East China Sea Sediments Research Articles

Environmental Adaptability and Roles in Ammonia Oxidation of Aerobic Ammonia-Oxidizing Microorganisms in the Surface Sediments of East China Sea.

This study investigated the community characteristics and environmental influencing factors of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) in the surface sediments of the East China Sea. The research found no consistent pattern in the richness and diversity of AOA and AOB with respect to the distance from the shore, indicating a complex interplay of factors. The expression levels of AOA amoA gene and AOB amoA gene in the surface sediments of the East China Sea ranged from 4.49 × 102 to 2.17 × 106 copies per gram of sediment and from 6.6 × 101 to 7.65 × 104 copies per gram of sediment, respectively. Salinity (31.77 to 34.53 PSU) and nitrate concentration (1.51 to 10.12 μmol/L) were identified as key environmental factors significantly affecting the AOA community, while salinity and temperature (13.71 to 19.50°C) were crucial for the AOB community. The study also found that AOA, dominated by the Nitrosopumilaceae family, exhibited higher gene expression levels than AOB, suggesting a more significant role in ammonia oxidation. The expression of AOB was sensitive to multiple environmental factors, indicating a responsive role in nitrogen cycles and ecosystem health. The findings contribute to a better understanding of the biogeochemical processes and ecological roles of ammonia-oxidizing microorganisms in marine sediments.

Coupling and Decoupling Between Sedimentary Mercury and Organic Carbon Preservation in the Oxygenated Marine Environment

AbstractMercury (Hg) enrichment relative to total organic carbon (TOC) in sedimentary records has been widely used as a volcanism proxy. However, the depositional and diagenetic effects on Hg burial are not well understood, limiting the reliability of the proxy. Here, we report a systematic investigation of Hg sedimentation under well‐oxygenated bottom water. Most of the studied cores show total mercury content (THg) to TOC ratio between 50 and 300 ppb/%, including northwest Pacific ODP Site 1208, East Equatorial Pacific ODP Sites 677 and 1241, the Antarctic Zone ODP Site 1094, and East China Sea sediment core EC2005. The consistent THg/TOC ratio confirms the strong coupling between Hg and particulate organic matter (POM) despite large differences in geographic locations, sedimentation rates, TOC content, POM sources, and early diagenetic environments. Nevertheless, the THg/TOC ratio is higher in sediments under well‐oxygenated bottom water than in those under oxygen‐depleted waters, probably as a result of a higher degree of organic matter degradation in oxygenated sediments during early diagenesis. The THg in the high TOC variability section at Site 1208 is abnormally high, resulting in decoupling between Hg and POM. Mercury in this section is still leachable by oxidizing solution and has a similar trend of variability with easily reducible iron content, implying that the metal oxide‐organic matter association might act as Hg bounding phase. We suggest that the enriched Hg is probably supplied by the neighboring high TOC sediment. Therefore, while THg/TOC > 300 ppb/% could be considered as distinct Hg enrichment in sedimentary records, the diagenetic mobilization effect should be first excluded as the possible cause as demonstrated by the records of site 1208. Our study therefore provides new insights into the Hg cycle in the modern ocean and the utilization of Hg enrichment as a volcanism proxy.

Linking Bacterial Communities to Optical-Derived Properties of Porewater DOM in Sediments in the Coastal East China Sea

