Rapid quadruple sulfur isotope analysis at the sub-micromole level by a flash heating with CoF3

Ueno, Yuichiro; Aoyama, Shigeyoshi; Endo, Yoshiaki; Matsu'ura, Fumihiro; Foriel, Julien

doi:10.1016/j.chemgeo.2015.10.032

Cited by 31 publications

(24 citation statements)

References 26 publications

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“…Geophysical Research Letters then purified by gas chromatography using the technique described in Ueno et al (2015). The isotopic composition of the purified SF 6 was determined by ThermoFishier MAT 253 mass spectrometer, equipped with a dual inlet system.…”

Section: 1029/2018gl080730mentioning

confidence: 99%

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis

Endo

Danielache

Ueno

2019

Geophysical Research Letters

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Sulfur Mass‐Independent Fractionation (S‐MIF) may provide a clue to understanding Earth's early atmosphere. We examined total pressure dependence of the S‐MIF produced by SO2 photolysis. Isotopic self‐shielding is known to produce S‐MIF, which could be changed by both the partial pressure of SO2 (pSO2) and by the total pressure (pTotal). Our experimental results show that both Δ33S and Δ36S values are constant when total pressure is below 10 kPa at constant pSO2, whereas they decrease as total pressure increases. The result suggests that pressure broadening of the SO2 absorption line is responsible for the S‐MIF. The modeled high‐resolution isotopologue cross sections can reproduce our experimental results and its changes depending on both pSO2 and pTotal. Consequently, we conclude that the Archean Δ33S and Δ36S correlation can only be achieved when the total pressure of the Archean atmosphere was below 100 kPa, or it was produced in the upper atmosphere.

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Section: 1029/2018gl080730mentioning

confidence: 99%

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis

Endo

Danielache

Ueno

2019

Geophysical Research Letters

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“…Schematic figure of the measurement procedure for quadruple sulfur isotopes. Extracted Ag 2 S powder was converted into SF 6 gas by a Curie‐point pyrolyzer (Ueno et al., ). Produced SF 6 gas was purified and introduced into a mass spectrometer…”

Section: Resultsmentioning

confidence: 99%

“…To measure the compositions of the quadruple sulfur isotopes, the Ag 2 S powder was converted into SF 6 gas and introduced into a mass spectrometer (Figure ). The SF 6 was generated by the flash‐fluorination method (Ueno, Aoyama, Endo, Matsu'ura, & Foriel, ); ~300 μg Ag 2 S powder together with ~10 mg CoF 3 powder was wrapped in pyrofoil (iron–nickel–cobalt alloy) and set in a Curie‐point pyrolyzer. Owing to the rapidly increasing, stable, and accurate temperature of the method (590°C in this case), SF 6 was generated in 3 s with highly reproducible sulfur isotopes.…”

Section: Methodsmentioning

confidence: 99%

“…Schematic figure of the measurement procedure for quadruple sulfur isotopes. Extracted Ag 2 S powder was converted into SF 6 gas by a Curie-point pyrolyzer (Ueno et al, 2015). Produced SF 6 gas was purified and introduced into a mass spectrometer Atmospherically derived sulfate is a counterpart of the specific sulfide mineral with negative correlations in the Δ 33 S′δ 34 S diagrams (felsic volcanic array), which only occurred during the barite deposition period (Philippot, Van Zuilen, & Rollion-Bard, 2012).…”

Section: Origin Of the Archean Seawater Sulfatementioning

confidence: 99%

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Multiple sulfur isotope constraints on microbial sulfate reduction below an Archean seafloor hydrothermal system

