Seasonal impact of acid mine drainage on water quality and potential ecological risk in an old sulfide exploitation.

Sulfides are usually associated with deposits of metals and coal. The reactive wastes from their exploitation, typically stored in piles and tailings dams, are often the mining sector's primary source of environmental problems. The surrounding river waters can present signs of acid mine drainage, responsible for aquatic ecosystem degradation. So, the main target of the present study is to investigate the impact of this process on the water's environmental quality and potential ecological risk. The study area is located at the Iberian Pyrite Belt, in an old sulfide exploitation, closed without environmental rehabilitation measures. The results exhibit high sulfate concentrations (410,601 mg/L) and potentially toxic elements, with prominence of Fe (134,000 mg/L), overcoming many other extreme cases of AMD pollution. The Ficklin diagram exposes that most samples are classified as "high-acid, high-metal." Two of them have extreme classifications (high-acid, extreme-metal). The pH value is well below the acceptable range for the environmental quality of superficial waters (5-7), measuring at a minimum of 0.84. Regarding seasonal variability, the study showed a higher degree of contamination in dry conditions (e.g., 4,420 mg/L of Cu), while the rainy month had lower concentrations of PTE (186.8 mg/L of Cu for the same sampling point). In addition, the water does not accomplish the environmental objectives established by the EU Water Framework Directive. According to the new approach developed based on a scale adjustment, the potential ecological risk index studied indicates that most sampled sites present strong, very strong, and even extremely potential ecological risk. With a typical Mediterranean climate, the region suffers from water scarcity, predicting increasingly in the future more degrading scenarios for water environmental quality. Consequently, urgent mitigation and remediation measures are necessary to improve and preserve water quality and fulfill the objectives of the United Nations Sustainability Development Goals.

Identifying sources of acid mine drainage and major hydrogeochemical processes in abandoned mine adits (Southeast Shaanxi, China).

Acid mine drainage (AMD) has resulted in significant risks to both human health and the environment of the Han River watershed. In this study, water and sediment samples from typical mine adits were selected to investigate the hydrogeochemical characteristics and assess the environmental impacts of AMD. The interactions between coexisting chemical factors, geochemical processes in the mine adit, and the causes of AMD formation are discussed based on statistical analysis, mineralogical analysis, and geochemical modeling. The results showed that the hydrochemical types of AMD consisted of SO4-Ca-Mg, SO4-Ca, and SO4-Mg, with low pH and extremely high concentrations of Fe and SO42-. The release behaviors of most heavy metals are controlled by the oxidation of sulfide minerals (mainly pyrite) and the dissolution/precipitation of secondary minerals. Along the AMD pathway in the adit, the species of Fe-hydroxy secondary minerals tend to initially increase and later decrease. The inverse model results indicated that (1) oxidative dissolution of sulfide minerals, (2) interconversion of Fe-hydroxy secondary minerals, (3) precipitation of gypsum, and (4) neutralization by calcite are the main geochemical reactions in the adit, and chlorite might be the major neutralizing mineral of AMD with calcite. Furthermore, there were two sources of AMD in abandoned mine adits: oxidation of pyrite within the adits and infiltration of AMD from the overlying waste rock dumps. The findings can provide deeper insight into hydrogeochemical processes and the formation of AMD contamination produced in abandoned mine adits under similar mining and hydrogeological conditions.

Dimethyl Sulfide (DMS) in Amarone Wines: Influence of Aging, Withering, Grape Variety, and Geographical Origin.

