Historical construction, quantitative source identification and risk assessment of heavy metals contamination in sediments from the Pearl River Estuary, South China.

Historical reconstruction of heavy metals (HMs) contamination in sediments is a key for understanding the effects of anthropogenic stresses on water bodies and predicting the variation trends of environmental state. In this work, eighteen sediment cores from the Pearl River Estuary (PRE) were collected to determine concentrations and geochemical fractions of HMs. Then, their potential sources and the relative contributions during different time periods were quantitatively identified by integrating lead-210 (210Pb) radioisotope dating technique into positive matrix factorisation (PMF) method. Pollution levels and potential ecological risks (PERs) caused by HMs were accurately assessed by enrichment factors (EF) based on establishment of their geochemical baselines (GCBs) and multiparameter evaluation index (MPE). HMs concentrations generally showed a particle size- and organic matter-dependent distribution pattern. During the period of 1958-1978, HMs concentrations remained at low levels with agricultural activities and natural processes being identified as the predominant sources and averagely contributing >60%. Since the reform and opening-up in 1978, industrial and traffic factors become the primary anthropogenic sources of HMs (such as Cu, Zn, Cd, Pb, Cr, and Ni), averagely increasing from 22.1% to 28.1% and from 11.6% to 23.4%, respectively. Conversely, the contributions of agricultural and natural factors decreased from 37.0% to 28.5% and from 29.3% to 20.0%, respectively. Subsequently, implementation of environmental preservation policies was mainly responsible for the declining trend of HMs after 2010. Little enrichment of sediment Cu, Zn, Pb, Cr and Ni with EFs (0.15-1.43) was found in the PRE, whereas EFs of Cd (1.16-2.70) demonstrated a slight to moderate enrichment. MPE indices of Cu (50.7-252), Pb (52.0-147), Zn (35.5-130), Ni (19.6-71.5), Cr (14.2-68.8) and Cd (0-9.90) highlighted their potential ecological hazards due to their non-residual fractions and anthropogenic sources.

["Load-Unload" Effect of Manganese Oxides on Phosphorus in Surface Water of the Pearl River Estuary].

Phosphorus (P) conveyed by surface runoff plays an essential role in regulating nutrient balance and primary production in estuarine waters. In this study, basic physiochemical properties, total phosphorus (TP, including speciation), particulate iron (PFe), particulate manganese (PMn), and particulate aluminum (PAl) of the surface water in the Pearl River Estuary (PRE) in different seasons were determined to investigate the spatiotemporal distribution characteristics of P and to identify the crucial factor controlling P migration and transformation in the freshwater-saltwater interaction zone. TP concentrations (28.88-233.68 µg·L-1) decreased with increasing salinity gradient owing to deposition and dilution. The proportions of P speciation followed a decreasing order as dissolved inorganic phosphorus (DIP, 37.3%) > particulate inorganic phosphorus (PIP, 22.7%) > dissolved organic phosphorus (DOP, 21.0%) > particulate organic phosphorus (POP, 19.0%). PIP was positively related to PFe, PMn, and PAl (P < 0.05), confirming their concurrent migration behaviors. In addition, the increase in salinity promoted the desorption of phosphate on the suspended particulate matters, which mainly took place near the freshwater-saltwater interface. A significant positive correlation (P < 0.001) between the solid-liquid phase partitioning coefficient (Kd) of phosphate and salinity indicated that PIP was present mainly in more stable forms in the brackish water. Most importantly, a better relationship between Kd and PMn (P < 0.01) supported our scientific hypothesis of the "load-unload" effect of Mn oxides on P:particulate-carrying phosphates transported from the freshwater zone tend to be desorbed and released into the brackish water.

Estimation of water quality variables based on machine learning model and cluster analysis-based empirical model using multi-source remote sensing data in inland reservoirs, South China.

