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Widespread oceanic anoxia, biological crises, and volcanic activity are associated with the onset of Early Aptian (ca. 120 Ma) Oceanic Anoxic Event 1a (OAE1a). Reconstructions of oceanic deoxygenation and its links to broadly contemporaneous volcanism, however, remain poorly resolved. We use geochemical data, including δ53Cr ratios and rare Earth element abundances, to define the timing and tempo of submarine volcanism and global oceanic deoxygenation across this event. Pacific Ocean sediments deposited in the run up to OAE1a record multiple phases of marine volcanism associated with the emplacement of Ontong Java Plateau lavas. Rapid oceanic deoxygenation followed the initial phases of volcanism and a biocalcification crisis. Large swaths of the oceans likely became anoxic from the Tethys to the Pacific Oceans in

Since the 1980–1990s, international research efforts have augmented our knowledge of the physical and chemical properties of the Arctic Ocean water masses, and recent studies have documented changes. Understanding the processes responsible for these changes is necessary to be able to forecast the local and global consequences of these property evolutions on climate. The present work investigates the distributions of geochemical tracers of particle fluxes and circulation in the Amerasian Basin and their temporal evolution over the last three decades (from stations visited between 1983 and 2015). Profiles of 230‐thorium (230Th) and 231‐protactinium (231Pa) concentrations and neodymium isotopes (expressed as εNd) measured in the Amerasian Basin prior to 2000 are compared to a new, post‐2000s data set. The comparison shows a large scale decrease in dissolved 230Th and 231Pa concentrations, suggesting intensification of scavenging by particle flux, especially in coastal areas. Higher productivity and sediment resuspension from the shelves appear responsible for the concentration decrease along the margins. In the basin interior, increased lateral exchanges with the boundary circulation also contribute to the decrease in concentration. This study illustrates how dissolved 230Th and 231Pa, with εNd support, can provide unique insights not only into changes in particle flux but also into the evolution of ocean circulation and mixing., Key Points Concentration decreases of 230Thd and 231Pad suggest an enhancement of particulate scavenging since the 2000s in the Amerasian BasinParticulate scavenging results from higher productivity and sediment resuspension from the shelvesPost‐2000s changes in intermediate and deep layers suggest enhanced lateral mixing between the margins and central areas of the basins

A high-resolution dinoflagellate cyst analysis on a sediment core GLW31D from the northern South China Sea (SCS) was performed to reconstruct paleoceanographic conditions over the last 12,500 years through qualitative, semi-quantitative, and quantitative methods. A modern dataset with 398 reference sites in the northern Pacific was assembled and used to identify the relationship between dinoflagellate cyst assemblages and sea-surface temperature (SST), sea-surface salinity (SSS) and primary productivity (PP). Modern analog technique (MAT) was applied to offer first dinoflagellate-cyst-based quantitative estimates of Holocene sea-surface conditions in the western North Pacific. The downcore reconstructions show that SST, SSS and PP were predominantly controlled by the changes in coastal and oceanic currents due to the changes in sea level and monsoon systems. Our results indicate that SST increased while SSS and PP decreased from 12,500 to ~6800 cal yr BP, reaching the maximum SST and the minimum SSS and PP during ~6800–5000 cal yr BP, and followed by a slight decline in SST with minor increases in SSS and PP. The three intervals correspond to the regional onshore sea-level stages of rising, stabilization in a highstand and slight drop, respectively. The Kuroshio Current strongly influenced the core site before ~9900 cal yr BP, reflected by the highest abundances of oceanic Impagidinium spp. and high reconstructed SSS values. This can be explained by a lack of water input from the East China Sea before the opening of the Taiwan Strait. The warmest period, from ~6800 cal yr BP to ~5500 cal yr BP, is recorded by the highest Dapsilidinium pastielsii abundances. Two short-term high-PP events of ~2700–2400 cal yr BP and ~1000–600 cal yr BP, which were characterized by opposite climatic conditions, coincided with two notable societal (dynasty) collapses of China. Enhanced anthropogenic activities since the Late Bronze Age most likely partially affected the high PP through influencing river inputs to the northern SCS.

