Differentiated cognition of the effects of human activities on typical persistent organic pollutants and bacterioplankton community in drinking water source.

Accelerated urbanization in developing countries led to a typical gradient of human activities (low, moderate and high human activities), which affected the pollution characteristics and ecological functions of aquatic environment. However, the occurrence characteristics of typical persistent organic pollutants, including organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs), and bacterioplankton associated with the gradient of human activities in drinking water sources is still lacking. Our study focused on a representative case - the upper reaches of the Dongjiang River (Pearl River Basin, China), a drinking water source characterized by a gradient of human activities. A comprehensive analysis of PAHs, OCPs and bacterioplankton in the water phase was performed using gas chromatography-mass spectrometry (GC-MS) and the Illumina platform. Moderate human activity could increase the pollution of OCPs and PAHs due to local agricultural activities. The gradient of human activities obviously influenced the bacterioplankton community composition and interaction dynamics, and low human activity resulted in low bacterioplankton diversity. Co-occurrence network analysis indicated that moderate human activity could promote a more modular organization of the bacterioplankton community. Structural equation models showed that nutrients could exert a negative influence on the composition of bacterioplankton, and this phenomenon did not change with the gradient of human activities. OCPs played a negative role in shaping bacterioplankton composition under the low and high human activities, but had a positive effect under the moderate human activity. In contrast, PAHs showed a strong positive effect on bacterioplankton composition under low and high human activities and a weak negative effect under moderate human activity. Overall, these results shed light on the occurrence characteristics of OCPs, PAHs and their ecological effects on bacterioplankton in drinking water sources along the gradient of human activities.

Biological upcycling of nickel and sulfate as electrocatalyst from electroplating wastewater.

Upcycling nickel (Ni) to useful catalyst is an appealing route to realize low-carbon treatment of electroplating wastewater and simultaneously recovering Ni resource, but has been restricted by the needs for costly membranes or consumption of large amount of chemicals in the existing upcycling processes. Herein, a biological upcycling route for synchronous recovery of Ni and sulfate as electrocatalysts, with certain amount of ferric salt (Fe3+) added to tune the product composition, is proposed. Efficient biosynthesis of bio-NiFeS nanoparticles from electroplating wastewater was achieved by harnessing the sulfate reduction and metal detoxification ability of Desulfovibrio vulgaris. The optimal bio-NiFeS, after further annealing at 300 °C, served as an efficient oxygen evolution electrocatalyst, achieving a current density of 10 mA·cm-1 at an overpotential of 247 mV and a Tafel slope of 60.2 mV·dec-1. It exhibited comparable electrocatalytic activity with the chemically-synthesized counterparts and outperformed the commercial RuO2. The feasibility of the biological upcycling approach for treating real Ni-containing electroplating wastewater was also demonstrated, achieving 99.5 % Ni2+removal and 41.0 % SO42- removal and enabling low-cost fabrication of electrocatalyst. Our work paves a new path for sustainable treatment of Ni-containing wastewater and may inspire technology innovations in recycling/ removal of various metal ions.

Critical role of zero-valent iron in the efficient activation of H2O2 for 4-CP degradation by bimetallic peroxidase-like.

Peroxidase-like based on double transition metals have higher catalytic activity and are considered to have great potential for application in the field of pollutant degradation. First, in this paper, a novel Fe0-doped three-dimensional porous Fe0@FeMn-NC-like peroxidase was synthesized by a simple one-step thermal reduction method. The doping of manganese was able to reduce part of the iron in Fe-Mn binary oxides to Fe0 at high temperatures. In addition, Fe0@FeMn-NC has excellent peroxidase-like mimetic activity, and thus, it was used for the rapid degradation of p-chlorophenol (4-CP). During the degradation process, Fe0 was able to rapidly replenish the constantly depleted Fe2+ in the reaction system and brought in a large number of additional electrons. The ineffective decomposition of H2O2 due to the use of H2O2 as an electron donor in the reduction reactions from Fe3+ to Fe2+ and from Mn3+ to Mn2+ was avoided. Finally, based on the experimental results of LC-MS and combined with theoretical calculations, the degradation process of 4-CP was rationally analyzed, in which the intermediates were mainly p-chloro-catechol, p-chloro resorcinol, and p-benzoquinone. Fe0@FeMn-NC nano-enzymes have excellent catalytic activity as well as structural stability and perform well in the treatment of simulated wastewater containing a variety of phenolic pollutants as well as real chemical wastewater. It provides some insights and methods for the application of peroxidase-like enzymes in the degradation of organic pollutants.

