Simultaneous Degradation, Dehalogenation, and Detoxification of Halogenated Antibiotics by Carbon Dioxide Radical Anions

Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promising method for their regulation during water or wastewater treatment.

New Insights into Microplastic Contamination in Different Types of Leachates: Abundances, Characteristics, and Potential Sources

Municipal solid waste(MSW)is an important destination for abandoned plastics.During the waste disposal process,large plastic debris is broken down into microplastics(MPs)and released into the leachate.However,current research only focuses on landfill leachates,and the occurrence of MPs in other leachates has not been studied.Therefore,herein,the abundance and characteristics of MPs in three types of leachates,namely,landfill leachate,residual waste leachate,and household food waste leachate,were studied,all leachates were collected from the largest waste disposal center in China.The results showed that the average MP abundances in the different types of leachates ranged from(129±54)to(1288±184)MP particles per liter(particlesL1)and the household food waste leachate exhibited the highest MP abundance(p<0.05).Polyethylene(PE)and fragments were the dominant polymer type and shape in MPs,respectively.The characteristic polymer types of MPs in individual leachates were different.Furthermore,the conditional fragmentation model indicated that the landfilling process considerably affected the size distribution of MPs in leachates,leading to a higher percentage(>80%)of small MPs(20–100 lm)in landfill leachates compared to other leachates.To the best of our knowledge,this is the first study discussing the sources of MPs in different leachates,which is important for MP pollution control during MSW disposal.

Promoting Environmental Risk Assessment and Control of Emerging Contaminants in China

1.Introduction In recent years,China has carried out an extensive preventative battle against air,water,and soil pollution,and the nation’s environmental quality-as reflected by conventional pollutant indicators—has significantly improved.At the same time,the issue of emerging contaminants(ECs)is beginning to receive increasing attention.ECs generally refer to newly discovered or noticeable pollutants that pose risks to the ecological environment or human health.Either they have not been included in environmental management,or existing management measures are insufficient to effectively prevent and control their risks.The ECs of greatest concern generally include persistent organic pollutants(POPs),endocrine-disrupting chemicals(EDCs),pharmaceuticals and personal care products(PPCPs),and microplastics.These four categories of ECs are not entirely separate,as they interrelate with each other(Fig.1).Chemical production and product usage are the main sources of ECs.China is the world’s largest producer and consumer of bulk chemicals,and the production value of China’s chemical industry is predicted to reach 50%of the global total by 2030[1].Scientific control of ECs based on their environmental risk assessment is a necessary way to support the prevention and legal governance of ECs.

Model Hamiltonian for the Quantum Anomalous Hall State in Iron-Halogenide

We examine quantum anomalous Hall(QAH)insulators with intrinsic magnetism displaying quantized Hall conductance at zero magnetic fields.The spin-momentum locking of the topological edge stats promises QAH insulators with great potential in device applications in the field of spintronics.Here,we generalize Haldane’s model on the honeycomb lattice to a more realistic two-orbital case without the artificial real-space complex hopping.Instead,we introduce an intraorbital coupling,stemming directly from the local spin-orbit coupling(SOC).Our dxy/dx2-y2 model may be viewed as a generalization of the bismuthene px/py-model for correlated d-orbitals.It promises a large SOC gap,featuring a high operating temperature.This two-orbital model nicely explains the low-energy excitation and the topology of two-dimensional ferromagnetic iron-halogenides.Furthermore,we find that electronic correlations can drive the QAH states to a c=0 phase,in which every band carries a nonzero Chern number.Our work not only provides a realistic QAH model,but also generalizes the nontrivial band topology to correlated orbitals,which demonstrates an exciting topological phase transition driven by Coulomb repulsions.Both the model and the material candidates provide excellent platforms for future study of the interplay between electronic correlations and nontrivial band topology.

