Precipitation Of Hydrous Ferric Oxide Research Articles

Physicochemical patterns observed in a groundwater well with CO2 stratification: Learnings from an automated monitoring from South Korean national groundwater monitoring network

Unusual episodic fluctuations of electrical conductivity (EC) were observed twice a year in a national groundwater monitoring network well in South Korea where EC was automatically monitored at a depth of 20 m below ground level (bgl). To address the causes of the observed EC fluctuations, this study examined the depth profile of wellbore water in the 70-meter-deep monitoring well screened between 50 and 70 m bgl and cased down to 50 m bgl. The results of well logging, borehole video recording, and hydrochemical analysis of wellbore water indicated that the CO2-rich groundwater entering through the screened zones below 50 m bgl was physicochemically stratified into three layers with distinct EC that were separated by two transition zones in the well: a bottom layer (70–43 m bgl) with an EC of ∼3900 μS/cm, intermediate layer (35–24 m bgl) of ∼1800 μS/cm, and top layer (16–3 m bgl) of ∼300 μS/cm. The first transition zone at depths of 43–35 m bgl was attributed to CO2 exsolution in the open system and the subsequent physicochemical changes of wellbore water, while the second transition zone at depths of 24–16 m bgl was formed by the precipitation of hydrous ferric oxides with consequent sorption of remaining ions due to a sudden change toward the oxidizing environment. The monitoring probe installed at a depth of 20 m bgl was found to be located within the upper transition zone, which caused EC peaks when the well was purged at a depth of 25 m bgl for well maintenance twice a year. This study shows that automated groundwater monitoring systems may misguide one about the groundwater quality if an unexpected physicochemical variation (such as stratification) occurs in a monitoring well. Therefore, the presence of interface zones caused by abrupt changes in EC must be carefully considered when an automated monitoring well is designed. The screened zone is a suitable location for installing an automated monitoring probe to measure the representative water quality (i.e., EC), in particular, in an aquifer that is under the influence of inputs of low-pH and high-TDS fluids (e.g., CO2-rich groundwater and acid mine drainage).

Quick-fix agarose beads impregnated with hydrous ferric oxide for As(III) species removal from pharmaceutical wastewater

ABSTRACT Hydrous ferric oxide (HFO)-impregnated agarose beads were prepared as an adsorbent to reduce As(III) concentration in the pharmaceutical wastewater effluent generated from the manufacturing process of an arsenic-containing chemotherapeutic drug. The adsorbent was prepared by immersing wet agarose beads into FeCl3 (aq), followed by another immersion into NaOH (aq), resulting in HFO precipitation directly within the agarose beads. The As(III) adsorption rate of HFO-impregnated agarose beads was determined to be external diffusion-limited, and having a Langmuir maximum adsorption capacity of 76.1 mg As(III)/g. Passing 6 L of the pharmaceutical wastewater through a packed column filled with the adsorbent in an upflow mode of 50 mL/min repeatedly for five times resulted in the reduction of As(III) concentration from 250 to 10 μg of As(III)/L of H2O. Column desorption was performed by passing 0.6 L of 0.1 M NaOH (aq) through the column in an upflow mode of 50 mL/min repeatedly for five times to regenerate the As(III)-adsorbed HFO-impregnated agarose beads. Chemical characterizations revealed that the As(III) species were adsorbed on HFO by the “inner-sphere” bidentate complexation via ligand exchange or “outer-sphere” association via electrostatic interaction, while the “outer-sphere”-associated As(III) species were most likely desorbed.

Reactive transport modelling of push-pull tests: A versatile approach to quantify aquifer reactivity

