Controllable Pyridine N-Oxidation-Nucleophilic Dechlorination Process for Enhanced Dechlorination of Chloropyridines: The Cooperation of HCO4- and HO2.

Dechlorination of chloropyridines can eliminate their detrimental environmental effects. However, traditional dechlorination technology cannot efficiently break the C-Cl bond of chloropyridines, which is restricted by the uncontrollable nonselective species. Hence, we propose the carbonate species-activated hydrogen peroxide (carbonate species/H2O2) process wherein the selective oxidant (peroxymonocarbonate ion, HCO4-) and selective reductant (hydroperoxide anion, HO2-) controllably coexist by manipulation of reaction pH. Taking 2-chloropyridine (Cl-Py) as an example, HCO4- first induces Cl-Py into pyridine N-oxidation intermediates, which then suffer from the nucleophilic dechlorination by HO2-. The obtained dechlorination efficiencies in the carbonate species/H2O2 process (32.5-84.5%) based on the cooperation of HCO4- and HO2- are significantly higher than those in the HO2--mediated sodium hydroxide/hydrogen peroxide process (0-43.8%). Theoretical calculations confirm that pyridine N-oxidation of Cl-Py can effectively lower the energy barrier of the dechlorination process. Moreover, the carbonate species/H2O2 process exhibits superior anti-interference performance and low electric energy consumption. Furthermore, Cl-Py is completely detoxified via the carbonate species/H2O2 process. More importantly, the carbonate species/H2O2 process is applicable for efficient dehalogenation of halogenated pyridines and pyrazines. This work offers a simple and useful strategy to enhance the dehalogenation efficiency of halogenated organics and sheds new insights into the application of the carbonate species/H2O2 process in practical environmental remediation.

Targeted Decomplexation of Metal Complexes for Efficient Metal Recovery by Ozone/Percarbonate.

Traditional methods cannot efficiently recover Cu from Cu(II)-EDTA wastewater and encounter the formation of secondary contaminants. In this study, an ozone/percarbonate (O3/SPC) process was proposed to efficiently decomplex Cu(II)-EDTA and simultaneously recover Cu. The results demonstrate that the O3/SPC process achieves 100% recovery of Cu with the corresponding kobs value of 0.103 min-1 compared with the typical •OH-based O3/H2O2 process (81.2%, 0.042 min-1). The carbonate radical anion (CO3•-) is generated from the O3/SPC process and carries out the targeted attack of amino groups of Cu(II)-EDTA for decarboxylation and deamination processes, resulting in successive cleavage of Cu-O and Cu-N bonds. In comparison, the •OH-based O3/H2O2 process is predominantly responsible for the breakage of Cu-O bonds via decarboxylation and formic acid removal. Moreover, the released Cu(II) can be transformed into stable copper precipitates by employing an endogenous precipitant (CO32-), accompanied by toxic-free byproducts in the O3/SPC process. More importantly, the O3/SPC process exhibits excellent metal recovery in the treatment of real copper electroplating wastewater and other metal-EDTA complexes. This study provides a promising technology and opens a new avenue for the efficient decomplexation of metal-organic complexes with simultaneous recovery of valuable metal resources.

Validation and application of diffusive gradient in thin-film (DGT) equipped novel cyclodextrin polymer gels for monitoring endocrine disrupting chemicals (EDCs) and environmental risk assessment in the Taihu lake basin.