Bacterial communities and porewater dissolved organic matter (DOM) pool are intimately interactive in sedimentary environments. Estuarine coastal regions are an interactive area between terrestrial and marine influences in terms of DOM origins and freshness. Yet, we know little about the relationships between the bacterial communities and DOM in those regions. In this study, porewater DOM samples were collected from 42 sites in the coastal East China Sea. The porewater DOM optical properties were determined by fluorescence and absorption spectra, while the corresponding bacterial community compositions of those sediments were examined by 16S rRNA gene high-throughput sequencing. The results showed that bacterial species richness was positively correlated with multiple terrestrial indicators based on the optical properties of DOM, which implied that heterogeneous DOM from terrestrial origins might harbor a wider spectrum of bacterial taxa in marine sediments. The analysis of the co-occurrence network of the bacterial communities showed that the edges and density for samples with low DOM freshness were 3.4 times and 3 times those for the samples with high DOM freshness, respectively. This suggested that the connection among the bacterial taxa under the lower DOM freshness condition were enhanced and that reduced freshness of DOM may encourage more complimentary utilization of resources. The findings provide a new insight into such interactive processes of heterogeneous organic matter utilization meditated by microorganisms in coastal sediments.

Methanococcoides orientis sp. nov., a methylotrophic methanogen isolated from sediment of the East China Sea.

A novel methylotrophic methanogen Methanococcoides orientis sp. nov. was isolated from East China Sea sediment. Type strain LMO-1T of Methanococcoides orientis sp. nov. was irregular 1-2 µm cocci without flagella. Strain LMO-1T could utilize a variety of methylated compounds including methanol, methylamine, dimethylamine and trimethylamine for growth and methanogenesis, while H2/CO2 or acetate could not be used for growth or methanogenesis. Optimum growth temperature was 30-35 °C, optimum pH range for growth was 7.0-7.5, while the optimum salinity spectrum for growth was 1.0%-5.0% NaCl. Based on 16S rRNA gene similarity, strain LMO-1T belongs to Methanococcoides, with the highest sequence similarity to Methanococcoides methylutens DSM 2657T (99.8 %), Methanococcoides vulcani SLH33T(99.4 %), followed by Methanococcoides alaskense AK-5T(98.1 %), Methanococcoides burtonii DSM 6242T (98.0 %). Digital DNA-DNA hybridization also showed highest similarity with Methanococcoides methylutens DSM 2657T, with the value of 58.4 %. The average nucleotide identity between strain LMO-1T and Methanococcoides methylutens DSM 2657T was 94.06 %. In summary, LMO-1T represents a novel species of the genus Methaococcoides, for which the name Methanococcoides orientis sp. nov. is proposed. The type strain is LMO-1T (=MCCC 4K00106T=JCM 39195T).

Bacterial community response to chronic heavy metal contamination in marine sediments of the East China Sea

Marine sediments act as a sink for various heavy metals, which may have profound impact on sedimentary microbiota. However, our knowledge about the collaborative response of bacterial community to chronic heavy metal contamination remains little. In this study, concentrations of seven heavy metals (As, Cd, Cr, Cu, Hg, Pb, and Zn) in sediments collected from the East China Sea were analyzed and Illumina Miseq 16 S rRNA sequencing was applied to characterize the structure of bacterial community. Microbiota inhabiting sediments in the East China Sea polluted with heavy metals showed different community composition from relatively pristine sites. The response of bacterial community to heavy metal stress was further interrogated with weighted correlation network analysis (WGCNA). WGCNA revealed ten bacterial modules exhibiting distinct co-occurrence patterns and among them, five modules were related to heavy metal pollution. Three of them were positively correlated with an increase in at least one heavy metal concentration, hubs (more influential bacterial taxa) of which were previously reported to be involved in the geochemical cycling of heavy metals or possess tolerance to heavy metals, while another two modules showed opposite patterns. Our research suggested that ecological functional transition might have occurred in East China Sea sediments by shifts of community composition with sensitive modules majorly involved in the meaningful global biogeochemical cycling of carbon, sulfur, and nitrogen replaced by more tolerant groups of bacteria due to long-term exposure to low-concentration heavy metals. Hubs may serve as indicators of perturbations of benthic bacterial community caused by heavy metal pollution and support monitoring remediation of polluted sites in marine environments.

Occurrence, congener patterns, and potential ecological risk of chlorinated paraffins in sediments of Yangtze River Estuary and adjacent East China Sea.

