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Estuarine sedimentation is an important historical record of potentially toxic metal (PTM) emissions from human activities that can be used to improve environmental management. However, the contribution of different human activities to PTM deposition has not been accurately estimated, and their coupled relationship with riverine organic matter is typically not considered. In this study, we reconstruct the century-scale PTM depositional history of sediment cores from the Yangtze Grand Delta. Eight potential metal sources (PMSs) were identified using positive matrix factorization, and the results of lagged correlation determined the PMSs associated with the riverine discharge of the Yangtze River. Riverine PTMs were predominantly composed of Cr (79.0%), Ni (77.3%), and Pb (64.1%) but were deprived in Cu (34.9%). Glomalin-related soil protein (GRSP), which is a typical terrestrial refractory carbon, has a strong affinity for Cu, and contributed to 2.82-22.6% Cu deposition. The change in the PMS is mainly related to power generation, whereas the GRSP-bound PTM is mainly related to road construction and transportation. We advocate for responsible management of human activities in river catchments, particularly on coal-based power generation and road transportation, to maintain ecological security and promote the overall achievement of the Sustainable Development Goals., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Iron (Fe) plaques in coastal wetlands are widely recognized because of their strong adsorption affinity for natural particles, but their interaction behaviors and mechanisms with plastics remain unknown. Through laboratory incubation experiments, paired with multiple characterization methods and microbial analysis, this work focused on the characteristics of Fe plaques on low-density polyethylene plastic surfaces and their relationship with environmental factors in coastal wetlands (Mangrove and Spartina alterniflora soil). The results showed that iron plaques increased the adhesive force of the plastic surface from 65.25 to 300 nN and promoted the oxidation of the plastic surface. Fe plaque formation was stimulated by salinity, anaerobic conditions, natural organic matter, and a weak alkaline scenario (pH 8.0-8.3). The Fe content showed a stable positive correlation with heavy metals loading (i.e., As, Mn, Co, Cr, Pb, and Zn). Furthermore, we revealed that Fe plaque was positively regulated by Nitrospirae through 16S rRNA high-throughput sequencing analysis. Meanwhile, Verrucomicrobia and Kiritimatiellaeota. may act as depressants by consuming salt. This work illustrated that iron plaques could enhance the role of plastics in contaminant migration by altering their adsorption performance, providing new insights into plastic interface behavior and potential ecological effects in coastal wetlands., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Glomalin-related soil protein (GRSP) is a widespread recalcitrant soil protein complex that promotes the immobilization of metals in soils. Herein, we combined indoor simulation and field investigation to reveal the interfacial behaviors and ecological functions of GRSP to the three typical metals (Sr(II), Ni(II), and Cd(II)). The kinetic and isotherm data suggested that GRSP had a strong ability to adsorb the metals, which was closely related to the Hard-Soft-Acid-Base theory and the film diffusion mechanisms. Regarding environmental factors, the higher solution pH was beneficial to the adsorption of the metals onto GRSP, while the adsorption capacity decreased at lower or higher salinity due to the salting-out and Na + competition effects. Moreover, Sr(II), Ni(II), and Cd(II) showed competitive adsorption onto GRSP, which was associated with the spatial site resistance effect. By comparing the retention factors of seven natural and artificial particles, GRSP had elevated distribution coefficients in high metal concentration, while its retention factors showed a relatively lower decrease, suggesting that GRSP had excellent buffer performance for a potential metal pollution emergency. Through the continental-scale coastal regions investigation, GRSP sequestered 1.05-3.11 μmol/g Ni, 0.31-1.49 μmol/g Sr, and 0.01-0.06 μmol/g Cd with 0.54-0.91 % of the sediment mass, demonstrating its strong ability to adsorb the metals. Therefore, we advocate that GRSP, as a recalcitrant protein complex, can be considered an effective tool for buffering capacity of metal pollution and environmental capacity within coastal wetlands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Glomalin-related soil protein (GRSP) plays an important role in soil metal sequestration in coastal wetlands. Additionally, it can release dissolved organic matter (GDOM) in water-soaked condition. The purpose of this study was to clarify the variation of GRSP's heavy metal immobilisation capacity at soil profiles of coastal wetland, and explore the compositional characteristics of GDOM and its influence on the heavy metals' environmental behaviour. The results indicated that the metal immobilisation capacity of GRSP decreased with increasing burial depth. The contributions of GRSP to soil Cr, As, and Pb were higher in both mangrove soils (K. obovata and A. marina forests) than in the mudflat. Oxygen-containing