Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FO...Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FOT have not been well explored.The current study aims to investigate the formation of chlorinated phenolic byproducts upon ferrate(VI)oxidation processes.The obtained results indicate that chlorides suffering ferrate(VI)attack will be transformed to active chlorine species(ACS),which will subsequently lead to the formation of highly toxic aromatic chlorinated byproducts.The identified byproducts include common chlorinated phenolic derivatives,as well as complex chlorinated oligomer byproducts with ether structures(mainly dimers and trimers).While the formation of common chlorophenols can be ascribed to the electrophilic substitution reactions mediated by ACS,the oligomer byproducts are generated via coupling reactions between chlorinated phenoxy radicals.ECOSAR software predicts that the generated chlorinated oligomer byproducts exhibit high ecotoxicological effects.As a whole,the above findings shed light on the potential risk of FOT in real practice.展开更多
Designing novel nonfullerene acceptors(NFAs)is of vital importance for the development of organic solar cells(OSC).Modification on the side chain and end group are two powerful tools to construct efficient NFAs.Here,b...Designing novel nonfullerene acceptors(NFAs)is of vital importance for the development of organic solar cells(OSC).Modification on the side chain and end group are two powerful tools to construct efficient NFAs.Here,based on the high-performance L8BO,we selected 3-ethylheptyl to substitute the inner chain of 2-ethylhexyl,obtaining the backbone of BON3.Then we introduced different halogen atoms of fluorine and chlorine on 2-(3-oxo-2,3-dihydro-1Hinden-1-ylidene)malononitrile end group(EG)to construct efficient NFAs named BON3-F and BON3-Cl,respectively.Polymer donor D18 was chosen to combine with two novel NFAs to construct OSC devices.Impressively,D18:BON3-Cl-based device shows a remarkable power conversion efficiency(PCE)of 18.57%,with a high open-circuit voltage(V_(OC))of 0.907 V and an excellent fill factor(FF)of 80.44%,which is one of the highest binary PCE of devices based on D18 as the donor.However,BON3-F-based device shows a relatively lower PCE of 17.79%with a decreased FF of 79.05%.The better photovoltaic performance is mainly attributed to the red-shifted absorption,higher electron and hole mobilities,reduced charge recombination,and enhanced molecular packing in the D18:BON3-Cl films.Also,we performed stability tests on two binary systems;the D18:BON3-Cl and D18:BON3-F devices maintain 88.1%and 85.5%of their initial efficiencies after 169 h of storage at 85°C in an N2-filled glove box,respectively.Our work demonstrates the importance of selecting halogen atoms on EG and provides an efficient binary system of D18:BON3-Cl for further improvement of PCE.展开更多
Selected persistent organochlorine pesticides (OCPs), including 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its principal metabolites 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) and 1,1-dichloro-2,2...Selected persistent organochlorine pesticides (OCPs), including 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its principal metabolites 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) and 1,1-dichloro-2,2-bis(p-chlorophenyl)e- thane (DDD), hexachlorocyclohexane (HCH) and its isomers (α-,β-, γ-, and δ-HCH), hexachlorobenzene (HCB), endo- sulfan, dieldrin, and endrin were quantified to determine current levels of organochlorine pesticides, to assess the eco- toxicological potential, and to distin…展开更多
Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/...Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/serum, mainly due to the difficulty of sample preparation and quantitative analysis. A method using high resolution gas chromatography coupled with electron capture negative ionization low resolution mass spectrometry(HRGC–ECNI/LRMS) was developed and validated to measure SCCPs in human plasma. The pretreatment process included protein denaturation and lipid elimination, liquid–liquid extraction with a mixture of n-hexane/dichloromethane(1:1, V/V), and cleanup on a multilayer silica column. The blank controls, including procedural blank, vacuum blood collection tube blank, and instrumental blank, were the most pivotal points for the reliable analysis of SCCPs. The average value of procedural blanks was 9.0 ng/g; and the method detection limit(MDL), calculated as the sum of the average procedural blank value and 3 times of the standard deviation of the procedural blanks, was 12.6 ng/g plasma. The validated method was applied to measure the concentrations of the total SCCPs(∑ SCCPs) in50 plasma samples from a general population. The measured plasma concentrations of ∑SCCPs ranged from <MDL to 203 ng/g wet weight(ww), with an average value of 32.0 ng/g ww.The relative abundance profiles of SCCPs in plasma samples were dominated by C10- and C11-CP congener groups centered on Cl6–7. The developed method can be used for the comprehensive and large-scale investigation of SCCP levels in human plasma.展开更多