Chlorinated paraffins (CPs) are high production volume chemicals with immense scientific research interest due to their wide distribution, persistence, toxicity, and bioaccumulation potential. In this study, 87 surface sediments were collected from the Yangtze River Estuary (YRE) and the adjacent East China Sea (ECS). We investigated the concentrations, spatial distribution, and composition profiles of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) using ultra-high-performance liquid chromatography coupled with Orbitrap Fusion Tribrid mass spectrometry. The sedimentary concentrations of SCCPs and MCCPs ranged from 2.85 to 94.7 ng·g-1 (median 13.7 ng·g-1) and 3.33 to 77.8 ng·g-1 (median 13.3 ng·g-1), respectively. Higher CP concentrations were found in YRE sediments. The values decreased away from the location, implying a direct influence of the Yangtze River. The SCCP concentrations were higher than those of MCCPs in most sediment samples. Overall, the predominant homologs were C13Cl5-7 and C14Cl6-8 for MCCPs and SCCPs, respectively. Overall, the sediment-dwelling organisms in the region are susceptible to low ecological risks.

Distribution and environmental risk assessment of microplastics in continental shelf sediments in the southern East China Sea: A high-spatial-resolution survey

We report a high-spatial-resolution study on the distributions, characteristics, and environmental risks of microplastics in surface sediments of the southern East China Sea. Microplastics were omnipresent in the sediments (concentration range: 53.3–246.7; mean: 138.4 particles/kg dry-weight sediment) and enriched in nearshore areas close to urban centers relative to lower offshore concentrations. The microplastics identified were dominated by polyethylene (41.2%) and polyethylene terephthalate (19.9%) in polymer type, fibers (45.8%) and fragments (40.3%) in shape, 0.1–0.5 mm (61.0%) in size, and black (52.0%) in color. The benthic environment experienced low to moderate microplastic pollution, with polyvinylchloride exhibiting the highest ecological risk index. The high-resolution sampling revealed highly diverse polymer types and strongly patchy distributions of microplastic abundance and pollution indices in sediments. Results from this study imply that complex physical, biological, and topographic interactions control the distribution of microplastics and the associated environmental risks in coastal sediments.

Heavy metals in sediments of Yellow Sea and East China Sea: Chemical speciation, distribution, influence factor, and contamination

Metal species and the degree of environmental pollution are related to the hydrogen sulfide (H2S), an important product of early diagenesis that can react with metals to form stable compounds. To investigate the effects of H2S to metals and evaluate metal environment effect in the sediments of the East China Sea (ECS) and Yellow Sea (YS), geochemical characteristic and spatial distribution of nine heavy metals and H2S profile were studied. Higher H2S content and lower metal content was observed in the sediments 10 cm in depth in the North Yellow Sea and the west coast of South Korea. The pollution load index (Ipl) indicates that the southern coast of Shandong Peninsula underwent moderate pollution (Ipl=1) of heavy metals and no heavy metal pollution appeared in other areas (Ipl < 1). To some extents, the ecological risk of Cd and As enrichment was moderately severe in all stations. The chance of heavy metal combination to be toxic in ECS and YS during summer was 21%. In addition, correlation between H2S content and metals in both solid and porewater phases was obvious, corroborating important effect of H2S on metal distribution. Moreover, H2S could affect the spatial distributions of heavy metals in porewater directly and be indicative of potential biological effects of combined toxicant groups in the study region.

