Beschreibung: Nutrients limiting phytoplankton growth in the ocean are a critical control on ocean productivity and can underpin predicted responses to climate change. The extensive western subtropical North Pacific is assumed to be under strong nitrogen limitation, but this is not well supported by experimental evidence. Here, we report the results of 14 factorial nitrogen–phosphorus–iron addition experiments through the Philippine Sea, which demonstrate a gradient from nitrogen limitation in the north to nitrogen–iron co-limitation in the south. While nitrogen limited sites responded weakly to nutrient supply, co-limited sites bloomed with up to ~60-fold increases in chlorophyll a biomass that was dominated by initially undetectable diatoms. The transition in limiting nutrients and phytoplankton growth capacity was driven by a gradient in deep water nutrient supply, which was undetectable in surface concentration fields. We hypothesize that this large-scale phytoplankton response gradient is both climate sensitive and potentially important for regulating the distribution of predatory fish.

Beschreibung: Stable barium isotopes are a potential proxy for riverine inputs into the ocean that reflect monsoon variability and climate change. However, dissolved Ba isotope (δ138BaDBa) geochemistry in river estuaries, a dynamic land to ocean transition zone, has rarely been systematically examined to date. Here, we show that significant Ba isotope fractionation occurs at near-zero salinities in the Yangtze and Pearl River Estuary, whereas conservative mixing dominates δ138BaDBa distributions beyond low salinities, which are well predicted by an ion exchange model. Elevated δ138BaDBa in the river endmember results from preferential removal of light Ba isotopes by adsorption to fluvial particles. Subsequently, δ138BaDBa rapidly drops to minimum signatures at increased salinities indicating particle desorption of isotopically light Ba. Nevertheless, the apparently conservative δ138BaDBa-salinity relationship beyond the low-salinity minimum in both estuaries provides a modern calibration for using Ba isotopes as a proxy for paleosalinity and river water inputs into the ocean.

Beschreibung: The development of stable barium (Ba) isotope measurements provides a novel tool to investigate the geochemical cycling of Ba in the ocean and its sediments. In sediment pore waters, gradients of dissolved Ba concentrations result from various diagenetic processes. The distribution and fractionation of Ba isotopes in the pore waters are expected to further improve our understanding of these early diagenetic control mechanisms. Here, we present pore water profiles of dissolved stable Ba isotopic signatures (δ138Bapw) from shallow water sediments covering the entire Pearl River Estuary (PRE) in Southern China. We find pronounced depth-dependent Ba isotope variations generally showing a shift from heavy to light δ138Bapw signatures from the sediment surface down to 15 cm depth. These gradients are well reproduced by a diffusion-reaction model, which generates an apparent fractionation factor (138ε) of −0.60 ± 0.10‰ pointing to preferential removal of low-mass Ba isotopes from the pore water during solution-solid phase interactions. Consequently, the combined diagenetic processes induce the highest δ138Bapw values of +0.5 to +0.7‰ in the pore waters of the topmost sediment layer. Although the detrital fraction dominates the Ba content in the PRE surface sediments, the determined gradients of pore water Ba isotopes, together with concentration variations of Ba and other redox-sensitive elements such as manganese (Mn), show that non-detrital excess Ba carriers including Mn oxides and authigenic barite clearly affect the post-depositional Ba dynamics. Stable Ba isotopes are thus a potentially powerful tracer of Ba geochemistry during early sediment diagenesis in estuarine depositional environments. Key Points We present a data set of dissolved stable Ba isotopic compositions in surface sediment pore waters of a large river estuary Pore water Ba isotope values generally decrease with increasing sediment depth, reflecting post-depositional Ba isotope fractionation A diffusion-reaction model predicts the distribution and fractionation of stable Ba isotopes in the sediment pore waters well

Beschreibung: Subtropical gyres cover 26%-29% of the world's surface ocean and are conventionally regarded as ocean deserts due to their permanent stratification, depleted surface nutrients, and low biological productivity. Despite tremendous advances over the past three decades, particularly through the Hawaii Ocean Time-series and the Bermuda Atlantic Time-series Study, which have revolutionized our understanding of the biogeochemistry in oligotrophic marine ecosystems, the gyres remain understudied. We review current understanding of upper ocean biogeochemistry in the North Pacific Subtropical Gyre, considering other subtropical gyres for comparison. We focus our synthesis on spatial variability, which shows larger than expected dynamic ranges of properties such as nutrient concentrations, rates of N-2 fixation, and biological production. This review provides new insights into how nutrient sources drive community structure and export in upper subtropical gyres. We examine the euphotic zone (EZ) in subtropical gyres as a two-layered vertically structured system: a nutrient-depleted layer above the top of the nutricline in the well-lit upper ocean and a nutrient-replete layer below in the dimly lit waters. These layers vary in nutrient supply and stoichiometries and physical forcing, promoting differences in community structure and food webs, with direct impacts on the magnitude and composition of export production. We evaluate long-term variations in key biogeochemical parameters in both of these EZ layers. Finally, we identify major knowledge gaps and research challenges in these vast and unique systems that offer opportunities for future studies. Key Points Subtropical gyres display larger spatiotemporal dynamics in biogeochemical properties than previously considered An improved two-layer framework is proposed for the study of nutrient-driven and biologically mediated carbon export in the euphotic zone Future research will benefit from high-resolution samplings, improved sensitivity of nutrient analyses, and advanced modeling capabilities