Christopher G. Weisener

Alteration of Iron-rich Lacustrine Sediments by Dissimilatory Iron-reducing Bacteria

The reactivity of trace elements in lake sediments towards microbial metal reduction was evaluated using spectroscopy, chemical extractions and incubations in a minimal media with the DIR bacterium Shewanella putrefaciens 200R. Micro-XRF measurements demonstrated the association of Cr, and Ni with Mn-rich phases. The onset of anaerobic conditions resulted in the rapid release of trace metals (Cr, Ni, Co) from the sediments with the progressive dissolution of a reactive Mn component. This fraction was approximately equivalent to that liberated by chemical extractions designed to operationally select for Mn phases. These results suggest that studies aiming to assess metal dissolution in anaerobic soils and sediments should attempt to discriminate between metals associated with Mn and Fe (hydr)oxides, the former being more reactive and likely dissolved to a greater extent.

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.

Microbial Dissolution of Silver Jarosite: Examining Its Trace Metal Behaviour in Reduced Environments

Iron sulfate minerals such as jarosite-group compounds (e.g., M Fe3(SO 4 ) 2 (OH) 6 ) can be of considerable environmental importance because of their ability to scavenge trace elements and thus contribute to some degree of metal cycling. Jarosite forms in low temperature hydrothermal, acidic, sulfate-rich environments often yielding a range of elemental substituted forms: plumbojarosite (M = Pb), argentojarosite (M = Ag), jarosite (M = K), natrojarosite (M = Na), hydroniumjarosite (M = H3O), and ammoniojarosite (M = NH4). Anthropogenic sources of jarosite are common in mine waste environments, most often associated with the waste products resulting from base metal recovery. Few studies have investigated the effect that dissimilatory metal reducing bacteria may have in the presence of these compounds following the onset of reducing conditions. Jarosite reactivity may differ systematically as a function of its chemical properties. For example, the incorporation of Ag in the mineral lattice may have inhibitory affects on the growth of microbial strains. In this study the reductive dissolution of argentojarosite (M = Ag) in the presence of Shewanella putrefaciens CN32 (10 9 cells ml 1 , pH 7.1) was examined. Using the silver (argento)jarosite, Ag Fe 3 (SO 4 ) 2 (OH) 6 , as a sole terminal electron acceptor we observed the reduction of structural Fe(III) and Ag(I) by CN32 through the release of Fe(II) ions to solution. Aqueous silver concentrations were below instrumental detection. Environmental SEM (ESEM) and TEM micrographs of the microbial clusters revealed the progressive heterogeneous nucleation of Ag(0) nanoparticles within cellular structures and also on adjacent mineral grains. The results of this study are the first presented for the anaerobic dissolution of silver jarosite. This has implications for understanding the processes leading to the mobility or retention of silver in mine waste and industrial landfill environments. It also provides insight into the microbial mechanisms of silver resistance and nanoparticle formation with potential applications for bioleaching and/or biotechnology.

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.

Bio-Physicochemical Effects of Gamma Irradiation Treatment for Naphthenic Acids in Oil Sands Fluid Fine Tailings

Naphthenic acids (NAs) are persistent compounds that are components of most petroleum, including those found in the Athabasca oil sands. Their presence in freshly processed tailings is of significant environmental concern due to their toxicity to aquatic organisms. Gamma irradiation (GI) was used to reduce the toxicity and concentration of NAs in oil sands process water (OSPW) and fluid fine tailings (FFT). This investigation systematically studied the impact of GI on the biogeochemical development and progressive reduction of toxicity using laboratory incubations of fresh and aged tailings under anoxic and oxic conditions. GI reduced NA concentrations in OSPW by up to 97% in OSPW and in FFT by 85%. The GI-treated FFT exhibited increased rates of biogeochemical change, dependent on the age of the tailings source. Dissolved oxygen (DO) flux was enhanced in GI-treated FFT from fresh and aged source materials, whereas hydrogen sulfide (HS(-)) flux was stimulated only in the fresh FFT. Acute toxicity to Vibrio fischeri was immediately reduced following GI treatment of fresh OSPW. GI treatment followed by 4-week incubation reduced toxicity of aged OSPW to V. fischeri.

