Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

Macromolecular fractions, isolated from the solvent extract of sulfur-rich Recent (Siders Pond, USA; Lake Cadagno, Switzerland; Walvis Bay, Namibia) and immature sediments (Gibellina, Messinian of Sicily; Vena del Gesso, Messinian of Italy), were investigated by chemical degradation using sodium ethanethiolate/methyliodide. This mild reagent which cleaves polysulfide bonds to yield methylsulfides has the advantage over other methods of leaving intact other functionalities (like double bonds) and preserving sulfur atoms at their incorporation site. The method is, therefore, well-suited to the molecular level investigation of sulfur-rich macromolecules from Recent sediments containing highly functionalized polysulfide-bound subunits. In Recent anoxic sulfur-rich sediments, the release of various methylthioethers clearly demonstrates that intermolecular sulfurization of organic matter does occur at the earliest stages of diagenesis. Steroids and phytane derivatives are the major sulfurized lipids, a feature also observed in more mature sulfur-rich sediments. Several phytene derivatives, such as cis and trans 1-methylthiophyt-2-enes, as well as methylthiosteroids, including 5α- and 5β-3-(methylthio)-cholest-2-enes, were identified by comparison with synthesized standards. Steroid methylthioenolethers are released from polysulfide-bound steroid enethiols present in the macromolecular fractions. The latter, which correspond to thioketones, can be considered as intermediates in the reductive sulfurization pathway leading from steroid ketones to polysulfide-bound saturated steroid skeletons and are characterized for the first time in the present study. Thus, it could be shown that the major part of the polysulfide-bound lipids occurring in Recent sediments is apparently the result of sulfurization processes affecting carbonyls (aldehydes and ketones). The unsaturated methylthioethers obtained from Recent sediments were not present in more mature evaporitic samples, which suggests that polysulfide-bound unsaturated thiols are intermediates formed during the first sulfurization steps occurring soon after deposition and that they are rapidly transformed by various processes taking place during early diagenesis, notably to yield their saturated counterparts.