Urban and regional air pollutions are characterized by high concentrations of secondary pollutants such as photo-oxidants （mainly ozone） and fine particulate matter, which are formed through chemical reactions of th...Urban and regional air pollutions are characterized by high concentrations of secondary pollutants such as photo-oxidants （mainly ozone） and fine particulate matter, which are formed through chemical reactions of the primary pollutants emitted from various sources. The accumulation of these pollutants under stagnant meteorological conditions results in the formation of gray haze, reducing visibility and causing major impacts on human health and climate. In an air pollution complex, the co- existence of high concentrations of primary and secondary gaseous and particulate pollutants provides a large amount of reac- tants for heterogeneous reactions on the surface of fine particles; these reactions change the oxidizing capacity of the atmos- phere, as well as chemical compositions along with the physicochemical and optical properties of particulate matter, thereby accelerating formation of the air pollution complex and gray haze. Using in situ technologies, such as diffuse reflectance infra- red Fourier-transform spectroscopy and single-particle Raman spectroscopy, we systematically investigated the reaction kinet- ics and mechanisms of gaseous pollutants （i.e., NO2, SO2, 03, and formaldehyde） on the surfaces of the major components of atmospheric particles such as CaCO3, kaolinite, montmorillonite, NaC1, sea salt, A1203, and Tit2. We found that the main re- action products were sulfate, nitrate, or formate, which can change the hygroscopicity and light extinction parameters of those particles significantly. By analyzing the reaction kinetics of these heterogeneous reactions, we identified synergetic mechanisms of the three ternary reaction systems, ,i.e., NOE-particles-H2O, SO2-particles-O3, and organics/SO2-particles-UV illumination. These synergetic mechanisms can provide experimental and theoretical bases for understanding the feedback mechanisms and nonlinear processes in the formation of an air pollution complex and gray haze.展开更多
It is shown by the the law of mass action in combination with the coexistence theory of slag structure that KMn n =NMno /(NFeo [%Mn] does not change with basicities and maintains constant at constant temperature; the...It is shown by the the law of mass action in combination with the coexistence theory of slag structure that KMn n =NMno /(NFeo [%Mn] does not change with basicities and maintains constant at constant temperature; the oxidizing capabilities of multicomponent slag systems containing CaO, MgO etc., can be expressed by NFe tO =NFeO + 6NFe2 O3 + 8NFe3O4; the desulfurizing capabilities of various basic oxides for multicomponent slag systems can be calculated by Ls=8(KCaSNCaO+KMgsNMgo +KFeSNFeO)∑n/[%O]; the dephosphorizing capabili- ties of CaO-MgO-FeO-FeO O3-P2 O5 as well as CaO-FeO-Fe2 O3-A12 O3-P2 O5 molten slags expressed respectively by Lpo=(%P2O5)/[P]2 = 141.94[%O]5∑nK00(1 + K5N2Cao + K6N3CaO + K7N4CaO + K8N2MgO + K9N3MgO + K10N3FeO + K11N4Feo); LPO=(%P2O5)/[P]2= 141.94[%O]5∑nK00(1 + K10N2CaO+ K11N3CaO+ K12N4CaO + K13N3FeO + K14N4FeO) have good agreement with practical values.展开更多
Atmospheric oxidizing capacity(AOC)is the fundamental driving factors of chemistry process(e.g.,the formation of ozone(O_(3))and secondary organic aerosols(SOA))in the troposphere.However,accurate quantification of AO...Atmospheric oxidizing capacity(AOC)is the fundamental driving factors of chemistry process(e.g.,the formation of ozone(O_(3))and secondary organic aerosols(SOA))in the troposphere.However,accurate quantification of AOC still remains uncertainty.In this study,a comprehensive field campaign was conducted during autumn 2019 in downtown of Beijing,where O_(3) and PM_(2.5) episodes had been experienced successively.The observation-based model(OBM)is used to quantify the AOC at O_(3) and PM_(2.5) episodes.The strong intensity of AOC is found at O_(3) and PM2.5 episodes,and hydroxyl radical(OH)is the dominating daytime oxidant for both episodes.The photolysis of O_(3) is main source of OH at O_(3) episode;the photolysis of nitrous acid(HONO)and formaldehyde(HCHO)plays important role in OH formation at PM_(2.5) episode.The radicals loss routines vary according to precursor pollutants,resulting in different types of air pollution.O_(3) budgets and sensitivity analysis indicates that O_(3) production is transition regime(both VOC and NOx-limited)at O3 episode.The heterogeneous reaction of hydroperoxy radicals(HO_(2))on aerosol surfaces has significant influence on OH and O_(3) production rates.The HO_(2) uptake coefficient(γHO_(2))is the determining factor and required accurate measurement in real atmospheric environment.Our findings could provide the important bases for coordinated control of PM_(2.5) and O_(3) pollution.展开更多
Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants whi...Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants which further affects secondary OA formation.Here we provide an observational analysis of secondary OA(SOA)variation properties in Yangtze River Delta(YRD)of eastern China in response to large scale of emission reduction during Chinese New Year(CNY)holidays from 2015 to 2020,and the COVID-19 pandemic period from January to March,2020.We found a 17%increase of SOA proportion during the COVID lockdown.The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions.Two types of oxygenated OA(OOA)influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region.Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures.展开更多
Atmospheric oxidizing capacity(AOC)is an essential driving force of troposphere chemistry and self-cleaning,but the definition of AOC and its quantitative representation remain uncertain.Driven by national demand for ...Atmospheric oxidizing capacity(AOC)is an essential driving force of troposphere chemistry and self-cleaning,but the definition of AOC and its quantitative representation remain uncertain.Driven by national demand for air pollution control in recent years,Chinese scholars have carried out studies on theories of atmospheric chemistry and have made considerable progress in AOC research.This paper will give a brief review of these developments.First,AOC indexes were established that represent apparent atmospheric oxidizing ability(AOIe)and potential atmospheric oxidizing ability(AOIp)based on aspects of macrothermodynamics and microdynamics,respectively.A closed study refined the quantitative contributions of heterogeneous chemistry to AOC in Beijing,and these AOC methods were further applied in Beijing-Tianjin-Hebei and key areas across the country.In addition,the detection of ground or vertical profiles for atmospheric OH·,HO_(2)·,NO_(3)·radicals and reservoir molecules can now be obtained with domestic instruments in diverse environments.Moreover,laboratory smoke chamber simulations revealed heterogeneous processes involving reactions of O_(3)and NO_(2),which are typical oxidants in the surface/interface atmosphere,and the evolutionary and budgetary implications of atmospheric oxidants reacting under multispecies,multiphase and multi-interface conditions were obtained.Finally,based on the GRAPES-CUACE adjoint model improved by Chinese scholars,simulations of key substances affecting atmospheric oxidation and secondary organic and inorganic aerosol formation have been optimized.Normalized numerical simulations of AOIe and AOIp were performed,and regional coordination of AOC was adjusted.An optimized plan for controlling O_(3)and PM2.5was analyzed by scenario simulation.展开更多
The exchanges of NOx between snow and air have significant impact on the atmospheric components and photochemical processes in the overlying boundary layer. Such exchanges increase the oxidizing capacity of the atmosp...The exchanges of NOx between snow and air have significant impact on the atmospheric components and photochemical processes in the overlying boundary layer. Such exchanges increase the oxidizing capacity of the atmosphere and may have a crucial impact on the air signals that are retrieved from ice cores. In the recent years, sunlit snow and ice have been demonstrated to be important NOx sources in the polar atmospheric boundary layer. This paper makes a thorough review on the release of NOx from snow and ice, including field observations and experimental evidences, release mechanisms and influential parameters that affect such a release process, polar NOx concentrations and fluxes, and environmental impacts of the chemical processes of NOx in the polar atmospheric boundary layer. In the Tibetan Plateau, the released NOx observed recently in the sunlit snow/ice-cover is 1-order magnitude more than that in polar regions, but further scientific research is still needed to reveal its impact on the atmospheric oxidizing capacity.展开更多
Atmospheric oxidizing capacity is the essen- tial feature of urban and regional air. And OH and HO2 radicals are the key species indicating atmospheric oxidizing capacity. Using Guangzhou City as a case, this work has...Atmospheric oxidizing capacity is the essen- tial feature of urban and regional air. And OH and HO2 radicals are the key species indicating atmospheric oxidizing capacity. Using Guangzhou City as a case, this work has conducted field measurements of photochemistry relevant pollutants including O3, NOx, VOCs, H2O2, HNO2 and CO, SO2. The concentrations of OH radical are measured simul- taneously by impregnated filter trapping and HPLC (IFT- HPLC) method. The factors influencing OH levels are as- sessed. Based on understanding of OH and HO2 air chemis- try, the production and removal rates of these 2 radicals are calculated. The results show that the budget of OH and HO2 can generally be closed, the radical transformation between OH and HO2 dominates the sources and sinks of them, and also the photolysis of HNO2 and HCHO is the significant source of OH and HO2 respectively.展开更多
