The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technol...The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.展开更多
This study addresses the global problem of the detoxification of cadmium(Cd)-containing solid waste by developing an eco-friendly thiosulfate system for extracting the negative electrode materials from spent Ni–Cd ba...This study addresses the global problem of the detoxification of cadmium(Cd)-containing solid waste by developing an eco-friendly thiosulfate system for extracting the negative electrode materials from spent Ni–Cd batteries and proposing an ultraviolet(UV)photolysis technology for the green recycling of the Cd in the resultant leached solution.Cd extraction is performed using both simple thiosulfate and cuprous thiosulfate systems,with the cuprous thiosulfate system exhibiting a superior leaching performance(80%),as compared with that of the simple thiosulfate system(36%).X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)analyses reveal the formation of copper sulfide on the surface of the Ni–Cd batteries leaching residue,which is confirmed by Cdleaching kinetics fitting using the shrinking-core model.Following UV exposure,95%of the Cd precipitates from the leaching solution to form CdS.Transmission electron microscopy(TEM)characterization and particle size distribution reveal that the CdS contains 100–150 nm-diameter spherical particles with compact surface structures.Electrochemical performance tests and UV–visible diffuse reflectance spectra(UV–Vis DRS)analyses demonstrate that the UV-photolysis product exhibits excellent photoelectric conversion characteristics.Photocatalytic activity tests of the recovered CdS confirm that the photocatalytic degradation ratio of methyl orange is 87%,indicating the successful green recycling of Cd from spent Ni–Cd batteries,which improves its potential application in the field of photocatalysis.展开更多
The photochemical reaction process of anthraquinone-2-sodium sulfonate （AQS） in the mixture of water （H2O） and N-butylpyridinium tetrafluoroborate （[BPy] [BF4]） was studied using the laser flash photolysis techn...The photochemical reaction process of anthraquinone-2-sodium sulfonate （AQS） in the mixture of water （H2O） and N-butylpyridinium tetrafluoroborate （[BPy] [BF4]） was studied using the laser flash photolysis technique. Experimental results show that the excited triplet of AQS （3AQS＊） could react rapidly with H2O and the transient absorption spectra greatly changed by increasing the volume fraction of the ionic liquid （VIL） in [BPy][BF4]/H2O mixtures. The absorbance at 510 nm increased gradually with increasing VIL when 0〈VIL〈0.1. By contrast, the absorbance decreased gradually when VIL〉0.1. Otherwise, the absorbance of the band near 380 nm steadily increased. The apparent kinetic parameters of transient species B and ^3AQS＊ are obtained approximately. 3AQS＊ abstracting hydrogen from [BPy]＋ was also explored. It was deduced that the 350-420 nm band was the superposition of the peaks of 3AQS＊ and AQSH＇. The two reactions of 3AQS＊ with [BPy][BF4] and H2O are a pair of competitive reactions. We also concluded that the entire reaction processes slow down in the case of high [BPy] [BF4] concentrations.展开更多
The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of P...The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of PCBs follows pseudo-first-order reaction kinetics, with photolysis rate constants ranging between 0.0011 s^-1 for PCB-52 and 0.0574 s^-1 for PCB-118. The degradation rates of PCBs by high-pressure mercury lamp irradiation were remarkably independent with respect to the degree of chlorination. Furthermore, partial least squares （PLS） models were developed to provide insight into which aspect of the molecular structure influenced PCB photolysis rate constants. It was found that the photolysis rates of PCBs increased with an increase in the net charge on the carbon atom （qc）, （ELUMO-EHOMO）^2, and the Y-axis dipole moment （μy） values, or the decrease in the energy of the second highest occupied molecular orbital （EHOMO-1）, energy of the lowest unoccupied molecular orbital （ELUMO）, ELUMO ＋ EHOMO, ELUMO - EHOMO, most positive atomic charge （q^＋）, and the twist angle of the chlorine atom （TA） values.展开更多
Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct ...Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.展开更多
