Biogeochemical Cycling Of Arsenic Research Articles

Soil Microbiomes and their Arsenic Functional Genes in Chronically High-Arsenic Contaminated Soils.

Microbial arsenic transformations play essential roles in controlling pollution and ameliorating risk. This study combined high-throughput sequencing and PCR-based approaches targeting both the 16S rRNA and arsenic functional genes to investigate the temporal and spatial dynamics of the soil microbiomes impacted by high arsenic contamination (9.13 to 911.88mg/kg) and to investigate the diversity and abundance of arsenic functional genes in soils influenced by an arsenic gradient. The results showed that the soil microbiomes were relatively consistent and mainly composed of Actinobacteria (uncultured Gaiellales and an unknown_67 - 14 bacterium), Proteobacteria, Firmicutes (particularly, Bacillus), Chloroflexi, and Acidobacteria (unknown_Subgroup_6). Although a range of arsenic functional genes (e.g., arsM, arsC, arrA, and aioA) were identified by shotgun metagenomics, only the arsM gene was detected by the PCR-based method. The relative abundance of the arsM gene accounted for 0.20%-1.57% of the total microbial abundance. Combining all analyses, arsenic methylation mediated by the arsM gene was proposed to be a key process involved in the arsenic biogeochemical cycle and mitigation of arsenic toxicity. This study advances our knowledge about arsenic mechanisms over the long-term in highly contaminated soils.

Arsenic biogeochemical cycling association with basin-scale dynamics of microbial functionality and organic matter molecular composition

Geogenic arsenic (As)-contaminated groundwater is a sustaining global health concern that is tightly constrained by multiple interrelated biogeochemical processes. However, a complete spectrum of the biogeochemical network of high-As groundwater remains to be established, concurrently neglecting systematic zonation of groundwater biogeochemistry on the regional scale. We uncovered the geomicrobial interaction network governing As biogeochemical pathways by merging in-field hydrogeochemical monitoring, metagenomic analyses, and ultrahigh resolution mass spectrometry (FT-ICR MS) characterization of dissolved organic matter. In oxidizing to weakly reducing environments, the nitrate-reduction and sulfate-reduction encoding genes (narGHI, sat) inhibited the dissolution of As-bearing iron minerals, leading to lower As levels in groundwater. In settings from weakly to moderately reducing, high abundances of sulfate-reduction and iron-transport encoding genes boosted iron mineral dissolution and consequent As release. As it evolved to strongly reducing stage, elevated abundance of methane cycle-related genes (fae, fwd, fmd) further enhanced As mobilization in part by triggering the formation of gaseous methylarsenic. During redox cycling of N, S, Fe, C and As in groundwater, As migration to groundwater and immobilization in mineral particles are geochemically constrained by basin-scale dynamics of microbial functionality and DOM molecular composition. The study constructs a theoretical model to summarize new perspectives on the biogeochemical network of As cycling.

Genome sequence and characterisation of a freshwater photoarsenotroph, Cereibacter azotoformans strain ORIO, isolated from sediments capable of cyclic light-dark arsenic oxidation and reduction.

A freshwater photosynthetic arsenite-oxidizing bacterium, Cereibacter azotoformans strain ORIO, was isolated from Owens River, CA, USA. The waters from Owens River are elevated in arsenic and serve as the headwaters to the Los Angeles Aqueduct. The complete genome sequence of strain ORIO is 4.8 Mb genome (68% G + C content) and comprises two chromosomes and six plasmids. Taxonomic analysis placed ORIO within the Cereibacter genus (formerly Rhodobacter). The ORIO genome contains arxB2 AB1 CD (encoding an arsenite oxidase), arxXSR (regulators) and several ars arsenic resistance genes all co-localised on a 136 kb plasmid, named pORIO3. Phylogenetic analysis of ArxA, the molybdenum-containing arsenite oxidase catalytic subunit, demonstrated photoarsenotrophy is likely to occur within members of the Alphaproteobacteria. ORIO is a mixotroph, oxidises arsenite to arsenate (As(V)) photoheterotrophically, and expresses arxA in cultures grown with arsenite. Further ecophysiology studies with Owens River sediment demonstrated the interconversion of arsenite and As(V) was dependent on light-dark cycling. arxA and arrA (As(V) respiratory reductase) genes were detected in the light-dark cycled sediment metagenomes suggesting syntrophic interactions among arsenotrophs. This work establishes C. azotoformans str. ORIO as a new model organism for studying photoarsenotrophy and light-dark arsenic biogeochemical cycling.