Taihu Lake is the most important drinking water source of the major cities in the Yangtze River Delta. The pollution of endocrine disruptors (EDCs)in Taihu Lake has been increasing recently, the accurate determination is an important guide for predicting its health risks and developing appropriate controls. Monitoring organic pollutants in water using the diffusive gradient in thin film technique (DGT) has attracted much attention due to more accuracy and convenience than the grab sampling methods. In this study, a novel cyclodextrin polymer (CDP) synthesized by the simple and green method in water was taken as an adsorbent for the binding gel. Four endocrine-disrupting chemicals (EDCs), bisphenol A (BPA), 17α-ethinylestradiol (EE2), 17ß-estradiol (E2), and estriol (E3), were taken as models to determine the diffusion coefficients (4.68 × 10-6, 3.38 × 10-6, 3.34 × 10-6 and 4.31 × 10-6 cm2/s) and to test the performance of DGT, such as adsorption capacity and deployment time (1-5 day). The assembled CDP-DGT was adopted to determine four EDCs in a simulated water environment (3-9 of pH, 0.001-0.5 M of ionic strength (IS), and dissolved organic matter (DOM) of 0-20 mg/L). The ability of CDP-DGT sampling was verified in the Jiuxiang River and was carried out for a large-scale field application of in situ sampling EDCs in Taihu Lake basin. The results show that the total EDCs concentration range and the estradiol equivalent concentrations (EEQ) in Taihu Lake and its main rivers are 2.78 ng/L to 11.08 ng/L and 2.62 ng/L to 10.91 ng/L, respectively. The risk quotients (RQs) of all sampling sites in the region were greater than 1, indicating that EDCs pose a serious threat to aquatic organisms in the area. Therefore, the monitoring of EDCs in the Taihu Lake basin should be further strengthened.

Insights into the photocatalytic activation of peroxymonosulfate by visible light over BiOBr-cyclodextrin polymer complexes for efficient degradation of dye pollutants in water.

The combination of adsorption-photocatalysis and advanced oxidation processes (AOP) based on sulfate (SO4•-) for the treatment of organic pollution has the advantages of a high degradation rate, affordability, and an absence of secondary pollution. This study combined amphiphilic super-crosslinked porous cyclodextrin resin (PBCD-B-D), bismuth oxybromide (BiOBr), a composite material with dual functions of adsorption and photocatalysis, and AOP based on SO4•- for the treatment of Acid Orange 7 (AO7) in water. The combination of BiOBr/PBCD-B-D (BOP-24) with peroxymonosulfate (PMS) showed an optimal adsorption-photocatalytic effect. Compared to the 24% PBCD-B-D (BOP-24)/visible light system, the degradation efficiency of BOP-24/PMS system for AO7 is increased from 64.1% to 99.2% within shorter time (∼60 min). Moreover, the BOP-24/PMS system showed a wide range of pH application (pH = 3-11). The addition of Cl-, SO42-, and NO3- promoted the photodegradation of AO7, whereas the addition of CO32- did not. The free radical capture experiments of the BOP-24/PMS AO7 degradation system showed that •O2-, h+, •OH, and SO4•- are reactive species. The proposed BOP-24 system used adsorption and a unique cavity structure to enrich AO7 near the active site, thereby reducing the path for PMS activation. PMS also acted as an electron (e-) acceptor to promote the transfer of part of e- to PMS, thereby further improving the efficiency of carrier separation. The proposed system is an effective method to improve the degradation of pollutants and broadens the range of application of SO4•--based AOP technology.

High Fe and Mn groundwater in the Nanchang, Poyang Lake Basin of China: hydrochemical characteristics and genesis mechanisms.

Based on the water quality test data of 257 groups of phreatic groundwater and 165 groups of confined groundwater in the Nanchang area and the redox conditions, acid-base conditions and the organic matter content in groundwater, we identified hydrochemical characteristics and genesis of groundwater with high Fe and Mn contents in Nanchang. The results showed that Fe and Mn exceeded the standard in both phreatic and confined groundwater. The over-standard rates of Fe and Mn in groundwater were 8.56-11.52% and 33.07-36.36%, respectively. The degree of pollution Fe and Mn in the confined groundwater is higher than that in the phreatic groundwater, and the degree of pollution caused by Mn is higher than that caused by Fe. The high Fe and Mn contents in groundwater were caused by the release of Fe and Mn minerals from the native environment due to changes in the groundwater environment of the study area. A mild redox environment (Eh < 100) and low pH value are favorable for Fe and Mn enrichment in groundwater. The presence of organic matter accelerates microbial activity and promotes the release of Fe and Mn from aquifer sediments. Therefore, the change in the native environment played an important role in the increase in Fe and Mn content in the study area.