Reservoirs play important roles in the drinking water supply for urban residents, agricultural water provision, and the maintenance of ecosystem health. Satellite optical remote sensing of water quality variables in medium and micro-sized inland waters under oligotrophic and mesotrophic status is challenging in terms of the spatio-temporal resolution, weather conditions and frequent nutrient status changes in reservoirs, etc., especially when quantifying non-optically active components (non-OACs). This study was based on the surface reflectance products of unmanned aerial vehicle (UAV) multispectral images, Sentinel-2B Multispectral instrument (MSI) images and Landsat 7 Enhanced Thematic Mapper Plus (ETM+) by utilizing fuzzy C-means (FCM) clustering algorithm was combined with band combination (BC) model to construct the FCM-BC empirical model, and used mixed density network (MDN), extreme gradient boosting (XGBoost), deep neural network (DNN) and support vector regression (SVR) machine learning (ML) models to invert 12 kinds of optically active components (OACs) and non-OACs. Compared with the unclustered BC (UC) model, the mean coefficient of determination (MR) of the FCM-BC models was improved by at least 46.9%. MDN model showed best accuracy (R2 in the range of 0.60-0.98) and stability (R2 decreased by up to 13.2%). The accuracy of UAV was relatively higher in both empirical methods and machine learning methods. Additionally, the spatio-temporal distribution maps of four water quality variables were mapped based on the MDN model and UAV images, all platforms showed good consistency. An inversion strategy of water quality variables in various monitoring frequencies and weather conditions were proposed finally. The purpose of introducing the UAV platform was to cooperate with the satellite to improve the monitoring response ability of OACs and non-OACs in small and micro-sized oligotrophic and mesotrophic water bodies.

Spatial and temporal dynamics and fluxes estimation of manganese fractions in sediments from the Pearl River Estuary, southern China.

Sequential extraction was used to study the historical dynamics and fluxes of the chemical fractions of manganese (Mn) in sediments collected from the Pearl River Estuary (PRE), southern China. Results revealed that the proportion of Mn associated with different fractions decreased in the order of acid-soluble fraction (F1) > reducible fraction (F2) > residual fraction (F4) > oxidizable fraction (F3). F1 (47%) was the dominant Mn fraction, indicating the strong bioavailability of Mn to aquatic organisms in the PRE. In addition, the Mn fraction F2 was present at an average rate of 27.93 % in surface sediments, indicating that it could be mobilized when environmental conditions become increasingly reducing or oxidizing. The decline in Mn fraction fluxes after 2006 indicated that the region has partially decreased due to the removal of heavily polluting industries and effective control of sewage discharge.

Tracking contaminants in groundwater flowing across a river bottom within a complex karst system: Clues from hydrochemistry, stable isotopes, and tracer tests.

Tracking contaminants in karst aquifers is challenging because of the high heterogeneity encountered in carbonate rocks. Multi-tracer tests, combined with chemical and isotopic analyses, were conducted to solve a groundwater contamination incident within a complex karst aquifer in Southwest China. Results showed that: (1) the wastewater from a paper mill, public sewers, and septic tanks were the three main potential contaminant sources identified by chemical and isotopic methods; (2) a direct effect of the paper mill wastewater with high Na+ (up to 2230.5 mg/L) and chemical oxygen demand (COD) concentrations on spring water quality was confirmed by multi-tracer tests, which changed the water type from Ca-HCO3 in the 1970s to Ca-Na-HCO3 in the present study and resulted in a depleted carbon isotope value (-16.5‰); and (3) the studied aquifer is a highly complex karst system, due to two conduits crossed each other without mixing, contaminants traveled a long distance (up to 14 km) within the lower conduit, paper mill-contaminated groundwater flowed across a river bottom and discharged to the opposite bank, and an active subsurface divide occurred. After several months of operation, the groundwater restoration measure based on karst hydrogeologic conditions proved that cutting off contaminant sources for karst aquifer self-restore was effective in practice, which contributed to the decline in NH4+ (from 7.81 mg/L to 0.04 mg/L), Na+ (from 50.12 mg/L to 4.78 mg/L), and COD (from 16.42 mg/L to 0.9 mg/L) concentrations coupled with an increase in δ13C-DIC value (from -16.5‰ to -8.4‰) in the earlier contaminated karst spring. This study's integrated method is expected to screen and confirm contaminant sources within complex karst systems rapidly and effectively, thereby contributing to karst groundwater environmental management.

Remobilization characteristics and diffusion kinetic processes of sediment zinc (Zn) in a tidal reach of the Pearl River Estuary, South China.

