Christina M. Smeaton

Simultaneous Release of Fe and As during the Reductive Dissolution of Pb-As Jarosite by Shewanella putrefaciens CN32

Jarosites are produced during metallurgical processing, on oxidized sulfide deposits, and in acid mine drainage environments. Despite the environmental relevance of jarosites, few studies have examined their biogeochemical stability. This study demonstrates the simultaneous reduction of structural Fe(III) and aqueous As(V) during the dissolution of synthetic Pb-As jarosite (PbFe(3)(SO(4),AsO(4))(2)(OH)(6)) by Shewanella putrefaciens using batch experiments under anaerobic circumneutral conditions. Fe(III) reduction occurred immediately in inoculated samples while As(V) reduction was observed after 72 h. XANES spectra showed As(III) (14.7%) in the solid phase at 168 h coincident with decreased aqueous As(V). At 336 h, XANES spectra and aqueous speciation analysis demonstrated 20.2% and 3.0% of total As was present as As(III) in the solid and aqueous phase, respectively. In contrast, 12.4% of total Fe was present as aqueous Fe(II) and was below the detection limits of XANES in the solid phase. TEM-EDS analysis at 336 h showed secondary precipitates enriched in Fe and O with minor amounts of As and Pb. Based on experimental data and thermodynamic modeling, we suggest that structural Fe(III) reduction was thermodynamically driven while aqueous As(V) reduction was triggered by detoxification induced to offset the high As(V) (328 μM) concentrations released during dissolution.

Intracellular Precipitation of Pb by Shewanella putrefaciens CN32 during the Reductive Dissolution of Pb-Jarosite

Jarosites (MFe(3)(SO(4))(2)(OH)(6)) are precipitated in the Zn industry to remove impurities during the extraction process and contain metals such as Pb and Ag. Jarosite wastes are often confined to capped tailings ponds, thereby creating potential for anaerobic reductive dissolution by microbial populations. This study demonstrates the reductive dissolution of synthetic Pb-jarosite (PbFe(6)(SO(4))(4)(OH)(12)) by a subsurface dissimilatory Fe reducing bacterium (Shewanella putrefaciens CN32) using batch experiments under anaerobic circumneutral conditions. Solution chemistry, pH, Eh, and cell viability were monitored over time and illustrated the reduction of released structural Fe(III) from the Pb-jarosite to Fe(II). Inoculated samples containing Pb-jarosite also demonstrated decreased cellular viability coinciding with increased Pb concentrations. SEM images showed progressive nucleation of electron dense nanoparticles on the surface of bacteria, identified by TEM/EDS as intracellular crystalline precipitates enriched in Pb and P. The intracellular precipitation of Pb by S. putrefaciens CN32 observed in this study provides potential new insight into the biogeochemical cycling of Pb in reducing environments.

Bacterially enhanced dissolution of meta-autunite

Abstract The release of U from the mineral meta-autunite {Ca[(UO2)(PO2)](H2O)6} was evaluated using spectroscopy, aqueous geochemistry, and electron microscopy in a minimal media with the dissimilatory metal-reducing bacterium Shewanella putrefaciens 200R. The onset of anaerobic conditions resulted in the rapid release of U and phosphate to solution followed by the reprecipitation of meta-autinite. Spectroscopy measurements (XANES) indicated that the U was not released via reduction during the bacterial incubations, but instead dissolution was promoted by uptake and immobilization of P by the bacterial cells. Our results suggest that U(VI) in “refractory” P mineral phases may be mobilized from U mill tailings and/or U disposal sites and that the nutrient status (P) of the geologic setting may be a predictor for the lability of U in these environments.

Reductive dissolution of Tl(I)-jarosite by Shewanella putrefaciens: providing new insights into Tl biogeochemistry.