Metagenome based analysis of groundwater from arsenic contaminated sites of West Bengal revealed community diversity and their metabolic potential

The study of microbial community in groundwater systems is considered to be essential to improve our understanding of arsenic (As) biogeochemical cycling in aquifers, mainly as it relates to the fate and transport of As. The present study was conducted to determine the microbial community composition and its functional potential using As-contaminated groundwater from part of the Bengal Delta Plain (BDP) in West Bengal, India. Geochemical analyses indicated low to moderate dissolved oxygen (0.42-3.02 mg/L), varying As (2.5-311 µg/L) and Fe (0.19-1.2 mg/L) content, while low concentrations of total organic carbon (TOC), total inorganic carbon (TIC), nitrate, and sulfate were detected. Proteobacteria was the most abundant phylum, while the indiscriminate presence of an array of archaeal phyla, Euryarchaeota, Crenarchaeota, Nanoarchaeota, etc., was noteworthy. The core community members were affiliated to Sideroxydans, Acidovorax, Pseudoxanthomonas, Brevundimonas, etc. However, diversity assessed over multiple seasons indicated a shift from Sideroxydans to Pseudomonas or Brevundimonas dominant community, suggestive of microbial response to seasonally fluctuating geochemical stimuli. Taxonomy-based functional potential showed prospects for As biotransformation, methanogenesis, sulfate respiration, denitrification, etc. Thus, this study strengthened existing reports from this region by capturing the less abundant or difficult-to-culture taxa collectively forming a major fraction of the microbial community.

Deciphering roles of microbiota in arsenic biotransformation from the earthworm gut and skin

Biotransformation mediated by microbes can affect the biogeochemical cycle of arsenic. However, arsenic biotransformation mediated by earthworm-related microorganisms has not been well explored, especially the role played by earthworm skin microbiota. Herein, we reveal the profiles of arsenic biotransformation genes (ABGs) and elucidate the microbial communities of the earthworm gut, skin, and surrounding soil from five different soil environments in China. The relative abundance of ABGs in the earthworm skin microbiota, which were dominated by genes associated with arsenate reduction and transport, was approximately three times higher than that in the surrounding soil and earthworm gut microbiota. The composition and diversity of earthworm skin microbiota differed significantly from those of the soil and earthworm gut, comprising a core bacterial community with a relative abundance of 96% Firmicutes and a fungal community with relative abundances of 50% Ascomycota and 13% Mucoromycota. In addition, stochastic processes mainly contributed to the microbial community assembly across all samples. Moreover, fungal genera such as Vishniacozyma and Oomyces were important mediators of ABGs involved in the biogeochemical cycle of arsenic. This is the first study to investigate earthworm skin as a reservoir of microbial diversity in arsenic biotransformation. Our findings broaden the current scientific knowledge of the involvement of earthworms in the arsenic biogeochemical cycle.

Selective Methylation by an ArsM S-Adenosylmethionine Methyltransferase from Burkholderia gladioli GSRB05 Enhances Antibiotic Production.

Arsenic methylation contributes to the formation and diversity of environmental organoarsenicals, an important process in the arsenic biogeochemical cycle. The arsM gene encoding an arsenite (As(III)) S-adenosylmethionine (SAM) methyltransferase is widely distributed in members of every kingdom. A number of ArsM enzymes have been shown to have different patterns of methylation. When incubated with inorganic As(III), Burkholderia gladioli GSRB05 has been shown to synthesize the organoarsenical antibiotic arsinothricin (AST) but does not produce either methylarsenate (MAs(V)) or dimethylarsenate (DMAs(V)). Here, we show that cells of B. gladioli GSRB05 synthesize DMAs(V) when cultured with either MAs(III) or MAs(V). Heterologous expression of the BgarsM gene in Escherichia coli conferred resistance to MAs(III) but not As(III). The cells methylate MAs(III) and the AST precursor, reduced trivalent hydroxyarsinothricin (R-AST-OH) but do not methylate inorganic As(III). Similar results were obtained with purified BgArsM. Compared with ArsM orthologs, BgArsM has an additional 37 amino acid residues in a linker region between domains. Deletion of the additional 37 residues restored As(III) methylation activity. Cells of E. coli co-expressing the BgarsL gene encoding the noncanonical radical SAM enzyme that catalyzes the synthesis of R-AST-OH together with the BgarsM gene produce much more of the antibiotic AST compared with E. coli cells co-expressing BgarsL together with the CrarsM gene from Chlamydomonas reinhardtii, which lacks the sequence for additional 37 residues. We propose that the presence of the insertion reduces the fitness of B. gladioli because it cannot detoxify inorganic arsenic but concomitantly confers an evolutionary advantage by increasing the ability to produce AST.