Overcoming Electrostatic Interaction via Strong Complexation for Highly Selective Reduction of CN- into N2.

Limited by the electrostatic interaction, the oxidation reaction of cations at the anode and the reduction reaction of anions at the cathode in the electrocatalytic system nearly cannot be achieved. This study proposes a novel strategy to overcome electrostatic interaction via strong complexation, realizing the electrocatalytic reduction of cyanide (CN- ) at the cathode and then converting the generated reduction products into nitrogen (N2 ) at the anode. Theoretical calculations and experimental results confirm that the polarization of the transition metal oxide cathodes under the electric field causes the strong chemisorption between CN- and cathode, inducing the preferential enrichment of CN- to the cathode. CN- is hydrogenated by atomic hydrogen at the cathode to methylamine/ammonia, which are further oxidized into N2 by free chlorine derived from the anode. This paper provides a new idea for realizing the unconventional and unrealizable reactions in the electrocatalytic system.

Chemical forms governing Cd tolerance and detoxification in duckweed (Landoltia punctata).

Duckweed (Landoltia punctata) is an ideal species to restore cadmium (Cd)-polluted waters due to its fast growth and easy harvesting. To understand its tolerance and detoxification mechanism, the Cd stress responses, subcellular Cd distribution and chemically bound Cd forms (especially protein-bound Cd) were surveyed in this study. L. punctata, a potential Cd bioremediation plant, was cultured hydroponically with Cd concentrations of 0.0, 0.5, 2.0, and 5.0 mg L-1 for 5 days. The results showed that the Cd content in L. punctata increased significantly as the Cd content increased. The majority of Cd was localized in the soluble fraction (23-55%) and the cell wall fraction (21-54%), and only 14-23% of Cd was located in cell organelles. Analysis of the Cd chemical forms demonstrated that the largest portion of Cd was found in 1 M NaCl extracts, followed by d-H2O and 2% HAc extracts, indicating that Cd was mainly bound to different proteins. Albumin- and globulin-bound Cd forms were predominant, together accounting for over 80% of the total protein-bound Cd in L. punctata. These results indicate that cell wall immobilization and vacuolar dissociation of Cd are possible primary strategies for Cd biosorption and detoxification in L. punctata, which occur mainly through chemical forms changes, especially the binding of Cd to proteins.

Abiotic and Biological Degradation of Atmospheric Proteinaceous Matter Can Contribute Significantly to Dissolved Amino Acids in Wet Deposition.

Atmospheric proteinaceous matter is characterized by ubiquity and potential bioavailability. However, little is known about the origins, secondary production processes, and biogeochemical role of proteinaceous matter in wet deposition. Precipitation samples were collected in suburban Guiyang (southwestern China) over a 1 year period to investigate their chemical components, mainly including dissolved combined amino acids (DCAAs), dissolved free AAs (DFAAs), and nonleachable particulate AAs (PAAs). Glycine was most abundant in the DFAAs, while the dominant species in DCAAs and PAAs was glutamic acid (including deaminated glutamine). The total DCAA, DFAA, and PAA concentrations peaked on average in spring (min. in summer). On average, the contribution of DCAA-nitrogen (median of 3.44%) to dissolved organic nitrogen was 5-fold higher than that of DFAA-nitrogen (median of 0.60%). Correlation analyses of AAs with ozone, nitrogen dioxide, and the quantitative degradation index suggest that DC(/F)AAs are linked with both abiotic and biological degradation of proteinaceous matter. Moreover, the high FAA scavenging ratios indicate the presence of postdepositional degradation of atmospheric proteinaceous matter. Further, the positive matrix factorization results suggest that the degradation of atmospheric proteinaceous matter markedly contributes to DCAAs and DFAAs in precipitation. Overall, the results suggest that the secondary processes involved in the degradation of atmospheric proteinaceous matter significantly promote direct bioavailability of AA-nitrogen.

Effects of selenium on antioxidant enzyme activity and bioaccessibility of arsenic in arsenic-stressed radish.