Norfloxacin（NOR）, an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity.Therefore, we investigated t...Norfloxacin（NOR）, an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity.Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter（DOM）, which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance（EPR） were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical（U OH） and singlet oxygen（1O2） based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of U OH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and1O2. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.展开更多
The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated. Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroq...The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated. Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroquinone, nitrosobenzene, nitrocatechol, catechol and phenol. Nitrite and nitrate ions were also detected in the irradiated solution indicating direct photolysis of nitrobenzene or nitrophenols. The degradation of nitrobenzene and nitrophenols and the formation of three nitrophenol isomers were observed to follow zero-order kinetics. The quantum yields for nitrobenzene and nitrophenols removal are about 10~ -3 and 10~ -3 —10~ -4 respectively. The mechanism for nitrobenzene degradation was suggested to follow mainly nitro-nitrite intramolecular arrangement.展开更多
The luminescent properties of microwave discharge electrodeless mercury lamp（MDEL-Hg） which was ignited within the resonant cavity and photolysis of hydrogen sulfide with low concentration were studied in this paper...The luminescent properties of microwave discharge electrodeless mercury lamp（MDEL-Hg） which was ignited within the resonant cavity and photolysis of hydrogen sulfide with low concentration were studied in this paper.Experiment results indicated that the Interior MDEL-Hg could be made the best of energy utihzation and the efficiency of photolysis of H2S was very significant under the experimental conditions with the initial H2S concentration of 7.9 mg m^-1.With residence time of 1.5 s,the removal efficiency of hydrogen sulfide was 91%,the absolute removal amount（ARA） was 3.24μg s^-1 and the energy consumption was 58.23 mg（kWh）^-1.展开更多
The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of...The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO 2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO 2, Cl- and NO- 3. Complete photo-oxidation of nitrogen to NO- 3 occurred very slowly via the intermediate formation of NH+ 4 and NO- 2.展开更多
The photodegradation of anthracene(AN)and benzo[a]pyrene(BaP),two priority polycyclic aromatic hydrocarbons(PAHs),was examined at ultra-trace levels in surface water to elucidate their behaviour under several irradian...The photodegradation of anthracene(AN)and benzo[a]pyrene(BaP),two priority polycyclic aromatic hydrocarbons(PAHs),was examined at ultra-trace levels in surface water to elucidate their behaviour under several irradiance values and types of radiation.The emitting flux and the spectrum of the lamps were found to develop a crucial role in AN and BaP degradation since removal efficiencies of the target contaminants higher than 99%were found after 15 min of irradiation under an ultraviolet C(UVC)irradiance of 0.63 mW/cm^2,corresponding to a fluence of 560.25 mJ/cm^2.On the other hand,although ultraviolet A(UVA)lamps exhibited a higher irradiance compared to that of UVC lamps,they were not efficient for degrading the target PAHs.The removal kinetic studies corroborated these findings,being the AN elimination rate in surface water higher than that in deionized water at optimal operating conditions.Disinfection potential was also measured.A rapid microbial load inactivation,in terms of total coliforms naturally contained in the water matrix studied,was evidenced within 15 min of treatment for the fluence referred.However,after 24 hr in the dark,a regrowth was observed.Additionally,photolysis products more toxic than the parent compounds were found,which were not removed even by extending the treatment time.In this regard,it can be concluded that the individual action of UVC light for removing AN and BaP with disinfection purposes is not an efficient treatment;therefore,the use of radiation in combination with other kinds of treatments is required.展开更多
The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. ...The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identiifed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions （（25±2）°C, pH （4.5±0.1）, pH （7.4±0.1）, pH （9.0±0.1）;（50±2）°C, pH （4.5±0.1）, pH （7.4±0.1）） or in natural water up to 90 d. At pH （9.0±0.1） and （50±2）°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed ifrst-order kinetics. Degradation rates were faster under UV light （half-life of 51-59 min） compared to sunlight （half-life of 87-136 d）. Under UV light, four major photoproducts were detected and tentatively identiifed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-（2-benzyl）-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl-3-isoxazolidinone and 2-[（4,6-dihydroxyl-2-chlorine phenol）]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways：1） dehalogenation;2） substitution of chlorine group by hydroxyl;3） cleavage of the side chain. Photosensitizers, such as H2O2 and ribolfavin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.展开更多