functional groups of GRSP (CO, -COO - , etc.) played a positive role in heavy metals accumulation. Redundancy analysis (RDA) showed that high soil pH was not conducive to the enrichment of heavy metals by GRSP. Besides, the concentrations of GRSP-Fe showed a significant positive correlation with the concentrations of other metals (Cu, As, and Pb) in GRSP. It is speculated that the Fe minerals in GRSP contributed the enrichment of heavy metals. Based on PARAFAC modelling, four fluorescent components of GDOM were identified, including three humic-like fluorescent components and one tyrosine-like fluorescent component. The contributions of GDOM to GRSP-bound heavy metals fluctuated between 4.05 % and 88.80 %, which could enhance the fluidity of heavy metals in water and weaken the soil heavy metal immobilisation capacity of GRSP. High salinity exerted an inhibitory effect on the heavy metal content of the GDOM. This study comprehensively explored the potential of GRSP to immobilise heavy metals in wetland soils and highlighted the potential heavy metal risks associated with the GDOM component in water, which could contribute to the multidimensional assessment and control of heavy metal pollution in coastal wetlands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Microplastics (MPs) are known to act as carriers of heavy metals; however, little is known about the intrinsic chemical additives of MPs, such as hexabromocyclododecane (HBCD), in terms of the adsorption behaviors and migration risks of heavy metals on MPs. Here, we reported the potential mechanisms and risks of HBCD inherent in polystyrene (PS) MPs with Cu(II), Ni(II), and Zn(II) adsorption/desorption. A comparison of the adsorption capacity of the metals onto HBCD/PS composites (HBCD/PS) MPs (10.31-20.76 μmol/g), pure MPs (0-3.60 μmol/g), and natural minerals (0.11-13.88 μmol/g) showed that the addition of HBCD significantly promoted the metals adsorption onto the HBCD/PS MPs, and even exceeded that of natural particles. Isotherms and thermodynamic data suggested that the adsorption process of the metals onto the HBCD/PS MPs was spontaneous and endothermic, and that the adsorption was a mainly multi-ion process with an inclined direction. Furthermore, the results of SEM-EDS, FTIR, and XPS analyses, as well as density functional theory well explained that the metals were mainly adsorbed on the -O and -Br groups of the HBCD/PS MPs via electrostatic interactions and surface complexation. More importantly, by comparing the desorption activity with natural river water and seawater, HBCD inherent in MPs can enhance the long-range transfer of metals carried by the HBCD/PS MPs from contamination sources to potential sink like oceans. Thus, the HBCD/PS MPs with high loading of Cu(II), Ni(II), and Zn(II) could be potential secondary sources of these metals in seawater. Overall, these findings revealed the potential risks of flame retardant in MPs associated with metal migration, and advocated that flame retardant-related waste MPs should be included in coastal sustainable development., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

Coastal reclamation has created enormous extra land for the rapidly growing economy, but it has also caused serious environmental pollution problems and threatened the sustainable development of coastal areas. However, there are few studies focusing on the distribution patterns, geochemical speciation and ecological risks of heavy metals along the land-to-sea belt, as well as the differences between reclamation and non-reclamation. Here, we collected 69 sediment samples from four sediment types along the land-to-sea sampling belts in the reclaimed and non-reclaimed tidal flats of Jiangsu, China. Geochemical speciation and contents of heavy metals were determined to investigate their spatial distributions, ecological risks and effect factors. Results showed that As, Cd, Cr and Ni in the sediments posed considerable or moderate ecological risk according to the Ontario guidelines and sediment quality guidelines (SQGs) of USEPA, but they were lower than the SQGs of China. Higher geoaccumulation index and potential ecological risk index suggested that the sediments were moderately to heavily polluted by Cd and As. Generally, reclaimed sediments exhibited higher metal pollution levels. Additionally, reclaimed areas showed a unimodal pattern of metal content along the direction of land-to-sea, suggesting that Spartina alterniflora could accelerate the deposition and accumulation of metal pollutants caused by reclamation, and ultimately control the transfer of terrigenous metals to marine environment. We found that residual fraction was the dominant geochemical fraction for the metals determined. Reclamation processes have changed the composition of heavy metal fractions, especially Cd, Pb, Zn, and Ni. Approximately 20% of Cd existed in the acid extractable/exchangeable fraction and posed medium ecological risk according to the risk assessment code. The principal component analysis and correlation matrix further indicate that organic matter and particle size of sediment could be the major factors regulating the metal distribution, and Cd and Zn might be anthropogenic sources., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2022. Published by Elsevier B.V. All rights reserved.)