Exploration of the remobilization mechanism of trace metals in estuarine sediments remain challenging because of dynamic hydrochemical conditions. This study integrated a chemical sequential extraction procedure (BCR), the diffusive gradient in thin films (DGT) and high-resolution dialysis techniques, and Visual MINTEQ ver.3.1 to identify the seasonal mobilization characteristics of sediment Zn within a tidal reach, South China. The mobility of sediment Zn based on the BCR procedure contradicted the results of DGT analysis. In summer, reductive dissolution of Fe/Mn oxides was the key driver of sediment Zn remobilization; during winter, cation exchange reactions facilitated the mobilization of Zn in the brackish water zone. The time-dependence ratios of DGT-labile Zn and dissolved Zn concentrations (mean: 0.34-0.81) indicated the sediment solid phase had partially sustained capacity to resupply Zn to the porewater in both seasons. Sediments generally functioned as a source of Zn in the freshwater zone with organically complexed Zn being diffusively released into the water column at rates of 0.3-15.5 µg·m-2·d-1. In the brackish water zone, the dominant Zn species were transformed into free Zn ions and Zn-inorganic complexes and migrated into sediment, with respective influxes of 18.9-70.7 µg·m-2·d-1 and 18.9-68.3 µg·m-2·d-1, which shifted to a sink of Zn.

Spatial and Temporal Variations and Risk Assessment of Heavy Metal Fractions in Sediments of the Pearl River Estuary, Southern China.

Sequential extraction was used to study the mobility and ecological risk of chemical fractions of six heavy metals in sediments collected from the Pearl River Delta (PRE) in China. Results revealed that residual fractions (F4) were the dominant forms for Cr and Ni in surface sediments, indicating that they were primarily stable in nature and had low bioavailability and ecotoxicity. Cd had a high environmental risk owing to its higher availability in acid-soluble fraction (F1), whereas Pb occurred predominantly in the reducible fraction (F2) in surface sediments. The profile variations of bioavailable fractions were generally consistent with socioeconomic development in the Pearl River Delta (PRD). A decreasing trend after 2006 suggested a reduction in heavy metal bioavailable fractions owing to the removal of heavy polluting industries and the effective control of sewage discharge. The risk assessment code suggested that the high mobility of Cd posed an extremely high risk and a threat to the aquatic environment.

Dual diffusive gradients in the thin films (DGT) probes provide insights into speciation and mobility of sediment chromium (Cr) from the Xizhi River basin, South China.

Investigation of the speciation and remobilization mechanisms of chromium (Cr) in sediment is essential for accurate estimation of its ecological risks in aquatic systems. In this work, a three-step chemical extraction procedure and diffusive gradient in thin films (DGT) technique were combined to investigate the geochemical speciation, mobility potentials, and release characteristics of sediment Cr. The geochemical speciation of sediment Cr decreased in the following order: oxidizable > reducible > residual > acid-soluble fraction. Dissociation of OM-bound Cr(III) and oxidation by Mn oxides contributed to higher labile Cr(III) and Cr(VI) levels in winter, with the labile Cr(III) being the dominant species and accounting for 48.1%65.5% of the total concentration of labile Cr; whereas, reductive dissolution of Mn oxides was responsible for the remobilization of labile Cr(VI) in summer, leading to a shift in dominant Cr species to Cr(VI) (48.9%65.7%) due to rapid precipitation of Cr(III). Sediment acted as a major sink for labile Cr(VI) in two sampling campaigns. For labile Cr(III), sediment converted from source in winter to sink in summer. The diffusive release of labile Cr(III) deserves preferential concern due to its potential to be re-oxidized to more toxic Cr(VI) under the oxic conditions of river water in winter.

Heavy metals and Pb isotopes in a marine sediment core record environmental changes and anthropogenic activities in the Pearl River Delta over a century.

