Redox Transformation Of Arsenic Research Articles

The impact of electron transfer between structural Fe(II) and aqueous Fe(III) on the redox transformation of arsenic

The impact of electron transfer between structural Fe(II) and aqueous Fe(III) on the redox transformation of arsenic

Single Strain-Triggered Biogeochemical Cycle of Arsenic.

The microbial metabolism of arsenic plays a prominent role in governing the biogeochemical cycle of arsenic. Although diverse microbes are known to be involved in the redox transformation of inorganic arsenic, the underlying mechanisms about the arsenic redox cycle mediated by a single microbial strain remain unclear yet. Herein, we discover that Shewanella putrefaciens CN32, a well-known arsenate-respiring and dissimilatory metal-reducing bacterium, could mediate the reversible arsenic redox transformation under aerobic conditions. Genetic analysis shows that S. putrefaciens CN32 contains both ars and arr operon but lacks an As(III) oxidase encoding gene. Arsenic(V) reduction tests demonstrate that the ars operon is advantageous but not essential for As(V) respiration in S. putrefaciens CN32. The Arr complex encoded by the arr operon not only plays a crucial role in arsenate respiration under anaerobic conditions but also participates in the sequential process of As(V) reduction and As(III) oxidation under aerobic conditions. The Arr enzyme also contributes to the microbial As(III) resistance. The expression and catalysis directionality of Arr in S. putrefaciens CN32 are regulated by the carbon source types. Our results highlight the complexity of arsenic redox biotransformation in environments and provide new insights into the important contribution of Arr to the As biogeochemical cycle in nature.

Photooxidation of arsenic in pristine and mine-impacted Canadian subarctic freshwater systems

The redox transformations of arsenic (As) in lakes are thought to be mainly controlled by algal/microbial processes. We tested if photochemical oxidation could also be a significant redox process in northern freshwater systems. We exposed filtered natural water samples from four northern mine-impacted lakes (Northwest Territories, Canada) and three unimpacted ponds (Nunavik, Canada) to simulated solar radiation, and followed As(III) oxidation. During short-term incubation experiments (less than 8 h), all samples amended with As(III) displayed a rapid photooxidation (ca. 0.06-0.27 h−1) whereas no significant oxidation was observed in the dark. This photooxidation process was controlled by UV radiation, was influenced by short-lived oxidants and was partly driven by the concentrations of organic matter. Natural As complexes in unamended water samples were more rapidly photooxidized than in samples with As(III) amendments. Addition of goethite or simulation of snowmelt did not alter photooxidation rates significantly. Overall, these results imply that photooxidation of As should be considered as a potentially significant mechanism controlling inorganic As speciation in aquatic systems. This is particularly true for northern systems affected by mining activities and by changes of inputs of organic matter related to climate change.

New insights on nanostructure of ordered mesoporous Fe[sbnd]Mn bimetal oxides (OMFMs) by a novel inverse micelle method and their superior arsenic sequestration performance: Effect of calcination temperature and role of Fe/Mn oxides

A series of ordered mesoporous FeMn bimetal oxides (OMFMs) were fabricated by using a novel inverse micelle method, and the texture, nanostructure and interface chemistry properties of OMFMs were closely correlated to the calcination temperature. Due to the amorphous regular inner-connected nanostructure and bimetallic synergistic effect, the obtained OMFMs exhibited superior arsenic sequestration performance than pure mesoporous Fe oxides (PMF) and Mn oxides (PMM). The optimum ratio of Fe/Mn and calcination temperature for arsenic removal was 3/1 and 350 °C (OMFM-3), and the maximum As(III) and As(V) adsorption capacities of OMFM-3 were 174.59 and 134.58 mg/g, respectively. Solution pH value negligibly affected the uptake of arsenic (ranged from 3.0 to 7.0), while SiO32−/PO43− ions and humic acid (HA) displayed significant inhibitory effect on arsenic removal by OMFM-3. According to the mechanism of arsenic removal, which simultaneously analyzed the arsenic redox transformation in aqueous phase and on solid phase interface, it was concluded that manganese oxides in OMFM-3 mainly played the role as a remarkable As(III) oxidant in water, whereas iron oxides dominantly acted as an excellent arsenic species adsorbent. Finally, the prominent arsenic sequestration behavior and performance in surface water suggested that OMFM-3 could be a promising and hopeful candidate for arsenic-contaminated (especially As(III)) surface water and groundwater remediation and treatment.

