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This study examined carbonate dynamics in the northwestern South China Sea (NWSCS), an area jointly influenced by upwelling, river plumes and submarine groundwater discharge. Data were obtained from two cruises conducted in summer 2009 and 2012. In 2009, a high salinity-low temperature water mass occurred nearshore off northeastern Hainan Island, indicative of upwelling, commonly referred to as HNEU. A river plume fueled primarily by local rivers and characterized by low salinity and high temperature was observed in the NWSCS off the mainland roughly along the 30 m isobath. In 2012, coastal upwelling off northeastern Hainan Island was not detectable at the surface, but was observed at a different location off eastern Hainan Island (HEU). River plume waters in 2012 were patchily distributed, with a low salinity zone further westerly than that in 2009 and another on the mid-shelf of the NWSCS sourced from the Pearl River which reached out ∼250 km from the mouth of the Pearl River Estuary. In 2009, elevated dissolved inorganic carbon (DIC) and total alkalinity (TA) occurred in the coastal plume, where submarine groundwater discharge contributed DIC and TA additions of 38.9±20.5 and 42.5±22.3 µmol kg−1, respectively, with a DIC/TA ratio of ∼0.92, which made a minor contribution to the variation of seawater partial pressure of CO2 (pCO2), pH and the aragonite saturation state index (Ωarag). Additionally, high surface phytoplankton production consumed DIC of 10.0±10.4 µmol kg−1 but did not significantly affect TA, which dominated pCO2 drawdown in the coastal plume water and increased the pH and Ωarag at surface. Submarine groundwater discharge was also observed in the region influenced by upwelling, but to a lesser degree than that impacted by coastal plume. Lower pH and Ωarag and higher pCO2 values than in offshore waters were observed downstream of the upwelling system, attributable largely to organic matter remineralization with a DIC addition of 23.8±8.4 µmol kg−1. In 2012, submarine groundwater discharge was not detected but high phytoplankton production dominated carbonate dynamics in the coastal plume water with a net DIC consumption of 104.2 µmol kg−1, which markedly drew down sea surface pCO2 and increased pH and Ωarag. In the Pearl River Plume, the solubility-driven CO2 sink exceeded biological CO2 uptake, resulting in an additional decrease of pH and Ωarag and increase of seawater pCO2. Taken together, this study demonstrated complex spatial and year-to-year variability, and the controls of the carbonate system under the joint modulations of upwelling, river plumes and submarine groundwater discharge. A first order estimate that considered the rise of atmospheric CO2 and seawater temperature further suggested a high risk of ocean acidification in this coastal area by the end of this century, which could be amplified under the stresses of river plumes, submarine groundwater discharge and organic matter remineralization. [ABSTRACT FROM AUTHOR]

Salinity, as one of the essential physical properties of seawater, is a common tracer differentiating water masses in the ocean, which often require relatively high-resolution datasets. Limited by the coverage of direct observations, however, high-resolution spatial and temporal salinity data are not always available, which hinders the fine application of salinity data in discerning ocean processes and improved modeling of ocean physics and biogeochemistry. To supplement the salinity database, we reconstructed sea surface salinity (SSS) with reasonably high spatial resolution (0.05° × 0.05°) over 2003–2020 in the South China Sea (SCS) with a machine learning algorithm based on a combination of MODIS-Aqua remote sensing data and a large cruise observation-based dataset. The reconstructed SSS has a mean absolute error (MAE) of 0.2 when compared with our underway observations with a corresponding root mean square error (RMSE) of 0.3. The MAE between station-based observations and our reconstruction was 0.5, and the RMSE was 0.7. These validations strongly suggest that our reconstruction is highly adequate, representing at most a quarter of the identified discrepancies compared to the remote sensing SSS or two other prevalent model-derived datasets. Based on our reconstruction, the SSS in the SCS is relatively low in coastal waters, but high in the ocean basin, with a seasonal pattern with a minimum in the summer and a maximum in the winter. This spatio-temporal distribution is well consistent with the observations and is affected by the Pearl River plume, sea surface circulation, and precipitation. Using our reconstructed SSS, we were able to successfully characterize the spreading of the Pearl River and Mekong River plumes and the intrusion of the Kuroshio Current from the Pacific Ocean into the SCS. [ABSTRACT FROM AUTHOR]

