Articles | Volume 25, issue 22
https://doi.org/10.5194/acp-25-15819-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-25-15819-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
18 Nov 2025
Research article |
| 18 Nov 2025
Speciated measurement of bicyclic peroxy radicals via iodide-CIMS and its implication on OH-initiated aromatic oxidation
Yi Liu
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Nanjing University of Information Science & Technology, Nanjing, 210044, P.R. China
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Shuyu He
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Yuqing Qiu
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Mengdi Song
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Jiarong Ye
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Shengrong Lou
State Environmental Protection Key Laboratory of Formation and Prevention of Urban Air Pollution Complex, Shanghai Academy of Environmental Sciences, Shanghai, 200233, P.R. China
Sihua Lu
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Limin Zeng
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
Yuanhang Zhang
State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, P.R. China
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Atmos. Meas. Tech., 16, 501–512, https://doi.org/10.5194/amt-16-501-2023, https://doi.org/10.5194/amt-16-501-2023, 2023
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Revised manuscript not accepted
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We hypothesize that the cause of the worsening O3 trends in the Beijing-Tianjin-Hebei region, the Yangtze River Delta, and the Pearl River Delta from 2015 to 2020 is attributable to the increased occurrence of meteorological conditions of high solar radiation and positive temperature anomaly under the influence of West Pacific Subtropical High, tropical cyclones as well as mid-high latitude wave activities.
Xinping Yang, Keding Lu, Xuefei Ma, Yue Gao, Zhaofeng Tan, Haichao Wang, Xiaorui Chen, Xin Li, Xiaofeng Huang, Lingyan He, Mengxue Tang, Bo Zhu, Shiyi Chen, Huabin Dong, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 22, 12525–12542, https://doi.org/10.5194/acp-22-12525-2022, https://doi.org/10.5194/acp-22-12525-2022, 2022
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Gang Zhao, Tianyi Tan, Shuya Hu, Zhuofei Du, Dongjie Shang, Zhijun Wu, Song Guo, Jing Zheng, Wenfei Zhu, Mengren Li, Limin Zeng, and Min Hu
Atmos. Chem. Phys., 22, 10861–10873, https://doi.org/10.5194/acp-22-10861-2022, https://doi.org/10.5194/acp-22-10861-2022, 2022
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Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841, https://doi.org/10.5194/acp-22-9827-2022, https://doi.org/10.5194/acp-22-9827-2022, 2022
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Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Wenjie Wang, David D. Parrish, Siwen Wang, Fengxia Bao, Ruijing Ni, Xin Li, Suding Yang, Hongli Wang, Yafang Cheng, and Hang Su
Atmos. Chem. Phys., 22, 8935–8949, https://doi.org/10.5194/acp-22-8935-2022, https://doi.org/10.5194/acp-22-8935-2022, 2022
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Tropospheric ozone is an air pollutant that is detrimental to human health, vegetation and ecosystem productivity. A comprehensive characterisation of the spatial and temporal distribution of tropospheric ozone is critical to our understanding of these issues. Here we summarise this distribution over China from the available observational records to the extent possible. This study provides insights into efficient future ozone control strategies in China.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Cuiqi Zhang, Zhijun Wu, Jingchuan Chen, Jie Chen, Lizi Tang, Wenfei Zhu, Xiangyu Pei, Shiyi Chen, Ping Tian, Song Guo, Limin Zeng, Min Hu, and Zamin A. Kanji
Atmos. Chem. Phys., 22, 7539–7556, https://doi.org/10.5194/acp-22-7539-2022, https://doi.org/10.5194/acp-22-7539-2022, 2022
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The immersion ice nucleation effectiveness of aerosols from multiple sources in the urban environment remains elusive. In this study, we demonstrate that the immersion ice-nucleating particle (INP) concentration increased dramatically during a dust event in an urban atmosphere. Pollutant aerosols, including inorganic salts formed through secondary transformation (SIA) and black carbon (BC), might not act as effective INPs under mixed-phase cloud conditions.