Toward a rapid and convenient nanoplastic quantification method in laboratory-scale study based on fluorescence intensity

The thorough investigation of nanoplastics(NPs)in aqueous environments requires efficient and expeditious quantitative analytical methods that are sensitive to environmentally relevant NP concentrations and convenient to employ.Optical analysis-based quantitative methods have been acknowledged as effective and rapid approaches for quantifying NP concentrations in laboratory-scale studies.Herein,we compared three commonly used optical response indicators,namely fluorescence intensity(FI),ultraviolet absorbance,and turbidity,to assess their performance in quantifying NPs.Furthermore,orthogonal experiments were conducted to evaluate the influence of various water quality parameters on the preferred indicator-based quantification method.The results revealed that FI exhibits the highest correlation coefficient(>0.99)with NP concentration.Notably,the limit of quantification(LOQ)for various types of NPs is exceptionally low,ranging from 0.0089 to 0.0584 mg/L in ultrapure water,well below environmentally relevant concentrations.Despite variations in water quality parameters such as pH,salinity,suspended solids(SS),and humic acid,a robust relationship between detectable FI and NP concentration was identified.However,an increased matrix,especially SS in water samples,results in an enhanced LOQ for NPs.Nevertheless,the quantitative method remains applicable in real water bodies,especially in drinking water,with NP LOQ as low as 0.0157–0.0711 mg/L.This exceeds the previously reported detectable concentration for 100 nm NPs at 40µg/mL using surface-enhanced Raman spectroscopy.This study confirms the potential of FI as a reliable indicator for the rapid quantification of NPs in aqueous environments,offering substantial advantages in terms of both convenience and cost-effectiveness.

Insight of chemical environmental risk and its management from the vinyl chloride accident

The combustion of vinyl chloride(VC)after the train derailment accident in Ohio,USA in February,2023 has caused widespread concern around the world.This paper tried to analyze several issues concerning the accident,including the appropriateness of the VC combustion in the emergency response in this accident,the meanings of so-called“controlled combustion”,the potential environmental risks caused by VC and combustion by-products,and follow-up work.In our view,this accident had surely caused environmental and health risks to some extent.Hence,a comprehensive environmental risk assessment is necessary,and then the site with risk should be comprehensively remediated,hazardous waste should be harmlessly treated as soon as possible.Finally,this accident suggests that further efforts should be taken to bridge the gap between chemical safety management and their environmental risk management.

Mechanism and characterization of microplastic aging process: A review

With the increasing production of petroleum-based plastics,the problem of environmental pollution caused by plastics has aroused widespread concern.Microplastics,which are formed by the fragmentation of macro plastics,are bio-accumulate easily due to their small size and slow degradation under natural conditions.The aging of plastics is an inevitable process for their degradation and enhancement of adsorption performance toward pollutants due to a series of changes in their physiochemical properties,which significantly increase the toxicity and harm of plastics.Therefore,studies should focus on the aging process of microplastics through reasonable characterization methods to promote the aging process and prevent white pollution.This review summarizes the latest progress in natural aging process and characterization methods to determine the natural aging mechanism of microplastics.In addition,recent advances in the artificial aging of microplastic pollutants are reviewed.The degradation status and by-products of biodegradable plastics in the natural environment and whether they can truly solve the plastic pollution problem have been discussed.Findings from the literature pointed out that the aging process of microplastics lacks professional and exclusive characterization methods,which include qualitative and quantitative analyses.To lessen the toxicity of microplastics in the environment,future research directions have been suggested based on existing problems in the current research.This review could provide a systematic reference for in-depth exploration of the aging mechanism and behavior of microplastics in natural and artificial systems.

Bridging science,technology and policy in emerging contaminants control

Emerging contaminants refer to newly discovered or previously overlooked contaminants that pose potential risks to the ecological environment and human health.They have not been included in environmental management practices or are inadequately addressed by existing management measures.Main focuses of emerging contaminants include persistent organic pollutants,endocrine disrupting chemicals,antibiotics and microplastics,among others.These contaminants have been widely detected in the environment and are considered urgent concerns for environmental safety and human health.However,compared to traditional pollutants,emerging contaminants are generally not well regulated by law-enforcement agencies.