Aoyama

Ueno

2017

Geobiology

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Microbial sulfate reduction is among the most ubiquitous metabolic processes on earth. The oldest evidence of microbial sulfate reduction appears in the ca. 3.5 Ga Dresser Formation in the North Pole area of Pilbara Craton in Western Australia. That evidence was found through analysis of quadruple sulfur isotopes of sulfate and sulfide minerals deposited on the seafloor. However, the activity of microbial sulfate reduction below the Archean seafloor remains poorly understood. Here, we report the quadruple sulfur isotopic compositions of sulfide minerals within hydrothermally altered seafloor basalt and less altered basaltic komatiite collected from the North Pole Dome area. The Δ S values of the sulfide minerals were nonzero negative, suggesting that sulfate reduction occurred below the Archean seafloor. To constrain the substrate sulfate sources and sulfate reduction processes, we constructed a numerical model. Comparing the modeled and observed sulfur isotopes, we show that the substrate sulfate comprises seawater sulfate with a negative Δ S anomaly and S-enriched sulfate with no anomalous Δ S. The latter component probably represents sulfate produced by local hydrothermal processes. The maximum sulfur isotopic fractionation between the putative substrate sulfate and the observed sulfide minerals within the altered basalt and basaltic komatiite is 35‰, which is consistent with a microbial origin. Alternatively, thermochemical sulfate reduction may also produce sulfide. However, considering the hydrothermal temperature inferred from the metamorphic grade of the altered basalt, the sulfur isotopic fractionation produced by inorganic sulfate reduction is probably below 20‰. Collectively, larger fractionations imply the involvement of biological sulfate reduction processes, both in the hydrothermal system below the seafloor and in less altered subsurface settings.

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“…The isotopic analysis is conventionally performed by reducing sulfate (SO 4 2− ) to hydrogen sulfide (H 2 S), converting H 2 S into silver sulfide (Ag 2 S), and fluorinating Ag 2 S to sulfur hexafluoride (SF 6 ) for isotopic composition analysis by isotope ratio mass spectrometry (IRMS) . The reduction from SO 4 2− to H 2 S is mainly achieved by two different reducing agents: tin(II) (Sn 2+ ) solutions and hydroiodic acid (HI)/hypophosphorous acid (H 3 PO 2 ) mixtures .…”

Section: Introductionmentioning

confidence: 99%

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis

Geng

Savarino

et al. 2018

Rapid Comm Mass Spectrometry

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RationalePrecise analysis of four sulfur isotopes of sulfate in geological and environmental samples provides the means to extract unique information in wide geological contexts. Reduction of sulfate to sulfide is the first step to access such information. The conventional reduction method suffers from a cumbersome distillation system, long reaction time and large volume of the reducing solution. We present a new and simple method enabling the process of multiple samples at one time with a much reduced volume of reducing solution.MethodsOne mL of reducing solution made of HI and NaH2PO2 was added to a septum glass tube with dry sulfate. The tube was heated at 124°C and the produced H2S was purged with inert gas (He or N2) through gas‐washing tubes and then collected by NaOH solution. The collected H2S was converted into Ag2S by adding AgNO3 solution and the co‐precipitated Ag2O was removed by adding a few drops of concentrated HNO3.ResultsWithin 2–3 h, a 100% yield was observed for samples with 0.2–2.5 μmol Na2SO4. The reduction rate was much slower for BaSO4 and a complete reduction was not observed. International sulfur reference materials, NBS‐127, SO‐5 and SO‐6, were processed with this method, and the measured against accepted δ34S values yielded a linear regression line which had a slope of 0.99 ± 0.01 and a R 2 value of 0.998.ConclusionsThe new methodology is easy to handle and allows us to process multiple samples at a time. It has also demonstrated good reproducibility in terms of H2S yield and for further isotope analysis. It is thus a good alternative to the conventional manual method, especially when processing samples with limited amount of sulfate available.

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Rapid quadruple sulfur isotope analysis at the sub-micromole level by a flash heating with CoF3

Cited by 31 publications

References 26 publications

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis

Multiple sulfur isotope constraints on microbial sulfate reduction below an Archean seafloor hydrothermal system

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis

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Rapid quadruple sulfur isotope analysis at the sub-micromole level by a flash heating with CoF3

Cited by 31 publications

References 26 publications

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO2Photolysis

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO2Photolysis

Multiple sulfur isotope constraints on microbial sulfate reduction below an Archean seafloor hydrothermal system

A simple and reliable method reducing sulfate to sulfide for multiple sulfur isotope analysis

Contact Info

Product

Resources

About

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis

Total Pressure Dependence of Sulfur Mass‐Independent Fractionation by SO₂Photolysis