Occurrence of dimethyl sulfide (DMS), a potent aroma compound accumulating during aging, was investigated in commercial and experimental Amarone wines. In commercial Amarone, DMS was observed in concentrations ranging from 2.9 to 64.3 µg/L. Model aging studies on experimental wines indicated that DMS in Amarone is strongly associated with aging and that wines from different vineyards can vary significantly in their ability to accumulate DMS during aging. The capacity of certain vineyards to give wines with higher DMS-forming potential was consistent across three consecutive vintages, representing a true terroir factor to be expressed with aging. Wine content of primary amino acids (PAN), a commonly analyzed enological parameter of grape must, was shown to be positively correlated with DMS accumulation during aging. Grape withering also increased DMS-forming potential mostly due to increased PAN resulting from concentration due to water loss. Increased pH due to withering also contributed to a higher DMS content of withered wines, but to a lower extent. In certain vineyard sites, an influence of vintage conditions on DMS-forming potential was also observed.

High-resolution temporal monitoring of rare earth elements in acidic drainages from an abandoned sulphide mine (iberian pyrite belt, Spain).

Rare earth elements (REE) are strategic elements due to their economic importance. However, the studies dedicated to the distribution and behaviour of REE in aquatic systems have been scarce until a few decades ago. This work studies the seasonal variations of REE concentrations in acid mine drainage (AMD) affected water courses and the factors controlling their mobility under different hydrological conditions. To address this issue, a high-resolution sampling was performed for two years in selected sampling sites. REE concentrations were very high (median values of 2.7-3.4 mg/L, maximum of 7.0 mg/L). These values are several orders of magnitude higher than those found in natural waters, highlighting the importance of AMD processes on the release of REE to the hydrosphere. No good correlations were found between pH and REE concentration, while REE correlated positively (r Spearman coefficient of 0.78-0.94) with EC and negatively (r -0.88 to -0.90) with discharge in AMD-affected streams. A conservative behaviour of REE was observed due to the strongly acidic conditions observed in the study area. The waters also showed an enrichment in MREEs over LREEs and HREEs (mean values of GdN/LaN>1.8 and YbN/GdN < 0.7), typical of AMD waters. An asymmetry in the content of LREE and HREE was observed in AMD samples studied, which could be explained by the preferential dissolution of LREE or HREE-enriched minerals within each waste heaps. Multivariate analysis suggests the influence of Mn-rich minerals existent in the study area as a potential source of LREE.

Improving toxicity prediction of metal-contaminated sediments by incorporating sediment properties.

For the purpose of sediment quality assessment, the prediction of toxicity risk-levels for aquatic organisms based on simple environmental measurements is desirable. One commonly used approach is the comparison of total contaminant concentrations with corresponding water and sediment quality guideline values, serving as a Line of Evidence (LoE) based on chemistry-toxicity effects relationships. However, the accuracy of toxicity predictions can be improved by considering the factors that modify contaminant bioavailability. In this study we used paired chemistry-ecotoxicity data sets for sediments to evaluate the improvement in toxicity risk predictions using bioavailability-modified guidelines. The sediments were predominantly contaminated with metals, and measurements of sediment particle size, total organic carbon (TOC) and acid volatile sulfide (AVS) were used to modify hazard quotients (HQ). To further assess the predictive efficacy of the bioavailability-modified guideline models, sediments with differing contamination levels were tested for toxicity to a benthic amphipod's reproduction. To account for differences between laboratory exposure and field exposure scenarios, where the latter creates greater dilution, both static-renewal and flow-through test procedures were employed, and flow-through resulted in lower dissolved metal concentrations in the overlying waters. We also investigated how lower AVS concentration by oxidation modified the toxicity. This study reaffirmed that consideration of factors that influence contaminant bioavailability improves toxicity risk predictions, however the improvements may be modest. The sediment particle size data had the greatest influence on the modified HQ, indicating that higher percentage of fine particle size (<63 µm) contributed most to a lower predicted toxicity. The comparison of the static-renewal and flow-through test results continue to raise important questions about the relevance of static or static-renewal toxicity test results for risk assessment decisions, as both these test designs may cause unrealistically high contributions of dissolved metals in overlying waters to toxicity. Overall, this study underscores the value of incorporating outcomes from simple and routine sediment analysis (e.g., particle size, TOC, and consideration of AVS) to enhance the predictive efficacy of toxicity risk assessments in the context of sediment quality risk assessment.

