The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount...The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.展开更多
US EPA's Community Multiscale Air Quality modeling system(CMAQ) with Process Analysis tool was used to simulate and quantify the contribution of individual atmospheric processes to PM_(2.5) concentration in Qingda...US EPA's Community Multiscale Air Quality modeling system(CMAQ) with Process Analysis tool was used to simulate and quantify the contribution of individual atmospheric processes to PM_(2.5) concentration in Qingdao during three representative PM_(2.5) pollution events in the winter of 2015 and 2016. Compared with the observed surface PM_(2.5) concentrations, CMAQ could reasonably reproduce the temporal and spatial variations of PM_(2.5) during these three events. Process analysis results show that primary emissions accounted for 72.7%–93.2% of the accumulation of surface PM_(2.5) before and after the events.When the events occurred, primary emissions were still the major contributor to the increase of PM_(2.5) in Qingdao, however the contribution percentage reduced significantly,which only account for 51.4%–71.8%. Net contribution from horizontal and vertical transport to the accumulation of PM_(2.5) was also positive and its percentage increased when events occurred. Only 1.1%–4.6% of aerosol accumulation was due to PM processes and aqueous chemical processes before and after events. When the events occurred,contribution from PM processes and aqueous chemistry increased to 6.0%–11.8%. Loss of PM_(2.5) was mainly through horizontal transport, vertical transport and dry deposition, no matter during or outside the events. Wet deposition would become the main removal pathway of PM_(2.5), when precipitation occurred.展开更多
电光相位调制器(Phase Modulator,PM)因无需偏置,线性调制和插损小等优点,被广泛应用于相干光通信、微波信号产生、处理和测量等领域.调制指数和半波电压是评估PM性能的关键参数.传统基于(Optical Spectrum Analyzer,OSA)的方法面临测...电光相位调制器(Phase Modulator,PM)因无需偏置,线性调制和插损小等优点,被广泛应用于相干光通信、微波信号产生、处理和测量等领域.调制指数和半波电压是评估PM性能的关键参数.传统基于(Optical Spectrum Analyzer,OSA)的方法面临测量分辨率低和存在测量盲区问题.为此,本文提出了一种基于电谱分析(Unequal Voltage based on Electrical Spectrum Analyzer,UV-ESA)的自校准、高精度的PM特性参数测量方法.该方法利用同频、不同驱动电压比的情况下,通过分析失谐光学载波和调制边带分别与载波拍音电谱,实现PM调制指数和半波电压的高频特性参数测量.该方法不需改变测量链路结构,无需辅助宽带微波源或电光调制器,验证了所提方法的有效性,并对比OSA方法对结果的准确性进行了验证.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
Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we s...Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol（4-BP） by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH（6.1–10） and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.展开更多
The degradation of metoprolol(MTP)by the UV/sulfite with oxygen as an advanced reduction process(ARP)and that without oxygen as an advanced oxidation process(AOP)was comparatively studied herein.The degradation of MTP...The degradation of metoprolol(MTP)by the UV/sulfite with oxygen as an advanced reduction process(ARP)and that without oxygen as an advanced oxidation process(AOP)was comparatively studied herein.The degradation of MTP by both processes followed the first-order rate law with comparable reaction rate constants of 1.50×10^(-3)sec^(−1)and 1.20×10^(-3)sec^(−1),respectively.Scavenging experiments demonstrated that both e^(−)_(aq)and H·played a crucial role in MTP degradation by the UV/sulfite as an ARP,while SO_(4)^(·−)was the dominant oxidant in the UV/sulfite AOP.The degradation kinetics of MTP by the UV/sulfite as an ARP and AOP shared a similar pH dependence with a minimum rate obtained around pH 8.The results could be well explained by the pH impacts on the MTP speciation and sulfite species.Totally six transformation products(TPs)were identified from MTP degradation by the UV/sulfite ARP,and two additional ones were detected in the UV/sulfite AOP.The benzene ring and ether groups of MTP were proposed as the major reactive sites for both processes based on molecular orbital calculations by density functional theory(DFT).The similar degradation products of MTP by the UV/sulfite process as an ARP and AOP indicated that e^(−)_(aq)/H·and SO_(4)^(·−)might share similar reaction mechanisms,primarily including hydroxylation,dealkylation,and H abstraction.The toxicity of MTP solution treated by the UV/sulfite AOP was calculated to be higher than that in the ARP by the Ecological Struc-ture Activity Relationships(ECOSAR)software,due to the accumulation of TPs with higher toxicity.展开更多
Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irrad...Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.展开更多