Glomalin-related soil protein (GRSP), a microbial product that can be used as a bioflocculant, is critical to metal sequestration in the ecosystem. However, the relationship between GRSP and heavy metal has not been well explored. In this study, the adsorption behaviors and mechanisms of Pb(II) and Zn(II) ions on GRSP were investigated. Results reveal that the Pb(II) and Zn(II) adsorption closely conform to the pseudo second-order model, which indicates that the chemisorption of GRSP occurred after intra-particle diffusion. The adsorption process is influenced by the degree of pollution, pH value, GRSP content in the environment. In addition, scanning electron microscopy coupled with microanalysis (SEM-EDX) reveals that the surface structure of GRSP is irregularly blocky or flaky and metal ions are uniformly distributed on the surface of GRSP. Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) analysis show that the carboxyl and nitro groups on GRSP act as ligands to form complexes with two divalent metal ions. The interaction between GRSP and the metals is mainly surface complexation. This research further reveals the dynamic response of its structural components when GRSP sequestrates heavy metals in mangrove sediment and aqueous ecosystems, demonstrating a new perspective for the transport and transformation of heavy metals onto GRSP., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Glomalin-related soil protein (GRSP) has received extensive attention due to its ability to immobilize metals in the environment. However, whether it can enter the food chain through digestion is still unclear. Mangroves occupy the transition zone between the sea and land, have important ecological functions. Mangroves suffer from fragmentation due to human activities and urbanization. A variety of waterfowls inhabit near the mangroves and ingest sediment settled on their food inadvertently or for grit; therefore, they are ideal for revealing GRSP's role in metal enrichment. In this study, we investigated the release of metals from mangrove surface sediments and GRSP through a physiologically based extraction test. The investigated metals (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in sediments and those bound to GRSP would be mainly released in the gizzard phase. GRSP appeared to be an efficient carrier of Cu, Zn, Pb, and As from sediments to the waterfowls via direct sediment ingestion. For instance, 3.21% and 3.34% of sediment Cu were released in the gizzard and intestinal phases, respectively, meanwhile GRSP-bound Cu contributed 5.04% and 5.42% to this flux. The continuum of GRSP enrichment - complexation of GRSP and metals - biological accessibility of GRSP-bound metals, influenced by both direct and indirect effects from major nutrients (e.g., C, N, P, and S) and metal contents (e.g., Cu, Cd, Ni), controlled the release of GRSP-bound metals during simulated digestion. Overall, this study provides new insights into the potential risk of GRSP acting as a metal delivery vehicle in the food chain., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Mangrove wetlands are subjected to pollution due to anthropogenic activities. Mangrove fitness is mainly determined by root exudates and microorganisms activities belowground, but the mechanisms are not yet well known. Rhizospheric interactions among mangrove sediments, microorganisms and root exudates were simulated. In particular, low-molecular-weight organic acids (LMWOA), were examined to explore the metal(loid)s rhizospheric dynamics via batch experiments. Using a combination of comparative sterilised and unsterilised sediments, LMWOA extracts and sediments constituents were examined. Factors such as the solution pH, dissolved organic carbon (DOC), arsenic and iron species and metal(loid)s in the aqueous phase were evaluated. The results show that on an average, the As decreased by 68.3 % and 42.1 % under citric and malic acid treatments, respectively, after sterilisation. In contrast, the As content increased by 29.6 % under oxalic acid treatment. Microorganisms probably facilitate sediment As release in the presence of citric and malic acids but suppress As mobilisation in the presence of oxalic acid. Fe, Mn and Al were significantly (p < 0.05) positively correlated with the trace metal(loid)s (Zn, Pb, Ni, Cu, Cr, Co, Ba, Cd and As). The solution pH was negatively correlated with the solution As. Both DOC and pH reach the peaks at the end of all treatments. The As absorption-desorption dynamics are closely linked to proton consumption, Fe-Mn-Al sedimentation of ageing performance and