The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this probl...The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.展开更多
The occurrence and impacts of emerging organic contaminants(EOCs)in the aquatic environment have gained widespread attention over the past two decades.Due to large number of potential contaminants,monitoring campaigns...The occurrence and impacts of emerging organic contaminants(EOCs)in the aquatic environment have gained widespread attention over the past two decades.Due to large number of potential contaminants,monitoring campaigns,treatment plants,and proposed regulations should preferentially focus on specific pollutants with the highest potential for ecological and human health effects.In the present study,a multi-criteria screening approach based on hazard and exposure potentials was developed for prioritization of 405 unregulated EOCs already present in Chinese surface water.Hazard potential,exposure potential,and risk quotients for ecological and human health effects were quantitatively analyzed and used to screen contaminants.The hazard potential was defined by contaminant persistence,bioaccumulation,ecotoxicity,and human health effects;similarly,the exposure potential was a function of contaminant concentration and detection frequency.In total,123 compounds passed the preselection process,which involved a priority index equal to the normalized hazard potential multiplied by the normalized exposure potential.Based on the prioritization scheme,11 compounds were identified as top-priority,and 37 chemicals were defined as high-priority.The results obtained by the priority index were compared with four other prioritization schemes based on exposure potential,hazard potential,or risk quotients for ecological effects or human health.The priority index effectively captured and integrated the results from the more simplistic prioritization schemes.Based on identified data gaps,four uncertainty categories were classified to recommend:①regular monitoring,derivation of environmental quality standards,and development of control strategies;②increased monitoring;③fortified hazard assessment;and④increased efforts to collect occurrence and toxicity data.Overall,20 pollutants were recommended as priority EOCs.The prioritized list of contaminants provides the necessary information for authoritative regulations to monitor,control,evaluate,and manage the risks of environmentally-relevant EOCs in Chinese surface water.展开更多
It is a great discovery in physics of the twentieth century that the elementary particles in nature are dictated by gauge forces,characterized by a nonintegrable phase factor that an elementary particle of charge q ac...It is a great discovery in physics of the twentieth century that the elementary particles in nature are dictated by gauge forces,characterized by a nonintegrable phase factor that an elementary particle of charge q acquires from A to B points:P exp(iq/hc∫A^(B)A_(μ)dxμ),where Aμis the gauge potential and P stands for path ordering.In a many-body system of strongly correlated electrons,if the so-called Mott gap is opened up by interaction,the corresponding Hilbert space will be fundamentally changed.A novel nonintegrable phase factor known as phase-string will appear and replace the conventional Fermi statistics to dictate the low-lying physics.Protected by the Mott gap,which is clearly identified in the high-Tc cuprate with a magnitude>1.5 e V,such a singular phase factor can enforce a fractionalization of the electrons,leading to a dual world of exotic elementary particles with a topological gauge structure.A non-Fermi-liquid“parent”state will emerge,in which the gapless Landau quasiparticle is only partially robust around the so-called Fermi arc regions,while the main dynamics are dominated by two types of gapped spinons.Antiferromagnetism,superconductivity,and a Fermi liquid with full Fermi surface can be regarded as the low-temperature instabilities of this new parent state.Both numerics and experiments provide direct evidence for such an emergent physics of the Mottness,which lies in the core of a high-Tc superconducting mechanism.展开更多
It is essential to determine the occurrence of emerging organic contaminants(EOCs),such as pharmaceuticals and personal care products(PPCPs),in the ambient environment to address growing public concerns.However,such a...It is essential to determine the occurrence of emerging organic contaminants(EOCs),such as pharmaceuticals and personal care products(PPCPs),in the ambient environment to address growing public concerns.However,such analysis is quite challenging due to the low trace level of such contaminants in water,which therefore requires several litres of water samples.In this study,a large volume solid phase extraction(LV-SPE)device was developed and evaluated for its performance in monitoring PPCPs as an example.Relatively good recoveries and reproducibility were obtained under