Description: Precise U–Pb geochronology, Hf isotope compositions and trace element distributions in zircons are combined in the present study to define the timing and sources of the magmatism forming the Medet porphyry copper deposit, Bulgaria. ID-TIMS U–Pb-zircon dating demonstrates that ore-bearing magmatism extended for less than 1.12 Ma. As inferred from the field relationships, it started with the intrusion of a quartz-monzodiorite at 90.59 ± 0.29 Ma followed by granodiorite porphyries at 90.47 ± 0.30 and 90.27 ± 0.60 Ma and by crosscutting aplite dykes at 90.12 ± 0.36 Ma. These units were overprinted by potassic alteration and host economic copper-(Mo–Au) mineralization. The main magmatic–hydrothermal activity ceased after that, and a later quartz-granodiorite porphyry dyke, dated at 89.26 ± 0.32 Ma, only contains an uneconomic quartz–pyrite mineralization. Assimilation of Lower Paleozoic rocks with a mantle to mantle–crust signature is characteristic of the fertile magma in the Medet deposit, as defined by positive ɛ-Hf values of the inherited zircons. The positive Ce-anomalies and the higher Eu/Eu* ratios of the zircons in the mineralized Cretaceous rocks of Medet deposit argue for crystallization from a generally more oxidized magma compared to the later quartz-granodiorite porphyry dyke. A change in paleostress conditions occurred during the intrusion of the Medet pluton and its dykes. The initial stage reveals E–W extension associated with N–S compression, whereas the younger granodiorite dyke was emplaced during subsequent N–S extension. The large-scale switch of the extensional stress regime during the mineralization was favourable for ore deposition by channelling the fluids and increasing the effective permeability.

Description: High-resolution records of the natural radionuclide230Th were measured in sediments from the eastern Atlantic sector of the Antarctic circumpolar current to obtain a detailed reconstruction of the sedimentation history of this key area for global climate change during the late Quaternary. High-resolution dating rests on the assumption that the230Thex flux to the sediments is constant. Short periods of drastically increased sediment accumulation rates (up to a factor of 8) were determined in the sediments of the Antarctic zone during the climate optima at the beginning of the Holocene and the isotope stage 5e. By comparing expected and measured accumulation rate of230Thex, lateral sediment redistribution was quantified and vertical particle rain rates originating from the surface water above were calculated. We show that lateral contributions locally were up to 6.5 times higher than the vertical particle rain rates. At other locations only 15% of the expected vertical particle rain rate were deposited.

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: Ferromanganese crusts from the Atlantic, Indian and Pacific Oceans record the Nd and Pb isotope compositions of the water masses from which they form as hydrogenous precipitates. The10Be/9Be-calibrated time series for crusts are compared to estimates based on Co-contents, from which the equatorial Pacific crusts studied are inferred to have recorded ca. 60 Ma of Pacific deep water history. Time series of ɛNd show that the oceans have maintained a strong provinciality in Nd isotopic composition, determined by terrigenous inputs, over periods of up to 60 Ma. Superimposed on the distinct basin-specific signatures are variations in Nd and Pb isotope time series which have been particularly marked over the last 5 Ma. It is shown that changes in erosional inputs, particularly associated with Himalayan uplift and the northern hemisphere glaciation have influenced Indian and Atlantic Ocean deep water isotopic compositions respectively. There is no evidence so far for an imprint of the final closure of the Panama Isthmus on the Pb and Nd isotopic composition in either Atlantic or Pacific deep water masses.

Description: During late Early to Late Cretaceous, the Peruvian coastal margin underwent fast and oblique subduction and was characterized by important arc plutonism (the Peruvian Coastal Batholith) and formation of volcanosedimentary basins known as the Western Peruvian Trough (WPT). We present high-precision U–Pb ages and initial Hf isotopic compositions of zircon from conformable volcanic and crosscutting intrusive rocks within submarine volcanosedimentary strata of the WPT hosting the Perubar massive sulfide deposit. Zircons extracted from both the volcanic and intrusive rocks yield concordant U–Pb ages ranging from 67.89±0.18 Ma to 69.71±0.18 Ma, indicating that basin subsidence, submarine volcanism and plutonic activity occurred in close spatial and temporal relationship within the Andean magmatic arc during the Late Cretaceous. Field observations, satellite image interpretation, and plate reconstructions, suggest that dextral wrenching movements along crustal lineaments were related to oblique subduction. Wrench tectonics is therefore considered to be the trigger for the formation of the WPT as a series of pull-apart basins and for the emplacement of the Coastal Batholith. The zircon initial εHf values of the dated magmatic rocks fall between 5.5 and 7.4, and indicate only very subordinate influence of a sedimentary or continental component. The absence of inherited cores in the zircons suggest a complete lack of old basement below the WPT, in agreement with previous U–Pb and Sr isotopic data for batholithic rocks emplaced in the WPT area. This is supported by the presence of a most likely continuous block of dense (~3.0 g/cm3) material observed beneath the WPT area on gravimetric crustal cross sections. We suggest that this gravimetric anomaly may correspond to a piece of lithospheric mantle and/or oceanic crust inherited from a possible Late Permian–Triassic rifting. Such young and mafic crust was the most probable source for arc magmatism in the WPT area.

Description: In the early 1980s, Germany started a new era of modern Antarctic research. The Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI) was founded and important research platforms such as the German permanent station in Antarctica, today called Neumayer III, and the research icebreaker Polarstern were installed. The research primarily focused on the Atlantic sector of the Southern Ocean. In parallel, the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG) started a priority program ‘Antarctic Research’ (since 2003 called SPP-1158) to foster and intensify the cooperation between scientists from different German universities and the AWI as well as other institutes involved in polar research. Here, we review the main findings in meteorology and oceanography of the last decade, funded by the priority program. The paper presents field observations and modelling efforts, extending from the stratosphere to the deep ocean. The research spans a large range of temporal and spatial scales, including the interaction of both climate components. In particular, radiative processes, the interaction of the changing ozone layer with large-scale atmospheric circulations, and changes in the sea ice cover are discussed. Climate and weather forecast models provide an insight into the water cycle and the climate change signals associated with synoptic cyclones. Investigations of the atmospheric boundary layer focus on the interaction between atmosphere, sea ice and ocean in the vicinity of polynyas and leads. The chapters dedicated to polar oceanography review the interaction between the ocean and ice shelves with regard to the freshwater input and discuss the changes in water mass characteristics, ventilation and formation rates, crucial for the deepest limb of the global, climate-relevant meridional overturning circulation. They also highlight the associated storage of anthropogenic carbon as well as the cycling of carbon, nutrients and trace metals in the ocean with special emphasis on the Weddell Sea.

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.