Procedures from samples to sulfur isotopic data: A review.

RATIONALE: Sulfur isotopes have been widely used to solve some key scientific questions, especially in the last two decades with advanced instruments and analytical schemes. Different sulfur speciation and multiple isotopes analyzed in laboratories worldwide and in situ microanalysis have also been reported in many articles. However, methods of sampling to measurements are multifarious, and occasionally some inaccuracies are present in published papers. Vague methods may mislead newcomers to the field, puzzle readers, or lead to incorrect data-based correlations. METHODS: We have reviewed multiple methods on sulfur isotopic analyses from the perspectives of sampling, laboratory work, and instrumental analysis in order to help reduce operational inhomogeneity and ensure the fidelity of sulfur isotopic data. We do not deem our proposed solutions as the ultimate standard methods but as a lead-in to the overall introduction and summary of the current methods used. RESULTS: It has been shown that external contamination and transformation of different sulfur species should be avoided during the sampling, pretreatment, storage, and chemical treatment processes. Conversion rates and sulfur isotopic fractionations during sulfur extraction, purification, and conversion processes must be verified by researchers using standard or known samples. The unification of absence of isotopic fractionation is needed during all steps, and long-term monitoring of standard samples is recommended. CONCLUSION: This review compiles more details on different methods in sampling, laboratory operation, and measurement of sulfur isotopes, which is beneficial for researchers' better practice in laboratories. Microanalyses and molecular studies are the frontier techniques that compare the bulk sample with the elemental analysis/continuous flow-gas source stable isotope ratio mass spectrometry method, but the latter is widely used. The development of sulfur isotopic measurements will lead to the innovation in scientific issues with sulfur proxies.

Multiple Sulfur Isotopic Evidence for Sulfate Formation in Haze Pollution.

The mechanism of sulfate formation during winter haze events in North China remains largely elusive. In this study, the multiple sulfur isotopic composition of sulfate in different grain-size aerosol fractions collected seasonally from sampling sites in rural, suburban, urban, industrial, and coastal areas of North China are used to constrain the mechanism of SO2 oxidation at different levels of air pollution. The Δ33S values of sulfate in aerosols show an obvious seasonal variation, except for those samples collected in the rural area. The positive Δ33S signatures (0‰ < Δ33S < 0.439‰) observed on clean days are mainly influenced by tropospheric SO2 oxidation and stratospheric SO2 photolysis. The negative Δ33S signatures (-0.236‰ < Δ33S < ∼0‰) observed during winter haze events (PM2.5 > 200 µg/m3) are mainly attributed to SO2 oxidation by H2O2 and transition metal ion catalysis (TMI) in the troposphere. These results reveal that both the H2O2 and TMI pathways play critical roles in sulfate formation during haze events in North China. Additionally, these new data provide evidence that the tropospheric oxidation of SO2 can produce significant negative Δ33S values in sulfate aerosols.

Legacy phosphorus delays the accomplishment of expected phosphorus management object.

Legacy phosphorus (P) in watersheds continuously affects the water quality. The time lag between anthropogenic P input and algal bloom has made P dynamics prediction in aquatic ecosystems more challenging. Whether the legacy P in the Yangtze River Watershed (YRW) exceeds its storage threshold remains unknown, and the continuous impact of legacy P on the water quality has not been analyzed. This study aimed to evaluate variation trends (1970-2018) and influencing factors for accumulated P in the YRW under different economic development periods, quantitatively identify the watershed P storage threshold based on the two split line models and estimate the time required for the return of legacy P to the baseline level using an exponential decay process. The results showed that the P storage threshold of the YRW was surpassed due to intense anthropogenic activities, and the residual P still had an impact on aquatic ecosystems for a long time. The dissolved total P loadings may become the top priority to achieve better P management goals. The time lags for the legacy P restoration would require for about 1000 years to be exhausted. The legacy P in the YRW would continuously undermine the restoration efforts of the water quality. The combined effects of watershed P surplus reductions and depletion of residual P may become essential to better manage P in the future. We still need to strengthen our efforts to make soil legacy P more absorbed by crops and improve sewage treatment capacity to achieve sustainable development of YRW.