Interplay between arsenic and selenium biomineralization in Shewanella sp. O23S

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO42−) and selenite (SeO32−) to red Se(-S)0, and arsenate (AsO43−) to arsenite (AsO33−). The release of H2S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As2S3. When As and Se oxyanions were mixed, both As–S and Se(-S)0 biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (−24 to −38 mV). Kinetic analysis indicated the following reduction yields: SeO32− (90%), AsO43− (60%), and SeO42− (<10%). The mix of SeO32− with AsO43− led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO42− incubated with AsO43− boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Microbial reduction and migration of As/Fe mediated by electron shuttle: Differences between incorporated and adsorbed As(V)

Metal-reducing bacteria play a central and important role in the biogeochemical cycle of arsenic (As) and iron (Fe). Research on As/Fe migration from arsenic-containing iron minerals mediated by electronic shuttles is of significance to groundwater protection and human health. Further, the redox activity and bioavailability of goethite with differing occurrence and distribution of arsenic have not been studied clearly. In this study, the function of electron shuttle AQDS in Fe(III) bioreduction was determined. It was found that acidic conditions were conducive to the growth and reproduction of strain D2201, which was beneficial to the reduction of As(V)/Fe(III). The OD600nm value of the bacteria at pH 6 exceeded twice that at pH 8. Then, three types of goethite, namely pure goethite (Gt), coprecipitated As(V)-goethite (Gt-As), and adsorbed arsenic-goethite (Gt∗As), were compared for microbial reduction reactivity. X-ray photoelectron spectroscopy analysis illustrated the proportion of OH- content in Gt-As was much lower than that of Gt and Gt∗As, indicating Gt-As carried more surface defects and had higher bioavailability. The Fe(II) content released from AQDS-mediated bioreduction of Gt-As was two-fold higher than that of Gt and Gt∗As at pH 7. In addition, pH significantly affected goethite bioreduction efficiency and arsenic migration degree. The dissolved Fe(II) concentration for Gt-As was 0.98, 0.133, and 0.139 ​mM at pH 6, 7, and 8, respectively; corresponding to dissolved As(T) content of 3.51, 1.48, and 1.31 ​μM within 9 days of culture. This study highlights the significant influence of AQDS and mineral structure on the As/Fe biochemical cycle, which will help further develop the bioremediation of arsenic-contaminated sediments.

Isolation and Characterization of As (V)-reducing Bacillus sp. Strain SM-B1 from Arsenic Laden Gold Mine in Malaysia

Arsenic is a highly toxic element released into the environment naturally or through human activities. Bacteria are equipped with detoxification mechanisms that enable them to cope with the adverse effects of arsenic. These mechanisms play an important role in biogeochemical cycling of arsenic in the environment. Therefore, this study aimed to isolate arsenic resistant bacteria from arsenic-laden soils in a Malaysian gold mining environment and to characterize their arsenic-transformation ability. Culture enrichment was carried out in LB medium supplemented with As (III) or As (V), resulting in isolation of two bacterial strains. Bacillus sp. SM-B1 showed tolerance to 30 mM As (III) and 350 mM As (V). Acinetobacter sp. SM-S1 demonstrated tolerance to 25 mM As (III) and 300 mM As (V). Bacillus sp. SM-B1 completely reduced 1 mM As (V) in 36 h under aerobic conditions. Putative fragments of arsC and arsB gene were amplified from the genome of isolate SM-B1. Acinetobacter sp. SM-S1 did not show any arsenic transformation activity. Bacillus sp. SM-B1 grown at pH 9 showed potential in arsenic accumulation. Findings generated from this study provide additional details on arsenic-transforming bacteria associated with high arsenic soil and their roles in arsenic biogeochemical cycle in arsenic-contaminated mines in Malaysia.