The photodegradation of bisphenol S （BPS） in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH val...The photodegradation of bisphenol S （BPS） in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics： the rate was γ = 0.0161CBPS under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.展开更多
Perfluorooctanoic acid（PFOA）is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in...Perfluorooctanoic acid（PFOA）is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85℃ under UV light（201–600 nm）.The limited degree of decomposition at 25℃ was due to low quantum yield,which was increased by a factor of 12 at 85℃.Under the imposed conditions,the defluorination ratio increased from 8% at 25℃ to 50% at85℃ in 60 min.Production of perfluorinated carboxylic acids（PFCAs,C7–C5）,PFCAs（C4–C3）and TFA（trifluoroacetic acid,C2）accelerated and attained a maximum within 30 to 90 min at 85℃.However,these reactions did not occur at 25℃ despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25℃ to 10.9 k J at 85℃ using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.展开更多
Photolysis studies on formic acid （HCOOH） and formate ion （HCOO-） in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, ...Photolysis studies on formic acid （HCOOH） and formate ion （HCOO-） in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, CO, CO2 and CH4, generated during the experiments were monitored with varying the ambient, light exposure time, and the concentration of HCOOH/HCOO-. The yields of CO in all these systems increased with light exposure time. In aerated systems, CO yields were higher in contrast to the deoxygenated （Ar-purged） systems under identical conditions. It is proposed apparently that the formation of CO is taking place during the chemical reduction of in-situ generated CO2, a photo-mineralized product of HCOOH/HCOO-, but not through the direct photodecomposition or photodehydration （CO＋H2O） of solute molecules. The rates of CO formation during 1.3 M HCOOH photolysis in presence of TiO2 photocatalyst were evaluated to be 0.21 and 0.13 μl/min in aerated and Ar-purged systems, respectively. As compared with HCOOH systems, the CO yields are lower when 0.2 M HCOONa was exposed to light under identical conditions. The CO growth rates were evaluated to be 0.07 and 0.046 μl/min^-1 for aerated and deoxygenated HCOONa systems, respectively; moreover, the trend is quite similar to that of the HCOOH system. Under these conditions, the emission of H2 was also observed, and its yield was significantly higher in Ar-purged system as compared with the CO yields. However, in aerated system, the yields of these products were just opposite. The formation of low yield of methane was observed during photolysis of HCOOH/HCOO ions. In CO2 ambient, the yields of CO and H2 varied drastically with time.展开更多
Photolysis of some polycyclic aromatic hydrocarbons （PAHs） on soil surfaces may play an important role in the fate of PAHs in the environment.Photolysis of PAHs on soil surfaces under UV irradiation was investigated...Photolysis of some polycyclic aromatic hydrocarbons （PAHs） on soil surfaces may play an important role in the fate of PAHs in the environment.Photolysis of PAHs on soil surfaces under UV irradiation was investigated.The effects of oxygen,irradiation intensity and soil moisture on the degradation of the three PAHs were observed.The results showed that oxygen,soil moisture and irradiation intensity enhanced the photolysis of the three PAHs on soil surfaces.The degradation of the three PAHs on soil surfaces is related to their absorption spectra and the oxidation-half-wave potential.The photolysis of PAHs on soil surfaces in the presence of oxygen followed pseudo first-order kinetics.The photolysis half-lives ranged from 37.87 days for benzo[a]pyrene to 58.73 days for phenanthrene.The results indicate that photolysis is a successful way to remediate PAHs-contaminated soils.展开更多