Partition pattern and environmental consequences of the widespread coalmines and host rocks on the water of selected regions, China.

The massive exploration and random dumping of coals in various regions of China create serious environmental and health problems because of the presence of toxic trace elements (TTEs), which possibly transfer to environment and cause serious health issues. This study was conducted to probe the environmental consequences of coalmines on the aquifer water and their association with health risks and the environment. For this purpose, 100 s of water samples was collected from the typical coalmine regions of Hancheng, Huanglong, Binxian, Handan, Langao, and Fusui and analyzed for various parameters. In Handan mining areas, Se, Mn, Fe, TDS, SO42-, and total hardness were higher than the WHO standard, while in Hancheng, SO42- was > 95%, Ca2+ 40-96%, and Mg2+ was 0-40%, which caused permanent hardness. In the Fusui and Huanglong areas, the SO42- concentration was > 95%, Ca2+ 60-100%, and Mg2+ 20%, causing permanent hardness. In Binxian, HCO3- was 70-90%, Ca2+ 60-80%, and Cl- and SO42- were 20%, causing temporary hardness. In the Kashin-Beck disease (KBD) area, Se in the Middle Triassic was 0.3, Upper Triassic 0.23, and Quaternary 0.01, while fluoride (F) was 124.7, 141.6, and 159 in µg L-1. The Handan water is included in rock-evaporation dominance (a mixed controlling mechanism), Hancheng, Binxian, Huanglong, and Langao water was included in rock dominance, while the Fusui water was included in rock-precipitation dominance. The average daily intake ((ADI) mg kg-1 d-1) of Ba, Cd, Co, Cr, Cu, Fe, Ti, Tl, Mo, Ni, Zn, Pb, Be, U, and Sr was comparably higher than No Observed Adverse Effect Level (NOAEL), which surely causes high health risk in selected regions. The elemental contaminants in the water were attributed to the geological environment, geochemical processes, ion exchanges, redox reactions, and dissolution of mineralized rock. For aquifer safety, coal mining, and other geological activities should be avoided to protect the water for future generations.

Environmental challenges from the increasing medical waste since SARS outbreak.

Medical waste is a special class of hazardous pollutants. Improper treatment would cause secondary environmental pollution, especially when responding to public health emergencies. However, there are relatively few researches on the generation of medical waste, and there is a lack of basic understanding of its spatial-temporal heterogeneity. The outbreak of SARS in 2002 is a turning point in China's medical system reform. We estimated the production of medical waste and pollutants on a provincial scale in China from 2002 to 2018, using the data of medical statistics. Moreover, we forecasted the trend of medical waste in China until 2030, using a combination of environmental pressure model (STIRPAT) and time series model (ARIMA). We found that with the development of China's medical system and economy (such as the increase in personal income and popularization of universal health care), the number of seeking medical treatment rapidly increase led to explosive growth in medical waste (∼240%) and pollutants (∼260%), and large hospitals are the major sources. By 2030, the production of medical waste would still increase by more than 50% compared with 2018 even there is no the pandemic due to the huge population. The production of medical waste in the eastern region was higher than that in the west under the influence of higher population and GDP, while the per capita medical waste was only affected by household consumption level which had no regional characteristic. Additionally, Hg loads from medical waste are more than twice as high as that from discharged wastewater in some regions, which are facing great control pressures. In the future, when planning for medical waste disposal, policymakers shall increase the disposal facilities based on population and promote mobile treatment equipment to improve efficiency, increase the number of beds in medical institutions rather than building more hospitals, and strengthen basic research on the environmental impact.

Pioglitazone Metformin Complex Improves Polycystic Ovary Syndrome Comorbid Psychological Distress via Inhibiting NLRP3 Inflammasome Activation: A Prospective Clinical Study.

