A study of the rates of sulfur production in acid thiosulfate solutions using S-35

Johnston, F. J.; McAmish, L.H.

doi:10.1016/0021-9797(73)90013-1

Cited by 56 publications

(39 citation statements)

References 5 publications

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“…A second example is the rate of thiosulfate acid decomposition to form sulfite and S 8 . The pHdependent reaction rate has been determined experimentally around a pH of 2 (40), much lower than that expected in the Archean ocean (∼7; SI Materials and Methods). If the pH dependence determined under acidic conditions is valid at neutral pH, then this reaction provides an avenue for spreading S MIF from atmospheric SO 2 to thiosulfate and from it to S 8 , thereby mixing Δ 33 S of opposite signs.…”

Section: Resultsmentioning

confidence: 99%

Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

Halevy

2013

Proc. Natl. Acad. Sci. U.S.A.

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Mass-independent fractionation of sulfur isotopes (S MIF) in Archean and Paleoproterozoic rocks provides strong evidence for an anoxic atmosphere before ∼2,400 Ma. However, the origin of this isotopic anomaly remains unclear, as does the identity of the molecules that carried it from the atmosphere to Earth's surface. Irrespective of the origin of S MIF, processes in the biogeochemical sulfur cycle modify the primary signal and strongly influence the S MIF preserved and observed in the geological record. Here, a detailed model of the marine sulfur cycle is used to propagate and distribute atmospherically derived S MIF from its delivery to the ocean to its preservation in the sediment. Bulk pyrite in most sediments carries weak S MIF because of microbial reduction of most sulfur compounds to form isotopically homogeneous sulfide. Locally, differential incorporation of sulfur compounds into pyrite leads to preservation of S MIF, which is predicted to be most highly variable in nonmarine and shallow-water settings. The Archean ocean is efficient in diluting primary atmospheric S MIF in the marine pools of sulfate and elemental sulfur with inputs from SO 2 and H 2 S, respectively. Preservation of S MIF with the observed range of magnitudes requires the S MIF production mechanism to be moderately fractionating ( ± 20-40‰). Constraints from the marine sulfur cycle allow that either elemental sulfur or organosulfur compounds (or both) carried S MIF to the surface, with opposite sign to S MIF in SO 2 and H 2 SO 4 . Optimal progress requires observations from nonmarine and shallow-water environments and experimental constraints on the reaction of photoexcited SO 2 with atmospheric hydrocarbons.W ith few exceptions, the enrichment or depletion of the rare, stable isotopes of sulfur ( 33 S, 34 S, and 36 S) relative to the abundant isotope ( 32 S) scale as the mass difference between the isotopes (1). Sulfur isotope mass-independent fractionation (S MIF) is defined as a departure from these theoretically derived and empirically observed mass laws, and denoted Δ 33 S and Δ 36 S. S MIF is observed in modern atmospheric sulfate aerosols, as well as in sulfate-bearing layers hosted in glacial ice (2, 3), but is conspicuously absent from the sedimentary record of the last 2,400 My. In contrast, older rocks of the Archean and early Paleoproterozoic eons preserve large and variable S MIF (4, 5). On the basis of experimental SO 2 photolysis and atmospheric chemistry models, the prevailing hypothesis to explain this observation is that the absence of atmospheric oxygen before ∼2,400 Ma allowed both the photochemical production of S MIF and its delivery to the surface in the reduced and oxidized products of sulfur photochemistry (4-7). Thus, S MIF is considered strong geochemical evidence for an anoxic atmosphere before ∼2,400 Ma.Although research converges on atmospheric processes as the source of S MIF, its production mechanism and the identity of its vectors to the surface remain unclear. A focus on photolysis experiments and meas...

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Section: Resultsmentioning

confidence: 99%

Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

Halevy

2013

Proc. Natl. Acad. Sci. U.S.A.

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“…The stability of Au(S 2 O 3 ) 2 3Ϫ in the abiotic pH 5.7 reaction systems was not surprising, considering that thiosulfate is generally stable at this pH value (Johnston and McAmish, 1972). In the abiotic pH 1.9 reaction systems, thiosulfate was partly disproportionated to elemental sulfur, sulfate, and possibly other intermediate sulfur species such sulfite and tetrathionate (Williamson and Rimstidt, 1994) due to exposure of oxygen and a low pH value; however, this disproportionation did not affect the stability of Au(S 2 O 3 ) 2 3Ϫ in this reaction system with a duration of 75 days.…”

Section: Comparison Of Bacterial Experimental Systems and Abiotic Expmentioning

confidence: 92%

The effect of thiosulfate-oxidizing bacteria on the stability of the gold-thiosulfate complex

Lengke

Southam

2005

Geochimica et Cosmochimica Acta

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“…The reaction of thiosulfate to tetrathionate is also catalyzed by pyrite surfaces (Xu and Schoonen, 1995) and thiosulfate will disproportionate into elemental sulfur and sulfite ðSO 3 2À Þ in acidic media: (Johnston and McAmish, 1973;Xu and Schoonen, 1995). Competition between these processes (reactions 1 and 2) resulting in thiosulfate conversion to either elemental sulfur and sulfite, or tetrathionate, only becomes critical when the supply of ferric iron becomes limiting (Williamson and Rimstidt, 1993).…”

Section: Fate Of Thiosulfate After Releasementioning

confidence: 98%

Comment on “Pyrite dissolution in acidic media” by M. Descostes, P. Vitorge, and C. Beaucaire

Druschel

Borda

2006

Geochimica et Cosmochimica Acta

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A study of the rates of sulfur production in acid thiosulfate solutions using S-35

Cited by 56 publications

References 5 publications

Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

Production, preservation, and biological processing of mass-independent sulfur isotope fractionation in the Archean surface environment

The effect of thiosulfate-oxidizing bacteria on the stability of the gold-thiosulfate complex

Comment on “Pyrite dissolution in acidic media” by M. Descostes, P. Vitorge, and C. Beaucaire

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