Screening of indicator pharmaceuticals and personal care products in landfill leachates: a case study in Shanghai, China

Identifying potential sources of pharmaceuticals and personal care products(PPCPs)in the environment is critical for the effective control of PPCP contamination.Landfill leachate is an important source of PPCPs in water;however,it has barely been involved in source apportionment due to the lack of indicator-PPCPs(i-PPCPs)in landfill leachates.This study provides the first systematic framework for identifying i-PPCPs for landfill leachates based on the wide-scope target monitoring of PPCPs.The number of target PPCPs increased from<20 in previous studies to 68 in the present study.Fifty-nine PPCPs were detected,with median concentrations in leachate samples ranging from below the method quantification limit(MQL)to 41μg/L,and 19 of them were rarely reported previously.A total of 29 target compounds were determined to be PPCPs of high concern by principal component analysis according to multiple criteria,including occurrence,exposure potential,and ecological effect.Coupled with source-specificity and representativeness analysis,erythromycin,gemfibrozil,and albendazole showed a significant difference in their occurrence in leachate compared to other potential sources(untreated and treated municipal wastewater and livestock wastewater)and correlated with total PPCP concentrations;these were recommended as i-PPCPs for leachates.Indicator screening procedure can be used to develop a sophisticated source apportionment method to identify sources of PPCPs from adjacent landfills.

Coking wastewater treatment for industrial reuse purpose: Combining biological processes with ultrafiltration, nanofiltration and reverse osmosis

A full-scale plant using anaerobic, anoxic and oxic processes （A1/A2/O）, along with a pilot-scale membrane bioreactor （MBR）, nanofiltration （NF） and reverse osmosis （RO） integrated system developed by Shanghai Baosteel Chemical Co. Ltd., was investigated to treat coking wastewater for industrial reuse over a period of one year. The removals reached 82.5% （COD）, 89.6% （BOD）, 99.8% （ammonium nitrogen）, 99.9% （phenol）, 44.6% （total cyanide （T-CN））, 99.7% （thiocyanide （SCN-）） and 8.9% （fluoride）, during the A1/A2/O biological treatment stage, and all parameters were further reduced by over 96.0%, except for fluoride （86.4%）, in the final discharge effluent from the currently operating plant. The pilot-scale MBR process reduced the turbidity to less than 0.65 NTU, and most of the toxic organic compounds were degraded or intercepted by the A1/A2/O followed MBR processes. In addition, parameters including COD, T-CN, total nitrogen, fluoride, chloride ion, hardness and conductivity were significantly reduced by the NF-RO system to a level suitable for industrial reuse, with a total water production ratio of 70.7%. However, the concentrates from the NF and RO units were highly polluted and should be disposed of properly or further treated before being discharged.

Rapid removal of bisphenol A on highly ordered mesoporous carbon

Bisphenol A （BPA） is of global concern due to its disruption of endocrine systems and ubiquity in the aquatic environment. It is important, therefore, that efforts are made to remove it from the aqueous phase. A novel adsorbent, mesoporous carbon CMK-3, prepared from hexagonal SBA- 15 mesoporous silica was studied for BPA removal from aqueous phase, and compared with conventional powdered activated carbon （PAC）. Characterization of CMK-3 by transmission electron microscopy （TEM）, X-ray diffraction, and nitrogen adsorption indicated that prepared CMK-3 had an ordered mesoporous structure with a high specific surface area of 920 m^2/g and a pore-size of about 4.9 nm. The adsorption of BPA on CMK-3 followed a pseudo second-order kinetic model. The kinetic constant was 0.00049 g/（mg.min）, much higher than the adsorption of BPA on PAC. The adsorption isotherm fitted slightly better with the Freundlich model than the Langmuir model, and adsorption capacity decreased as temperature increased from 10 to 40℃. No significant influence of pH on adsorption was observed at pH 3 to 9; however, adsorption capacity decreased dramatically from pH 9 to 13.

