Cinder pool's sulfur chemistry : implications for the origin of life in hydrothermal envrionments

One chemoautotrophic origin of life theory posits the abiotic formation of alkyl thiols as an initial step to forming biomolecules and eventually a simple chemoautotrophic cell. The premise of this theory is that a recurring reaction on the charged surfaces of pyrite served as a primordial metabolism analogous to the reductive acetyl-CoA pathway (Wächtershäuser 1988) that was later enveloped by a primitive cellular membrane. Alkyl thiols have not previously been identified in terrestrial hot springs as unequivocally abiogenic, but they have been produced in the laboratory under hydrothermal conditions in the presence of a catalyst. I analyzed the dissolved gas content of several hot springs and conducted sterile laboratory experiments in order to evaluate the abiogenic formation of methanethiol (CH3SH), the simplest of the alkyl thiols. Specifically of interest was Cinder Pool, an acid-sulfate-chloride hot spring in Yellowstone National Park. This spring is unusual in that it contains a subaqueous molten sulfur layer (~18 m depth) and thousands of iron- vii sulfur-spherules floating on the surface, which are created by gas bubbling through the molten floor of the spring. This material could potentially serve as a reactive and catalytic surface for abiogenic CH3SH formation in Cinder Pool. Gas samples were collected from Cinder Pool and an adjacent hydrothermal feature in fall of 2011 using the bubble strip method. Two samples contained measurable quantities of CH3SH and other organic sulfur gases, with concentrations of all gases generally higher at the bottom of the pool. Laboratory microcosm experiments were conducted to replicate these findings in a sterile environment. Analog Cinder Pool water was injected into serum bottles containing different iron-sulfur compounds, including cinders collected from the pool itself, as catalytic surfaces for the CH3SH generating reaction. The bottles were then charged with hydrogen (H2), carbon dioxide (CO2), and carbon disulfide (CS2) as reaction gases and incubated for a week at temperatures between 60 and 100oC. Bottles used either powdered FeS, FeS2 (pyrite) or cinder material as a catalytic surface, and all of these surfaces were capable of catalyzing CH3SH formation. In bottles without imposed CS2, however, cinder material was the only surface that produced any detectable CH3SH. While CH3SH is central to the autotroph-first theory and has been synthesized in the laboratory (e.g. Heinen and Lauwers 1996), it has not previously been observed to form abiotically in natural systems. I have identified CH3SH in a natural hydrothermal feature where it is unlikely to have formed secondary to microbial activity, and I have duplicated these field findings in sterile laboratory experiments using the cinders as a reactive surface for formation.