基金financially supported by the National Natural Science Foundation of China (20637020, 40490265 & 20077001)National Basic Research Program of China (2002CB410802)special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control
文摘Urban and regional air pollutions are characterized by high concentrations of secondary pollutants such as photo-oxidants （mainly ozone） and fine particulate matter, which are formed through chemical reactions of the primary pollutants emitted from various sources. The accumulation of these pollutants under stagnant meteorological conditions results in the formation of gray haze, reducing visibility and causing major impacts on human health and climate. In an air pollution complex, the co- existence of high concentrations of primary and secondary gaseous and particulate pollutants provides a large amount of reac- tants for heterogeneous reactions on the surface of fine particles; these reactions change the oxidizing capacity of the atmos- phere, as well as chemical compositions along with the physicochemical and optical properties of particulate matter, thereby accelerating formation of the air pollution complex and gray haze. Using in situ technologies, such as diffuse reflectance infra- red Fourier-transform spectroscopy and single-particle Raman spectroscopy, we systematically investigated the reaction kinet- ics and mechanisms of gaseous pollutants （i.e., NO2, SO2, 03, and formaldehyde） on the surfaces of the major components of atmospheric particles such as CaCO3, kaolinite, montmorillonite, NaC1, sea salt, A1203, and Tit2. We found that the main re- action products were sulfate, nitrate, or formate, which can change the hygroscopicity and light extinction parameters of those particles significantly. By analyzing the reaction kinetics of these heterogeneous reactions, we identified synergetic mechanisms of the three ternary reaction systems, ,i.e., NOE-particles-H2O, SO2-particles-O3, and organics/SO2-particles-UV illumination. These synergetic mechanisms can provide experimental and theoretical bases for understanding the feedback mechanisms and nonlinear processes in the formation of an air pollution complex and gray haze.
文摘It is shown by the the law of mass action in combination with the coexistence theory of slag structure that KMn n =NMno /(NFeo [%Mn] does not change with basicities and maintains constant at constant temperature; the oxidizing capabilities of multicomponent slag systems containing CaO, MgO etc., can be expressed by NFe tO =NFeO + 6NFe2 O3 + 8NFe3O4; the desulfurizing capabilities of various basic oxides for multicomponent slag systems can be calculated by Ls=8(KCaSNCaO+KMgsNMgo +KFeSNFeO)∑n/[%O]; the dephosphorizing capabili- ties of CaO-MgO-FeO-FeO O3-P2 O5 as well as CaO-FeO-Fe2 O3-A12 O3-P2 O5 molten slags expressed respectively by Lpo=(%P2O5)/[P]2 = 141.94[%O]5∑nK00(1 + K5N2Cao + K6N3CaO + K7N4CaO + K8N2MgO + K9N3MgO + K10N3FeO + K11N4Feo); LPO=(%P2O5)/[P]2= 141.94[%O]5∑nK00(1 + K10N2CaO+ K11N3CaO+ K12N4CaO + K13N3FeO + K14N4FeO) have good agreement with practical values.
基金supported by the National Key Research and Development Program of China (No. 2017YFC0210001)the National Natural Science Foundation of China (Nos. 41830106, 42022039)+1 种基金Beijing National Laboratory for Molecular Sciences (No. BNLMS-CXXM-202011)the Youth Innovation Promotion Association CAS (No. 2017042)
文摘Atmospheric oxidizing capacity(AOC)is the fundamental driving factors of chemistry process(e.g.,the formation of ozone(O_(3))and secondary organic aerosols(SOA))in the troposphere.However,accurate quantification of AOC still remains uncertainty.In this study,a comprehensive field campaign was conducted during autumn 2019 in downtown of Beijing,where O_(3) and PM_(2.5) episodes had been experienced successively.The observation-based model(OBM)is used to quantify the AOC at O_(3) and PM_(2.5) episodes.The strong intensity of AOC is found at O_(3) and PM2.5 episodes,and hydroxyl radical(OH)is the dominating daytime oxidant for both episodes.The photolysis of O_(3) is main source of OH at O_(3) episode;the photolysis of nitrous acid(HONO)and formaldehyde(HCHO)plays important role in OH formation at PM_(2.5) episode.The radicals loss routines vary according to precursor pollutants,resulting in different types of air pollution.O_(3) budgets and sensitivity analysis indicates that O_(3) production is transition regime(both VOC and NOx-limited)at O3 episode.The heterogeneous reaction of hydroperoxy radicals(HO_(2))on aerosol surfaces has significant influence on OH and O_(3) production rates.The HO_(2) uptake coefficient(γHO_(2))is the determining factor and required accurate measurement in real atmospheric environment.Our findings could provide the important bases for coordinated control of PM_(2.5) and O_(3) pollution.
