Arsenics as bioenergetic substrates

AbstractAlthough at low concentrations, arsenic commonly occurs naturally as a local geological constituent. Whereas both arsenate and arsenite are strongly toxic to life, a number of prokaryotes use these compounds as electron acceptors or donors, respectively, for bioenergetic purposes via respiratory arsenate reductase, arsenite oxidase and alternative arsenite oxidase. The recent burst in discovered arsenite oxidizing and arsenate respiring microbes suggests the arsenic bioenergetic metabolisms to be anything but exotic. The first goal of the present review is to bring to light the widespread distribution and diversity of these metabolizing pathways. The second goal is to present an evolutionary analysis of these diverse energetic pathways. Taking into account not only the available data on the arsenic metabolizing enzymes and their phylogenetical relatives but also the palaeogeochemical records, we propose a crucial role of arsenite oxidation via arsenite oxidase in primordial life. This article is part of a Special Issue entitled: The evolutionary aspects of bioenergetic systems

Enzyme phylogenies as markers for the oxidation state of the environment: The case of respiratory arsenate reductase and related enzymes

<p>Abstract</p> <p>Background</p> <p>Phylogenies of certain bioenergetic enzymes have proved to be useful tools for deducing evolutionary ancestry of bioenergetic pathways and their relationship to geochemical parameters of the environment. Our previous phylogenetic analysis of arsenite oxidase, the molybdopterin enzyme responsible for the biological oxidation of arsenite to arsenate, indicated its probable emergence prior to the Archaea/Bacteria split more than 3 billion years ago, in line with the geochemical fact that arsenite was present in biological habitats on the early Earth. Respiratory arsenate reductase (Arr), another molybdopterin enzyme involved in microbial arsenic metabolism, serves as terminal oxidase, and is thus situated at the opposite end of bioenergetic electron transfer chains as compared to arsenite oxidase. The evolutionary history of the Arr-enzyme has not been studied in detail so far.</p> <p>Results</p> <p>We performed a genomic search of genes related to <it>arrA </it>coding for the molybdopterin subunit. The multiple alignment of the retrieved sequences served to reconstruct a neighbor-joining phylogeny of Arr and closely related enzymes. Our analysis confirmed the previously proposed proximity of Arr to the cluster of polysulfide/thiosulfate reductases but also unravels a hitherto unrecognized clade even more closely related to Arr. The obtained phylogeny strongly suggests that Arr originated after the Bacteria/Archaea divergence in the domain Bacteria, and was subsequently laterally distributed within this domain. It further more indicates that, as a result of accumulation of arsenate in the environment, an enzyme related to polysulfide reductase and not to arsenite oxidase has evolved into Arr.</p> <p>Conclusion</p> <p>These findings are paleogeochemically rationalized by the fact that the accumulation of arsenate over arsenite required the increase in oxidation state of the environment brought about by oxygenic photosynthesis.</p

The marker quantification of the Shared Socioeconomic Pathway 2: A middle-of-the-road scenario for the 21st century

AbstractStudies of global environmental change make extensive use of scenarios to explore how the future can evolve under a consistent set of assumptions. The recently developed Shared Socioeconomic Pathways (SSPs) create a framework for the study of climate-related scenario outcomes. Their five narratives span a wide range of worlds that vary in their challenges for climate change mitigation and adaptation. Here we provide background on the quantification that has been selected to serve as the reference, or ‘marker’, implementation for SSP2. The SSP2 narrative describes a middle-of-the-road development in the mitigation and adaptation challenges space. We explain how the narrative has been translated into quantitative assumptions in the IIASA Integrated Assessment Modelling Framework. We show that our SSP2 marker implementation occupies a central position for key metrics along the mitigation and adaptation challenge dimensions. For many dimensions the SSP2 marker implementation also reflects an extension of the historical experience, particularly in terms of carbon and energy intensity improvements in its baseline. This leads to a steady emissions increase over the 21st century, with projected end-of-century warming nearing 4°C relative to preindustrial levels. On the other hand, SSP2 also shows that global-mean temperature increase can be limited to below 2°C, pending stringent climate policies throughout the world. The added value of the SSP2 marker implementation for the wider scientific community is that it can serve as a starting point to further explore integrated solutions for achieving multiple societal objectives in light of the climate adaptation and mitigation challenges that society could face over the 21st century

A Tale of Two Oxidation States: Bacterial Colonization of Arsenic-Rich Environments

Microbial biotransformations have a major impact on contamination by toxic elements, which threatens public health in developing and industrial countries. Finding a means of preserving natural environments—including ground and surface waters—from arsenic constitutes a major challenge facing modern society. Although this metalloid is ubiquitous on Earth, thus far no bacterium thriving in arsenic-contaminated environments has been fully characterized. In-depth exploration of the genome of the β-proteobacterium Herminiimonas arsenicoxydans with regard to physiology, genetics, and proteomics, revealed that it possesses heretofore unsuspected mechanisms for coping with arsenic. Aside from multiple biochemical processes such as arsenic oxidation, reduction, and efflux, H. arsenicoxydans also exhibits positive chemotaxis and motility towards arsenic and metalloid scavenging by exopolysaccharides. These observations demonstrate the existence of a novel strategy to efficiently colonize arsenic-rich environments, which extends beyond oxidoreduction reactions. Such a microbial mechanism of detoxification, which is possibly exploitable for bioremediation applications of contaminated sites, may have played a crucial role in the occupation of ancient ecological niches on earth

Arsenics, astrobiology and scientific deontology

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Comment on Arsenic (III) Fuels Anoxygenic with a model based on measured kinetic parameters

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The 'green' phylogenetic clade of Rieske/cytb complexes

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Evolution of arsenite oxidation

Evolution of arsenite oxidatio

Conformation of the c552:aa3 electron transfer complex in Paracoccus denitrificans studied by EPR on oriented samples

International audienceThe EPR spectral parameters of aa3 oxidase and cyt c552 from Paracoccus denitrificans were studied in purified oxidase and enriched cyt c552. The orientation of the g-tensors of hemes a and c552 were determined on partially ordered membranes, enriched cyt c552 and a c552:aa3 subcomplex. The known correlation of g-tensor to molecular axes in histidine/methionine ligated hemes permits us to position cyt c552 with respect to the parent membrane. Taken together with previous data on the interaction surface between aa3 oxidase and cyt c552, these results allow us to arrive at a single conformation for the c552:aa3 electron transfer complex. Cop. 2006 Federation of European Biochemical Societies