Degree of human activity exert differentiated influence on conventional and emerging pollutants in drinking water source.

Anthropogenic pollution poses a significant threat to drinking water sources worldwide. Previous studies have focused on the occurrence of pollutants in drinking water sources, but the impact of human activities on different types of pollutants in drinking water sources is still unclear. In this study, we chose the upper reaches of the Dongjiang River (URDR) as a case study to investigate the distribution characteristics of conventional pollutants, pesticides, and antibiotics along the gradient of human intervention. Our findings reveal that human activities can effect both conventional pollutants and emerging pollutants in the URDR to varying degrees. The escalation of human activities correlates with a rising trend in conventional pollutants, such as nitrogen (N) and phosphorus (P). Notably, only C1 (terrestrial humus) in dissolved organic matter (DOM) exhibits this increasing pattern. Pesticide and antibiotic concentrations are highest in areas with moderate and high levels of human activity, respectively, and the degree of eutrophication of drinking water closely follows the gradient of human activity. Our results also indicate that most pesticides pose a significant risk in the URDR, particularly pyrethroid pesticides (PYRs). Out of all antibiotics, only Norfloxacin (NFX) and Penicillin G (PENG) are classified as high-risk, with NFX exhibiting significant variation across different degrees of human activity. C1 and TP were the most important factors affecting the distribution of organophosphorus (OPPs) and PYRs, respectively. In conclusion, varying degrees of human activity exert differentiated influences on conventional and emerging pollutants in drinking water sources.

Efficient Degradation of Sulfamethoxazole by Diatomite-Supported Hydroxyl-Modified UIO-66 Photocatalyst after Calcination.

Sulfamethoxazole (SMX) is a widely used antibiotic to treat bacterial infections prevalent among humans and animals. SMX undergoes several transformation pathways in living organisms and external environments. Therefore, the development of efficient remediation methods for treating SMX and its metabolites is needed. We fabricated a photo-Fenton catalyst using an UIO-66 (Zr) metal-organic framework (MOF) dispersed in diatomite by a single-step solvothermal method for hydroxylation (HO-UIO-66). The HO-UIO-66-0/DE-assisted Fenton-like process degraded SMX with 94.7% efficiency; however, HO-UIO-66 (Zr) is not stable. We improved the stability of the catalyst by introducing a calcination step. The calcination temperature is critical to improving the catalytic efficiency of the composite (for example, designated as HO-UIO-66/DE-300 to denote hydroxylated UIO-66 dispersed in diatomite calcined at 300 °C). The degradation of SMX by HO-UIO-66/DE-300 was 93.8% in 120 min with 4 mmol/L H2O2 at pH 3 under visible light radiation. The O1s XPS signatures signify the stability of the catalyst after repeated use for SMX degradation. The electron spin resonance spectral data suggest the role of h+, •OH, •O2-, and 1O2 in SMX degradation routes. The HO-UIO-66/DE-300-assisted Fenton-like process shows potential in degrading pharmaceutical products present in water and wastewater.

Microbial community and gene dynamics response to high concentrations of gadolinium and sulfamethoxazole in biological nitrogen removal system.

The impact of high antibiotic and heavy metal pollution levels on biological nitrogen removal in wastewater treatment plants (WWTPs) remains poorly understood, posing a global concern regarding the issue spread of antibiotic resistance induced by these contaminants. Herein, we investigated the effects of gadolinium (Gd) and sulfamethoxazole (SMX), commonly found in medical wastewater, on biological nitrogen removal systems and microbial characteristics, and the fate of antibiotic resistance genes (ARGs), metal resistance genes (MRGs), and mobile genetic elements (MGEs). Our findings indicated that high SMX and Gd(III) concentrations adversely affected nitrification and denitrification, with Gd(III) exerting a strong inhibitory effect on microbial activity. Metagenomic analysis revealed that high SMX and Gd(III) concentrations could reduce microbial diversity, with Thauera and Pseudomonas emerging as dominant genera across all samples. While the relative abundance of most ARGs decreased under single Gd(III) stress, MRGs increased, and nitrification functional genes were inhibited. Conversely, combined SMX and Gd(III) pollution increased the relative abundance of intl1. Correlation analysis revealed that most genera could host ARGs and MRGs, indicating co-selection and competition between these resistance genes. However, most denitrifying functional genes exhibited a positive correlation with MRGs. Overall, our study provides novel insights into the impact of high concentrations of antibiotics and heavy metal pollution in WWTPs, and laying the groundwork for the spread and proliferation of resistance genes under combined SMX and Gd pollution.

