Regeneration of sedimentary manganese in coastal sediments deciphered by 224Ra/228Th disequilibria.

Manganese (Mn) is a vital micronutrient and participates in multiple biochemical reactions and enzyme catalytic activities. Its cycling is tightly connected with iron (Fe) and nitrogen (N). Although coastal sediments are recognized as an important source of dissolved Mn to marine waters, this contribution remains inadequately quantified. In the summer of 2019 and 2020, we investigated benthic fluxes of dissolved Mn, Fe and ammonia (NH4+) in the Changjiang Estuary and East China Sea shelf using the 224Ra/228Th disequilibrium approach. Our results showed that the availability of reactive Mn oxides (MnD) played a crucial role in sedimentary Mn regeneration, as revealed by the positive correlation (r = 0.75, P < 0.05) between Mn fluxes and MnD contents. In addition, the positive correlation (r = 0.80, P < 0.01) between the decomposition rates of sedimentary organic matter (NH4+ flux) and Mn fluxes suggested that the reduction of MnD was mainly driven by the organic carbon oxidation. Furthermore, NH4+ and Mn fluxes exhibited an exponential increase against the product of dissolved oxygen concentration (DO) and the amplification factor of sediment surface area (ξ). In this context, ξ represents the rate of bottom water DO pumped into the sediment via physical reworking and bio-irrigation. In contrast to the most efficient Fe released from sediment overlain by hypoxic waters (DO <62.5 µM), the maximum Mn flux (63.5 ± 9.4 mmol m-2 d-1) was observed at sediment with oxygenated bottom waters (DO = 158 µM). This implies that the regeneration of Mn was associated with a more permissive redox state compared to that of Fe. We further demonstrated that Mn flux was 1-2 orders of magnitude higher than those estimated through traditional methods. Therefore, coastal sediments may contribute more Mn to ocean waters than previously thought. The precise estimation of Mn release from coastal sediments holds critical significance for research on the global Mn budget.

Spatial heterogeneity of sedimentary organic matter sources in the Yangtze River estuary: Implications from fatty acid biomarkers.

This study investigated the sources of sedimentary organic matter (OM) in the Yangtze River estuary (YRE), using multiple biomarkers. The results of stable carbon isotope (δ13C) and total organic carbon to nitrogen ratio (TOC/TN) suggests the contribution of marine-derived OM significantly increased seawards, while fatty acid (FA) composition provides more specific information on OM sources. In total, 30 components of FAs were identified at the studied 17 sites, which mainly composed of phytoplankton FA, followed by ubiquitous FA and bacterial FA, while terrestrial FA contributed less to the total FAs. Under the strong impacts of the large physicochemical gradients in the YRE, TOC, TN and FA components showed higher concentrations in the estuary mixing zone (especially within the turbidity maximum zone), attributing to their strong binding with OM-enriched fine particles. The spatial heterogeneity of sedimentary OM sources was highly impacted by salinity and Chl-a, as well as bacteria-mediated OM degradation.

Preferential remineralization of phosphorus from organic matter in river-dominated coastal sediments.

In coastal sediments characterized by substantial terrestrial input, the Redfield ratio may not be adequate to determine whether phosphorus (P) is preferentially remineralized relative to carbon (C). Employing a two end-member δ13C mixing model, we observed a gradual decrease in the fraction of terrestrial organic matter as the distance from the river mouth increased. Consequently, the C/P ratio of sedimentary organic matter before early diagenetic alteration (Cu/Pu) decreased from 213 ± 26 to 126 ± 4. In contrast, the C/P ratio of sedimentary organic matter after early diagenetic alteration (Corg/Porg) increased from 208 ± 32 to 265 ± 23. The deviation of Corg/Porg ratios from Cu/Pu ratios suggests that P was preferentially remineralized from organic matter relative to C. Moreover, the degree of preferential remineralization (DPR) of P, represented by (Corg/Porg)/(Cu/Pu), increased with the distance from the river mouth, suggesting a connection to cross-shelf transport. Besides preferential P remineralization, the control mechanisms for P regeneration from sediments strongly depend on the dissolved oxygen (DO) levels of bottom water. Under oxygenated bottom water (DO >120 µM), the precipitation of Fe oxides reduced benthic DIP flux, resulting in a C/P ratio in flux well above the Cu/Pu ratio (1813 ± 725 vs. 213 ± 26). Conversely, when bottom water DO was low (DO<100 µM), the dissolution of Fe oxides and preferential P remineralization increased DIP fluxes, but the precipitation of authigenic apatite suppressed DIP fluxes, leading to C/P ratios in flux approximating Cu/Pu ratios (129 ± 35 vs. 158 ± 10 and 200 ± 82 vs. 141 ± 7). In a moderate redox state (100 < DO <120 µM), preferential P remineralization and the dissolution of Fe oxides increased DIP fluxes, resulting in C/P ratios in flux below Cu/Pu ratios (29 ± 8 vs. 131 ± 5 and 15 ± 6 vs. 126 ± 4).

