Rapid time series D33S profiles of deep time drill cores by EA combustion techniquesEA SO combustion techniqueSlide 3Slide 4Slide 5EA-CF-SO method drift correctionSlide 7Slide 8Slide 9Slide 10Conclusions methodologyConclusions time series resultsRapid time series 33S profiles of deep time drill cores by EA combustion techniquesAlan J. Kaufman, James Farquhar, and David T. JohnstonDepartment of Geology, University of Maryland Timothy W. LyonsDepartment of Earth Sciences, University of California, RiversideGail L. Arnold and Ariel AnbarDepartment of Geological Sciences, Arizona State UniversityDeep Time Drilling Project of the NASA Astrobiology Drilling ProgramEA SO combustion techniqueBaublys et al. (2004) Rapid Commun. Mass Spectrom. 2004; 18: 2765–2769HeO2ventpurgeEA SO combustion technique•peak height on m/z 48 up to ~2.0 nA•peak height on m/z 50 saturated at ~8E-11 A•~100 g NBS 127 (barite), NZ1, NZ3 interspersed with samples•~100 to 5000 g powdered shale200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200Scan11100%11100%AJK Ham 3-24-06 112_52 SIR of 5 Channels EI+ TIC2.29e60.742.55AJK Ham 3-24-06 NBS127 R8 SIR of 5 Channels EI+ TIC2.29e60.742.54•As elemental Cu in the combustion tube is progressively oxidized there is a correctable drift in the raw sulfur isotope values.EA-CF-SO drift correctionsEA-CF-SO method drift correctionrun no. 33S raw 34S raw 34S corr wt. %S raw1 13.43 25.15 25.14 22.172 12.24 25.09 25.06 21.393 12.77 24.86 24.82 21.444 12.85 25.07 25.02 21.455 12.87 25.37 25.31 23.4214 12.75 24.96 24.79 22.0115 12.50 25.16 24.97 21.4326 12.68 25.26 24.94 22.7927 12.63 25.17 24.83 22.6438 12.79 25.27 24.80 22.6839 12.40 25.21 24.72 17.7750 12.85 25.52 24.90 22.8451 12.60 25.65 25.02 21.4362 12.72 25.72 24.95 22.3763 12.92 25.87 25.09 22.5574 12.95 26.17 25.25 22.1975 12.91 25.93 25.00 19.2686 12.96 26.30 25.24 22.2287 12.76 26.14 25.06 21.6598 13.08 26.17 24.96 18.8999 13.20 26.68 25.45 20.54110 13.08 26.47 25.10 20.39111 13.05 26.35 24.97 18.80122 13.10 26.34 24.83 22.99123 12.87 26.07 24.54 19.0212.84 25.68 24.99 21.370.26 0.55 0.20 1.54 averagestdev (1)After drift correction, a correction for the interference of 32S18O and 33S17O on 34S16O and for 32S17O on 33S16O is applied (not done by Baublys et al., 2004). This brings the 34S values into a few tenths of a ‰ consistency of IAEA values.Hamersley Group stratigraphy in ADBP 9 drill core100 m2561 ± 8 Ma2479 ± 3 MaWhile the total sulfur data conform to ranges defined by CRS analyses from multiple Archean basins, the scatter in this data set may reflect the contribution of organic S in the samples, as well as bacterial processing of sulfur in the oceans.Conclusionsmethodology•The modified EA-CF-SO technique (using both drift and interference corrections) allows for rapid measurement of S-33 and S-34 abundances in bulk sulfur-rich samples.•Corrections are consistent with IAEA values and uncertainties are better than 0.3‰ (1) for both 33S and 34S compositions. •Modifications to the collector array may reduce scattering resulting in even smaller uncertainties. •The total sulfur method integrates both organic and sulfide S, so future comparison with CRS will be an important consideration.Conclusionstime series results•Bed-to-bed variations in 34S and 33S are geologically rapid and are broadly correlated.•Scatter in the data greater than the uncertainty of the analyses likely reflects the contribution of organic S (a largely uninvestigated reservoir) as well as bacterial redistribution of mass dependent sulfur isotopes. •Rapid variations are likely the result of variable preservation of the atmospheric rain of sulfate (with negative 33S) and organic S (with positive 33S), which may be mixed during bacterial pyrite formation. •Although the terrestrial input of sulfur to the oceans is considered to be negligible, if seawater sulfate concentrations are low this flux may also have a dilution effect on 33S values.•It is highly unlikely that the rapid variations result from oscillations in atmospheric oxygenation, highlighting the necessity to construct high-resolution time series trends in 33S through the deep time drill cores.Fe2+ + H2S → FeS + 2H+FeS + So →