Molecular and taxonomic characterization of arsenic (As) transforming Bacillus sp. strain IIIJ3\u20131 isolated from As-contaminated groundwater of Brahmaputra river basin, India

BackgroundMicrobe-mediated redox transformation of arsenic (As) leading to its mobilization has become a serious environmental concern in various subsurface ecosystems especially within the alluvial aquifers. However, detailed taxonomic and eco-physiological attributes of indigenous bacteria from As impacted aquifer of Brahmaputra river basin has remained under-studied.ResultsA newly isolated As-resistant and -transforming facultative anaerobic bacterium IIIJ3–1 from As-contaminated groundwater of Jorhat, Assam was characterized. Near complete 16S rRNA gene sequence affiliated the strain IIIJ3–1 to the genus Bacillus and phylogenetically placed within members of B. cereus sensu lato group with B. cereus ATCC 14579(T) as its closest relative with a low DNA-DNA relatedness (49.9%). Presence of iC17:0, iC15:0 fatty acids and menaquinone 7 corroborated its affiliation with B. cereus group, but differential hydroxy-fatty acids, C18:2 and menaquinones 5 & 6 marked its distinctiveness. High As resistance [Maximum Tolerable Concentration = 10 mM As3+, 350 mM As5+], aerobic As3+ (5 mM) oxidation, and near complete dissimilatory reduction of As 5+ (1 mM) within 15 h of growth designated its physiological novelty. Besides O2, cells were found to reduce As5+, Fe3+, SO42−, NO3−, and Se6+ as alternate terminal electron acceptors (TEAs), sustaining its anaerobic growth. Lactate was the preferred carbon source for anaerobic growth of the bacterium with As5+ as TEA. Genes encoding As5+ respiratory reductase (arr A), As3+ oxidase (aioB), and As3+ efflux systems (ars B, acr3) were detected. All these As homeostasis genes showed their close phylogenetic lineages to Bacillus spp. Reduction in cell size following As exposure exhibited the strain’s morphological response to toxic As, while the formation of As-rich electron opaque dots as evident from SEM-EDX possibly indicated a sequestration based As resistance strategy of strain IIIJ3–1.ConclusionThis is the first report on molecular, taxonomic, and ecophysiological characterization of a highly As resistant, As3+ oxidizing, and dissimilatory As5+ reducing Bacillus sp. IIIJ3–1 from As contaminated sites of Brahmaputra river basin. The strain’s ability to resist and transform As along with its capability to sequester As within the cells demonstrate its potential in designing bioremediation strategies for As contaminated groundwater and other ecosystems.

Mobility and redox transformation of arsenic during treatment of artificially recharged groundwater for drinking water production

In this study we investigate opportunities for reducing arsenic (As) to low levels, below 1 μg/L in produced drinking water from artificially infiltrated groundwater. We observe that rapid sand filtration is the most important treatment step for the oxidation and removal of As at water treatment plants which use artificially recharged groundwater as source. Removal of As is mainly due to As co-precipitation with Fe(III)(oxyhydr)oxides, which shows higher efficiency in rapid sand filter beds compared to aeration and supernatant storage. This is due to an accelerated oxidation of As(III) to As(V) in the filter bed which may be caused by the manganese oxides and/or As(III) oxidizing bacteria, as both are found in the coating of rapid sand filter media grains by chemical analysis and taxonomic profiling of the bacterial communities. Arsenic removal does not take place in treatment steps such as granular activated carbon filtration, ultrafiltration or slow sand filtration, due to a lack of hydrolyzing iron in their influent and a lack of adsorption affinity between As and the filtration surfaces. Further, we found that As reduction to below 1 μg/L can be effectively achieved at water treatment plants either by treating the influent of rapid sand filters by dosing potassium permanganate in combination with ferric chloride or by treating the effluent of rapid sand filters with ferric chloride dosing only. Finally, we observe that reducing the pH is an effective measure for increasing As co-precipitation with Fe(III)(oxyhydr)oxides, but only when the oxidized arsenic, As(V), is the predominant species in water.

Arsenic and the gastrointestinal tract microbiome.

