Peroxyacetyl nitrate(PAN)is an important photochemical pollutant in the troposphere,whereas long-term measurements are scarce in rural areas in North China Plain(NCP),resulting in unclear seasonal variations and sourc...Peroxyacetyl nitrate(PAN)is an important photochemical pollutant in the troposphere,whereas long-term measurements are scarce in rural areas in North China Plain(NCP),resulting in unclear seasonal variations and sources of PAN in rural NCP.In this study,we conducted a 1-year observation of PAN during 2021-2022 at the rural NCP site.The average concentrations of PAN were 1.10,0.75,0.65,and 0.88 ppbv in spring,summer,autumn,and winter,respectively,with a 1-year average of 0.81±0.60 ppbv.Calculations indicate that the loss of PAN through thermal decomposition in summer accounts for 43.2% of the total formed PAN,which is an important reason for the low concentration of PAN in summer.We speculate that since the correlation between PAN and O_(3) in winter is significantly lower than that in other seasons,the observed regional transport of PAN cannot be ignored in winter.Through budget analysis,regional transport accounted for 12.8% and 55.9% of the observed PAN on the spring and winter pollution days,respectively,which showed that regional transport played key roles during the photochemical pollution of the rural NCP in winter.The potential source contribution function revealed that the transported PAN mainly comes from southern Hebei in spring.In winter,the transported PAN was mainly from Langfang,Hengshui,and southern Beijing.Our findings may aid in understanding PAN variations in different seasons in rural areas and highlight the impact of regional transport on the PAN budget.展开更多
Peroxyacetyl nitrate （PAN）, as a major secondary pollutant, has gained increasing worldwide attentions, but relevant studies in China are still quite limited. During winter of 2015 to summer of 2016, the ambient lev...Peroxyacetyl nitrate （PAN）, as a major secondary pollutant, has gained increasing worldwide attentions, but relevant studies in China are still quite limited. During winter of 2015 to summer of 2016, the ambient levels of PAN were measured continuously by an automatic gas chromatograph equipped with an electron capture detector （GC-ECD） analyzer at an urban site in Jinan （China）, with related parameters including concentrations of 03, NO, NO2, PM2.5, HONO, the photolysis rate constant of NO2 and meteorological factors observed concurrently. The mean and maximum values of PAN concentration were （1.89 ± 1.42） and 9.61 ppbv respectively in winter, and （2.54 ± 1.44） and 13.47 ppbv respectively in summer. Unusually high levels of PAN were observed during severe haze episodes in winter, and the formation mechanisms of them were emphatically discussed, Study showed that high levels of PAN in winter were mainly caused by local accumulation and strong photochemical reactions during haze episodes, while mass transport played only a minor role. Accelerated photochemical reactions （compared to winter days without haze） during haze episodes were deduced by the higher concentrations but shorter lifetimes of pAN, which was further supported by the sufficient solar radiation in the photolysis band along with the high concentrations of precursors （NO2, VOCs） and HONO during haze episodes. In addition, significant PAN accumulation during calm weather of haze episodes was verified by meteorological data.展开更多
Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., mad...Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site （CMA） in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10^-9 mol/mol （0.23 × 10^9-3.51 × 10^9 mol/mol） and was well correlated with that of NOa but not O3, indicating that the variations of the winter concentrations of PAN and O3 in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3 ratio smaller than 0.O31, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3 ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3 decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl （PA） radicai was estimated to be in the range of 0.0014 × 10^-12～0.0042 × 10^-12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN＇s variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.展开更多
Atmospheric peroxyacetyl nitrate （PAN）, peroxypropionyl nitrate （PPN）, and carbon tetrachloride （CCl4） were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to ear...Atmospheric peroxyacetyl nitrate （PAN）, peroxypropionyl nitrate （PPN）, and carbon tetrachloride （CCl4） were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring （October to March） with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer （March to August）, ranging from 1.37-3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values （below detection limit to 0.18 ppbV） from mid-autumn to early spring, and a monthly maximum in September （1.14 ppbV）. The monthly variation of CCl4 was tightly related to the variation of temperature, exhibiting a minimum in winter （69.3 pptV） and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3 showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon （ca. 15：00 to 16：00 local time） and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn （R = 0.91）, spring （R = 0.94）, and summer （R = 0.81）, with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes （AO3/APAN） ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3 consumption by NO titration and less thermal decompositin of PAN.展开更多
