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The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene–Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene–Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic–anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals. [ABSTRACT FROM AUTHOR]

Abstract: Calcium carbonate can crystallize in a hydrated form as ikaite at low temperatures. The hydration water in ikaite grown in laboratory experiments records the δ18O of ambient water, a feature potentially useful for reconstructing δ18O of local seawater. We report the first downcore δ18O record of natural ikaite hydration waters and crystals collected from the Antarctic Peninsula (AP), a region sensitive to climate fluctuations. We are able to establish the zone of ikaite formation within shallow sediments, based on porewater chemical and isotopic data. Having constrained the depth of ikaite formation and δ18O of ikaite crystals and hydration waters, we are able to infer local changes in fjord δ18O versus time during the late Holocene. This ikaite record qualitatively supports that both the Medieval Warm Period and Little Ice Age extended to the Antarctic Peninsula. [Copyright &y& Elsevier]

Abstract: Hydrate Ridge off the coast of Oregon, USA, is a prime example for gas hydrate occurrences in active margin settings. It is part of the Cascadia Margin and was the focus of Ocean Drilling Program (ODP) Leg 204, which successfully recovered fluids from nine sites from the southern part of the ridge. Iodide concentrations in pore fluids associated with gas hydrates are strongly enhanced, by factors up to 5000 compared to seawater, which allows the use of this biophilic element as tracer for organic source regions. We applied the cosmogenic isotope 129I (T 1/2 =15.7 Ma) system to determine the age of the organic source formation responsible for the iodide enrichment. In all sites at ODP Leg 204, 129I/I ratios were found to decrease with depth to values around 250×10−15, corresponding to minimum ages of 40 Ma, but in several sites, maxima in the 129I/I ratios point to the local addition of young iodide. The results indicate that a large amount of iodide was derived from deep accreted sediments of Eocene age, and that additional source regions provide iodide of Late Miocene age. The presence of old iodide in the pore waters suggests that fluid pathways are open to allow transport over large distances into the gas hydrate fields. The strong correlation between iodide and methane in hydrate fields coupled with the similarity in transport parameters in aqueous solutions suggests that a large fraction of methane in gas hydrates also has old sources and is transported into the present locations from source regions of Eocene age. [Copyright &y& Elsevier]

Abstract: Iodine and its radioisotope 129I have been successfully used to trace the origin of pore waters in submarine fluid escape structures because of their close association with organic material in deeply buried sediments. We report here halogen concentrations and 129I/I ratios for fluids of five mud volcanoes sampled along an E–W transect across the Gulf of Cadiz in the NE Atlantic Ocean. Concentrations of iodide and bromide increase consistently seaward accompanied by a decrease in 129I/I ratios from 6490×10−15 to 663×10−15. The exceptionally high 129I/I ratios at the near-shore locations reflect the presence of fissiogenic 129I, produced in situ by spontaneous fission of 238U within terrigenous sediments and released into pore water during clay mineral diagenetic processes. The observed 129I/I and halogen trends, together with similar changes in 87Sr/86Sr ratios, indicate a progressive seaward transition from inorganic-terrigenous to organic-marine fluid sources. Comparison of our results with literature data for varying geological settings reveals a general relationship between fissiogenic 129I, radiogenic 87Sr and the lithology or provenance of rocks and sediments, respectively. While 129I/I ratios in continental rock-hosted aquifers and terrigenous sedimentary systems are dominated by in situ production of fissiogenic 129I, iodine isotopes in oceanic settings or volcanogenic marine sediments reflect the release of ‘old’ iodine from deeply buried organic matter. The Gulf of Cadiz represents the full transition between these continental and oceanic 129I/I and 87Sr/86Sr end members. This is the first systematic investigation of fissiogenic 129I production in marine sedimentary environments. [Copyright &y& Elsevier]