Consuming arsenic (As)-contaminated vegetables is the main route of As exposure in humans. The present study focused on the alterations in antioxidant enzymatic activities and As bioaccessibility in As-contaminated radish subjected to Se. Compared to the CK group, the total As content in raw radish was reduced by 27.5 ± 1.3%, and the bioaccessibility of As was reduced by 21.9 ± 2.3% in the 6 mg Se kg-1 treatment group. The total As content in the treatment groups decreased first but then increased with increasing Se application in raw radish, gastric (G) fraction and gastrointestinal (GI) fraction, while the antioxidant activity exhibited the opposite trend. The results revealed that a low amount of Se effectively blocks the accumulation of As in radish, improves the antioxidant activity in radish and reduces the bioaccessibility of As. These findings provide new ideas for effectively alleviating the spread of As to the human body through the food chain.

Assessment of soil and maize contamination by TE near a coal gangue-fired thermal power plant.

Coal preparation by-products, such as coal gangue, are inferior fuels enriched with trace elements (TEs). Owing to the issues surrounding the disposal of coal preparation by-products and energy shortages, Chinese researchers have strongly advocated harvesting energy from by-products. However, the secondary environmental pollution caused by such by-products has been overlooked. In this study, we aimed to assess the contamination of soil and maize (Zea mays L.) near a coal gangue-fired power plant (CGPP) in Liupanshui City, Guizhou Province, China, by TEs. The contents of 11 TEs (Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sb, V, and Zn) in soil samples and different maize tissues were measured, and their chemical speciation in soil was also determined. The results showed that the soil in the study area was polluted by the above elements to varying degrees at a very high potential ecological risk. The Cr and Pb levels in niblets of partial samples exceeded the Chinese food safety standards. The TE contents of maize tissues largely depend on the bioavailable fraction of the same elements in the soils, rather than their total contents. Pearson's correlation and hierarchical cluster analyses resulted in three clusters:(1) Pb-Zn-Cd; (2) Co-Cu-Mn-Sb-V-Be; and (3) Cr-Ni. Coal preparation by-products should not be directly combusted without pre-treatment. These results will aid readers and engineers in understanding the adverse effect of CGPPs and provide regulators and policymakers with relevant data to scientifically guide the utilisation of coal preparation by-products.

Silver Single Atom in Carbon Nitride Catalyst for Highly Efficient Photocatalytic Hydrogen Evolution.

Single atom catalysts (SACs) with the maximized metal atom efficiency have sparked great attention. However, it is challenging to obtain SACs with high metal loading, high catalytic activity, and good stability. Herein, we demonstrate a new strategy to develop a highly active and stable Ag single atom in carbon nitride (Ag-N2 C2 /CN) catalyst with a unique coordination. The Ag atomic dispersion and Ag-N2 C2 configuration have been identified by aberration-correction high-angle-annular-dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and extended X-ray absorption. Experiments and DFT calculations further verify that Ag-N2 C2 can reduce the H2 evolution barrier, expand the light absorption range, and improve the charge transfer of CN. As a result, the Ag-N2 C2 /CN catalyst exhibits much better H2 evolution activity than the N-coordinated Ag single atom in CN (Ag-N4 /CN), and is even superior to the Pt nanoparticle-loaded CN (PtNP /CN). This work provides a new idea for the design and synthesis of SACs with novel configurations and excellent catalytic activity and durability.

Influence of Hardness and Dissolved Organic Carbon on the Acute Toxicity of Copper to Zebrafish (Danio rerio) at Different Life Stages.

Copper (Cu) bioavailability varies under water conditions. In the present study, the whole life of zebrafish was divided into three different life stages (larvae, juvenile and adult) based on the growth curve, then the influences of water hardness and dissolved organic carbon (DOC) concentration on the acute toxicity of zebrafish were respectively investigated. The results indicated that the life stages had significant effects on Cu toxicity. The larvae stage was less sensitive to Cu than both the juvenile and adult stages. With the increase of water hardness, the toxicity of Cu on zebrafish was decreased, a linear relationship was observed between water hardness and Cu toxicity, and the same was true for DOC concentration. The results showed that taking the 24 days juvenile zebrafish to study the water quality criteria of Cu was stable, sensitive and economical.

