Reactions of iron monosulfide solids with aqueous hydrogen sulfide up to 160°C

Taylor, Peter G.; Rummery, T. E.; Owen, Derrek G.

doi:10.1016/0022-1902(79)80106-2

Cited by 59 publications

(23 citation statements)

References 8 publications

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“…X-ray diffraction (XRD) patterns were recorded with the D8 Discover system (Bruker) with IµS radiation source (2 mm in diameter), and a Lynxexe XE detector. Samples were dried for 2 h under a continuous stream of 100% N 2 and measured within 48 h under air as described previously (49). Measurements were done using CuKα rays in angles ranging from 10–70° 2θ in 0.02° steps with 2,880 sec measuring time and a total measuring time of 12 h and 47 min.…”

Section: Methodsmentioning

confidence: 99%

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism

Thiel

Byrne

Kappler

et al. 2018

Preprint

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23The exergonic reaction of FeS with H 2 S to form FeS 2 (pyrite) and H 2 was postulated to have 24 operated as an early form of energy metabolism on primordial Earth. Since the Archean, 25 sedimentary pyrite formation played a major role in the global iron and sulfur cycles, with direct 26 impact on the redox chemistry of the atmosphere. To date, pyrite formation was considered a 27 purely geochemical reaction. Here, we present microbial enrichment cultures, which grew with 28FeS, H 2 S, and CO 2 as their sole substrates to produce FeS 2 and CH 4 . Cultures grew over 29 periods of three to eight months to cell densities of up to 2-9×10 6 cells mL −1 . Transformation of 30FeS with H 2 S to FeS 2 was followed by 57 Fe Mössbauer spectroscopy and showed a clear 31 biological temperature profile with maximum activity at 28°C and decreasing activities towards 32 4°C and 60°C. CH 4 was formed concomitantly with FeS 2 and exhibited the same temperature 33 dependence. Addition of either penicillin or 2-bromoethanesulfonate inhibited both FeS 2 and 34 CH 4 production, indicating a syntrophic coupling of pyrite formation to methanogenesis. This 35 hypothesis was supported by a 16S rRNA gene-based phylogenetic analysis, which identified 36 at least one archaeal and five bacterial species. The archaeon was closely related to the 37 hydrogenotrophic methanogen Methanospirillum stamsii while the bacteria were most closely 38 related to sulfate-reducing Deltaproteobacteria, as well as uncultured Firmicutes and 39Actinobacteria. We identified a novel type of microbial metabolism able to conserve energy 40 from FeS transformation to FeS 2 , which may serve as a model for a postulated primordial iron-41 sulfur world. 42 Microbial pyrite formation Thiel et al. 3 of 34 Significance statement 43Pyrite is the most abundant iron-sulfur mineral in sediments. Over geological times, its burial 44 controlled oxygen levels in the atmosphere and sulfate concentrations in seawater. Its 45 formation in sediments is so far considered a purely geochemical process that is at most 46 indirectly supported by microbial activity. We show that lithotrophic microorganisms can directly 47 transform FeS and H 2 S to FeS 2 and use this exergonic reaction as a novel form of energy 48 metabolism that is syntrophically coupled to methanogenesis. Our results provide insights into 49 a syntrophic relationship that could sustain part of the deep biosphere and lend support to the 50 iron-sulfur-world theory that postulated FeS transformation to FeS 2 as a key energy-delivering 51 reaction for life to emerge. 52 Microbial pyrite formation Thiel et al. 4 of 34

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Section: Methodsmentioning

confidence: 99%

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism

Thiel

Byrne

Kappler

et al. 2018

Preprint

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“…Russell et al, 1989Russell et al, , 1994Russell 2003, 2007) from the alternative, avowedly non-cellular hypothesis, namely the ''Theory of Surface Metabolism'' energized by ''pyrite-pulled reactions'' proposed by Wächtershäuser (1988aWächtershäuser ( , b, 2006; and see Taylor et al 1979). Huber and Wächtershäuser (2006, p 631) have underscored one particular distinction between the two hypotheses when they remark their ''proposal of primordial carbon fixation within a quenched flow of volcanic fluids contrasts with the proposal of primordial carbon-fixation reactions at the interface between aqueous, hydrothermal H 2 and aqueous CO 2 in an acidic ocean (Martin and Russell 2003;Russell and Martin 2004)''.…”

Section: The Two Autogenic Hypothesesmentioning

confidence: 96%

The Alkaline Solution to the Emergence of Life: Energy, Entropy and Early Evolution