Remediating thiacloprid-contaminated soil utilizing straw biochar-loaded iron and manganese oxides activated persulfate: Removal effects and soil environment changes.

Thiacloprid (THI) has accumulated significantly in agricultural soil. Herein, a novel approach to removing THI was explored by straw biochar-loaded iron and manganese oxides (FeMn@BC) to activate the persulfate (PS). The factors influencing the removal of 5 mg kg-1 THI from the soil by FeMn@BC/PS were investigated, including FeMn@BC dosing, PS dosing, temperature, and soil microorganisms. The feasibility was demonstrated by the 75.22% removal rate of THI with 3% FeMn@BC and 2% PS at 7 days and a 92.50% removal rate within 60 days. Compared to the THI, NH4+-N and available potassium were 3.96 and 3.25 times, and urease and phosphatase activities were increased by 22.54% and 33.28% in the FeMn@BC/PS at the 15 days, respectively. THI was found to seriously alter the structure of the genus in the 15 days by 16 S rRNA analysis; however, the FeMn@BC/PS group alleviated the damage, compared to the THI with 658 more operational taxonomic units. Actinobacteriota accounted for 51.48% of the microbial community in the FeMn@BC/PS group after 60 days, possibly converting transition products of THI into smaller molecules. This article provides a novel insight into advanced oxidative remediation of soils.

In-situ preparation of yeast-supported Fe0@Fe2O3 as peroxymonosulfate activator for enhanced degradation of tetracycline hydrochloride.

Nano zero-valent iron (nZVI) is extensively used as a peroxymonosulfate (PMS) activator but suffers from the ease of oxidation and agglomeration due to its high surface energy and inherent magnetism. Here, green and sustainable yeast was selected as a support material to firstly in-situ prepare yeast-supported Fe0@Fe2O3 and used for activating PMS to degrade tetracycline hydrochloride (TCH), one of the common antibiotics. Due to the anti-oxidation ability of the Fe2O3 shell and the support effect of yeast, the prepared Fe0@Fe2O3/YC exhibited a superior catalytic activity for the removal of TCH as well as some other typical refractory contaminants. The chemical quenching experiments and EPR results demonstrated SO4•- was the main reactive oxygen species while O2•-, 1O2 and •OH played a minor role. Importantly, the crucial role of the Fe2+/Fe3+ cycle promoted by the Fe0 core and surface iron hydroxyl species in PMS activation was elucidated in detail. The TCH degradation pathways were proposed by LC-MS and density functional theory (DFT) calculation. In addition, the outstanding magnetic separation property, anti-oxidation ability, and high environmental resistance of the catalyst were demonstrated. Our work may inspire the development of green, efficient, and robust nZVI-based materials for wastewater treatment.

Insights into characteristics of white rot fungus during environmental plastics adhesion and degradation mechanism of plastics.

Since the 1980s, plastic waste in the environment has been accumulating, and little is known about fungi biodegradation, especially in dry environments. Therefore, the research on plastic degradation technology is urgent. In this study, we demonstrated that Phanerochaete chrysosporium (P. chrysposporium), a typical species of white rot fungi, could react as a highly efficient biodegrader of polylactic acid (PLA), and 34.35 % of PLA degradation was obtained during 35-day incubation. A similar mass loss of 19.71 % could be achieved for polystyrene (PS) degradation. Here, we presented the visualization of the plastic deterioration process and their negative reciprocal on cell development, which may be caused by the challenge of using PS as a substrate. The RNA-seq analysis indicated that adaptations in energy metabolism and cellular defense were downregulated in the PS group, while lipid synthesis was upregulated in the PLA-treated group. Possible differentially expressed genes (DEG) of plastic degradation, such as hydrophobic proteins, lignin peroxidase (LiP), manganese peroxidase (MnP) and laccase (Lac), Cytochrome P450 (CYP450), and genes involved in styrene or benzoic acid degradation pathways have been recorded, and we proposed a PS degradation pathway.

