Abstract
We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5μm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the δ34S value was 1.5% at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6% at the level of 1 sigma of standard deviation (named 1SD, n1/425). For each separate sample, the average δ 34S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3%. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 mm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a 34S-depleted core and 34S-enriched rim, suggesting isotopic evolution of the source H2S from 15 to 5%. Production of H2S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the 34S-depleted initial H2S and the progressive increase in the δ 34SH2S value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.
| Original language | English |
|---|---|
| Pages (from-to) | 1397-1404 |
| Number of pages | 8 |
| Journal | Rapid Communications in Mass Spectrometry |
| Volume | 24 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - May 30 2010 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Spectroscopy
- Analytical Chemistry
- Organic Chemistry
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Micro-scale (1.5μm) sulphur isotope analysis of contemporary and early archean pyrite. / Nishizawa, Manabu; Maruyama, Shigenori; Urabe, Tetsuro; Takahata, Naoto; Sano, Yuji.
In: Rapid Communications in Mass Spectrometry, Vol. 24, No. 10, 30.05.2010, p. 1397-1404.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Micro-scale (1.5μm) sulphur isotope analysis of contemporary and early archean pyrite
AU - Nishizawa, Manabu
AU - Maruyama, Shigenori
AU - Urabe, Tetsuro
AU - Takahata, Naoto
AU - Sano, Yuji
PY - 2010/5/30
Y1 - 2010/5/30
N2 - We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5μm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the δ34S value was 1.5% at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6% at the level of 1 sigma of standard deviation (named 1SD, n1/425). For each separate sample, the average δ 34S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3%. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 mm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a 34S-depleted core and 34S-enriched rim, suggesting isotopic evolution of the source H2S from 15 to 5%. Production of H2S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the 34S-depleted initial H2S and the progressive increase in the δ 34SH2S value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.
AB - We present a method for in situ sulphur (S) isotopic analysis of significantly small areas (1.5μm in diameter) in pyrite using secondary ion mass spectrometry (NanoSIMS) to interpret microbial sulphur metabolism in the early earth. We evaluated the precision and accuracy of S isotopic ratios obtained by this method using hydrothermal pyrite samples with homogeneous S isotopic ratios. The internal precision of the δ34S value was 1.5% at the level of 1 sigma of standard error (named 1SE) for a single spot, while the external reproducibility was estimated to be 1.6% at the level of 1 sigma of standard deviation (named 1SD, n1/425). For each separate sample, the average δ 34S value was comparable with that measured by a conventional method, and the accuracy was better than 2.3%. Consequently, the in situ method is sufficiently accurate and precise to detect the S isotopic variations of small sample of the pyrite (less than 20 mm) that occurs ubiquitously in ancient sedimentary rocks. This method was applied to measure the S isotopic distribution of pyrite within black chert fragments in early Archean sandstone. The pyrite had isotopic zoning with a 34S-depleted core and 34S-enriched rim, suggesting isotopic evolution of the source H2S from 15 to 5%. Production of H2S by microbial sulphate reduction (MSR) in a closed system provides a possible explanation for both the 34S-depleted initial H2S and the progressive increase in the δ 34SH2S value. Although more extensive data are necessary to strengthen the explanation for the origin of the MSR, the results show that the S isotopic distribution within pyrite crystals may be a key tracer for MSR activity in the early earth.
UR - http://www.scopus.com/inward/record.url?scp=77951929796&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77951929796&partnerID=8YFLogxK
U2 - 10.1002/rcm.4517
DO - 10.1002/rcm.4517
M3 - Article
C2 - 20411578
AN - SCOPUS:77951929796
VL - 24
SP - 1397
EP - 1404
JO - Rapid Communications in Mass Spectrometry
JF - Rapid Communications in Mass Spectrometry
SN - 0951-4198
IS - 10
ER -