Distribution of eight heavy metals in the inner shelf sediments of East China Sea: Risk assessments and sources analysis

ABSTRACT Although numerous studies on heavy metals (HMs) in sediments have been carried out in the East China Sea (ECS), the knowledge on the recent pollution levels of HMs in coastal region remains not well understood due to the rapid developments of urbanization in eastern China. In this study, 23 surface samples and 4 core samples are collected in the inner shelf of the ECS. The average dry-weight concentrations follow the descending order of Zn, Cr, Ni, Pb, Cu, As, Cd, and Hg (103.6 ± 26.0, 42.8 ± 12.4, 37.0 ± 9.1, 34.7 ± 11.1, 19.5 ± 10.3, 15.7 ± 11.6, 0.056 ± 0.017, and 0.041 ± 0.017 μg g−1, respectively). HMs concentrations share a similar spatial distribution pattern of TOC content with a decreasing trend from coastline to outer sea. Additionally, HMs concentrations exhibit a decreasing trend from top to bottom sediments, especially for Hg at the open sites due to the wet and dry deposition of atmospheric Hg besides the riverine inputs. The potential ecological risk indices (PERI) values in coastal sediments were about 2–4 times higher than those in open sea. Although the Hg and Cd concentrations were lower by 2–3 orders of magnitude than those of other six metals, the PERI values of Hg (65.5) and Cd (52.1) were 3–40 times higher than those of others. The hierarchical cluster result is consistent with the PCA result, suggesting that Hg, Cd, and As have similar sources and probably mainly originated from anthropogenic emissions.

Mini review of trace metal contamination status in East China Sea sediment

This study reviewed the published papers and employed the guideline values of USEPA (ERL and ERM) and China (MSQ, Class I, II, III) to assess the contamination status of potential toxic metals in East China Sea sediment (ECS). The percentages of metal concentrations exceeding the ERL value follow the sequences: Ni (96%) > As(71%) > Cr(53%) > Cu (19%) > Zn (2.4%) > Hg (0.5%) > Pb (0.4%) > Cd (0%). The similar ranking is also seen for MSQ class I. All metal concentrations were less than the ERM value, except Ni of which value 10.3% exceeded the ERM value. The potentially ecological risk from these sedimentary metals could be reduced because they were mainly present in the residual fraction, which is not available for marine organisms. It seems that the Ni ERL value is too low (20.8. mg kg−1), close to the value (18.6 mg kg−1) of the upper continental crust, to obey.

Distribution and source of heavy metals in the sediments of the coastal East China sea: Geochemical controls and typhoon impact

The present study conducted a comprehensive study on the distribution and source of heavy metals (Cu, Zn, Ni, Pb, Cd) in the sediments of the coastal East China Sea (ECS), one of the most developed regions in China with very active land-sea interactions, using 119 surface sediment samples and a 2-m sediment core collected after super Typhoon Chan-hom in 2015. Heavy metals in the surface sediments exhibited metal-dependent and regional distribution patterns, showing higher levels in the southern inner shelf (SIS) than the Yangtze River estuary (YRE), and generally being evaluated as unpolluted to moderately polluted in the coastal ECS (except few sites adjacent to Xiangshan Harbor were strongly polluted by Cd). Based on the organic carbon isotope compositions (δ13C) data as well as the strong correlations between heavy metals and natural major elemental contents (Al2O3, Fe2O3, and SiO2), we suggest natural weathering detritus as the major source of heavy metals in the YRE region and the spatial distributions were highly controlled by sediment grain size and organic matter. In contrast, the spatial distributions of heavy metals in the SIS region were less correlated with sediment properties, due to more complex sources and stronger hydrodynamic impacts. The vertical distribution of heavy metals in the sediment core indicated significant enrichments since 1950s, but showed unusual gradually decreasing trends in top layer (30 cm–0.5 cm), attributing to the strong disturbance of super Typhoon Chan-hom on sediment transportation and metal partitioning. Besides, we also observed that heavy metal levels in shallow water regions of Zhejiang coast were reduced due to the passage of typhoon. Such strong impacts of super Typhoon Chan-hom on heavy metal distributions in the ECS indicates that the impacts of extreme hydrodynamic events should raise more concern when assessing the distribution and potential risks of contaminants in coastal regions.