Distribution of metal and metalloid elements in human scalp hair in Taiyuan, China.

This study investigated the levels of metal and metalloid elements (As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Ni, Pb, and Zn) in scalp hair samples collected from 161 people of different age and gender groups living in the six districts of Taiyuan, an industrial city with rich coal reserve in Shanxi province in China. Levels of most elements in the hair were high in the 26-40 age groups and increased with the length of residence. Calcium, Cr, Mg, Ni and Zn levels in the females' hair were significantly higher than those in the males' (p < 0.05). Element levels in the hair didn't have significantly differences between industrial and non-industrial districts because most of industry factories are in the upper wind position in Taiyuan, and contamination is prone to spread to non-industrial districts. The principal component analysis indicates that the main sources of these elements are mining activities, the neighboring stainless steel industry, and coal combustion. These results indicate that the industrial activities primarily contribute to the metal and metalloid pollution in Taiyuan, whereas numerous factors caused the metals accumulation in hair.

Health and ecological risk of heavy metals in agricultural soils related to Tungsten mining in Southern Jiangxi Province, China.

Background: Dayu County, a major tungsten producer in China, experiences severe heavy metal pollution. This study evaluated the pollution status, the accumulation characteristics in paddy rice, and the potential ecological risks of heavy metals in agricutural soils near tungsten mining areas of Dayu County. Furthermore, the impacts of soil properties on the accumulation of heavy metals in soil were explored. Methods: The geo-accumulation index (Igeo), the contamination factor (CF), and the pollution load index (PLI) were used to evaluate the pollution status of metals (As, Cd, Cu, Cr, Pb, Mo, W, and Zn) in soils. The ecological risk factor (RI) was used to assess the potential ecological risks of heavy metals in soil. The health risks and accumulation of heavy metals in paddy rice were evaluated using the health risk index and the translocation factor (TF), respectively. Pearson's correlation coefficient was used to discuss the influence of soil factors on heavy metal contents in soil. Results: The concentrations of metals exceeded the respective average background values for soils (As: 10.4, Cd: 0.10, Cu: 20.8, Cr: 48.0, Pb: 32.1, Mo: 0.30, W: 4.93, Zn: 69.0, mg/kg). The levels of As, Cd, Mo, and tungsten(W) exceeded the risk screening values for Chinese agricultural soil contamination and the Dutch standard. The mean concentrations of the eight tested heavy metals followed the order FJ-S > QL > FJ-N > HL > CJ-E > CJ-W, with a significant distribution throughout the Zhangjiang River basin. Heavy metals, especially Cd, were enriched in paddy rice. The Igeo and CF assessment indicated that the soil was moderately to heavily polluted by Mo, W and Cd, and the PLI assessment indicated the the sites of FJ-S and QL were extremely severely polluted due to the contribution of Cd, Mo and W. The RI results indicated that Cd posed the highest risk near tungsten mining areas. The non-carcinogenic and total carcinogenic risks were above the threshold values (non-carcinogenic risk by HQ > 1, carcinogenic risks by CR > 1 × 10-4 a-1) for As and Cd. Correlation analysis indicated that K2O, Na2O, and CaO are main factors affecting the accumulation and migration of heavy metals in soils and plants. Our findings reveal significant contamination of soils and crops with heavy metals, especially Cd, Mo, and W, near mining areas, highlighting serious health risks. This emphasizes the need for immediate remedial actions and the implementation of stringent environmental policies to safeguard health and the environment.

Effects of calcium-to-silicon ratio on the properties of fly ash-based tobermorite and its removal performance of Zn2+ and Mn2.