Push-pull tests (PPTs) were evaluated with 1-D radially axisymmetric multi-component geochemical reactive transport modelling (RTM) to assess aquifer reactivity controlling groundwater quality. Nutrient fate and redox processes were investigated in an Aquifer Storage and Recovery (ASR) system, in which oxic tile drainage water (TDW; nitrate ~14 mg/L; phosphate ~17 mg/L) was stored in an anoxic aquifer for later re-use as irrigation water. During the PPTs, the ASR system did not operate. PPTs were performed in two monitoring wells (MW2, MW3), with 1 m well screens in contrasting geochemical formations at different depths. In these wells, 300 L TDW was injected, and consecutively 720 L was abstracted within 12 days, during which water quality changes were studied. The RTM simulated cation exchange, precipitation of Hydrous Ferric Oxides, Iron (III)-phosphate and Calcium-phosphate minerals, and surface complexation as equilibrium processes. Oxidation of Pyrite, soil organic matter, and dissolved ferrous iron were simulated with kinetic rate expressions. Oxygen (within 2 days) and nitrate (within 4–7 days) were fully reduced during the PPTs. The main reductants were ferrous iron (Monitoring Well (MW) 2: 2%, MW3: 13%), soil organic matter (MW2: 93%, MW3: 6%), and Pyrite (MW2: 5%, MW3: 81%). The intra aquifer differences in dominant reduction pathways are remarkable as higher reduction rates coincided with lower contents of soil organic matter and Pyrite, respectively. Phosphate was mostly re-abstracted (MW2: 73%, MW3: 64%) and partially immobilized due to precipitation of Iron-hydroxyphosphates (MW2: 4.6%, MW3: 35%), Hydroxyapatite (MW2: 23%, MW3: 0%), and to a lesser extent by surface complexation on various minerals (MW2-3: <1%). The PPT-RTM approach enables a better understanding of reaction networks controlling water quality changes, and the reaction kinetics. PPT-RTM is a promising tool in exploratory studies or regular monitoring of water quality aspects of subsurface water technologies.

In situ precipitation of hydrous ferric oxide (HFO) for remediation of subsurface iodine contamination

A practical approach for in situ hydrous ferric oxide (HFO) precipitation was developed for iodine immobilization under field-scale conditions at the Hanford Site. A series of 1D meter-long bench-top column experiments packed with Hanford sediments was conducted with a single acidic ferric solution (0.1 M, pH = 1.5) injection. Because carbonate and clay minerals are widely present in sediments, self-pH buffering of the injected acidic ferric solution occurred due to mineral dissolution, leading to HFO precipitation under a neutral condition. Up to ~12 mg/g Fe as HFO successfully precipitated and evenly distributed in the column sediments, and the remobilization of the neoformed HFO precipitates was limited (≤ ~3.16 wt% after over 100 pore volumes (pv) of flushing). The transport of iodate (IO3−) in the HFO-amended sediments was strongly retarded through both adsorption and co-precipitation processes. However, reversible adsorption of iodine on HFO was observed, which might limit its application to slow-moving groundwater systems.

Dependence of In Situ Bacterial Fe(II)-Oxidation and Fe(III)-Precipitation on Sequential Reactive Transport

ABSTRACTA study was conducted to determine in situ rates of Fe(II) oxidation and Fe(III) precipitation along a 5.0 m reach of a ferruginous groundwater discharge zone under two distinct conditions; (i) the natural state featuring abundant flocculent mats of bacteriogenic iron oxides (BIOS) produced by Fe(II)-oxidizing bacteria, and (ii) after a manual washout of the streambed to remove the microbial mat. Examination of mat samples by differential interference contrast light microscopy revealed tangled meshworks of filamentous Leptothrix sheaths and helical Gallionella stalks intermixed with fine-grained hydrous ferric oxide (HFO) precipitates. The greatest accumulation of BIOS mat was 1.0 m downstream of the groundwater spring. Redox potential (Eh) increased sharply from 200 mV to over 300 mV over the last 2.0 m of the reach. Similarly, dissolved oxygen increased from < 10% saturation to almost 100% saturation over the last 2.0 m of the reach, whereas pH increased from 6.4 to 7.3. Pseudo-first-order rate constants determined on the basis of analytical solutions to sequential partial differential advection-dispersion-reaction equations for the linear Fe(II)→Fe(III)→HFO reaction network yielded in situ Fe(II) oxidation rate constants (kox) of 1.70 ± 0.20 min−1 in natural conditions and 0.48 ± 0.14 min−1 after washout. Corresponding Fe(III)-precipitation rates (kp) before and after washout were 3.45 ± 0.10 min−1 and 0.90 ± 0.01 min−1, respectively. These values for kox and kp are higher than estimates obtained from closed batch microcosm and laboratory experiments, underscoring the crucial dependence of in situ Fe(II) oxidation and Fe(III) precipitation rates on advective and dispersive mass transport. The results also highlight the influence that BIOS microbial mats exert on the reaction kinetics of the multiple heterogeneous reactions contributing not only to Fe(II)/Fe(III) redox transformations in groundwater discharge zones, but also the precipitation of HFO.