Hydrodynamic sorting controls the transport and hampers source identification of terrigenous organic matter: A case study in East China Sea inner shelf and its implication

Transport of terrigenous organic matter (TerOM) in marginal seas plays an important role in marine carbon cycle which is closely related to global climate change. Suspended particulates in East China Sea (ECS) inner shelf are subject to strong influence of seasonally varied Zhe-Min Coastal Current (ZMCC) and Taiwan Warm Current (TWC). Transport of TerOM attached to the mineral particulates is therefore largely dependent on these hydrodynamic conditions. To address the transport pattern of TerOM in highly dynamic marginal seas and its implication, sediment samples were collected from ECS inner shelf and fractionated by water elutriation to simulate the hydrodynamic sorting process. Lignin phenols were determined for each fraction. The abundance of C phenols preferentially concentrated in the finer fractions, which is believed as a collective effect of hydrodynamic sorting, diagenetic reactivity and association preference of C phenols with finer sediments. In contrast to the expectation, sediments at the southernmost site did not have the highest mass percentage for the finest fraction, the lowest lignin abundance and the highest degradation status. Combining the results of lignin parameters with seawater temperature and salinity profiles, it is proposed that sediments are transported along the inner shelf southward in winter and northward in summer to some extent with the influence of seasonally varied ZMCC and TWC, induced by the seasonality of East Asia Monsoon (EAM). Finer grained sediments are more susceptible to this process. This transport pattern, which was only reported previously in ocean modeling, was firstly supported by the observation of lignin biomarkers. It is suggested that cross-shelf transport of sediments in ECS seems to be possible, but is complicated and is also affected by the seasonal variation of EAM. This study improved the understanding of hydrodynamic sorting on the transport of TerOM and carbon cycling in the marine system.

Geochemical controls on the distribution of mercury and methylmercury in sediments of the coastal East China Sea

We examined the spatial and vertical distribution of total mercury (THg) in 119 surface sediment samples and 4 sediment cores from the coastal East China Sea. The THg concentrations (3.6–69.2 μg kg−1, average 34.7 μg kg−1) in surface sediments exhibited a decreasing trend from the inner shelf towards the outer shelf. The THg levels in sediment cores showed a significant increasing trend from the bottom to the top layer. Both the spatial and vertical distribution of THg indicates the impacts of anthropogenic inputs. The THg concentrations in the surface sediments of Yangtze River estuary were strongly correlated with sediment particle size and organic matter, governing by the Yangtze River inputs. The relatively higher THg levels in the surface sediments of southern inner shelf were attributed to the stronger binding affinity of the finer-grained sediments, the nature of organic matter, as well as local inputs. The spatial distribution of toxic methylmercury (MeHg) was distinct from THg, controlled by direct terrigenous MeHg inputs and in situ MeHg formation. The net Hg methylation potential (indicated by MeHg/THg ratio) in surface sediments were significantly influenced by both geochemical factors (DO, temperature and water depth) and the physicochemical properties of sediments (grain size, TOC, S, Fe2O3 and MnO), and exhibited the highest correlation with TOC, suggesting the key role of organic matter in governing net MeHg production. Moreover, sites with high MeHg/THg ratios mainly occurred within the summer hypoxia zones adjacent to the Yangtze River estuary, suggesting special attention on Hg ecological risks should be paid in this region.

Sources and dry deposition of carbonaceous aerosols over the coastal East China Sea: Implications for anthropogenic pollutant pathways and deposition

