Transformations in organic sulfur speciation during maturation of Monterey shale: Constraints from laboratory experiments

A series of hydrous pyrolysis experiments were conducted at temperatures ranging from 125 to 360C at 350 bars pressure to examine variations in sulfur speciation during thermal maturation of Monterey shale. The total sediment, kerogen and bitumen from each experiment in addition to unheated representatives were analyzed via x-ray absorption spectroscopy, pyrolysis-gas chromatography, {sup 30}NMR spectrometry, elemental analysis, thin-layer chromatography and reflected light microscopy. Based on these measurements, it was possible to recognize three distinct temperature regimes, within which the type and amount of sulfur in the analyzed fractions underwent transformations: (1) between 150 and 225C significant proportion of kerogen-bound sulfur is lost probably due to the collapse of polysulfide bridges; (2) between 225 and 275C, cleavage of -S-S- and -S-C- linkages within the kerogen is believed to occur, resulting in substantial production of polar sulfur-rich bitumen; (3) above 275C total bitumen yields as well as the proportion of bitumen sulfur decrease, while C-C bond scission leads to increased yields of saturated and aromatic hydrocarbons. The results from this study clearly and quantitatively establish a link between organically-bound sulfur, and more specifically, organic polysulfides, and the low-temperature evolution of soluble petroleum-like products (bitumen) from sulfur-rich source rocks