Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

(Appendix) Relative abundance of planktonic foraminifera in ODP Site 138-846 late Quaternary sediments

High-resolution records of d18O and relative abundances of planktonic foraminifers were generated for ODP Leg 138 Site 846 for the past 800 k.y., with an average sampling interval of 3.6 k.y. The time scale was constructed by correlating the benthic d18O record to the SPECMAP and ODP Site 677 d18O time scales using the mapping function technique of Martinson et al. (1981). Our observations show that variations in the foraminiferal assemblages, although influenced by dissolution, are interpretable in terms of changing characteristics of upper ocean waters. Carbonate dissolution as indicated by fragmentation of planktonic foraminifers shows concentrated variance that is coherent with d18O at the 100 and 41 k.y. orbital periods. At these periods, maximum dissolution occurs during interglacial extremes. This finding differs from previous studies that have indicated that in this region percent carbonate minimum lags global ice volume minimum. N. dutertrei and dextral N. pachyderma dominate the assemblages, but do not show consistent relationships relative to glacial-interglacial cycles. However, less abundant species G. ruber, G. menardii, G. glutinata and G. sacculifer show positive and G. bulloides negative correlation with the d18O record. Q-mode factor analysis of the Site 846 assemblages and comparison with modern assemblages suggest the following. Prior to and during interglacials, the area was considerably warmer and more subtropical than at present; during glacials, the area was colder than at present with greater upwelling and advection off the eastern boundary, and possibly a stronger Peru Current; the equatorial ôcool tongueö was also possibly stronger.