Description: The Rare Earth Elements (REEs) have been widely used to investigate marine biogeochemical processes as well as the sources and mixing of water masses. However, there are still important uncertainties about the global aqueous REE cycle with respect to the contributions of highly reactive basaltic minerals originating from volcanic islands and the role of Submarine Groundwater Discharge (SGD). Here we present dissolved REE concentrations obtained from waters at the island-ocean interface (including SGD, river, lagoon and coastal waters) from the island of Tahiti and from three detailed open ocean profiles on the Manihiki Plateau (including neodymium (Nd) isotope compositions), which are located in ocean currents downstream of Tahiti. Tahitian fresh waters have highly variable REE concentrations that likely result from variable water–rock interaction and removal by secondary minerals. In contrast to studies on other islands, the SGD samples do not exhibit elevated REE concentrations but have distinctive REE distributions and Y/Ho ratios. The basaltic Tahitian rocks impart a REE pattern to the waters characterized by a middle REE enrichment, with a peak at europium similar to groundwaters and coastal waters of other volcanic islands in the Pacific. However, the basaltic island REE characteristics (with the exception of elevated Y/Ho ratios) are lost during transport to the Manihiki Plateau within surface waters that also exhibit highly radiogenic Nd isotope signatures. Our new data demonstrate that REE concentrations are enriched in Tahitian coastal water, but without multidimensional sampling, basaltic island Nd flux estimates range over orders of magnitude from relatively small to globally significant. Antarctic Intermediate Water (AAIW) loses its characteristic Nd isotopic signature (-6 to-9) around the Manihiki Plateau as a consequence of mixing with South Equatorial Pacific Intermediate Water (SEqPIW), which shows more positive values (-1 to -2). However, an additional Nd input/exchange along the pathway of AAIW, eventually originating from the volcanic Society, Tuamotu and Tubuai Islands (including Tahiti), is indicated by an offset from the mixing array of AAIW and SEqPIW to more radiogenic Nd isotope compositions.

Description: A high-resolution multiparameter stratigraphy allows the identification of late Quaternary glacial and interglacial cycles in a central Arctic Ocean sediment core. Distinct sandy layers in the upper part of the otherwise fine-grained sediment core from the Lomonosov Ridge (lat 87.5°N) correlate to four major glacials since ca. 0.7 Ma. The composition of these ice-rafted terrigenous sediments points to a glaciated northern Siberia as the main source. In contrast, lithic carbonates derived from North America are also present in older sediments and indicate a northern North American glaciation since at least 2.8 Ma. We conclude that large-scale northern Siberian glaciation began much later than other Northern Hemisphere ice sheets.

Description: We report here the discovery of Miocene, Pliocene, and early Pleistocene shallow-marine carbonates on Mayaguana Island (southeastern Bahamas) that have so far not been observed on any other Bahamian island. Spanning more than 17 m.y., but 〈12 m thick, this stratigraphic succession only occurs along the northern coast of the island, indicating that the Mayaguana Bank underwent minor subsidence throughout the late Cenozoic and was tilted toward the south during the Quaternary. In addition to considerably extending the stratigraphic record of the Bahamas Islands, our findings demonstrate that these carbonate banks were at different elevations and subsided at different rates during the Neogene. The young age of the tilting event detected on Mayaguana further shows that parts of the southeastern margin of North America have recently undergone tectonic activity a long way from its actual boundary with the Caribbean plate.

Description: Early diagenetic dolomite formation in methanogenic marine sediments is enigmatic because acidifi cation by CO2, a by-product of methanogenesis, should lead to carbonate dissolution and not precipitation. However, petrographic relationships indicate that dolomite breccia layers with δ13C values of ~+15‰, recovered from the lower slope of the Peru continental margin (Ocean Drilling Program Site 1230), formed deep in the methanogenic zone during tectonic activity of a décollement. Based on radiogenic Sr isotope ratios (87Sr/86Sr 〉 0.711) and positive δ18O values (+6‰), we present evidence that the dolomite breccias mainly formed from fl uids originating from deep sedimentary units within the accretionary prism, where they interacted with continental crust and/or siliciclastic rocks of continental affi nity. Due to silicate alteration and dehydration, such fl uids are likely alkaline and thus have the potential to neutralize the acidifi cation imposed by the high dissolved CO2 concentrations. This scenario provides a potential mechanism by which dolomite formation can be induced deep in a highly active methanogenic zone.