Reza Bashiri Khuzestani, Keren Liao, Ying Liu, Ruqian Miao, Yan Zheng, Xi Cheng, Tianjiao Jia, Xin Li, Shiyi Chen, Guancong Huang, and Qi Chen
Atmos. Chem. Phys., 22, 7389–7404, https://doi.org/10.5194/acp-22-7389-2022, https://doi.org/10.5194/acp-22-7389-2022, 2022
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This work characterized the spatial variabilities of air pollutants in a megacity by advanced mobile measurements. The results show a large spatial heterogeneity in the distributions of PM2.5 composition and volatile organic compounds under non-haze conditions, and relatively uniform spatial distributions under haze conditions that may indicate a chemical homogeneity on an intracity scale. The findings improve our understanding of urban air pollution.
Xuefei Ma, Zhaofeng Tan, Keding Lu, Xinping Yang, Xiaorui Chen, Haichao Wang, Shiyi Chen, Xin Fang, Shule Li, Xin Li, Jingwei Liu, Ying Liu, Shengrong Lou, Wanyi Qiu, Hongli Wang, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 22, 7005–7028, https://doi.org/10.5194/acp-22-7005-2022, https://doi.org/10.5194/acp-22-7005-2022, 2022
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This paper presents the first OH and HO2 radical observations made in the Yangtze River Delta in China, and strong oxidation capacity is discovered based on direct measurements. The impacts of new OH regeneration mechanisms, monoterpene oxidation, and HO2 uptake processes are examined and discussed. The sources and the factors to sustain such strong oxidation are the key to understanding the ozone pollution formed in this area.
Yuanzheng Gong, Kai Song, Song Guo, Daqi Lv, Yuan Zhang, Zichao Wan, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, and Yunfa Chen
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-326, https://doi.org/10.5194/acp-2022-326, 2022
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Herein we applied thermal desorption comprehensive two-dimensional gas chromatography-mass spectrometer (TD-GCxGC-MS) for synchronous analysis of gaseous and particulate organics emitted from cooking fumes. With a systematic 4-step qualitative procedure and precise quantitative and semi-quantitative method, 170 and 352 compounds from C2 (acetic acids) – C30 (squalene) occupying 95 % and 90 % of the total ion current for gaseous and particulate samples were identified and quantified.
Hao Yang, Lei Chen, Hong Liao, Jia Zhu, Wenjie Wang, and Xin Li
Atmos. Chem. Phys., 22, 4101–4116, https://doi.org/10.5194/acp-22-4101-2022, https://doi.org/10.5194/acp-22-4101-2022, 2022
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Aerosols can influence O3 through aerosol–radiation interactions, including aerosol–photolysis interaction (API) and aerosol–radiation feedback (ARF). The weakened photolysis rates and changed meteorological conditions reduce surface-layer O3 concentrations by up to 9.3–11.4 ppb, with API and ARF contributing 74.6 %–90.0 % and 10.0 %–25.4 % of the O3 decrease in three episodes, respectively, which indicates that API is the dominant way for O3 reduction related to aerosol–radiation interactions.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091, https://doi.org/10.5194/acp-21-16067-2021, https://doi.org/10.5194/acp-21-16067-2021, 2021
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The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Huan Song, Keding Lu, Can Ye, Huabin Dong, Shule Li, Shiyi Chen, Zhijun Wu, Mei Zheng, Limin Zeng, Min Hu, and Yuanhang Zhang
Atmos. Chem. Phys., 21, 13713–13727, https://doi.org/10.5194/acp-21-13713-2021, https://doi.org/10.5194/acp-21-13713-2021, 2021
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Secondary sulfate aerosols are an important component of fine particles in severe air pollution events. We calculated the sulfate formation rates via a state-of-the-art multiphase model constrained to the observed values. We showed that transition metals in urban aerosols contribute significantly to sulfate formation during haze periods and thus play an important role in mitigation strategies and public health measures in megacities worldwide.