OBJECTIVE: This study aimed at investigating the therapeutic effect and mechanism of pioglitazone metformin complex preparation (PM) in polycystic ovary syndrome (PCOS) comorbid psychological distress. METHODS: Seventy-five patients with PCOS comorbid psychological distress were randomly allocated into the PM, metformin, and placebo groups. The primary efficacy measure was the change from baseline to week 12 on the Symptom Checklist 90-R (SCL-90-R) scores. NLRP3 inflammasome, IL-1ß, IL-6, TNF-α, and biochemical parameters were determined at baseline and at week 12. The participants were required to meet the criteria for PCOS (Rotterdam, NIH) and psychological distress (any factor scores of SCL - 90 - R > 2). RESULTS: The participants had significantly high scores on the SCL-90-R scales of anxiety and depression. PM significantly decreased anxiety and depression symptom severity (from 2.31 ± 0.75 to 1.65 ± 0.38, p < 0.001, and from 2.08 ± 0.74 to 1.61 ± 0.46, p = 0.010, at week 12, respectively). PM significantly decreased the expression of NRPL3 and caspase-1. Patients in the PM group experienced a significant reduction in IL-1ß (from 98.42 ± 14.38 to 71.76 ± 13.66, p = 0.02), IL-6 (from 87.51 ± 8.74 to 71.98 ± 15.87, p = 0.02), and TNF-α (from 395.33 ± 88.55 to 281.98 ± 85.69, p = 0.04). PM was superior to metformin in reducing total testosterone (2.24 ± 0.74 versus 3.06 ± 0.83, p = 0.024, at week 12). CONCLUSIONS: This study is the first to reveal that PM alleviates psychological distress via inhibiting NLRP3 inflammasome and improves several markers, including total testosterone.

Qualitative and quantitative analysis of source for organic carbon and nitrogen in sediments of rivers and lakes based on stable isotopes.

Sediment is the most dominant reservoir of organic pollutants in the aquatic environment. Understanding carbon and nitrogen sources in sediments and factors that controls distribution enhances our understanding of biogeochemical cycles of carbon and nitrogen. Different end-members and surface sediments of rivers and sediments profiles of lakes were collected. The concentrations of TOC and TON and their δ13C and δ15N were studied for qualitative and quantitative analysis of natural and anthropogenic sources. The results show that TOC and TON concentrations of the sediments from rivers range from 0.63% to 10.83% and 0.06%-0.86%, respectively, indicating substantial great environmental risks in these rivers. The concentrations of TOC and TON for the four sediment profiles below the 5 cm, increase in the order of Miyun < Chuidiao < Qunming < Houhai, as influenced by their respective environment condition. Moreover, water quality was quite good and there was no risk of eutrophication in Miyun reservoir. δ13Corg and δ15Norg in surface sediments of the studied 18 rivers range from -27.2‰ to -24.9‰ and -2.2‰ to +10.9‰, respectively. Based on a simple δ13C-based end-member mixing and a C/N ratio model, organic matter in the surface sediments of these rivers were mainly derived from sewage and C3 plant. In addition, the sources of organic matter differed in each layer of the four sediment profiles. This study provides a reliable method for qualitative and quantitative identification of the source of organic matter in sediments, and offers theoretical basis for better management of rivers and lakes.

Characteristics of cadmium accumulation and isotope fractionation in higher plants.

Cadmium (Cd) pollution of the soil is an important global environmental issue owing to its great toxicity. The study of metal isotope fractionation is a novel technique that could be used to identify and quantify metal uptake and transport mechanisms in plant. In this study, cadmium tolerant Ricinus communis and hyperaccumulator Solanum nigrum have been cultured in different Cd concentration nutrient solutions. The Cd isotope values, metal elements concentrations in the organs (root, stem and leaf) in the two plant species have been measured during the growth periods (10d, 15d, 20d, 25d, and 30d). The results indicate that the organs of S. nigrum could be enriched with lighter Cd isotopes compared with R. communis. In addition, the Cd isotope fractionation become smaller when the plants were subjected to high Cd toxicity, which indicates that Cd isotope fractionation reflected the extent of Cd toxicity to plants. This study advances our current view of Cd translocation machination in plants.

Effects of cadmium stress on growth and amino acid metabolism in two Compositae plants.