specific operating conditions:a water sample volume of no more than 20 L,a flow rate not exceeding 120 mL/min,and a methanol elution volume of at least 30 mL.In addition,the results from the onsite enrichment approach using LV-SPE were compared with those from the conventional approach using a standard SPE device in the laboratory for real groundwater samples.Among the eight selected PPCPs(nalidixic acid,carbamazepine,bezafibrate,clofibric acid,sulfadiazine,sulfamethoxypyridazine,sulfamethazine and sulfamonomethoxine),LV-SPE approach detected more target compounds.While the detected concentrations were generally comparable,slightly higher concentrations were observed for carbamazepine,clofibric acid,sulfadiazine and sulfamethazine using the LV-SPE method.The developed LV-SPE device provides an alternative approach for trace analysis of PPCPs and may also be applicable for other emerging organic contaminants.展开更多
Developing an efficient photocatalytic system for hydrogen peroxide(H_(2)O_(2))activation in Fenton-like processes holds significant promise for advancing water purification technologies.However,challenges such as hig...Developing an efficient photocatalytic system for hydrogen peroxide(H_(2)O_(2))activation in Fenton-like processes holds significant promise for advancing water purification technologies.However,challenges such as high carrier recombination rates,limited active sites,and suboptimal H_(2)O_(2)activation efficiency impede optimal performance.Here we show that single-iron-atom dispersed Bi_(2)WO_(6)monolayers(SIAD-BWOM),designed through a facile hydrothermal approach,can offer abundant active sites for H_(2)O_(2)activation.The SIAD-BWOM catalyst demonstrates superior photo-Fenton degradation capabilities,particularly for the persistent pesticide dinotefuran(DNF),showcasing its potential in addressing recalcitrant organic pollutants.We reveal that the incorporation of iron atoms in place of tungsten within the electron-rich[WO_(4)]^(2-)layers significantly facilitates electron transfer processes and boosts the Fe(II)/Fe(III)cycle efficiency.Complementary experimental investigations and theoretical analyses further elucidate how the atomically dispersed iron induces lattice strain in the Bi_(2)WO_(6)monolayer,thereby modulating the d-band center of iron to improve H_(2)O_(2)adsorption and activation.Our research provides a practical framework for developing advanced photo-Fenton catalysts,which can be used to treat emerging and refractory organic pollutants more effectively.展开更多
Presence of emerging organic contaminants(EOCs)in water is one of the major threats to water safety.In recent decades,an increasing number of studies have investigated new approaches for their effective removal.Among ...Presence of emerging organic contaminants(EOCs)in water is one of the major threats to water safety.In recent decades,an increasing number of studies have investigated new approaches for their effective removal.Among them,metal-organic frameworks(MOFs)have_attracted increasing attention since their first development thanks to their tunable metal nodes and versatile,functional linkers.However,whether or not MOFs have a promising future for practical application in emerging contaminants-containing wastewater is debatabie.This review summarizes recent studies about the removal of EOCs using MOFs-related material.The synthesis strategies of both MOF particles and composites,including thin-film nanocomposite and mixed matrix membranes,are criticaily reviewed,as well as various characterization technologies.The application of the MOF-based composite membranes in adsorption,separation(nanofiltration and ultrafiltration),and catalytic degradation are discussed.Overall,literature survey shows that MOFs-based composite could play a crucial role in eliminating EOCs in the future.In particular,modified membranes that realize separation and degradation might be the most promising materials for such application.展开更多
Perfluoroalkyl acids(PFAAs)are considered forever chemicals,gaining increasing attention for their hazardous impacts.However,the ecological effects of PFAAs remain unclear.Environmental DNA(eDNA),as the environmental ...Perfluoroalkyl acids(PFAAs)are considered forever chemicals,gaining increasing attention for their hazardous impacts.However,the ecological effects of PFAAs remain unclear.Environmental DNA(eDNA),as the environmental gene pool,is often collected for evaluating the ecotoxicological effects of pollutants.In this study,we found that all PFAAs investigated,including perfluorohexanoic acid,perfluorooctanoic acid,perfluorononanoic acid,and perfluorooctane sulfonate,even at low concentrations(0.02 and 0.05 mg/L),expedited the enzymatic degradation of DNA in a nonlinear dose–effect relationship,with DNA degradation fragment sizes being lower than 1,000 bp and 200 bp after 15 and 30 min of degradation,respectively.This phenomenon was attributed to the