75 paired TSP and PM2.5 samples were collected over four seasons on Huaniao Island (HNI), an island that lies downwind of continental pollutants emitted from mainland China to the East China Sea (ECS). These samples were analyzed for organic carbon (OC) and elemental carbon (EC), with a special focus on char-EC (char) and soot-EC (soot), to understand their sources, and the scale and extent of pollution and dry deposition over the coastal ECS. The results showed that char concentrations in PM2.5 and TSP averaged from 0.13 to 1.01 and 0.31–1.44 μg m−3; while for soot, they were from 0.03 to 0.21 and 0.16–0.56 μg m−3, respectively. 69.0% of the char and 36.4% of the soot were present in PM2.5. The char showed apparent seasonal variations, with highest concentrations in winter and lowest in summer; while soot displayed maximum concentrations in fall and minimum in summer. The char/soot ratios in PM2.5 averaged from 3.29 to 17.22; while for TSP, they were from 1.20 to 7.07. Both of the ratios in PM2.5 and TSP were highest in winter and lowest in fall. Comparisons of seasonal variations in OC/EC and char/soot ratios confirmed that char/soot may be a more effective indicator of carbonaceous aerosol source identification than OC/EC. Annual average atmospheric dry deposition fluxes of OC and EC into ECS were estimated to be 229 and 107 μg m−2 d−1, respectively, and their deposition fluxes significantly increased during episodes. It was estimated that the loadings of OC + EC and EC accounted for 1.3% and 4.1% of the total organic carbon and EC in ECS surface sediments, respectively, implying a relatively small contribution of OC and EC dry deposition to organic carbon burial. This finding also indicates a possibly more important contribution of wet deposition to organic carbon burial in sediments of ECS, and this factor should be considered for future study.

Spatial distributions and sources of heavy metals in sediments of the Changjiang Estuary and its adjacent coastal areas based on mercury, lead and strontium isotopic compositions

The distribution, source and fate of the heavy metals mercury (Hg) and lead (Pb) in surface sediments from the East China Sea (ECS) were studied using mercury, lead and strontium (Sr) isotopic ratios. Hydrodynamic circulation and the sedimentary depositional process within the ECS were the dominant factors controlling the distribution and fate of heavy metals, referring from relationships of heavy metals (Hg and Pb) concentrations and total organic carbon (TOC) and clay contents. Spatial variations in Hg isotopic compositions (δ202Hg) were observed in the ECS, with δ202Hg ranging from −1.86 to −0.83‰ and Δ199Hg ranging from −0.07 to +0.26‰. The high δ202Hg values and relatively negative Δ199Hg values in estuarine and inner shelf sites indicated that the riverine inputs from Changjiang River played an important role in delivering Hg to ECS. In contrast, Hg isotopic signatures in outer shelf sediments had relatively low δ202Hg and positive Δ199Hg, implying that atmospheric Hg deposition could be a relatively dominant source for Hg. Using these Hg isotope compositions, the source attributions of sediments in ECS were estimated based on a triple mixing model, suggesting that river-dominated inputs, discharging pollutants from industrial sources, and atmospheric deposition could dominate in the occurrence and fate of Hg in surface sediments of ECS. Moreover, the results of Pb and Sr isotopic ratios in surface sediment samples and potential sources showed that the Pb accumulated in the ECS was mainly from background and anthropogenic sources, with the contribution rates of 45% and 55%, respectively.

The Contribution of Opal-Associated Phosphorus to Bioavailable Phosphorus in Surface and Core Sediments in the East China Sea