Thallium (Tl) is emerging as a metal of concern in countries such as China due to its release during the natural weathering of Tl-bearing ore deposits and mining activities. Despite the high toxicity of Tl, few studies have examined the reductive dissolution of Tl mineral phases by microbial populations. In this study we examined the dissolution of synthetic Tl(I)-jarosite, (H(3)O)(0.29)Tl(0.71)Fe(2.74)(SO(4))(2)(OH)(5.22)(H(2)O)(0.78), by Shewanella putrefaciens CN32 using batch experiments under anaerobic circumneutral conditions. Fe(II) concentrations were measured over time and showed Fe(II) production (4.6 mM) in inoculated samples by 893 h not seen in mineral and dead cell controls. Release of aqueous Tl was enhanced in inoculated samples whereby maximum concentrations in inoculated and cell-free samples reached 3.2 and 2.1 mM, respectively, by termination of the experiment. Complementary batch Tl/S. putrefaciens sorption experiments were conducted under experimentally relevant pH (5 and 6.3) at a Tl concentration of 35 μM and did not show significant Tl accumulation by either live or dead cells. Therefore, in contrast to many metals such as Pb and Cd, S. putrefaciens does not represent a sink for Tl in the environment and Tl is readily released from Tl-jarosite during both abiotic and biotic dissolution.

Iron Isotope Fractionations Reveal a Finite Bioavailable Fe Pool for Structural Fe(III) Reduction in Nontronite

We report on stable Fe isotope fractionation during microbial and chemical reduction of structural Fe(III) in nontronite NAu-1. (56)Fe/(54)Fe fractionation factors between aqueous Fe(II) and structural Fe(III) ranged from -1.2 to +0.8‰. Microbial (Shewanella oneidensis and Geobacter sulfurreducens) and chemical (dithionite) reduction experiments revealed a two-stage process. Stage 1 was characterized by rapid reduction of a finite Fe(III) pool along the edges of the clay particles, accompanied by a limited release to solution of Fe(II), which partially adsorbed onto basal planes. Stable Fe isotope compositions revealed that electron transfer and atom exchange (ETAE) occurred between edge-bound Fe(II) and octahedral (structural) Fe(III) within the clay lattice, as well as between aqueous Fe(II) and structural Fe(III) via a transient sorbed phase. The isotopic fractionation factors decreased with increasing extent of reduction as a result of the depletion of the finite bioavailable Fe(III) pool. During stage 2, microbial reduction was inhibited while chemical reduction continued. However, further ETAE between aqueous Fe(II) and structural Fe(III) was not observed. Our results imply that the pool of bioavailable Fe(III) is restricted to structural Fe sites located near the edges of the clay particles. Blockage of ETAE distinguishes Fe(III) reduction of layered clay minerals from that of Fe oxyhydroxides, where accumulation of structural Fe(II) is much more limited.

Deconstructing the redox cascade: what role do microbial exudates (flavins) play?

Environmental context Redox potential is a controlling variable in aquatic chemistry. Through time series data, we show that microbial exudates released by bacteria may control trends in redox potential observed in natural waters. In particular, electron transfer between these exudates and the electrode could explain the values measured in the presence of abundant oxidants such as oxygen and nitrate. Abstract Redox electrodes are commonly used to measure redox potentials (EH) of natural waters. The recorded EH values are usually interpreted in terms of the dominant inorganic redox couples. To further advance the interpretation of measured EH distributions along temporal and spatial redox gradients, we performed a series of reactor experiments in which oxidising and reducing conditions were alternated by switching between sparging with air and N2. Starting from a simple electrolyte solution and ending with a complex biogeochemical system, common groundwater solutes, metabolic substrates (NO3− and C3H5O3−), bacteria (Shewanella oneidensis MR-1) and goethite (α-FeOOH(s)) were tested by increasing the system complexity with each subsequent experiment. This systematic approach yielded a redox cascade ranging from +500 to −350 mV (pH ~7.4). The highest and lowest EH values registered by the platinum (Pt) electrode agreed with Nernstian redox potentials predicted for the O2/H2O2 and FeOOH/Fe2+(aq) couples respectively. Electrode poisoning by the organic pH buffer (MOPS) and addition of bacteria to the aerated solutions resulted in marked decreases in measured EH values. The latter effect is attributed to the release of flavins by Shewanella oneidensis MR-1 to the medium. As expected, equilibrium with the non-electroactive NO3−/NO2−/NH4+ redox couples could not account for the EH values recorded during dissimilatory nitrate reduction to ammonium (DNRA). However, the observed EH range for DNRA coincided with that bracketed by EH values measured in separate abiotic solutions containing either the oxidised (+324 ± 29 mV) or reduced (−229 ± 40 mV) forms of flavins. The results therefore suggest that the Pt electrode detected the presence of the electroactive flavins, even at submicromolar concentrations. In particular, flavins help explain the fairly low EH values measured in the presence of strong oxidants, such as O2 and NO3−.