The formation of disinfection by-products（DBPs） from the degradation of N,N-diethyl-3-methyl benzoyl amide（DEET） and ibuprofen（IBP） by the ultraviolet irradiation（UV）/chlorine process and subsequent post-chlor...The formation of disinfection by-products（DBPs） from the degradation of N,N-diethyl-3-methyl benzoyl amide（DEET） and ibuprofen（IBP） by the ultraviolet irradiation（UV）/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H_2O_2 process.The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H_2O_2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species U（RCS） and hydroxyl radicals（HO） in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50%after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine（TOCl）, respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H_2O_2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%–63% higher,Ulikely due to the generation of more DBP precursors from the attack of RCS, in addition to HO.展开更多
The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the ...The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the photodegradation behaviors of EE2 in the UV/H2O2 process.The results indicated that the addition of coexisting substances can influence the photodegradation behaviors of EE2 and it also follows the first-order kinetics.The acidic (pH 2-4) and alkaline (pH 10-12) medium benefit the photodegradation of EE2,but the photodegradation rate constant of EE2 keeps almost constant in the pH value of 4-10.The addition of anions,such as HCO3-,Cl-and NO3-,can inhibit the photodegradation of EE2,and the rate constant has a negative linear relationship with the concentration of the anions.However,the reduction degrees vary with the anions kinds,and the inhibition effect of the three anions is in the order of HCO3->NO3->Cl-.Addition of 5 mg/L methanol and bisphenol A can reduce the photodegradation rate constant of EE2by 84.31% and 72%,respectively.By comparison,the retardant effect of methanol is much more evident.In the studied concentrations range,the photodegradation rate constant of EE2 is the unary quadratic function of the organic compounds concentrations.展开更多
基金Project supported by the Science Project of Harbin City(No. H2001-12)the Youth Foundation of School of Municipal and Environmental Engineering in Harbin Institute of Technology(No. 01306914).
文摘The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.
基金supported by the National Natural Science Foundation of China(Nos.41430646,41305087)the Shandong Provincial Natural Science Foundation,China(No.ZR2013DQ022)+1 种基金the National Key Basic Research Program of China(No.2014CB953701)the Qingdao science and technology project(14-8-3-10-NSH)
文摘US EPA's Community Multiscale Air Quality modeling system(CMAQ) with Process Analysis tool was used to simulate and quantify the contribution of individual atmospheric processes to PM_(2.5) concentration in Qingdao during three representative PM_(2.5) pollution events in the winter of 2015 and 2016. Compared with the observed surface PM_(2.5) concentrations, CMAQ could reasonably reproduce the temporal and spatial variations of PM_(2.5) during these three events. Process analysis results show that primary emissions accounted for 72.7%–93.2% of the accumulation of surface PM_(2.5) before and after the events.When the events occurred, primary emissions were still the major contributor to the increase of PM_(2.5) in Qingdao, however the contribution percentage reduced significantly,which only account for 51.4%–71.8%. Net contribution from horizontal and vertical transport to the accumulation of PM_(2.5) was also positive and its percentage increased when events occurred. Only 1.1%–4.6% of aerosol accumulation was due to PM processes and aqueous chemical processes before and after events. When the events occurred,contribution from PM processes and aqueous chemistry increased to 6.0%–11.8%. Loss of PM_(2.5) was mainly through horizontal transport, vertical transport and dry deposition, no matter during or outside the events. Wet deposition would become the main removal pathway of PM_(2.5), when precipitation occurred.
文摘电光相位调制器(Phase Modulator,PM)因无需偏置,线性调制和插损小等优点,被广泛应用于相干光通信、微波信号产生、处理和测量等领域.调制指数和半波电压是评估PM性能的关键参数.传统基于(Optical Spectrum Analyzer,OSA)的方法面临测量分辨率低和存在测量盲区问题.为此,本文提出了一种基于电谱分析(Unequal Voltage based on Electrical Spectrum Analyzer,UV-ESA)的自校准、高精度的PM特性参数测量方法.该方法利用同频、不同驱动电压比的情况下,通过分析失谐光学载波和调制边带分别与载波拍音电谱,实现PM调制指数和半波电压的高频特性参数测量.该方法不需改变测量链路结构,无需辅助宽带微波源或电光调制器,验证了所提方法的有效性,并对比OSA方法对结果的准确性进行了验证.