To improve the burial flux calculations of bioavailable phosphorus (P) and study opal-associated P (Opal-P) in the East China Sea (ECS), surface and core sediments were collected in the Changjiang Estuary (CE) and the south of the Cheju Island. In this study, sedimentary P was operationally divided into seven different forms using modified sedimentary extraction (SEDEX) technique: LSor-P (exchangeable or loosely sorbed P), Fe-P (easily reducible or reactive ferric Fe-bound P), CFA-P (authigenic carbonate fluorapatite and biogenic apatite and CaCO3-bound P), Detr-P (detrital apatite), Org-P (organic P), Opal-P and Ref-P (refractory P). The data revealed that the concentrations of the seven different P forms rank as Detr-P > CFA-P > Org-P > Ref-P > Opal-P > Fe-P > LSor-P in surface sediments and CFA-P > Detr-P > Org-P > Ref-P > Fe-P > Opal-P > LSor-P in core sediments. The distributions of the total phosphorus (TP), TIP, CFA-P, Detr-P are similar and decrease from the CE to the south of the Cheju Island. Meanwhile, Org-P and Opal-P exhibit different distribution trends; this may be affected by the grain size and TOM. The concentrations of potentially bioavailable P are 9.6-13.0 μmol g−1 and 10.0-13.6 μmol g−1, representing 61%-70% and 41%-64% of the TP in surface and core sediments, respectively. The concentrations of Opal-P are 0.6-2.3 μmol g−1 and 0.6-1.4 μmol g−1 in surface and core sediments, accounting for 5.3%-19.8% and 4.2%-10.6% of bioavailable P, respectively. The total burial fluxes of Opal-P and bioavailable P are 1.4×109 mol yr−1 and 1.1×1010 mol yr−1 in the ECS, respectively. Opal-P represents about 12.7% of potentially bioavailable P, which should be recognized when studying P cycling in marine ecosystems.

Historical records, distributions and sources of mercury and zinc in sediments of East China sea: Implication from stable isotopic compositions

The distribution and source of mercury (Hg) and zinc (Zn) in surface sediments from East China Sea (ECS) were studied using stable isotopes. Hg concentrations in surface sediments varied from 12.6 to 133.2 ng g−1. Zn concentrations ranged between 45.9 and 133.6 ng g−1. Hydrodynamic circulation and sedimentary process within the ECS were the dominant factors controlling the distribution and fate of heavy metals, referring from relationships of Hg and Zn concentrations and total organic carbon (TOC) and clay contents. Spatial variations in Hg isotopic compositions (δ202Hg) were observed in the ECS, with δ202Hg ranging from −1.86 to −0.83‰ and Δ199Hg ranging from −0.07 to +0.26‰. The high δ202Hg values and relatively negative Δ199Hg values in estuarine and inner shelf sites indicated that the riverine inputs from Yangtze River played an important role in delivering Hg to ECS. In contrast, Hg isotopic signatures in outer shelf sediments had relatively low δ202Hg and positive Δ199Hg, implying that atmospheric Hg deposition could be relatively dominant source for Hg. Moreover, application of zinc isotopes to trace anthropogenic sources has been tested, with δ66Zn ranging from 0.20 to 0.67‰. The results showed significant variations of δ66Zn in the ECS, implying that Zn isotope compositions can be tracers of anthropogenic sources. Using these Hg isotope compositions, the source attributions of sediments in ECS were estimated based on a mixing model, suggesting that river-dominated inputs, discharging pollutants from industrial sources, and atmospheric deposition could dominate in the occurrence and fate of Hg in sediments of ECS.

Iron geochemistry and organic carbon preservation by iron (oxyhydr)oxides in surface sediments of the East China Sea and the south Yellow Sea

Abstract In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (FeAVS + carb) and magnetite (Femag) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fecarb and Femag, a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (FeHR) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of FeHR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions (fFe-OC) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the fFe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO2 release to the atmosphere. In the SYS, consistently less 13C-depleted Fe-OC relative to 13C of non-Fe-bound OC (13Cnon-Fe-OC) suggests selective sequestration of labile marine OC in the marine OC-dominated sediments of the central SYS. In the ECS, however, efficient oxidation of OC and frequent redox cycling of Fe in the unsteady depositional regimes may complicate the isotopic compositions of Fe-OC. A combination of our results and literature data demonstrates that Fe-OC contents are strongly dependent on the availability of TOC and reactive Fe, but the fFe-OC is primarily controlled by the processes of Fe redox cycling in the sediments.