organic ligand complexation. The study provides an insight into the rhizospheric processes of microbial involvement and gives an enlightening understanding of the metal(loid)s redeployment for plant adaptation in mangrove wetlands., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Aquaculture effluent discharge containing heavy metals affects estuarine mangrove wetlands. Glomalin-related soil protein (GRSP) is recalcitrant organic matter that can be trapped in mangrove wetlands and is critical to metal sequestration. However, studies on the effects of long-term aquaculture effluents on metal pollution in adjacent mangrove wetlands and the ecological role of GRSP are lacking. For the first time, we revealed the effects of discharge histories (0, 8, and 14 years) of shrimp pond effluents on metals (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), including the entire process from feed to metals binding with GRSP in mangrove soils. Results showed that mangrove soils receiving the effluents generally had higher or similar metal loadings compared to the control, and long-term effluent discharge increased the potential toxicity of the metals. Aquaculture feed could be a main source of metal input. Redundancy analysis indicated that 14-year effluent discharge increased the pH, bulk density, total nitrogen, and total phosphorus of mangrove soils, reducing the potential of GRSP-bound metals. Scanning electron microscopy and infrared spectroscopy characterisation revealed that effluent disturbances changed the surface morphology and functional group contents of GRSP. This study provides insights into using GRSP as an aquaculture pollution bioindicator., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Mangroves are inter-tidal ecosystems with important global ecological roles. Today, mangroves around the world are at risk of fragmentation, especially in areas with rapid urbanization. Mangroves experiencing habitat fragmentation may be more intensely affected by human activities and a scenario that might have been ignored by previous studies on trace metal (TM) environmental geochemistry. Here, we investigated the typically fragmented habitats in a subtropical mangrove estuary (the Danshuei Basin in Taiwan Strait) to evaluate how human activities affect the geochemical behaviors of TMs. Ni, Sb, Zn, Cr, Cu, and Cd were the primary contaminants found in the mangrove patches. Metal sequestration from the riverine (Ni, Cr) and in-patch activity (Sb, Zn, Cu, Cd) are primary sources of TM's risk. Using the synthesized pollution risk assessment, we showed that most of the mangrove patches are under moderate pollution risk. A significant relationship between the TMs pollution indicators and the absorption coefficient at 254 nm (a 254 ), implying that the a 254 could be a potential convenient parameter in the TMs risk assessment, which might be partly explained by the bio-remediation of sulfate-reduction microorganism. This study demonstrates the ecological risks posed by TM pollution on urban mangrove patches and emphasizes the importance of a more comprehensive survey for estuarine mangrove patch environments to achieve Sustainable Development Goals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

River management, both modern and historical, have dramatically modified offshore environments. While numerous studies have described the modern impacts, very few have evaluated the legacies remaining from hundreds of years ago. Herein, we show trace metal enrichment in the surface sediment of the abandoned Yellow River Delta, hypothesized to be associated with ancient river management. Essentially, anthropogenic modification caused the river to shift, creating a 12.4×10 3 km 2 area with elevated trace metals; characterized by clear metal deposition gradients. Geographical factors related to the ancient river mouth had the most significant influences on Zn (explained by distance to the river mouth, DTM) and Cd (DTM and sediment salinity), while the sediment absorptive capacity was associated with the reallocation of Cu (clay, silt, and iron), Ni (clay and iron), and Pb (silt and iron). Trace metal legacies showed stronger influences on prokaryotic diversity than on micro-eukaryotic diversity, with the former best described by changes in rare, rather than dominant families and classes, and explainable by an "overlapping micro-niche" model. The ancient river's legacies provide evidence of longer-term human disturbance over hundreds of years; as its impacts on associated benthic microbiomes have led to lessons for modern-day waterway management of