Ba/Sr ratio in marine barite from five DSDP and ODP holes

The Paleocene-Eocene Thermal Maximum (PETM), ca. 55 Ma, was a period of extreme global warming caused by rapid emission of greenhouse gases. It is unknown what ended this episode of greenhouse warming, but high oceanic export productivity over thousands of years (as indicated by high accumulation rates of barium, Ba) may have been a factor in ending this warm period by carbon sequestration. However, Ba has a short oceanic residence time (~10 k.y.), so a prolonged global increase in Ba accumulation rates requires an increase in input of Ba to the ocean, increasing barite saturation. We use a novel proxy for barite saturation (Sr/Ba in marine barite) to demonstrate that the seawater saturation state with respect to barite did not change across the PETM. The observations of increased barite burial, no change in saturation, and the short residence time can be reconciled if Ba burial decreased at continental margin and shelf sites due to widespread occurrence of suboxic conditions, leading to Ba release into the water column, combined with increased biological export production at some pelagic sites, resulting in Ba sink reorganization.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.