzes the transformations of Fe(III) minerals but does not enter the mineral structures until the mineralization of magnetite. The simulated abiotic reaction between Fe(II) and lepidocrocite in pH-buffered, anaerobic media shows the simultaneous formation of green rust and its gradual transformation to magnetite plus a small fraction of goethite. We suggested that the dynamics of Fe(II) supply is a critical factor for the mineral transformation in the dissimilatory iron-reducing cultures.     

Phosphate bonding configuration on ferrihydrite based on molecular orbital calculations and XANES fingerprinting

Sorption of phosphate by Fe(III)- and Al(III)-(hydr)oxide minerals regulates the mobility of this potential water pollutant in the environment. The objective of this research was to determine the molecular configuration of phosphate bound on ferrihydrite at pH 6 by interpreting P K-edge XANES spectra in terms of bonding mode. XANES and UV-visible absorption spectra for aqueous Fe(III)-PO₄ solutions (Fe/P molar ratio = 0-2.0) provided experimental trends for energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals. Molecular orbitals for Fe(III)-PO₄ or Al(III)-PO₄ complexes in idealized monodentate or bidentate bonding mode were generated by conceptual bonding arguments, and Extended-Hückel molecular orbital computations were used to understand and assign XANES spectral features to bound electronic states. The strong white line at the absorption edge in P K-edge XANES spectra for Fe-PO₄ or Al-PO₄ systems is attributable to an electronic transition from a P 1s atomic orbital into P(3p)-O(2p) or P(3p)-O(2p)-Al(3p) antibonding molecular orbitals, respectively. For Fe-PO₄ systems, a XANES peak at 2-5 eV below the edge was assigned to a P 1s electron transition into Fe(4p)-O(2p) antibonding molecular orbitals. Similarly, a shoulder on the low-energy side of the white line for variscite corresponds to a transition into Al(3p)-O(2p) orbitals. In monodentate-bonded phosphate, Fe-O bonding is optimized and P-O bonding is weakened, and the converse is true of bidentate-bonded phosphate. These differences explained an inverse correlation between energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals consistent with a monodentate-to-bidentate transition in aqueous Fe(III)-PO₄ solutions. The intensity of the XANES pre-edge feature in Fe(III)-bonded systems increased with increasing number of Fe(III)-O-P bonds. Based on the similarity of intensity and splitting of the pre-edge feature for phosphate sorbed on ferrihydrite at 750 mmol/kg at pH 6 and aqueous Fe-PO₄ solutions containing predominantly bidentate complexes, XANES results indicated that phosphate adsorbed on ferrihydrite was predominantly a bidentate-binuclear surface complex.     

Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium

The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.     

Characterization of Fe(III) (hydr)oxides in arsenic contaminated soil under various redox conditions by XAFS and Mössbauer spectroscopies

Characterization of Fe(III) (hydr)oxides in soils near the Ichinokawa mine was conducted using X-ray absorption fine structure (XAFS) and Mössbauer spectroscopies, and the structural changes were correlated with the release of As into pore-water. The Eh values decreased monotonically with depth. Iron is mainly present as poorly-ordered Fe(III) (hydr)oxides, such as ferrihydrite, over a wide redox range (from Eh = 360 to −140 mV). Structural details of the short-range order of these Fe(III) (hydr)oxides were examined using Mössbauer spectroscopy by comparing the soil phases with synthesized ferrihydrite samples having varying crystallinities. The crystallinity of the soil Fe (hydr)oxides decreased slightly with depth and Eh. Thus, within the redox range of this soil profile, ferrihydrite dominated, even under very reducing conditions, but the crystalline domain size, and, potentially, particle size, changed with the variation in Eh. In the soil–water system examined here, where As concentration and the As(III)/As(V) ratio in soil water increased with depth, ferrihydrite persisted and maintained or even enhanced its capacity for As retention with increased reducing conditions. Therefore, it is concluded that As release from these soils largely depends on the transformation of As(V) to As(III) rather than reductive dissolution of Fe(III) (hydr)oxide.