binding interaction between PFAAs and AT bases in DNA via groove binding.van der Waals force(especially dispersion force)and hydrogen bonding are the main binding forces.DNA binding with PFAAs led to decreased base stacking and right-handed helicity,resulting in loose DNA structure exposing more digestion sites for degrading enzymes,and accelerating the enzymatic degradation of DNA.The global ecological risk evaluation results indicated that PFAA contamination could cause medium and high molecular ecological risk in 497 samples from 11 contamination-hot countries(such as the USA,Canada,and China).The findings of this study show new insights into the influence of PFAAs on the environmental fates of biomacromolecules and reveal the hidden molecular ecological effects of PFAAs in the environment.展开更多
The engineering of carbon nanocatalysts for the persulfate activated elimination of emerging organic contaminants(EOCs)demonstrates promising potential compared with metal-based counterparts due to their unique advant...The engineering of carbon nanocatalysts for the persulfate activated elimination of emerging organic contaminants(EOCs)demonstrates promising potential compared with metal-based counterparts due to their unique advantage of high stability and low toxicity.The early reviews introduced the theoretical background of persulfate activation together with a detailed summary of different mechanisms responsible for degradation of EOCs.To further unify the state of knowledge,identify the research gaps,and prompt new research in this area,we present a thorough review on current trends in research on metal-free carbon nanocatalysts(e.g.,0D nanodiamond,1D carbon nanotubes and carbon nanofibers,2D graphene and graphitic carbon nitride,and 3D carbon nanocatalysts),with emphasis on their applications in persulfate activation and EOCs decontamination.We also discuss the current challenges and future perspectives in practically relevant applications.Last,we highlight that the development of sustainable carbon nanocatalysts/persulfate systems lies at the interface of multiple disciplines,which calls for future in-depth interdisciplinary collaborations.展开更多
Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous re...Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous researches reported the application of metal-organic frameworks(MOFs)materials for PAA activation.In this study,zeolitic imidazole framework(ZIF)-67,a representative MOFs,was facile synthesized via direct-mixing method at room temperature,and tested for PAA activation and sulfachloropyridazine(SCP)degradation.The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100%of SCP degraded within 3 min,owing to the specific MOFs structure and abundant Co^(2+) sites.The pseudo-first-order kinetic model was applied to fit the kinetic data,with rate constant k_(1) of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co_(3)O_(4)activated PAA and direct oxidation by PAA.Radical quenching experiments and electron paramagnetic resonance(EPR)analysis indicated that CH_(3)C(O)OO^(·)played a major role in this PAA activation system.Then,the Fukui index based on density functional theory(DFT)calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH_(3)C(O)OO^(·).In addition,the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection,which mainly included the S-N bond cleavage and SO_(2)extrusion and followed by further oxidation,dechlorination,and hydroxylation.Therefore,ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants(EOCs)from water.展开更多
In this study,natural mackinawite (Fe S),a chalcophilic mineral,was utilized to prepare iron/copper bimetallic oxides (Cu^(O)@Fe_(x)O_(y)) by displacement plating and calcination process.Various characterization metho...In this study,natural mackinawite (Fe S),a chalcophilic mineral,was utilized to prepare iron/copper bimetallic oxides (Cu^(O)@Fe_(x)O_(y)) by displacement plating and calcination process.Various characterization methods prove that Cu;is successfully coated on the surface of Fe S,which were further oxidized to Cu^(O),Fe_(3)O_(4)and/or Fe_(2)O_(3)during calcination process,respectively.Cu^(O)@Fe_(x)O_(y)performed highly efficient capacity to activate PMS for the degradation of various emerging pollutants including sulfamethoxazole(SMX),carbamazepine (CBZ),bisphenol A (BPA),2,4-dichlorophenol (2,4-DCP) and diclofenac (DCF) in aqueous solution.Complete removal of the above pollutants was observed after 8 min of Cu^(O)@Fe_(x)O_(y)/PMS treatment.Taking SMX as an example,the key parameters including Cu^(O)@Fe_(x)O_(y)dosage,PMS dosage and initial p H were optimized.The results show that the catalytic system can be worked in a wide p H range (3.0-9.0).The quenching experiments and electron spin resonance (ESR) test demonstrated that the main reactive oxygen species in Cu^(O)@Fe_(x)O_(y)/PMS system were hydroxyl radicals (^(·)OH) and sulfate radicals(SO_(4)^(·ˉ)),and SO_(4)^(·ˉ)was the primary reactive species.Besides,the influence of coexisting anions (i.e.,Cl^(ˉ),NO_(3)^(ˉ),HCO_(3)^(ˉ)and H_(2)PO_(4)^(ˉ)) for the degradation of SMX was explored.Cu^(O)@Fe_(x)O_(y)/PMS system can maintain good catalytic activity and reusability in different water bodies and long-term running.This work provided a green strategy to fabricate the efficient catalyst in PMS-based advanced oxidation processes.展开更多