Reactive transport modeling of subsurface arsenic removal systems in rural Bangladesh

Subsurface Arsenic Removal (SAR) is a technique for in-situ removal of arsenic from groundwater. Extracted groundwater is aerated and re-injected into an anoxic aquifer, where the oxygen in the injected water reacts with ferrous iron in the aquifer to form hydrous ferric oxide (HFO). Subsequent extraction of groundwater contains temporarily lower As concentrations, because As sorbs onto the HFO. Injection, storage, and extraction together is called a cycle. A reactive transport model (RTM) was developed in PHREEQC to determine the hydrogeochemical processes responsible for As (im)mobilization during experimental SAR operation performed in Bangladesh. Oxidation of Fe(II) and As(III) were modeled using kinetic-rate expressions. Cation exchange, precipitation of HFO, and surface complexation, were modeled as equilibrium processes. A best set of surface complexation reactions and corresponding equilibrium constants was adopted from previous studies to simulate all 20cycles of a SAR experiment. The model gives a reasonable match with observed concentrations of different elements in the extracted water (e.g., the r2 value of As was 0.59 or higher). As concentrations in the extracted water are governed by four major processes. First, As concentration decreases in response to the elevated pH of injection water and likewise increases when native neutral pH groundwater flows in. Second, the sorption capacity for As increases due to the gradual buildup of HFO. Third, As sorption is enhanced by preferential removal of As(V). Fourth, competitive sorption of Si limits the capacity of freshly precipitated HFO for As sorption. Transferability of the developed reactive transport model was demonstrated through successful application of the model, without further calibration, to two additional SAR sites in Bangladesh. This gives confidence that the model could be useful to assess potential SAR performance at locations in Bangladesh based on local hydrogeochemical conditions.

A dynamic physicochemical model for chemical phosphorus removal

A dynamic physico-chemical model for chemical phosphorus removal in wastewater is presented as a tool to optimize chemical dosing simultaneously while ensuring compliant effluent phosphorus concentration. This new model predicts the kinetic and stoichiometric variable processes of precipitation of hydrous ferric oxides (HFO), phosphates adsorption and co-precipitation. It is combined with chemical equilibrium and physical precipitation reactions in order to model observed bulk dynamics in terms of pH. The model is calibrated and validated based on previous studies and experimental data from Smith et al. (2008) and Szabo et al. (2008) as a first step for full-plant implementation. The simulation results show that the structure of the model describes adequately the mechanisms of adsorption and co-precipitation of phosphate species onto HFO and that the model is robust under various experimental conditions.

A Dynamic Physicochemical Model for Chemical Phosphorus Removal

A dynamic physico-chemical model for chemical phosphorus removal in wastewater is presented as a tool to optimize chemical dosing simultaneously while ensuring compliant effluent phosphorus concentration. This new model predicts the kinetic and stoichiometric variable processes of precipitation of hydrous ferric oxides (HFO), phosphates adsorption and co-precipitation. It is combined with chemical equilibrium and physical precipitation reactions in order to model observed bulk dynamics in terms of pH. The model is calibrated and validated based on previous studies and experimental data from Smith et al. (2008) and Szabo et al. (2008) as a first step for full-plant implementation. The simulation results show that the structure of the model describes adequately the mechanisms of adsorption and co-precipitation of phosphate species onto HFO and that the model is robust under various experimental conditions.

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.