o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyanine bromide (C1), 3,3'-diethyl thiacarbocyanine iodide (C2), and cyclopentanone 2,5-bis[2-(1,3 -dihy...o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyanine bromide (C1), 3,3'-diethyl thiacarbocyanine iodide (C2), and cyclopentanone 2,5-bis[2-(1,3 -dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass), the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate the polymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R-p = K [C2](0.75)[o-Cl-HABI](0.44)[MTA](0.12)[MMA](1.0). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.展开更多
The frequent detection of pharmaceutical compounds in the environment has led to a growing awareness,which may pose a major threat to the aquatic environment.In this study,photodegradation(direct and indirect photolys...The frequent detection of pharmaceutical compounds in the environment has led to a growing awareness,which may pose a major threat to the aquatic environment.In this study,photodegradation(direct and indirect photolysis)of two different dissociation states of fluoxetine(FLU)was investigated in water,mainly including the determination of photolytic transition states and products,and the mechanisms of indirect photodegradation with·OH,CO_(3)^(*-)and NO_(3)^(*).The main direct photolysis pathways are defluorination and C–C bond cleavage.In addition,the indirect photodegradation of FLU in water is mainly through the reactions with·OH and NO_(3)^(*),and the photodegradation reaction with CO_(3)^(*-)is relatively difficult to occur in the water environment.Our results provide a theoretical basis for understanding the phototransformation process of FLU in the water environment and assessing its potential risk.展开更多
The emissions of NO_(2)and HONO from the KNO_(3)photolysis in the presence of TiO_(2)were measured using a round-shape reactor coupled to a NO_(x)analyzer.TiO_(2)played important roles in the emission flux density of ...The emissions of NO_(2)and HONO from the KNO_(3)photolysis in the presence of TiO_(2)were measured using a round-shape reactor coupled to a NO_(x)analyzer.TiO_(2)played important roles in the emission flux density of NO_(2)(R_(NO_(2)))and HONO(R HONO),depending on crystal structures and mass ratios of TiO_(2).R NO_(2)and R HONO significantly decreased with increasing the rutile and anatase mass ratios from 0 to 8 and 0.5 wt.%,respectively.Nevertheless,with further increasing the anatase mass ratio to 8 wt.%,there was an increase in R_(NO_(2))and R HONO.R NO_(2)on KNO_(3)/TiO_(2)/SiO_(2)had positive correlation with the KNO_(3)mass(1–20 wt.%),irradiation intensity(80–400 W/m^(2))and temperature(278–308 K),while it had the maximum value at the relative humidity(RH)of 55%.R HONO on KNO_(3)/TiO_(2)/SiO_(2)slightly varied with the KNO_(3)mass and temperature,whereas it increased with the irradiation intensity and RH.In addition,the mechanism for NO_(2)and HONO emissions from the nitrates photolysis and atmospheric implications were discussed.展开更多
The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to...The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.展开更多
Acetylacetone was firstly introduced into the aqueous media with the presence of aluminum sec-butoxide and pep-tizator. It was confirmed that the UV (ultraviolet) absorption band of acetylacetone underwent 14 nm of re...Acetylacetone was firstly introduced into the aqueous media with the presence of aluminum sec-butoxide and pep-tizator. It was confirmed that the UV (ultraviolet) absorption band of acetylacetone underwent 14 nm of red-shift due to the formation of the six-membered ring of the complex between alumina and acetylacetone in the aqueous solution. It was also found that the chemical modification can be dissociated by the UV irradiation with a wavelength shorter than 286 nm as a result of the excitation of π-π* transition in the complex.展开更多
基金supported by the grants PID2020-113371RA-C22 and TED2021-130845A-C32,funded by MCIN/AEI/10.13039/501100011033.M.Marín-García,R.González-OlmosC.Gómez-Canela are members of the GESPA group(Grup d’Enginyeria i Simulacióde Processos Ambientals)at IQS-URL,which has been acknowledged as a Consolidated Research Group by the Government of Catalonia(No.2021-SGR-00321)+1 种基金In addition,M.Marín-García has been awarded a public grant for the Investigo Programme,aimed at hiring young job seekers to undertake research and innovation projects under the Recovery,Transformation,and Resilience Plan(PRTR),European Union Next Generation,for the year 2022,through the Government of Catalonia and the Spanish Ministry for Work and Social Economy(No.100045ID16)Ana Belén Cuenca for her support and expertise,which helped to confirm the proposed reaction mechanism involved in the UV photolysis of cloperastine.
文摘The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.
