Abiogenic and Microbial Controls on Volatile Fatty Acids in Precambrian Crustal Fracture Waters

Abstract:

Saline fracture waters within the Precambrian Shield rocks of Canada and South Africa have been sequestered underground over geologic timescales up to 1.1-1.8 Ga [1, 2]. These fluids are rich in H₂ derived from radiolysis and hydration of mafic and ultramafic rocks [1, 2, 3] and host a low-biomass, low-diversity microbial ecosystem at some sites [2]. The abiogenic or biogenic nature of geochemical processes has important implications for bioavailable carbon sources and the role played by abiotic organic synthesis in sustaining a chemosynthetic deep biosphere. Volatile fatty acids (VFAs) are simple carboxylic acids that may support microbial communities in such environments, such as those found in terrestrial [4] and deep-sea [5] hot springs. We present abundance and δ¹³C analysis for VFAs in a spectrum of Canadian Shield fluids characterized by varying dissolved H₂, CH₄, and C₂₊ n-alkane compositions. Isotope mass balance indicates that microbially mediated fermentation of carbon-rich graphitic sulfides may produce the elevated levels of acetate (39-273 μM) found in Birchtree and Thompson mine. In contrast, thermodynamic considerations and isotopic signatures of the notably higher acetate (1.2-1.9 mM), as well as formate and propionate abundances (371-816 μM and 20-38 μM, respectively) found at Kidd Creek mine suggest a role for abiogenic production via reduction of dissolved inorganic carbon with H₂ for formate, and oxidation of C₂₊ n-alkanes for acetate and propionate, along with possible microbial cycling. VFAs comprise the bulk of dissolved and total organic carbon in the mines surveyed, and as such represent a potential key substrate for life.

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