Cadmium, a high toxic heavy metal, is one of the most serious contaminants in soil and a potential threat to plant growth and human health. Amino acid metabolism has the central role in heavy metal stress resistance of plants. In this paper, a pot experiment was carried out to study the effects of different concentrations of cadmium (0, 3, 6, 12, 30 mg kg-1) on the growth, Cd accumulation and amino acid metabolism in two Compositae plants (Ageratum conyzoides L. and Crassocephalum crepidioides). The results showed that under cadmium stress, C. crepidioides accumulated more Cd in its shoot and was tolerant to Cd, whereas its low Cd-accumulating relative, A. conyzoides, suffered reduced growth. The Cd content in the aerial part of C. crepidioides exceeded the threshold of Cd-hyperaccumulator. Furthermore, the bioaccumulation factor (BCF) and biological transfer factor (BTF) values for Cd in C. crepidioides were > 1. Thus, C. crepidioides can be regarded as Cd-hyperaccumulator. The comparison between both studied plants indicated that Cd stress resulted in a differential but coordinated response of amino acid levels, which are playing a significant role in plant adaptation to Cd stress. Glu, Gln, Asp, Asn, Gaba, Val and Ala dominated the major amino acids. Higher Cd tolerance and Cd accumulation in C. crepidioides was associated with greater accumulation of free amino acids, especially for Gln and Asn, in C. crepidioides than in A. conyzoides.

Heavy metal contents and enrichment characteristics of dominant plants in wasteland of the downstream of a lead-zinc mining area in Guangxi, Southwest China.

A field investigation on the content of heavy metals in soils and 17 kinds of dominant plants from wasteland of the downstream of a Pb-Zn mine in Northwest Guangxi Zhuang Autonomous Region was carried out. The absorption and accumulation characteristics of heavy metals between plants and soil were compared, and the candidate species for ecosystem restoration of the area were selected. The results indicated that the soils had been subjected to pollution of heavy metals in varying degrees. The concentrations of Cd, Pb, Zn were 46.5, 57.3 and 23.7 times higher than their corresponding background values, respectively. The contents of Cd, Pb and Zn in the most analyzed plants exceed the normal ranges and the phytotoxic level. C. crepidioides, S. nigrum, B. pilosa, C. Canadensis, A. conyzoides, I. denticulata and E. crusgali showed strong capability in accumulation and transport of Cd, and they could be used as good candidates for Cd- phytoextraction. Among which, Cd concentration in the aerial part of C. crepidioides exceeded the threshold of Cd-hyperaccumulator. Thus, C. crepidioides demonstrated the basic characteristics of a Cd-hyperaccumulator. The lower translocation ratios for Cd, Cu, Zn and Pb in P. vittata and C. chinensis make them suitable for phytostabilization in the study area.

Multiple Sulfur Isotope Constraints on Sources and Formation Processes of Sulfate in Beijing PM2.5 Aerosol.

Recently air pollution is seriously threatening the health of millions of people in China. The multiple sulfur isotopic composition of sulfate in PM2.5 samples collected in Beijing is used to better constrain potential sources and formation processes of sulfate aerosol. The Δ33S values of sulfate in PM2.5 show a pronounced seasonality with positive values in spring, summer and autumn and negative values in winter. Positive Δ33S anomalies are interpreted to result from SO2 photolysis with self-shielding, and may reflect air mass transport between the troposphere and the stratosphere. The negative Δ33S signature (-0.300‰ < Δ33S < 0‰) in winter is possibly related to incomplete combustion of coal in residential stoves during the heating season, implying that sulfur dioxide released from residential stoves in more rural areas is an important contributor to atmospheric sulfate. However, negative Δ33S anomalies (-0.664‰ < Δ33S ← 0.300‰) in winter and positive Δ33S anomalies (0.300‰ < Δ33S < 0.480‰) in spring, summer, and autumn suggest sulfur isotopic equilibrium on an annual time frame, which may provide an implication for the absence of mass-independent fractionation of sulfur isotopes (S-MIF) in younger sediments. Results obtained here reveal that reducing the usage of coal and improving the heating system in rural areas will be important for efficiently decreasing the emissions of sulfur in China and beyond.

