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
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
Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter,for which the reason have not been...Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter,for which the reason have not been clearly elucidated.Here we measured carbonyl compounds and other trace gasses together with PM_(2.5)over urban Jinan in North China Plain during the winter.Markedly higher carbonyl concentrations(average:14.63±4.21 ppbv)were found during wintertime haze pollution,about one to three-times relative to those on nonhaze days,with slight difference in chemical composition except formaldehyde(HCHO).HCHO(3.68 ppbv),acetone(3.17 ppbv),and acetaldehyde(CH_3CHO)(2.83 ppbv)were the three most abundant species,accounting for~75% of the total carbonylson both haze and non-haze days.Results from observational-based model(OBM)with atmospheric oxidation capacity(AOC)indicated that AOC significantly increased with the increasing carbonyls during the winter haze events.Carbonyl photolysis have supplied key oxidants such as RO_(2) and HO_(2),and thereby enhancing the formation of fine particles and secondary organic aerosols,elucidating the observed haze-carbonyls inter-correlation.Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources.1-butene was further confirmed to be the major precursor for HCHO.This study confirms the great contribution of carbonyls to AOC,and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.展开更多
The pollution of atmospheric ozone in China shows an obvious upward trend in the past decade.However,the studies on the atmospheric oxidation capacity and O_(3)formation in four seasons in the southeastern coastal reg...The pollution of atmospheric ozone in China shows an obvious upward trend in the past decade.However,the studies on the atmospheric oxidation capacity and O_(3)formation in four seasons in the southeastern coastal region of China with the rapid urbanization remain limited.Here,a four-season field observation was carried out in a coastal city of southeast China,using an observation-based model combining with the Master Chemical Mechanism,to explore the atmospheric oxidation capacity(AOC),radical chemistry,O_(3)formation pathways and sensitivity.The results showed that the average net O_(3)production rate(14.55 ppbv/hr)in summer was the strongest,but the average O_(3)concentrations in autumn was higher.The AOC and ROx levels presented an obvious seasonal pattern with the maximum value in summer,while the OH reactivity in winter was the highest with an average value of 22.75 sec^(-1).The OH reactivity was dominated by oxygenated VOCs(OVOCs)(30.6%-42.8%),CO(23.2%-26.8%),NO_(2)(13.6%-22.0%),and alkenes(8.4%-12.5%)in different seasons.HONO photolysis dominated OH primary source on daytime in winter,while in other seasons,HONO photolysis in the morning and ozone photolysis in the afternoon contributed mostly.Sensitivity analysis indicated that O_(3)production was controlled by VOCs in spring,autumn and winter,but a VOC-limited and NOx-limited regime in summer,and alkene and aromatic species were the major controlling factors to O_(3)formation.Overall,the study characterized the atmospheric oxidation capacity and elucidated the controlling factors for O_(3)production in the coastal area with the rapid urbanization in China.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
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.
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.
基金supported by the National Natural Science Foundation of China(Nos.42005092,42275127,42075112and 41775127)the Natural Science Foundation of Shandong Province(No.ZR2020QD058)。
文摘Atmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter,for which the reason have not been clearly elucidated.Here we measured carbonyl compounds and other trace gasses together with PM_(2.5)over urban Jinan in North China Plain during the winter.Markedly higher carbonyl concentrations(average:14.63±4.21 ppbv)were found during wintertime haze pollution,about one to three-times relative to those on nonhaze days,with slight difference in chemical composition except formaldehyde(HCHO).HCHO(3.68 ppbv),acetone(3.17 ppbv),and acetaldehyde(CH_3CHO)(2.83 ppbv)were the three most abundant species,accounting for~75% of the total carbonylson both haze and non-haze days.Results from observational-based model(OBM)with atmospheric oxidation capacity(AOC)indicated that AOC significantly increased with the increasing carbonyls during the winter haze events.Carbonyl photolysis have supplied key oxidants such as RO_(2) and HO_(2),and thereby enhancing the formation of fine particles and secondary organic aerosols,elucidating the observed haze-carbonyls inter-correlation.Diurnal variation with carbonyls exhibiting peak values at early-noon and night highlighted the combined contribution of both secondary formation and primary diesel-fuel sources.1-butene was further confirmed to be the major precursor for HCHO.This study confirms the great contribution of carbonyls to AOC,and also suggests that reducing the emissions of carbonyls would be an effective way to mitigate haze pollution in urban area of the NCP region.
基金funded by the Cultivating Project of Strategic Priority Research Program of Chinese Academy of Sciences (No.XDPB1903)the Science and Technology Department of Fujian Province (No.2022L3025)+1 种基金the National Natural Science Foundation of China (No.U22A20578&42277091)the Center for Excellence in Regional Atmospheric Environment Project (No.E0L1B20201)。
文摘The pollution of atmospheric ozone in China shows an obvious upward trend in the past decade.However,the studies on the atmospheric oxidation capacity and O_(3)formation in four seasons in the southeastern coastal region of China with the rapid urbanization remain limited.Here,a four-season field observation was carried out in a coastal city of southeast China,using an observation-based model combining with the Master Chemical Mechanism,to explore the atmospheric oxidation capacity(AOC),radical chemistry,O_(3)formation pathways and sensitivity.The results showed that the average net O_(3)production rate(14.55 ppbv/hr)in summer was the strongest,but the average O_(3)concentrations in autumn was higher.The AOC and ROx levels presented an obvious seasonal pattern with the maximum value in summer,while the OH reactivity in winter was the highest with an average value of 22.75 sec^(-1).The OH reactivity was dominated by oxygenated VOCs(OVOCs)(30.6%-42.8%),CO(23.2%-26.8%),NO_(2)(13.6%-22.0%),and alkenes(8.4%-12.5%)in different seasons.HONO photolysis dominated OH primary source on daytime in winter,while in other seasons,HONO photolysis in the morning and ozone photolysis in the afternoon contributed mostly.Sensitivity analysis indicated that O_(3)production was controlled by VOCs in spring,autumn and winter,but a VOC-limited and NOx-limited regime in summer,and alkene and aromatic species were the major controlling factors to O_(3)formation.Overall,the study characterized the atmospheric oxidation capacity and elucidated the controlling factors for O_(3)production in the coastal area with the rapid urbanization in China.
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.