Junhua Wang, Baozhu Ge, Xueshun Chen, Jie Li, Keding Lu, Yayuan Dong, Lei Kong, Zifa Wang, and Yuanhang Zhang
Geosci. Model Dev. Discuss., https://doi.org/10.5194/gmd-2021-259, https://doi.org/10.5194/gmd-2021-259, 2021
Revised manuscript not accepted
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This paper developed a novel quantitative decoupling analysis (QDA) method to quantify the contributions of emission, meteorology, chemical reaction, and their nonlinear interactions on PM2.5 and applied it to a pollution episode in Beijing. This method can provides the researchers and policy makers with valuable information for understanding of key factors to heavy pollution, but also help the modelers to find out the sources of uncertainties among numerical models.
Kun Qu, Xuesong Wang, Yu Yan, Jin Shen, Teng Xiao, Huabin Dong, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 21, 11593–11612, https://doi.org/10.5194/acp-21-11593-2021, https://doi.org/10.5194/acp-21-11593-2021, 2021
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Typhoons above the Northwest Pacific frequently lead to severe ambient ozone pollution in the Pearl River Delta, China, in autumn and summer. However, typhoons do not enhance ozone transport, production and accumulation at the same time, and differences also exist between these influences in two seasons. Through systematic comparisons, we revealed the complex interactions between local meteorology and ozone processes, which is essential for understanding the causes of regional ozone pollution.
Tianyi Tan, Min Hu, Zhuofei Du, Gang Zhao, Dongjie Shang, Jing Zheng, Yanhong Qin, Mengren Li, Yusheng Wu, Limin Zeng, Song Guo, and Zhijun Wu
Atmos. Chem. Phys., 21, 8499–8510, https://doi.org/10.5194/acp-21-8499-2021, https://doi.org/10.5194/acp-21-8499-2021, 2021
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Every year in the pre-monsoon season, the black carbon (BC) aerosols originated from biomass burning in southern Asia are easily transported to the Tibetan Plateau (TP) by the convenience of westerly wind. This study reveals that the BC aerosols in the aged biomass burning plumes strongly enhance the total light absorption over the TP, and the aging process during the long-range transport will further strengthen the radiative heating of those BC aerosols.
Chunmeng Li, Haichao Wang, Xiaorui Chen, Tianyu Zhai, Shiyi Chen, Xin Li, Limin Zeng, and Keding Lu
Atmos. Meas. Tech., 14, 4033–4051, https://doi.org/10.5194/amt-14-4033-2021, https://doi.org/10.5194/amt-14-4033-2021, 2021
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We present a feasible instrument for the measurement of NO2, total peroxy nitrates (PNs, RO2NO2), and total alkyl nitrates (ANs, RONO2) in the atmosphere. The instrument samples sequentially from three channels at different temperature settings and then measures spectra using one cavity-enhanced absorption spectrometer. The concentrations are determined by spectral fitting and corrected using the lookup table method conveniently. The instrument will promote the study of PNs and ANs.
Kai Song, Song Guo, Haichao Wang, Ying Yu, Hui Wang, Rongzhi Tang, Shiyong Xia, Yuanzheng Gong, Zichao Wan, Daqi Lv, Rui Tan, Wenfei Zhu, Ruizhe Shen, Xin Li, Xuena Yu, Shiyi Chen, Liming Zeng, and Xiaofeng Huang
Atmos. Chem. Phys., 21, 7917–7932, https://doi.org/10.5194/acp-21-7917-2021, https://doi.org/10.5194/acp-21-7917-2021, 2021
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Nitrated phenols (NPs) are crucial components of brown carbon. To comprehend the constitutes and sources of NPs in winter of Beijing, their concentrations were measured by a CI-LToF-MS. The secondary formation process was simulated by a box model. NPs were mainly influenced by primary emissions and regional transport. Primary emitted phenol rather than benzene oxidation was crucial in the heavy pollution episode in Beijing. This provides more insight into pollution control strategies of NPs.