As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-conta...As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.展开更多
Dissolved organic matter plays a critical role in affecting sorption properties of biochar for organic contaminants.In this study,dissolved humic acid(DHA)as a representative of dissolved organic matter and oak sawdus...Dissolved organic matter plays a critical role in affecting sorption properties of biochar for organic contaminants.In this study,dissolved humic acid(DHA)as a representative of dissolved organic matter and oak sawdust-derived biochar as a sorbent were prepared and characterized.Roles of DHA in sorption of benzotriazole(BTA),an emerging organic contaminant,to biochar in different electrolyte solutions were investigated.The results revealed the dual roles of DHA in BTA sorption to biochar.On the one hand,DHA can compete for sites and/or block pores available for BTA to inhibit the adsorption of BTA to biochar.On the other hand,the sorbed DHA on biochar can serve as additional partitioning phase to promote the partition of BTA.The finding was in accordance with the site energy distribution analysis of BTA sorption that the site energy of the highest occurring frequency in the DHA-BTA system was lower than that in the DHA-free system(3.41-10.4 versus 13.1-20.1 kJ mol^(−1)).The variation in apparent BTA sorption to biochar affected by DHA was thus a combination of changes in both its partition and adsorption properties.A modified Dual-mode model including the aqueous concentration of DHA was proposed to predict the effect of DHA on BTA sorption to biochar in different electrolyte solutions,which showed good prediction performance with most BTA sorption coefficient(K_(d),L g^(−1))deviations within 0.1 log unit.展开更多
The occurrence of emerging organic contaminants(EOCs)was investigated in vulnerable Dinaric karst catchment of Jadro andZrnovnica springs in Croatia,under varying flow conditions and across three different water reso...The occurrence of emerging organic contaminants(EOCs)was investigated in vulnerable Dinaric karst catchment of Jadro andZrnovnica springs in Croatia,under varying flow conditions and across three different water resource types(groundwater,springs,and surface water).The maximal EOCs concentration in both springs were observed following autumn recharge events,while during peak discharge no detection above the limits of detection(LOD)was recorded due to dilution process.Contrarily to springs,groundwater from deep borehole exhibited highest total EOCs concentration under low flow conditions,underscoring the considerable karst aquifer vulnerability and its oligotrophic nature.The peak EOCs concentration in karstic Cetina River coincided with the river's lowest discharge.The highest mass flux of 1013 g/day was determined for very mobile pharmaceutical metformin detected in Cetina.The presence of potentially persistent to very persistent compounds,like DEET and 1H-benzotriazole,which exhibited highest detection frequencies across all sampling sites,was observed in association with varying hydrological conditions.Hypotheses regarding the occurrence of identified EOCs include surface contamination infiltrating directly through ponors and highly karstified areas,potential persistence in the epikarst and aquifer matrix,and site-specific contamination sources for compounds such as 1H-benzotriazole,gabapentin,and ketoprofen found in groundwater.To evaluate the risk of inadvertent human exposure to EOCs across various age groups,we utilized measured spring concentrations and calculated drinking water equivalent levels(DWEL),which ranged from 1.4 mg/L for cotinine to 503 mg/L for sucralose,both detected in Jadro spring.Although EOCs concentrations in ng/L are unlikely to pose a significant risk to healthy population,long-term exposure to EOCs mixture remains unknown.Given scarcity of research on EOCs in karst environments on both global and national levels,our study enhances comprehension of their occurrence and behaviour across different karst water resources that hold crucial importance for drinking water supply in regions like Dinarides.展开更多
基金supported by the National Natural Science Foundation of China(No.21906056No.22176060)+2 种基金the Undergraduate Training Program on Innovation and Entrepreneurship(S202110251087)the Science and Technology Commission of Shanghai Municipality(22ZR1418600)Shanghai Municipal Science and Technology(No.20DZ2250400).
文摘The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.