Phosphate Complexation Model and Its Implications for Chemical Phosphorus Removal

A phosphate complexation model is developed, in an attempt to understand the mechanistic basis of chemically mediated phosphate removal. The model presented here is based on geochemical reaction modeling techniques and uses known surface reactions possible on hydrous ferric oxide (HFO). The types of surface reactions and their reaction stoichiometry and binding energies (logK values) are taken from literature models of phosphate interactions with iron oxides. The most important modeling parameter is the proportionality of converting moles of precipitated HFO to reactive site density. For well-mixed systems and phosphate exposed to ferric chloride during HFO precipitation, there is a phosphate capacity of 1.18 phosphate ions per iron atom. In poorly mixed systems with phosphate exposed to iron after HFO formation, the capacity decreased to 25% of the well-mixed value. The same surface complexation model can describe multiple data sets, by varying only a single parameter proportional to the availability of reactive oxygen functional groups. This reflects the unavailability of reactive oxygen groups to bind phosphate. Electron microscope images and dye adsorption experiments demonstrate changes in reactive surface area with aging of HFO particles. Engineering implications of the model/mechanism are highlighted.

Removal of Arsenic from High Ionic Strength Solutions: Effects of Ionic Strength, pH, and preformed versus in situ formed HFO

Arsenic sorption to hydrous ferric oxide (HFO) is an effective treatment method for removing dissolved arsenic from fresh drinking water sources. However, detailed information is limited regarding arsenic removal from solutions of high ionic strength such as brackish groundwater, seawater, or high-pressure membrane process residuals. Bench-scale treatment experiments were conducted exploring arsenic removal from simple solutions with ionic strengths ranging from 0.008 to 1.5 M by addition of ferric chloride followed by solid/liquid separation (microfiltration or ultrafiltration). Arsenic removal from these solutions during in situ iron precipitation was approximately 90% at Fe:As molar ratios of 10 to 15 and > 95% for Fe:As molar ratios greater than 20. Arsenic removal at iron doses of 10(-6) to 10(-4) mol-Fe/L improved when pH was lowered from 8 to less than 6.5 at ionic strength 0.2 M; this improvement was not as significant at ionic strength 0.7 M. Arsenic removal diminished when alkalinity was increased from 400 to 1,400 mg/L as calcium carbonate; however, arsenic removal at the higher alkalinity improved when pH was lowered from approximately 8 to less than 7. Arsenic removal with preformed HFO solids and subsequent microfiltration was significantly less than that observed with in situ HFO precipitation. Increased removal by in situ precipitation compared to that of preformed solids is explained by an increased number of adsorption sites due to uptake during iron oxy-hydroxide polymerization as well as an increase in surface area resulting in diminished surface charge effects. Model simulations of arsenic uptake by in situ precipitation adequately captured these effect by changing the model parameters used to model arsenic uptake by preformed HFO, specificallythe total number of surface sites and surface area.

Geochemistry of Champagne Hot Springs shallow hydrothermal vent field and associated sediments, Dominica, Lesser Antilles

The Champagne Hot Springs (CHS) shallow submarine hydrothermal system is located along the submerged flank of the Plat Pays volcanic system on the southwest section of the island of Dominica, Lesser Antilles. We have conducted a detailed geochemical study of the hydrothermal system, with the objectives to investigate the source of the hydrothermal fluids and gases, their effect on sediment and precipitate chemistry, as well as comparing the submarine vent chemistry with nearby on-land hydrothermal vents. Finally, we compare our findings to previous preliminary data from CHS, and compare sediment chemistry to that of average Caribbean sediments. We also report on a newly discovered area of submarine hydrothermal venting, located approximately 40 m to the north of CHS. This area consists of hydrothermally altered areas of sand that contain abundant coatings of hydrous ferric oxides (HFO) on sediment grains. Geochemical and mineralogical analyses of vent waters, pore waters, gases, sediments and precipitates reveal that the vent fluids consist of a mixture of entrained seawater and meteorically derived hydrothermal fluid in varying proportions. Vent fluids are depleted in Br −, SO 4 2−, Cl −, Na +, K +, and Sr 2+ relative to ambient seawater. These species are all positively correlated with Mg 2+, which is also depleted relative to seawater. Boron, Fe, As, Sb, Mn, Si and Li are all enriched relative to ambient seawater. Pore waters in the hydrothermally altered sand patches have essentially the same chemistry. Mixing between Fe 2+ rich vent fluids and seawater causes rapid oxidation of Fe 2+ to insoluble Fe 3+ and leads to precipitation of HFO at the vent site and subsequent formation of hydrothermally altered sand patches. The elevated concentrations of As and Sb in the precipitates and sediments relative to average Caribbean seafloor sediments reflect adsorption by HFO. Gas samples from the vent site are typical arc-type gases and have both meteoric and magmatic signatures.

