miR397 regulates cadmium stress response by coordinating lignin polymerization in the root exodermis in Kandelia obovata.

Secondary lignification of the root exodermis of Kandelia obovata is crucial for its response to adversity such as high salinity and anaerobic environment, and this lignification is also effective in blocking cadmium transport to the roots. However, how the differences in lignification of root exodermis at different developmental stages respond to Cd stress and its regulatory mechanisms have not been revealed. In this study, after analyzing the root structure and cell wall thickness using a Phenom scanning electron microscope as well as measuring cadmium content in the root cell wall, we found that the exodermis of young and mature roots of K. obovata responded to Cd stress through the polymerization of different lignin monomers, forming two different mechanisms: chelation and blocking. Through small RNA sequencing, RLM-5'-RACE and dual luciferase transient expression system, we found that miR397 targets and regulates KoLAC4/17/7 expression. The expression of KoLAC4/17 promoted the accumulation of guaiacyl lignin during lignification and enhanced the binding of cadmium to the cell wall. Meanwhile, KoLAC7 expression promotes the accumulation of syringyl lignin during lignification, which enhances the obstruction of cadmium and improves the tolerance to cadmium. These findings enhance our understanding of the molecular mechanisms underlying the differential lignification of the root exodermis of K. obovata in response to cadmium stress, and provide scientific guidance for the conservation of mangrove forests under heavy metal pollution.

Immobilization mechanisms of Sr(II), Ni(II), and Cd(II) on glomalin-related soil protein in mangrove sediments at the microscopic scale.

Glomalin-related soil protein (GRSP) is a significant component in the sequestration of heavy metal in soils, but its mechanisms for metal adsorption are poorly known. This study combined spectroscopic data with molecular docking simulations to reveal metal adsorption onto GRSP's surface functional groups at the molecular level. The EXAFS combined with FTIR and XPS analyses indicated that the adsorption of Cd(II), Sr(II), and Ni(II) by GRSP occurred mainly through the coordination of -OH and -COOH groups with the metal. The -COOH and -OH groups bound to the metal as electron donors and the electron density of the oxygen atom decreased, suggesting that electrostatic attraction might be involved in the adsorption process. Two-dimensional correlation spectroscopy revealed that preferential adsorption occurred on GRSP for the metal in sequential order of -COOH groups followed by -OH groups. The presence of the Ni-C shell in the Ni EXAFS spectrum suggested that Ni formed organometallic complexes with the GRSP surface. However, Sr-C and Cd-C were absent in the second shell of the Sr and Cd spectra, which was attributed to the adsorption of Sr and Cd ions with large hydration ion radius by GRSP to form outer-sphere complexes. Through molecular docking simulations, negatively charged residues such as ASP151 and ASP472 in GRSP were found to provide electrostatic attraction and ligand combination for the metal adsorption, which was consistent with the spectroscopic analyses. Overall, these findings provided new insights into the interaction mechanisms between GRSP and metals, which will help deepen our understanding of the ecological functions of GRSP in metal sequestration.

Enhanced Cr(VI) stabilization by terrestrial-derived soil protein: Photoelectrochemical properties and reduction mechanisms.

Glomalin-related soil protein (GRSP) is a stable iron-organic carbon mixture that can enhance heavy metal sequestration in soils. However, the roles of GRSP in the transformation and fate of Cr(VI) have been rarely reported. Herein, we investigated the electrochemical and photocatalytic properties of GRSP and its mechanisms in Cr(VI) adsorption and reduction. Results showed that GRSP had a stronger ability for Cr(VI) adsorption and reduction than other biomaterials, with the highest adsorption amount of up to 0.126 mmol/g. The removal efficiency of Cr(VI) by GRSP was enhanced (4-7%) by ultraviolet irradiation due to the hydrated electrons produced by GRSP. Fe(II) ions, persistent free radicals, and oxygen-containing functional groups on the GRSP surface as electron donors participated in the reduction of Cr(VI) under dark condition. Moreover, Cr(III) was mainly adsorbed on the -COOH groups of GRSP via electrostatic interactions. Based on 2D correlation spectroscopy, the preferential adsorption occurred on the GRSP surface for Cr(VI) in the sequential order of CO → COO- → O-H → C-O. This work provides new insights into the Cr(VI) adsorption and reduction mechanism by GRSP. Overall, GRSP can serve as a natural iron-organic carbon for the photo-reduction of Cr(VI) pollution in environments.

Combined use of positive matrix factorization and 13C15N stable isotopes to trace organic matter-bound potential toxic metals in the urban mangrove sediments.

Coastal sediments act as sinks of sediment organic matter (SOM) and metals because of their special land-sea location and depositional properties. However, there are few reports on the correlation between the sources of organic matter (OM) and associated potential toxic metals (PTMs). In this study, we combined CN stable isotope analysis and positive matrix factorization to identify the matter and metal sources of OM and glomalin-related soil protein (GRSP) in an estuary under several decades of urbanization. The results of the positive matrix factorization (PMF) reveal a correlation between the sources of total sediment metals and the sources of OM-related metals. The sources of both SOM-bound PTMs and GRSP-bound PTMs are significantly related to the sources of total PTMs. OM sources were elucidated through 13C-15 N stable isotopes, and the potential sources of different types of OM differed. In addition, there is a significant correlation between OM-associated PTMs and organic matter sources. Interestingly, the functional groups of SOM were mainly influenced by multiple PTM sources but no OM source, while the functional groups of GRSP were regulated by a single metal source and OM source. This study deepened the understanding of the coupling between PTMs and SOM. The possibility of combined use of positive matrix factorization and 13C-15 N stable isotope tracing of metals as well as the sources of each metal fractions has been evaluated, which will provide new insights for the transportation of PTMs.

Change in glomalin-related soil protein along latitudinal gradient encompassing subtropical and temperate blue carbon zones.

Glomalin-related soil protein (GRSP), an abundant and eco-friendly bioproduct associated with arbuscular mycorrhizal fungi (AMF), contributes significantly to the soil particle aggregation and carbon sequestration. Although much research has been conducted on the storage of GRSP at different spatio-temporal scales in terrestrial ecosystems. However, the deposition of GRSP in large-scale coastal environments has not been revealed, which hinders an in-depth understanding of GRSP storage patterns and environmental controls, and this knowledge gap has become one of the key uncertainties in understanding the ecological functions of GRSP as blue carbon components in coastal environments. Therefore, we conducted large-scale experiments (spanning subtropical and warm temperate climate zones, coastlines over 2500 km) to test the relative contributions of environmental drivers that shape unique GRSP storage. In salt marshes of China, we found that the abundance of GRSP ranges from 0.29 mg g-1 to 1.10 mg g-1, and its concentration decreases with increasing latitude (R2 = 0.30, p < 0.01). The GRSP-C/SOC of salt marshes ranged from 4 % to 43 % and increased with the increase in latitude (R2 = 0.13, p < 0.05). The carbon contribution of GRSP does not follow the trend of increasing abundance, but is limited by the total amount of background organic carbon. In salt marsh wetlands, precipitation, clay content and pH are the main factors influencing GRSP storage. GRSP is positively correlated with precipitation (R2 = 0.42, p < 0.01) and clay content (R2 = 0.59, p < 0.01), but negatively correlated with pH (R2 = 0.48, p < 0.01). The relative contributions of the main factors to the GRSP differed across climatic zones. Soil properties, such as clay content and pH, explained 19.8 % of the GRSP in subtropical salt marshes (20°N < 34°N), however, in warm temperate salt marshes (34°N < 40°N), precipitation explained 18.9 % of the GRSP variation. Our study provides insight into the distribution and function of GRSP in coastal environments.

Sequestration of strontium, nickel, and cadmium on glomalin-related soil protein: Interfacial behaviors and ecological functions.

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.

Variation of glomalin-metal binding capacity in 1 m soil profiles from mangrove forests to mudflat and affected factor analysis.

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.

Uncovering the disposable face masks as vectors of metal ions (Pb(â ¡), Cd(â ¡), Sr(â ¡)) during the COVID-19 pandemic.

The demand for disposable face masks (DFMs) increased sharply in response to the COVID-19 pandemic. However, information regarding the underlying roles of the largely discarded DFMs in the environment is extremely lacking. This study focused on the pristine and UV-aged DFMs as vectors of metal ions (Pb(Ⅱ), Cd(Ⅱ), and Sr(Ⅱ)). Further, the aging mechanism of DFMs with UV radiation as well as the interaction mechanisms between DFMs and metal ions were investigated. Results revealed that the aging process would help to promote more metal ions adsorbed onto DFMs, which was mainly attributed to the presence of oxygen-containing groups on the aged DFMs. The adsorption affinity of pristine and aged DFMs for the metal ions followed Pb(Ⅱ) > Cd(Ⅱ) > Sr(Ⅱ), which was positively corrected with the electronegativity of the metals. Interestingly, we found that even if DFMs were not disrupted, DFMs had similar or even higher adsorption affinity for metals compared with other existing microplastics. Besides, regarding environmental factors, including salinity and solution pH played a crucial role in the adsorption processes, with greater adsorption capacities for pristine and aged DFMs at higher pH values and low salinity. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory further confirmed that the pristine DFMs interacted with the metals mainly through electrostatic interaction, while electrostatic interaction and surface complexation jointly regulated the adsorption of the metals onto aged DFMs. Overall, these findings would help to evaluate environmental behaviors and risks of DFMs associated with metals.

Enhanced heavy metal adsorption on microplastics by incorporating flame retardant hexabromocyclododecanes: Mechanisms and potential migration risks.

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.

Spatial heterogeneity in chemical composition and stability of glomalin-related soil protein in the coastal wetlands.

GRSP is widely distributed in coastal wetlands, and there is a tendency for it to degrade with increasing burial depth. However, the dynamic changes in the chemical composition and stability of GRSP during the burial process are still unclear. The purpose of this study is to clarify the chemical composition and accumulation characteristics of GRSP during the burial process in the Zhangjiang estuary. In a field study, soil cores to the depth of 100 cm were collected in the estuary from mangrove forests dominated by Kandelia obovata and Avicennia marina, and from mudflat. The results showed that the concentration of GRSP in mangrove forest soil was significantly higher than that in the mudflat (p < 0.05), and the C/N ratio of GRSP increased with depth at all sites. Analysis of Fourier transform infrared (FTIR) data showed that the degradation rates of the GRSP's compositions varied with increasing burial depth, with microbial action and pH possibly being the main factors affecting degradation. Values of recalcitrance index (RI) showed that the stability of GRSP increased with increasing depth, and the contribution of GRSP to soil organic carbon (SOC) also increased. This suggests that the burial process plays a role in screening and storing the stable components of GRSP. Overall, our findings suggest that the concentration and chemical composition of GRSP vary dynamically according to habitat and burial processes. In addition, the improved stability of GRSP could contribute to carbon sequestration in coastal wetlands.

Immobilization of lead(â ¡) and zinc(â ¡) onto glomalin-related soil protein (GRSP): Adsorption properties and interaction mechanisms.

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.

Extraction and purification of glomalin-related soil protein (GRSP) to determine the associated trace metal(loid)s.

Glomalin-related soil protein (GRSP) is recalcitrant compound in the soil and sediment and plays a crucial role in metal transportation. However, potential metal speciation changes during GRSP extraction remain unreported. Here, a feasible GRSP extraction and purification procotol is described for robust determination of GRSP-bound metal(loid)s. Several spectrum patterns measured before and after GRSP extraction indicate that the GRSP extraction process does not significantly affect the mineral state of the samples. Potential bias generated by simultaneous metal release during GRSP extraction can be effectively eliminated by applying complete and independent dialysis.•Na signal appeared in the X-ray photoelectron survey spectrum after GRSP extraction, suggesting that Na exchange may be a critical process in releasing metal(loid)s.•Element maps obtained using secondary ion mass spectroscopy exhibited different distribution of C-N and Fe after GRSP extraction, thus suggesting that uncoupling of the Fe-organic framework occurred during GRSP extraction, which could result in the release of organic matter and metal(loid)s.•European Community Bureau of Reference (BCR) subsequent extraction reveals that most of the metal(loid)s were extracted from the acid-exchangeable and residual fraction during GRSP extraction. Remarkable differences in the GRSP-bound metal content before and after dialysis implied that the dialysis could remove most metal(loid)s.

Coastal reclamation mediates heavy metal fractions and ecological risk in saltmarsh sediments of northern Jiangsu Province, China.

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.

Polycyclic aromatic hydrocarbons at subcritical levels as novel indicators of microbial adaptation in a pre-industrial river delta.

Marine sediment is considered a vast sink for organic pollutants including polycyclic aromatic hydrocarbons (PAHs). However, little is known about the relationship between subcritical PAH allocation and benthic microbial patterns. Thus, we carried out a field investigation at the abandoned Yellow River Delta (AYRD) to deepen the understanding of PAHs' horizontal distribution and ecological roles on the continental shelf. The PAH level in the AYRD is relatively low and distance-independent, indicating it resulted from long-term, chronic, anthropogenic input. The combined application of diagnostic molecular ratios reported inconsistent PAH sources, which might be due to the low PAH concentrations and the complexity of contributing sources. Positive Matrix Factorization provided a more robust source classification and identified three main PAH sources-coal combustion and vehicle emissions, petrogenic process, and fossil fuels. The benthic microbiome did not show a significant response to PAHs in terms of microbial assemblage or alpha-diversity. However, Operational Taxonomic Units in some specific phyla, like Thaumarchaeota, Proteobacteria, Acidobacteria, and Chytridiomycota, correlated with the PAH source indicators, supporting the notion that PAH source indicators can act as a novel environmental indicator for microbial adaption. What's more, Microbial Ecological Networks show more connection at sites identified as biomass combustion by both Fluoranthene/(Fluoranthene + Pyrene) and Indeno(1,2,3-cd)pyrene/(Indeno(1,2,3-cd)pyrene + Benzo(ghi)perylene) compared to the ones identified as biomass combustion by Fluoranthene/(Fluoranthene + Pyrene) and petroleum combustion by Indeno(1,2,3-cd)pyrene/(Indeno(1,2,3-cd)pyrene + Benzo(ghi)perylene). Herein, we demonstrate that the PAHs' source indicator can serve as a novel indicator of the interactions between microorganisms, and thus, should be applied to the sustainable management effort in the offshore area.

Post COVID-19 pandemic: Disposable face masks as a potential vector of antibiotics in freshwater and seawater.

With the outbreak and widespread of the COVID-19 pandemic, large numbers of disposable face masks (DFMs) were abandoned in the environment. This study first investigated the sorption and desorption behaviors of four antibiotics (tetracycline (TC), ciprofloxacin (CIP), sulfamethoxazole (SMX), and triclosan (TCS)) on DFMs in the freshwater and seawater. It was found that the antibiotics in the freshwater exhibited relatively higher sorption and desorption capacities on the DFMs than those in the seawater. Here the antibiotics sorption processes were greatly related to their zwitterion species while the effect of salinity on the sorption processes was negligible. However, the desorption processes were jointly dominated by solution pH and salinity, with greater desorption capacities at lower pH values and salinity. Interestingly, we found that the distribution coefficient (Kd) of TCS (0.3947 L/g) and SMX (0.0399 L/g) on DFMs was higher than those on some microplastics in freshwater systems. The sorption affinity of the antibiotics onto the DFMs followed the order of TCS > SMX > CIP > TC, which was positively correlated with octanol-water partition coefficient (log Kow) of the antibiotics. Besides, the sorption processes of the antibiotics onto the DFMs were mainly predominated by film diffusion and partitioning mechanism. Overall, hydrophobic interaction regulated the antibiotics sorption processes. These findings would help to evaluate the environmental behavior of DFMs and to provide the analytical framework of their role in the transport of other pollutants.

Dynamics of low-molecular-weight organic acids for the extraction and sequestration of arsenic species and heavy metals using mangrove sediments.

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.

Release of sediment metals bound by glomalin related soil protein in waterfowls inhabiting mangrove patches.

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.

Effect of land-use and land-cover change on mangrove soil carbon fraction and metal pollution risk in Zhangjiang Estuary, China.

Land-use and land-cover change (LULCC) is the main cause of mangrove deforestation and degradation. However, the effect of LULCC on mangrove soil organic carbon (SOC) fractions and metal pollution risks, and the difference between the effects of those two soil evolutions are largely unknown. Here, we collected soil samples from natural systems (mangroves and mudflat), land-cover changes (Spartina alterniflora invasion), and anthropogenic land-use changes (cropland and culture pond) in Zhangjiang Estuary. We determined the soil aggregate fractions (macro-aggregate, micro-aggregate, and silt-clay fraction) and the associated carbon, and heavy metal dynamics. Our findings suggested that LULCC did not remarkably affect SOC contents, but changed the soil aggregate structures. LULCC significantly increased aggregate-associated carbon fractions, especially macro-aggregate carbon fraction. The large proportion of silt-clay fraction in natural systems was corresponding to a high percentage of mineral organic carbon, indicating that LULCC decreases the mangrove SOC stability. Land-cover change promoted the accumulation of SOC, nitrogen, and heavy metals compared with uninvaded mudflat. The heavy metal contents in mangrove soil were highest among all studied soils, expect for Cd, which suggested that mangrove soil had high metal accumulation. However, land-use changes could stimulate the mobility and dynamics of metals enriched in mangrove soils; these changes, especially in cropland, will also cause a large amount of exogenous Cd being exported into the adjacent aquatic environment. Thus, mangrove shifts metal pollutant from sink to source when affected by land-use changes. The contamination index demonstrated that heavy metals have posed ecological risks, especially for Cd in cropland. Compared with mangrove, land-use change was dominated by single-element pollution, but land-cover change showed low multiple-element complex pollution. These findings elucidate the effects of LULCC on mangrove SOC fraction and metal pollution risk, and are of great significance for designing the long-term management and conservation policies for mangrove managers.

Glomalin-related soil protein: The particle aggregation mechanism and its insight into coastal environment improvement.

Glomalin-related soil protein (GRSP), a ubiquitous microbial product, plays a crucial role in particle aggregation and metal adsorption, but the underlying mechanisms remain unknown. Here, GRSP fraction was extracted from estuarine ecosystems and systematically characterized to elucidate the aggregation mechanisms and its impact on coastal environment improvement. We found that GRSP fraction (gravimetric mass of extracted GRSP, 5.1-24.3 mg g-1) was a globally relevant novel bioflocculant and that protein (linked to Bradford protein assay, 1.64-4.37 mg g-1) was the active flocculant constituent. The zeta potential, FTIR, XPS, and 13C NMR analyses identified its key constituents and structure, and revealed that the charge neutralization and bridging were GRSP fraction aggregation mechanisms. Thermogravimetric-infrared spectrometry analysis showed that GRSP fraction was highly thermostable, and the main volatile pyrolysis products included H2O, CO2, CO, and CH4. The SEM-EDX and XPS Fe valence spectroscopy suggested that GRSP fraction contained rich Fe (11.91 ± 0.48%) and could form Fe-rich flocs with particles. We also found that GRSP fraction has a high adsorption capacity (76-95%) for Cu, Zn, Pb and Cd, and its flocculation properties provide new insights into metal adsorption. The analysis of particle aggregation mechanism and its metal adsorption capacity is of great significance to elucidate the role of GRSP fraction in coastal environment improvement.

Potential and mechanism of glomalin-related soil protein on metal sequestration in mangrove wetlands affected by aquaculture effluents.

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.