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The triple oxygen isotope composition (Δ’ 17 O) of sulfate minerals is widely used to constrain ancient atmospheric p O 2 / p CO 2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O 2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the δ 18 O and Δ’ 17 O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ’ 17 O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably.

Epikarst estuary response to hydroclimate change remains poorly understood, despite the well-studied link between climate and karst groundwater aquifers. The influence of sea-level rise and coastal geomorphic change on these estuaries obscures climate signals, thus requiring careful development of paleoenvironmental histories to interpret the paleoclimate archives. We used foraminifera assemblages, carbon stable isotope ratios (δ¹³C) and carbon:nitrogen (C:N) mass ratios of organic matter in sediment cores to infer environmental changes over the past 5300 years in Celestun Lagoon, Yucatan, Mexico. Specimens (> 125 µm) from modern core top sediments revealed three assemblages: (1) a brackish mangrove assemblage of agglutinatedMiliamminaandAmmotiumtaxa and hyalineHaynesina(2) an inner-shelf marine assemblage ofBolivina,Hanzawaia, andRosalina,and (3) a brackish assemblage dominated byAmmoniaandElphidium. Assemblages changed along the lagoon channel in response to changes in salinity and vegetation, i.e. seagrass and mangrove. In addition to these three foraminifera assemblages, lagoon sediments deposited since 5300 cal yr BP are comprised of two more assemblages, defined byArchaiasandLaevipeneroplis,which indicate marineThalassiaseagrasses, andTrichohyalus,which indicates restricted inland mangrove ponds. Our data suggest that Celestun Lagoon displayed four phases of development: (1) an inland mangrove pond (5300 BP) (2) a shallow unprotected coastline with marine seagrass and barrier island initiation (4900 BP) (3) a protected brackish lagoon (3000 BP), and (4) amore »protected lagoon surrounded by mangroves (1700 BP). Stratigraphic (temporal) changes in core assemblages resemble spatial differences in communities across the modern lagoon, from the southern marine sector to the northern brackish region. Similar temporal patterns have been reported from other Yucatan Peninsula lagoons and fromcenotes(Nichupte, Aktun Ha), suggesting a regional coastal response to sea level rise and climate change, including geomorphic controls (longshore drift) on lagoon salinity, as observed today. Holocene barrier island development progressively protected the northwest Yucatan Peninsula coastline, reducing mixing between seawater and rain-fed submarine groundwater discharge. Superimposed on this geomorphic signal, assemblage changes that are observed reflect the most severe regional wet and dry climate episodes, which coincide with paleoclimate records from lowland lake archives (Chichancanab, Salpeten). Our results emphasize the need to consider coastal geomorphic evolution when using epikarst estuary and lagoon sediment archives for paleoclimate reconstruction and provide evidence of hydroclimate changes on the Yucatan Peninsula.

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Abstract Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.

Marine barite (BaSO4) is a relatively ubiquitous, though minor, component of ocean sediments. Modern studies of the accumulation of barite in ocean sediments have demonstrated a robust correlation between barite accumulation rates and carbon export to the deep ocean. This correlation has been used to develop quantitative relationships between barite accumulation rates and export production and is used to reconstruct export production in the geologic past, particularly during times of dynamic changes in the carbon cycle. We review the processes that affect the formation and preservation of marine barite, as well as those controlling the relationship between the barium (Ba) and carbon biogeochemical cycles. Additionally, we take a new approach to modeling the marine Ba cycle as a two-box model, specifically evaluating Ba utilization in the surface ocean and refining the equation describing the relationship between export production and barite formation. We compare these new results with past modeling efforts. The new model demonstrates that increases in export production can lead to sustained increases in barite accumulation in marine sediments without resulting in complete surface water Ba depletion, which is distinctly different from previous modeling results.

Changes in the concentration and isotopic composition of the major constituents in seawater reflect changes in their sources and sinks. Because many of the processes controlling these sources and sinks are tied to the cycling of carbon, such records can provide insights into what drives past changes in atmospheric carbon dioxide and climate. Here, we present a stable strontium (Sr) isotope record derived from pelagic marine barite. Our δ^88/86Sr record exhibits a complex pattern, first declining between 35 and 15 million years ago (Ma), then increasing from 15 to 5 Ma, before declining again from ~5 Ma to the present. Numerical modeling reveals that the associated fluctuations in seawater Sr concentrations are about ±25% relative to present-day seawater. We interpret the δ^88/86Sr data as reflecting changes in the mineralogy and burial location of biogenic carbonates.