基金financially supported by the National Natural Science Foundation of China(No.52104349)Henan Provincial Science and Technology R&D Plan Joint Fund Project(No.232103810032)+1 种基金the Funds for HAUST Young Cadre Teacher(No.400213450022)supporting by China Postdoctoral Science Foundation(No.2022M721031)。
文摘This study addresses the global problem of the detoxification of cadmium(Cd)-containing solid waste by developing an eco-friendly thiosulfate system for extracting the negative electrode materials from spent Ni–Cd batteries and proposing an ultraviolet(UV)photolysis technology for the green recycling of the Cd in the resultant leached solution.Cd extraction is performed using both simple thiosulfate and cuprous thiosulfate systems,with the cuprous thiosulfate system exhibiting a superior leaching performance(80%),as compared with that of the simple thiosulfate system(36%).X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)analyses reveal the formation of copper sulfide on the surface of the Ni–Cd batteries leaching residue,which is confirmed by Cdleaching kinetics fitting using the shrinking-core model.Following UV exposure,95%of the Cd precipitates from the leaching solution to form CdS.Transmission electron microscopy(TEM)characterization and particle size distribution reveal that the CdS contains 100–150 nm-diameter spherical particles with compact surface structures.Electrochemical performance tests and UV–visible diffuse reflectance spectra(UV–Vis DRS)analyses demonstrate that the UV-photolysis product exhibits excellent photoelectric conversion characteristics.Photocatalytic activity tests of the recovered CdS confirm that the photocatalytic degradation ratio of methyl orange is 87%,indicating the successful green recycling of Cd from spent Ni–Cd batteries,which improves its potential application in the field of photocatalysis.
基金This work was supported by the National Natural Science Foundation of China （No.21173002） and the Anhui Provincial Natural Science Foundation, China （No.1308085MB20）.
文摘The photochemical reaction process of anthraquinone-2-sodium sulfonate （AQS） in the mixture of water （H2O） and N-butylpyridinium tetrafluoroborate （[BPy] [BF4]） was studied using the laser flash photolysis technique. Experimental results show that the excited triplet of AQS （3AQS＊） could react rapidly with H2O and the transient absorption spectra greatly changed by increasing the volume fraction of the ionic liquid （VIL） in [BPy][BF4]/H2O mixtures. The absorbance at 510 nm increased gradually with increasing VIL when 0〈VIL〈0.1. By contrast, the absorbance decreased gradually when VIL〉0.1. Otherwise, the absorbance of the band near 380 nm steadily increased. The apparent kinetic parameters of transient species B and ^3AQS＊ are obtained approximately. 3AQS＊ abstracting hydrogen from [BPy]＋ was also explored. It was deduced that the 350-420 nm band was the superposition of the peaks of 3AQS＊ and AQSH＇. The two reactions of 3AQS＊ with [BPy][BF4] and H2O are a pair of competitive reactions. We also concluded that the entire reaction processes slow down in the case of high [BPy] [BF4] concentrations.
基金This work was supported by the National Natural Science Foundation of China(No.20507010)the Excellent Young Scientist Fund of China(No.50625823).
文摘The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of PCBs follows pseudo-first-order reaction kinetics, with photolysis rate constants ranging between 0.0011 s^-1 for PCB-52 and 0.0574 s^-1 for PCB-118. The degradation rates of PCBs by high-pressure mercury lamp irradiation were remarkably independent with respect to the degree of chlorination. Furthermore, partial least squares （PLS） models were developed to provide insight into which aspect of the molecular structure influenced PCB photolysis rate constants. It was found that the photolysis rates of PCBs increased with an increase in the net charge on the carbon atom （qc）, （ELUMO-EHOMO）^2, and the Y-axis dipole moment （μy） values, or the decrease in the energy of the second highest occupied molecular orbital （EHOMO-1）, energy of the lowest unoccupied molecular orbital （ELUMO）, ELUMO ＋ EHOMO, ELUMO - EHOMO, most positive atomic charge （q^＋）, and the twist angle of the chlorine atom （TA） values.
文摘Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.
基金supported by the National Basic Research Program (973) of China (No. 2013CB430403)
文摘Norfloxacin（NOR）, an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity.Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter（DOM）, which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance（EPR） were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical（U OH） and singlet oxygen（1O2） based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of U OH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and1O2. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.
文摘The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated. Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroquinone, nitrosobenzene, nitrocatechol, catechol and phenol. Nitrite and nitrate ions were also detected in the irradiated solution indicating direct photolysis of nitrobenzene or nitrophenols. The degradation of nitrobenzene and nitrophenols and the formation of three nitrophenol isomers were observed to follow zero-order kinetics. The quantum yields for nitrobenzene and nitrophenols removal are about 10~ -3 and 10~ -3 —10~ -4 respectively. The mechanism for nitrobenzene degradation was suggested to follow mainly nitro-nitrite intramolecular arrangement.