Simultaneous adsorption of Cd(II) and degradation of OTC by activated biochar with ferrate: Efficiency and mechanism.

Biochar-supported zero-valent iron nanocomposites have received much attention due to their application potential in environmental pollution remediation. However, in many occasions, zero-valent iron loading improves the electron transfer efficiency and catalytic oxidation capacity of biochar while blocking the original pore structure of biochar, limiting its application potential. In this study, a zero-valent iron composites with large SSA (865.86 m2/g) was prepared in one step using pre-pyrolysis of biochar powder and K2FeO4 grinding for co-pyrolysis. The processes of ZVI generation and SSA expansion during the pyrolysis were investigated. The factors affecting the removal process of Cd and OTC in water by the composites were investigated. The mechanisms of Cd fixation and OTC degradation by the composites were explored by experiments, characterization, and DFT calculations. The OTC degradation pathway was proposed by theoretical predication and LC-MS spectrometry. The results indicate that ion exchange, complexation with oxygen-containing functional groups, electrostatic attraction, and interaction with π-electrons are the main mechanisms of Cd immobilization. The degradation pathways of OTC mainly include dehydroxylation, deamination and dealkylation.

Carbonyl heterocycle modified mesoporous carbon nitride in photocatalytic peroxydisulfate activation for enhanced ciprofloxacin removal: Performance and mechanism.

Polymer carbon nitride is considered to be a promising photocatalyst with broad application prospects in water treatment. However, the defects of pristine polymer carbon nitride (PCN), such as small specific surface area, fast photogenerated electron-hole recombination, and low mass transfer efficiency, limit its photocatalytic activity. In this work, by introducing 2-thiouracil into the precursor, a carbonyl heterocycle-containing mesoporous carbon nitride photocatalyst (TCN) was successfully obtained with significantly enhanced peroxydisulfate (PDS) photocatalytic activity. In this study, the modulation mechanism of carbonyl heterocycle introduction on surface electronic structure and the band structure were fully discussed by means of a combination of experiments and theoretical calculations. The carbonyl and vicinal carbon-modified heterocycles dominated the electrons, while the adjacent heptazine ring dominated the holes. The photogenerated electron-hole pair recombination efficiency and the electron transition energy barrier were greatly reduced. According to the findings of density functional theory (DFT) calculations, the introduction of carbonyl and vicinal C modulated the electronic structure of catalyst, enhanced the adsorption of PDS at the carbonyl ortho N site, which promoted the electronic interaction between TCN and PDS molecules. Experiments showed that the free radical pathway and non-radical pathway coexisted in TCN/PDS/Vis system. The reactive oxygen species were mainly derived from PDS molecules. DFT calculations provided a more comprehensive theoretical basis for the experimental results. This study provided a fresh perspective on the rational design of carbon nitride-based catalysts and the reaction mechanism of persulfate advanced oxidation systems.

Efficient peroxymonosulfate activation by biochar-based nanohybrids for the degradation of pharmaceutical and personal care products in aquatic environments.

Recently, pharmaceutical and personal care products (PPCPs) have been of wide concern due to their ecological toxicity, persistence, and ubiquity in aquatic environments. Peroxymonosulfate-based advanced oxidation processes (PMS-AOPs) have shown great potential for eliminating PPCPs due to their superior oxidation ability and adaptability. Biochar-based nanohybrids have been employed as emerging catalysts for peroxymonosulfate (PMS) activation. Until now, few researchers have summarized PMS activation by biochar-based catalysts for PPCPs removal. In this review, the types, sources, fates, and ecological toxicities of PPCPs were first summarized. Furthermore, various preparation and modification methods of biochar-based catalysts were systematically introduced. Importantly, the application of activating PMS with biochar-based multifunctional nanocomposites for eliminating PPCPs was reviewed. The influencing factors, such as catalysts dosage, PMS dosage, solution pH, temperature, anions, natural organic matters (NOMs), and pollutants concentration were broadly discussed. Biochar-based catalysts can act as electron donors, electron acceptors, and electron shuttles to activate PMS for the removal of PPCPs through radical pathways or/and non-radical pathways. The degradation mechanisms of PPCPs are correlated with persistent free radicals (PFRs), metal species, defective sites, graphitized degree, functional groups, electronic attributes, and the hybridization modes of biochar-based catalysts. Finally, the current problems and further research directions on the industrial application of biochar-based nanocomposites were proposed. This study provides some enlightenment for the efficient removal of PPCPs with biochar-based catalysts in PMS-AOPs.

