The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trio...The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.展开更多
Atmospheric sulfur deposition onto typical farmland in East China was investigated using both field measurements and numerical modeling. The field measurements were conducted at the Experiment Station of Red Soil Ecol...Atmospheric sulfur deposition onto typical farmland in East China was investigated using both field measurements and numerical modeling. The field measurements were conducted at the Experiment Station of Red Soil Ecology, Chinese Academy of Sciences, 10 km from Yingtan, Jiangxi Province, East China, between November 1998 and October 1999, and at the Changshu Ecological Experiment Station, Chinese Academy of Sciences, in a rapidly developing region of Jiangsu Province, East China, between April 2001 and Marc…展开更多
A two-year study in a typical red soil region of Southern China was conductedto determine 1) the dry deposition velocity (V_d) for SO_2 and particulate SO_4^(2-) above abroadleaf forest, and 2) atmospheric sulfur flux...A two-year study in a typical red soil region of Southern China was conductedto determine 1) the dry deposition velocity (V_d) for SO_2 and particulate SO_4^(2-) above abroadleaf forest, and 2) atmospheric sulfur fluxes so as to estimate the contribution of variousfractions in the total. Using a resistance model based on continuous hourly meteorological data,atmospheric dry sulfur deposition in a forest was estimated according to V_d and concentrations ofboth atmospheric SO_2 and particulate SO_4^(2-). Meanwhile, wet S deposition was estimated based onrainfall and sulfate concentrations in the rainwater. Results showed that about 99% of the drysulfur deposition flux in the forest resulted from SO_2 dry deposition. In addition, the observeddry S deposition was greater in 2002 than in 2000 because of a higher average concentration of SO_2in 2002 than in 2000 and not because of the average dry deposition velocity which was lower for SO_2in 2002. Also, dry SO_2 deposition was the dominant fraction of deposited atmospheric sulfur inforests, contributing over 69% of the total annual sulfur deposition. Thus, dry SO_2 depositionshould be considered when estimating sulfur balance in forest ecological systems.展开更多
Ultrafine particles are associated with adverse health effects. Total Particle Number Concentration（TNC） of fine particles were measured during 2002 at the St. Louis — Midwest supersite. The time series showed over...Ultrafine particles are associated with adverse health effects. Total Particle Number Concentration（TNC） of fine particles were measured during 2002 at the St. Louis — Midwest supersite. The time series showed overall low level with frequent large peaks. The time series was analyzed alongside criteria pollutant measurements and meteorological observations. Multiple regression analysis was used to identify further contributing factors and to determine the association of different pollutants with TNC levels. This showed the strong contribution of sulfur dioxide（SO2） and nitrogen oxides（NO x） to high TNC levels. The analysis also suggested that increased dispersion resulting from faster winds and higher mixing heights led to higher TNC levels. Overall, the results show that there were intense particle nucleation events in a SO2 rich plume reaching the site which contributed around 29% of TNC. A further 40% was associated with primary emissions from mobile sources. By separating the remaining TNC by time of day and clear sky conditions,we suggest that most likely 8% of TNC are due to regional nucleation events and 23% are associated with the general urban background.展开更多
We present in-situ measurements of atmospheric sulfur hexafluoride（SF6） conducted by an automated gas chromatograph–electron capture detector system and a gas chromatography/mass spectrometry system at a regional b...We present in-situ measurements of atmospheric sulfur hexafluoride（SF6） conducted by an automated gas chromatograph–electron capture detector system and a gas chromatography/mass spectrometry system at a regional background site, Shangdianzi,in China, from June 2009 to May 2011, using the System for Observation of Greenhouse gases in Europe and Asia and Advanced Global Atmospheric Gases Experiment（AGAGE）techniques. The mean background and polluted mixing ratios for SF6 during the study period were 7.22 × 10-12（mol/mol, hereinafter） and 8.66 × 10-12, respectively. The averaged SF6 background mixing ratios at Shangdianzi were consistent with those obtained at other AGAGE stations located at similar latitudes（Trinidad Head and Mace Head）, but larger than AGAGE stations in the Southern Hemisphere（Cape Grim and Cape Matatula）. SF6 background mixing ratios increased rapidly during our study period, with a positive growth rate at 0.30 × 10-12year-1. The peak to peak amplitude of the seasonal cycle for SF6 background conditions was 0.07 × 10-12, while the seasonal fluctuation of polluted conditions was 2.16 × 10-12. During the study period, peak values of SF6 mixing ratios occurred in autumn when local surface horizontal winds originated from W/WSW/SW/SWS/S sectors, while lower levels of SF6 mixing ratios appeared as winds originated from N/NNE/NE/ENE/E sectors.展开更多
基金supported by the Budget Surplus of Central Financial Science and Technology Plan (No.2021-JY-14)the Project funded by China Postdoctoral Science Foundation (No.2020M680636)+3 种基金the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of China,Chinese Research Academy of Environmental Sciences (Nos.2022YSKY-21 and 2022YSKY-27)the National Natural Science Foundation of China (No.41375133)the Science Foundation of Chinese Research Academy of Environmental Sciences (No.JY-41375133)Tian He Qingsuo Project-special fund project.
