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2014 Annual Science Report

University of Wisconsin Reporting  |  SEP 2013 – DEC 2014

Project 4B: New SIMS Procedures for in Situ Analysis of Mass-Independent Fractionation of S Isotopes

Project Summary

An in situ sulfur four-isotope analysis technique with multiple Faraday cup detectors by ion microprobe was developed and applied to detrital pyrite grains in ~2.4 Ga glaciogenic sandstone from the Meteorite Bore Member of the Turee Creek Group, Western Australia.

4 Institutions
3 Teams
1 Publication
0 Field Sites
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Project Progress

An in situ sulfur four-isotope analysis technique with multiple Faraday cup detectors by ion microprobe was developed and applied to detrital pyrite grains in ~2.4 Ga glaciogenic sandstone from the Meteorite Bore Member of the Turee Creek Group, Western Australia. Data are standardized with the UWPy-1 pyrite standard (δ34S =16.04 ± 0.18‰, Δ33S = −0.003 ± 0.009‰, and Δ36S = −0.21 ± 0.24‰, 2 SD) whose sulfur four isotopes were newly determined by gas-source mass spectrometry. Typical reproducibility at two standard deviations (2 SD) of spot-to-spot analyses of standard UWPy-1 pyrite with a primary beam size of ~20 μm were ±0.23, ±0.05, and ±0.86‰ for δ34S, Δ33S, and Δ36S, respectively. The measured 36S/32S ratio [1 / (6641 ± 27)] is approximately 19‰ lower than the published ratio for VCDT, and we propose a revision of the 36S abundance in VCDT. Pyrite grains in ~2.4 Ga glaciogenic sandstone have wide ranging sulfur isotope ratios (−32.7 to 13.5 for δ34S, −3.03 to 11.66 for Δ33S, and−9.7 to 4.6 for Δ36S, respectively). Some pyrite grains are zoned in δ34S values within a grain. Sulfur isotope ratios of most pyrite grains are distributed along a line with slope = −0.9 for Δ33S vs. Δ36S, suggesting that pyrite grains mostly derived from a limited range of source rocks and near-surface sulfur reservoirs. One pyrite aggregate has a distinct texture from other pyrite grains in the same sandstone, and yields a significant mass-independent deficit in 36S with a small excess in 33S (Δ36S/Δ33S ~−4‰). This is used to suggest that this grain authigenically formed by biological activity during or after sedimentation. This work demonstrates that the use of multiple Faraday cup detectors provides improved accuracy and precision for in situ sulfur four isotope analysis with secondary ion mass spectrometry.

Figure 1. Backscattered electron (BSE) images of typical detrital pyrite grains in the 2.4 Ga glaciogenic sandstone from the Meteorite Bore Member of the Turee Creek Group MB190583, after sulfur four-isotope analyses by SIMS. Rounded or irregular anhedral shape pyrite grains: (a) g1, (b) g14, (c) g30, and (d) g44, (e) a subhedral pyrite grain g13, (f) a pyrite aggregate g9. The 34S value for each analysis is also shown. Scale bars indicate 50 microns.

Figure 2. Sulfur isotope compositions of detrital pyrite grains in the glaciogenic sandstone, MB190583, from the 2.4 Ga Meteorite Bore Member of the Turee Creek Group. (a) δ34S vs. Δ33S, and (b) Δ33S vs. Δ36S of individual pyrite grains (filled symbol = single analysis data, open symbol = averaged values of multiple analyses). Pyrite grain names that have distinct sulfur isotope ratios are shown. The dashed line in (a) indicates the slope = −0.89 Archean reference array (Ono et al., 2009b). The dashed line in (b) is the regression line (Δ36S=−0.96×Δ33S+0.72) of detrital pyrite grain data (excluding g9). The dashed-dotted line in (b) indicates the slope = −6.85 line observed in sedimentary sulfides of Phanerozoic age (Ono et al., 2006).