The coastal ocean and marginal sea play a disproportionally important role in the release of nitrous oxide (N2O) into the atmosphere. The spatial and temporal distribution of N2O in these important source regions remains highly uncertain due to the scarcity of N2O measurements. Here we present a large data set of N2O concentrations and fluxes obtained from 10 cruises covering four seasons in the Northern South China Sea (NSCS). The study area is overall a net source of atmospheric N2O with an annual flux of 1.9 ± 1.2 × 108, 0.8 ± 0.5 × 108 and 1.2 ± 0.7 × 108 mol N2O yr−1 in the shelf, slope and basin regions, respectively. In terms of global warming potentials, the N2O emissions offset 27.8% of the CO2 sink on the shelf, and are equivalent to 3.5 and 0.2‐fold of the CO2 emission in the slope and basin of the NSCS. On the seasonal time scale, N2O flux was significantly higher in autumn and winter than in the warm seasons. The spatial variability was contrastingly less pronounced. The seasonality of N2O distribution in the shelf region was modulated by the riverine discharge, while intrusion of the Kuroshio Current exerted profound control on N2O distribution in the open waters of the NSCS. The variable relationships between N2O excess, apparent oxygen utilization, and nitrate in the shelf, NSCS basin and the Luzon Strait indicated a regional difference in N2O cycling pathways along with the impact of water mass mixing. Our study establishes a robust baseline to understand N2O distribution and flux in the NSCS. Key Points: N2O dynamics demonstrate significant seasonal, but much less pronounced spatial variations in the Northern South China SeaAnnual N2O emmision offset 28% of the CO2 sink on the shelf, and are equivalent to 249% and 23% of the CO2 emission in the slope and basinRiverine discharge and Kuroshio Current intrusions are the main drivers of N2O dynamics in the Northern South China Sea [ABSTRACT FROM AUTHOR]

Global coastal oceans as a whole represent an important carbon sink but, due to high spatial–temporal variability, a mechanistic conceptualization of the coastal carbon cycle is still under development, hindering the modelling and inclusion of coastal carbon in Earth System Models. Although temperature is considered an important control of sea surface p CO2, we show that the latitudinal distribution of global coastal surface p CO2 does not match that of temperature, and its inter-seasonal changes are substantially regulated by non-thermal factors such as water mass mixing and net primary production. These processes operate in both ocean-dominated and river-dominated margins, with carbon and nutrients sourced from the open ocean and land, respectively. These can be conceptualized by a semi-analytical framework that assesses the consumption of dissolved inorganic carbon relative to nutrients, to determine how a coastal system is a CO2 source or sink. The framework also finds utility in accounting for additional nutrients in organic forms and testing hypotheses such as using Redfield stoichiometry, and is therefore an essential step toward comprehensively understanding and modelling the role of the coastal ocean in the global carbon cycle. [ABSTRACT FROM AUTHOR]

The Indo-Pacific Intersection (IPI), centered in the Indonesian Seas (IS) and South China Sea (SCS), is a convergence zone of both hydrological and atmospheric circulations and plays an important role in the water cycle and global climatic system. This study presents a unique dataset of both 239+240Pu activities and 240Pu/239Pu atom ratios to trace Plutonium (Pu) source terms and their transport in the IPI, to examine constituent water masses, notably freshwater fluxes. The 240Pu/239Pu atom ratios in surface IPI seawater ranged from 0.194 to 0.258 with an average of 0.223 ± 0.021, values that were consistently higher than global fallout (~0.18). 239+240Pu activities ranged widely from 0.55 to 2.8 mBqm−3 with a generally accumulating trend from the western Pacific Ocean (WP) to the IPI as previously observed. We further reveal, using a two end-member mixing model between global fallout and Pacific Proving Grounds (PPG), that the PPG source contributes 34 ± 8% of the Pu to the IS. In the IS, both 239+240Pu activities and 240Pu/239Pu atom ratios further show values between those in the WP and SCS, indicating a two-endmember mixing scheme between the SCS (characteristically lower-salinity but higher PPG Pu-fraction) and the WP (higher-salinity and higher PPG Pu-fraction). We estimate the fractional contribution of the SCS water mass as 35 ± 16% in the surface mixed layer and 49 ± 14% in the IS 50–235 m depth interval. This water mass transport is equivalent to a freshwater influx of 80 ± 47 mSv from the SCS to the IS (known as the South China Sea Throughflow (SCSTF), a branch of the Indonesian Throughflow (ITF)). It accounts for over half (53 ± 31%) of the total freshwater flux transported by the ITF into the Indian Ocean and supplies ~24% the freshwater net evaporation in the Indian Ocean over the 8°N – 32°S latitudinal range, and it is thus crucial in maintaining the fresh water balance therein. This freshwater influx to the IS from the SCS also leads to a ~ 0.2 kg m−3 decrease in the mean density of the upper 235 m water layer, which serves to inhibit the transport of upper layer warm water from the western tropical Pacific warm pool into the Indian Ocean. Therefore, the SCS, together with the SCSTF, play a critical role in regulating freshwater and heat balance in the IPI and Indian Ocean. These findings have strong implications for the integrative role of the SCS and SCSTF on the Indo-Pacific climate and water cycle. • The isotopic ratio of 240Pu/239Pu in the Indo-Pacific Intersection (IPI) ranges 0.194–0.258. • Pu isotopes in the IPI suggest mixed sources from both global and Pacific Proving Grounds close-in fallouts. • The freshwater flux from the SCS to the IS amounts to 80 ± 47 mSv, contributing over half of the total ITF freshwater flux. [ABSTRACT FROM AUTHOR]