Comprehensive study of the occurrence and characteristics of organic matter, nitrogen, and phosphorus in sediments and riparian soils of a large drinking water reservoir.

The contamination of nutrients has caused considerable worry about the environment, resource value, and ecological worth of drinking water reservoirs. Therefore, we comprehensively studied the abundance, sources, distribution, and environmental behavior of carbon, nitrogen, and phosphorus in Fengshuba Reservoir (FSBR) (a large drinking reservoir, China). A graded leaching technique (introduced in 2003), the European Standard, Measurement and Testing (SMT) protocol, and spectrometry combined with parallel factor analysis (EEMs-PARAFAC) were used to assess nitrogen, phosphorus forms, and spectra data in the sediment and soil phases, respectively. The study demonstrates that seasonal hydrological variation had no significant effect on the nutrient abundance and nutrient structure composition of the FSBR, while different environmental media (e.g., sediment and soil phase) exhibited considerable differences in nutrient abundance, composition, and environmental behavior. The abundance of colored dissolved organic matter (CDOM), as well as molecular weight, aromatization degree, and humification degree of dissolved organic matter (DOM) were all lower in sediments than in soils, whereas the authigenic component was greater than in soils. Microbial-derived humus (C1), terrestrial-derived humus (C2), and protein-like tryptophan (C3) were identified as the three primary fluorescence components. Principal component analysis indicated that three components were closely associated with phosphorus in the sediment phase, whereas nitrogen and phosphorus in the soil phase were mainly related to C1 and C2. In summary, soil media (drawdown area) must be carefully considered in the management and control of water environment nutrients in reservoirs.

A high-precision prediction for spatiotemporal distribution and risk assessment of antibiotics in an urban watershed using a hydrodynamic model.

A methodology for the high-precision prediction and risk assessment of antibiotics at the watershed scale was established. Antibiotic emission inventory and attenuation processes were integrated into the MIKE 11 model to predict the spatiotemporal distribution of norfloxacin, ofloxacin, enrofloxacin, erythromycin, roxithromycin, and sulfamethoxazole in the Nanfei River watershed, China. Considering the variations in antibiotic removal in sewage treatment plants, manure composting, and lagoon systems, the high, medium, and low removal efficiencies of selected antibiotics across China were obtained and used as the best, expected, and worst scenarios, respectively, to evaluate the uncertainty of antibiotic emissions. The predicted concentrations were comparable to antibiotic measurements after flow calibration. The prediction results showed that the highest concentration exposures were mainly concentrated in urban areas with a dense population. Flow variations controlled the temporal distribution characteristics of antibiotics via the dilution effect, and the concentrations of antibiotics in the dry season were 3.1 times higher than those in the wet season. The median concentrations of norfloxacin and erythromycin ranged from 111.36 ng/L to 592.33 ng/L and 106.63 ng/L to 563.01 ng/L, respectively, which both posed a high risk to cyanobacteria and a medium risk to spreading antibiotic resistance. Scenario analysis further demonstrated that high removal efficiencies of these antibiotics can considerably reduce the potential ecotoxicity risks and bacterial resistance selection. The developed methodology for predicting the distribution and risk of antibiotics was suitable for the risk assessment and control strategy of human- and livestock-sourced pollutants.

Enhanced degradation of sulfamethoxazole by non-radical-dominated peroxymonosulfate activation with Co/Zn co-doped carbonaceous catalyst: Synergy between Co and Zn.