Arsenic Accumulation and Biotransformation Affected by Nutrients (N and P) in Common Blooming-Forming Microcystis wesenbergii (Komárek) Komárek ex Komárek (Cyanobacteria)

Arsenic accumulation and biotransformation in algae was mostly carried out in a medium that contained far higher nutrient concentrations than that in natural freshwaters. The obtained results might have limited environmental validity and result in a failure to describe authentic arsenic biogeochemical cycles in natural freshwater systems. To validate the assumption, arsenic accumulation, and biotransformation in common bloom forming Microcystis wesenbergii was performed under a high nutrient concentration in BG11 medium (N = 250 mg/L, P = 7.13 mg/L), and adjusted low nutrients that mimicked values in natural freshwaters (N = 1.5 mg/L, P = 0.3 mg/L). The growth rate and maximum M. wesenbergii cell density were much lower in the high nutrient set, but more inhibition was shown with increasing ambient iAs(V) concentrations both in the high and low nutrient sets. The proportion of intracellular contents in total arsenicals decreased with increasing iAs(V) concentrations in both high and low nutrient sets but increased with incubation time. Intracellular iAs(III) was not found in the high nutrient set, while it formed high concentrations that could be comparable to that of an extracellular level in the low nutrient set. M. wesenbergii could methylate arsenic, and a higher proportion of organoarsenicals was formed in the low nutrient set. Lower intracellular MMA(V) and DMA(V) concentrations were found in the high nutrient set; contrarily, they presented a higher concentration that could be comparable to the extracellular ones in the low nutrient set. The results demonstrated that different nutrient regimes could affect arsenic accumulation and biotransformation in M. wesenbergii, and low nutrient concentrations could inhibit the excretion of iAs(III), MMA(V) and DMA(V) out of cells. Further investigations should be based on natural freshwater systems to obtain an authentic arsenic accumulation and biotransformation in cyanobacteria.

Identification of the Biosynthetic Gene Cluster for the Organoarsenical Antibiotic Arsinothricin.

ABSTRACTThe soil bacterium Burkholderia gladioli GSRB05 produces the natural compound arsinothricin [2-amino-4-(hydroxymethylarsinoyl) butanoate] (AST), which has been demonstrated to be a broad-spectrum antibiotic. To identify the genes responsible for AST biosynthesis, a draft genome sequence of B. gladioli GSRB05 was constructed. Three genes, arsQML, in an arsenic resistance operon were found to be a biosynthetic gene cluster responsible for synthesis of AST and its precursor, hydroxyarsinothricin [2-amino-4-(dihydroxyarsinoyl) butanoate] (AST-OH). The arsL gene product is a noncanonical radical S-adenosylmethionine (SAM) enzyme that is predicted to transfer the 3-amino-3-carboxypropyl (ACP) group from SAM to the arsenic atom in inorganic arsenite, forming AST-OH, which is methylated by the arsM gene product, a SAM methyltransferase, to produce AST. Finally, the arsQ gene product is an efflux permease that extrudes AST from the cells, a common final step in antibiotic-producing bacteria. Elucidation of the biosynthetic gene cluster for this novel arsenic-containing antibiotic adds an important new tool for continuation of the antibiotic era.IMPORTANCE Antimicrobial resistance is an emerging global public health crisis, calling for urgent development of novel potent antibiotics. We propose that arsinothricin and related arsenic-containing compounds may be the progenitors of a new class of antibiotics to extend our antibiotic era. Here, we report identification of the biosynthetic gene cluster for arsinothricin and demonstrate that only three genes, two of which are novel, are required for the biosynthesis and transport of arsinothricin, in contrast to the phosphonate counterpart, phosphinothricin, which requires over 20 genes. Our discoveries will provide insight for the development of more effective organoarsenical antibiotics and illustrate the previously unknown complexity of the arsenic biogeochemical cycle, as well as bring new perspective to environmental arsenic biochemistry.

The Pedosphere as a Sink, Source, and Record of Anthropogenic and Natural Arsenic Atmospheric Deposition.