Heavy metal accumulation in marine sediments is associated with changes in both the natural environment and human activities. This study used heavy metals and Pb isotopes in a precisely dated (by 210Pb and 137Cs) sediment core from the Macao Sea to reconstruct the historical changes in anthropogenic activities and the environment in the western Pearl River Estuary (PRE). The distribution of heavy metals in the sediment core could be divided into four stages (pre-1950, 1950-1976, 1976-2000, and post-2000), which corresponded to the changes in anthropogenic activities and environment of the Pearl River Delta during the past 100 years. The contribution of anthropogenic metals (Pb and Zn) in the sediments increased gradually over time. However, the concentrations, enrichment factors, and fluxes of heavy metals in the sediments all displayed a downward trend since 2010, revealing a decline in metal pollutant input due to strict emission reduction policies implemented in the last decade. The Pb isotopes in the sediments showed a similar trajectory to the heavy metals, reflecting the changes in Pb sources in the sediments at different stages. Based on a binary Pb isotope mixing model, the calculated proportions of anthropogenic and natural Pb in the sediments were 0-50.9% (mean 15.9%) and 49.1-100% (mean 84.1%), respectively, suggesting that the Pb in the PRE sediments is mainly controlled by natural sources.

Microbial community structure characteristics among different karst aquifer systems, and its potential role in modifying hydraulic properties of karst aquifers.

Little is known about how microbial activity affects the hydraulic properties of karst aquifers. To explore the potential impacts of microbial activity on the hydraulic properties of karst aquifers, microbiological analysis, heat tracer, isotope (dissolved inorganic carbon isotope, δ13CDIC) and aqueous geochemical analyses were conducted at six monitoring wells in Northern Guangdong Province, China. Greater hydraulic conductivity corresponded to a low temperature gradient to an extent; the temperature gradient in karst groundwater aquifers can reflect the degree of dissolution. Higher HCO3 - concentrations coupled with lower d-excess and pH values at B2 and B6 reflect potential microbial activity (e.g., Sulfuricurvum kujiense) causing carbonate dissolution. Microbial activity or the input of anthropogenic acids, as evidenced by significantly more positive δ13CDIC values, potentially affect carbonate dissolution in deep karst aquifers, which eventually alters hydraulic properties of karst aquifer. However, more direct evidence is needed to quantify the effects of microbial activity on carbonate dissolution in karst aquifers.

Seasonal variations of cadmium (Cd) speciation and mobility in sediments from the Xizhi River basin, South China, based on passive sampling techniques and a thermodynamic chemical equilibrium model.

Understanding the speciation and mobilization mechanisms of potentially toxic metals in sediments is critical to aquatic ecosystem health and contamination remediation in urban rivers. In this study, chemical sequential extraction, a thermodynamic chemical equilibrium model (Visual MINTEQ ver. 3.1), diffusive gradient in thin films (DGT), and high-resolution dialysis (HR-Peeper) techniques were integrated to identify seasonal variations in cadmium (Cd) mobility in sulfidized sediments. Acid-soluble Cd was the dominant geochemical fraction in sediments, followed by residual, oxidizable, and reducible Cd. The DGT-labile Cd concentration was associated with various geochemical processes and was independent of the total concentration and geochemical fractionation of Cd in sediments. Sulfate reduction facilitated the formation of insoluble CdS and induced low Cd concentrations in sediment porewater. Sulfide oxidation was principally responsible for lowered porewater pH and elevated Cd concentrations in summer. Strongly acidic conditions promoted release of sediment Cd but might reduce the binding efficiency of Chelex resin gel for dissolved Cd, leading to underestimation of the mobility of sediment Cd. Sediments generally functioned as a sink for Cd in winter and shifted to acting as a source in summer, releasing Cd into the overlying water mainly as Cd-S complexes with high potential to migrate downstream.

Distribution, Risk Assessment, and Sources of Trace Metals in Surface Sediments from the Sea Area of Macao, South China.

Due to rapid economic development in the Pearl River Delta, South China, trace metals pose a significant threat to the coastal ecosystems. In this study, we investigated the spatial distribution, contamination status, ecological risk, and possible sources of trace metals in 150 surface sediment samples from the Macao sea area. The results showed that concentrations of Ag, Pb, Cu, Zn, and Cd were highest in the Inner Harbour, whereas Cr, Co, As, and Ni were mainly accumulated in the downstream area of the Maliuzhou Waterway and the eastern area of Macao International Airport. Sediment grain composition, organic matter, total phosphorus, and hydrological regime were key factors influencing the spatial distribution patterns of trace metals. According to the environmental contamination indices of the enrichment factor, geo-accumulation index, and contamination factor, moderate contamination of trace metals occurs in the study area, while Ag and Pb contribute significantly to the contamination. Based on the potential ecological risk index, trace metals in surface sediments pose a low ecological risk. Correlation analysis and principal component analysis indicated that Cr, Co, Ni, and As were mainly derived from natural sources, whereas Ag, Pb, Cu, Zn, and Cd were mainly associated with anthropogenic sources.