Arsenic is a toxin, ranking first on the Agency for Toxic Substances and Disease Registry and the Environmental Protection Agency Priority List of Hazardous Substances. Chronic exposure increases the risk of a broad range of human illnesses, most notably cancer; however, there is significant variability in arsenic-induced disease among exposed individuals. Human genetics is a known component, but it alone cannot account for the large inter-individual variability in the presentation of arsenicosis symptoms. Each part of the gastrointestinal tract (GIT) may be considered as a unique environment with characteristic pH, oxygen concentration, and microbiome. Given the well-established arsenic redox transformation activities of microorganisms, it is reasonable to imagine how the GIT microbiome composition variability among individuals could play a significant role in determining the fate, mobility and toxicity of arsenic, whether inhaled or ingested. This is a relatively new field of research that would benefit from early dialogue aimed at summarizing what is known and identifying reasonable research targets and concepts. Herein, we strive to initiate this dialogue by reviewing known aspects of microbe-arsenic interactions and placing it in the context of potential for influencing host exposure and health risks. We finish by considering future experimental approaches that might be of value.

Simultaneous oxidation and immobilization of arsenite from water by nanosized magnetic mesoporous iron manganese bimetal oxides (Nanosized-MMIM): Synergistic effect and interface catalysis

Abstract Toxic arsenic species cycle in the geochemical process are strongly influenced by iron and manganese elements, thus understanding mutual transformation of multiple Fe/Mn redox states is essential to predict the redox transformation and sequestration of arsenic in natural environment. Herein, a nanosized magnetic mesoporous iron manganese bimetal oxides (Nanosized-MMIM) with highly well-ordered inner-connected structure and large surface area was fabricated, the obtained Nanosized-MMIM possessed higher content of surface-bound Fe(II) than Commercial Fe3O4 and Templated Fe3O4 due to the difference of standard redox potential of multiple Fe(II-III)-Mn(II-III) valence states and the synergistic effect of Fe-Mn bimetal oxides. This structural surface-bound Fe(II) was greatly associated to the OHads radicals that generated from the interface catalysis of materials via the Fenton-like pathway. The potential redox transformation of arsenic in liquid-solid two phase by using HPLC-ICP-MS and XPS investigation indicated that As(III) in water was mainly oxidized into As(V) by bulk solution OHfree radicals (30.39%) and surface-bound OHads radicals (69.16%), then the generated As(V) was subsequently adsorbed on the Nanosized-MMIM surface. This study could further improve the deeply understanding on the As(III) abiotic oxidation and sequestration in Fe-Mn co-existed natural environment such as minerals, soils and sediments.

Nitrate reduced arsenic redox transformation and transfer in flooded paddy soil-rice system

Inhibition of reductive transformation of arsenic (As) in flooded paddy soils is of fundamental importance for mitigating As transfer into food chain. Anaerobic arsenite (As(III)) oxidizers maintain As in less mobile fraction under nitrate-reducing conditions. In this study, we explored the dynamic profile of As speciation in porewater and As distribution among the pools of differential bioavailability in soil solid phase with and without nitrate treatment. In parallel, the abundance and diversity of As(III) oxidase gene (aioA) in flooded paddy soil with nitrate amendment was examined by quantitative PCR and aioA gene clone library. Furthermore, the impact of nitrate on As accumulation and speciation in rice seedlings was unraveled. With nitrate addition (25 mmol NO3− kg−1 soil), porewater As(III) was maintained at a consistently negligible concentration in the flooded paddy soil and the reductive dissolution of As-bearing Fe oxides/hydroxides was significantly restrained. Specifically, nitrate amendment kept 81% of total soil As in the nonlabile fraction with arsenate (As(V)) dominating after 30 days of flooding, compared to only 61% in the unamended control. Nitrate treatment induced 4-fold higher abundance of aioA gene, which belonged to domains of bacteria and archaea under the classes α-Proteobacteria (6%), ß-Proteobacteria (90%), ɣ-Proteobacteria (2%), and Thermoprotei (2%). By nitrate addition, As accumulation in rice seedlings was decreased by 85% with simultaneously elevated As(V) ratio in rice plant relative to control after 22 days of growth under flooded conditions. These results highlight that nitrate application can serve an efficient method to inhibit reductive dissolution of As in flooded paddy soils, and hence diminish As uptake by rice under anaerobic growing conditions.

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O2 during XAS measurements. With strict O2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Influence of the Chemical Form of Antimony on Soil Microbial Community Structure and Arsenite Oxidation Activity.