Air samples were collected simultaneously at platform,mezzanine and outdoor in five typical stations of subway system in Shanghai,China using stainless steel canisters and analyzed by gas chromatography-mass selective...Air samples were collected simultaneously at platform,mezzanine and outdoor in five typical stations of subway system in Shanghai,China using stainless steel canisters and analyzed by gas chromatography-mass selective detector （GC-MSD） after cryogenic pre-concentration.Benzene,toluene,ethylbenzene and xylenes （BTEX） at the platforms and mezzanines inside the stations averaged （10.3±2.1）,（38.7±9.0）,（19.4±10.1） and （30.0±11.1） μg/m 3,respectively;while trichloroethylene （TrCE）,tetrachloroethylene （TeCE） and para-dichlorobenzene （pDCB）,vinyl chloride and carbon tetrachloride were the most abundant chlorinated hydrocarbons inside the stations with average levels of （3.6±1.3）,（1.3±0.5）,（4.1±1.1）,（2.2±1.1） and （1.2±0.3） μg/m 3,respectively.Mean levels of major aromatic and chlorinated hydrocarbons were higher indoor （platforms and mezzanines） than outdoor with average indoor/outdoor （I/O） ratios of 1.1–9.5,whereas no significant indoor/outdoor differences were found except for benzene and TrCE.The highly significant mutual correlations （p0.01） for BTEX between indoor and outdoor and their significant correlation （p0.05） with methyl tert-butyl ether （MTBE）,a marker of traffic-related emission without other indoor and outdoor sources,indicated that BTEX were introduced into the subway stations from indoor/outdoor air exchange and traffic emission should be their dominant source.TrCE and pDCB were mainly from indoor emission and TeCE might have both indoor emission sources and contribution from outdoor air,especially in the mezzanines.展开更多
Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future.Here,the strategy that uses chemical structure modification to optimize t...Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future.Here,the strategy that uses chemical structure modification to optimize the photoelectric properties is reported.A new narrow bandgap(1.30 eV)chlorinated non-fullerene electron acceptor(Y15),based on benzo[d][1,2,3] triazole with two 3-undecylthieno[2’,3’:4,5] thieno[3,2-b] pyrrole fused-7-heterocyclic ring,with absorption edge extending to the near-infrared(NIR) region,namely A-DA’D-A type structure,is designed and synthesized.Its electrochemical and optoelectronic properties are systematically investigated.Benefitting from its NIR light harvesting,the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency(PCE) of 14.13%,when blending with a wide bandgap polymer donor PM6.Our results show that the A-DA’D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells(PSCs).展开更多
Montmorillonite(MMT) was modified by ultrasound and castor oil quaternary ammonium salt intercalation method to prepare a new type of organic montmorillonite(OMMT). The surface structure, particle morphology, interlay...Montmorillonite(MMT) was modified by ultrasound and castor oil quaternary ammonium salt intercalation method to prepare a new type of organic montmorillonite(OMMT). The surface structure, particle morphology, interlayer distance, and thermal behavior of the samples obtained were characterized. The modified OMMT was then added to chlorinated butyl rubber(CIIR) by mechanical blending, and a composite material with excellent damping properties was obtained. The mechanical experiment results of CIIR nanocomposites showed that the addition of OMMT improved their tensile strength, hardness,and stress relaxation rate. Compared with pure CIIR, when the content of OMMT was 5 phr(part per hundred of rubber), the tensile strength of the nanocomposite was increased by 677% and the elongation at break was also increased by 105.4%. The enhancement of this performance was mainly due to the dispersion of the nanosheets in CIIR rubber and the chemical interaction between the organoclay and the polymer matrix, which was confirmed by morphology and spectral analysis. OMMT also endowed a positive effect on the damping properties of CIIR nanocomposites. After adding 5 phr of OMMT, the nanocomposite owned the best damping performance, and the damping factor, tanδmax, was 37.9% higher than that of pure CIIR. Therefore, the good damping and mechanical properties of these CIIR nanocomposites provided some novel and promising methods for preparing high-damping rubber in a wide temperature range.展开更多
A treatability study of industrial wastewater containing chlorinated nitroaromatic compounds （CNACs） by a catalytic ozonation process （COP） with a modified Mn/Co ceramic catalyst and an aerobic sequencing batch re...A treatability study of industrial wastewater containing chlorinated nitroaromatic compounds （CNACs） by a catalytic ozonation process （COP） with a modified Mn/Co ceramic catalyst and an aerobic sequencing batch reactor （SBR） was investigated. A preliminary attempt to treat the diluted wastewater with a single SBR resulted in ineffective removal of the color, ammonia, total organic carbon （TOC） and chemical oxygen demand （COD）. Next, COP was applied as a pretreatment in order to obtain a bio-compatible wastewater for SBR treatment in a second step. The effectiveness of the COP pretreatment was assessed by evaluating wastewater biodegradability enhancement （the ratio of biology oxygen demand after 5 d （BOD5） to COD）, as well as monitoring the evolution of TOC, carbon oxidation state （COS）, average oxidation state （AOS）, color, and major pollutant concentrations with reaction time. In the COP, the catalyst preserved its catalytic properties even after 70 reuse cycles, exhibiting good durability and stability. The performance of SBR to treat COP effluent was also examined. At an organic loading rate of 2.0 kg COD/（m^3.d）, with hydraulic retention time （HRT）=10 h and temperature （30±2） ℃, the average removal efficiencies of NH3-N, COD, BOD5, TOC, and color in a coupled COP/SBR process were about 80%, 95.8%, 93.8%, 97.6% and 99.3%, respectively, with average effluent concentrations of 10 mg/L, 128 mg/L, 27.5 mg/L, 25.0 mg/L, and 20 multiples, respectively, which were all consistent with the national standards for secondary discharge of industrial wastewater into a public sewerage system （GB 8978-1996）. The results indicated that the coupling of COP with a biological process was proved to be a technically and economically effective method for treating industrial wastewater containing recalcitrant CNACs.展开更多
