Photochemical properties and source of pollutants during continuous pollution episodes in Beijing, October, 2011

Beijing suffered from serious air pollution in October, 2011 with the occurrence of three continuous episodes. Here we analyze the pollution status of particulate matter, the relationship between the gaseous pollutants, physical and chemical properties of single particles, and the profile of water-soluble ions in PM2.5 during the three episodes. Regional and photochemically aged air masses, which were characterized as having high values of O3 and SO2, were hypothesized to have played a dominant role in the first episode. After mixing local air masses with freshly-emitted primary pollutants, the concentration of NOx continued to increase and the size of SO42-, NO3- and NH4＋ in the particle population continued to become smaller. The amount of elemental carbon-rich and organic carbonrich particles in the scaled single particles （0.2-2 μm） and water-soluble K＋ in PM2.s also increased in the episodes. All the available information suggests that the biomass or fuel burning sources in or around Beijing may have had a huge impact on the last two episodes.

Characteristics and sources of peroxyacetyl nitrate(PAN)in the rural North China Plain:Results from1-year continuous observations

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.

Effects of pH on photochemical decomposition of perfluorooctanoic acid in different atmospheres by 185 nm vacuum ultraviolet

Perfluorooctanoic acid （PFOA）, a persistent organic pollutant, receives increasing concerns due to its worldwide occurrence and resistance to most conventional treatment processes. The photochemical decomposition by 185 nm vacuum ultraviolet （VUV） is one of the efficient methods for PFOA decomposition. The effects of pH on PFOA decomposition in nitrogen atmosphere or oxygen atmosphere were investigated. At its original pH （4.5） of PFOA aqueous solution, PFOA decomposed efficiently both in nitrogen and in oxygen atmosphere. However, when the pH increased to 12.0, PFOA decomposition was greatly inhibited in oxygen atmosphere, while it was greatly accelerated in nitrogen atmosphere with a very short half-life time （9 rain）. Furthermore, fluorine atoms originally contained in PFOA molecules were almost completely transformed into fluoride ions. Two decomposi- tion pathways have been proposed to explain the PFOA decomposition under different conditions. In acidic and neutral solutions, PFOA predominantly decomposes via the direct photolysis in both atmospheres; while in the alkaline solution and in the absence of oxygen, the decomposition of PFOA is mainly induced by hydrated electrons.

Peroxyacetyl nitrate measurements by thermal dissociation-chemical ionization mass spectrometry in an urban environment： performance and characterizations

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.