The effect of sulfate-delta18O upon on-line sulfate-delta34S analysis, and implications for measurements of delta33S and Delta33S.

On-line delta34S analysis of sulfate using an elemental analyzer has a number of advantages vs. conventional off-line techniques, such as ease of operation, rapidity, and the requirement for small amounts of material. Although the analyses are performed by converting sulfate into SO2 gas, the effect of sulfate-delta18O composition upon the SO2-delta18O composition and the value of delta66 during elemental analysis, and ultimately the calculated sulfate-delta34S composition, has rarely been addressed. Three BaSO4 samples were prepared with known identical delta34S compositions, but with a wide range of delta18O compositions. delta18O values were shown to range over 40 per thousand, but conventional on-line delta34S analyses verified that the sulfate-delta34S compositions were identical. These results indicate that conventional on-line analysis of sulfate-delta34S is unaffected by the value of sulfate-delta18O, and suggest that sulfide-delta34S standards can be used to calibrate sulfate-delta34S analyses (and vice versa). Moreover, these results suggest that it may be possible to use on-line sulfur isotope analysis of SO2 to measure delta33S and Delta33S in addition to delta34S, as a faster and safer alternative to the SF6 technique currently utilized, and hence promote further study of mass-independent sulfur isotope fractionation effects.