Variability of sedimentary pyrite δ34S records: A case study of slope shale of the Green Point Formation in western Newfoundland, Canada

Abstract

The Green Point Formation in western Newfoundland, GSSP of the Cambrian-Ordovician (Є-O) boundary, is dominated by slope rhythmites of alternating lime mudstone and shale interbeds. This formation was deposited in a semi-restricted basin with varying connectivity to the open ocean. In the current study, we investigate textures and bulk δ34S signatures of pyrite (δ34Spy) in the shale to better understand factors influencing the sedimentary δ34Spy fluctuation. Petrographic and SEM examinations reveal two major types of pyrite: (1) framboidal pyrite and (2) anhedral to euhedral pyrite. The latter is further categorized into two subtypes: type 2a anhedral to subhedral pyrite characterized by relict framboidal textures and larger sizes (∼10 to 300 μm), and type 2b smaller (typically <10 μm) subhedral to euhedral pyrite. Type 1 pyrite was precipitated near the sediment-water interface (SWI), whereas type 2b pyrite was formed in sediments below the SWI with limited access to the overlying seawater sulfate. Type 2a pyrite was evolved from framboids during early and burial diagenesis. The bulk δ34Spy values, marked by a significant scatter (1σ =10.62‰), range broadly from −17.6 to +22.4‰ (VCDT) and exhibit a pronounced positive excursion of ∼20‰ near the Є-O boundary. The abundance of type 2b pyrite generally mimics the changes in δ34Spy, suggesting that the substantial δ34Spy dispersion could be partially attributed to differing proportions of type 2b pyrite within the samples. Moreover, notable negative correlations exist between the δ34Spy values and the abundances of Al, Th, ∑REE, and Fe, indicating that riverine fluxes might have influenced the Δ34Sseawater – pyrite by modulating the regional seawater sulfate and iron reservoir sizes. Therefore, rather than being indicative of oceanic redox oscillations, the positive δ34Spy excursion of ∼20‰ of this interval was probably driven by decreased sulfate and iron levels in the local waterbody. The decline in terrestrial input during this δ34Spy shift might have also contributed to a negative δ13Ccarb excursion by reducing nutrient supply and inhibiting primary productivity. Collectively, the bulk sedimentary δ34Spy variability recorded by the Green Point shale may be attributed to a combination of changes in regional terrigenous input and varying amounts of pyrite formed at different diagenetic stages within the samples. The general opposing trends between the δ34Spy signals and the abundances of Al, Th, ∑REE, and Fe, however, imply that fluctuations in riverine influxes might exert a stronger influence on the major δ34Spy trend. These findings suggest that bulk sedimentary δ34Spy variations may not be reliable evidence for perturbations of the global sulfur cycle.