Chlorinated organic pollutants(COPs)have caused serious contaminants in soil and groundwater,hence developing methods to remove these pollutants is necessary and urgent.By a simple hydrothermal method,we synthesized t...Chlorinated organic pollutants(COPs)have caused serious contaminants in soil and groundwater,hence developing methods to remove these pollutants is necessary and urgent.By a simple hydrothermal method,we synthesized the bimetallic iron-nickel sulfide(FeNiS)particles which exhibited excellent catalytic property of COPs removal.FeNiS was chosen as the peroxydisulfate(PDS)activator to removal COPs including 4-chlorophenol(4-CP),1,4-dichlorophenol(1,4-DCP)and 2,4,6-trichlorophenol(2,4,6-TCP).The results show that FeNiS can efficiently activate PDS to produce sulfate radical(SO4·-)which plays major role in the oxidative dechlorination and degradation due to its strong oxidizing property and the ability of producing hydroxyl radicals(·OH)in the alkaline condition.Meanwhile,the Cl-abscised from COPs during the dechlorination can turn into the chlorine radicals and enhance the degradation and cause further mineralization of intermediate products.This bimetallic FeNiS catalyst is a promising PDS activator for removal of chlorinated organics.展开更多
Practicability of method for the Hydra regeneration assay on the prescreening teratogenic potential of chlorinated drinking water disinfection by products was studied through both the assays of toxicity of adult ...Practicability of method for the Hydra regeneration assay on the prescreening teratogenic potential of chlorinated drinking water disinfection by products was studied through both the assays of toxicity of adult Hydra (T) and inhibition of the growth of regeneration Hydra (I) by using chloroform, dichloromethane and chloroacetic acid. The results showed that T 50 / I 50 ratios of chloroform and chloroacetic acid were 2 77 and 6 16 respectively, with teratogenic potential. T 50 / I 50 ratio of dichloromethane was 1.69, with weaker teratogenic potential. These experimental results indicated preliminarily that the Hydra regeneration assay has certainly applied value as a prescreening assay for developmental toxicity.展开更多
Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advance...Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.展开更多
Mono-chlorinated products of cyclic volatile methylsiloxanes(cVMS),i.e.,Monochlormethylheptamethylcyclotetrasiloxane[D3D(CH_(2)Cl)],monochlormethylnonamethylcyclopentasiloxane[D4D(CH_(2)Cl)],and monochlormethylundemet...Mono-chlorinated products of cyclic volatile methylsiloxanes(cVMS),i.e.,Monochlormethylheptamethylcyclotetrasiloxane[D3D(CH_(2)Cl)],monochlormethylnonamethylcyclopentasiloxane[D4D(CH_(2)Cl)],and monochlormethylundemethylcyclohexasiloxane[D5D(CH_(2)Cl)],were detected in water[<LOQ(Limit of quantitation)-86.3 ng/L,df(detection frequency)=23%-38%,n=112]and sediment samples[<LOQ-504 ng/g dw(dry weight),df=33%-38%,n=112]from 16 lakes located in Shengli oilfield of China,and had apparent increasing trends(31%-34%per annum)in sediments during Year 2014-2020.Simulated experiments showed that chloro-cVMS in sediment-water system had approximately 1.7-2.0 times slower elimination rates than parent cVMS.More specifically,compared with those of parent cVMS,volatilization(86-2558 days)and hydrolysis(135-549 days)half-lives of chlorocVMS were respectively 1.3-2.0 and 1.8-2.1 times longer.In two species of freshwater mussels(n=1050)collected from six lakes,concentrations of chloro-cVMS ranged from 9.8-998 ng/g dw in Anodonta woodiana and 8.4-970 ng/g dw in Corbicula fluminea.Compared with parent cVMS,chloro-cVMS had 1.1-1.5 times larger biota-sediment accumulation factors(2.1-3.0)and 1.1-1.7 times longer half-lives(13-42 days).Their stronger persistence in sediment and bioaccumulation in freshwatermussels suggested that environmental emission,distribution and risks of chloro-cVMS deserve further attention.展开更多
Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as ...Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV light was affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly.Different affiliation methods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature(Tg) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.展开更多
Recently,the degradation of organic compounds in saline dye wastewater by sulfate radicals(SO4·-)-based advanced oxidation processes(AOPs) have attracted much attention.However,previous studies on these systems h...Recently,the degradation of organic compounds in saline dye wastewater by sulfate radicals(SO4·-)-based advanced oxidation processes(AOPs) have attracted much attention.However,previous studies on these systems have selected non-chlorinated dyes as model compounds,and little is known about the transformation of chlorinated dyes in such systems.In this study,acid yellow 17(AY-17) was selected as a model of chlorinated contaminants,and the degradation kinetics and evolution of oxidation byproducts were investigated in the UV/PDS system.AY-17 can be efficiently degraded(over 98% decolorization)under 90 min irradiation at pH 2.0-3.0,and the reaction follows pseudo-first order kinetics.Cl-accelerated the degradation of AY-17,but simultaneously led to an undesirable increase of absorbable organic halogen(AOX).Several chlorinated byproducts were identified by liquid chromatography-mass spectrometry(LC-MS/MS) in the UV/PDS system.It indicates that endogenic chlorine and exogenic Cl-reacted with SO_(4)·- to form chloride radicals,which are involved in the dechlorination and rechlorination of AY-17 and intermediates.The possible degradation mechanisms of AY-17 photooxidative degradation are proposed.This work provides valuable information for further studies on the role of exogenic chloride in the degradation of chlorinated azo dyes and the kinetic parameters in the PDS-based oxidation process.展开更多
The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chl...The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.展开更多
Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work...Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work, an efficient, reliable and rapid pretreatment method based on matrix solid-phase dispersion（MSPD） was developed for the analysis of short-chain CPs（SCCPs） in human placenta by gas chromatograph-electron capture negative ion low-resolution mass spectrometry（GC-ECNI-LRMS） and gas chromatography–quadrupole time-of-flight mass spectrometry（GC–QTOF-HRMS）. The MSPD-relevant parameters including dispersing sorbent,sample-to-sorbent mass ratio, and elution solvent were optimized using the orthogonal test.Silica gel was found to be the optimal dispersing sorbent among the selected matrices. Under the optimal conditions, 44% acidic silica gel can be used as the co-sorbent to remove lipid and eluted by the mixture of hexane and dichloromethane（7：3, V/V）. The spiked recoveries of the optimized method were 77.4% and 91.4% for analyzing SCCPs in human placenta by GC-ECNI-LRMS and GC–QTOF-HRMS, and the corresponding relative standard deviations were10.2% and 5.6%, respectively. The method detection limit for the total SCCPs was 36.8 ng/g（dry weight, dw） and 19.2 ng/g（dw） as measured by GC-ECNI-LRMS and GC–QTOF-HRMS,respectively. The concentrations of SCCPs in four human placentas were in the range of展开更多
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 t...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.展开更多
Chlorinated aliphatic hydrocarbons （CAHs）, significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical se...Chlorinated aliphatic hydrocarbons （CAHs）, significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical sensitivity or not ideal for natural samples with low concentrations of CAHs. This method is reported here to carry out simultaneously carbon and chlorine isotope analyses for mieromolar concentrations of dissolved CAHs. It was executed by extracting and converting CAHs to carbon dioxide and methyl chloride （CH3CI）. Specially, a continuous-flow interface GasBench Ⅱ was used to extract CH3CI for online chlorine isotope analysis. As a result, it greatly enhances the efficiency for isotope analysis by eliminating procedures for offline CH3CI preparation and separation. Sample size requirement was reduced to approximately 11 pmol chlorine. The standard deviation of δ^＋3C and δ^37CI for both TCE solvents and water samples was better than 0.30‰ and 0.20%0 （1σ）, respectively.Carbon and chlorine isotope analyses can be used as an important tool to study the sources of organic contaminants in groundwater and their behaviors in the aquifers. The method is applicable to manufacturers＇ products as well as a sample from a polluted site in principle, which will be validated in our field studies.展开更多
Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing t...Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing the possibilities of such risk by reducing the entrance, and increasing the excretion, of these chemicals. In addition, there are supplementary measures that could be employed in order to reduce this risk further, such as boiling the drinking water, revising the standard concentrations of calcium, magnesium and iron in the public drinking water and prescribing oestrogen in susceptible individuals. Hypo-methylation of genomic DNA could be used as a biological marker for screening for the potential development of colorectal cancers.展开更多
Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by p...Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicant. Biodegradability of chlorinated anilines was determined using domesticated complex bacteria as an inoculum by shaking-flask test. Results The complex bacteria were identified, consisting of Xanthomonas, Bacillus alcaligenes, Acinetobacter, Pseudomonas, and Actinomycetaceae nocardia. The obtained complex bacteria were more tolerant to o-chloroaniline than mixture bacteria in natural river waters. The effects of exposure concentration and inoculum size on the biodegradability of o-chloroaniline were analyzed, and the biodegradation characteristics of single o-chloroaniline and 2, 4-dichloroaniline were compared with the coexistent compounds. Conclusion The biodegradation rates can be improved by decreasing concentration of compounds and increasing inoculum size of complex bacteria. When o-chloroaniline coexists with aniline, the latter is biodegraded prior to the former, and as a consequence the metabolic efficiency of o-chloroaniline is improved with the increase of aniline concentration. Meanwhile, when o-chloroaniline coexists with 2,4-dichloroaniline, the metabolic efficiency of 2,4-dichloroaniline is markedly improved.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(Nos.KYCYXT2023001,and XUEKEN2022034).
文摘Currently,ferrate(VI)oxidation technology(FOT)has been regarded as one of the most promising options for the degradation of emerging organic pollutants.However,the role and transformation of chloride ions(Cl^(−))in FOT have not been well explored.The current study aims to investigate the formation of chlorinated phenolic byproducts upon ferrate(VI)oxidation processes.The obtained results indicate that chlorides suffering ferrate(VI)attack will be transformed to active chlorine species(ACS),which will subsequently lead to the formation of highly toxic aromatic chlorinated byproducts.The identified byproducts include common chlorinated phenolic derivatives,as well as complex chlorinated oligomer byproducts with ether structures(mainly dimers and trimers).While the formation of common chlorophenols can be ascribed to the electrophilic substitution reactions mediated by ACS,the oligomer byproducts are generated via coupling reactions between chlorinated phenoxy radicals.ECOSAR software predicts that the generated chlorinated oligomer byproducts exhibit high ecotoxicological effects.As a whole,the above findings shed light on the potential risk of FOT in real practice.
基金supported by the National Natural Science Foundation of China(No.U21A20331)the National Science Fund for Distinguished Young Scholars(No.21925506)+3 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ22E030013)Ningbo Key Scientific and Technological Project(2022Z117)Ningbo Public Welfare Science and Technology Planning Project(2021S149)ZBTI Scientific Research Innovation Team(KYTD202105).