基金supported by the Shanghai Natural Science Foundation(No.07ZR14004)
文摘The luminescent properties of microwave discharge electrodeless mercury lamp（MDEL-Hg） which was ignited within the resonant cavity and photolysis of hydrogen sulfide with low concentration were studied in this paper.Experiment results indicated that the Interior MDEL-Hg could be made the best of energy utihzation and the efficiency of photolysis of H2S was very significant under the experimental conditions with the initial H2S concentration of 7.9 mg m^-1.With residence time of 1.5 s,the removal efficiency of hydrogen sulfide was 91%,the absolute removal amount（ARA） was 3.24μg s^-1 and the energy consumption was 58.23 mg（kWh）^-1.
文摘The direct and sensitized photodegradations of imidacloprid, 1-(6-chloro-3-pyridinylmethyl)-N-nitro-2-imidazolidinimine, were investigated in aqueous solution and with and without various photo-sensitizers. Results of the study revealed that the intensity of lamp-house and irradiation wavelength had significant effects on the photolysis of imidacloprid. Complete degradation of 20 mg/L imidacloprid in aqueous phase was observed in 40 min under ultraviolet(UV) irradiation system, suggesting the ultraviolet ray played significant role in direct photolysis of imidacloprid. The additions of various photo-sensitizers lead to improve the degradation efficiency of imidacloprid under the irradiation of black light fluorescent lamp. TiO 2 was the most efficient in the photo-catalytic degradation of imidacloprid among other photo-sensitizers in used this study. However, addition of acetone inhibited the photolysis of imidacloprid under the irradiation of UV, indicating the occurrence of competition between acetone and imidacloprid for photos. Mineralization of the imidacloprid was examined to clarify the final photochemical degradation products of the insecticide which were CO 2, Cl- and NO- 3. Complete photo-oxidation of nitrogen to NO- 3 occurred very slowly via the intermediate formation of NH+ 4 and NO- 2.
基金financial support obtained from the Colombian Administrative Department of Science,Technology and Innovation(COLCIENCIAS)。
文摘The photodegradation of anthracene(AN)and benzo[a]pyrene(BaP),two priority polycyclic aromatic hydrocarbons(PAHs),was examined at ultra-trace levels in surface water to elucidate their behaviour under several irradiance values and types of radiation.The emitting flux and the spectrum of the lamps were found to develop a crucial role in AN and BaP degradation since removal efficiencies of the target contaminants higher than 99%were found after 15 min of irradiation under an ultraviolet C(UVC)irradiance of 0.63 mW/cm^2,corresponding to a fluence of 560.25 mJ/cm^2.On the other hand,although ultraviolet A(UVA)lamps exhibited a higher irradiance compared to that of UVC lamps,they were not efficient for degrading the target PAHs.The removal kinetic studies corroborated these findings,being the AN elimination rate in surface water higher than that in deionized water at optimal operating conditions.Disinfection potential was also measured.A rapid microbial load inactivation,in terms of total coliforms naturally contained in the water matrix studied,was evidenced within 15 min of treatment for the fluence referred.However,after 24 hr in the dark,a regrowth was observed.Additionally,photolysis products more toxic than the parent compounds were found,which were not removed even by extending the treatment time.In this regard,it can be concluded that the individual action of UVC light for removing AN and BaP with disinfection purposes is not an efficient treatment;therefore,the use of radiation in combination with other kinds of treatments is required.