Removal of Heavy Metals from Mine Waters by Natural Zeolites

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe 2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.

Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

We have used room temperature and cryogenic 57Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells ( Bacillus subtilis or Bacillus licheniformis, ∼10 8 cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10 −2, 10 −3, or 10 −4 mol/L) under open oxic conditions and at different pH (6–9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall ( Bacillus subtilis) surface complexed Fe, where Fe(III) (10 −3.5–10 −4.5 mol/L) was added to a fixed concentration of cells (∼10 8 cells/mL) under open oxic conditions and at various pH (2.5–4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe 2+ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe 2+ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary particle size (magnetometry blocking temperature), weaker Fe to particle bond strength (Mössbauer center shift), and no six-line Fh (6L-Fh) admixture (pXRD, magnetometry). Contrary to current belief, we find that 6L-Fh appears to be precipitated directly, under a-HFO conditions, from either Fe(II) or Fe(III), and depending on Fe concentration and pH, whereas the presence of bacteria disables all such 6L-Fh precipitation and produces two-line Fh (2L-Fh)-like biotic coprecipitates. Given the nature of the differences between a-HFO and b-HFO and their synthesis condition dependences, several biotic precipitation mechanisms (template effect, near-cell environment effect, catalyzed nucleation and/or growth effect, and substrate-based coprecipitation) are ruled out. The prevailing present view of a template or heterogeneous nucleation barrier reduction effect, in particular, is shown not to be the cause of the large observed biotic effects on the resulting HFOs. The only proposed mechanism (relevant to Fh) that is consistent with all our observations is coprecipitation with and possible surface poisoning by ancillary bacteriagenic compounds. That bacterial cell wall functional groups are redox active and the characteristics of biotic (i.e., natural) HFOs compared to those of abiotic (i.e., synthetic) HFOs have several possible biogeochemical implications regarding Fe cycling, in the photic zones of water columns in particular.

Mechanisms of arsenic attenuation in acid mine drainage from Mount Bischoff, western Tasmania

There is a dearth of research concerning the geochemistry of arsenic in acid mine drainage (AMD) in western Tasmania. To help address this, the controls on the mobility and fate of arsenic in AMD and its associated sediment at the Mount Bischoff mine site in western Tasmania were investigated. AMD issuing from the adit mouth contained dissolved arsenic and iron concentrations of 2.5 and 800 mg L −1, respectively. The aqueous concentration of both arsenic and iron decreased markedly over a 150-m stretch from the adit mouth due to precipitation of hydrous ferric oxides (HFO) and jarosite, both of which are effective scavengers of arsenic. Microwave-assisted digestion of the sediment collected at the adit mouth revealed that the arsenic concentration exceeded 1%. Sequential extraction of this sediment showed that the bulk of arsenic was associated with amorphous and crystalline hydrous oxides of Al and/or Fe. Extended X-ray absorption fine structure (EXAFS) analysis indicated that the solid phase arsenic exists as As(V). EXAFS data were consistent with arsenate tetrahedra substituting for sulphate in jarosite and with corner-sharing complexes adsorbed on ferric oxyhydroxide octahedra. Erosional transport of AMD sediment downstream to higher pH waters may increase the mobility (and hence bioavailablity) of arsenic through dissolution of As-rich jarosite.

Iron isotope fractionation by Fe(II)-oxidizing photoautotrophic bacteria

Photoautotrophic bacteria that oxidize ferrous iron (Fe[II]) under anaerobic conditions are thought to be ancient in origin, and the ferric (hydr)oxide mineral products of their metabolism are likely to be preserved in ancient rocks. Here, two enrichment cultures of Fe(II)-oxidizing photoautotrophs and a culture of the genus Thiodictyon were studied with respect to their ability to fractionate Fe isotopes. Fe isotope fractionations produced by both the enrichment cultures and the Thiodictyon culture were relatively constant at early stages of the reaction progress, where the 56Fe/54Fe ratios of poorly crystalline hydrous ferric oxide (HFO) metabolic products were enriched in the heavier isotope relative to aqueous ferrous iron (Fe[II]aq) by ∼1.5 ± 0.2‰. This fractionation appears to be independent of the rate of photoautotrophic Fe(II)-oxidation, and is comparable to that observed for Fe isotope fractionation by dissimilatory Fe(III)-reducing bacteria. Although there remain a number of uncertainties regarding how the overall measured isotopic fractionation is produced, the most likely mechanisms include (1) an equilibrium effect produced by biological ligands, or (2) a kinetic effect produced by precipitation of HFO overlaid upon equilibrium exchange between Fe(II) and Fe(III) species. The fractionation we observe is similar in direction to that measured for abiotic oxidation of Fe(II)aq by molecular oxygen. This suggests that the use of Fe isotopes to identify phototrophic Fe(II)-oxidation in the rock record may only be possible during time periods in Earth’s history when independent evidence exists for low ambient oxygen contents.