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 (δ30Si Si(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 δ30Si Si(OH)4 behaved conservatively in the YRE and PRE supporting a dominant control by water mass mixing, significantly increased δ30Si Si(OH)4 signatures due to diatom utilization of Si(OH) 4 were observed in the ARE and reflected a Si isotopic enrichment factor 30ε 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 30ε value obtained for the ARE, we estimate that the global average δ30Si Si(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. [ABSTRACT FROM AUTHOR]

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 ( δ 137 Ba DBa ) 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 δ 137 Ba DBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to + 0.3 ‰ ), the δ 137 Ba DBa values in the upper water column are significantly higher ( + 0.9 ‰ ) than those in the deep waters ( + 0.5 ‰ ). Moreover, δ 137 Ba DBa 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 δ 137 Ba DBa 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 δ 137 Ba DBa 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. [ABSTRACT FROM AUTHOR]

We present tritium (3H) and helium isotope (δ3He) data from the South China Sea (SCS), to estimate apparent oxygen utilization rates (AOURs). The observed δ3He values are close to the theoretical solubility equilibrium value of -1.7% in the upper mixed layer, followed by an increase with depth down to ~1500 m. Below 1500 m depth, δ3He is homogenously distributed with a value of 20.9% ± 1.0%. The distribution of δ3He reveals that a significant fraction of 3He throughout the water column over the entire SCS basin is allochthonous, derived from mantle sources originated from the Pacific Ocean. By using the salinity-normalized "potential" alkalinity (NPA) as a conservative mixing tracer, 3He produced by tritium decay (tritiogenic) was separated from mantle 3He, and the apparent 3H–3He ages of the SCS water masses were subsequently calculated to be 11 ± 5 years at 100 m depth and 50 ± 4 years at 1000 m. Together with the observed dissolved oxygen concentrations, we estimated the mean AOURs and obtained values of 4.15 ± 0.27 μmol kg−1·yr−1 for the depth range of 100–500 m, and 0.81 ± 0.23 μmol kg−1·yr−1 for that between 800 and 1000 m depth. The depth-integrated AOURs between 100 and 1000 m depth, yield a spatially and temporally averaged export flux of organic carbon of 1.96 ± 0.16 mol-C·m−2·yr−1, comparable with previous estimates based on either 238U/234Th disequilibrium or nutrient and oxygen mass balance calculations in the SCS. • For the first time in a marginal sea of the Pacific Ocean, "tritiogenic" 3He was separated from mantle 3He. • Apparent 3H–3He ages of the SCS water masses range from 11 ± 5 years at 100 m to 50 ± 4 years at 1000 m. • The spatially and temporally averaged export flux of organic carbon is 1.96 ± 0.16 mol-C·m−2·year−1 in the SCS. [ABSTRACT FROM AUTHOR]