基金supported by the Major Science and Technology Program for Water Pollution Control and Treatment in China (2017ZX07202)Beijing Science and Technology Planning Project (Z191100006919003)
文摘The occurrence and impacts of emerging organic contaminants(EOCs)in the aquatic environment have gained widespread attention over the past two decades.Due to large number of potential contaminants,monitoring campaigns,treatment plants,and proposed regulations should preferentially focus on specific pollutants with the highest potential for ecological and human health effects.In the present study,a multi-criteria screening approach based on hazard and exposure potentials was developed for prioritization of 405 unregulated EOCs already present in Chinese surface water.Hazard potential,exposure potential,and risk quotients for ecological and human health effects were quantitatively analyzed and used to screen contaminants.The hazard potential was defined by contaminant persistence,bioaccumulation,ecotoxicity,and human health effects;similarly,the exposure potential was a function of contaminant concentration and detection frequency.In total,123 compounds passed the preselection process,which involved a priority index equal to the normalized hazard potential multiplied by the normalized exposure potential.Based on the prioritization scheme,11 compounds were identified as top-priority,and 37 chemicals were defined as high-priority.The results obtained by the priority index were compared with four other prioritization schemes based on exposure potential,hazard potential,or risk quotients for ecological effects or human health.The priority index effectively captured and integrated the results from the more simplistic prioritization schemes.Based on identified data gaps,four uncertainty categories were classified to recommend:①regular monitoring,derivation of environmental quality standards,and development of control strategies;②increased monitoring;③fortified hazard assessment;and④increased efforts to collect occurrence and toxicity data.Overall,20 pollutants were recommended as priority EOCs.The prioritized list of contaminants provides the necessary information for authoritative regulations to monitor,control,evaluate,and manage the risks of environmentally-relevant EOCs in Chinese surface water.
基金by the National Key R&D Program of China(Grant No.2017YFA0302902)。
文摘It is a great discovery in physics of the twentieth century that the elementary particles in nature are dictated by gauge forces,characterized by a nonintegrable phase factor that an elementary particle of charge q acquires from A to B points:P exp(iq/hc∫A^(B)A_(μ)dxμ),where Aμis the gauge potential and P stands for path ordering.In a many-body system of strongly correlated electrons,if the so-called Mott gap is opened up by interaction,the corresponding Hilbert space will be fundamentally changed.A novel nonintegrable phase factor known as phase-string will appear and replace the conventional Fermi statistics to dictate the low-lying physics.Protected by the Mott gap,which is clearly identified in the high-Tc cuprate with a magnitude>1.5 e V,such a singular phase factor can enforce a fractionalization of the electrons,leading to a dual world of exotic elementary particles with a topological gauge structure.A non-Fermi-liquid“parent”state will emerge,in which the gapless Landau quasiparticle is only partially robust around the so-called Fermi arc regions,while the main dynamics are dominated by two types of gapped spinons.Antiferromagnetism,superconductivity,and a Fermi liquid with full Fermi surface can be regarded as the low-temperature instabilities of this new parent state.Both numerics and experiments provide direct evidence for such an emergent physics of the Mottness,which lies in the core of a high-Tc superconducting mechanism.
基金This research was financially supported by the Major Science and Technology Program for Water Pollution Control and Treatment in China(Grant No.2017ZX07202004).
文摘It is essential to determine the occurrence of emerging organic contaminants(EOCs),such as pharmaceuticals and personal care products(PPCPs),in the ambient environment to address growing public concerns.However,such analysis is quite challenging due to the low trace level of such contaminants in water,which therefore requires several litres of water samples.In this study,a large volume solid phase extraction(LV-SPE)device was developed and evaluated for its performance in monitoring PPCPs as an example.Relatively good recoveries and reproducibility were obtained under specific operating conditions:a water sample volume of no more than 20 L,a flow rate not exceeding 120 mL/min,and a methanol elution volume of at least 30 mL.In addition,the results from the onsite enrichment approach using LV-SPE were compared with those from the conventional approach using a standard SPE device in the laboratory for real groundwater samples.Among the eight selected PPCPs(nalidixic acid,carbamazepine,bezafibrate,clofibric acid,sulfadiazine,sulfamethoxypyridazine,sulfamethazine and sulfamonomethoxine),LV-SPE approach detected more target compounds.While the detected concentrations were generally comparable,slightly higher concentrations were observed for carbamazepine,clofibric acid,sulfadiazine and sulfamethazine using the LV-SPE method.The developed LV-SPE device provides an alternative approach for trace analysis of PPCPs and may also be applicable for other emerging organic contaminants.
