Dissolved silicon isotopic compositions in the East China Sea: Water mass mixing vs. biological fractionation

We present the first set of dissolved silicon isotope data in seawater (delta Si-30(Si(OH)4)) from the East China Sea, a large and productive marginal sea significantly influenced by the Kuroshio Current and freshwater inputs from the Changjiang (Yangtze River). In summer (August 2009), the lowest surface delta Si-30(Si(OH)4) signatures of +2.1 parts per thousand corresponding to the highest Si(OH)(4) concentrations (similar to 30.0 mu mol L-1) were observed nearshore in Changjiang Diluted Water. During advection on the East China Sea inner shelf, surface delta Si-30(Si(OH)4) increased rapidly to +3.2 parts per thousand while Si(OH)(4) became depleted, indicating increasing biological utilization of the Si(OH)(4) originating from the Changjiang Diluted Water. This is also reflected in the water column profiles characterized by a general decrease of delta Si-30(Si(OH)4) and an increase of Si(OH)(4) with depth on the East China Sea mid-shelf and slope. In winter (December 2009-January 2010), however, the delta Si-30(Si(OH)4) was nearly constant at +1.9 parts per thousand throughout the water column on the East China Sea shelf beyond the nearshore, which was a consequence of enhanced vertical mixing of the Kuroshio subsurface water. Horizontal admixture of Kuroshio surface water, which is highly fractionated in Si isotopes, was observed only beyond the shelf break. Significant seasonal differences in delta Si-30(Si(OH)4) were detected in the surface waters beyond the Changjiang Diluted Water-influenced region on the East China Sea shelf, where the winter values were similar to 1.0 parts per thousand lower than those in summer, despite the same primary Si(OH)(4) supply from the Kuroshio subsurface water during both seasons. This demonstrates significantly higher biological consumption and utilization of Si(OH)(4) in summer than in winter

Constraining the oceanic barium cycle with stable barium isotopes

Highlights • We present a Ba isotope data set of seawater, river waters and biogenic particles. • Ba isotope signatures of upper ocean waters are heavier than river and deep waters. • Adsorption of lighter Ba isotopes on biogenic particles induces the fractionation. • Ba isotopes trace land–sea interactions and ocean mixing processes. • Decoupling of Ba from major nutrients confirms Ba to be a biointermediate element. Abstract The distribution of barium (Ba) concentrations in seawater resembles that of nutrients and Ba has been widely used as a proxy of paleoproductivity. However, the exact mechanisms controlling the nutrient-like behavior, and thus the fundamentals of Ba chemistry in the ocean, have not been fully resolved. Here we present a set of full water column dissolved Ba (DBa) isotope (δ137BaDBa) profiles from the South China Sea and the East China Sea that receives large freshwater inputs from the Changjiang (Yangtze River). We find pronounced and systematic horizontal and depth dependent δ137BaDBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to +0.3‰+0.3‰), the δ137BaDBa values in the upper water column are significantly higher (+0.9‰+0.9‰) than those in the deep waters (+0.5‰+0.5‰). Moreover, δ137BaDBa signatures are essentially constant in the entire upper 100 m, in which dissolved silicon isotopes are fractionated during diatom growth resulting in the heaviest isotopic compositions in the very surface waters. Combined with the decoupling of DBa concentrations and δ137BaDBa from the concentrations of nitrate and phosphate this implies that the apparent nutrient-like fractionation of Ba isotopes in seawater is primarily induced by preferential adsorption of the lighter isotopes onto biogenic particles rather than by biological utilization. The subsurface δ137BaDBa distribution is dominated by water mass mixing. The application of stable Ba isotopes as a proxy for nutrient cycling should therefore be considered with caution and both biological and physical processes need to be considered. Clearly, however, Ba isotopes show great potential as a new tracer for land–sea interactions and ocean mixing processes

Nutrient co‐limitation in the subtropical Northwest Pacific

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

Dissolved silicon isotope dynamics in large river estuaries

Estuarine systems are of key importance for the riverine input of silicon (Si) to the ocean, which is a limiting factor of diatom productivity in coastal areas. This study presents a field dataset of surface dissolved Si isotopic compositions (30SiSi(OH)4) obtained in the estuaries of three of the world’s largest rivers, the Amazon (ARE), Yangtze (YRE), and Pearl (PRE), which cover different climate zones. While 30SiSi(OH)4 behaved conservatively in the YRE and PRE supporting a dominant control by water mass mixing, significantly increased 30SiSi(OH)4 signatures due to diatom utilization of Si(OH)4 were observed in the ARE and reflected a Si isotopic enrichment factor 30 of −1.0±0.4‰ (Rayleigh model) or −1.6±0.4‰ (steady state model). In addition, seasonal variability of Si isotope behavior in the YRE was observed by comparison to previous work and most likely resulted from changes in water residence time, temperature, and light level. Based on the 30 value obtained for the ARE, we estimate that the global average 30SiSi(OH)4 entering the ocean is 0.2-0.3‰ higher than that of the rivers due to Si retention in estuaries. This systematic modification of riverine Si isotopic compositions during estuarine mixing, as well as the seasonality of Si isotope dynamics in single estuaries, needs to be taken into account for better constraining the role of large river estuaries in the oceanic Si cycle