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 Natural Science Foundation of China(No.21307057)the Natural Science Foundation of Jiangsu Province(No.BK20130577)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education of China(SRFDP,No.20130091120014)the Fundamental Research Funds for the Central Universities(No.20620140128)
文摘Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol（4-BP） by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH（6.1–10） and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.
基金This study was supported by the Guangdong introducing innovative and entrepreneurial teams(No.2019ZT08L213)the Key Special Project for Introduced Talents Team of Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(No.GML2019ZD0403)+2 种基金the National Natural Science Foundation of China(Nos.51979044 and 42177045)the Young Talent Project of Beijing Normal University at Zhuhai(No.310432101)We also thank the support received from China Scholarship Council(CSC)for providing a graduate fellowship to Y.C.(No.202006120356).
文摘The degradation of metoprolol(MTP)by the UV/sulfite with oxygen as an advanced reduction process(ARP)and that without oxygen as an advanced oxidation process(AOP)was comparatively studied herein.The degradation of MTP by both processes followed the first-order rate law with comparable reaction rate constants of 1.50×10^(-3)sec^(−1)and 1.20×10^(-3)sec^(−1),respectively.Scavenging experiments demonstrated that both e^(−)_(aq)and H·played a crucial role in MTP degradation by the UV/sulfite as an ARP,while SO_(4)^(·−)was the dominant oxidant in the UV/sulfite AOP.The degradation kinetics of MTP by the UV/sulfite as an ARP and AOP shared a similar pH dependence with a minimum rate obtained around pH 8.The results could be well explained by the pH impacts on the MTP speciation and sulfite species.Totally six transformation products(TPs)were identified from MTP degradation by the UV/sulfite ARP,and two additional ones were detected in the UV/sulfite AOP.The benzene ring and ether groups of MTP were proposed as the major reactive sites for both processes based on molecular orbital calculations by density functional theory(DFT).The similar degradation products of MTP by the UV/sulfite process as an ARP and AOP indicated that e^(−)_(aq)/H·and SO_(4)^(·−)might share similar reaction mechanisms,primarily including hydroxylation,dealkylation,and H abstraction.The toxicity of MTP solution treated by the UV/sulfite AOP was calculated to be higher than that in the ARP by the Ecological Struc-ture Activity Relationships(ECOSAR)software,due to the accumulation of TPs with higher toxicity.
文摘Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.
基金supported by the Hong Kong Research Grant Council (grant number 16208914)
文摘The formation of disinfection by-products（DBPs） from the degradation of N,N-diethyl-3-methyl benzoyl amide（DEET） and ibuprofen（IBP） by the ultraviolet irradiation（UV）/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H_2O_2 process.The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H_2O_2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species U（RCS） and hydroxyl radicals（HO） in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50%after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine（TOCl）, respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H_2O_2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%–63% higher,Ulikely due to the generation of more DBP precursors from the attack of RCS, in addition to HO.
基金Sponsored by the Key Project of National Science Foundation of China (Grant NO.50638020)the National High Technology Research and Development Program of China (Grant No.2007AA06A411)the State Key Laboratory of Urban Water Resource & Environment (Grant No.2009TS04)
文摘The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the photodegradation behaviors of EE2 in the UV/H2O2 process.The results indicated that the addition of coexisting substances can influence the photodegradation behaviors of EE2 and it also follows the first-order kinetics.The acidic (pH 2-4) and alkaline (pH 10-12) medium benefit the photodegradation of EE2,but the photodegradation rate constant of EE2 keeps almost constant in the pH value of 4-10.The addition of anions,such as HCO3-,Cl-and NO3-,can inhibit the photodegradation of EE2,and the rate constant has a negative linear relationship with the concentration of the anions.However,the reduction degrees vary with the anions kinds,and the inhibition effect of the three anions is in the order of HCO3->NO3->Cl-.Addition of 5 mg/L methanol and bisphenol A can reduce the photodegradation rate constant of EE2by 84.31% and 72%,respectively.By comparison,the retardant effect of methanol is much more evident.In the studied concentrations range,the photodegradation rate constant of EE2 is the unary quadratic function of the organic compounds concentrations.