Removal of Cr (VI) and microbial community analysis in PCB wastewater treatment based on the BESI® process.

The treatment efficiency of Chromium (Cr)-containing Printed Circuit Board (PCB) wastewater is significantly hampered by the limited physiological activity of microorganisms when activated sludge is applied. In this study, the biodegradation and electron transfer based on sulfur metabolism in the integrated (BESI®) process use sulfur as the electron acceptor to achieve sulfate reduction and sulfide oxidation, leading to efficient removal of Cr. The concentrations of total Cr and Cr(VI) in the effluent were reduced to 0.5 mg/L and 0.1 mg/L, respectively, from an initial range of 25-32 mg/L in the influent. The removal of Cr (ΔC(Cr(VI))) mainly occurred in the Sulfate Reduction (SR) reactor, which was significantly correlated with the generation of sulphide ([Formula: see text]) (R2 = 0.9987). Meantime, analysis of the microbial community showed that Cr (VI) stress increased the diversity of the bacterial community in sludge. The presence of Clostridium (52.54% and 47.78%) in SR & Sulfide Oxidation (SO) reactor, along with the Synergistaceae (31.90%) and Trichococcus (26.59%) in aerobic reactor, might contribute to the gradient degradation of COD, resulting in a removal efficiency exceeding 80% when treating an influent with a concentration of 1000 mg/L. In addition, the main precipitation components in the SR reactor were identified by scanning electron microscope, indicating that Cr has been removed from wastewater as Cr(OH)3 precipitation. This study sheds light on the potential of using the BESI® process for the real PCB wastewater treatment.

Sulfur fertilization and water management ensure phytoremediation coupled with argo-production by mediating rhizosphere microbiota in the Oryza sativa L.-Sedum alfredii Hance rotation system.

Sulfur (S) fertilizers, water management and crop rotation are important agronomic practices, related to soil heavy metal bioavailability. However, the mechanisms of microbial interactions remain unclear. Herein, we investigated how S fertilizers (S0 and Na2SO4) and water management affected plant growth, soil cadmium (Cd) bioavailability, and rhizospheric bacterial communities in the Oryza sativa L. (rice)-Sedum alfredii Hance (S. alfredii) rotation system through 16S rRNA gene sequencing and ICP-MS analysis. During rice cultivation, continuous flooding (CF) was better than alternating wetting and drying (AWD). CF treatment decreased soil Cd bioavailability by the promotion of insoluble metal sulfide production and soil pH, thus lowering Cd accumulation in grains. S application recruited more S-reducing bacteria in the rhizosphere of rice, whilst Pseudomonas promoted metal sulfide production and rice growth. During S. alfredii cultivation, S fertilizer recruited S-oxidizing and metal-activating bacteria in the rhizosphere. Thiobacillus may oxidize metal sulfides and enhance Cd and S absorption into S. alfredii. Notably, S oxidation decreased soil pH and elevated Cd content, thereby promoting S. alfredii growth and Cd absorption. These findings showed rhizosphere bacteria were involved in Cd uptake and accumulation in the rice-S. alfredii rotation system, thus providing useful information for phytoremediation coupled with argo-production.

Arsenic release pathway and the interaction principle among major species in vacuum sulfide reduction roasting of copper smelting flue dust.