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.

The symbiotic relationship of sediment and biofilm dynamics at the sediment water interface of oil sands industrial tailings ponds.

Within the oil sands industry, tailings ponds are used as a means of retaining tailings until a reclamation technology such as end pit lakes (EPLs) can be developed and optimized to remediate such tailings with a water cap (although dry-land strategies for tailing reclamation are also being developed). EPLs have proven successful for other mining ventures (e.g. metal rock mines) in eventually mitigating contaminant loads to receiving waters once biochemical remediation has taken place (although the duration for this to occur may be decades). While the biological interactions at the sediment water interface of tailings ponds or EPLs have been shown to control biogeochemical processes (i.e. chemical fluxes and redox profiles), these have often been limited to static microcosm conditions. Results from such experiments may not tell the whole story given that the sediment water interface often represents a dynamic environment where erosion and deposition may be occurring in association with microbial growth and decay. Mobilization of sediments and associated contaminants may therefore have a profound effect on remediation rates and, as such, may decrease the effectiveness of EPLs as viable reclamation strategies for mining industries. Using a novel core erosion system (U-GEMS), this paper examines how the microbial community can influence sediment water interface stability and how the biofilm community may change with tailings age and after disturbance (biofilm reestablishment). Shear strength, eroded mass measurements, density gradients, high-resolution microscopy, and microbial community analyses were made on 2 different aged tailings (fresh and ∼38 years) under biotic and abiotic conditions. The same experiments were repeated as duplicates with both sets of experiments having consolidation/biostabilization periods of 21 days. Results suggest that the stability of the tailings varies between types and conditions with the fresh biotic tailings experiencing up to 75% more biostabilization than the same abiotic tailings. Further, greater microbial diversity in the aged pond could be a contributing factor to the overall increase in stability of this material over the fresh tailings source.

Investigating sources and sinks of N2O expression from freshwater microbial communities in urban watershed sediments

Wastewater treatment plants (WWTPs) serve as point-source inputs for a variety of nutrients often dominated by nitrogenous compounds as a result of anthropogenic influence. These effluents can impact biogeochemical cycles in freshwater estuaries, influencing microbial communities in both the water and sediment compartments. To assess the impact of point source nutrients, a transect of sediment and pore water samples were collected from 4 locations in the Little River Sub-watershed including locations above and below the Little River Pollution Control Plant (LRPCP). Variation in chemistry and microbial community/gene expression revealed significant influences of the effluent discharge on the adjacent sediments. Phosphorus and sulfur showed high concentrations within plume sediments compared to the reference sediments while nitrate concentrations were low. Increased abundance of denitrifiers Dechloromonas, Dok59 and Thermomonas correlating with increased expression of nitrous-oxide reductase suggests a conversion of N2O to N2 within the LRPCP effluent sediments. This study provides valuable insight into the gene regulation of microbes involved in N metabolism (denitrification, nitrification, and nitrite reduction to ammonia) within the sediment compartment influenced by wastewater effluent.

Novel insights into freshwater hydrocarbon-rich sediments using metatranscriptomics: Opening the black box

Baseline biogeochemical surveys of natural environments is an often overlooked field of environmental studies. Too often research begins once contamination has occurred, with a knowledge gap as to how the affected area behaved prior to outside (often anthropogenic) influences. These baseline characterizations can provide insight into proposed bioremediation strategies crucial in cleaning up chemical spill sites or heavily mined regions. Hence, this study was conducted to survey the in-situ microbial activity within freshwater hydrocarbon-rich environments cutting through the McMurray formation - the geologic strata constituting the oil sands. We are the first to report in-situ functional variations among these freshwater microbial ecosystems using metatranscriptomics, providing insight into the in-situ gene expression within these naturally hydrocarbon-rich sites. Key genes involved in energy metabolism (nitrogen, sulfur and methane) and hydrocarbon degradation, including transcripts relating to the observed expression of methane oxidation are reported. This information provides better linkages between hydrocarbon impacted environments, closing knowledge gaps for optimizing not only oil sands mine reclamation but also enhancing microbial reclamation strategies in various freshwater environments. These finding can also be applied to existing contaminated environments, in need of efficient reclamation efforts.