Description: The Asian summer monsoon affects the lives of billions of people. With the aim of identifying geochemical tracers for the monsoon-related freshwater input from the major rivers draining into the Bay of Bengal (BoB) and the Andaman Sea (AnS), we have analyzed the yttrium and rare earth element (YREE) concentration of surface seawater samples from various locations spanning the Andaman Islands in 2011 to 2013. In some locations, samples have been taken in March, July, and November 2011, thus spanning the seasonal cycle and including different monsoon phases. Generally, the YREE patterns are similar to those reported for offshore samples from the BoB and AnS in January 1997, with seawater-normalized patterns of most samples characterized by middle REE enrichments. An enhancement of these middle REE bulges accompanies large increases in dissolved REE concentrations from streams and sediment-rich areas such as mangrove environments. Conversely, some samples, in particular those taken 1–2 days after heavy rainfall in March 2011, show pronounced REE scavenging accompanied by the preferential removal of dissolved light REEs (LREEs) and by higher Y/Ho ratios. The Nd isotope signature of the remaining dissolved REE phase of these low YREE samples is more radiogenic than local rocks and sediments. The time series at a location away from local input sources show remarkably similar REE patterns and concentrations in March and July. Then in October–November, following the peak in monsoon-induced river discharge, the dissolved REE concentrations increase by almost a factor of two, whereas Nd isotopes become less radiogenic by 1.5 εNd units. These unradiogenic values are found at the same site in the winter dry season of the following year, demonstrating the decoupling of sea surface salinity (SSS) and Nd. The large sub-annual variability of YREE concentrations and Nd isotopes encountered was likely caused by the conversion of YREE from the dissolved (probably colloidal) pool to the labile particulate fraction. The comparison of unfiltered and filtered sample concentrations reveals the existence of a large labile particulate pool in the BoB and AnS that most likely originates from the massive river sediment fluxes and is instrumental in the seasonal changes observed.

Description: Largely continuous millennial-scale records of benthic delta O-18, Mg/Ca-based temperature, and salinity variations in bottom waters were obtained from Deep Sea Drilling Project (DSDP) Site 548 (East Atlantic continental margin near Ireland, 1250 m water depth) for the period 3.7-3.0 Ma ago. High epsilon(Nd) values of -10.7 to -9 show that this site monitored changes in Mediterranean Outflow Water (MOW) throughout the mid-Pliocene. Bottom water variability at Ocean Drilling Progam (ODP) Site 978 (Alboran Sea, 1930 m water depth) provides a complementary record of MOW composition near its West Mediterranean source. Both sites show a singular and persistent rise in bottom water salinities by 0.7-1.4 psu, and in densities by similar to 1 kg m(-3) from 3.5 to 3.3 Ma ago, which is matched by an similar to 3 degrees C increase in bottom water temperature at Site 548. This event suggests the onset of strongly enhanced deep-water convection in the Mediterranean Sea and a related increase in MOW flow as a result of major aridification in the Mediterranean source region. In harmony with model suggestions, the enhanced MOW flow has possibly intensified Upper North Atlantic Deep Water formation.

Description: Two Nd and Pb isotope time series of hydrogenous ferromanganese crusts, one from the Tehuantepec Ridge in the deep eastern equatorial Pacific and the other from Blake Plateau in the shallow northwestern Atlantic, which cover the past 7–8 m.y., show no variations coincident with the final closure of the Panama gateway, estimated as ca. 3.5 Ma. The record of the Atlantic crust located in the present-day Gulf Stream shows a shift in isotope composition from ca. 8 to 5 Ma that is explained by a diminishing supply of Pacific water. It is argued that the major restriction of water-mass exchange through the Panama gateway occurred before 5 Ma and thus cannot serve as a direct cause of the onset of Northern Hemisphere glaciation. The absence of a significant signature in the isotope records from the Pacific crust suggests that the volume of water exchanged with the Atlantic through shallow archipelagic straits of the gateway during the 3–4 m.y. prior to closure was too small to influence the radiogenic isotope composition of Pacific deep water.

Description: The upwelling area off Peru is characterized by exceptionally high rates of primary productivity, mainly dominated by diatoms, which require dissolved silicic acid (dSi) to construct their frustules. The silicon isotope compositions of dissolved silicic acid (δ 30 Si dSi ) and biogenic silica (δ 30 Si bSi ) in the ocean carry information about dSi utilization, dissolution, and water mass mixing. Diatoms are preserved in the underlying sediments and can serve as archives for past nutrient conditions. However, the factors influencing the Si isotope fractionation between diatoms and seawater are not fully understood. More δ 30 Si bSi data in today’s ocean are required to validate and improve the understanding of paleo records. Here, we present the first δ 30 Si bSi data (together with δ 30 Si dSi ) from the water column in the Peruvian Upwelling region. Samples were taken under strong upwelling conditions and the bSi collected from seawater consisted of more than 98% diatoms. The δ 30 Si dSi signatures in the surface waters were higher (+1.7‰ to +3.0‰) than δ 30 Si bSi (+1.0‰ to +2‰) with offsets between diatoms and seawater (Δ 30 Si) ranging from −0.4‰ to −1.0‰. In contrast, δ 30 Si dSi and δ 30 Si bSi signatures were similar in the subsurface waters of the oxygen minimum zone (OMZ) as a consequence of a decrease in δ 30 Si dSi . A strong relationship between δ 30 Si bSi and [dSi] in surface water samples supports that dSi utilization of the available pool (70 and 98%) is the main driver controlling δ 30 Si bSi . A comparison of δ 30 Si bSi samples from the water column and from underlying core-top sediments (δ 30 Si bSi_ sed. ) in the central upwelling region off Peru (10°S and 15°S) showed good agreement (δ 30 Si bSi_ sed. = +0.9‰ to +1.7‰), although we observed small differences in δ 30 Si bSi depending on the diatom size fraction and diatom assemblage. A detailed analysis of the diatom assemblages highlights apparent variability in fractionation among taxa that has to be taken into account when using δ 30 Si bSi data as a paleo proxy for the reconstruction of dSi utilization in the region.