The efficient release of arsenic in copper smelting flue dust (CSFD) with complicated production conditions and composition under the premise of environmental safety is difficult for the copper smelting industry. The vacuum environment is conducive to the volatilization of low-boiling arsenic compounds, which is beneficial to the physical process and chemical reaction of increasing the volume. In the present study, combined with thermodynamic calculations, the roasting process of pyrite and CSFD mixed in proportion in vacuum was simulated. Additionally, the release process of arsenic and the interaction mechanism of the main phases were performed in detail. The addition of pyrite facilitated the decomposition of stable arsenate in CSFD into volatile arsenic oxides. The results indicated that exceeding 98% of arsenic in CSFD volatilized into the condenser, while the arsenic content in the residue was reduced to 0.32% under optimal conditions. Pyrite could reduce the oxygen potential during the chemical reaction with CSFD, reacting with sulfates in CSFD to convert into sulfides and magnetic iron oxide (Fe3O4) simultaneously, and Bi2O3 would be transformed into metallic Bi. These findings are significant for developing arsenic-containing hazardous waste treatment routes and the application of innovative technical approaches.

A method for the quantitative and reversible trapping of sulfidic gases from headspaces and its application to the study of wine reductive off-odors.

Some relevant food systems release tiny amounts of sulfidic gases, whose measurement is difficult because of their inherent instability. The present paper demonstrates that Cu(I) solutions trap quantitatively and stabilize sulfidic gases. Once trapped, the gases remain stable for weeks at 4 °C and at least 8 days at 75 °C. Trapped gases can be quantitatively released with tris(2-carboxyethyl) phosphine (TCEP) and brine dilution and then determined by GC. Trapping solutions, placed in 20-mL opened vials housed in 100 mL hermetically-sealed flasks containing wine in anoxia, have been used to monitor the release of sulfidic gases by wines, revealing that at 50 °C, up to 400 µg/L of H2S and 58 µg/L of MeSH can be released in 68 days, and 3-5 times more at 75 °C in 28 days. The possibility to differentiate between released and accumulated amounts provides key clues to understanding the fate of sulfidic gases in wine and other food systems.

Sulfide inhibition on polyphosphate accumulating organisms and glycogen accumulating organisms: Cumulative inhibitory effect and recoverability.

Sulfate in wastewater can be reduced to sulfide and its impact on the stability of enhanced biological phosphorus removal (EBPR) is still unclear. In this study, the metabolic changes and subsequent recovery of polyphosphate accumulating organisms (PAOs) and glycogen accumulating organisms (GAOs) were investigated at different sulfide concentrations. The results showed that the metabolic activity of PAOs and GAOs was mainly related to H2S concentration. Under anaerobic conditions, the catabolism of PAOs and GAOs was promoted at H2S concentrations below 79 mg/L S and 271 mg/L S, respectively, and inhibited above these concentrations; whereas anabolism was consistently inhibited in the presence of H2S. The phosphorus (P) release was also pH-dependent due to the intracellular free Mg2+ efflux from PAOs. H2S was more destructive to the esterase activity and membrane permeability of PAOs than those of GAOs and prompted intracellular free Mg2+ efflux of PAOs, resulting in worse aerobic metabolism and subsequent recovery of PAOs than GAOs. Additionally, sulfides facilitated the production of extracellular polymeric substances (EPS), especially tightly bound EPS. The amount of EPS in GAOs was significantly higher than that in PAOs. The above results indicated that sulfide had a stronger inhibition to PAOs than GAOs, and when sulfide was present, GAOs had a competitive advantage over PAOs in EBPR.

Observational evidence linking ocean sulfur compounds to atmospheric dimethyl sulfide during Icelandic Sea phytoplankton blooms.