The neodymium isotope composition ( ɛ Nd) of authigenic phases in marine sediment is widely used to reconstruct the origin and mixing of water masses of overlying seawater through time. However, at some locations in the modern ocean, the ɛ Nd of authigenic phases in surface sediment is not consistent with that of local seawater, raising concerns about its current interpretation as a paleotracer of water masses. To further investigate this question, we conducted a laboratory-based incubation experiment with a Mn-oxide phase placed at the sediment–water interface of multicores to assess the extent to which the authigenic phase records seawater ɛ Nd. Multicores were collected from the Strait of Georgia (SoG), which is a relatively deep coastal waterway with high sedimentation rates, oxygenated surface sediments, and active macrofauna, separating the mainland coast of British Columbia and Vancouver Island. Manganese oxide-coated XAD resin beads were placed at the sediment surface and the cores were incubated for 6 months in a tank filled with SoG seawater spiked with 150 Nd. While the ɛ Nd of the Mn-oxide coated resin (−4.0) was similar to that of SoG seawater used for the incubation (−3.7), the 150 Nd/ 144 Nd of the Mn-oxide phase measured after the incubation indicates that, under our experimental conditions, a minimum of 83% of the Nd associated with the Mn-oxide phase is not sourced from seawater, but from pore water. The 150 Nd/ 144 Nd ratio of the Mn-oxide resin is necessary to determine the predominant source of Nd to the resin because the ɛ Nd of SoG pore water (−3.9) is within analytical error of seawater (−3.7). Using field data and constraints from the Nd mass balance during the incubation, we conclude that the similarity of ɛ Nd in pore water and seawater in the SoG is fortuitous and not a result of a top-down or bottom-up control. Although the setting of our sediments is not directly comparable to open ocean locations, this study raises concerns about the use of ɛ Nd in paleocirculation studies, and points to the necessity of elucidating the factors controlling local lithogenic dissolution in pore waters as a prerequisite for the correct interpretation of ɛ Nd in the authigenic phases of marine sediments.

International audience; Global climate change has had large impacts on the Arctic region including rapid reductions in sea ice and rapid increases in surface air temperatures. Documenting the consequences of these changes in the Arctic Ocean is difficult, however, because accessibility limits observations in space and time and aliases measurements. This problem can be alleviated by using geochemical tracers, which can act as natural integrators, allowing us to determine net changes over regions and years. One such tracer is 230 Th. We use measurements and an off-line scavenging model forced by ANHA4, a regional configuration of the NEMO general circulation model, to investigate changes in the Canada Basin in the years 2002-2015. Observations show a clear decrease in 230 Th in intermediate layers, particularly in the internal Canada Basin. The model reproduces the observed changes in 230 Th concentration profiles. Using the model to determine the origin of the reduction shows that the decrease is due to both higher particle fluxes from increased productivity resulting from the reduction in sea ice cover and increased circulation and stirring by mesoscale eddies increasing lateral exchange between the productive coastal regions and less productive internal Canada Basin. The circulation model clearly shows increased velocities as the ice cover has decreased and storms have increased.

Chromium (Cr) stable isotopes have emerged as a powerful tool for tracking environmental redox transfor- mations. This is because Cr isotopes are fractionated during redox reactions between Cr(III) and Cr(VI). In order to fully exploit the information recorded within Cr isotope compositions, we must be able to track changes in Cr speciation throughout the environment and, in particular, the changes in speciation between input to the ocean and eventual deposition in sediments. We must also be able to access the isotope compositions of each Cr species, rather than only total dissolved Cr. We have thus developed a magnesium hydroxide coprecipitation method that meets these objectives. This method achieves complete recovery and has a typical precision on concentration measurements of !8% (1σ). It was tested using seawater collected from Saanich Inlet, a persis- tently anoxic fjord on the Pacific coast of Canada. Chromium speciation profiles and proof-of-concept isotope ratio measurements on selected samples indicate that isotopically lighter Cr(III) can be isolated from coexisting isotopically heavier Cr(VI), effectively resolving species-specific Cr isotope compositions. While the oxygenated surface waters of Saanich Inlet follow the generally observed correlation between seawater Cr concentration and its isotopic composition, seawater from anoxic depths diverges from this array, indicating that different pro- cesses are responsible for setting the isotope composition of these deeper waters. Broader application of Mg(OH)2 coprecipitation has strong potential to yield new insights into the fractionation of Cr isotopes in the oceans and the pathways that ultimately set the Cr isotopic composition of marine sediments and sedimentary archives.