As an important secondary photochemical pollutant,peroxyacetyl nitrate(PAN)has been studied over decades,yet its simulations usually underestimate the corresponding observations,especially in polluted areas.Recent obs...As an important secondary photochemical pollutant,peroxyacetyl nitrate(PAN)has been studied over decades,yet its simulations usually underestimate the corresponding observations,especially in polluted areas.Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events,but the current model still cannot reproduce the observations,and researchers speculated that nitrous acid(HONO)played a key role in PAN formation.For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry(WRF-Chem)model in February of 2017.The results showed that the potential HONO sources significantly improved the PAN simulations,remarkably accelerated the RO x(sum of hydroxyl,hydroperoxyl,and organic peroxy radicals)cycles,and resulted in 80%–150%enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50%enhancements in the areas around 35–40°N within 3 km during a heavy haze period.The direct precursors of PAN were aldehyde and methylglyoxal,and the primary precursors of PAN were alkenes with C>3,xylenes,propene and toluene.The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.展开更多
As a secondary pollutant of photochemical pollution,peroxyacetyl nitrate(PAN)has attracted a close attention.A four-month campaign was conducted at a rural site in North China Plain(NCP)including the measurement of PA...As a secondary pollutant of photochemical pollution,peroxyacetyl nitrate(PAN)has attracted a close attention.A four-month campaign was conducted at a rural site in North China Plain(NCP)including the measurement of PAN,O_(3),NO_(x),PM_(2.5),oxygenated volatile organic compounds(OVOCs),photolysis rate constants of NO_(2)and O_(3)and meteorological parameters to investigate the wintertime characterization of photochemistry from November 2018 to February 2019.The results showed that the maximum and mean values of PAN were 4.38 and 0.93±0.67 ppbv during the campaign,respectively.The PAN under different PM_(2.5)concentrations from below 75μg/m^(3)up to 250μg/m^(3),showed different diurnal variation and formation rate.In the PM_(2.5)concentration range of above 250μg/m^(3),PAN had the largest daily mean value of 0.64 ppbv and the fastest production rate of 0.33 ppbv/hr.From the perspective of PAN’s production mechanism,the light intensity and precursors concentrations under different PM_(2.5)pollution levels indicated that there were sufficient light intensity and high volatile organic compounds(VOCs)and NO_(x)precursors concentration even under severe pollution level to generate a large amount of PAN.Moreover,the bimodal staggering phenomenon of PAN and PM_(2.5)provided a basis that PAN might aggravate haze through secondary organic aerosols(SOA)formation.展开更多
Peroxyacetyl nitrate （PAN） is an important indicator of photochemical smog and has adverse effects on human health and vegetation growth. A rapid and h!ghly selective technique of thermal dissociation chemical ioniz...Peroxyacetyl nitrate （PAN） is an important indicator of photochemical smog and has adverse effects on human health and vegetation growth. A rapid and h!ghly selective technique of thermal dissociation chemical ionization mass spectrometry （TD-CIMS） was recently developed to measure the abundance of PAN in real time; however, it may be subject to artifact in the presence of nitric oxide （NO）. In this study, we tested the interference of the PAN signal induced by NO, evaluated the performance of TD- CIMS in an urban environment, and investigated the concentration and formation of PAN in urban Hong Kong. NO caused a significant underestimation of the PAN signal in TD-CIMS, with the underestimation increasing sharply with NO concentration and decreasing slightly with PAN abundance. A formula was derived to link the loss of PAN signal with the concentrations of NO and PAN, which can be used for data correction in PAN measurements. The corrected PAN data from TD- CIMS were consistent with those from the commonly used gas chromatography with electron capture detection, which confirms the utility of TD-CIMS in an urban environment in which NO is abundant. In autumn of 2010, the hourly average PAN mixing ratio varied from 0.06 ppbv to 5.17 ppbv, indicating the occurrence of photochemical pollution in urban Hong Kong. The tbrmation efficiency of PAN during pollution episodes was as high as 3.9 to 5.9 ppbv per 100 ppbv ozone. The efficiency showed a near-linear increase with NO, concentration, suggesting a control policy of NO,. reduction for PAN pollution.展开更多
基金supported by the National Natural Science Foundation of China[grant number 42205121]the Natural Science Foundation of Guangxi Province[grant number 2018JJA150164]the Guangxi Engineering Technology Research Center of Source Analysis and Forecasting of Air Pollution.