Template-free electrodeposition of AlFe alloy nanowires from a room-temperature ionic liquid as an anode material for Li-ion batteries.

AlFe alloy nanowires were directly electrodeposited on copper substrates from trimethylamine hydrochloride (TMHC)-AlCl3 ionic liquids with small amounts of FeCl3 at room temperature without templates. Coin cells composed of AlFe alloy nanowire electrodes and lithium foils were assembled to characterize the alloy electrochemical properties by galvanostatic charge/discharge tests. Effects of FeCl3 concentration, potential and temperature on the alloy morphology, composition and cyclic performance were examined. Addition of Fe into the alloy changed the nanowires from a 'hill-like' bulk morphology to a free-standing morphology, and increased the coverage area of the alloy on Cu substrates. As an inactive element, Fe could also buffer the alloys' large volume changes during Li intercalation and deintercalation. AlFe alloy nanowires composed of a small amount of Fe with an average diameter of 140 nm exhibited an outstanding cyclic performance and delivered a specific capacity of about 570 mA h g(-1) after 50 cycles. This advanced template-free method for the direct preparation of high performance nanostructure AlFe alloy anode materials is quite simple and inexpensive, which presents a promising prospect for practical application in Li-ion batteries.

Comparison of chelates for enhancing Ricinus communis L. phytoremediation of Cd and Pb contaminated soil.

We studied chelate effects on castor bean (Ricinus communis L.) growth. These effects included Cd and Pb accumulation in plant tissues and the chemical behavior of Cd and Pb in the plant rhizosphere and non-rhizosphere. Tests were conducted in a glasshouse using the rhizobag method. Two castor bean cultivars (Zibo-3 and Zibo-9) were grown in soil contaminated with 3.53mg/kg Cd and 274mg/kg Pb. The soil was treated with citric acid (CA), ethylenediamine disuccinic acid (EDDS) or ethylenediamine tetraacetic acid (EDTA) (5mmol/kg). EDDS-treated soil produced 28.8% and 59.4% greater biomass for Zibo-3 and Zibo-9 respectively. In contrast, CA and EDTA inhibited the growth of the two cultivars. Zibo-9 had greater tolerance than Zibo-3 to chelate toxicity. Based on Cd and Pb plant uptake, EDDS could substitute for EDTA for phytoremediation of Cd in soil. EDTA was the most effective of the three chelates for Pb phytoremediation but it is less suitable for field use due to toxicology environmental persistence. Acid extractable Cd and Pb in the rhizosphere or reducible Cd and Pb in the non-rhizosphere of soil were the main influences on Cd and Pb accumulation in castor bean.

Interaction between sulfur and lead in toxicity, iron plaque formation and lead accumulation in rice plant.

Human activities have resulted in lead and sulfur accumulation in paddy soils in parts of southern China. A combined soil-sand pot experiment was conducted to investigate the influence of S supply on iron plaque formation and Pb accumulation in rice (Oryza sativa L.) under two Pb levels (0 and 600 mg kg(-1)), combined with four S concentrations (0, 30, 60, and 120 mg kg(-1)). Results showed that S supply significantly decreased Pb accumulation in straw and grains of rice. This result may be attributed to the enhancement of Fe plaque formation, decrease of Pb availability in soil, and increase of reduced glutathione (GSH) in rice leaves. Moderate S supply (30 mg kg(-1)) significantly increased Fe plaque formation on the root surface and in the rhizosphere, whereas excessive S supply (60 and 120 mg kg(-1)) significantly decreased the amounts of iron plaque on the root surface. Sulfur supply significantly enhanced the GSH contents in leaves of rice plants under Pb treatment. With excessive S application, the rice root acted as a more effective barrier to Pb accumulation compared with iron plaque. Excessive S supply may result in a higher monosulfide toxicity and decreased iron plaque formation on the root surface during flooded conditions. However, excessive S supply could effectively decrease Pb availability in soils and reduce Pb accumulation in rice plants.