Trace elements of marine shells are important tools for reconstructing past ocean conditions, which are usually obtained through empirical calibrations with ocean parameters. For example, Mg/Ca ratios of ostracod shells have been linked to ocean temperature. However, some uncertainties usually arise from extraneous impacts, such as the selection of cleaning methods, specimen ontogenetic stage and shell preservation. Here, we present an evaluation of trace elements (Ca, Mg, Sr, Na, Al and Fe) in a shallow marine ostracod, Sinocytheridea impressa, and their potential utility as paleoceanographic proxies. We investigated single-shell variability of trace-element-to‑calcium ratios through Inductively Couple Plasma Mass Spectrometry (ICP-MS). In addition, the internal distribution of trace-elements was studied by Electron Probe Micro Analysis (EPMA) and Flow-Through Time-Resolved Analysis (FT-TRA). We conducted these analyses on ostracod specimens of different life stages and preservation conditions, subject to different cleaning methods, to resolve the suitability of this species as a new paleoenvironmental archive. Based on cleaning tests, we observe that clays stuck to the shells are the major contaminants in our specimens. We report an optimal cleaning procedure using sodium hypochlorite, which reduced the adherence of clays to the organism without significantly dissolving adult and juvenile calcite. We additionally find that the internal Mg distribution of S. impressa specimens is different for adults and the oldest stage of juveniles, namely A-1, with only the former having an enriched inner Mg layer. Therefore, precautions should be taken when combining life stages for trace-element analysis. While Sr and Mn are found to be mostly homogenous throughout all shells, the distribution of Na was found to be heterogeneous, which suggests that the incorporation of Na is controlled by a different mechanism than Mg, Sr and Mn. Finally, we report that transparent and opaque shells show similar Mg/Ca, Sr/Ca and Na/Ca ratios, unlike Mn/Ca and Fe/Ca, which suggests that opaque shells result from Mn- and Fe-enriched porewaters and Mn-enriched waters from the Pearl River. Our combined analysis suggests that Mg, Sr and Mn of adult S. impressa are incorporated into the carbonate matrix during calcification, and may therefore be suitable proxies of important environmental variables such as temperature and aqueous elemental concentrations.

Trace element concentrations in ostracod shells are a vital tool for paleoenvironmental reconstructions. The most common approach used to measure trace element concentrations in ostracod shells is batch dissolution followed by analysis of the resulting solution. However, oxide coatings, secondary carbonate crusts, or adhering clay minerals can contaminate their surface with significant quantities of the trace elements of interest, which requires thorough cleaning to prevent biasing the results. Cleaning ostracod shells is time consuming and, more importantly, it is difficult to verify whether the cleaning procedure used has effectively removed all contamination. There is also the possibility that chemical cleaning procedures affect the elemental composition of the biogenic calcite, so that manual removal of contaminant phases is often the method of choice. To address this cleaning conundrum, it would be beneficial to develop a method which could identify and correct for contamination, instead of attempting to remove contaminants as has been done so far. In this study, we explore the applicability of flow-through time-resolved analysis (FT-TRA) to determine the contamination-free trace element composition of biogenic carbonate in ostracod shells. In this system, for shells with a relatively simple surface geometry, such as most ostracods, dissolution proceeds gradually from their outer to inner layers. Time-resolved eluate composition thus documents the initial dissolution of the surface layers, often contaminated with Mn-carbonates and Fe-Mn oxides coatings, followed by the dissolution of the inner layers of uncontaminated biogenic carbonate, whose elemental composition can thus be retrieved from the time series data. Partial dissolution of adhering clays can also be corrected using elemental ratios measured after total dissolution of the carbonates. As a result, unbiased elemental data can be obtained even when the shells have not been sufficiently cleaned, and the cleaning step could even be omitted. The method is sensitive enough to allow single shell measurements for many elements of interest (Mg, Sr, Ba, Mn), although elements with lower concentration (U) or higher background (Fe) require multiple shell measurements. Comparing FT-TRA and laser ablation measurements of manually cleaned ostracod shells indicate that Mg, Ba, Mn, Fe and U surface contamination can still remain despite prior manual cleaning and bias the laser ablation data. FT-TRA demonstrates that, while thorough manual cleaning can remove adhering clay minerals, it cannot effectively remove Fe-Mn oxides or Mn-carbonates incrustations. FT-TRA is thus preferable to LA-ICP-MS because it does not rely on questionable cleaning procedures.