Mobilization mechanisms and toxicity risk of sediment trace metals (Cu, Zn, Ni, and Pb) based on diffusive gradients in thin films: A case study in the Xizhi River basin, South China.

Identifying the mobilization mechanisms and predicting the potential toxicity risk of metals in sediment are essential to contamination remediation in river basins. In this study, a sequential extraction procedure and diffusive gradients in thin film (DGT) were employed to investigate the mobilization mechanisms, release characteristics, and potential toxicity of sediment metals (Cu, Zn, Ni, and Pb). Acid-soluble and reducible fractions were the dominant geochemical species of Cu, Zn, Ni, and Pb in sediments, indicating high mobility potentials for these metals under reducing conditions. In summer, the sediment acted as a source of water-column metals due to mineralization of organic matter and reductive dissolution of iron/manganese oxides in surface sediments, and the formation of metal sulfide precipitates markedly lowered DGT-labile metal concentrations with depth, while localized sulfide oxidation was responsible for fluctuating labile metal concentrations. Stable distribution patterns of labile metals resulted from the weak reducing conditions of sediment in winter, when the sediment shifted to a metal sink. The interstitial water criteria toxicity unit (IWCTU), calculated from DGT measurements, indicated no and low-to-moderate toxic risk of sediments in summer and winter seasons, respectively, and Pb was the major contributor to the predicted toxic effects in the soft interstitial water.

Release characteristics and mechanisms of sediment phosphorus in contaminated and uncontaminated rivers: A case study in South China.

Phosphorus (P) cycling present in sediments associated with iron (Fe), manganese (Mn) and sulfur (S) geochemical processes may cause secondary pollution in overlying water. Understanding the mechanisms of P release from sediments should help to restore water quality. This study used the diffusive gradients in thin film (DGT) technique to investigate the seasonal variation in the lability, remobilization mechanisms, and release characteristics of sediment P in the uncontaminated Xizhi River and the severely contaminated Danshui River, South China. P accumulation in sediments contributed to higher DGT-labile P concentrations in contaminated reaches, and the highest labile P concentrations were generally observed in summer season at each site. The significant positive relationships (p < 0.05) between labile Fe and P confirmed the Fe-P coupling release mechanism in uncontaminated sediments. Stronger relationships between labile Mn and P at contaminated sites indicated that Mn oxides played an important role in P remobilization. However, sulfate reduction associated with microbial activities (crucial genera: Desulfobulbus, Desulfomicrobium and Desulforhabdus) was considered to decouple the Fe & Mn-P cycling relationship, promoting P release at contaminated sites. The effluxes of sediment P were much higher in the Danshui River (mean 0.132 mg cm-2·d-1) than in the Xizhi River (mean 0.038 mg cm-2·d-1). And hot season led to growth in P effluxes that was much greater in contaminated river.

[Pollution and Ecological Risk Assessment and Source Apportionment of Heavy Metals in Sediments of Qingliangshan Reservoir in the Meijiang Basin].