• Analgorithm is developed to predict nutrient concentrations in the South China Sea. • Nutrient climatology is reconstructed based on ~ 5 million data points. • Upwelling/downwelling and the Kuroshio intrusion control the nutrient distributions. Nutrients are typically the most important determinant of the productivity of marine ecosystems. Hence, nutrients have been an essential variable of ocean observations in the modern oceanography era. Understanding of marine ecosystems and biogeochemistry, however, is largely limited by the spatiotemporal coverage of nutrient data. Herein, we developed a novel algorithm based on a large observational dataset of nutrients and their relationship with water masses indexed by temperature and salinity in the South China Sea (SCS). The algorithm yielded errors of ≤ 1.3, ≤ 0.10 and ≤ 3.5 μmol L−1 for NO 3 – + NO 2 – (N + N), phosphate and silicate, respectively. It is then applied to reconstruct nutrient concentrations primarily using temperature and salinity data archived in the World Ocean Database and Argo database during 1940–2018. It increases the nutrient data to ~ 5 million, by ca. three orders of magnitude compared to direct measurements in the SCS. This allows for a full examination of the seasonal climatology of nutrients in the SCS. In summer, in the upper 200 m, nutrient concentrations in the northwest and southernmost SCS are higher than in the rest of the SCS. An overall reversed pattern is revealed in winter, when higher nutrient concentrations are found in the central basin rather than basin margins. The Kuroshio intrusion and the vertical displacement of the nutricline, driven by upwelling/downwelling induced by horizontal convergences/divergences at both meso- and basin scales, determine the spatial and seasonal variation of nutrients. Seasonally, the Kuroshio intrusion and vertical displacements of the nutricline tend to offset the spatial variation of nutrient concentrations in spring, while they show an additive effect in the fall. [ABSTRACT FROM AUTHOR]

We examined the diurnal to seasonal dynamics of the sea surface partial pressure of carbon dioxide (p CO 2) in a subtropical nearshore estuarine system, Hangzhou Bay, adjacent to the Changjiang Estuary in the vicinity of the East China Sea, based on data collected between July 30, 2010 to September 20, 2011 by a surface buoy equipped with an autonomous p CO 2 system along with hydrological and other chemical sensors. The study site (122.37° E, 30.55° N) is influenced by the river plumes of both the Changjiang and Qiantang River and is characterized by strong tidal circulation and highly turbid waters. The amplitude of p CO 2 changes increased from winter to summer over both diurnal and spring-neap tidal cycle timescales. The average surface water p CO 2 was slightly undersaturated with respect to the atmosphere in winter (382 ± 18 μatm), but supersaturated in spring (500 ± 56 μatm) and summer (687 ± 110 μatm). Overall the study site was a source of atmospheric CO 2 with an average sea to air flux of 14 ± 9 mmol C m−2 d−1 from January to October 2011. We revealed factors controlling the p CO 2 dynamics at different timescales. Over seasonal timescales, temperature and estuarine mixing dominated the seawater p CO 2 variability. Over spring-neap tidal timescales in winter and spring, the major drivers were similarly water mass mixing and temperature. However, in summer, biological activity and air-sea exchange became the two principal factors controlling the variations in surface seawater p CO 2. Our mass balance models further suggested that biological processes impacted surface p CO 2 differently during different tidal phases. Respiration was revealed to promote the increase in p CO 2 during spring tide in August, but in neap tides of the same month biological production was evident and resulted in the drawdown of p CO 2. This is because photosynthesis was generally limited by light in summer at the study site due to high turbidity, except during neap tides when turbidity was dramatically drawn down, triggering high biological productivity. At the diurnal timescale, sea surface p CO 2 was primarily controlled by tidal mixing, except during neap tides in summer when sea surface p CO 2 was greatly influenced by biological metabolism. This study also revealed significant inter-summer differences between 2010 and 2011, showing lower sea surface p CO 2 in August 2010 as compared to August 2011, which was likely due to the enhanced biological uptake as a result of the relatively low turbidity caused by weak tidal currents and enhanced river flow in August 2010. Our study highlights a highly dynamic system primarily driven by tidal mixing, which not only modulates water mass mixing but also affects turbidity, which subsequently controls biological production. These processes led to a synergy of CO 2 dynamics in a tidally driven and highly turbid nearshore system, where high frequency time-series observations are essential to reveal the complex controls of CO 2 dynamics. • Overall tidal mixing drove seawater p CO 2 although biological metabolism did in summer. • Inter-summer variability of p CO 2 was associated with tidal currents and river inputs. • Temporally under-sampling summer neap tides can overestimate air-sea CO 2 fluxes. [ABSTRACT FROM AUTHOR]