Geochemical controls on the distribution and bioavailability of heavy metals in sediments from Yangtze River to the East China Sea: Assessed by sequential extraction versus diffusive gradients in thin-films (DGT) technique.

This study conducted a comprehensive investigation on the distribution and bioavailability of heavy metals (Cr, Co, Ni, Cu, Zn, Cd and Pb) in sediments along two typical transects from Yangtze River to the East China Sea continental shelf that spanning large physicochemical gradients. Heavy metals were mainly associated with the fine-grained sediments (enriched with organic matter), exhibiting decreasing trends from nearshore to offshore sites. The turbidity maximum zone showed the highest metal concentrations, which evaluated as polluted for some tested metals (especially Cd) using the geo-accumulation index. Based on the modified BCR procedure, the non-residual fractions of Cu, Zn and Pb were higher within the turbidity maximum zone, and significantly negatively correlated with bottom water salinity. The DGT-labile metals all positively correlated with the acid-soluble metal fraction (especially for Cd, Zn and Cr), and negatively correlated with salinity (except Co). Therefore, our results suggest salinity as the key factor controlling metal bioavailability, which could further modulate metal diffusive fluxes at the sediment-water interface. Considering that DGT probes could readily capture the bioavailable metal fractions, and reflect the impacts of salinity, we suggest DGT technique can be used as a robust predictor for metal bioavailability and mobility in estuary sediments.

A global assessment of the mixed layer in coastal sediments and implications for carbon storage.

The sediment-water interface in the coastal ocean is a highly dynamic zone controlling biogeochemical fluxes of greenhouse gases, nutrients, and metals. Processes in the sediment mixed layer (SML) control the transfer and reactivity of both particulate and dissolved matter in coastal interfaces. Here we map the global distribution of the coastal SML based on excess 210Pb (210Pbex) profiles and then use a neural network model to upscale these observations. We show that highly dynamic regions such as large estuaries have thicker SMLs than most oceanic sediments. Organic carbon preservation and SMLs are inversely related as mixing stimulates oxidation in sediments which enhances organic matter decomposition. Sites with SML thickness >60 cm usually have lower organic carbon accumulation rates (<50 g C m-2 yr-1) and total organic carbon/specific surface area ratios (<0.4 mg m-2). Our global scale observations reveal that reworking can accelerate organic matter degradation and reduce carbon storage in coastal sediments.

Bacterial and Protistan Community Variation across the Changjiang Estuary to the Ocean with Multiple Environmental Gradients.

Plankton microorganisms play central roles in the marine food web and global biogeochemical cycles, while their distribution and abundance are affected by environmental variables. The determinants of microbial community composition and diversity in estuaries and surrounding waters with multiple environmental gradients at a fine scale remain largely unclear. Here, we investigated bacterial and protistan community assembly in surface waters from 27 stations across the Changjiang Estuary to the ocean, with salinity ranging from 0 to 32.1, using 16S rRNA and 18S rRNA gene amplicon sequencing. Statistical analyses revealed that salinity is the major factor structuring both bacterial and protistan communities. Salinity also acted as a significant environmental determinant influencing alpha-diversity patterns. Alpha diversity indices for bacterial and protistan communities revealed a species minimum in higher-salinity waters (22.1-32.1). Contrary to the protistan community, the highest bacterial diversity was identified in medium-salinity waters (2.8-18.8), contrasting Remane's Artenminimum concept. The distribution of major planktonic taxa followed the expected pattern, and the salinity boundary for Syndiniales was specifically identified. These findings revealed the significant effects of salinity on the microbial community across an estuary to ocean transect and the distinct response to salinity between bacterial and protistan communities.