Bimetallic catalysts are often used for peroxymonosulfate (PMS) activation in recent years due to the synergistic effects between two different metal species. However, the synergy between Zn and other transition metal in PMS activation are rarely studied because of the ease of evaporation of Zn species at high temperature. In this work, a Co/Zn co-doped carbonaceous catalyst derived from ZIF-67@ZIF-8 (Z67@8D) was prepared successfully by the core-shell replacement strategy, and used to activate PMS for sulfamethoxazole (SMX) degradation. Due to the co-existence of Co/Zn species (e.g., Co/Zn-N site), Z67@8D showed a much higher catalytic activity than that of Z8D, Z67D, and several commercial oxides. Importantly, the CoZn synergy was deeply revealed by combining experiments and density functional theory (DFT) calculations, in which Zn could adjust the electron distribution of Co, reducing the PMS adsorption energy and thus enhancing PMS decomposition and singlet oxygen (1O2) formation. Moreover, formed ZnO and graphitic structure of Z67@8D could also promote the catalytic activity. In addition, the good stability and reusability, universal applicability, and high environmental robustness of Z67@8D were demonstrated. Our findings may provide a new insight into the Zn-based bimetallic catalysts for PMS activation and pollutant degradation.

Degradation of Tetracycline Hydrochloride by Cu-Doped MIL-101(Fe) Loaded Diatomite Heterogeneous Fenton Catalyst.

In this work, the combination of high surface area diatomite with Fe and Cu bimetallic MOF material catalysts (Fe0.25Cu0.75(BDC)@DE) were synthesized by traditional solvothermal method, and exhibited efficient degradation performance to tetracycline hydrochloride (TC). The degradation results showed: Within 120 min, about 93% of TC was degraded under the optimal conditions. From the physical-chemical characterization, it can be seen that Fe and Cu play crucial roles in the reduction of Fe3+ because of their synergistic effect. The synergistic effect can not only increase the generation of hydroxyl radicals (•OH), but also improve the degradation efficiency of TC. The Lewis acid property of Cu achieved the pH range of reaction system has been expanded, and it made the material degrade well under both neutral and acidic conditions. Loading into diatomite can reduce agglomeration and metal ion leaching, thus the novel catalysts exhibited low metal ion leaching. This catalyst has good structural stability, and less loss of performance after five reaction cycles, and the degradation efficiency of the material still reached 81.8%. High performance liquid chromatography-mass spectrometry was used to analyze the degradation intermediates of TC, it provided a deep insight of the mechanism and degradation pathway of TC by bimetallic MOFs. This allows us to gain a deeper understanding of the catalytic mechanism and degradation pathway of TC degradation by bimetallic MOFS catalysts. This work has not only achieved important progress in developing high-performance catalysts for TC degradation, but has also provided useful information for the development of MOF-based catalysts for rapid environmental remediation.

Lignin peroxidase-catalyzed direct oxidation of trace organic pollutants through a long-range electron transfer mechanism: Using propranolol as an example.

In this work, lignin peroxidase (LiP) was extracted for the in vitro degradation of a persistent compound (propranolol, PPN). The results showed that 94.2% of PPN was degraded at 30 U L-1 LiP activity and 10 mg L-1 PPN. The PPN degradation rate increased from 33.5% to 94.2% when the veratryl alcohol (VA) concentration varied from 0 to 180 µM, but decreased to 73.1% with further VA addition. This phenomenon confirmed that VA was indispensable, however, it also acted as a competitive inhibitor of PPN oxidation. Computational analysis revealed that the Trp171…iron porphyrin (TRP-FeP) path was responsible for specific substrate (e.g., VA) transformation, and another long-range electron transfer (LRET) path through His-Asp…FeP (HSP-FeP) was discovered for non-specific substrate (e.g., PPN) degradation. These two electron-transfer routes shared one catalytic center, and VA protected the enzyme from H2O2-dependent inactivation. The HSP-FeP path transformed PPN through single electron transfer or H abstraction mechanisms. In addition, hydroxyl radicals generated in the LiP/H2O2 system were involved in the hydroxylation of the PPN intermediates. Possible degradation pathways were deduced using these degradation mechanisms and mass-spectrometry analysis. The multipath degradation mechanism endowed LiP with a remarkable capacity for removing various recalcitrant pollutants in environmental remediation.

