Abstract

We present a high-resolution δ 34S (sulfate and pyrite) and δ 13C carbonate record from the Middle–Upper Cambrian Port au Port Group, a mixed carbonate-siliciclastic succession exposed in western Newfoundland, Canada. The results illustrate systematic δ 34S sulfate shifts of > 15‰ over relatively short stratigraphic intervals (10 m, likely < 1 m.y.), low average Δ 34S sulfate–pyrite (ca. 23‰) and a generally positive coupling between changes in δ 13C carbonate and δ 34S sulfate. Together, these results indicate that Middle to Late Cambrian sulfate concentrations were low and that the sulfate reservoir was more sensitive to change than it was in either terminal Neoproterozoic or Cenozoic oceans. However, a simple carbon (C) and sulfur (S) isotope box model of the Late Cambrian ocean illustrates that low sulfate concentrations alone fail to account for the > 15‰ δ 34S sulfate shifts recognized in Port au Port strata. Such large shifts can be generated only if fluctuating oceanic redox is invoked; marine anoxia forces reduced C/S burial and elevated Δ 34S, driving larger δ 34S changes per mole of organic carbon buried. The conclusion that later Cambrian oceans featured both low sulfate levels and widespread subsurface anoxia supports hypotheses that link fluctuating marine redox conditions in the delayed recovery of skeletal animals and metazoan reefs from late Early Cambrian extinction.

Highlights

  • The biogeochemical cycles of carbon (C) and sulfur (S) are intimately linked through a variety of feedbacks that operate on timescales of days to millions of years

  • The C and S isotope models presented in this study indicate that fluctuating water column anoxia in a low sulfate ocean generates the largest δ34S

  • A significant increase in Δ34S, as recorded in terminal Neoproterozoic rocks, suggests that an increase in the oxidation state of the ocean-atmosphere system facilitated an increase in seawater sulfate concentrations just prior to the appearance of the Ediacaran Fauna (Fike et al, 2006)

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Summary

Introduction

The biogeochemical cycles of carbon (C) and sulfur (S) are intimately linked through a variety of feedbacks that operate on timescales of days to millions of years. O2 concentration which, in turn, facilitates an increase in the extent to which sulfides on land are 8 oxidatively weathered and, delivered to the oceans as riverine sulfate. These two processes impose very different relationships between the C isotope composition of dissolved inorganic carbon (DIC) and the sulfur isotope composition of sulfate in seawater. Analogous to the C cycle, the primary input of S (as sulfate) to seawater is riverine delivery resulting from the oxidative weathering of sulfides and dissolution of evaporites (principally calcium sulfates) and carbonates (e.g., CAS) on land. Either within the water column or sediments, some microbes decompose OC via BSR, reducing sulfate to sulfide that may react with available iron (Fe) to form sedimentary pyrite

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