Description: Barium (Ba) isotopes are a promising new tracer for riverine freshwater input to the ocean and marine biogeochemical cycling. However, many processes that affect Ba cycling at continental margins have not yet been investigated with respect to Ba isotope fractionation. Here, we present a comprehensive data set of Ba concentration and isotope data for water column, pore water and sediment samples from Kiel Bight, a seasonally stratified and hypoxic fjord in the southwestern Baltic Sea. The surface water Ba concentration and Ba isotope inventory of the water column can generally be explained by mixing of riverine freshwater and Atlantic seawater. However, the deep-water below the seasonal pycnocline (10 - 15 m water depth) is characterized by a pronounced positive Ba concentration anomaly (up to 915 nM) that is accompanied by a δ138Ba of ~+0.25 ‰, which is lighter than expected from the seawater-freshwater mixing line (Ba: 77 nM, δ138Ba: +0.32 ‰ at a salinity of 18). Pore water profiles indicate a Ba flux across the sediment-water interface, which contributes to the enrichment in isotopically light Ba in the deep-water. Pore waters of surface sediments and deep-waters are oversaturated with respect to barite. Therefore, barite dissolution is unlikely to account for the benthic Ba flux. Water column Ba concentrations closely correlate with those of the nutrients phosphate and silica, which are removed from surface waters by biological processes and recycled from the sediment by diffusion across the sediment-water interface. As nutrient-to-Ba ratios differ among sites and from those observed in open-marine systems, we propose that Ba is removed from surface waters by adsorption onto biogenic particles (rather than assimilation) and regenerated within surface sediments upon organic matter degradation. Pore water data for subsurface sediments in Kiel Bight indicate preferential transfer of isotopically heavy Ba into an authigenic phase during early diagenesis. Quantifying the burial flux associated with this authigenic Ba phase along continental margins could potentially help to settle the isotopic imbalance between known Ba source and sink fluxes in the ocean.

Description: The global silicon (Si) cycle plays a critical role in regulating the biological pump and the carbon cycle in the oceans. A promising tool to reconstruct past dissolved silicic acid (DSi) concentrations is the silicon isotope signature of radiolaria (δ 30 Si rad ), siliceous zooplankton that dwells at subsurface and intermediate water depths. However, to date, only a few studies on sediment δ 30 Si rad records are available. To investigate its applicability as a paleo proxy, we compare the δ 30 Si rad of different radiolarian taxa and mixed radiolarian samples from surface sediments off Peru to the DSi distribution and its δ 30 Si signatures (δ 30 Si DSi ) along the coast between the equator and 15°S. Three different radiolarian taxa were selected according to their specific habitat depths of 0–50 m ( Acrosphaera murrayana ), 50–100 m ( Dictyocoryne profunda/truncatum ), and 200–400 m ( Stylochlamydium venustum ). Additionally, samples containing a mix of species from the bulk assemblage covering habitat depths of 0 to 400 m have been analyzed for comparison. We find distinct δ 30 Si rad mean values of +0.70 ± 0.17‰ ( Acro ; 2 SD), +1.61 ± 0.20 ‰ ( Dictyo ), +1.19 ± 0.31 ‰ ( Stylo ) and +1.04 ± 0.19 ‰ (mixed radiolaria). The δ 30 Si values of all individual taxa and the mixed radiolarian samples indicate a significant ( p 〈 0.05) inverse relationship with DSi concentrations of their corresponding habitat depths. However, only δ 30 Si of A. murrayana are correlated to DSi concentrations under normally prevailing upwelling conditions. The δ 30 Si of Dictyocoryne sp., Stylochlamydium sp., and mixed radiolaria are significantly correlated to the lower DSi concentrations either associated with nutrient depletion or shallower habitat depths. Furthermore, we calculated the apparent Si isotope fractionation between radiolaria and DSi (Δ 30 Si ∼ 30 ε = δ 30 Si rad − δ 30 Si DSi ) and obtained values of −1.18 ± 0.17 ‰ ( Acro ), −0.05 ± 0.25 ‰ ( Dictyo ), −0.34 ± 0.27 ‰ ( Stylo ), and −0.62 ± 0.26 ‰ (mixed radiolaria). The significant differences in Δ 30 Si between the order of Nassellaria ( A. murrayana ) and Spumellaria ( Dictyocoryne sp. and Stylochlamydium sp.) may be explained by order-specific Si isotope fractionation during DSi uptake, similar to species-specific fractionation observed for diatoms. Overall, our study provides information on the taxon-specific fractionation factor between radiolaria and seawater and highlights the importance of taxonomic identification and separation to interpret down-core records.