文摘Designing novel nonfullerene acceptors(NFAs)is of vital importance for the development of organic solar cells(OSC).Modification on the side chain and end group are two powerful tools to construct efficient NFAs.Here,based on the high-performance L8BO,we selected 3-ethylheptyl to substitute the inner chain of 2-ethylhexyl,obtaining the backbone of BON3.Then we introduced different halogen atoms of fluorine and chlorine on 2-(3-oxo-2,3-dihydro-1Hinden-1-ylidene)malononitrile end group(EG)to construct efficient NFAs named BON3-F and BON3-Cl,respectively.Polymer donor D18 was chosen to combine with two novel NFAs to construct OSC devices.Impressively,D18:BON3-Cl-based device shows a remarkable power conversion efficiency(PCE)of 18.57%,with a high open-circuit voltage(V_(OC))of 0.907 V and an excellent fill factor(FF)of 80.44%,which is one of the highest binary PCE of devices based on D18 as the donor.However,BON3-F-based device shows a relatively lower PCE of 17.79%with a decreased FF of 79.05%.The better photovoltaic performance is mainly attributed to the red-shifted absorption,higher electron and hole mobilities,reduced charge recombination,and enhanced molecular packing in the D18:BON3-Cl films.Also,we performed stability tests on two binary systems;the D18:BON3-Cl and D18:BON3-F devices maintain 88.1%and 85.5%of their initial efficiencies after 169 h of storage at 85°C in an N2-filled glove box,respectively.Our work demonstrates the importance of selecting halogen atoms on EG and provides an efficient binary system of D18:BON3-Cl for further improvement of PCE.
基金1Project supported by the National Key Basic Research Support Foundation (NKBRSF) of China (No. 2002CB410805)and the Outstanding Youth Fund of National Natural Science Foundation of China (No. 40325001).
文摘Selected persistent organochlorine pesticides (OCPs), including 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its principal metabolites 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) and 1,1-dichloro-2,2-bis(p-chlorophenyl)e- thane (DDD), hexachlorocyclohexane (HCH) and its isomers (α-,β-, γ-, and δ-HCH), hexachlorobenzene (HCB), endo- sulfan, dieldrin, and endrin were quantified to determine current levels of organochlorine pesticides, to assess the eco- toxicological potential, and to distin…
基金supported by the National Natural Science Foundation of China (No.21337002)the National Basic Research Program (973) of China (No.2015CB453100)
文摘Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/serum, mainly due to the difficulty of sample preparation and quantitative analysis. A method using high resolution gas chromatography coupled with electron capture negative ionization low resolution mass spectrometry(HRGC–ECNI/LRMS) was developed and validated to measure SCCPs in human plasma. The pretreatment process included protein denaturation and lipid elimination, liquid–liquid extraction with a mixture of n-hexane/dichloromethane(1:1, V/V), and cleanup on a multilayer silica column. The blank controls, including procedural blank, vacuum blood collection tube blank, and instrumental blank, were the most pivotal points for the reliable analysis of SCCPs. The average value of procedural blanks was 9.0 ng/g; and the method detection limit(MDL), calculated as the sum of the average procedural blank value and 3 times of the standard deviation of the procedural blanks, was 12.6 ng/g plasma. The validated method was applied to measure the concentrations of the total SCCPs(∑ SCCPs) in50 plasma samples from a general population. The measured plasma concentrations of ∑SCCPs ranged from <MDL to 203 ng/g wet weight(ww), with an average value of 32.0 ng/g ww.The relative abundance profiles of SCCPs in plasma samples were dominated by C10- and C11-CP congener groups centered on Cl6–7. The developed method can be used for the comprehensive and large-scale investigation of SCCP levels in human plasma.
基金supported by the National Natural Science Foundation of China (No. 40821003)the Guangdong Natural Science Foundation (No. 7118013)the State Key Laboratory of Organic Geochemistry and the Hong Kong Polytechnic University Joint Student Program
文摘Air samples were collected simultaneously at platform,mezzanine and outdoor in five typical stations of subway system in Shanghai,China using stainless steel canisters and analyzed by gas chromatography-mass selective detector （GC-MSD） after cryogenic pre-concentration.Benzene,toluene,ethylbenzene and xylenes （BTEX） at the platforms and mezzanines inside the stations averaged （10.3±2.1）,（38.7±9.0）,（19.4±10.1） and （30.0±11.1） μg/m 3,respectively;while trichloroethylene （TrCE）,tetrachloroethylene （TeCE） and para-dichlorobenzene （pDCB）,vinyl chloride and carbon tetrachloride were the most abundant chlorinated hydrocarbons inside the stations with average levels of （3.6±1.3）,（1.3±0.5）,（4.1±1.1）,（2.2±1.1） and （1.2±0.3） μg/m 3,respectively.Mean levels of major aromatic and chlorinated hydrocarbons were higher indoor （platforms and mezzanines） than outdoor with average indoor/outdoor （I/O） ratios of 1.1–9.5,whereas no significant indoor/outdoor differences were found except for benzene and TrCE.The highly significant mutual correlations （p0.01） for BTEX between indoor and outdoor and their significant correlation （p0.05） with methyl tert-butyl ether （MTBE）,a marker of traffic-related emission without other indoor and outdoor sources,indicated that BTEX were introduced into the subway stations from indoor/outdoor air exchange and traffic emission should be their dominant source.TrCE and pDCB were mainly from indoor emission and TeCE might have both indoor emission sources and contribution from outdoor air,especially in the mezzanines.