Enhanced reductive degradation of carbon tetrachloride by carbon dioxide radical anion-based sodium percarbonate/ Fe（ll）/formic acid system in aqueous solution

The performance of sodium percarbonate （SPC） activated with ferrous ion （Fe（Ⅱ） with the addition of formic acid （FA） to stimulate the degradation of carbon tetrachloride （CT） was investigated. Results showed that CT could be entirely reduced within 15 min in the system at a variety of SPC/Fe（Ⅱ）/FA/CT molar ratios in experimental level. Scavenging tests indicated that carbon dioxide radical anion （CO2-） was the dominant reactive oxygen species responsible for CT degradation. CT degradation rate, to a large extent, increased with increasing dosages of chemical agents and the optimal molar ratio of SPC/Fe（Ⅱ）/FAJCT was set as 60/60/60/1. The initial concentration of CT can hardly affect the CT removal, while CT degradation was favorable in the pH range of 3.0-9.0, but apparently inhibited at pH 12. C1- and HCO3 of high concentration showed negative impact on CT removal. Cl- released from CT was detected and the results confirmed nearly complete mineralization ofCT. CT degradation was proposed by reductive C-C1 bond splitting. This study demonstrated that SPC activated with Fe（Ⅱ） with the addition of FA may be promising technique for CT remediation in contaminated groundwater.

Occurrence, sources and fate of pharmaceuticals and personal care products in the groundwater: A review

The presence of pharmaceuticals and personal care products(PPCPs)in the aquatic environment may pose potential threat to the ecosystem and human health,hence PPCPs have aroused much concern over the world.The contamination of PPCPs in the groundwater,the main source of drinking water supply in many countries and regions,has been extensively studied in the last decade.This paper reviews the occurrence of frequently detected PPCPs,including antibiotics,anti-inflammatories,lipid-regulators,carbamazepine,caffeine,and N,N-diethyl-m-toluamide in groundwater,with special concern to the progress made over the past three years.Possible emission sources for PPCPs in groundwater,such as wastewater and contaminated surface water,landfills,septic systems,livestock breeding and sewer leakage,are summarized.Besides,adsorption,migration and degradation,the dominant mechanisms in the subsurface transport and fate of PPCPs,are discussed,and the insights into the future study of PPCPs in the groundwater are provided.

Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

The thermally activated persulfate （PS） degradation of carbon tetrachloride （CT） in the presence of formic acid （FA） was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO2^- was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^- had a negative effect on CT degradation, and high concentration of Cl^- displayed much strong inhibition. Ten mmol·L^-1HCO3^- promoted CT degradation, while 100mmol·L^-1NO3^- inhibited the degradation of CT, but SO4^2- promoted CT degradation in the presence of FA. The measured Cl^- concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation （ISCO） remediation for CT contaminated site.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe（III） in the presence of citric acid

Trichloroethene （TCE） degradation by Fe（III）- activated calcium peroxide （CP） in the presence of citric acid （CA） in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concen- tration of soluble Fe（III） and promoting H202 generation. The generation of HO· and O2^-· in both the CP/Fe（III） and CP/Fe（III）/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly to direct oxidation by HO·, while O2^-· strengthened the generation of HO· by promoting Fe（III） transformation in the CP/Fe （III）/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl·-, HCO3·-, and humic acid （HA） inhibited TCE degradation to different extents for the CP/Fe（III）/CA system. Analysis of Cl·- production suggested that TCE degradation in the CP/Fe （III）/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe（III）-activated calcium peroxide for treating TCE contaminated groundwater.

Recent advances in pharmaceuticals and personal care products in the surface water and sediments in China

Pharmaceuticals and personal care products （PPCPs） have been regarded as an emerging problem in the surface water environment in the past few decades. In China, although related studies were initiated several years ago, an increasing number of studies on this topic have been conducted in recent years. These studies have expanded knowledge of their occurrence, behavior and associated risk in the surface water environment in China. This review compiles the most recent literature related to the studies of PPCPs in the surface water environment in China. It includes PPCP occurrence in surface water and sediments, their geographical distribution, and outcomes of the associated risk assessment. It shows that antibiotics have received much more attention in both surface water and sediments than other PPCPs. Compared to other countries; most antibiotics in the collected sediments in China showed higher contamination levels. Many more study areas have been covered in recent years; however, attention has been given to only specific areas. Environmental risk assessment based on risk quotients indicated that sulfamethoxazole presents the most significant environmental risk to relevant aquatic organisms; followed by ofloxacin, ciprofloxacin, enrofloxacin, 17α-ethynylestradiol, ibuprofen and diclofenac. Despite limited research on the environmental risk assessment of PPCPs in sediments, higher risks posed by PPCPs in the sediments rather than surfhce water were identified highlighting the need for further risk assessment of PPCPs in sediment samples.