In two Icelandic Sea spring blooms (May 2018 and 2019) in the North Atlantic Ocean (62.9-68.0°N, 9.0-28.0°W), chlorophyll-a and dimethylsulfoniopropionate (DMSP) concentrations and DMSP lyase activity (the DMSP-to-dimethyl sulfide (DMS) conversion efficiency) were measured at 67 stations, and the hourly atmospheric DMS mixing ratios were concurrently measured only in May 2019 at Storhofdi on Heimaey Island, located south of Iceland (63.4°N, 20.3°W). The ocean parameters for biology (i.e., chlorophyll-a, DMSP, and DMSP lyase activity) were broadly associated in distribution; however, the statistical significance of the association differed among four ocean domains and also between 2018 and 2019. Specifically, the widespread dominance of Phaeocystis, coccolithophores, and dinoflagellates (all rich in DMSP and high in DMSP lyase activity) across the study area is a compelling indication that variations in DMSP-rich phytoplankton were likely a main cause of the variations in statistical significance. For all the ocean domains defined here, we found that the DMS production capacity (calculated using the exposures of air masses to ocean biology prior to their arrivals at Heimaey and the atmospheric DMS mixing ratios of those air masses at Heimaey) was surprisingly consistent with in situ ocean S data (i.e., DMSP and DMSP lyase activity). Our study shows that the proposed computational approach enabled the detection of changes in DMS production and emission in association with changes in ocean primary producers.

Development of methods for quantitative determination of the total and reactive polysulfides: Reactive polysulfide profiling in vegetables.

Alliaceous and cruciferous vegetables are rich in bioactive organosulfur compounds, including polysulfides, which exhibit a broad spectrum of potential health benefits. Here, we developed novel, accurate, and reproducible methods to quantify the total polysulfide content (TPsC) and the reactive polysulfide content (RPsC) using liquid chromatography-electrospray ionization-tandem mass spectrometry, and analyzed the reactive polysulfide profiles of 22 types of fresh vegetables, including onions, garlic, and broccoli. Quantitative analyses revealed that onions contained the largest amounts of polysulfides, followed by broccoli, Chinese chive, and garlic. A strong positive correlation was observed between the TPsC and RPsC, whereas only a moderate positive correlation was found between the total sulfur content and TPsC. These results suggest that reactive polysulfide profiling can be a novel criterion for evaluating the beneficial functions of vegetables and their derivatives, which may lead to an understanding of the detailed mechanisms underlying their bioactivities.

Reactive sulfide dynamic models for predicting metal hazardous in sediments of two northern Egyptian Lakes.

To track pollution status and bioavailability of Cu, Zn, Cd, Pb, and Ni, the current study's acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) models were compared to previous studies in Edku and Mariut lakes prior to 8 years. Sediment samples were collected in winter and summer 2019 from the two lakes. Metal pollution is higher in the winter than in the summer, according to SEM/AVS models. Metal toxicity is reported to have increased slightly in both lakes. According to risk quotients (RQSEM-PEL and RQSEM-TEL) the two lakes are moderately polluted. The results of the Fe/AVS ratio were in the range of 6.77 to 226.87 and 2.88 to 36.38 µmol/g for Edku and Mariut lakes, respectively. This indicated that [SEM]/[AVS] ratios overestimate the availability of metals. A positive correlation was reported between total organic matter and ∑SEM (r = 0.74 and 0.39 at p < 0.05) in Mariut and Edku lakes, respectively. Multiple-year SEM-AVS studies are recommended.

Volatile sulfide compounds and oral microorganisms on the inner surface of masks in individuals with halitosis during COVID-19 pandemic.

