An ultraviolet laser microprobe for the in situ analysis of multisulfur isotopes and its use in measuring Archean sulfur isotope mass-independent anomalies
Journal
Geochimica et Cosmochimica Acta
Journal Volume
67
Journal Issue
17
Pages
3101-3117
Date Issued
2003
Author(s)
Abstract
A laser fluorination microprobe system has been constructed for high-accuracy, high-precision multisulfur isotope analysis with improved spatial resolution. The system uses two lasers: (a) a KrF excimer laser for in situ spot analysis by ultraviolet (UV) photoablation with λ = 248 nm and (b) a CO2 laser for whole-grain analysis of powdered samples by infrared heating at λ = 10.6 μm. A CO2 laser is necessary for the analysis of interlaboratory isotope reference materials because they are supplied as powders. The δ34S and δ33S compositions of reference materials measured with a CO2 laser fluorination system agree (±0.2‰, 1σ) with the recommended values by the Sulfur Isotope Working Group of the International Atomic Energy Agency (Ding et al., 2001; Taylor, in press). The precision of replicate analyses of powdered sulfide minerals with the CO2 laser is typically ±0.2‰ (1σ) for δ34S. The in situ fluorination of sulfides with a KrF excimer laser (λ = 248 nm) was validated by comparison of measurements of side-by-side laser craters and powders excavated from drill holes. Powders from drill holes were analyzed with the CO2 laser. In situ laser craters and drill hole powders give the same δ34SV-CDT and δ33SV-CDT values within 0.2‰. The δ34SV-CDT and δ33 SV-CDT values of both powders and in situ analyses are independent of F2 gas pressure over a range of 15 to 65 torr. No dependence of δ34SV-CDT and δ33SV-CDT values on UV laser energy fluence has been observed. Mineral-specific fractionation of sulfur isotopes in analyzing pyrite, sphalerite, galena, troilite, and chalcopyrite has not been observed with a KrF excimer laser (λ = 248 nm). Test analyses with an ArF excimer laser (λ = 193 nm), however, gave fractionated sulfur isotope ratios. A range of Δ33S anomalies of from - 1.5 to +3.0‰ in Archean samples from the North Pole district, Pilbara Craton, Australia, and from black shale of the Lokamonna Formation, South Africa, were verified by in situ analysis of individual pyrite grains with a KrF excimer laser. These results show that a combination of high-accuracy, high-precision analyses with improved spatial resolution permits locating and analyzing host minerals of non-mass-dependent sulfur isotope anomalies. © 2002 Elsevier Ltd.
SDGs
Type
journal article