基金financially supported by the National Natural Science Foundation of China (Nos.51811530096, 21875286)the National Key Research & Development Projects of China (No.2017YFA0206600)Science Fund for Distinguished Young Scholars of Hunan Province (No.2017JJ1029)
文摘Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future.Here,the strategy that uses chemical structure modification to optimize the photoelectric properties is reported.A new narrow bandgap(1.30 eV)chlorinated non-fullerene electron acceptor(Y15),based on benzo[d][1,2,3] triazole with two 3-undecylthieno[2’,3’:4,5] thieno[3,2-b] pyrrole fused-7-heterocyclic ring,with absorption edge extending to the near-infrared(NIR) region,namely A-DA’D-A type structure,is designed and synthesized.Its electrochemical and optoelectronic properties are systematically investigated.Benefitting from its NIR light harvesting,the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency(PCE) of 14.13%,when blending with a wide bandgap polymer donor PM6.Our results show that the A-DA’D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells(PSCs).
基金supported by the National Natural Science Foun-dation of China(51873103)Capacity Building Project of Some Local Colleges and Universities in Shanghai(17030501200)+2 种基金Scien-tific and Technological Support Projects in the Field of Biomedicine(19441901700)Talent Program of Shanghai University of Engi-neering Science(2017RC422017)First-rate Discipline Con-struction of Applied Chemistry(2018xk-B-06).
文摘Montmorillonite(MMT) was modified by ultrasound and castor oil quaternary ammonium salt intercalation method to prepare a new type of organic montmorillonite(OMMT). The surface structure, particle morphology, interlayer distance, and thermal behavior of the samples obtained were characterized. The modified OMMT was then added to chlorinated butyl rubber(CIIR) by mechanical blending, and a composite material with excellent damping properties was obtained. The mechanical experiment results of CIIR nanocomposites showed that the addition of OMMT improved their tensile strength, hardness,and stress relaxation rate. Compared with pure CIIR, when the content of OMMT was 5 phr(part per hundred of rubber), the tensile strength of the nanocomposite was increased by 677% and the elongation at break was also increased by 105.4%. The enhancement of this performance was mainly due to the dispersion of the nanosheets in CIIR rubber and the chemical interaction between the organoclay and the polymer matrix, which was confirmed by morphology and spectral analysis. OMMT also endowed a positive effect on the damping properties of CIIR nanocomposites. After adding 5 phr of OMMT, the nanocomposite owned the best damping performance, and the damping factor, tanδmax, was 37.9% higher than that of pure CIIR. Therefore, the good damping and mechanical properties of these CIIR nanocomposites provided some novel and promising methods for preparing high-damping rubber in a wide temperature range.
基金Project supported by the National Natural Science Foundation of China (No.50378082)the Key Project of Science and Technology Plan of Zhejiang Province (No.2004C23021),China
文摘A treatability study of industrial wastewater containing chlorinated nitroaromatic compounds （CNACs） by a catalytic ozonation process （COP） with a modified Mn/Co ceramic catalyst and an aerobic sequencing batch reactor （SBR） was investigated. A preliminary attempt to treat the diluted wastewater with a single SBR resulted in ineffective removal of the color, ammonia, total organic carbon （TOC） and chemical oxygen demand （COD）. Next, COP was applied as a pretreatment in order to obtain a bio-compatible wastewater for SBR treatment in a second step. The effectiveness of the COP pretreatment was assessed by evaluating wastewater biodegradability enhancement （the ratio of biology oxygen demand after 5 d （BOD5） to COD）, as well as monitoring the evolution of TOC, carbon oxidation state （COS）, average oxidation state （AOS）, color, and major pollutant concentrations with reaction time. In the COP, the catalyst preserved its catalytic properties even after 70 reuse cycles, exhibiting good durability and stability. The performance of SBR to treat COP effluent was also examined. At an organic loading rate of 2.0 kg COD/（m^3.d）, with hydraulic retention time （HRT）=10 h and temperature （30±2） ℃, the average removal efficiencies of NH3-N, COD, BOD5, TOC, and color in a coupled COP/SBR process were about 80%, 95.8%, 93.8%, 97.6% and 99.3%, respectively, with average effluent concentrations of 10 mg/L, 128 mg/L, 27.5 mg/L, 25.0 mg/L, and 20 multiples, respectively, which were all consistent with the national standards for secondary discharge of industrial wastewater into a public sewerage system （GB 8978-1996）. The results indicated that the coupling of COP with a biological process was proved to be a technically and economically effective method for treating industrial wastewater containing recalcitrant CNACs.
基金supported by the National Natural Science Foundation of China(Nos.21806106,51861145101,21777096 and 21777097)Shanghai Shuguang Grant(No.17SG11)the China Postdoctoral Science Foundation(Nos.2017M621483 and 2018T110397)。
文摘Chlorinated organic pollutants(COPs)have caused serious contaminants in soil and groundwater,hence developing methods to remove these pollutants is necessary and urgent.By a simple hydrothermal method,we synthesized the bimetallic iron-nickel sulfide(FeNiS)particles which exhibited excellent catalytic property of COPs removal.FeNiS was chosen as the peroxydisulfate(PDS)activator to removal COPs including 4-chlorophenol(4-CP),1,4-dichlorophenol(1,4-DCP)and 2,4,6-trichlorophenol(2,4,6-TCP).The results show that FeNiS can efficiently activate PDS to produce sulfate radical(SO4·-)which plays major role in the oxidative dechlorination and degradation due to its strong oxidizing property and the ability of producing hydroxyl radicals(·OH)in the alkaline condition.Meanwhile,the Cl-abscised from COPs during the dechlorination can turn into the chlorine radicals and enhance the degradation and cause further mineralization of intermediate products.This bimetallic FeNiS catalyst is a promising PDS activator for removal of chlorinated organics.