基金financial support from the Natural Science Foundation of China(51979081,52100179)Fundamental Research Funds for the Central Universities(B200202103)+1 种基金National Science Funds for Creative Research Groups of China(No.51421006)PAPD and Photon Science Research center for Carbon Dioxide.
文摘Developing an efficient photocatalytic system for hydrogen peroxide(H_(2)O_(2))activation in Fenton-like processes holds significant promise for advancing water purification technologies.However,challenges such as high carrier recombination rates,limited active sites,and suboptimal H_(2)O_(2)activation efficiency impede optimal performance.Here we show that single-iron-atom dispersed Bi_(2)WO_(6)monolayers(SIAD-BWOM),designed through a facile hydrothermal approach,can offer abundant active sites for H_(2)O_(2)activation.The SIAD-BWOM catalyst demonstrates superior photo-Fenton degradation capabilities,particularly for the persistent pesticide dinotefuran(DNF),showcasing its potential in addressing recalcitrant organic pollutants.We reveal that the incorporation of iron atoms in place of tungsten within the electron-rich[WO_(4)]^(2-)layers significantly facilitates electron transfer processes and boosts the Fe(II)/Fe(III)cycle efficiency.Complementary experimental investigations and theoretical analyses further elucidate how the atomically dispersed iron induces lattice strain in the Bi_(2)WO_(6)monolayer,thereby modulating the d-band center of iron to improve H_(2)O_(2)adsorption and activation.Our research provides a practical framework for developing advanced photo-Fenton catalysts,which can be used to treat emerging and refractory organic pollutants more effectively.
基金the National Natural Science Foundation of China(Nos.21625102,21971017,and 21906007)the National Key Research and Development Program of China(No.2020YFB1506300),the Beijing Institute of Technology Research Fund Program.
文摘Presence of emerging organic contaminants(EOCs)in water is one of the major threats to water safety.In recent decades,an increasing number of studies have investigated new approaches for their effective removal.Among them,metal-organic frameworks(MOFs)have_attracted increasing attention since their first development thanks to their tunable metal nodes and versatile,functional linkers.However,whether or not MOFs have a promising future for practical application in emerging contaminants-containing wastewater is debatabie.This review summarizes recent studies about the removal of EOCs using MOFs-related material.The synthesis strategies of both MOF particles and composites,including thin-film nanocomposite and mixed matrix membranes,are criticaily reviewed,as well as various characterization technologies.The application of the MOF-based composite membranes in adsorption,separation(nanofiltration and ultrafiltration),and catalytic degradation are discussed.Overall,literature survey shows that MOFs-based composite could play a crucial role in eliminating EOCs in the future.In particular,modified membranes that realize separation and degradation might be the most promising materials for such application.
基金This work was funded by the National Natural Science Foundation of China(42030713,42107221,42177187)Fundamental Research Funds for the Cornell University(21622109)the Natural Science Foundation of Guangdong Province(2020A1515110535,2018A030310629).
文摘Perfluoroalkyl acids(PFAAs)are considered forever chemicals,gaining increasing attention for their hazardous impacts.However,the ecological effects of PFAAs remain unclear.Environmental DNA(eDNA),as the environmental gene pool,is often collected for evaluating the ecotoxicological effects of pollutants.In this study,we found that all PFAAs investigated,including perfluorohexanoic acid,perfluorooctanoic acid,perfluorononanoic acid,and perfluorooctane sulfonate,even at low concentrations(0.02 and 0.05 mg/L),expedited the enzymatic degradation of DNA in a nonlinear dose–effect relationship,with DNA degradation fragment sizes being lower than 1,000 bp and 200 bp after 15 and 30 min of degradation,respectively.This phenomenon was attributed to the binding interaction between PFAAs and AT bases in DNA via groove binding.van der Waals force(especially dispersion force)and hydrogen bonding are the main binding forces.DNA binding with PFAAs led to decreased base stacking and right-handed helicity,resulting in loose DNA structure exposing more digestion sites for degrading enzymes,and accelerating the enzymatic degradation of DNA.The global ecological risk evaluation results indicated that PFAA contamination could cause medium and high molecular ecological risk in 497 samples from 11 contamination-hot countries(such as the USA,Canada,and China).The findings of this study show new insights into the influence of PFAAs on the environmental fates of biomacromolecules and reveal the hidden molecular ecological effects of PFAAs in the environment.