文摘The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.
文摘Atmospheric sulfur deposition onto typical farmland in East China was investigated using both field measurements and numerical modeling. The field measurements were conducted at the Experiment Station of Red Soil Ecology, Chinese Academy of Sciences, 10 km from Yingtan, Jiangxi Province, East China, between November 1998 and October 1999, and at the Changshu Ecological Experiment Station, Chinese Academy of Sciences, in a rapidly developing region of Jiangsu Province, East China, between April 2001 and Marc…
基金Project supported by the National Key Basic Research Support Foundation (NKBRSF) of China (No. 1999011805)the Knowledge Innovation Program of Chinese Academy of Sciences (No.ISSASIP0205) the State Key Laboratory of Soil and Sustainable Agriculture, C
文摘A two-year study in a typical red soil region of Southern China was conductedto determine 1) the dry deposition velocity (V_d) for SO_2 and particulate SO_4^(2-) above abroadleaf forest, and 2) atmospheric sulfur fluxes so as to estimate the contribution of variousfractions in the total. Using a resistance model based on continuous hourly meteorological data,atmospheric dry sulfur deposition in a forest was estimated according to V_d and concentrations ofboth atmospheric SO_2 and particulate SO_4^(2-). Meanwhile, wet S deposition was estimated based onrainfall and sulfate concentrations in the rainwater. Results showed that about 99% of the drysulfur deposition flux in the forest resulted from SO_2 dry deposition. In addition, the observeddry S deposition was greater in 2002 than in 2000 because of a higher average concentration of SO_2in 2002 than in 2000 and not because of the average dry deposition velocity which was lower for SO_2in 2002. Also, dry SO_2 deposition was the dominant fraction of deposited atmospheric sulfur inforests, contributing over 69% of the total annual sulfur deposition. Thus, dry SO_2 depositionshould be considered when estimating sulfur balance in forest ecological systems.
基金funded the present analysis through grant number RD-83455701the original measurements through cooperative agreement R-82805901-0
文摘Ultrafine particles are associated with adverse health effects. Total Particle Number Concentration（TNC） of fine particles were measured during 2002 at the St. Louis — Midwest supersite. The time series showed overall low level with frequent large peaks. The time series was analyzed alongside criteria pollutant measurements and meteorological observations. Multiple regression analysis was used to identify further contributing factors and to determine the association of different pollutants with TNC levels. This showed the strong contribution of sulfur dioxide（SO2） and nitrogen oxides（NO x） to high TNC levels. The analysis also suggested that increased dispersion resulting from faster winds and higher mixing heights led to higher TNC levels. Overall, the results show that there were intense particle nucleation events in a SO2 rich plume reaching the site which contributed around 29% of TNC. A further 40% was associated with primary emissions from mobile sources. By separating the remaining TNC by time of day and clear sky conditions,we suggest that most likely 8% of TNC are due to regional nucleation events and 23% are associated with the general urban background.
基金supported by the Natural Science Foundation of China(Nos.41030107,41205094)the National Basic Research Program of China"973"(No.2010CB950601)the CAMS Fundamental Research Funds(No.2014Z004)
文摘We present in-situ measurements of atmospheric sulfur hexafluoride（SF6） conducted by an automated gas chromatograph–electron capture detector system and a gas chromatography/mass spectrometry system at a regional background site, Shangdianzi,in China, from June 2009 to May 2011, using the System for Observation of Greenhouse gases in Europe and Asia and Advanced Global Atmospheric Gases Experiment（AGAGE）techniques. The mean background and polluted mixing ratios for SF6 during the study period were 7.22 × 10-12（mol/mol, hereinafter） and 8.66 × 10-12, respectively. The averaged SF6 background mixing ratios at Shangdianzi were consistent with those obtained at other AGAGE stations located at similar latitudes（Trinidad Head and Mace Head）, but larger than AGAGE stations in the Southern Hemisphere（Cape Grim and Cape Matatula）. SF6 background mixing ratios increased rapidly during our study period, with a positive growth rate at 0.30 × 10-12year-1. The peak to peak amplitude of the seasonal cycle for SF6 background conditions was 0.07 × 10-12, while the seasonal fluctuation of polluted conditions was 2.16 × 10-12. During the study period, peak values of SF6 mixing ratios occurred in autumn when local surface horizontal winds originated from W/WSW/SW/SWS/S sectors, while lower levels of SF6 mixing ratios appeared as winds originated from N/NNE/NE/ENE/E sectors.
