Activity of Sulfur Reducing Bacteria in Deep Bedrock Fractures Revealed by Variability of δ34S in Pyrite and Dissolved Sulfate

Euhedral pyrite crystals coating 46 granite fractures at depths down to nearly 1 km at Laxemar, Sweden, were analysed for sulfur isotopes (δ34Spyr) by in situ SIMS (secondary ion mass spectrometry) analysis. Most of these fractures had corresponding chemical and isotopic groundwater data, providing a unique opportunity of pyrite-sulfate comparison within the same fracture network. Comparison of the isotopic ratios (δ18O, δ13C, 87Sr/86Sr) of co-genetic calcite with the groundwater showed that the sampled fractures carried pyrite and calcite that are of low-temperature origin, and with some exceptions, possibly precipitated from the present groundwater, or similar pre-modern fluids. 4Spyr showed huge variations across individual crystals (such as -32 to +73‰) and an extreme overall range (-50‰ to +91‰), which can only be explained by the activity of sulfur reducing bacteria (SRB). The most common sub-grain features were an increase in δ34Spyr with crystal growth related to successively higher δ34SSO4 caused by ongoing SRB activity and Rayleigh fractionation in fractures with low flow. The groundwater δ34SSO4 values (+9 to +37‰) are, in particular in the sulfate-poor waters down to -400 m, higher than the anticipated initial values, and this can also be explained by SRB-related Rayleigh distillation. The δ34SSO4 of the groundwater is, however, lower than that required to produce the highest δ34Spyr values, which may be due to the signal of groundwater in low-flow fractures (carrying 34S-rich sulfate and pyrite) being masked in the water data by high-flow parts of the water-flowing structure carrying abundant and less fractionated sulfate.