Historical changes in 239Pu and 240Pu sources in sedimentary records in the East China Sea: Implications for provenance and transportation

Concentrations and isotopic compositions of plutonium (Pu) are widely used for its source identification and to determine transport processes of Pu-associated particulate matter and water. We investigated the concentrations of 239Pu and 240Pu and their ratios in a number of sediment samples from the East China Sea (ECS) collected in the summer of 2013 (August 6–28). The 239+240Pu activity concentrations in surface sediment samples were found to range between 0.048 and 0.492 Bq kg−1 and the 240Pu/239Pu atom ratios showed a similar trend as that of the 239, 240Pu activities; the Pu atom ratios ranged from 0.158 to 0.297 and were mostly higher than the mean global fallout value of 0.18. The 239, 240Pu inventories in the ECS varied widely, from 2 to 807 Bq m−2, with the highest values commonly found in the coastal areas. In the Yangtze Estuary, the mean 239+240Pu activity concentration is close to the estimated value of the suspended material from the Yangtze River catchment (0.18 Bq kg−1), and the 240Pu/239Pu atom ratio was found to be ∼0.18, which indicates that the Yangtze River input is the dominant source of Pu for this area. The total annual Yangtze River input of 239+240Pu was estimated to be 2.4×1010 Bq, which is small compared to the total amount of 239+240Pu buried, 3.1×1013 Bq in the whole ECS. The Pacific Proving Ground input appears to be the dominant source of Pu to the ECS, accounting for 45%–52% of the total inventory. The fractional amount of 239+240Pu scavenged from the total 239+240Pu transported by the Kuroshio Current (KC) and Taiwan Warm Current (TWC) into ECS sediments is estimated to be ∼10%. Our study shows that the 240Pu/239Pu atom ratio is useful not only to obtain a better insight of the biogeochemistry influenced by the KC, but also to trace the long-range transport of other particle-reactive species. Besides, the sedimentation rates obtained based on the penetration depths of 239+240Pu and vertical profiles of excess 210Pb agree within uncertainties, which suggests that 239+240Pu can potentially be used as a chronostratigraphic time marker in the marine environment.

Composition of organic sulfur in riverine and marine sediments: Insights from sulfur stable isotopes and XANES spectroscopy

Sulfur isotopes and X-ray absorption near edge structure (XANES) spectroscopy were combined to characterize/compare three operational organic sulfur (OS) pools, i.e. fulvic acid sulfur (FA-S), humic acid sulfur (HA-S) and non-chromium reducible organic sulfur (non-CROS) in marine [the East China Sea (ECS) and Jiaozhou Bay (JZB)] vs. riverine [Yangtze River (YR) and JZB tributaries] sediments. XANES results indicate that in marine sediments high valency S was the dominant OS functionality in both HA-S and FA-S, while non-CROS was dominated by low valency OS (80–92%). In the riverine sediments FA-S was dominated by high valency OS, while the average fractions of low and high valency OS in HA-S were comparable. The isotopic composition of FA-S (δ34SFA-S) and HA-S (δ34SHA-S) indicated that a substantial fraction of sulfide was incorporated into FA via sulfurization in the marine sediments, whereas terrigenous OS was almost the sole important source of HA-S. Compared with the ECS sediments, JZB sediments had more depleted 34SFA-S and a higher fraction of highly reduced FA-S due to eutrophication induced sulfurization. Relative to riverine FA-S, substantial sulfurization had not resulted in an increase in the fraction of highly reduced FA-S in marine sediments. This implies that the terrestrial systems may be much more favorable for the formation and/or preservation of highly reduced biogenic FA-S than the marine settings. The fraction of highly reduced HA-S in the JZB and its tributaries was similar, whereas the fraction was much lower in the ECS than in the YR. This indicates that highly reduced HA-S moieties in the YR may have been subject to extensive mineralization loss during transport in the large riverine/estuarine system, whereas the process in the JZB tributaries may be much weakened due to a relatively small catchment area. Distinct differences in isotopic and structural composition between humic-S (FA-S+HA-S) and non-CROS in the ECS sediments indicate that a combination of S isotopes and S-XANES is needed for characterizing the two operational pools for a better understanding the nature of OS in the ocean.