Stable isotopes and trace elements in ostracod shells have been used widely in paleolimnological investigations of past lake hydrochemistry and climate because they provide insights into past water balance and solute evolution of lakes. Regional differences in lake characteristics and species-specific element fractionation, however, do not permit generalization of results from other regions or ostracod species to the southern Tibetan Plateau, in part because most common taxa from the southern Tibetan Plateau are endemic to the area. This study evaluated relations between present-day environmental conditions and the geochemical composition of modern ostracod shells from the southern Tibetan Plateau, to assess the suitability of using shell chemistry to infer hydrological conditions. We studied nine lakes and their catchments, located along a west–east transect in the south-central part of the Tibetan Plateau. Stable oxygen and carbon isotope values and trace element concentrations in recent shells from the four most abundant ostracod species (Leucocytherella sinensis, ?Leucocythere dorsotuberosa, Limnocythere inopinata, Tonnacypris gyirongensis) were measured, together with hydrochemical properties of host waters at the time of sampling. Results revealed significant between-species differences in stable isotope fractionation and trace element incorporation into shell calcite. Stable oxygen and carbon isotope values of ostracod shells were correlated significantly with the stable isotope composition of the respective water body $$ \left( {\updelta^{18} {\text{O}}_{{{\text{H}}_{ 2} {\text{O}}}} \,{\text{and }}\updelta^{13} {\text{C}}_{{{\text{H}}_{ 2} {\text{O}}}} } \right) $$ , reflecting salinity and productivity, respectively. Offsets between δ18Oshell and δ13Cshell and inorganic calcite, the latter representing isotopic equilibrium, suggest shell formation of T. gyirongensis during spring melt. L. sinensis reproduces throughout the monsoon season until September and shows several consecutive generations, and L. inopinata molts to the adult stage after the monsoon season in August/September. The influence of pore water δ13C was displayed by L. inopinata, suggesting shell calcification within the sediment. Mg/Cashell is primarily influenced by water Mg/Ca ratios and salinity and confirms the use of this shell ratio as a proxy for precipitation-evaporation balance and lake level. In addition, Sr/Ca and Ba/Ca can be used to infer changes in salinity, at least in closed-basin lakes with calcite saturation. Observed effects of water Sr/Ca and salinity on Sr/Ca incorporation are biased by the presence of aragonite precipitation in the lakes, which removes bioavailable Sr from the host water, resulting in low Sr/Cashell values. Changes in carbonate mineralogy affect the bioavailability of trace elements, a process that should be considered in paleoclimate reconstructions. Oxygen isotopes and Mg/Cashell ratios were unaffected by water temperature. Positive correlations among Fe/Ca, Mn/Ca and U/Ca in ostracod shells, and their negative correlation with δ13C, which reflects organic matter decay, show the potential to infer changes in redox conditions that can be used to reconstruct past oxygen supply to bottom waters and thus past water-circulation changes within lakes. The intensity of microbial activity, associated with organic matter decomposition, can be inferred from U/Ca ratios in ostracod shells. These findings highlight the value of fossil ostracod records in lake deposits for inferring paleoenvironmental conditions on the southern Tibetan Plateau.

