Hydrodynamics and dissolved organic matter components shaped the fate of dissolved heavy metals in an intensely anthropogenically disturbed estuary.

Anthropogenic activities and natural erosion caused abundant influx of heavy metals (HMs) and organic matter (OM) into estuaries characterized by the dynamic environments governed by tidal action and river flow. Similarities and differences in the fate of HM and OM as well as the influences of OM on HMs remain incomplete in estuaries with seasonal human activity and hydrodynamic force. To address this gap, dissolved HMs (dHMs) and fluorescence dissolved OM (FDOM) were investigated in the Pearl River Estuary, a highly seasonally anthropogenic and dynamic estuary. It aimed to elucidate the effects of hydrodynamic conditions and DOM on the seasonal fate of dHMs via the multivariate statistical methods. Our findings indicated dHMs and FDOM exhibited consistently higher levels in the upper estuarine and coastal waters in both seasons, predominantly controlled by the terrestrial/anthropogenic discharge. In the wet season, dHMs and humic-like substances (HULIS) were positively correlated, showing that dHMs readily combined with HULIS. This association led to a synchronous decrease offshore along the axis of the estuary and the transport following the river plume in the surface affected by the salt wedge. Contrarily, dHMs were prone to complex with protein-like components impacted by the hydrodynamics during the dry season. Principal component analysis (PCA) results revealed the terrestrial/anthropogenic inputs and the fresh-seawater mixing process were the most crucial factors responsible for the fate of dHM in wet and dry seasons, respectively, with DOM identified as a secondary but significant influencing factor in both seasons. This study holds significance in providing valuable insights into the migration, transformation, the ultimate fate of dHMs in anthropogenically influenced estuaries, as well as the intricate dynamics governing coastal ecosystems.

Identification of anthropogenic source of Pb and Cd within two tropical seagrass species in South China: Insight from Pb and Cd isotopes.

Seagrass beds are susceptible to deterioration and heavy metals represent a crucial impact factor. The accumulation of heavy metal in two tropical seagrass species were studied in South China in this study and multiple methods were used to identify the heavy metal sources. E. acoroides (Enhalus acoroides) and T. hemperichii (Thalassia hemperichii) belong to the genus of Enhalus and Thalassia in the Hydrocharitaceae family, respectively. Heavy metal concentrations in the two seagrasses followed the order of Cr > Zn > Cu > Ni > As > Pb > Co > Cd based on the whole plant, and their bioconcentration factors were 31.8 ± 29.3 (Cr), 5.7 ± 1.3 (Zn), 7.0 ± 3.8 (Cu), 3.0 ± 1.9 (Ni), 1.2 ± 0.3 (As), 1.7 ± 0.9 (Pb), 9.1 ± 11.1 (Co) and 2.8 ± 0.6 (Cd), indicating the intense enrichment in Co and Cr within the two seagrasses. The two seagrasses were prone to accumulate all the listed heavy metals (except for As in E. acoroides), especially Co (BCFs of 1124) and Cr (BCFs of 2689) in the aboveground parts, and the belowground parts of both seagrasses also accumulated most metals (BCFs of 27) excluding Co and Pb. The Pb isotopic ratios (mean 208Pb/204Pb, 207Pb/204Pb and 206Pb/204Pb values of 38.2054, 15.5000 and 18.3240, respectively) and Cd isotopic compositions (δ114/110Cd values ranging from -0.09‰ to 0.58‰) within seagrasses indicated the anthropogenic sources of Pb and Cd including coal combustion, traffic emissions and agricultural activities. This study described the absorption characteristics of E. acoroides and T. hemperichii to some heavy metals, and further demonstrated the successful utilization of Pb and Cd isotopes as discerning markers to trace anthropogenic origins of heavy metals (mainly Pb and Cd) in seagrasses. Pb and Cd isotopes can mutually verify and be helpful to understand more information in pollution sources and improve the reliability of conclusion deduced from concentrations or a single isotope.

Saltwater intrusion regulates the distribution and partitioning of heavy metals in water in a dynamic estuary, South China.