基金supported by the Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.QAK202108)the National Natural Science Foundation of China(No.51822806)。
文摘The engineering of carbon nanocatalysts for the persulfate activated elimination of emerging organic contaminants(EOCs)demonstrates promising potential compared with metal-based counterparts due to their unique advantage of high stability and low toxicity.The early reviews introduced the theoretical background of persulfate activation together with a detailed summary of different mechanisms responsible for degradation of EOCs.To further unify the state of knowledge,identify the research gaps,and prompt new research in this area,we present a thorough review on current trends in research on metal-free carbon nanocatalysts(e.g.,0D nanodiamond,1D carbon nanotubes and carbon nanofibers,2D graphene and graphitic carbon nitride,and 3D carbon nanocatalysts),with emphasis on their applications in persulfate activation and EOCs decontamination.We also discuss the current challenges and future perspectives in practically relevant applications.Last,we highlight that the development of sustainable carbon nanocatalysts/persulfate systems lies at the interface of multiple disciplines,which calls for future in-depth interdisciplinary collaborations.
基金the National Natural Science Foundation of China(Nos.21906001 and 52100069)the National Key Research and Development Program of China(No.2021YFA1202500)+2 种基金Beijing Nova Program(No.Z191100001119054)the Fundamental Research Funds for the Central Universities(No.BFUKF202118)China Postdoctoral Science Foundation(No.2021M690208)。
文摘Peracetic acid(PAA)-based system is becoming an emerging advanced oxidation process(AOP)for effective removal of organic contaminants from water.Various approaches have been tested to activate PAA,while no previous researches reported the application of metal-organic frameworks(MOFs)materials for PAA activation.In this study,zeolitic imidazole framework(ZIF)-67,a representative MOFs,was facile synthesized via direct-mixing method at room temperature,and tested for PAA activation and sulfachloropyridazine(SCP)degradation.The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100%of SCP degraded within 3 min,owing to the specific MOFs structure and abundant Co^(2+) sites.The pseudo-first-order kinetic model was applied to fit the kinetic data,with rate constant k_(1) of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co_(3)O_(4)activated PAA and direct oxidation by PAA.Radical quenching experiments and electron paramagnetic resonance(EPR)analysis indicated that CH_(3)C(O)OO^(·)played a major role in this PAA activation system.Then,the Fukui index based on density functional theory(DFT)calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH_(3)C(O)OO^(·).In addition,the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection,which mainly included the S-N bond cleavage and SO_(2)extrusion and followed by further oxidation,dechlorination,and hydroxylation.Therefore,ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants(EOCs)from water.
基金financial support from National Natural Science Foundation of China (No.51878423)China Postdoctoral Science Foundation (No.2019T120843)Sichuan Science and Technology Program (No.2019YJ0091)。
文摘In this study,natural mackinawite (Fe S),a chalcophilic mineral,was utilized to prepare iron/copper bimetallic oxides (Cu^(O)@Fe_(x)O_(y)) by displacement plating and calcination process.Various characterization methods prove that Cu;is successfully coated on the surface of Fe S,which were further oxidized to Cu^(O),Fe_(3)O_(4)and/or Fe_(2)O_(3)during calcination process,respectively.Cu^(O)@Fe_(x)O_(y)performed highly efficient capacity to activate PMS for the degradation of various emerging pollutants including sulfamethoxazole(SMX),carbamazepine (CBZ),bisphenol A (BPA),2,4-dichlorophenol (2,4-DCP) and diclofenac (DCF) in aqueous solution.Complete removal of the above pollutants was observed after 8 min of Cu^(O)@Fe_(x)O_(y)/PMS treatment.Taking SMX as an example,the key parameters including Cu^(O)@Fe_(x)O_(y)dosage,PMS dosage and initial p H were optimized.The results show that the catalytic system can be worked in a wide p H range (3.0-9.0).The quenching experiments and electron spin resonance (ESR) test demonstrated that the main reactive oxygen species in Cu^(O)@Fe_(x)O_(y)/PMS system were hydroxyl radicals (^(·)OH) and sulfate radicals(SO_(4)^(·ˉ)),and SO_(4)^(·ˉ)was the primary reactive species.Besides,the influence of coexisting anions (i.e.,Cl^(ˉ),NO_(3)^(ˉ),HCO_(3)^(ˉ)and H_(2)PO_(4)^(ˉ)) for the degradation of SMX was explored.Cu^(O)@Fe_(x)O_(y)/PMS system can maintain good catalytic activity and reusability in different water bodies and long-term running.This work provided a green strategy to fabricate the efficient catalyst in PMS-based advanced oxidation processes.