文摘Practicability of method for the Hydra regeneration assay on the prescreening teratogenic potential of chlorinated drinking water disinfection by products was studied through both the assays of toxicity of adult Hydra (T) and inhibition of the growth of regeneration Hydra (I) by using chloroform, dichloromethane and chloroacetic acid. The results showed that T 50 / I 50 ratios of chloroform and chloroacetic acid were 2 77 and 6 16 respectively, with teratogenic potential. T 50 / I 50 ratio of dichloromethane was 1.69, with weaker teratogenic potential. These experimental results indicated preliminarily that the Hydra regeneration assay has certainly applied value as a prescreening assay for developmental toxicity.
文摘Micro-scale Al-Zn-Mg/Fe composite powders (MAF) with high reactivity and good storage properties were prepared by reducing iron onto the surface of Al-Zn-Mg alloy powders. Experimental results show that MAF as advanced zero-valent iron are highly effective for degradation of chlorinated organic compounds. The efficiency of degradation for carbon tetrachloride and perchloroethylene is higher than 99% within a period of 2 h. The efficiency of degradation for trichloroethylene by MAF after storing for one month is equivalent to that by freshly prepared nano-size zero-valent iron particles.
基金supported by the National Key Research and Development Program of China (No.2019YFC1804501)the National Natural Science Foundation of China (Nos.22036007,21876189, 21607112)+1 种基金the Youth Innovation Promotion Association CAS, China Postdoctoral Science Foundation (No.2021M693320)the Tianjin Fundamental Research Program of the Tianjin Committee of Science and Technology (No.19JCQNJC08200)。
文摘Mono-chlorinated products of cyclic volatile methylsiloxanes(cVMS),i.e.,Monochlormethylheptamethylcyclotetrasiloxane[D3D(CH_(2)Cl)],monochlormethylnonamethylcyclopentasiloxane[D4D(CH_(2)Cl)],and monochlormethylundemethylcyclohexasiloxane[D5D(CH_(2)Cl)],were detected in water[<LOQ(Limit of quantitation)-86.3 ng/L,df(detection frequency)=23%-38%,n=112]and sediment samples[<LOQ-504 ng/g dw(dry weight),df=33%-38%,n=112]from 16 lakes located in Shengli oilfield of China,and had apparent increasing trends(31%-34%per annum)in sediments during Year 2014-2020.Simulated experiments showed that chloro-cVMS in sediment-water system had approximately 1.7-2.0 times slower elimination rates than parent cVMS.More specifically,compared with those of parent cVMS,volatilization(86-2558 days)and hydrolysis(135-549 days)half-lives of chlorocVMS were respectively 1.3-2.0 and 1.8-2.1 times longer.In two species of freshwater mussels(n=1050)collected from six lakes,concentrations of chloro-cVMS ranged from 9.8-998 ng/g dw in Anodonta woodiana and 8.4-970 ng/g dw in Corbicula fluminea.Compared with parent cVMS,chloro-cVMS had 1.1-1.5 times larger biota-sediment accumulation factors(2.1-3.0)and 1.1-1.7 times longer half-lives(13-42 days).Their stronger persistence in sediment and bioaccumulation in freshwatermussels suggested that environmental emission,distribution and risks of chloro-cVMS deserve further attention.
基金Supported by the National Science and Technology Key Supporting Project(2013BAF08B05)the National Natural Science Foundation of China(21176137)
文摘Dynamic characteristics of UV enhanced gas–solid PVC chlorination process were revealed by a UV–Vis spectral online analysis method. Experimental results showed an instantaneous increase of the chlorination rate as soon as UV light was affiliated, which demonstrated the intensified effect of UV radiation on PVC chlorination directly.Different affiliation methods of UV light were then studied, proving that continuous UV radiation could enhance the chlorination process significantly while intermittent UV radiation was able to initiate the chlorination reaction once it was conducted. Besides, experiments were carried out to study the influences of parameters on the chlorination process such as UV wavelength, chlorination temperature, partial pressure of chlorine gas and PVC raw materials. Among all the parameters, chlorination temperature and partial pressure of chlorine gas were testified as two key factors to determine the chlorination performance. Thermal analysis of CPVC products showed that their corresponding properties such as the glass transition temperature(Tg) and the homogeneity of chlorine distribution in polymer phase were improved with the increase of chlorine content.
基金supported by National Key Research Development Program of China (No.2019YFC0408304)the National Natural Science Foundation of China (No.21677031)+1 种基金the Jiangsu Provincial Key Laboratory of Environmental Science and Engineering (No.Zd1901)Ningbo Natural Science Foundation (No.202003N4135)。
文摘Recently,the degradation of organic compounds in saline dye wastewater by sulfate radicals(SO4·-)-based advanced oxidation processes(AOPs) have attracted much attention.However,previous studies on these systems have selected non-chlorinated dyes as model compounds,and little is known about the transformation of chlorinated dyes in such systems.In this study,acid yellow 17(AY-17) was selected as a model of chlorinated contaminants,and the degradation kinetics and evolution of oxidation byproducts were investigated in the UV/PDS system.AY-17 can be efficiently degraded(over 98% decolorization)under 90 min irradiation at pH 2.0-3.0,and the reaction follows pseudo-first order kinetics.Cl-accelerated the degradation of AY-17,but simultaneously led to an undesirable increase of absorbable organic halogen(AOX).Several chlorinated byproducts were identified by liquid chromatography-mass spectrometry(LC-MS/MS) in the UV/PDS system.It indicates that endogenic chlorine and exogenic Cl-reacted with SO_(4)·- to form chloride radicals,which are involved in the dechlorination and rechlorination of AY-17 and intermediates.The possible degradation mechanisms of AY-17 photooxidative degradation are proposed.This work provides valuable information for further studies on the role of exogenic chloride in the degradation of chlorinated azo dyes and the kinetic parameters in the PDS-based oxidation process.