Subcellular cadmium distribution and antioxidant enzymatic activities in the leaves of two castor (Ricinus communis L.) cultivars exhibit differences in Cd accumulation.

The aims of this study were: (1) the study of cadmium (Cd) accumulation and toxicity in different castor cultivars (Ricinus communis L.); (2) to investigate changes in antioxidant enzymatic activities and the subcellular distribution of Cd in young and old leaves from two different castor cultivars, after exposure to two different Cd concentrations, and explore the underlying mechanism of Cd detoxification focusing on antioxidant enzymes and subcellular compartmentalization. The Cd concentration, toxicity, and subcellular distribution, as well as superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) activities were measured in Zibo-3 and Zibo-9 cultivars after exposure to two different concentrations of Cd (2mg/L and 5mg/L) for 10 days. This research revealed Cd accumulation characteristics in castor are root>stem>young leaf>old leaf. Castor tolerance was Cd dose exposure and the cultivars themselves dependent. Investigation of subcellular Cd partitioning showed that Cd accumulated mainly in the heat stable protein (HSP) and cellular debris fractions, followed by the Cd rich granule (MRG), heat denatured protein (HDP), and organelle fractions. With increasing Cd concentration in nutrient solution, the decreased detoxified fractions (BDM) and the increased Cd-sensitive fractions (MSF) in young leaves may indicate the increased Cd toxicity in castor cultivars. The BDM-Cd fractions or MSF-Cd in old leaves may be linked with Cd tolerance of different cultivars of castor. The antioxidant enzymes that govern Cd detoxification were not found to be active in leaves. Taken together, these results indicate Cd tolerance and toxicity in castor can be explained by subcellular partitioning.

Cadmium accumulation and tolerance of two castor cultivars in relation to antioxidant systems.

To investigate the effects of Cd on tolerance and antioxidant activities of castor, two different castor (Ricinus communis L.) cultivars (Zibo No. 5 and Zibo No. 8) were used for a hydroponic experiment (0, 1 and 2mg/L Cd) and a pot experiment using Cd-contaminated soil (34mg/kg) with the addition of ethylenedinitrilotetraacetic acid (EDTA). The results indicated that there were significant differences between the two cultivars with respect to Cd uptake in shoots (113-248mg/kg for Zibo No. 5 and 130-288mg/kg Zibo No. 8), biomass tolerance indexes (64.9%-74.6% for Zibo No. 5 and 80.1%-90.9% for Zibo No. 8) in the hydroponic experiment and survival rates (0% for Zibo No. 5 and 100% for Zibo No. 8) determined by the addition of EDTA in the pot experiment, suggesting that Zibo No. 8 has higher tolerance than Zibo No. 5. Moreover, the castor cultivars have low bioconcentration factors (4.80% for Zibo No. 5 and 5.43% for Zibo No. 8) and low translocation factors (<1%). Consequently, Zibo No. 8 can participate in Cd phytostabilization in highly Cd-polluted areas. The results indicated that glutathione (GSH) as a non-enzymatic antioxidant, and antioxidant enzymes including superoxide dismutase (SOD), catalase (CAT) and guaiacol peroxidase (GPX), were cultivar- and dose-dependent. The higher tolerance of Zibo No. 8 compared with Zibo No. 5 can be attributed to the higher GSH levels in the root and higher GPX activity in the leaf.

Global scale identification of catchments phosphorus source shifts with urbanization: A phosphate oxygen isotope and Bayesian mixing model approach.