Specific surface chemical interactions between hydrous ferric oxide and iron-reducing bacteria determined using p Ka spectra

A modified regularized least squares p K a spectrum approach is applied to determine disassociation constants and proton binding site concentrations on bacteria, hydrous ferric oxide (HFO), and bacteria/HFO composite surfaces. This involves fitting experimental acid–base titration data to a continuous binding site model for a chemically heterogeneous surface with a variety of reactive groups yielding a p K a spectrum. The modified parameter fitting method optimizes simultaneously for both smoothness of the p K a spectrum and goodness of fit, whereas other methods optimize for goodness of fit given a fixed smoothness factor. Uncertainty estimates in p K a spectra were made by taking the mean and standard deviation of the spectra from replicate titration data. Titration of Shewanella putrefaciens strain CN32, a facultative iron-reducing bacterial species, demonstrate five types of binding sites consistent with known cell surface groups on bacteria, with mean p K a values of 3.62, 4.97, 6.92, 8.22, and 9.97. Composite surfaces formed by precipitation of HFO onto bacteria surfaces were also titrated. These surfaces no longer yielded low p K a sites in p K a spectra, indicating that ferric iron interacts with the bacteria via carboxylic (low p K a ) sites during precipitation. In addition, mechanically mixed HFO bacterial samples also showed removal of carboxylic binding sites, suggesting that solid phase HFO interacts directly with carboxylic sites on bacterial cells. Moreover, the p K a spectra for HFO bacterial composites were not dependent on how the composite was formed; the mechanically mixed or surface-precipitated samples exhibited very similar binding site distributions. The determined p K a spectra imply that the overall binding mechanism for bacteria interactions with HFO involve carboxylic groups on the bacteria binding to the most basic sites on the HFO surface in approximately 1:1 stoichiometry.

Precipitation of iron, silica, and sulfate on bacterial cell surfaces

The present study documents the precipitation of Fe(III), silica, and sulfate in the presence of 3 different bacteria (Bacillus subtilus, Bacillus licheniformis, and Pseudomonas aeruginosa), under different total Fe(III) concentrations (10−2 M, 10−3 M, 10−4 M) at constant pH (4.0). Morphology and chemical composition of the precipitates were compared with those formed in abiotic control systems, while chemical composition and precipitation of the precipitates were modeled according to solution chemistry data. Transmission electron microscopy (TEM) observations showed morphological differences between the biotic and abiotic systems. All systems contained small grains (diam. 2–50 nm), but amorphous material (i.e., material without any specific morphology) and nodules were present only in the cell systems. This is because bacterial surfaces and exopolymers provided numerous binding sites for metal and anion sorption and promoted heterogeneous nucleation of hydrous ferric oxides (HFO). The initial Fe/Si and Fe/SO4 molar ratios of the solutions dictated the type of precipitates in most systems, since abiotic control systems were saturated to oversaturated with respect to amorphous silica, siliceous ferrihydrite, schwertmannite, ferrihydrite, goethite, or combinations of these. Of the three strains studied, B. licheniformis appeared to have the greatest influence on the chemical composition of the precipitates, especially in the presence of Si. B. licheniformis (a gram‐positive bacterium with a large capsule) favored the precipitation of HFO containing less Si than the predicted solids, because Si rather than Fe oxides was preferentially sorted to extracellular polymers (capsule). On the other hand, the formation of SO4‐rich HFO (similar to schwertmannite) did not seem to be affected by the presence of bacteria.