基金supported by the National Natural Science Foundation of China (Nos.21625702,21337002,21621064)the National Basic Research Program of China (No.2015CB453102)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB14010400)
文摘The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.
基金supported by the National Natural Science Foundation of China(Nos.21625702,21337002,21621064)the National Basic Research Program of China(No.2015CB453102)the Strategic Priority Research Program of the Chinese Academy of Science(No.XDB14010400)for the joint financial support
文摘Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work, an efficient, reliable and rapid pretreatment method based on matrix solid-phase dispersion（MSPD） was developed for the analysis of short-chain CPs（SCCPs） in human placenta by gas chromatograph-electron capture negative ion low-resolution mass spectrometry（GC-ECNI-LRMS） and gas chromatography–quadrupole time-of-flight mass spectrometry（GC–QTOF-HRMS）. The MSPD-relevant parameters including dispersing sorbent,sample-to-sorbent mass ratio, and elution solvent were optimized using the orthogonal test.Silica gel was found to be the optimal dispersing sorbent among the selected matrices. Under the optimal conditions, 44% acidic silica gel can be used as the co-sorbent to remove lipid and eluted by the mixture of hexane and dichloromethane（7：3, V/V）. The spiked recoveries of the optimized method were 77.4% and 91.4% for analyzing SCCPs in human placenta by GC-ECNI-LRMS and GC–QTOF-HRMS, and the corresponding relative standard deviations were10.2% and 5.6%, respectively. The method detection limit for the total SCCPs was 36.8 ng/g（dry weight, dw） and 19.2 ng/g（dw） as measured by GC-ECNI-LRMS and GC–QTOF-HRMS,respectively. The concentrations of SCCPs in four human placentas were in the range of
基金supported by the National Environmental Protection Public Welfare Science and Technology Research Program of China(No.201109013)the National Natural Science Foundation of China(No.41373094,51208199)+2 种基金the Shanghai Natural Science Funds(No.12ZR1408000)the China Postdoctoral Science Foundation(No.2013T60429)the China Scholarship Councilfor PhD program at East China University of ScienceTechnology
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 40772156 and 41072179)
文摘Chlorinated aliphatic hydrocarbons （CAHs）, significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical sensitivity or not ideal for natural samples with low concentrations of CAHs. This method is reported here to carry out simultaneously carbon and chlorine isotope analyses for mieromolar concentrations of dissolved CAHs. It was executed by extracting and converting CAHs to carbon dioxide and methyl chloride （CH3CI）. Specially, a continuous-flow interface GasBench Ⅱ was used to extract CH3CI for online chlorine isotope analysis. As a result, it greatly enhances the efficiency for isotope analysis by eliminating procedures for offline CH3CI preparation and separation. Sample size requirement was reduced to approximately 11 pmol chlorine. The standard deviation of δ^＋3C and δ^37CI for both TCE solvents and water samples was better than 0.30‰ and 0.20%0 （1σ）, respectively.Carbon and chlorine isotope analyses can be used as an important tool to study the sources of organic contaminants in groundwater and their behaviors in the aquifers. The method is applicable to manufacturers＇ products as well as a sample from a polluted site in principle, which will be validated in our field studies.
文摘Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing the possibilities of such risk by reducing the entrance, and increasing the excretion, of these chemicals. In addition, there are supplementary measures that could be employed in order to reduce this risk further, such as boiling the drinking water, revising the standard concentrations of calcium, magnesium and iron in the public drinking water and prescribing oestrogen in susceptible individuals. Hypo-methylation of genomic DNA could be used as a biological marker for screening for the potential development of colorectal cancers.
基金This work was supported by the National Natural Science Foundation of China (No. 50379012)Program for New Century Excellent Talents in University (No. 05-0481).
文摘Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicant. Biodegradability of chlorinated anilines was determined using domesticated complex bacteria as an inoculum by shaking-flask test. Results The complex bacteria were identified, consisting of Xanthomonas, Bacillus alcaligenes, Acinetobacter, Pseudomonas, and Actinomycetaceae nocardia. The obtained complex bacteria were more tolerant to o-chloroaniline than mixture bacteria in natural river waters. The effects of exposure concentration and inoculum size on the biodegradability of o-chloroaniline were analyzed, and the biodegradation characteristics of single o-chloroaniline and 2, 4-dichloroaniline were compared with the coexistent compounds. Conclusion The biodegradation rates can be improved by decreasing concentration of compounds and increasing inoculum size of complex bacteria. When o-chloroaniline coexists with aniline, the latter is biodegraded prior to the former, and as a consequence the metabolic efficiency of o-chloroaniline is improved with the increase of aniline concentration. Meanwhile, when o-chloroaniline coexists with 2,4-dichloroaniline, the metabolic efficiency of 2,4-dichloroaniline is markedly improved.
