Investigating pathways of diagenetic organic matter sulfurization using compound-specific sulfur isotope analysis

We present the results of compound-specific sulfur isotope analyses performed on organic sulfur compounds (OSCs) isolated from sediments deposited in the euxinic Cariaco Basin, Venezuela. Individual OSCs (sulfurized highly branched isoprenoids and malabaricatriene) have sulfur isotope compositions of ca. −15‰, which is 34S enriched by 5–15‰ relative to coeval bulk organic and inorganic sulfur pools. These observed differences in the sulfur isotope composition of bulk organic sulfur in the kerogen and bitumen pools and individual OSCs demonstrate that there are multiple pathways of organic sulfur formation operating simultaneously in marine sediments. Comparison of our measured compound-specific sulfur isotope data with values predicted using simple isotopic mass balance assumptions suggests that the sulfurization process likely involves multiple sources of inorganic sulfur. Further, the isotopic composition of these various precursor inorganic sulfur species and the specific pathway of sulfur incorporation into organic matter (OM) impart distinct isotopic compositions to the resulting organic sulfur compounds. These data represent the first compound-specific sulfur isotope measurements made in marine sediments, and demonstrate the utility of compound-specific sulfur isotope analysis in identification of inorganic sulfur sources for OM sulfurization and tracking pathways of sulfur incorporation, which will lead to a more complete understanding of diagenetic sulfurization of OM.