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Measurement of gas-phase total peroxides at the summit of Mount Tai in China
Authors:Yu Ren  Aijun Ding  Tao Wang  Xinhua Shen  Jia Guo  Jiamin Zhang  Yan Wang  Pengju Xu  Xinfeng Wang  Jian Gao  Jeffrey L Collett
Institution:1. School of Environmental Science and Engineering, Shandong University, Jinan, 250100, China;2. Environmental Monitoring Central Station of Shandong Province, Jinan, 250101, China;3. Department of Civil and Structural Engineering, The Hong Kong Polytechnic University, Hong Kong, China;4. Environment Research Institute, Shandong University, Jinan, 250100, China;1. Environment Research Institute, Shandong University, Ji''nan, Shandong, China;2. Department of Civil and Environmental Engineering, Hong Kong Polytechnic University, Hong Kong, China;3. Chinese Research Academy of Environmental Sciences, Beijing, China;4. Joint International Research Laboratory of Atmospheric and Earth System Sciences, School of Atmospheric Sciences, Nanjing University, Nanjing, Jiangsu, China;5. Department of Chemistry, University of California at Irvine, Irvine, CA, USA
Abstract:Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NOx, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NOx) was often associated with very low peroxides due to the chemical suppression of HO2 by high NOx and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NOy.
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