Mask-wearing is still recommended owing to the continuing impact of the COVID-19 pandemic. Within the closed chamber created by the mask, people are increasingly self-aware of their oral malodor. In this prospective and cross-sectional study, we aimed to measure volatile sulfide compound (VSC) levels in patients with halitosis and investigate the oral microbiome profile on the inner surface of their KF94 masks. We also investigated which oral microbiota increases VSC levels and whether the oral microbiomes of oral saliva and mask are correlated. A total of 50 subjects (41 women, average age 38.12 ± 12.58 years old) were included in the study, 25 healthy subjects and 25 patients with halitosis who wore masks for more than 3 h. The dominant bacterial species, bacterial profile, and Shannon diversity index of whole unstimulated saliva and the inner surface of the mask were investigated. The bacterial 16S ribosomal RNA genes of the major oral bacterial species were analyzed using real-time PCR. Gas chromatography was used to measure hydrogen sulfide (H2S) and methyl mercaptan (CH3SH), which are representative VSCs. The total bacterial DNA copy number was significantly higher in the saliva sample than in the mask sample (p < 0.001), and the average value was 276 times greater. Shannon diversity index was also significantly higher in saliva than in the inner surface of the mask (2.62 ± 0.81 vs. 1.15 ± 1.52, p < 0.001). The most common Gram-negative and Gram-positive species in the masks were Porphyromonas gingivalis (Pg) and Lactobacillus casei (Lc), respectively. The bacterial species with significant positive correlations between saliva and mask samples were Prevotella intermedia (Pi) (r = 0.324, p = 0.022), Eikenella corrodens (r = 0.309, p = 0.029), Lc (r = 0.293, p = 0.039), and Parvimonas micra (Pm) (r = 0.366, p = 0.009). The mean value of CH3SH was significantly higher in the halitosis group than in the non-halitosis group (17.84 ± 29.00 vs. 3.84 ± 10.57 ppb, p = 0.031). In the halitosis group, the DNA copy numbers and VSC levels showed highly positive correlation coefficients in the order Pg, Treponema denticola (Td), Tannerella forsythia (Tf), Pi, and Prevotella nigrescens (Pn) (all p < 0.05). Regarding bacterial profiles of the mask, Td was strongly correlated with CH3SH (r = 0.414, p = 0.040) and total VSCs (r = 0.374, p = 0.033) only in halitosis group. Mask-wearing time was strongly correlated with total VSCs, H2S, and CH3SH (all r > 0.8, p < 0.001). Oral bacteria, whose association with halitosis has been identified, increased VSC levels in mask-wearing subjects during the COVID-19 pandemic, particularly the number of Gram-negative anaerobes such as Pg and Td. Mask-wearing time was a major factor in increasing VSC levels. The study results suggest that people with halitosis could control these Gram-negative bacteria by improving oral hygiene and regularly changing masks.

Characteristics, sources, and risk assessment of thallium and associated with metal(loid)s in the Yarlung Tsangpo River Basin, southern Tibetan Plateau.

The Tibetan Plateau (TP) is known as the water tower of Asia, and the water quality has long been a focus of public concern, especially in the Yarlung Tsangpo River Basin (YTRB), a unique area that is climate-sensitive, geologically complex, eco-fragile, and densely populated. Thallium (Tl) is a typical metal that is more toxic than Pb, Cd, and As and often occurs in sulfide minerals. Although large-scale polymetallic sulfide mineralization developed in the YTRB, the geochemical dispersion and potential risk of Tl in aquatic environments of the YTRB remain poorly understood. In this study, the concentration, distribution, source, and health risk of Tl and associated metal(loid)s in the hot springs and surface water in the YTRB were systematically analyzed. The results showed that the trace elements (Cd, Cr, Zn, Cu, Al, Sr, Ni, Co, Mn, Pb) in water environments are within the recommended limits, except for Tl and As. Principal component analysis (PCA) and correlation analysis (CA) showed that the elements of Tl and As were positively related to each other in either both hot spring water and surface water, indicating their common origin. Spatial variations suggested that high levels of Tl and As observed in the north YTRB, which may be relevant to the reduction-dissolution of Tl (As)-bearing minerals and the magmatic hydrothermal system formed in the shallow part of the northern YTRB. Furthermore, source apportionment identified natural sources of Cu, Ni, Cr, Co, Mn, Zn, and Cd and anthropogenic inputs of Al and Pb. Exposure assessment studies have found that ingestion is the primary route of As and Tl exposure to local population, and balneological and bathing purposes do not constitute a human health concern. This study offers valuable insights into the risk of naturally occurring Tl enrichment being hidden in As-rich hydrosphere in the YTRB and other regions with similar geoenvironmental contexts.

Quantitative identification of groundwater contamination sources by combining isotope tracer technique with PMF model in an arid area of northwestern China.