Reservoir sediment is an important sink for pollutants such as heavy metals. Under the changes in acid-base and redox conditions, there is a potential risk of heavy metals release into the water environment, which are transmitted through the food chain and threaten human health. Therefore, this study investigates the Qingliangshan Reservoir in the Meijiang River Basin, and conducts research concerning the contents and speciation of heavy metals in the sediments, potential ecological risks, and source apportionment. This study found that the content of heavy metals in the sediments of the reservoir area was in the order:Xitian tributary > dam front and reservoir center > Xintian-Baishui tributary. There is a large difference in the speciation of heavy metals in the sediments. Zn is mainly acid-soluble and in the residual state, Pb is mainly in an Fe/Mn oxide bound state, Cd is mainly in an acid-soluble state, and Cu, Ni, and Cr are in the residual state. Mainly, the percentage of bioavailable states are Cd(89%) > Pb(76%) > Zn(54%) > Cu(43%) > Ni(28%) > Cr(10%). The geoaccumulation index method shows that the pollution degree of heavy metal elements in reservoir sediments is in the order Cd > Pb > Zn > Cu > Cr > Ni, and the potential hazard ecological index method shows that the pollution degree of heavy metals is Cd > Pb > Cu > Ni > Zn > Cr. The potential ecological risk of Cd in the reservoir sediments is the largest, and the biological impact is greatest. Correlation analysis and principal component analysis results show that heavy metals Cu, Zn, Pb, and Cd in reservoir sediments are mainly from agricultural pollution, and Ni and Cr are mainly from natural background. Combined with the analysis of soil heavy metal content in the watershed, heavy metal pollution in the Qingliangshan Reservoir sediments originates from the effect of rainfall runoff and the use of agricultural chemical fertilizers before flooding in the upstream of the reservoir tributaries. There are significant spatial differences in heavy metal pollution in the sediments of the reservoir area. The Xintian-Baishui River recharge area is the least polluted, and it is closely related to the land use in the controlled watershed, which is mainly forest land, with fewer sources of pollution. The Xitian River replenishment area has the heaviest pollution. It controls many tea gardens and farmlands in the watershed, and the load of external fertilizer pollution is the largest. The pollution degree of heavy metals in front of the dam and the center of the reservoir area is between the two tributary replenishment areas, showing an obvious mixing effect.

Quantifying the impacts of anthropogenic activity on chemical weathering based on source identification of hydrochemistry: the Liuxi river basin, southern China.

The impact of anthropogenic activity on chemical weathering is still an open and significant topic that requires clarification to improve the understanding of watershed evolution. We analyzed river water and rainwater samples to characterize the variation in hydrochemical characteristics and influencing factors. Samples were taken from the Liuxi River Basin (LRB), the only local drinking water supply for Guangzhou, and we studied geochemical parameters, major ions, and Si concentrations. Moreover, elemental ratios of end-members were determined and a modified-forward model was constructed to identify ion sources and estimate the chemical weathering rate (CWR) and anthropogenic input rate (AIR). Finally, we quantified the impacts of anthropogenic activity on the chemical weathering process. The results showed that the dominant hydrochemical type of river water was identified as HCO3-Ca, and rock weathering was the main contributor to river Na+, Mg2+, Ca2+ and HCO3-, whereas anthropogenic activity contributed the most to K+, Cl-, SO42-, and NO3-. The relatively high silicate weathering rate (SWR) (17.8-18.4 t per km2 per year) and AIR (37.8-60.3 t per km2 per year) were mainly attributed to erosion by nitric and sulfuric acid. The contribution rate of these acids to CWR could be regarded as a proxy quantifying the impact of anthropogenic activity on the chemical weathering process. This accounted for approximately 30% of the total SWR in the LRB. Our results demonstrate the effectiveness of hydrochemical source identification for quantifying the impacts of anthropogenic activity on chemical weathering.

Characteristics, Sources, and Risks of Polycyclic Aromatic Hydrocarbons in Topsoil and Surface Water from the Liuxi River Basin, South China.

The concentrations, composition, sources, and risks of polycyclic aromatic hydrocarbons (PAHs) in topsoil and surface water of the Liuxi River basin, south China were analyzed in this study. The total concentrations of 16 PAHs ranged from 296.26 to 888.14 ng/g in topsoil and from 156.73 to 422.03 ng/L in surface water, indicating mild pollution. The PAHs in topsoil exhibited an even spatial distribution, suggesting that they originated primarily from dry and wet deposition of transported pollutants. The concentration of PAHs in surface water did not differ significantly geographically, but the concentrations of total, three-, and four-ring PAHs were significantly lower in the Liuxi River than in its tributaries. Three- and two-ring PAHs predominated in topsoil and surface water, respectively. A correlation analysis suggested that the total organic carbon content and pH exerted a negligible effect on the spatial distribution of PAHs in topsoil, and they may have common sources. Fossil fuel combustion (particularly vehicle emissions) and coking production were the dominant sources of PAHs in topsoil, whereas those in surface water were derived from a variety of sources. The total toxic equivalent concentrations of 16 PAHs in topsoil ranged from 3.73 to 105.66 ng/g (mean, 30.93 ng/g), suggesting that exposure to the basin's topsoil does not pose a risk to the environment or public health according to the Canadian soil quality guidelines. A risk assessment revealed that the total PAH concentrations in surface water posed a low ecological risk.