In the present study, the influence of the co-contamination with various chemical forms of antimony (Sb) with arsenite (As[III]) on soil microbial communities was investigated. The oxidation of As(III) to As(V) was monitored in soil columns amended with As(III) and three different chemical forms of Sb: antimony potassium tartrate (Sb[III]-tar), antimony(III) oxide (Sb2O3), and potassium antimonate (Sb[V]). Soil microbial communities were examined qualitatively and quantitatively using 16S rDNA- and arsenite oxidase gene (aioA)-targeted analyses. Microbial As(III) oxidation was detected in all soil columns and 90–100% of added As(III) (200 μmol L−1) was oxidized to As(V) in 9 d, except in the Sb(III)-tar co-amendments that only oxidized 30%. 16S rDNA- and aioA-targeted analyses showed that the presence of different Sb chemical forms significantly affected the selection of distinct As(III)-oxidizing bacterial populations. Most of the 16S rRNA genes detected in soil columns belonged to Betaproteobacteria and Gammaproteobacteria, and some sequences were closely related to those of known As(III) oxidizers. Co-amendments with Sb(III)-tar and high concentrations of Sb2O3 significantly increased the ratios of aioA-possessing bacterial populations, indicating the enrichment of As(III) oxidizers resistant to As and Sb toxicity. Under Sb co-amendment conditions, there was no correlation between aioA gene abundance and the rates of As(III) oxidation. Collectively, these results demonstrated that the presence of different Sb chemical forms imposed a strong selective pressure on the soil bacterial community and, thus, the co-existing metalloid is an important factor affecting the redox transformation of arsenic in natural environments.

Rethinking anaerobic As(III) oxidation in filters: Effect of indigenous nitrate respirers

Microorganisms play a key role in the redox transformation of arsenic (As) in aquifers. In this study, the impact of indigenous bacteria, especially the prevailing nitrate respirers, on arsenite (As(III)) oxidation was explored during groundwater filtration using granular TiO2 and subsequent spent TiO2 anaerobic landfill. X-ray absorption near edge structure spectroscopy analysis showed As(III) oxidation (46% in 10 days) in the presence of nitrate in the simulated anaerobic landfills. Meanwhile, iron (Fe) species on the spent TiO2 were dominated by amorphous ferric arsenate, ferrihydrite and goethite. The Fe phase showed no change during the anaerobic landfill incubation. Batch incubation experiments implied that the indigenous bacteria completely oxidized As(III) to arsenate (As(V)) in 10 days using nitrate as the terminal electron acceptor under anaerobic conditions. The bacterial community analysis indicated that various kinds of microbial species exist in groundwater matrix. Phylogenetic tree analysis revealed that Proteobacteria was the dominant phylum, with Hydrogenophaga (34%), Limnohabitans (16%), and Simplicispira (7%) as the major bacterial genera. The nitrate respirers especially from the Hydrogenophaga genus anaerobically oxidized As(III) using nitrate as an electron acceptor instead of oxygen. Our study implied that microbes can facilitate the groundwater As oxidation using nitrate on the adsorptive media.

Non-thermal discharge plasma promoted redox transformation of arsenic(III) and chromium(VI) in an aqueous medium

A non-thermal plasma (NTP) reactor operating under ambient conditions was designed and tested for the redox transformation of As(III) and Cr(VI) in an aqueous medium. Influence of initial concentration and applied voltage was studied for the individual/simultaneous removal of the pollutants. Active species generated in the discharge, like hydrogen peroxide (H2O2), hydroxyl radicals (OH) were quantified and hydrated electrons (e−aq), hydrogen radicals (H) were identified. It has been observed that H2O2 decomposes to generate OH, which oxidizes As(III) to As(V). Typical results indicated that the simultaneous removal of As(III) and Cr(VI) is beneficial over the removal of individual pollutants. It has been observed that the presence of both the reactants complements the redox nature, where As(III) suppresses the re-oxidation of Cr(III) to Cr(VI) and promotes Cr(VI) reduction to Cr(III). Addition of Fe(II) salt to the reaction mixture significantly enhances the As(III) oxidation. The best energy yield obtained for the redox transformation of As(III) and Cr(VI) was ∼24g/kWh and ∼15g/kWh, respectively. These findings demonstrate the feasibility of the simultaneous transformations of toxic As(III) and Cr(VI) in an environmentally benign manner.