Nutrient regulation of biological nitrogen fixation across the tropical western North Pacific

Nitrogen fixation is critical for the biological productivity of the ocean, but clear mechanistic controls on this process remain elusive. Here, we investigate the abundance, activity, and drivers of nitrogen-fixing diazotrophs across the tropical western North Pacific. We find a basin-scale coherence of diazotroph abundances and N 2 fixation rates with the supply ratio of iron:nitrogen to the upper ocean. Across a threshold of increasing supply ratios, the abundance of nifH genes and N 2 fixation rates increased, phosphate concentrations decreased, and bioassay experiments demonstrated evidence for N 2 fixation switching from iron to phosphate limitation. In the northern South China Sea, supply ratios were hypothesized to fall around this critical threshold and bioassay experiments suggested colimitation by both iron and phosphate. Our results provide evidence for iron:nitrogen supply ratios being the most important factor in regulating the distribution of N 2 fixation across the tropical ocean

Diurnal variations of surface seawater pCO(2) in contrasting coastal environments

We examined diurnal variations of surface seawater pCO(2) (partial pressure of CO2) in a suite of coastal marine environmental systems in the vicinity of the South China Sea (SCS) from inshore and nearshore settings in Xiamen Bay, Shenhu Bay, and the southwestern Taiwan Strait, to offshore sites in the basin and on the slope of the northern South China Sea as well as in a coral reef system at Xisha Islands in the middle of the SCS. There were significant diurnal changes of surface pCO(2), ranging from 1.0 Pa to 1.6 Pa (10-16 mu atm) in the offshore and oligotrophic sites similar to 4.1 Pa in the Taiwan Strait, 5.1-15.2 Pa in Xiamen Bay and Shenhu Bay, to as high as 60.8 Pa in the coral reef system at Xisha Islands. Processes that modulate these pCO(2) diurnal variations were temperature, tide or current, and biological controls. Temperature was a major driver of the pCO(2) diurnal variability in the oligotrophic regions, while tidal effects were important in the nearshore. In the coral reef system, biological metabolism dominated variability. Diurnal variability could have a potentially important implication on the estimate of air-sea CO2 fluxes, which may result in an uncertainty of +/- 0.48-0.77 mmol C m(-2) d(-1) for the offshore sites in the SCS. Such uncertainties were larger in nearshore settings.National Science Foundation of China [90211002, 40490264, 40521003

Upper ocean biogeochemistry of the oligotrophic North Pacific Subtropical Gyre : from nutrient sources to carbon export

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 N2 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 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 euphotic zone layers. Finally, we identify major knowledge gaps and research challenges in these vast and unique systems that offer opportunities for future studies

Impact of human disturbance on the biogeochemical silicon cycle in a coastal sea revealed by silicon isotopes

Biogeochemical silicon (Si) cycling in coastal systems is highly influenced by anthropogenic perturbations in recent decades. Here, we present a systematic study on the distribution of stable Si isotopes of dissolved silicate (δ30SiDSi) in a highly eutrophic coastal system, the Baltic Sea. Besides the well-known processes, diatom production and dissolution regulating δ30SiDSi values in the water column, we combined field data with a box model to examine the role of human disturbances on Si cycling in the Baltic Sea. Results reveal that (1) damming led to increased δ30SiDSi values in water but had little impacts on their vertical distribution; (2) decrease in saltwater inflow due to enhanced thermal stratification had negligible impacts on the δ30SiDSi distribution. An atypical vertical distribution of δ30SiDSi with higher values in deep water (1.57–1.95‰) relative to those in surface water (1.24–1.68‰) was observed in the central basin. Model results suggest the role of enhanced biogenic silica (BSi) deposition and subsequently regenerated dissolved silicate (DSi) flux from sediments. Specifically, eutrophication enhances diatom production, resulting in elevated exports of highly fractionated BSi to deep water and sediments. In situ sedimentary geochemical processes, such as authigenic clay formation, further fractionate Si isotopes and increase pore-water δ30SiDSi values, which then leads to pore-water DSi flux carrying higher δ30SiDSi compositions into deep water. Our findings provide new quantitative information on how the isotope-based Si cycle responds to human perturbations in coastal seas and shed lights on shifts of Si export to open ocean