benthic ecosystems., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Knowledge regarding the exposure risk of heavy metals in estuarine wetland is important for people (especially fishermen and consumers of local fish) living in the coastal area and the coastal reclamation. Here, we assessed the ecological and human health risks of sediment-associated metals in the large-scale estuary area based on different sediment textures (Mud, Mud-Sand, and Sand). To investigate the potential impact of terrestrial material on the contamination risks, glomalin-related soil protein (GRSP), a recalcitrant soil protein fraction, was used. Results showed that the estuarine sediment texture played a rather important role in the heavy metal distribution, risk assessment, and the metal sequestration capacity of the land-derived GRSP fraction. We found arsenic, Pb, Cd, and Cr had the highest enrichment in the estuarine wetlands by calculating multiple contamination indices, and that confirmed similar findings of heavy metal contents, except Cd. The average pollution load index (PLI) was 1.67 in all the estuarine sediments, indicating multi-element contamination, with the Muddy sediments (PLI = 2.07) significantly higher than the Mud-Sand mixed sediments (PLI = 1.85), and the lowest (0.78 < 1) in the Sandy sediments. The health risk assessment suggested that the potential cancer risk occurred (>1.00E-6) but no obvious non-carcinogenic effects occurred (<1). Arsenic was found to be the primary contributor to non-carcinogenic risk, accounting for 44.2% of hazard index, while Ni is the primary control metal for carcinogenic risk (except arsenic in the Sandy sediments). As a proxy of terrestrial organic matter, GRSP fraction possessed a high sequestration capacity for heavy metal, especially in the Sandy sediments, and it was significantly associated with the mitigation of ecological and health risks, which may provide new insights into the in situ remediation of anoxic estuarine wetlands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Understanding bioavailable metal behaviour in situ is critical for pollution evaluation and contaminant management in mangrove wetland. Here, the diffusive gradients in thin films technique (DGT) was used for characterizing the (bio)available portions of Cr, Zn, Pb, Cu, Fe and Mn in two mangrove wetlands affected by industrial waste discharges (Jiulong Estuary) and domestic discharges (Zhangjiang Estuary), in Fujian Province, China. In addition, fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) was applied for characterizing the occurrence and behaviour of dissolved organic matter (DOM) in soil solution, as well as their feasibility for assessing behaviours of metals. The results demonstrated that the combination of DGT and EEM, which are well suitable for studying DOM impacted metal behaviors in mangrove sediments. Discharge of difference wastewater into the mangrove wetlands of Jiulong and Zhangjiang Estuaries, gave rise to the DGT-labile metal concentration of Zn > Cu > Cr > Pb and Zn > Cr > Pb > Cu, respectively. A variety of humic-like fluorescent components was characterized here, providing valuable insights into the chemical composition of DOM in rhizosphere and bulk sediment. Terrestrial humic-like compounds indicated a different binding affinity for heavy metals in mangrove sediments. These findings are useful for the future understanding of the metal speciation and molecular binding mechanisms in such mangrove wetlands., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The halophytic Avicennia marina (Forsk.) is one of the pioneer mangroves along the south coast of China. It is an appropriate material for understanding molecular mechanisms of heavy metal tolerance in mangrove plants. A forward and a reverse cDNA library was constructed by PCR-based suppressive subtractive hybridization (SSH) to isolate these tolerance-associated genes from A. marina leaves. A total of 99 ESTs obtained from the forward and reverse libraries showed significant differential expressions. Twenty-nine genes selected by SSH were studied by real-time PCR in order to analyze their expression level. Most of these genes' expression increased in leaves under Cd stress, which suggests that these genes contribute to the heavy metal tolerance in A. marina. The diversity of these genes indicated that heavy metal stress resulted in a complex response in mangrove plants. This could prove a useful approach for further exploring the molecular mechanisms behind such heavy metal tolerance., (Copyright © 2017 Elsevier Ltd. All rights reserved.)