Redox transformation of arsenic by magnetic thin-film MnO2 nanosheet-coated flowerlike Fe3O4 nanocomposites

Inorganic arsenic cycling in the natural environment is significantly controlled by manganese/iron oxides, and studying the redox transformation of arsenic in both aqueous and solid phase is therefore essential to understand its environmental toxicity and predict its environmental behavior. Herein, the synthesized magnetic thin-film MnO2 nanosheet-coated flowerlike Fe3O4 nanocomposites have been used to simultaneously investigate the potential redox transformation of arsenic in aqueous phase and arsenic speciation on the solid phase interface. The results showed the initial Mn/Fe ratio has serious influenced the morphologies, textural properties and uptake of arsenic in aqueous solution. The maximum adsorption capacities of As(III) and As(V) by MF2 were 76.73mg/g and 120.50mg/g, respectively. After 10h reaction, the total arsenic concentration in both As(III)-MF2 system and As(V)-MF2 system far below than that of 10μg/L, which was setted the maximum guideline concentration value in drinking water by World Health Organization (WHO). HPLC-ICP-MS revealed that in aqueous solution part of As(III) was oxidized into As(V), while As(V) was not reduced into As(III). X-ray absorption near edge structure (XANES) and XPS analysis from solid phase further confirmed that the MnO2 nanosheet mainly acted as an oxidant, while flowerlike Fe3O4 only played the role as an arsenic species adsorbent. Extended X-ray absorption fine structure (EXAFS) analysis indicated that both As(III) and As(V) formed inner-sphere bidentate binuclear corner-sharing (2C) complexes with an As-Fe interatomic distance of 3.32–3.34Å on the interface of As-MF2 solid phase.

Effect of dissimilatory iron and sulfate reduction on arsenic dynamics in the wetland rhizosphere and its bioaccumulation in wetland plants (Scirpus actus)

Microbial redox transformations of arsenic (As) are coupled to dissimilatory iron and sulfate reduction in the wetlands, however, the processes involved are complex and poorly defined. In this study, we investigated the effect of dissimilatory iron and sulfate reduction on As dynamics in the wetland rhizosphere and its bioaccumulation in plants using greenhouse mesocosms. Results show that high Fe (50μM ferrihydrite/g solid medium) and SO42− (5mM) treatments are most favorable for As sequestration in the presence of wetland plants (Scirpus actus), probably because root exudates facilitate the microbial reduction of Fe(III), SO42−, and As(V) to sequester As(III) by incorporation into iron sulfides and/or plant uptake. As retention in the solid medium and accumulation in plants were mainly controlled by SO42− rather than Fe levels. Compared to the low SO42− (0.1mM) treatment, high SO42− resulted in 2 times more As sequestered in the solid medium, 30 times more As in roots, and 49% less As in leaves. An As speciation analysis in pore water indicated that 19% more dissolved As was reduced under high SO42− than low SO42− levels, which is consistent with the fact that more dissimilatory arsenate-respiring bacteria were found under high SO42− levels.

Arsenic redox transformation by Pseudomonas sp. HN-2 isolated from arsenic-contaminated soil in Hunan, China

A mesophilic, Gram-negative, arsenite[As(III)]-oxidizing and arsenate[As(V)]-reducing bacterial strain, Pseudomonas sp. HN-2, was isolated from an As-contaminated soil. Phylogenetic analysis based on 16S rRNA gene sequencing indicated that the strain was closely related to Pseudomonas stutzeri. Under aerobic conditions, this strain oxidized 92.0% (61.4μmol/L) of arsenite to arsenate within 3hr of incubation. Reduction of As(V) to As(III) occurred in anoxic conditions. Pseudomonas sp. HN-2 is among the first soil bacteria shown to be capable of both aerobic As(III) oxidation and anoxic As(V) reduction. The strain, as an efficient As(III) oxidizer and As(V) reducer in Pseudomonas, has the potential to impact arsenic mobility in both anoxic and aerobic environments, and has potential application in As remediation processes.

Effect of humic acid on as redox transformation and kinetic adsorption onto iron oxide based adsorbent (IBA).

Due to the importance of adsorption kinetics and redox transformation of arsenic (As) during the adsorption process, the present study elucidated natural organic matter (NOM) effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA) as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA), as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions.