Hydrothermal chromium (Cr) cycling contributes to marine Cr inventories and their Cr isotopic composition, yet Cr isotope effects associated with this cycling remain poorly documented. Here we determine the distribution, isotopic composition, and diagenetic mobility of Cr in hydrothermal sediments from the distal flank of the South East Pacific Rise (SEPR, DSDP-site 598). We find that Cr is primarily associated with the metalliferous iron (oxyhydr) oxide and detrital components of the sediment (0.4–3.6 mg kg⁻¹), whereas Cr concentrations are much lower in the dominant carbonate phase (80% Cr from the sediment relative to Fe. We propose this loss is tied to oxidation of authigenic Cr(III) to Cr(VI) followed by diagenetic remobilization and efflux from the sediment pile. The bulk δ⁵³Cr composition of the SEPR sediments is isotopically light (−0.24 to −0.57 ± 0.05‰) and the authigenic δ⁵³Cr is as light as −1.2 ± 0.2‰, and we argue that this light Cr isotopic composition results from the partial reduction of oxic seawater-bearing Cr(VI) by reduced hydrothermal vent fluids enriched in Fe(II)aq. Diagenetic oxidation of the reactive Cr pool by Mn-oxides and loss of Cr(VI) from the sediment may further deplete the sediment in ⁵³Cr during diagenesis. The δ⁵³Cr composition of the detrital Cr fraction of the sediment (average δ⁵³Cr composition = −0.05 ± 0.04‰) falls within the igneous silicate earth (ISE) range, revealing that detrital Cr delivered to this region of the Pacific ocean is unfractionated, and has carried a relatively constant δ⁵³Cr composition over the last 5.7 million years. Together our results show that light δ⁵³Cr compositions in hydrothermal sediments are imparted through a combination of processes previously overlooked in the marine Cr biogeochemical cycle, and that the δ⁵³Cr composition of such sediments may provide a rich source of information on paleo-marine redox conditions.

Sedimentary 231Pa/230Th ratios have been used in the Atlantic Ocean as a proxy to reconstruct past changes in the strength and geometry of the Atlantic Meridional Overturning Circulation (AMOC), stemming from the southward export of 231Pa by the North Atlantic Deep Water (NADW). However, deep waters in the Pacific Ocean have a longer residence time, so that Pacific sedimentary 231Pa/230Th ratios are more strongly affected by particle/boundary scavenging, which obscures the influence of deep water circulation. The goal of this study is to examine how the Pacific Meridional Overturning Circulation (PMOC) affects the distribution of 231Pa and 230Th in the water column and sediment of the Pacific Ocean, and to explore whether sedimentary 231Pa/230Th ratios could provide useful constraints on past changes of the deep Pacific circulation. We examine the existing Pacific sedimentary 231Pa/230Th database and demonstrate that the Pacific Meridional Overturning Circulation (PMOC) has a distinctive influence on the distribution of sedimentary 231Pa/230Th. Using a 2D scavenging model with a simplified representation of the Pacific deep water circulation, we show that Pacific sedimentary 231Pa/230Th could potentially provide information on past variability in PMOC.

We examine the dissolved inorganic carbon maximum in the Canada Basin halocline using a suite of geochemical tracers to gain insight into the factors that contribute to the persistence of this feature. Hydrographic and geochemical samples were collected in the upper 500 m of the southwestern Canada Basin water column in the summer of 2008 and fall of 2009. These observations were used to identify conservative and nonconservative processes that contribute dissolved inorganic carbon to halocline source waters, including shelf sediment organic matter remineralization, air-sea gas exchange, and sea-ice brine export. Our results indicate that the remineralization of organic matter that occurs along the Bering and Chukchi Sea shelves is the overwhelming contributor of dissolved inorganic carbon to Pacific Winter Water that occupies the middle halocline in the southwestern Canada Basin. Nonconservative contributions from air-sea exchange and sea-ice brine are not significant. The broad salinity range associated with the DIC maximum, compared to the narrow salinity range of the nutrient maximum, is due to mixing between Pacific and Atlantic water and not abiotic addition of DIC.