Nowadays, groundwater quality has deteriorated because of intensive human activities. It is important to accurately identify the pollution source for controlling the deterioration of groundwater quality. However, the accuracy of the current source analysis method needs to be improved. In this study, we combined hydrochemical method, isotope tracing technique and PMF model, for the first time, to trace the source of groundwater pollution in Beichuan River basin, Qinghai Province, China. According to the results, there were 35.8% of Fe, 34.1% of total hardness, 24.3% of SO42- and 8.09% of NO3- samples exceeded the Grade III standards for Groundwater quality in China, which indicated that the groundwater in the study area has been significantly affected by human activities. Hydrochemical method suggested that the chemical component originated from rock weathering, cation exchange and mineral dissolution. Based on isotope tracing technique (δ15N-NO3-, δ18O-NO3-, δ34S-SO42- and δ18O-SO42-), the primary sources of nitrate and sulfate in groundwater were soil nitrogen and oxidation of sulfide minerals in the forest area, domestic sewage and oxidation of sulfide minerals in the urban and industrial area, and mixed sources in the village and agricultural area. Finally, the pollution source of groundwater was distinguished by combining the PMF model, isotope tracing technique and hydrochemical method. Results showed that the main pollutant of groundwater is domestic sewage in the urban, village and industrial area. The contribution rates to groundwater pollution were 60.7%, 60.8% and 57.8%, respectively. However, in the forest and agricultural area, the main source changed to water-rock interaction and chemical fertilizer, and the contribution rates to groundwater quality were 53.5% and 61.0%, respectively. Our results suggested that the coupling tracing methodology can improve the accuracy of source resolution in the water environment and it can be applied to other areas of the world.

Tracing Sulfate Source and Transformation in the Groundwater of the Linhuan Coal Mining Area, Huaibei Coalfield, China.

Mining activities cause surface sulfate enrichment, which has negative impacts on human health and ecosystems. These high concentrations of sulfate may enter groundwater through the unsaturated zone (UZ), threatening groundwater quality. Therefore, we combined hydrochemical and dual isotopic analyses of sulfate in surface water, soil water and groundwater with evaluations of the UZ to identify the groundwater sulfate source and transformation in the coal mining area. Soil profile samples were collected near gangue heaps (UZ-1, UZ-2) and the mean sulfate concentrations of the UZ-1 profile and UZ-2 profile were 35.4 mg/L and 69.63 mg/L, respectively. The shallow groundwater sulfate was mainly from dissolution of evaporite, sulfide oxidation and sewage. Different sulfate contaminated areas showed different characteristics of sulfate sources. The sulfate source to groundwater near the coal gangue heaps was sulfide oxidation. The groundwater sulfate near the gangue heaps and industrial park compound contamination area was mainly derived from industrial and domestic sewage and sulfide oxidation. In addition, the role of bacterial sulfate reduction (BSR) in the groundwater was not obvious. This research result is of great significance for promoting the safe mining of coal resources and sustainable utilization of groundwater in the Huaibei coal mining area and other coal mining areas in China.

A hydrochemical and multi-isotopic study of groundwater sulfate origin and contribution in the coal mining area.