Profound changes in environmental conditions, particularly atmospheric oxygen levels, are thought to be important drivers of several major biotic events (e.g. mass extinctions and diversifications). The early Paleozoic represents a key interval in the oxygenation of the ocean–atmosphere system and evolution of the biosphere. Global proxies (e.g. carbon ( δ 13 C) and sulfur ( δ 34 S) isotopes) are used to diagnose potential changes in oxygenation and infer causes of environmental change and biotic turnover. The Cambrian–Ordovician contains several trilobite extinctions (some are apparently local, but others are globally correlative) that are attributed to anoxia based on coeval positive δ 13 C and δ 34 S excursions. These extinction and excursion events have yet to be coupled with more recently developed proxies thought to be more reflective of local redox conditions in the water column (e.g. I/Ca) to confirm whether these extinctions were associated with oxygen crises over a regional or global scale. Here we examine an Early Ordovician (Tremadocian Stage) extinction event previously interpreted to reflect a continuation of recurrent early Paleozoic anoxic events that expanded into nearshore environments. δ 13 C, δ 34 S, and I/Ca trends were measured from three sections in the Great Basin region to test whether I/Ca trends support the notion that anoxia was locally present in the water column along the Laurentian margin. Evidence for anoxia is based on coincident, but not always synchronous, positive δ 13 C and δ 34 S excursions (mainly from carbonate-associated sulfate and less so from pyrite data), a 30% extinction of standing generic diversity, and near-zero I/Ca values. Although evidence for local water column anoxia from the I/Ca proxy broadly agrees with intervals of global anoxia inferred from δ 13 C and δ 34 S trends, a more complex picture is evident where spatially and temporally variable local trends are superimposed on time-averaged global trends. Stratigraphic sections from the distal and deeper part of the basin (Shingle Pass and Meiklejohn Peak) preserve synchronous global ( δ 13 C and δ 34 S) and water column (I/Ca) evidence for anoxia, but not at the more proximal section (Ibex, UT). Although geochemical and paleontological evidence point toward anoxia as the driver of this Early Ordovician extinction event, differences between I/Ca and δ 13 C– δ 34 S signals suggest regional variation in the timing, extent, and persistence of anoxia. [ABSTRACT FROM AUTHOR]

The decline in dissolved oxygen in global oceans (ocean deoxygenation) is a potential consequence of global warming which may have important impacts on ocean biogeochemistry and marine ecosystems. Current climate models do not agree on the trajectory of future deoxygenation on different timescales, in part due to uncertainties in the complex, linked effects of changes in ocean circulation, productivity and organic matter respiration. More (semi-)quantitative reconstructions of oceanic oxygen levels over the Pleistocene glacial cycles may provide a critical test of our mechanistic understanding of the response of oceanic oxygenation to climate change. Even the most promising proxies for bottom water oxygen (BWO) have limitations, which calls for new proxy development and a multi-proxy compilation to evaluate glacial ocean oxygenation. We use Holocene benthic foraminifera to explore I/Ca in Cibicidoides spp. as a BWO proxy. We propose that low I/Ca (e.g., <3 μmol/mol) in conjunction with benthic foraminiferal carbon isotope gradients and/or the surface pore area percentages in foraminiferal tests (e.g., >15%) may provide semi-quantitative estimates of low BWO in past oceans (e.g., <∼50 μmol/kg). We present I/Ca records in five cores and a global compilation of multiproxy data, indicating that bottom waters were generally less-oxygenated during glacial periods, with low O 2 waters (<∼50 μmol/kg) occupying some parts of the Atlantic and Pacific Oceans. Water mass ventilation and circulation may have been important in deoxygenation of the glacial deep Pacific and South Atlantic, whereas enhanced remineralization of organic matter may have had a greater impact on reducing the oxygen content of the interior Atlantic Ocean. • Validation of I/Ca as a bottom water oxygen proxy in epifaunal benthic foraminifera. • Down-core I/Ca records of glacial oceans from multiple basins. • Large compilation of (semi-)quantitative proxy data in comparison with I/Ca. [ABSTRACT FROM AUTHOR]