Russell

2007

Acta Biotheor

113

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The Earth agglomerates and heats. Convection cells within the planetary interior expedite the cooling process. Volcanoes evolve steam, carbon dioxide, sulfur dioxide and pyrophosphate. An acidulous Hadean ocean condenses from the carbon dioxide atmosphere. Dusts and stratospheric sulfurous smogs absorb a proportion of the Sun's rays. The cooled ocean leaks into the stressed crust and also convects. High temperature acid springs, coupled to magmatic plumes and spreading centers, emit iron, manganese, zinc, cobalt and nickel ions to the ocean. Away from the spreading centers cooler alkaline spring waters emanate from the ocean floor. These bear hydrogen, formate, ammonia, hydrosulfide and minor methane thiol. The thermal potential begins to be dissipated but the chemical potential is dammed. The exhaling alkaline solutions are frustrated in their further attempt to mix thoroughly with their oceanic source by the spontaneous precipitation of biomorphic barriers of colloidal iron compounds and other minerals. It is here we surmise that organic molecules are synthesized, filtered, concentrated and adsorbed, while acetate and methane--separate products of the precursor to the reductive acetyl-coenzyme-A pathway-are exhaled as waste. Reactions in mineral compartments produce acetate, amino acids, and the components of nucleosides. Short peptides, condensed from the simple amino acids, sequester 'ready-made' iron sulfide clusters to form protoferredoxins, and also bind phosphates. Nucleotides are assembled from amino acids, simple phosphates carbon dioxide and ribose phosphate upon nanocrystalline mineral surfaces. The side chains of particular amino acids register to fitting nucleotide triplet clefts. Keyed in, the amino acids are polymerized, through acid-base catalysis, to alpha chains. Peptides, the tenuous outer-most filaments of the nanocrysts, continually peel away from bound RNA. The polymers are concentrated at cooler regions of the mineral compartments through thermophoresis. RNA is reproduced through a convective polymerase chain reaction operating between 40 and 100 degrees C. The coded peptides produce true ferredoxins, the ubiquitous proteins with the longest evolutionary pedigree. They take over the role of catalyst and electron transfer agent from the iron sulfides. Other iron-nickel sulfide clusters, sequestered now by cysteine residues as CO-dehydrogenase and acetyl-coenzyme-A synthase, promote further chemosynthesis and support the hatchery--the electrochemical reactor--from which they sprang. Reactions and interactions fall into step as further pathways are negotiated. This hydrothermal circuitry offers a continuous supply of material and chemical energy, as well as electricity and proticity at a potential appropriate for the onset of life in the dark, a rapidly emerging kinetic structure born to persist, evolve and generate entropy while the sun shines.

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“…All three hydrogenases may ultimately go back to the conversion of FeS/H 2 S to FeS 2 /H 2 [38,39], for which a mechanism is postulated (Figure 1.3) that starts from aqueous [FeS] aq [40] and assumes a nucleophilic attack of a sulfide ligand on the sulfur atom of H 2 S to form a persulfide ligand (as source for FeS 2 ) [40] in combination with either formation of H 2 by reaction of a hydride ligand with H + or reduction of a substrate X by hydride or electron transfer. From this urhydrogenase/reductase chemistry, the evolution of hydrogenases began by abandonment of irreversible pyrite formation in favor of catalytic cycling, reversal of H 2 -formation into H 2 -uptake, and substrate reduction (e.g., persulfide cleavage).…”

Section: Retrodicting Pioneer Catalysismentioning

confidence: 99%

From Chemical Invariance to Genetic Variability

Wächtershäuser¹

2014

Bioinspired Catalysis

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The archaeologist of nature is at liberty to go back to the traces that remain of nature's earliest revolutions, and, appealing to all he knows or can conjecture about its mechanism, to trace the origin of that great family of creatures … down even to mosses and lichens, and finally down to the lowest perceivable stage of nature, to crude matter. From this and from the forces within, by mechanical laws, like those that are at work in the formation of crystals, seems to be derived the whole technique of nature.Immanuel Kant [1]

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Reactions of iron monosulfide solids with aqueous hydrogen sulfide up to 160°C

Cited by 59 publications

References 8 publications

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism

The Alkaline Solution to the Emergence of Life: Energy, Entropy and Early Evolution

From Chemical Invariance to Genetic Variability

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Reactions of iron monosulfide solids with aqueous hydrogen sulfide up to 160°C

Cited by 59 publications

References 8 publications

Pyrite formation from FeS and H2S is mediated by a novel type of microbial energy metabolism

Pyrite formation from FeS and H2S is mediated by a novel type of microbial energy metabolism

The Alkaline Solution to the Emergence of Life: Energy, Entropy and Early Evolution

From Chemical Invariance to Genetic Variability

Contact Info

Product

Resources

About

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism

Pyrite formation from FeS and H₂S is mediated by a novel type of microbial energy metabolism