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The shell material of marine benthic bivalves provides a sensitive archive of water chemistry immediately above the sediment–water interface, which in turn is affected by sedimentary geochemistry and redox reactions. Sulfate has a major controlling effect on sedimentary carbon cycling, particularly the processes of methane production and oxidation, with lower concentrations of sulfate likely resulting in an increase in sedimentary methane production. Whilst it is accepted that ocean sulfate varied markedly across the Phanerozoic, evidence of changes in methane production in sediments has so far been lacking. There is potential for the oxidation products of sedimentary methane to be preserved and detected in marine fossils. Here we present the results of high resolution carbonate isotope records from two taxa of well-preserved shallow-infaunal bivalve ( Lahillia and Cucullaea ) collected from the marine shelf succession across the Cretaceous–Paleogene (K–Pg) boundary in Seymour Island, Antarctica. The succession has pre-existing subtle indications of more abundant methane, and the time period is characterized by much lower marine sulfate concentrations than modern. These shell carbonate–carbon isotope records vary widely: at one extreme, shells have typical average values and small ranges compatible with a contemporaneous marine dissolved inorganic carbon (DIC) source and modern-style sedimentary carbon cycling. At the other, the shells have large-amplitude annual cycles of carbon isotopic variability of up to 23.8‰ within a single year of growth and shell carbonate δ 13 C compositions as negative as −34‰. Shells with these increased ranges and unusually negative values are found at discrete intervals and across both bivalve taxa. The contribution of methane required to explain the most negative carbonate–carbon isotopic values in the bivalve shells is extremely high (between 30 to 85% of bottom-water DIC based on mass balance calculations). Records of organic-carbon isotopes from the same succession remained between −26.1 and −21.7‰ throughout, suggesting that methane influence was restricted to bottom-waters. A lack of authigenic carbonate in the section indicates that methane oxidation progressed aerobically and may have provided a significant driver for transient bottom water de-oxygenation. Where methane addition is indicated, the seasonal sensitivity precludes control by methane hydrates. We argue that these data represent the increased importance and sensitivity of methanogenesis in the sediments, enabled by lower ocean sulfate concentrations during the Late Cretaceous. The tendency towards a more dynamic role for marine methane production and oxidation is likely to apply to other times of low marine sulfate in Earth's history. [ABSTRACT FROM AUTHOR]

The Cretaceous–Paleogene (K–Pg) mass extinction event 66 million years ago led to large changes to the global carbon cycle, primarily via a decrease in primary or export productivity of the oceans. However, the effects of this event and longer-term environmental changes during the Late Cretaceous on the global sulfur cycle are not well understood. We report new carbonate associated sulfate (CAS) sulfur isotope data derived from marine macrofossil shell material from a highly expanded high latitude Maastrichtian to Danian (69–65.5 Ma) succession located on Seymour Island, Antarctica. These data represent the highest resolution seawater sulfate record ever generated for this time interval, and are broadly in agreement with previous low-resolution estimates for the latest Cretaceous and Paleocene. A vigorous assessment of CAS preservation using sulfate oxygen, carbonate carbon and oxygen isotopes and trace element data, suggests factors affecting preservation of primary seawater CAS isotopes in ancient biogenic samples are complex, and not necessarily linked to the preservation of original carbonate mineralogy or chemistry. Primary data indicate a generally stable sulfur cycle in the early-mid Maastrichtian (69 Ma), with some fluctuations that could be related to increased pyrite burial during the ‘mid-Maastrichtian Event’. This is followed by an enigmatic +4‰ increase in δ 34 S CAS during the late Maastrichtian (68–66 Ma), culminating in a peak in values in the immediate aftermath of the K–Pg extinction which may be related to temporary development of oceanic anoxia in the aftermath of the Chicxulub bolide impact. There is no evidence of the direct influence of Deccan volcanism on the seawater sulfate isotopic record during the late Maastrichtian, nor of a direct influence by the Chicxulub impact itself. During the early Paleocene (magnetochron C29R) a prominent negative excursion in seawater δ 34 S of 3–4‰ suggests that a global decline in organic carbon burial related to collapse in export productivity, also impacted the sulfur cycle via a significant drop in pyrite burial. Box modelling suggests that to achieve an excursion of this magnitude, pyrite burial must be reduced by >15%, with a possible role for a short term increase in global weathering rates. Recovery of the sulfur cycle to pre-extinction values occurs at the same time (∼320 kyrs) as initial carbon cycle recovery globally. These recoveries are also contemporaneous with an initial increase in local alpha diversity of marine macrofossil faunas, suggesting biosphere-geosphere links during recovery from the mass extinction. Modelling further indicates that concentrations of sulfate in the oceans must have been 2 mM, lower than previous estimates for the Late Cretaceous and Paleocene and an order of magnitude lower than today. [ABSTRACT FROM AUTHOR]