Mengdi Song, Xin Li, Suding Yang, Xuena Yu, Songxiu Zhou, Yiming Yang, Shiyi Chen, Huabin Dong, Keren Liao, Qi Chen, Keding Lu, Ningning Zhang, Junji Cao, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 21, 4939–4958, https://doi.org/10.5194/acp-21-4939-2021, https://doi.org/10.5194/acp-21-4939-2021, 2021
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Due to their lower diffusion capacities and higher conversion capacities, urban areas in Xi’an experienced severe ozone pollution in the summer. In this study, a campaign of comprehensive field observations and VOC grid sampling was conducted in Xi’an from 20 June to 20 July 2019. We found that Xi'an has a strong local emission source of VOCs, and vehicle exhaust was the primary VOC source. In addition, alkenes, aromatics, and oxygenated VOCs played a dominant role in secondary transformations.
Rongzhi Tang, Quanyang Lu, Song Guo, Hui Wang, Kai Song, Ying Yu, Rui Tan, Kefan Liu, Ruizhe Shen, Shiyi Chen, Limin Zeng, Spiro D. Jorga, Zhou Zhang, Wenbin Zhang, Shijin Shuai, and Allen L. Robinson
Atmos. Chem. Phys., 21, 2569–2583, https://doi.org/10.5194/acp-21-2569-2021, https://doi.org/10.5194/acp-21-2569-2021, 2021
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We performed chassis dynamometer experiments to investigate the emissions and secondary organic aerosol (SOA) formation potential of intermediate volatility organic compounds (IVOCs) from an on-road Chinese gasoline vehicle. High IVOC emission factors (EFs) and distinct volatility distribution were recognized. Our results indicate that vehicular IVOCs contribute significantly to SOA, implying the importance of reducing IVOCs when making air pollution control policies in urban areas of China.
Christian Mark Garcia Salvador, Rongzhi Tang, Michael Priestley, Linjie Li, Epameinondas Tsiligiannis, Michael Le Breton, Wenfei Zhu, Limin Zeng, Hui Wang, Ying Yu, Min Hu, Song Guo, and Mattias Hallquist
Atmos. Chem. Phys., 21, 1389–1406, https://doi.org/10.5194/acp-21-1389-2021, https://doi.org/10.5194/acp-21-1389-2021, 2021
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High-frequency online measurement of gas- and particle-phase nitro-aromatic compounds (NACs) at a rural site in China, heavily influenced by biomass burning events, enabled the analysis of the production pathway of NACs, including an explanation of strong persistence in the daytime. The contribution of secondary processes was significant, even during the dominant wintertime influence of primary emissions, suggesting the important role of regional secondary chemistry, i.e. photochemical smog.
Huan Song, Xiaorui Chen, Keding Lu, Qi Zou, Zhaofeng Tan, Hendrik Fuchs, Alfred Wiedensohler, Daniel R. Moon, Dwayne E. Heard, María-Teresa Baeza-Romero, Mei Zheng, Andreas Wahner, Astrid Kiendler-Scharr, and Yuanhang Zhang
Atmos. Chem. Phys., 20, 15835–15850, https://doi.org/10.5194/acp-20-15835-2020, https://doi.org/10.5194/acp-20-15835-2020, 2020
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Accurate calculation of the HO2 uptake coefficient is one of the key parameters to quantify the co-reduction of both aerosol and ozone pollution. We modelled various lab measurements of γHO2 based on a gas-liquid phase kinetic model and developed a state-of-the-art parameterized equation. Based on a dataset from a comprehensive field campaign in the North China Plain, we proposed that the determination of the heterogeneous uptake process for HO2 should be included in future field campaigns.
Wenjie Wang, David D. Parrish, Xin Li, Min Shao, Ying Liu, Ziwei Mo, Sihua Lu, Min Hu, Xin Fang, Yusheng Wu, Limin Zeng, and Yuanhang Zhang
Atmos. Chem. Phys., 20, 15617–15633, https://doi.org/10.5194/acp-20-15617-2020, https://doi.org/10.5194/acp-20-15617-2020, 2020
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During the past decade, China has devoted very substantial resources to improving the environment. These efforts have improved atmospheric particulate matter loading, but ambient ozone levels have continued to increase. In this paper we investigate the causes of the increasing ozone concentrations through analysis of a data set that is, to our knowledge, unique: a 12-year data set including ground-level O3, NOx, and VOC precursors collected at an urban site in Beijing.