210Pb dating to investigate the historical variations and identification of different sources of heavy metal pollution in sediments of the Pearl River Estuary, Southern China.

In this study, we investigated the historical variation, source identification, and distribution of heavy metal pollution in sediments of the Pearl River Estuary (PRE) using 210Pb dating. Our results suggest that the heavy metal concentrations were higher in the western part of the estuary. For all heavy metals, Cd was significantly enriched in the sediments. The Pearl River Delta (PRD) has experienced rapid economic development in the past 40 years, a decreasing trend in heavy metal fluxes after 2004 was identified, which suggests a reduction in heavy metal concentrations due to the removal of heavy polluting industries and the effective control of sewage discharge. A binary mixing model reveals that the contributions of anthropogenic Pb ranged from 45.4 to 64%. Based on lead isotopic ratios (206/207Pb and 208/206Pb), it was found that geologic materials and industrial pollution were the main sources of heavy metals in the PRE sediments.

Remobilization mechanism and release characteristics of phosphorus in saline sediments from the Pearl River Estuary (PRE), South China, based on high-resolution measurements.

The internal loading of phosphorus (P) is commonly considered an essential factor contributing to eutrophication in freshwater bodies. However, investigation of the lability and remobilization characteristics of P in estuarine saline sediments has been limited. In this study, a sequential chemical extraction procedure and high-resolution measurement using the diffusive gradients in thin film (DGT) technique were employed to explore the lability, potential remobilization mechanism and release characteristics of sediment P in the Pearl River Estuary (PRE), South China. The P accumulated significantly in sediments along the west coast of the PRE due to the combined effects of terrestrial P inputs and specific hydrological conditions. The geochemical fractions of sediment P followed the order of organic P (Org-P) (mean: 58.6%) > iron-bound P (Fe-P) (23.4%) > calcium-bound P (Ca-P) (17.4%) > loosely bound P (LS-P) (0.63%). Synchronous vertical variations in DGT-labile Fe and P in the upper and middle parts of the sediment profiles confirmed that Fe-coupled P mobilization occurred in saline sediments. In contrast, sulfate reduction in bottom sediments supposed to decouple the Fe-P cycling relationship. Additionally, the formation of an "iron curtain" (Fe oxyhydroxides) in the oxic surface sediments efficiently prevented upward diffusion of P, leading to relatively low effluxes of P (0.098-6.59 ng cm-2 d-1) across the sediment-water interface.

Combined microbial and isotopic signature approach to identify nitrate sources and transformation processes in groundwater.

Nitrate (NO3-) pollution is a serious problem worldwide. Identification of NO3- sources and transformation processes in aquifers is a key step in effectively controlling and mitigating NO3- contamination. In this study, hydrochemical, microbial, and dual isotopic approaches were integrated to elucidate the sources and processes influencing NO3- contamination in the Pearl River Delta, China. The results showed a severe NO3- contamination, with 75% of the samples having NO3--N concentrations above the WHO standard of 10 mg L-1. The δ15NNO3- and δ18ONO3- values and a multivariate statistical analysis of hydrochemical data both revealed that manure and sewage were mainly responsible for NO3- contamination. Biological indicators further demonstrated that, manure and sewage had greater impacts on groundwater quality during the rainy season than during the dry season. Based on the significant relationships of δ15NNO3- and δ18ONO3- with the logarithmic NO3- concentration (Ln(NO3-)), denitrification was confirmed to occur in the discharge zone during the rainy season. Proteobacteria, Bacteroidetes, and Planctomycetes were identified as the dominant phyla, and Dechloromonas, Flavobacterium, and Nitrospira were dominant among the denitrifying bacteria in groundwater. The abundance of denitrifying bacteria had significant positive correlations with δ15NNO3- and NO2--N during the rainy season, further confirming the occurrence of denitrification during the rainy season. This study showed that dual isotope techniques combined with microbial data can be a powerful tool for identifying the sources and microbial processes affecting NO3- in groundwater. Moreover, the results can provide useful insights for environmental managers to verify groundwater pollution and better apply remediation solutions.