The effects of calcium-to-silicon ratio on the properties of fly ash (FA)-based tobermorite and its removal performance of Zn2+ and Mn2+ were studied. The calcium-to-silicon ratio had a significant effect on the structural properties of the tobermorite samples. The specific surface area, pore volume, and average pore size of mesoporous tobermorite samples with different calcium-to-silicon ratios (0.8TOB, 1.2TOB, and 1.6TOB) were much larger than those of FA, and those of 1.2TOB were the largest, which were 53.29 m2/g, 0.448 cm3/g, and 30.50 nm, respectively. The removal efficiencies of Zn2+ and Mn2+ by 1.2TOB were 84.19% and 47.67%, respectively, which were much higher than those of 0.8TOB (60.62% and 42.41%), 1.6TOB (46.69% and 24.31%), and FA (4.13% and 6.95%). The adsorption of Zn2+ and Mn2+ by 0.8TOB, 1.2TOB, and 1.6TOB was corresponding to the pseudo-second-order kinetic model and Langmuir isotherm model. Particularly, 1.2 TOB showed the highest maximum adsorption capacities of Zn2+ and Mn2+ calculated from the Langmuir model, which were 129.70 mg/g and 82.09 mg/g, respectively. Moreover, the adsorption mechanisms might be due to the combination with -OH and the interlayer adsorption of the samples. This research provides new insight into the fly ash-based adsorbents towards Zn2+ and Mn2+ in wastewater.

Lanthanum-modified tobermorite synthesized from fly ash for efficient phosphate removal.

Phosphate removal from water by lanthanum-modified tobermorite synthesized from fly ash (LTFA) with different lanthanum concentrations was studied. LTFA samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and Brunauer‒Emmett‒Teller specific surface area analysis. The results showed that the LTFA samples were mainly composed of mesoporous tobermorite-11 Å, and LTFA1 with a lanthanum concentration of 0.15 M had a high specific surface area (83.82 m2/g) and pore volume (0.6778 cm3/g). The phosphate adsorption capacities of LTFA samples were highest at pH 3 and gradually decreased with increasing pH. The phosphate adsorption kinetics data on LTFA samples were most accurately described by the Elovich model. The adsorption isotherms were in the strongest agreement with the Temkin model, and LTFA1 showed the highest phosphate adsorption capacity (282.51 mg P/g), which was higher than that of most other lanthanum-modified adsorbents. LTFA1 presented highly selective adsorption of phosphate with other coexisting ions (HCO3-, Cl-, SO42-, and NO3-). In addition, phosphate was adsorbed onto LTFA samples by forming inner-sphere phosphate complexes and amorphous lanthanum phosphate. This study provides technical support for development of efficient fly ash-based phosphate adsorbents.

Sulfuric acid-assisted ball milling for the preparation of Si-O-enriched straw biochar: removal efficiency of rhodamine B and adsorption mechanism.

Traditional pyrolysis biochar has been widely employed to treat dye wastewater. However, there are some problems in the pyrolysis process, such as the generation of harmful gases and the low content of silico-oxygen functional groups to promote adsorption. Straw biochar (Ac-BCbm) was prepared by sulfuric acid co-ball milling method. The adsorption performance and adsorption mechanism of rhodamine B (RhB) under different preparation conditions and factors were investigated. The results showed that the adsorption rate of Ac-BCbm on RhB was up to 94.9%, which was 60.5% and 55.8% higher than that of ball-milling straw (STbm) and biochar prepared by pyrolysis (STBC600), respectively. The Ac-BCbm had better adaptability under different pH and common interfering ions for remove RhB. Characterization and DFT simulation analysis revealed that the sulfuric acid co-ball milling process promoted the formation of Si-OH and Si-O-CH3 oxygen-containing functional groups of Si component in straw, which enhanced the hydrogen bonding interactions and effectively improved the adsorption efficiency. This study investigated a new strategy for biochar preparation by sulfuric acid co-ball milling, which provides an additional development direction for the efficient resource utilization of straw.

Selective anchoring of Pt NPs on covalent triazine-based frameworks via in situ derived bridging ligands for boosting photocatalytic hydrogen evolution.

