A novel chemolithotrophic metabolism based on a mixed arsenic-sulfur species has been discovered for the anaerobic deltaproteobacterium, strain MLMS-1, a haloalkaliphile isolated from Mono Lake, California, U.S. Strain MLMS-1 is the first reported obligate arsenate-respiring chemoautotroph which grows by coupling arsenate reduction to arsenite with the oxidation of sulfide to sulfate. In that pathway the formation of a mixed arsenic-sulfur species was reported. That species was assumed to be monothioarsenite ([H2As(III)S(-II)O2](-)), formed as an intermediate by abiotic reaction of arsenite with sulfide. We now report that this species is monothioarsenate ([HAs(V)S(-II)O3](2-)) as revealed by X-ray absorption spectroscopy. Monothioarsenate forms by abiotic reaction of arsenite with zerovalent sulfur. Monothioarsenate is kinetically stable under a wide range of pH and redox conditions. However, it was metabolized rapidly by strain MLMS-1 when incubated with arsenate. Incubations using monothioarsenate confirmed that strain MLMS-1 was able to grow (μ = 0.017 h(-1)) on this substrate via a disproportionation reaction by oxidizing the thio-group-sulfur (S(-II)) to zerovalent sulfur or sulfate while concurrently reducing the central arsenic atom (As(V)) to arsenite. Monothioarsenate disproportionation could be widespread in nature beyond the already studied arsenic and sulfide rich hot springs and soda lakes where it was discovered.

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Novel insights are provided regarding aerobic chemolithotrophic growth of Thermocrinis ruber OC14/7/2 on the electron donors arsenite and monothioarsenate. Thermocrinis ruber is a hyperthermophilic bacterium that thrives in pH-neutral to alkaline hot springs and grows on hydrogen, elemental sulfur, and thiosulfate. Our study showed that T. ruber can also utilize arsenite as sole electron donor producing arsenate. Growth rates of 0.024 h(-1) were lower than for oxidation of thiosulfate to sulfate (μ = 0.247 h(-1)). Fast growth was observed on monothioarsenate (μ = 0.359 h(-1)), comprising different abiotic and biotic redox interactions. The initial dominant process was abiotic transformation of monothioarsenate to arsenate and elemental sulfur, followed by microbial oxidation of sulfur to sulfate. Elevated microbial activity during stationary growth of T. ruber might be explained by microbial oxidation of thiosulfate and arsenite, both also products of abiotic monothioarsenate transformation. However, the observed rapid decrease of monothioarsenate, exceeding concentrations in equilibrium with its products, also indicates direct microbial oxidation of arsenic-bond S(-II) to sulfate. Free sulfide was oxidized abiotically too fast to play a role as electron donor for T. ruber. Our present laboratory and previous field studies suggest that thioarsenates can either indirectly or directly be used by (hyper)thermophiles in arsenic-sulfidic environments.

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