The Anthropocene has led to global-scale contamination of the biosphere through diffuse atmospheric dispersal of arsenic. This review considers the sources arsenic to soils and its subsequent fate, identifying key knowledge gaps. There is a particular focus on soil classification and stratigraphy, as this is central to the topic under consideration. For Europe and North America, peat core chrono-sequences record massive enhancement of arsenic depositional flux from the onset of the Industrial Revolution to the late 20th century, while modern mitigation efforts have led to a sharp decline in emissions. Recent arsenic wet and dry depositional flux measurements and modern ice core records suggest that it is South America and East Asia that are now primary global-scale polluters. Natural sources of arsenic to the atmosphere are primarily from volcanic emissions, aeolian soil dust entrainment, and microbial biomethylation. However, quantifying these natural inputs to the atmosphere, and subsequent redeposition to soils, is only starting to become better defined. The pedosphere acts as both a sink and source of deposited arsenic. Soil is highly heterogeneous in the natural arsenic already present, in the chemical and biological regulation of its mobility within soil horizons, and in interaction with climatic and geomorphological settings. Mineral soils tend to be an arsenic sink, while organic soils act as both a sink and a source. It is identified here that peatlands hold a considerable amount of Anthropocene released arsenic, and that this store can be potentially remobilized under climate change scenarios. Also, increased ambient temperature seems to cause enhanced arsine release from soils, and potentially also from the oceans, leading to enhanced rates of arsenic biogeochemical cycling through the atmosphere. With respect to agriculture, rice cultivation was identified as a particular concern in Southeast Asia due to the current high arsenic deposition rates to soil, the efficiency of arsenic assimilation by rice grain, and grain yield reduction through toxicity.

Arsenic bioaccumulation in the soil fauna alters its gut microbiome and microbial arsenic biotransformation capacity

The biotransformation of arsenic mediated by microorganisms plays an important role in the arsenic biogeochemical cycle. However, the fate and biotransformation of arsenic in different soil fauna gut microbiota are largely unknown. Herein the effects of arsenic contamination on five types of soil fauna were compared by examining variations in arsenic bioaccumulation, gut microbiota, and arsenic biotransformation genes (ABGs). Significant difference was observed in the arsenic bioaccumulation across several fauna body tissues, and Metaphire californica had the highest arsenic bioaccumulation, with a value of 107 ± 1.41 mg kg−1. Arsenic exposure significantly altered overall patterns of ABGs; however, dominant genes involved in arsenic redox and other genes involved in arsenic methylation and demethylation were not significantly changed across animals. Except for M. californica, the abundance of ABGs in other animal guts firstly increased and then decreased with increasing arsenic concentrations. In addition, exposure of soil fauna to arsenic led to shifts in the unique gut-associated bacterial community, but the magnitude of these changes varied significantly across ecological groups of soil fauna. A good correlation between the gut bacterial communities and ABG profiles was observed, suggesting that gut microbiota plays important roles in the biotransformation of arsenic. Overall, these results provide a universal profiling of a microbial community capable of arsenic biotransformation in different fauna guts. Considering the global distribution of soil fauna in the terrestrial ecosystem, this finding broadens our understanding of the hidden role of soil fauna in the arsenic bioaccumulation and biogeochemical cycle.

Effects of microplastic on arsenic accumulation in Chlamydomonas reinhardtii in a freshwater environment

Chlamydomonas reinhardtii plays a critical role in the biogeochemical cycling of arsenic (As) and purification of water bodies contaminated with As. We investigated the effects of microplastic pollution on the ability of C. reinhardtii to accumulate As. We revealed that different sized [100 nm (S) and 5 µm (L)] polystyrene microplastics (PSMP) at different concentrations (50 and 100 mg L−1) interacted with the phospholipid structure in C. reinhardtii. Dispersion forces disrupted the structure and function of membrane proteins, reducing the accumulation and efflux of As(III) and inhibiting the As(V)-As(III)-MMA-DMA detoxification process in C. reinhardtii cells. The maximum As accumulation rates of C. reinhardtii in the control groups, L50, L100, S50, and S100 treatments were 53.71, 50.95, 48.42, 43.83, and 39.11 μg g−1 h−1, respectively. Further, PSMPs and As(III) triggered “oxidative bursts” in cells, damaging cell membranes and reducing chlorophyll content and Rubisco activity. As a result, photosynthesis, respiration, and growth were inhibited. When compared with an absence of PSMP, the addition of L- (S-) sized PSMP to the As-containing solution would result in a lower (higher) impact on C. reinhardtii. Overall, this study demonstrated that microplastics significantly affect As accumulation in C. reinhardtii. Our results indicate that the critical role of this algal species in As cycling in earth’s pedo- and hydrosphere may be impeded by microplastic pollution.