Different scenarios of urban expansion can influence the dynamic characteristics of catchments in terms of phosphorus (P). It is important to identify the changes in P sources that occur during the process of urbanization to develop targeted policies for managing P in catchments. However, there is a knowledge gap in quantifying the variations of potential P sources associated with urbanization. By combining phosphate oxygen isotopes from global catchments with a Bayesian model and the urbanization process, we demonstrate that the characteristics of potential P sources (such as fertilizers, urban wastewater, faeces, and bedrock) change as urban areas expand. Our results indicate that using phosphate oxygen isotopes in conjunction with a Bayesian model provides direct evidence of the proportions of potential P sources. We classify catchment P loadings into three stages based on shifts in potential P sources during urban expansion. During the initial stage of urbanization (urban areas < 1.5 %), urban domestic and industrial wastewater are the main contributors to P loadings in catchments. In the mid-term acceleration stage (1.5 % ≤ urban areas < 3.5 %), efforts to improve wastewater treatment significantly reduce wastewater P input, but the increase in fertilizer P input offsets this reduction in sewage-derived P. In the high-level urbanization stage (urban areas ≥ 3.5 %), the proportions of the four potential P sources tend to stabilize. Remote areas bear the burden of excessive P loadings to meet the growing food demand and improved diets resulting from the increasing urban population. Our findings support the development of strategies for water quality management that better consider the driving forces of urbanization on catchment P loadings.

Elevated lead mobility in sediments of a eutrophic drinking water reservoir during spring and summer seasons: Insights from isotopic signatures.

Lead (Pb) pollution in sediments remains a major concern for ecosystem quality due to the robust interaction at the sediment/water interface, particularly in shallow lakes. However, understanding the mechanism behind seasonal fluctuations in Pb mobility in these sediments is lacking. Here, the seasonal variability of Pb concentration and isotopic ratio were investigated in the uppermost sediments of a shallow eutrophic drinking lake located in southeast China. Results reveal a sharp increase in labile Pb concentration during autumn-winter period, reaching ∼ 3-fold higher levels than during the spring-summer seasons. Despite these fluctuations, there was a notable overlap in the Pb isotopic signatures within the labile fraction across four seasons, suggesting that anthropogenic sources are not responsible for the elevated labile Pb concentration in autumn-winter seasons. Instead, the abnormally elevated labile Pb concentration during autumn-winter was probably related to reduction dissolution of Fe/Mn oxides, while declined labile Pb concentration during spring-summer may be attributed to adsorption/precipitation of Fe/Mn oxides. These large seasonal changes imply the importance of considering seasonal effects when conducting sediment sampling. We further propose a solution that using Pb isotopic signatures within the labile fraction instead of the bulk sediment can better reflect the information of anthropogenic Pb sources.

Impacts of mining activities on the spatial distribution and source apportionment of soil organic matter in a karst farmland.

Worldwide mining activities produce vast quantities of mine tailings, which pose a threat to soil quality, crop yields, and the regional environment in the adjacent agricultural soil, but little is known about the impact of mining activities on the SOM source and migration. In this study, soil samples of the topsoil (0-15 cm) and soil profiles (0-50 cm), as well as the potential sources samples (C3 plants, C4 plants and mining tailings) were collected from mine-contaminated karst farmland of four different pollution levels (NP, non-polluted; SP, slightly polluted; MP, moderately polluted; and HP, heavily polluted). Total organic carbon (TOC), total organic nitrogen (TON), and stable isotopic compositions (δ13Corg and δ15Norg) of soil and potential sources samples were determined. In the topsoil, the concentrations of TOC (1.9 ± 1.4 %) and TON (0.1 ± 0.1 %), and the value of δ13Corg (-25.4 ± 0.9 ‰) and δ15Norg (-3.6 ± 3.6 ‰), were not significantly different among HP, MP and SP farmland (P > 0.05). C3 plants (42.1 %-49.9 %) and mine tailings (32.3 %-40.1 %) were identified as the dominant source of topsoil SOM. In the soil profile, TOC%, TON%, δ13Corg, and δ15Norg were affected by soil depth and pollution level. TOC% and TON% in the soil profiles of NP changed slightly with soil depth, while that in the other soil profiles was decreased with the increasing of soil depth. The δ15Norg value in the SP soil dropped sharply when the soil depth was >15 cm, while that in the HP and MP soil was fluctuated and no obvious vertical pattern. Our findings provide valuable information regarding the impact of mining activities on SOM distribution and source apportionment in karst farmlands. The effects of mine tailings on SOM should be considered when the soil quality was estimated in the mine-grain composite area.