基金supported by National Natural Science Foundation of China(No.42005082).
文摘Organic aerosol(OA)is a major component of atmospheric particulate matter(PM)with complex composition and formation processes influenced by various factors.Emission reduction can alter both precursors and oxidants which further affects secondary OA formation.Here we provide an observational analysis of secondary OA(SOA)variation properties in Yangtze River Delta(YRD)of eastern China in response to large scale of emission reduction during Chinese New Year(CNY)holidays from 2015 to 2020,and the COVID-19 pandemic period from January to March,2020.We found a 17%increase of SOA proportion during the COVID lockdown.The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions.Two types of oxygenated OA(OOA)influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region.Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures.
基金supported by the Ministry of Science and Technology of the People’s Republic of China(No.2017YFC0210000)the Young Talent Project of the Center for Excellence in Regional Atmospheric Environment,CAS(No.CERAE202002)+1 种基金the National Natural Science Foundation of China(No.41705110)Beijing Major Science and Technology Project(No.Z211100004321006)。
文摘Atmospheric oxidizing capacity(AOC)is an essential driving force of troposphere chemistry and self-cleaning,but the definition of AOC and its quantitative representation remain uncertain.Driven by national demand for air pollution control in recent years,Chinese scholars have carried out studies on theories of atmospheric chemistry and have made considerable progress in AOC research.This paper will give a brief review of these developments.First,AOC indexes were established that represent apparent atmospheric oxidizing ability(AOIe)and potential atmospheric oxidizing ability(AOIp)based on aspects of macrothermodynamics and microdynamics,respectively.A closed study refined the quantitative contributions of heterogeneous chemistry to AOC in Beijing,and these AOC methods were further applied in Beijing-Tianjin-Hebei and key areas across the country.In addition,the detection of ground or vertical profiles for atmospheric OH·,HO_(2)·,NO_(3)·radicals and reservoir molecules can now be obtained with domestic instruments in diverse environments.Moreover,laboratory smoke chamber simulations revealed heterogeneous processes involving reactions of O_(3)and NO_(2),which are typical oxidants in the surface/interface atmosphere,and the evolutionary and budgetary implications of atmospheric oxidants reacting under multispecies,multiphase and multi-interface conditions were obtained.Finally,based on the GRAPES-CUACE adjoint model improved by Chinese scholars,simulations of key substances affecting atmospheric oxidation and secondary organic and inorganic aerosol formation have been optimized.Normalized numerical simulations of AOIe and AOIp were performed,and regional coordination of AOC was adjusted.An optimized plan for controlling O_(3)and PM2.5was analyzed by scenario simulation.
基金supported by the Fund of Polar Scientific Research(No.20080216) of State Ocean Administration, Chinaby Chinese Natural Science Foundation(No. 20407001,No.40701170)
文摘The exchanges of NOx between snow and air have significant impact on the atmospheric components and photochemical processes in the overlying boundary layer. Such exchanges increase the oxidizing capacity of the atmosphere and may have a crucial impact on the air signals that are retrieved from ice cores. In the recent years, sunlit snow and ice have been demonstrated to be important NOx sources in the polar atmospheric boundary layer. This paper makes a thorough review on the release of NOx from snow and ice, including field observations and experimental evidences, release mechanisms and influential parameters that affect such a release process, polar NOx concentrations and fluxes, and environmental impacts of the chemical processes of NOx in the polar atmospheric boundary layer. In the Tibetan Plateau, the released NOx observed recently in the sunlit snow/ice-cover is 1-order magnitude more than that in polar regions, but further scientific research is still needed to reveal its impact on the atmospheric oxidizing capacity.
文摘Atmospheric oxidizing capacity is the essen- tial feature of urban and regional air. And OH and HO2 radicals are the key species indicating atmospheric oxidizing capacity. Using Guangzhou City as a case, this work has conducted field measurements of photochemistry relevant pollutants including O3, NOx, VOCs, H2O2, HNO2 and CO, SO2. The concentrations of OH radical are measured simul- taneously by impregnated filter trapping and HPLC (IFT- HPLC) method. The factors influencing OH levels are as- sessed. Based on understanding of OH and HO2 air chemis- try, the production and removal rates of these 2 radicals are calculated. The results show that the budget of OH and HO2 can generally be closed, the radical transformation between OH and HO2 dominates the sources and sinks of them, and also the photolysis of HNO2 and HCHO is the significant source of OH and HO2 respectively.