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO_2 nano-sheets in aqueous phase

Titanium dioxide （TiO2）, which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabntyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetra- chloroethene （PCE）, tdchloroethene （TCE） and 1,1,l-trichloroethane （TCA）. The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commerciai P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene （NB） as a probe of hydroxyl radical （.OH）, the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of .OH generated in UV/synthesized TiO2 system. In addition, .OH concentration was confirmed by the strong peak displayed in EPR analysis over U~/synthesized TiO2 system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 rim, side length of 50 nm and width of 33 nra and a surface 90.3 m^2/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater.

Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes

The aim of this study was to identify the intermediates in clofibric acid degradation under various advanced oxidation processes, namely ultraviolet （UV）, UV/H2O2, vacuum ultraviolet （VUV）, VUV/H2O2, and solar/TiO2 processes, as well as to assess the toxicity of these intermediates. Eleven intermediates have been detected by gas chromatography-mass spectrometer, most of which were reported for the first time to our best knowledge. Combining the evolution of the dissolved organic carbon, CF and specific ultraviolet absorption at 254 nm, it could be deduced that cleavage of aromatic ring followed by dechlorination was the mechanism in solar/ TiO2 process, while dechlorination happened first and accumulation of aromatic intermediates occurred in the other processes. Different transformation pathways were proposed for UV-, VUV-assisted and solar/TiO2 processes, respectively. The acute toxicity was evaluated by means of Photobacterium phosphoreurn T3 spp. bioassay. It was believed that aromatic intermediates increased the toxicity and the ring-opening pathway in solar/TiO2 process could relieve the toxicity.

Biodegradation of bezafibrate by the activated sludge under aerobic condition:Effect of initial concentration,temperature and pH

Lab-scale experiments were conducted to investigate the effect of initial concentration,temperature and pH on the removal of bezafibrate(BF)by activated sludge under aerobic condition.The results showed that adsorption of BF onto activated sludge was negligible,and biodegradation was the main removal mechanism of BF.The removal of BF in the aqueous phase by the activated sludge can be described by a pseudo-first-order reaction.The reaction rate constants had a negative relationship with the initial concentration of BF,and dramatically reduced from 0.050 to 0.007 h^-1,when the temperature dropped from 20℃to 10℃.Variation of pH between 5.0 and 9.0 did not have significant influence on the removal of BF,indicating a high adaptation of microorganism in the activated sludge responsible for BF degradation to a wide pH range.The findings of this study are helpful to improve the removal of pharmaceuticals during the wastewater treatment plants by selecting the appropriate process variables,and eventually eliminate their release to the environment.

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

Hydroxyl radicals(HO*)show low reactivity with perchlorinated hydrocarbons,such as carbon tetrachloride(CT),in conventional Fenton reactions,therefore,the generation of reductive radicals has attracted increasing attention.This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine(HA)and formic acid(FA)(initial[CT]=0.13 mmol/L)in a Fe(il)activated calcium peroxide(CP)fenton process.CT degradation increased from 56.6%to 99.9%with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio o f 12/6/12/1.The results also showed that the presence of HA enhanced the regeneration of Fe(II)from Fe(III),and the production of HO*increased one-fold when employing benzoic acid as the HO*probe.Additionally,FA slightly improves the production of HO*.A study of the mechanism confirmed that the carbon dioxide radical(C02·),a strong reductant generated by the reaction between FA and HO*,was the dominant radical responsible for CT degradation.Almost complete CT dechlorination was achieved in the process.The presence of humic acid and chloride ion slightly decreased CT removal,while high doses of bicarbonate and high pH inhibited CT degradation.This study helps us to better understand the synergistic roles of FA and HA for HO·and C02·^-generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.