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.

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.

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.

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.

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.

Assessment of Metal Pollution, Its Potential Health Risks, and Origin in Different Land Use Types in Zhuhai City, China.

The purpose of this study was to evaluate the current status of metal concentrations in soil from Zhuhai City. We detected the concentrations of eight metal elements in 67 topsoil samples collected from three typical land use types (water source land, n = 27; industrial land, n = 25; and farmland, n = 15) in Zhuhai. Multivariate geostatistical analyses indicated that the concentrations of Cu, Zn, and Cd may have originated from anthropogenic sources, whereas Pb and As mostly originated from natural sources. Additionally, Cr, Ni, and Hg may have come from mixed sources. The pollution index and the potential ecological risk were used to identify the general contamination characteristics of soil metals. The soil samples from industrial land were more polluted (60% of soil samples in industrial land were unpolluted to moderately polluted, and 40% were moderately polluted) and posed greater risk (28.6% of industrial soil samples were very high risk, and 71.4% were considerable risk) than samples from water source land and farmland. On the whole, the health risks posed by soil metals were acceptable or close to tolerable, and Cd was the most important pollutant contributing to human health risks. Comparatively speaking, children were the most vulnerable population to the non-carcinogenic and carcinogenic risks of contaminated soils from industrial land. Our results provide fundamental information for improving soil environmental management and metal pollution prevention and control in Zhuhai City.

Seasonal characteristics of chemical compositions and sources identification of PM2.5 in Zhuhai, China.

Fine particulate matter is associated with adverse health effects, but exactly which characteristics of PM2.5 are responsible for this is still widely debated. We evaluated seasonal dynamics of the composition and chemical characteristics of PM2.5 in Zhuhai, China. PM2.5 characteristics at five selected sites within Zhuhai city were analyzed. Sampling began on January 10, 2015, and was conducted for 1 year. The ambient mass concentration, carbon content (organic and elemental carbon, OC and EC), level of inorganic ions, and major chemical composition of PM2.5 were also determined. Average concentrations of PM2.5 were lower than the National Ambient Air Quality Standard (NAAQS) 24-h average of 65 µg/m3. The daily PM2.5 concentration in Zhuhai city exhibited clear seasonal dynamics, with higher daily PM2.5 concentrations in autumn and winter than in spring and summer. Carbon species (OC and EC) and water-soluble ions were the primary components of the PM2.5 fraction of particles. Apart from OC and EC, chemical species in PM2.5 were mainly composed of NH4+ and SO42-. There was a marked difference between the summer and winter periods: the concentrations of OC and EC in winter were roughly 3.4 and 4.0 times than those in summer, while NH4+, SO42-, NO3-, and Na+ were 3.2, 4.5, 28.0, and 5.7 times higher in winter than those in summer, respectively. The results of chemical analysis were consistent with three sources dominating PM2.5: coal combustion, biomass burning, and vehicle exhaust; road dust and construction; and from reaction of HCl and HNO3 with NH3 to form NH4Cl and NH4NO3. However, additional work is needed to improve the mass balance and to obtain the source profiles necessary to use these data for source apportionment.

Contamination, potential mobility, and origins of lead in sediment cores from the Shima River, south China.

Identifying contamination sources of environmental media and revealing their changing trends over time is useful for regional contamination control and environmental improvements. Four sediment cores (S1-S4) were collected from the Shima River to determine lead (Pb) concentrations, geochemical fractions and isotopic compositions, as well as the geochronology of core S3. The results show that Pb concentrations decreased from the upper and middle reach sites (means: 57.6, 95.9, and 97.6 mg kg-1, respectively) to the lower reach site (43.8 mg kg-1), resulting in a minimal to moderate enrichment in the sediments; enrichment increased due to anthropogenic Pb inputs at the river middle reach site since the 1990s. Sediment Pb in the geochemical fractions followed a decreasing order of reducible (47.3%) > residual (37.8%) > oxidizable (11.2%) > acid-soluble fraction (3.68%), exhibiting high mobility, further verifying the anthropogenic inputs. A descending trend in the 206Pb/207Pb ratio of the top sediments was the result of anthropogenic activities. In the present study, coal combustion, which was the major anthropogenic Pb source determined by its isotopic composition, contributed significantly (means: 18.4-60.6%) to sediment Pb based on a three end-members model. Less of a contribution (0-10.6%) was derived from vehicle exhaust. The increasing trend in the coal contribution was in accordance with that of the coal consumption in the study area. These results suggest that Pb contamination resulting from coal combustion has grown to become a major environmental issue in the study area.

Identification of the dominant hydrogeochemical processes and characterization of potential contaminants in groundwater in Qingyuan, China, by multivariate statistical analysis.

In karst areas, groundwater is an important water source for drinking and irrigation purposes; however, karst aquifers are vulnerable and recovery from damage is difficult. We collected surface water (pond and river water) and groundwater (hand-pump well, dug well, and borehole water) samples in Qingyuan city, China, to determine the major chemicals in the water with the primary goals of evaluating the geochemical composition, identifying the geochemical processes governing the water chemistry, and identifying the probable sources of potential contaminants in shallow and deep groundwater in the study area. The results revealed marked differences in water chemistry between shallow and deep groundwater. The groundwater composition was largely controlled by rock-water interactions, particularly the dissolution of evaporite minerals (e.g., calcite, gypsum, and anhydrite), and ion exchange processes were important drivers of the chemical compositions of groundwater in the study area. Moreover, in shallow and deep groundwater, Mg2+ and SO4 2- concentrations were increased due to the long residence time of deep groundwater, while K+ and Na+ concentrations were decreased due to anthropogenic input. Finally, factor analysis of the major and trace elements differentiated between anthropogenic and geogenic sources of potential contaminants in karst aquifers.

[Sources and Variation Characteristics of Dissolved Lipid Biomarkers in a Typical Karst Underground River].

Water samples in Qingmuguan underground river were collected to determine the concentration of dissolved lipids, and their sources, composition and migration characteristics in underground river were studied. The results were obtained as follows. (1) The average content of various dissolved lipids decreased with increasing distance of migration in Qingmuguan underground river, and the most distinctive was dissolved saturated straight chain fatty acids with its content decreasing by about 81.71%, from the initial 5,704 ng · L⁻¹ to 1,043 ng · L⁻¹. (2) N-alkane could indicate the sources of dissolved organic matter in underground river, but saturated straight chain fatty acid and fatty alcohol had the advantage in indicating algae, bacteria and other microorganisms. (3) With the increasing migration distance of Qingmuguan underground river, the input type of dissolved organic matter in underground river was different, which might be resulted from the heterogeneity of karst surface. (4) In ternary plot of alkane sources, aquatic plants constituted the major contribution of dissolved organic matter in Qingmuguan underground river, followed by higher plant, algae/ bacteria. Unlike higher plants and algae/bacteria, the contribution from aquatic plants decreased with increasing migration distance of underground river. (5) To a certain extent, TAR (alkane) values could reflect the rainfall, and the values of CPI, L/H in saturated straight chain fatty acids might indicate the degradation activities of bacteria.