Beschreibung: New records of stable silicon isotope signatures (?30Si) together with concentrations of biogenic opal and organic carbon from the central (9°S) and northern (5°S) Peruvian margin reveal changes in diatom productivity and nutrient utilization during the past 20,000 years. The findings are based on a new approach using the difference between the ?30Si signatures of small (11-32 ?m) and large (〉150 ?m) diatom fractions (?30Si ) in combination with the variance in diatom assemblages for reconstruction Coscino-bSi of past upwelling intensity. Combination of our records with two previously published records from the southern upwelling area off Peru (12-15°S) shows a general decoupling of the environmental conditions at the central and southern shelf mainly caused by a northward shift of the main upwelling cell from its modern position (12-15°S) toward 9°S during Termination 1. At this time only moderate upwelling intensity and productivity levels prevailed between 9°S and 12°S interpreted by a more northerly position of Southern Westerly Winds and the South Pacific Subtropical High. Furthermore, a marked decrease in productivity at 12-15°S during Heinrich Stadial 1 coincided with enhanced biogenic opal production in the Eastern Equatorial Pacific, which was induced by a southward shift of the Intertropical Convergence Zone and enhanced northeasterly trade winds. Modern conditions were only established at the onset of the Holocene. Past changes in preformed ?30Si signatures of subsurface waters reaching the Peruvian Upwelling System did not significantly affect the preserved ?30Si signatures

Beschreibung: The data includes silicon isotope signatures, biogenic opal concentrations and bulk sediment nitrogen isotope signatures of three short cores between 11 and 15 degrees South of the Peruvian Coast.

Beschreibung: Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

Beschreibung: Dissolved silicon isotope compositions (d30Si) have been analysed for the first time in groundwaters of beach sediments, which represent a subterranean estuary with fresh groundwater discharge from a freshwater reservoir and mixing with recirculated seawater. The fresh groundwater reservoir has high and variable dissolved silica concentrations between 136 and 736 µM, but homogeneous d30Si of +1.0 ± 0.15 per mil. By contrast, the seawater is strongly depleted in dissolved silica with concentrations of 3 µM, and consequently characterised by high d30Si of +3.0 per mil. The beach groundwaters are variably enriched in dissolved silica compared to seawater (23-192 µM), and concentrations increase with depth at all sampling sites. The corresponding d30Si values are highly variable (+0.3 per mil to +2.2 per mil) and decrease with depth at each site. All groundwater d30Si values are lower than seawater and most values are lower than dissolved d30Si of freshwater discharge indicating a significant amount of lithogenic silica dissolution in beach sediments. In contrast to open North Sea sediments, diatom dissolution or formation of authigenic silica in beach sediments is very low (ca. 5 µmol Si g). Silica discharge from the beach to the coastal ocean is estimated as approximately 210 mol Si yr per meter shoreline. Considering the extent of coastline this is, at least for the study area, a significant amount of the total Si budget and amounts to ca. 1% of river and 3.5% of backbarrier tidal flat area Si input.

Beschreibung: Sediment pore water nutrient chemistry on surface sediments from the South Pacific Gyre. Pore waters were obtained by Rhizone sampling of sub-cores from box-cores retrieved during Expedition SO245. Nutrient were determined after three-fold dilution onboard on a QuAAtro39 autoanalyser (Seal Analytical) using the method based on Strickland and Parsons, 1972.

Beschreibung: Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.

Beschreibung: Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

Beschreibung: For this study two sediment cores from the Peruvian shelf covering the time period between the Little Ice Age (LIA) and present were examined for changes in productivity (biogenic opal concentrations (bSi)), nutrient utilisation (stable isotope compositions of silicon (δ30Siopal) and nitrogen (δ15Nsed)), as well as in ocean circulation and material transport (authigenic and detrital radiogenic neodymium (εNd) and strontium (87Sr/86Sr) isotopes). For the LIA the proxies recorded weak primary productivity and nutrient utilisation reflected by low average bSi concentrations of ~10%, δ15Nsed values of ~ +5‰ and intermediate δ30Siopal values of ~+0.97‰. At the same time the radiogenic isotope composition of the detrital sediment fraction indicates dominant local riverine input of lithogenic material due to higher rainfall in the Andean hinterland. These patterns were caused by permanent El Niño-like conditions characterized by a deeper nutricline, weak upwelling and low nutrient supply. At the end of the LIA, δ30Siopal dropped to low values of +0.6‰ and opal productivity reached its minimum of the past 650 years. During the following transitional period of time the intensity of upwelling, nutrient supply and productivity increased abruptly as marked by the highest bSi contents of up to 38%, by δ15Nsed of up to ~ +7‰, and by the highest degree of silicate utilisation with δ30Siopal reaching values of +1.1‰. At the same time detrital εNd and 87Sr/86Sr signatures documented increased wind strength and supply of dust to the shelf due to drier conditions. Since about 1870, productivity has been high but nutrient utilisation has remained at levels similar to the LIA indicating significantly increased nutrient availability. Comparison between the δ30Siopal and δ15Nsed signatures suggests that during the past 650 years the δ15Nsed signature in the Peruvian Upwelling area has most likely primarily been controlled by surface water utilisation and not, as previously assumed, by subsurface nitrogen loss processes in the water column.