Sarah E. Benish, Hao He, Xinrong Ren, Sandra J. Roberts, Ross J. Salawitch, Zhanqing Li, Fei Wang, Yuying Wang, Fang Zhang, Min Shao, Sihua Lu, and Russell R. Dickerson
Atmos. Chem. Phys., 20, 14523–14545, https://doi.org/10.5194/acp-20-14523-2020, https://doi.org/10.5194/acp-20-14523-2020, 2020
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Airborne observations of ozone and related pollutants show smog was pervasive in spring 2016 over Hebei Province, China. We find high amounts of ozone precursors throughout and even above the PBL, continuing to generate ozone at high rates to be potentially transported downwind. Concentrations even in the rural areas of this highly industrialized province promote widespread ozone production, and we show that to improve air quality over Hebei both NOx and VOCs should be targeted.
Cited articles
Aggarwal, S., Bansal, P., Wang, Y., Jorga, S., Macgregor, G., Rohner, U., Bannan, T., Salter, M., Zieger, P., Mohr, C., and Lopez-Hilfiker, F.: Identifying key parameters that affect sensitivity of flow tube chemical ionization mass spectrometers, Atmos. Meas. Tech., 18, 4227–4247, https://doi.org/10.5194/amt-18-4227-2025, 2025.
Arey, J., Obermeyer, G., Aschmann, S. M., Chattopadhyay, S., Cusick, R. D., and Atkinson, R.: Dicarbonyl Products of the OH Radical-Initiated Reaction of a Series of Aromatic Hydrocarbons, Environ. Sci. Technol., 43, 683–689, https://doi.org/10.1021/es8019098, 2009.
Atkinson, R., Aschmann, S. M., and Arey, J.: Formation of Ring-Retaining Products from the Oh Radical-Initated Reactions of Ortho-Xylene, Meta-Xylene, and Para-Xylene, Int. J. Chem. Kinet., 23, 77–97, https://doi.org/10.1002/kin.550230108, 1991.
Barber, V. P. and Kroll, J. H.: Chemistry of Functionalized Reactive Organic Intermediates in the Earth's Atmosphere: Impact, Challenges, and Progress, J. Phys. Chem. A, 125, 10264–10279, https://doi.org/10.1021/acs.jpca.1c08221, 2021.
Barker, J. R., Steiner, A. L., and Wallington, T. J.: Advances in atmospheric chemistry, World Scientific, New Jersey, Vols. 1–2, https://doi.org/10.1142/11031, 2017.
Berndt, T., Richters, S., Kaethner, R., Voigtländer, J., Stratmann, F., Sipilä, M., Kulmala, M., and Herrmann, H.: Gas-Phase Ozonolysis of Cycloalkenes: Formation of Highly Oxidized RO2 Radicals and Their Reactions with NO, NO2, SO2, and Other RO2 Radicals, J. Phys. Chem. A, 119, 10336–10348, https://doi.org/10.1021/acs.jpca.5b07295, 2015.
Berndt, T., Mender, B., Scholz, W., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion Product Formation from Ozonolysis and OH Radical Reaction of α-Pinene: Mechanistic Insight and the Influence of Isoprene and Ethylene, Environ. Sci. Technol., 52, 11069–11077, https://doi.org/10.1021/acs.est.8b02210, 2018a.
Berndt, T., Scholz, W., Mentler, B., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion Product Formation from Self- and Cross-Reactions of RO2 Radicals in the Atmosphere, Angew. Chem. Int. Edit., 57, 3820–3824, https://doi.org/10.1002/anie.201710989, 2018b.
Berndt, T., