Exploring the Contributions of Liquid - Phase Sulfur Chemistry to the Mass - Independent Sulfur Fractionation of the Archean Rock Record by MASSACH OFT Sebastian Hermann Kopf

Archean sulfur mass-independent fractionation (S-MIF) has been widely recognized as one of the strongest indicators for the rise of atmospheric oxygen in the Early Proterozoic. A decade after its discovery, the wide-ranging implications of Archean sulfur MIF have been discussed extensively and despite a number of recent studies on the gas-phase chemistry of sulfur, no definite overall picture has emerged to date as to the precise origin and preservation of the Archean mass-independent sulfur signal. The interpretation of the Archean sulfur MIF as a strong constraint for atmospheric oxygen levels, however, requires a dominant atmospheric source of sulfur MIF. This study was aimed at investigating the potential contribution of the poorly explored mass-independent effects from liquid-phase sulfur chemistry and focused on sulfur isotope fractionation during liquid-phase photolytic breakdown of phenacylphenylsulfone (PPS) as a model system for initial investigation. Results confirm that MIF in this system is caused by the magnetic 33S isotope and excludes other mechanisms such as nuclear volume effects or vibronic coupling that would produce concomitant MIF in the 32S-34_3-3S triad. This provides a starting point for discussing the implications of magnetic isotope effects as a mechanism for massindependent isotope fractionation in the chemical evolution of the sulfur cycle and suggests that liquid-phase processes such as the photolysis of PPS cannot constitute the principal source of mass-independent sulfur fractionation in the Archean. Thesis Supervisor: Shuhei Ono Title: Professor of Geochemistry