Microbial Diversity and Community Structure in Alpine Stream Soil

Investigations of microbial communities over arsenic-polluted soils in an alpine stream are vital to collect pieces of evidence for their in situ-mediated bioremediation. It is the first time that microbial community activities are described in arsenic-polluted soils due to natural and anthropogenic sources along the alpine stream. Greater than 40 phyla from domain bacteria the 16S rRNA Illumina sequencing amplicons are exposed. In overall samples, Unweighted Pair Group Method with Arithmetic Mean (UPGMA) states that the most dominant phyla were Proteobacteria, Cyanobacteria, and Actinobacteria. Our result described that canonical correspondence analysis was used to elaborate more geochemical factors including arsenic, sulfate, total organic carbon, redox potential, and pH influence on the distribution of microbial groups in studies soil samples. Furthermore, Spearman’s rank correlation demonstrates a positive correlation between several specific taxonomic groups, refers to the phylotypes’ possible role in arsenic biogeochemical cycling. The present research could link the knowledge gap and facilitate our understanding for the bioremediation of arsenic at contaminated sites. Highlights We described the microbial communities in arsenic-contaminated soils. CCA revealed that chemical parameters organized microbial communities. The effects of geochemical conditions on microbial community composition were examined.

The response of Pyropia haitanensis to inorganic arsenic under laboratory culture

Up to now, complicated organoarsenicals were mainly identified in marine organisms, suggesting that these organisms play a critical role in arsenic biogeochemical cycling because of low phosphate and relatively high arsenic concentration in the marine environment. However, the response of marine macroalgae to inorganic arsenic remains unknown. In this study, Pyropia haitanensis were exposed to arsenate [As(V)] (0.1, 1, 10, 100 μM) or arsenite [As(III)] (0.1, 1, 10 μM) under laboratory conditions for 3 d. The species of water-soluble arsenic, the total concentration of lipid-soluble and cell residue arsenic of the algae cells was analyzed. As(V) was mainly transformed into oxo-arsenosugar–phosphate, with other arsenic compounds such as monomethylated, As(III), demethylated arsenic and oxo-arsenosugar–glycerol being likely the intermediates of arsenosugar synthesis. When high concentration of As(III) was toxic to P. haitanensis, As(III) entered into the cells and was transformed into less toxic organoarsenicals and As(V). Transcriptome results showed genes involved in DNA replication, mismatch repair, base excision repair, and nucleotide excision repair were up-regulated in the algae cells exposed to 10 μM As(V), and multiple genes involved in glutathione metabolism and photosynthetic were up-regulated by 1 μM As(III). A large number of ABC transporters were down-regulated by As(V) while ten genes related to ABC transporters were up-regulated by As(III), indicating that ABC transporters were involved in transporting As(III) to vacuoles in algae cells. These results indicated that P. haitanensis detoxifies inorganic arsenic via transforming them into organoarsenicals and enhancing the isolation of highly toxic As(III) in vacuoles.

Influence of sulfur on the mobility of arsenic and antimony during oxic-anoxic cycles: Differences and competition

The biogeochemical cycling of arsenic (As) and antimony (Sb) is coupled with sulfur (S). Biogenic sulfide from microbial sulfate reduction under anaerobic conditions may enhance the release of coexisting As and Sb through the formation of labile thioarsenate (AsV-S) and thioantimonate (SbV-S). To understand the competition between As and Sb for thiolation and its effect on their mobility, we investigated the speciation and fate of As and Sb in the presence of indigenous microbiota in sediments during multiple oxic-anoxic cycles. Sediments with Sb contents at low (L-Sb, 570 mg/kg Sb, 50 mg/kg As), medium (M-Sb, 2,560 mg/kg Sb, 90 mg/kg As) and high (H-Sb, 10,090 mg/kg Sb, 190 mg/kg As) levels were collected in the Xikuangshan mining area, the largest Sb mine in the world. Our aqueous speciation analysis indicated that As was released under anoxic conditions whereas Sb was mobilized during oxic cycles in all samples. The As release was not driven by the transformation of Fe-bearing phases, but by biogenic sulfide through the formation of soluble AsV-S. AsV-S was the primary soluble species under anoxic conditions as evidenced by its high percentage, up to 80% in L- and M-Sb sediments, and 60% in H-Sb sediment. AsV-S was formed prior to SbV-S in L- and M-Sb sediments and even suppressed SbV-S formation in H-Sb sediment, indicating that limited biogenic sulfide preferentially bound with As rather than Sb. The Sb mobility was not associated with sulfide, but mainly regulated by its redox transformation between mobile antimonate and immobile antimonite. X-ray absorption near edge structure (XANES) spectra of Sb, As and S showed that no As or Sb sulfide precipitation was formed during the incubation. The Fe K-edge XANES analysis suggested the minor transformation of Fe-bearing phases between goethite (32 ± 8%), hematite (24 ± 7%) and magnetite (25 ± 4%), resulting in a limited effect of Fe cycling on As mobility. The results of our study signify the competition of As and Sb in thiolation and improve our understanding of the contrasting behaviors of As and Sb during oxic-anoxic cycles.