基金financial supports from the National Natural Science Foundation of China (Nos.41977365and 41425015)the National Key Research and Development Program of China (No.2019YFC1804503)+4 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No.2017BT01Z032) Natural Sciences and Engineering Research Council of Canadathe Canada Research Chairs ProgramAlberta InnovatesAlberta Health for their supportsupport of Guangdong University of Technology for her visiting scholarship.
文摘As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.
基金the National Natural Science Foundation of China(41172223 and 41902259)the Natural Science Foundation of Hebei Province of China(D2020504006).
文摘Dissolved organic matter plays a critical role in affecting sorption properties of biochar for organic contaminants.In this study,dissolved humic acid(DHA)as a representative of dissolved organic matter and oak sawdust-derived biochar as a sorbent were prepared and characterized.Roles of DHA in sorption of benzotriazole(BTA),an emerging organic contaminant,to biochar in different electrolyte solutions were investigated.The results revealed the dual roles of DHA in BTA sorption to biochar.On the one hand,DHA can compete for sites and/or block pores available for BTA to inhibit the adsorption of BTA to biochar.On the other hand,the sorbed DHA on biochar can serve as additional partitioning phase to promote the partition of BTA.The finding was in accordance with the site energy distribution analysis of BTA sorption that the site energy of the highest occurring frequency in the DHA-BTA system was lower than that in the DHA-free system(3.41-10.4 versus 13.1-20.1 kJ mol^(−1)).The variation in apparent BTA sorption to biochar affected by DHA was thus a combination of changes in both its partition and adsorption properties.A modified Dual-mode model including the aqueous concentration of DHA was proposed to predict the effect of DHA on BTA sorption to biochar in different electrolyte solutions,which showed good prediction performance with most BTA sorption coefficient(K_(d),L g^(−1))deviations within 0.1 log unit.
基金supported by Interreg Central Europe boDEREC-CE project co-funded by the European Regional Development Fund,GeoTwinn project funded under H2020-EU.4.b.,[grant number 809943]funded by National Recovery and Resilience Plan 2021e2026 of the European Union-NextGenerationEU.
文摘The occurrence of emerging organic contaminants(EOCs)was investigated in vulnerable Dinaric karst catchment of Jadro andZrnovnica springs in Croatia,under varying flow conditions and across three different water resource types(groundwater,springs,and surface water).The maximal EOCs concentration in both springs were observed following autumn recharge events,while during peak discharge no detection above the limits of detection(LOD)was recorded due to dilution process.Contrarily to springs,groundwater from deep borehole exhibited highest total EOCs concentration under low flow conditions,underscoring the considerable karst aquifer vulnerability and its oligotrophic nature.The peak EOCs concentration in karstic Cetina River coincided with the river's lowest discharge.The highest mass flux of 1013 g/day was determined for very mobile pharmaceutical metformin detected in Cetina.The presence of potentially persistent to very persistent compounds,like DEET and 1H-benzotriazole,which exhibited highest detection frequencies across all sampling sites,was observed in association with varying hydrological conditions.Hypotheses regarding the occurrence of identified EOCs include surface contamination infiltrating directly through ponors and highly karstified areas,potential persistence in the epikarst and aquifer matrix,and site-specific contamination sources for compounds such as 1H-benzotriazole,gabapentin,and ketoprofen found in groundwater.To evaluate the risk of inadvertent human exposure to EOCs across various age groups,we utilized measured spring concentrations and calculated drinking water equivalent levels(DWEL),which ranged from 1.4 mg/L for cotinine to 503 mg/L for sucralose,both detected in Jadro spring.Although EOCs concentrations in ng/L are unlikely to pose a significant risk to healthy population,long-term exposure to EOCs mixture remains unknown.Given scarcity of research on EOCs in karst environments on both global and national levels,our study enhances comprehension of their occurrence and behaviour across different karst water resources that hold crucial importance for drinking water supply in regions like Dinarides.