基金supported by the National Natural Science Foundation of China(Nos.21976190,41727805,41975164,22076202,42275111,41931287,and 42130714)。
文摘Peroxyacetyl nitrate(PAN)is an important photochemical pollutant in the troposphere,whereas long-term measurements are scarce in rural areas in North China Plain(NCP),resulting in unclear seasonal variations and sources of PAN in rural NCP.In this study,we conducted a 1-year observation of PAN during 2021-2022 at the rural NCP site.The average concentrations of PAN were 1.10,0.75,0.65,and 0.88 ppbv in spring,summer,autumn,and winter,respectively,with a 1-year average of 0.81±0.60 ppbv.Calculations indicate that the loss of PAN through thermal decomposition in summer accounts for 43.2% of the total formed PAN,which is an important reason for the low concentration of PAN in summer.We speculate that since the correlation between PAN and O_(3) in winter is significantly lower than that in other seasons,the observed regional transport of PAN cannot be ignored in winter.Through budget analysis,regional transport accounted for 12.8% and 55.9% of the observed PAN on the spring and winter pollution days,respectively,which showed that regional transport played key roles during the photochemical pollution of the rural NCP in winter.The potential source contribution function revealed that the transported PAN mainly comes from southern Hebei in spring.In winter,the transported PAN was mainly from Langfang,Hengshui,and southern Beijing.Our findings may aid in understanding PAN variations in different seasons in rural areas and highlight the impact of regional transport on the PAN budget.
基金supported by the National Key R&D Program of China(No.2016YFC0202700)the National Natural Science Foundation of China(Nos.41375126,21527814,91743202)the H2020 Marie Sklodowska-Curie Actions(No.H2020-MSCARISE-2015-690958)
文摘Peroxyacetyl nitrate （PAN）, as a major secondary pollutant, has gained increasing worldwide attentions, but relevant studies in China are still quite limited. During winter of 2015 to summer of 2016, the ambient levels of PAN were measured continuously by an automatic gas chromatograph equipped with an electron capture detector （GC-ECD） analyzer at an urban site in Jinan （China）, with related parameters including concentrations of 03, NO, NO2, PM2.5, HONO, the photolysis rate constant of NO2 and meteorological factors observed concurrently. The mean and maximum values of PAN concentration were （1.89 ± 1.42） and 9.61 ppbv respectively in winter, and （2.54 ± 1.44） and 13.47 ppbv respectively in summer. Unusually high levels of PAN were observed during severe haze episodes in winter, and the formation mechanisms of them were emphatically discussed, Study showed that high levels of PAN in winter were mainly caused by local accumulation and strong photochemical reactions during haze episodes, while mass transport played only a minor role. Accelerated photochemical reactions （compared to winter days without haze） during haze episodes were deduced by the higher concentrations but shorter lifetimes of pAN, which was further supported by the sufficient solar radiation in the photolysis band along with the high concentrations of precursors （NO2, VOCs） and HONO during haze episodes. In addition, significant PAN accumulation during calm weather of haze episodes was verified by meteorological data.
基金supported by the China Special Fund for Meteorological Research in the Public Interest(No.GY-HY201206015,GYHY201106050)the Basic Research Fund of CAMS(2011Z003)the National Natural Science Foundation of China(No.40775074)
文摘Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site （CMA） in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10^-9 mol/mol （0.23 × 10^9-3.51 × 10^9 mol/mol） and was well correlated with that of NOa but not O3, indicating that the variations of the winter concentrations of PAN and O3 in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3 ratio smaller than 0.O31, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3 ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3 decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl （PA） radicai was estimated to be in the range of 0.0014 × 10^-12～0.0042 × 10^-12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN＇s variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.
基金supported by the National Natural Science Foundation of China(No.41075094,21177140,20977097)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB05010100)the National Basic Research Program(973)of China(No.2010CB732304)
文摘Atmospheric peroxyacetyl nitrate （PAN）, peroxypropionyl nitrate （PPN）, and carbon tetrachloride （CCl4） were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring （October to March） with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer （March to August）, ranging from 1.37-3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values （below detection limit to 0.18 ppbV） from mid-autumn to early spring, and a monthly maximum in September （1.14 ppbV）. The monthly variation of CCl4 was tightly related to the variation of temperature, exhibiting a minimum in winter （69.3 pptV） and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3 showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon （ca. 15：00 to 16：00 local time） and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn （R = 0.91）, spring （R = 0.94）, and summer （R = 0.81）, with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes （AO3/APAN） ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3 consumption by NO titration and less thermal decompositin of PAN.