Rapid on‐site separation of As(III) and As(V) in waters using a disposable thiol‐modified sand cartridge

The rapid redox transformation of arsenic (As) species in waters presents a great environmental challenge in the accurate determination of its concentration and toxicity. The motivation of the present study was therefore to develop a method for rapid on-site separation of As(V) and As(III) in various aqueous matrices. The authors synthesized a thiol-modified sand (T-sand) that selectively removed As(III) but did not adsorb As(V). The novel application of this T-sand in a disposable cartridge was able to successfully separate As(V) (37-970 µg L(-1) ) and As(III) (not detected to 488 µg L(-1) ) in 23 groundwater samples collected in areas with naturally occurring As. The As speciation results determined with T-sand separation in the field were consistent with those obtained using high-performance liquid chromatography-atomic fluorescence spectrometry. Furthermore, the T-sand cartridge was applicable in a wide variety of matrices, including groundwater, leachants of the toxicity-characteristic leaching procedure, and extracts from the California waste extraction test; sequential extraction test; and in vitro gastrointestinal extraction. This easy-to-use separation method is especially suitable for routine field monitoring of As speciation.

Arsenic transforming abilities of groundwater bacteria and the combined use of Aliihoeflea sp. strain 2WW and goethite in metalloid removal

Several technologies have been developed for lowering arsenic in drinking waters below the World Health Organization limit of 10μg/L. When in the presence of the reduced form of inorganic arsenic, i.e. arsenite, one options is pre-oxidation of arsenite to arsenate and adsorption on iron-based materials. Microbial oxidation of arsenite is considered a sustainable alternative to the chemical oxidants. In this contest, the present study investigates arsenic redox transformation abilities of bacterial strains in reductive groundwater from Lombardia (Italy), where arsenite was the main arsenic species. Twenty isolates were able to reduce 75mg/L arsenate to arsenite, and they were affiliated to the genera Pseudomonas, Achromobacter and Rhodococcus and genes of the ars operon were detected. Three arsenite oxidizing strains were isolated: they belonged to Rhodococcus sp., Achromobacter sp. and Aliihoeflea sp., and aioA genes for arsenite oxidase were detected in Aliihoeflea sp. strain 2WW and in Achromobacter sp. strain 1L. Uninduced resting cells of strain 2WW were used in combination with goethite for arsenic removal in a model system, in order to test the feasibility of an arsenic removal process. In the presence of 200μg/L arsenite, the combined 2WW-goethite system removed 95% of arsenic, thus lowering it to 8μg/L. These results indicate that arsenite oxidation by strain 2WW combined to goethite adsorption is a promising approach for arsenic removal from contaminated groundwater.

Geochemistry and Microbiology in an Acidic, High Altitude (4,000 m) Salt Flat — High Andes, Northern Chile

Acidic saline lake systems are an uncommon type of natural extreme environment described in Northern Chile and in Australia. These environments are considered a terrestrial analogue to certain ancient Martian terrains and a source of new material for biotechnological applications as bioleaching at high ionic strength conditions and biological systems for precipitating metal sulfides. The aim of this study is to describe the occurrence of redox couples that support prokaryotic life in the system and to obtain representative cultures of predominant microorganisms/metabolisms. Mapping of the area of interest and geochemical analysis of sediments, bedrock and water samples were performed. The original microbial community and enriched cultures were studied by direct count and culturing dependent and independent techniques. In the distal part of the alluvial fans some ponds are found with acidic brines (up to pH 1) of the Cl-SO4-Na (-Mg) type that are surrounded by yellow efflorescences. Other ponds towards the basin center progressively increase in concentration due to capillary evaporation. Brines are rich in aluminium and boron with lower concentration of manganese, lithium, iron and arsenic. An advanced hydrothermal argillic alteration affecting the country rocks, native sulfur associated to active solfataras, alunite and jarosite occurrences in sediments and chloride and sulfate efflorescent salts were evidenced. The microbial community in brines and sediments (105 and 106 cells/mL, respectively) was dominated by Firmicutes, Proteobacteria and Actinobacteria, and by Proteobacteria and Cyanobacteria, respectively. Sulphur and iron oxidation activity were detected depending on the salinity of the samples. Culture enrichments that respire and reduce As (V) and sulfate have been only obtained from sites with the highest pH (4-5). Microbial assemblages in those heterotrophic cultures were closely related to the Gamma and Betaproteobacteria, meanwhile, Rhodanobacter and Shewanella were the only microorganisms detected in the autotrophic cultures supplemented by Na2S and by H2. Relevant information to describe the occurring surface biogeochemical processes in that acidic saline system has been obtained. In addition, the occurrence of new prokaryotic genera capable of arsenic redox transformation has been evidenced in acidic systems.