基金sponsored by Shandong Cynda Chemical Co.Ltd.(Shandong+1 种基金China)the Project of Pesticide Registration Residue of Ministry of Agriculture of China(FRF-SD-12-010B)
文摘The hydrolysis and photolysis of clomazone in aqueous solutions and natural water were assessed under natural and controlled conditions. Kinetics of hydrolysis and photolysis of clomazone were determined by HPLC-DAD. Photoproducts were identiifed by HPLC-MS. No noticeable hydrolysis occurred in aqueous buffer solutions （（25±2）°C, pH （4.5±0.1）, pH （7.4±0.1）, pH （9.0±0.1）;（50±2）°C, pH （4.5±0.1）, pH （7.4±0.1）） or in natural water up to 90 d. At pH （9.0±0.1） and （50±2）°C the half-life of clomazone was 50.2 d. Clomazone photodecomposition rate in aqueous solutions under UV radiation and natural sunlight followed ifrst-order kinetics. Degradation rates were faster under UV light （half-life of 51-59 min） compared to sunlight （half-life of 87-136 d）. Under UV light, four major photoproducts were detected and tentatively identiifed according to HPLC-MS spectral information such as 2-chlorobenzamide, N-hydroxy-（2-benzyl）-2-methylpropan-amide, 2-[2-phenol]-4,4-dimethyl-3-isoxazolidinone and 2-[（4,6-dihydroxyl-2-chlorine phenol）]-4,4-dimethyl-3-isoxazolidinone. These results suggested that clomazone photodegradation proceeds via several reaction pathways：1） dehalogenation;2） substitution of chlorine group by hydroxyl;3） cleavage of the side chain. Photosensitizers, such as H2O2 and ribolfavin, could enhance photolysis of clomazone in natural sunlight. In summary, we found that photoreaction is an important dissipation pathway of clomazone in natural water systems.
基金supported by the Major Projects of National Science and Technology on Water Pollution Control and Treatment (No. 2008ZX07101-003)the Natural Sciences Research Project of Changzhou Institute of Technology (No. YN1009)
文摘The photodegradation of bisphenol S （BPS） in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics： the rate was γ = 0.0161CBPS under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.
基金supported by the National Basic Research Program(973)of China(No.2010CB933600)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA09030203)+4 种基金the National Natural Science Foundation of China(Nos.2127716141103076)the special fund from the State Key Laboratory of Environmental Aquatic Chemistry(No.10Y10ESPCR)the Youth Innovation Promotion AssociationChinese Academy of Sciences(29QNCX2012005)
文摘Perfluorooctanoic acid（PFOA）is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85℃ under UV light（201–600 nm）.The limited degree of decomposition at 25℃ was due to low quantum yield,which was increased by a factor of 12 at 85℃.Under the imposed conditions,the defluorination ratio increased from 8% at 25℃ to 50% at85℃ in 60 min.Production of perfluorinated carboxylic acids（PFCAs,C7–C5）,PFCAs（C4–C3）and TFA（trifluoroacetic acid,C2）accelerated and attained a maximum within 30 to 90 min at 85℃.However,these reactions did not occur at 25℃ despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25℃ to 10.9 k J at 85℃ using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.
文摘Photolysis studies on formic acid （HCOOH） and formate ion （HCOO-） in presence of TiO2, a photocatalyst, as suspension in water were carried out separately using 350 nm ultraviolet light. The products, such as H2, CO, CO2 and CH4, generated during the experiments were monitored with varying the ambient, light exposure time, and the concentration of HCOOH/HCOO-. The yields of CO in all these systems increased with light exposure time. In aerated systems, CO yields were higher in contrast to the deoxygenated （Ar-purged） systems under identical conditions. It is proposed apparently that the formation of CO is taking place during the chemical reduction of in-situ generated CO2, a photo-mineralized product of HCOOH/HCOO-, but not through the direct photodecomposition or photodehydration （CO＋H2O） of solute molecules. The rates of CO formation during 1.3 M HCOOH photolysis in presence of TiO2 photocatalyst were evaluated to be 0.21 and 0.13 μl/min in aerated and Ar-purged systems, respectively. As compared with HCOOH systems, the CO yields are lower when 0.2 M HCOONa was exposed to light under identical conditions. The CO growth rates were evaluated to be 0.07 and 0.046 μl/min^-1 for aerated and deoxygenated HCOONa systems, respectively; moreover, the trend is quite similar to that of the HCOOH system. Under these conditions, the emission of H2 was also observed, and its yield was significantly higher in Ar-purged system as compared with the CO yields. However, in aerated system, the yields of these products were just opposite. The formation of low yield of methane was observed during photolysis of HCOOH/HCOO ions. In CO2 ambient, the yields of CO and H2 varied drastically with time.