Methane, arsenic, selenium and the origins of the DMSO reductase family

Mononuclear molybdoenzymes of the dimethyl sulfoxide reductase (DMSOR) family catalyze a number of reactions essential to the carbon, nitrogen, sulfur, arsenic, and selenium biogeochemical cycles. These enzymes are also ancient, with many lineages likely predating the divergence of the last universal common ancestor into the Bacteria and Archaea domains. We have constructed rooted phylogenies for over 1,550 representatives of the DMSOR family using maximum likelihood methods to investigate the evolution of the arsenic biogeochemical cycle. The phylogenetic analysis provides compelling evidence that formylmethanofuran dehydrogenase B subunits, which catalyze the reduction of CO2 to formate during hydrogenotrophic methanogenesis, constitutes the most ancient lineage. Our analysis also provides robust support for selenocysteine as the ancestral ligand for the Mo/W atom. Finally, we demonstrate that anaerobic arsenite oxidase and respiratory arsenate reductase catalytic subunits represent a more ancient lineage of DMSORs compared to aerobic arsenite oxidase catalytic subunits, which evolved from the assimilatory nitrate reductase lineage. This provides substantial support for an active arsenic biogeochemical cycle on the anoxic Archean Earth. Our work emphasizes that the use of chalcophilic elements as substrates as well as the Mo/W ligand in DMSORs has indelibly shaped the diversification of these enzymes through deep time.

Arsenic resistance in fungi conferred by extracellular bonding and vacuole-septa compartmentalization

Microbes play a crucial role in arsenic (As) biogeochemical cycling and show great potential for environmental detoxification and bioremediation. Efflux, transformation, and compartmentalization are key processes in microbial As resistance. However, organelle specific As detoxification and fate during intracellular transfer and compartmentalization is not well understood. We conducted a time course experiment (2–5 days) of the organelle separation for fungal strains to explore subcellular As distributions. After exposure to 10 mg L−1 of arsenate (As(V)), the As accumulation among fungal organelles was generally in the order of extracellular (65 %) > cell wall (15 %) > vacuole (10 %) > other organelles (8 %). The vacuole As accounted for 55 % of the protoplast As. Extracellular bonding and vacuole compartmentalization were the main mechanisms of As resistance in the fungal strains tested. Glutathione (GSH) increases in fungal protoplast in response to As toxicity, acting as a reasonable indicator of As tolerance. Fourier transform infrared (FT-IR) spectroscopy indicated that carboxyl and amines groups within fungal cell walls potentially bind with As preventing As influx. Further analysis using scanning transmission X-ray microscopy (STXM) identified that fungal septa besides vacuole could also immobilize As.

Bioaccumulation and biotransformation of arsenic in Leptolyngbya boryana.

Leptolyngbya boryana (L. boryana) is a typical filamentous cyanobacterium that is widely distributed in aquatic ecosystems and is considered to play an important role in the arsenic biogeochemical cycle. Our results showed that L. boryana resisted arsenite (As(III)) and arsenate (As(V)) concentrations up to 0.25mM and 5mM, respectively. When exposed to 100μM As(III) or As(V) for 4weeks, L. boryana accumulated as much arsenic as 570.0mgkg-1 and 268.5mgkg-1, respectively. After the 4-week exposure to As(III) and As(V), organoarsenicals including dimethylarsenate (DMAs(V)) and oxo-arsenosugar-phosphate (Oxo-PO4) were detected in the cells of L. boryana, while inorganic arsenic, especially As(V), was still the main species in both the cells and medium. Furthermore, arsenic oxidation was observed to be solely caused by L. boryana cells and was considered the dominant detoxification pathway. In conclusion, due to its powerful arsenic accumulation, biotransformation, and detoxification abilities, L. boryana might play an important role in arsenic remediation in aquatic environments.