Nutrient-rich submarine groundwater discharge fuels the largest green tide in the world.

One of the largest "green tide" (Ulva prolifera) outbreaks in the world has occurred every year from 2007 to present in the Southern Yellow Sea, China. Currently, the coastal area around Jiangsu Province (Subei Shoal region) is thought to be the origination point of these giant green tide blooms. The combination of high nutrient demand but low river discharge and other inputs suggests that there is a significant flux of submarine groundwater discharge (SGD) in this area. By using a radium mass balance model, we estimated the SGD flux in the area to be (0.7-1.4) × 109 m3 d-1 (6.1-12 cm d-1), at the high end of SGD fluxes worldwide. Geographically, Subei Shoal is less than 5% of the entire Southern Yellow Sea area, while our calculated SGD flux just for the shoal area is ~3 times larger than previously documented for the whole Southern Yellow Sea. Therefore, Subei Shoal may be considered a SGD hotspot that plays an important role in SGD associated material fluxes. Compared to inputs from local rivers, atmospheric deposition, and anthropogenic activities, SGD-derived nutrients are the main source term that can support the growth of macroalgae. We specifically highlight that this type of areas that are shallow, intensively mixed, anthropogenically polluted, sandy or muddy with heavy bio-irrigation, may have a higher risk of suffering harmful ecological problems, even with limited terrestrial runoff.

Does submarine groundwater discharge contribute to summer hypoxia in the Changjiang (Yangtze) River Estuary?

The Changjiang (Yangtze) River Estuary (CJE) is one of the largest and most intense seasonal hypoxic zones in the world. Here we examine the possibility that submarine groundwater discharge (SGD) may contribute to the summer hypoxia. Spatial distributions of bottom water 222Rn suggest a hotspot discharge area in the northern section of the CJE. SGD fluxes were estimated based on a 222Rn mass balance model and were found to range from 0.002 ± 0.004 to 0.022 ± 0.011 m3/m2/day. Higher SGD fluxes were observed during summer hypoxia period. The well-developed overlap of the distribution patterns for SGD flux and dissolved oxygen (DO) implies that SGD could be an important contributor to summer hypoxia in the region off the CJE. We suggest that SGD contributes to the seasonal hypoxia either: (1) directly via discharge of anoxic groundwaters together with reducing substances; and/or (2) indirectly by delivering excess nutrients that stimulate primary productivity with consequent consumption of DO during organic matter decomposition.

Three Gorges Dam alters the Changjiang (Yangtze) river water cycle in the dry seasons: Evidence from H-O isotopes.

As the largest hydropower project in the world, the Three Gorges Dam (TGD) has attracted great concerns in terms of its impact on the Changjiang (Yangtze) River and coastal marine environments. In this study, we measured or collected the H-O isotopic data of river water, groundwater and precipitation in the mid-lower Changjiang catchment during the dry seasons of recent years. The aim was to investigate the changes of river water cycle in response to the impoundment of the TGD. Isotopic evidences suggested that the mid-lower Changjiang river water was ultimately derived from precipitation, but dominated by the mixing of different water masses with variable sources and isotopic signals as well. The isotopic parameter "deuterium excess" (d-excess) yielded large fluctuations along the mid-lower mainstream during the initial stage of the TGD impoundment, which was inherited from the upstream water with inhomogeneous isotopic signals. However, as the reservoir water level rising to the present stage, small variability of d-excess was observed along the mid-lower mainstream. This discrepancy could be explained that the TGD impoundment had significantly altered the water cycle downstream the dam, with the rising water level increasing the residence time and enhancing the mixing of reservoir water derived from upstream. This eventually resulted in the homogenization of reservoir water, and thus small fluctuations of d-excess downstream the dam after the quasi-normal stage (2008 to present). We infer that the retention effect of large reservoirs has greatly buffered the d-excess natural variability of water cycle in large river systems. Nevertheless, more research attention has to be paid to the damming effect on the water cycle in the river, estuarine and coastal areas, especially during the dry seasons.