基金supported by the National Science Foundation for Young Scholars of China(No.41101474)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering(No.KLIEEE-09-04)+1 种基金the Liaoning Doctoral Funds(No.20111076)Liaoning University Environment Institute Key Discipline Project(No.2012J-001)
文摘Photolysis of some polycyclic aromatic hydrocarbons （PAHs） on soil surfaces may play an important role in the fate of PAHs in the environment.Photolysis of PAHs on soil surfaces under UV irradiation was investigated.The effects of oxygen,irradiation intensity and soil moisture on the degradation of the three PAHs were observed.The results showed that oxygen,soil moisture and irradiation intensity enhanced the photolysis of the three PAHs on soil surfaces.The degradation of the three PAHs on soil surfaces is related to their absorption spectra and the oxidation-half-wave potential.The photolysis of PAHs on soil surfaces in the presence of oxygen followed pseudo first-order kinetics.The photolysis half-lives ranged from 37.87 days for benzo[a]pyrene to 58.73 days for phenanthrene.The results indicate that photolysis is a successful way to remediate PAHs-contaminated soils.
基金This project financially supported by National Natural Science Foundation of China (Project number 59973023)
文摘o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyanine bromide (C1), 3,3'-diethyl thiacarbocyanine iodide (C2), and cyclopentanone 2,5-bis[2-(1,3 -dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass), the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate the polymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R-p = K [C2](0.75)[o-Cl-HABI](0.44)[MTA](0.12)[MMA](1.0). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.
基金supported by the National Natural Science Foundation of China(No.41601519)。
文摘The frequent detection of pharmaceutical compounds in the environment has led to a growing awareness,which may pose a major threat to the aquatic environment.In this study,photodegradation(direct and indirect photolysis)of two different dissociation states of fluoxetine(FLU)was investigated in water,mainly including the determination of photolytic transition states and products,and the mechanisms of indirect photodegradation with·OH,CO_(3)^(*-)and NO_(3)^(*).The main direct photolysis pathways are defluorination and C–C bond cleavage.In addition,the indirect photodegradation of FLU in water is mainly through the reactions with·OH and NO_(3)^(*),and the photodegradation reaction with CO_(3)^(*-)is relatively difficult to occur in the water environment.Our results provide a theoretical basis for understanding the phototransformation process of FLU in the water environment and assessing its potential risk.
基金financially supported by the Liao Ning Revitalization Talents Program(No.XLYC1907185)the Fundamental Research Funds for the Central Universities(Nos.N182505040 and N2025011)。
文摘The emissions of NO_(2)and HONO from the KNO_(3)photolysis in the presence of TiO_(2)were measured using a round-shape reactor coupled to a NO_(x)analyzer.TiO_(2)played important roles in the emission flux density of NO_(2)(R_(NO_(2)))and HONO(R HONO),depending on crystal structures and mass ratios of TiO_(2).R NO_(2)and R HONO significantly decreased with increasing the rutile and anatase mass ratios from 0 to 8 and 0.5 wt.%,respectively.Nevertheless,with further increasing the anatase mass ratio to 8 wt.%,there was an increase in R_(NO_(2))and R HONO.R NO_(2)on KNO_(3)/TiO_(2)/SiO_(2)had positive correlation with the KNO_(3)mass(1–20 wt.%),irradiation intensity(80–400 W/m^(2))and temperature(278–308 K),while it had the maximum value at the relative humidity(RH)of 55%.R HONO on KNO_(3)/TiO_(2)/SiO_(2)slightly varied with the KNO_(3)mass and temperature,whereas it increased with the irradiation intensity and RH.In addition,the mechanism for NO_(2)and HONO emissions from the nitrates photolysis and atmospheric implications were discussed.
基金supported by the National Natural Science Foundation of China(No.21933011,No.21873112)。
文摘The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.
文摘Acetylacetone was firstly introduced into the aqueous media with the presence of aluminum sec-butoxide and pep-tizator. It was confirmed that the UV (ultraviolet) absorption band of acetylacetone underwent 14 nm of red-shift due to the formation of the six-membered ring of the complex between alumina and acetylacetone in the aqueous solution. It was also found that the chemical modification can be dissociated by the UV irradiation with a wavelength shorter than 286 nm as a result of the excitation of π-π* transition in the complex.