The mixing processes of fresh-salt water in estuarine and coastal regions have a substantial impact on the characteristics of heavy metals. A study was conducted in the Pearl River Estuary (PRE), located in South China, to examine the distribution and partitioning of heavy metals and the factors that influence their presence. Results showed that the hydrodynamic force, caused by the landward intrusion of the salt wedge, was the major contributor to the aggregation of heavy metals in the northern and western PRE. Conversely, metals were diffused seaward at lower concentrations along the plume flow in surface water. The study found that some metals, including Fe, Mn, Zn and Pb, were significantly higher in surface water than in bottom water in eastern waters, but the reverse was true in the southern offshore area, where limited mixing hindered the vertical transfer of metals in the water column. The partitioning coefficients (KD) of metals varied, with Fe exhibiting the highest KD (1038 ± 1093 L/g), followed by Zn (579 ± 482 L/g) and Mn (216 ± 224). The highest KD values of metals in surface water were observed in the west coast, while the highest KD in bottom water was found in eastern areas. Furthermore, re-suspension of sediment and the mixing of seawater and freshwater offshore, caused by seawater intrusion, resulted in the partitioning of Cu, Ni and Zn towards particulate phases in offshore waters. This study provides valuable insights into the migration and transformation of heavy metals in dynamic estuaries influenced by the interaction of freshwater and saltwater and highlights the importance of continued research in this field.

Characteristics of sedimentary and dissolved heavy metals in the Chukchi plateau and adjacent waters.

Heavy metals in sediments and waters in the Chukchi Plateau and adjacent waters were investigated in this study. The results showed that most metals (especially Ni, As and Co) have accumulated in sediments, and their levels followed the order of Zn > Ni > Co > Cr > Cu > As > Pb > Cd. Spatial variations of environmental variables and metal characteristics were revealed based on the transect research. Furthermore, heavy metal concentrations presented vertical variations in water column with the levels of Ni > As > Zn > Cu > Cr > Pb > Cd > Co, and they were inhomogeneous in different water masses. This paper will be helpful to the study of the pollution and distribution of the heavy metals in Arctic Ocean and its surrounding environment.

Characteristics of nutrients and heavy metals and potential influence of their benthic fluxes in the Pearl River Estuary, South China.

Nutrient and heavy metal concentrations in porewater/overlying water and their benthic fluxes were investigated to study their accumulation and transport at the sediment-water interface and the influences of sediment in the Pearl River Estuary, China. Results revealed that distribution of nutrients and metals reflected the effects of terrestrial inputs and some physicochemical processes. Benthic fluxes also suggested that nutrients and heavy metals Pb, Zn and Cd diffused from sediment to overlying water, but not for As, Co, Cr, Fe, Mn and Ni. Exchange capacities showed that 106-108 mol nutrients and 105-107 g Pb, Zn and Cd released from sediment to overlying water annually, indicating their potential ecological threat. However, 105-109 g metals As, Co, Cr, Fe, Mn and Ni were deposited annually, which may reduce the pollution pressure caused by anthropogenic activities. This study will provide references for the potential influence of benthic fluxes on estuarine environment globally.

Heavy metal accumulation and ecological risk on four seagrass species in South China.

Zn, Pb, Cr, Cu, Ni, Cd concentration and ecological risk were studied in three bays to evaluate the heavy metal (HM) contamination of seagrasses. Seasonal HM accumulation varied according to locations, seagrass species and tissues. Halophila beccarii had much higher HM concentrations except for Cr in Zhelin Bay, however, bioconcentration factors (BCF) of Cu, Ni, Pb, Zn were higher in Liusha than Zhelin Bay. Cr was much enriched in Thalassia hemperichii and Enhalus acoroides than Halophila beccarii and Halophila ovalis. Cr, Cu, Ni, Pb were easy to accumulate in belowground tissues in Halophila ovalis. In contrast, almost all HM were more enriched in aboveground tissues in other species. Generally, BCF exceeding 1 and high metal pollution index suggested HM had potential ecological risk on seagrasses. The results provide the reference for managing and protecting seagrass ecosystem in South China, and are significant to expand the global seagrass detection network.

Distribution and potential provenance of trace elements in a 120-year dated sediment core from west Daya Bay, northeastern South China Sea.

Eighteen trace elements were analyzed in a 120-year sediment core from Daya Bay. Burial flux history and potential provenance, the relationships among trace elements, and biogenic compositions were analyzed for determining the trend and extent of trace element accumulation and identifying corresponding anthropogenic effects. Additionally, the effects of anthropogenic activities on Daya Bay were reconstructed, and a baseline/background estimation was provided for Daya Bay. The burial fluxes of V, Cr, Cd, Cu, Zn, Mn, Fe, Co, Ni, Pb, Hg, Zn, Mo, Ag, As, Se, and Tl increased from 1960 to 2010, especially after the late 1980s. Our results are useful for understanding pollution and land-sea interactions along the coasts of the South China Sea, especially in the Guangdong-Hong Kong-Macao Greater Bay Area.

Concentrations of porewater heavy metals, their benthic fluxes and the potential ecological risks in Daya Bay, South China.