Comment on “Predominance of Aqueous Tl(I) Species in the River System Downstream from the Abandoned Carnoules Mine (Southern France)”

System Downstream from the Abandoned Carnoules Mine (Southern France)” C et al. published a very interesting study on the speciation of Tl(I) in a river system downstream from an abandoned Pb−Zn mine. We agree that this is one of the best and most comprehensive papers to examine Tl speciation in a mining environment. It is of particular importance because Tl is highly toxic and is studied to a lesser degree than other prominent toxic metals such as Pb, Cd, and Hg. However, we recently discovered errors in the calculation of the theoretical solubility equilibrium constants (Log K) calculated by Casiot et al. (see Table 1) for the following thallium minerals: dorallcharite (TlFe3(SO4)2(OH)6), lanmuchangite (TlAl(SO4)2·12H2O) and lorandite (TlAsS2). The incorrect proposed stability field for dorallcharite within the circumneutral-alkaline pH region in the Eh-pH diagram of Tl (see Figure 2) raised some queries and prompted us to investigate the authors’ thermodynamic calculations and modelling. While it is a lesser studied member of the isostructural jarosite-alunite group of minerals, dorallcharite (TlFe3(SO4)2(OH)6), is expected to form under typical jarosite formation conditions which encompass oxidizing, ferric rich and acidic (pH < 3) environments. In fact, the authors previously demonstrated long-term abiotic and biotic K-jarosite precipitation at low pH values (1−3) in batch experiments containing Carnoules AMD water. At higher pH values, jarosites are unstable and will dissolve to form goethite or metastable phases such as schwertmannite or ferrihydrite. The dissolution and instability of various jarosite group minerals under circumneutral pH conditions has been extensively documented and it is highly unlikely that dorallcharite would form at the Amous DC station under the high pH values (∼8) shown in the Eh-pH diagram for Tl. It was unclear on how the authors calculated the Log K values, we recalculated the theoretical equilibrium solubility product constants and suggest the Log K values for dorallcharite (TlFe3(SO4)2(OH)6), lanmuchangite (TlAl(SO4)2·12H2O) and lorandite (TlAsS2) should be changed from 2.245, 16.551, and 38.256 to −9.90, −16.3 and −28.9, respectively. We calculated the new solubility product constants (Log Ksp) by combining the Gibbs free energy of reaction at 25 °C at equilibrium:

Linking spectral induced polarization (SIP) and subsurface microbial processes: Results from sand column incubation experiments

Geophysical techniques, such as spectral induced polarization (SIP), offer potentially powerful approaches for in situ monitoring of subsurface biogeochemistry. The successful implementation of these techniques as monitoring tools for reactive transport phenomena, however, requires the deconvolution of multiple contributions to measured signals. Here, we present SIP spectra and complementary biogeochemical data obtained in saturated columns packed with alternating layers of ferrihydrite-coated and pure quartz sand, and inoculated with Shewanella oneidensis supplemented with lactate and nitrate. A biomass-explicit diffusion-reaction model is fitted to the experimental biogeochemical data. Overall, the results highlight that (1) the temporal response of the measured imaginary conductivity peaks parallels the microbial growth and decay dynamics in the columns, and (2) SIP is sensitive to changes in microbial abundance and cell surface charging properties, even at relatively low cell densities (<108 cells mL-1). Relaxation times (τ) derived using the Cole-Cole model vary with the dominant electron accepting process, nitrate or ferric iron reduction. The observed range of τ values, 0.012-0.107 s, yields effective polarization diameters in the range 1-3 μm, that is, 2 orders of magnitude smaller than the smallest quartz grains in the columns, suggesting that polarization of the bacterial cells controls the observed chargeability and relaxation dynamics in the experiments.