Construction of Li/K dopants and cyano defects in graphitic carbon nitride for highly efficient peroxymonosulfate activation towards organic contaminants degradation.

As an emerging peroxymonosulfate (PMS) activation catalyst, graphitic carbon nitride (g-C3N4) is non-toxic and eco-friendly, while its poor catalytic performance hinders the application of pristine g-C3N4. Herein, a simple LiCl/KCl molten salts-assisted thermal polymerization method was adopted to promote the photocatalytic performance of g-C3N4. With the insertion of Li/K dopants and the introduction of surface cyano defects, the modified catalyst exhibited greatly enhanced ability on PMS activation towards acetaminophen removal, observing a 13 times higher rate constant than pristine g-C3N4 (k = 0.0435 min-1 vs. 0.0033 min-1). The main reactive oxygen species for pollutant degradation were identified as sulfate radicals and singlet oxygen. The wavefunction analysis at excited states based on density functional theory suggests that the introduction of cyano defects greatly promotes the separation of photo-generated electron-hole pairs, thereby achieving higher photocatalytic efficiency. In addition, the doping of Li/K significantly enhances the interaction between PMS and the catalyst surface, and orients the electron transfer from PMS to catalyst to generate non-radical species singlet oxygen, which improves the catalyst resistance to anions-containing water matrices.

Roles of alkali metal dopants and surface defects on polymeric carbon nitride in photocatalytic peroxymonosulfate activation towards water decontamination.

Polymeric carbon nitride (PCN) has been extensively employed in peroxymonosulfate (PMS) activation for water decontamination. However, limited photocatalytic efficiency can be achieved by pristine PCN due to its intrinsic deficiencies like high electron-hole recombination rate and resistance to charge transfer. Herein, in a two-stage thermal treatment process, the nontoxic and stable Na and K were successfully anchored among the PCN skeleton with surface defects created, leading to an elevated photocatalytic activity for PMS activation. The SO4·- and 1O2 were identified as the dominant reactive oxygen species, which were generated from electron transfer processes between PMS and catalyst. Experimental and theoretical analyses suggested that the defective structures and metal dopants improved the optical properties of catalyst, endowing it a wider light absorption range and a lower energy barrier for electron transitions. The modified structures were also beneficial to electron transfer processes due to the weaker electron confinement effect, accelerating the production of SO4·- on the defective sites and 1O2 on the metal sites. The synergy of radical and non-radical species weakened the influence of side reactions between radicals from PMS and coexisting inorganic anions in practical water, hence to promote the resistance of modified catalysts in complex water matrices.

Comprehensive insights into the occurrence, source, distribution and risk assessment of polycyclic aromatic hydrocarbons in a large drinking reservoir system.

The resource, environment, and ecological value of drinking reservoirs have received widespread concerns due to the pollution of persistent organic pollutants such as polycyclic aromatic hydrocarbons (PAHs). Therefore, we comprehensively studied the occurrence, source, distribution, and risk assessment of representative PAHs in Fengshuba Reservoir (FSBR) (large drinking reservoir, China). The total concentrations of 16 USEPA PAHs in the water phase, porewater phase, sediment phase, and soil phase were in ranges of 109.72-393.19 ng/L, 5.75-35.15 µg/L, 364.4-743.71 µg/kg, and 367.81-639.89 µg/kg, respectively. The naphthalene (Nap) was the dominant PAHs in the water phase, while it was Nap and phenanthrene (Phe) in porewater, sediment, and soil phase. The main sources of PAHs in FSBR were biomass combustion. Redundancy analysis indicated that the NTU, NO2-, NH4+, Chl-α, and IC were the dominant factors influencing the PAH distribution in water phase, and the PAHs in sediment phase was affected by T and NO3-. Pseudo-partitioning coefficients indicated that the PAHs in the porewater phase were more likely to migrate to the sediment phase. Risk assessment indicated that the PAHs both in the water and sediment phases were generally in a low-risk state, while the PAHs in the soil phase were in a moderate-risk state, and the Nap was in a high-risk state, and exposure to the PAHs in FSBR through drinking and skin exposure had little impact on consumers' health. In summary, Nap could be used as a key indicator to evaluate the existence and potential risk of PAHs in FSBR.