Heavy metal (Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb) concentrations in surface sediment porewater and their benthic fluxes were investigated in Daya Bay, South China, to study their accumulation and transfer at the sediment-water interface, as well as the impact of human activities on heavy metals. Heavy metals in porewater displayed different patterns in three partitions (top, center and inlet), which was mainly attributed to the difference in the biogeochemical conditions, hydrodynamic force inner the bay and the human activities along the bay. Ecological risk assessment results showed that heavy metals in porewater dramatically exceeded the background values. The average release of heavy metals from sediment were (6.1 ± 3.3) × 104-(2.7 ± 1.6) × 108 g a-1 in the bay, so they had potential risks to the water environment, and sediment should be paid more attention to as the endogenesis of contamination.

A 120-year sedimentary record and its environmental implications, in a dated marine sediment core from Daya Bay in the northeastern South China Sea.

In a Daya Bay 120-year dated sediment core(1892-2010), analyses were conducted of grain-size, water content, TOC, TIC, TC, loss on ignition, TN, BSi and TP, to reconstruct the anthropogenic activity history. The entire core was divided into four periods. Multi-parametric measurements, their ratios and interrelations are seen to clearly reflect the development of agriculture, aquaculture, industry and social economy surrounding Daya Bay. The trends of TOC, TOM and BSi after 1990 may be due to mass input of nutritious matter from aquaculture and industry, whereas the trends of BSi, TOC and TOM between 1960 and 1990 were owing to aquaculture and agriculture. Two peaks of BSi, TOC and TOM in 1994 and 2002 imply that the mass input of cooling water from nuclear power plants may be a significant contributor to ecological environment changes. Finally, some proposals were put forward for the healthy and sustainable development of Daya Bay.

Simultaneous uptake of Cd from sediment, water and diet in a demersal marine goby Mugilogobius chulae.

The embryonic state of our knowledge regarding the simultaneous uptake of trace metals via multiple routes in aquatic organisms makes it difficult to accurately assess the bioaccumulation and risk of metals. This study used cadmium (Cd) and a demersal marine fish (the yellowstripe goby) as a model system to determine tissue-specific uptake of Cd under conditions of simultaneous exposure to Cd from water, sediment and diet. A triple stable isotope tracing method was used in which each exposure route was spiked by a different stable isotope (110Cd, 111Cd and 113Cd). The results revealed that the fish took up waterborne and sedimentary Cd via gills and gastrointestinal tract (GT), and that of dietary Cd was via the GT. The gills absorbed Cd predominantly from water (77.2-89.4%) whilst the GT absorbed Cd mainly from diet (81.3-98.7%). In the muscle and carcass, the Cd uptake was mainly from the diet (47.1-80.4%) and water (22.8-51.6%). Our study demonstrated that when aquatic animals were subject to simultaneous exposure through multiple uptake routes, the uptake and relative importance of each route for metal accumulation was highly tissue-specific and more complex than a single route of metal exposure.

In situ arsenic speciation and the release kinetics in coastal sediments: A case study in Daya Bay, South China Sea.

In-situ study on arsenic speciation and the release kinetics in marine sediments was scarce. In this study, the distributions of labile As and their speciation in coastal sediments of Daya Bay were obtained by separate diffusive gradients in thin films (DGT) probes. Results showed that the DGT-labile As(V) was the main speciation in surface sediments (from -20 to 0 mm) with a concentration range of 0.07-3.05 µg·L-1, while the labile As(III) was the main speciation in deep layers of sediments (from -100 to -20 mm). In coastal areas, mariculture farms was the most dominated contributor to As(V) contamination in surface sediments. Both the apparent diffusion flux estimation and the DGT induced flux in sediments (DIFS) simulation indicated that As(V) contamination in surface sediments of mariculture, harbor and petrochemical areas suffered the potential risk of As(V) release into the overlying water from sediments. DIFS modeling also found that the sediments of mariculture farms were the main sediment As pools. Linear regression analysis indicated that the mobility of As mainly attributed to the As(V) in sediments.

Contamination level, chemical fraction and ecological risk of heavy metals in sediments from Daya Bay, South China Sea.

Contamination level, chemical fraction and ecological risk of heavy metals in sediments from Daya Bay (DYB) were conducted in this study. The results revealed that the concentration of Cr, Cu, Zn, As, Cd and Pb in sediments were in the range of 36.38-90.33, 9.54-61.32, 33.54-207.33, 7.80-18.43, 0.13-0.43 and 15.89-30.01 mg kg-1, respectively, with bioavailable fractions of 13.29, 54.16, 47.60, 32.74, 68.14, 26.59%, respectively. A modified potential ecological risk index (MRI) was used for the ecological risk assessment, with ecological risk contribution ratios of 75.73, 14.29, 5.47, 1.74, 1.57 and 1.21% for Cd, As, Cu, Cr, Pb and Zn, respectively. The main contaminants were Cd and As, with their ecological risks "High" and "Moderate" levels, and their enrichment degrees "Moderately Severe" and "Moderate", respectively. The multivariate statistical analysis suggested that the various anthropogenic activities along the bay might contribute mainly to the heavy metals contamination in DYB.