基金This work was partially supported by the National Key Research and Development Program of China(No.2017YFC0209801)the National Natural Science Foundation of China(Nos.91544221,41575124)the National Research Program for Key Issues in Air Pollution Control(Nos.DQGG0102,DQGG0103).
文摘As an important secondary photochemical pollutant,peroxyacetyl nitrate(PAN)has been studied over decades,yet its simulations usually underestimate the corresponding observations,especially in polluted areas.Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events,but the current model still cannot reproduce the observations,and researchers speculated that nitrous acid(HONO)played a key role in PAN formation.For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry(WRF-Chem)model in February of 2017.The results showed that the potential HONO sources significantly improved the PAN simulations,remarkably accelerated the RO x(sum of hydroxyl,hydroperoxyl,and organic peroxy radicals)cycles,and resulted in 80%–150%enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50%enhancements in the areas around 35–40°N within 3 km during a heavy haze period.The direct precursors of PAN were aldehyde and methylglyoxal,and the primary precursors of PAN were alkenes with C>3,xylenes,propene and toluene.The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.
基金supported by the National Natural Science Foundation of China(Nos.91843301,91743202,41805091)Ministry of Science and Technology of China(No.2016YFC0202700)+1 种基金National research program for key issues in air pollution control(Nos.DQGG0103,DQGG0102)Marie Sk?odowska-Curie Actions(No.690958-MARSU-RISE-2015)
文摘As a secondary pollutant of photochemical pollution,peroxyacetyl nitrate(PAN)has attracted a close attention.A four-month campaign was conducted at a rural site in North China Plain(NCP)including the measurement of PAN,O_(3),NO_(x),PM_(2.5),oxygenated volatile organic compounds(OVOCs),photolysis rate constants of NO_(2)and O_(3)and meteorological parameters to investigate the wintertime characterization of photochemistry from November 2018 to February 2019.The results showed that the maximum and mean values of PAN were 4.38 and 0.93±0.67 ppbv during the campaign,respectively.The PAN under different PM_(2.5)concentrations from below 75μg/m^(3)up to 250μg/m^(3),showed different diurnal variation and formation rate.In the PM_(2.5)concentration range of above 250μg/m^(3),PAN had the largest daily mean value of 0.64 ppbv and the fastest production rate of 0.33 ppbv/hr.From the perspective of PAN’s production mechanism,the light intensity and precursors concentrations under different PM_(2.5)pollution levels indicated that there were sufficient light intensity and high volatile organic compounds(VOCs)and NO_(x)precursors concentration even under severe pollution level to generate a large amount of PAN.Moreover,the bimodal staggering phenomenon of PAN and PM_(2.5)provided a basis that PAN might aggravate haze through secondary organic aerosols(SOA)formation.
基金This work was supported by the Environment and Conservation Fund of Hung Kong （Project No. 2009-07）, National Natural Science Foundation of China （Grant Nos. 41275123, 21407094 and 91544213）, China Postdoctoral Science Foundation （No. 2014M561932）, and the Jiangsu Collaborative Innovation Center for Climate Change. The authors thank Dr. Pamela Holt for proofreading the manuscript.
文摘Peroxyacetyl nitrate （PAN） is an important indicator of photochemical smog and has adverse effects on human health and vegetation growth. A rapid and h!ghly selective technique of thermal dissociation chemical ionization mass spectrometry （TD-CIMS） was recently developed to measure the abundance of PAN in real time; however, it may be subject to artifact in the presence of nitric oxide （NO）. In this study, we tested the interference of the PAN signal induced by NO, evaluated the performance of TD- CIMS in an urban environment, and investigated the concentration and formation of PAN in urban Hong Kong. NO caused a significant underestimation of the PAN signal in TD-CIMS, with the underestimation increasing sharply with NO concentration and decreasing slightly with PAN abundance. A formula was derived to link the loss of PAN signal with the concentrations of NO and PAN, which can be used for data correction in PAN measurements. The corrected PAN data from TD- CIMS were consistent with those from the commonly used gas chromatography with electron capture detection, which confirms the utility of TD-CIMS in an urban environment in which NO is abundant. In autumn of 2010, the hourly average PAN mixing ratio varied from 0.06 ppbv to 5.17 ppbv, indicating the occurrence of photochemical pollution in urban Hong Kong. The tbrmation efficiency of PAN during pollution episodes was as high as 3.9 to 5.9 ppbv per 100 ppbv ozone. The efficiency showed a near-linear increase with NO, concentration, suggesting a control policy of NO,. reduction for PAN pollution.