The efficient and stable production of hydrogen (H2) through Pt-containing photocatalysts remains a great challenge. Herein, we develop an effective strategy to selectively and uniformly anchor Pt NPs (∼1.2 nm) on a covalent triazine-based framework photocatalyst via in situ derived bridging ligands. Compared to Pt/CTF-1, the obtained Pt/AT-CTF-1 exhibits a considerable photocatalytic H2 evolution rate of 562.9 µmol g-1 h-1 under visible light irradiation. Additionally, the strong interaction between the Pt NPs and in situ derived bridging ligands provides remarkable stability to Pt/AT-CTF-1. Experimental investigations and photo/chemical characterization reveal the synergy of the in situ derived bridging ligands in Pt/AT-CTF-1, which can selectively anchor the Pt NPs with homogeneous sizes and efficiently improve the transmission of charge carriers. This work provides a new perspective toward stabilizing ultrasmall nanoclusters and facilitating electron transfer in photocatalytic H2 evolution materials.

Phosphorus flow characteristics in the waste system of Poyang Lake Watershed over the past 70 years.

With the intensification of human activities, the amount of phosphorus (P)-containing waste has increased. When such waste is not recycled, P is released into the environment, leading to environmental issues such as the eutrophication of water bodies. In this study, based on the material flow analysis method, a P Waste Flow analysis model (P-WFA) was developed to analyze the P flow in the waste system of Poyang Lake, the largest freshwater lake in China. To address the research gap in long-term P flow analysis at the watershed scale, this study quantified the P content in the waste system of the Poyang Lake Watershed from 1950 to 2020. The analysis revealed that from 1950 to 2020, the total P input into the waste system increased from 5.49 × 104 tons in 1950 to 2.28 × 105 tons in 2020. The breeding industry system was identified as the primary source, accounting for 25.19-41.59 % of the total waste system. Over the past 70 years, P loss to surface water from waste systems has been primarily facilitated by manure from the breeding industry, as well as drainage from crop farming systems (77.74 % in 2020). At the same time, the P recycling rate (PRR) of the waste system exhibited an initial increase followed by a decrease, increasing from 44.14 % to 47.75 % before dropping to 44.41 %. Population growth, urbanization, and changes in consumption levels in Jiangxi Province have led to changes in the dietary structure and fertilizer use, consequently affecting the P cycling pattern. This study presents a comprehensive P flow model for waste systems in the Poyang Lake Watershed. This model can be used as a reference to enhance P cycling and manage P loss in other large freshwater lakes.

Pollution and health risk assessment of rare earth elements in Citrus sinensis growing soil in mining area of southern China.

Background: Analyzing the pollution and health risk of rare earth elements (REEs) in crop-growing soils around rare earth deposits can facilitate the improvement of REE mining-influenced area. In this study, pollution status, fraction and anomaly, plant accumulation characteristics, and potential risks of REEs (including heavy and light rare earth elements, HREEs and LREEs) in C. sinensis planting soil near ion-adsorption deposits in southern Ganzhou were analyzed. The influence of the soil environment on REEs in soil and fruit of C. sinensis was also explored. Methods: The geo-accumulation index (Igeo) and ecological risk index(RI) were used to analyze the pollution potential and ecological risks of REEs in soils, respectively. Health risk index and translocation factor (TF) were applied to analyze the accumulation and health risks of REEs in fruit of C. sinensis. The influence of soil factors on REEs in soil and fruit of C. sinensis were determined via correlation and redundancy analysis. Results: Comparison with background values and assessment of Igeo and RI indicated that the soil was polluted by REEs, albeit at varying degrees. Fractionation between LREEs and HREEs occurred, along with significant positive Ce anomaly and negative Eu anomaly. With TF values < 1, our results suggest that C. sinensis has a weak ability to accumulate REEs in its fruit. The concentrations of REEs in fruit differed between LREEs and HREEs, with content of HREE in fruit ordered as Jiading > Anxi > Wuyang and of LREE in fruit higher in Wuyang. Correlation and redundancy analysis indicated that K2O, Fe2O3 and TOC are important soil factors influencing REE accumulation by C. sinensis, with K2O positively related and Fe2O3 and TOC negatively related to the accumulation process.