Atmospheric deposition of trace elements to Daya Bay, South China Sea: Fluxes and sources.

This study was conducted from October 2015 to March 2017, with the aim of providing the first data on the fluxes and sources of wet and dry deposition of trace elements (TEs) in Daya Bay, South China Sea. Wet deposition flux of TEs was always preponderant and orders of magnitude higher than that of dry deposition owing to the high rainfall frequency in Daya Bay. The total deposition fluxes of TEs in the target area were higher than in most places worldwide, but at a moderate level within China. Wet deposition was highest in summer and lowest in winter, whereas dry deposition showed an opposite seasonal trend. The main sources of TEs in wet deposition were seasalt/dust, fossil fuel combustion, and crustal sources, and in dry deposition, they were dust/metallurgic, fossil fuel, petrochemical industry and crustal sources.

Microplastics in oysters Saccostrea cucullata along the Pearl River Estuary, China.

As a transitional zone between riverine and marine environments, an estuary plays an important role for the sources, accumulation and transport of microplastics. Although estuarine environments are hotspots of microplastic pollution, the correlation between microplastic pollution and aquatic organisms is less known. Here we investigated microplastic pollution in wild oysters Saccostrea cucullata from 11 sampling sites along the Pearl River Estuary in South China. The microplastic abundances in oysters ranged from 1.4 to 7.0 items per individual or from 1.5 to 7.2 items per gram tissue wet weight, which were positively related to those in surrounding waters. The oysters near urban areas contained significantly more microplastics than those near rural areas. Fibers accounted for 69.4% of the total microplastics in oysters. Microplastic sizes varied from 20 to 5000 µm and 83.9% of which were less than 100 µm. Light color microplastics were significantly more common than dark color ones. Based on the results, oysters are recommended as a biomonitor for the microplastic pollution in estuaries.

The porewater nutrient and heavy metal characteristics in sediment cores and their benthic fluxes in Daya Bay, South China.

Nutrient and heavy metal (Fe, Mn, Ni, Cu, Pb, Zn, Cr, Cd and As) concentrations in porewater in sediment cores and their diffusive benthic fluxes were investigated in Daya Bay, South China, to study the accumulation and transfer of nutrients/metals at the sediment-water interface, and to discuss the impact of human activities on nutrients/metals. Nutrients and heavy metals displayed different profiles in porewater, which was mainly attributed to the distinct biogeochemical conditions in sediments. Total mean fluxes of nutrients (except NO3 and NO2) and metals in study area were positive, indicating nutrients and metals diffused from the sediment to overlying water, and sediment was generally the source of nutrients/metals. Human activities and the weak hydrodynamic force made nutrients/metals accumulate in sediment, so the sediment should be paid more attention to as the endogenesis of contamination in Daya Bay waters.

Picoplankton and virioplankton abundance and community structure in Pearl River Estuary and Daya Bay, South China.

By using flow cytometry techniques, we investigated the abundance and composition of the heterotrophic prokaryotes, virioplankton and picophytoplankton community in the Pearl River Estuary and Daya Bay in the summer of 2012. We identified two subgroups of prokaryotes, high nucleic acid (HNA) and low nucleic acid (LNA), characterized by different nucleic acid contents. HNA abundance was significantly correlated with larger phytoplankton and Synechococcus (Syn) abundance, which suggested the important role of organic substrates released from primary producers on bacterial growth. Although LNA did not show any association with environmental variables, it was a vital component of the microbial community. In contrast to previous studies, the total virioplankton concentration had a poor relationship with nutrient availability. The positive relationship between large-sized phytoplankton abundance and the V-I population confirmed that V-I was a phytoplankton-infecting viral subgroup. Although the V-II group (bacteriophages) was dominant in the virioplankton community, it was not related with prokaryotic abundance, which indicated factors other than hosts controlling V-II abundance or the uncertainty of virus-host coupling. With respect to the picophytoplankton community, our results implied that river input exerted a strong limitation to Syn distribution in the estuary, while picoeukaryotes (Euk) were numerically less abundant and showed a quite different distribution pattern from that of Syn, and hence presented ecological properties distinct from Syn in our two studied areas.