Coal mining cities are universally confronted with the degradation of groundwater quality, and the sulfate pollution of groundwater has become a widely studied environmental problem. In this study, we combined multi-isotope (δ34S, δ18O-SO42- and 87Sr/86Sr) approach with hydrochemical technique and a Bayesian mixed model to clarify sources and transformations and to quantitatively assess the contribution of sulfate from potential sources. The concentrations of SO42- in groundwater ranged from 7.7 mg/L to 172.9 mg/L, and the high-value areas were located in coal mining area and residential area. The total values of δ34S and δ18O-SO42- varied from 10.6‰ to 26.9‰ and 6.9‰ to 14.1‰, respectively, in the groundwater. Analyses of SO42- and Sr isotopes and water chemistry indicated that SO42- in groundwater originated from various sources, such as atmospheric precipitation, sulfide mineral oxidation, evaporite dissolution, sewage and mine drainage. The oxidation of pyrite and bacterial sulfate reduction (BSR) had no significant impact on the stable isotopes of groundwater. At the same time, the calculation results of the Bayesian mixed model showed that the sources of SO42- in groundwater mainly include evaporite dissolution in aquifer and mine drainage in the mixture of shallow and deep groundwater, with high contribution proportions of 39.8 ± 10.9% and 31.9 ± 5.7%, respectively, while the contributions of sewage (13.9 ± 8.5%), atmospheric precipitation (9.6 ± 8.6%) and the oxidation of sulfide (4.7 ± 3.3%) to SO42- were lower. The research results revealed the source of SO42- pollution in shallow groundwater in the coal mine area and provided an important scientific basis for the effective management and protection of groundwater resources.

Highly selective and sensitive spectrofluorimetric method for determination of cypermethrin in different environmental samples.

A sensitive, selective, and simple spectrofluorimetric method for the detection and determination of cypermethrin (CYP) in various samples based on thioglycolic acid-caped Mn-doped ZnS quantum dots (TGA@Mn-ZnS-QDs) is reported. These quantum dots were synthesized using the Gonzalez method. The synthesized quantum dots were structurally characterized with the help of different spectroscopic techniques including X-ray diffraction (XRD) and energy dispersive X-ray (EDX) techniques and fluorescence spectroscopy. The quantum dots were used for spectrofluorimetric detection and determination of CYP. The emission peak of these quantum dots at 632 nm showed a linear quenching with increasing the concentration of CYP, noticing an excellent linear relationship between F°/F values and CYP in the range of 0.5-12 µg mL-1 with a correlation coefficient (R2) of 0.992. The influence of different physiochemical parameters such as time, pH, the concentration of quantum dots, and other pesticides interference on the fluorescence quenching was investigated. The detection limit was calculated to be 0.132 µg mL-1. The developed method was successfully applied for the detection and determination of CYP in various spiked samples (tomato, okra, pea, spinach, soil, and water) using the spike and recovery methods. The percent recoveries of CYP from these samples were found to be 77 ± 0.05% to 95 ± 0.12% at various levels.

Developing ecological risk assessment of metals released from sediment based on sediment quality guidelines linking with the properties: A case study for Kaohsiung Harbor.

This study aimed to introduce sediment properties (total organic carbon (TOC), acid-volatile sulfides (AVS), particle size distribution) into sediment quality guideline-based risk quotients to assess the potential toxicity of metals (Ni, Cu, Zn, Cr, Cd, and Pb) released from sediments. Sediment was collected at three times points in 20 sampling sites in Kaohsiung Harbor. The Microtox® toxicity test was used to assess the sediment toxicity and the relationship between sediment toxicity and risk quotient estimated based on the metal concentration was constructed. To improve the toxicity prediction and modify the risk quotient according to the sediment properties, stepwise multiple linear regression (MLR) models that have been tested over wide ranges of TOC, AVS, and particle size distribution to determine the key sediment properties. Common multimetal indices, including the pollution load index, modified degree of contamination index, Nemerow pollution index, potential ecological risk index, and total toxic risk index, were compared with sediment toxicity to evaluate the degrees of correlation. By modifying the relationship between metal toxicity and the risk quotient by including TOC and AVS, the prediction showed that sediments in Kaohsiung Harbor were generally of slight acute toxicity to acute toxicity to organisms, with sampling sites near an industrial zone showing a higher probability of high acute toxicity. In particular, the acute risk of adverse effects on aquatic organisms from sediments in the Salt River estuary was significantly higher than that at other sites, which was consistent with the results of assessment based on the multimetal indices. This study suggests that the MLR-based approach may facilitate the adoption of updated site-specific metals standards that more accurately account for the parameters affecting metal bioavailability than metal concentration standard alone.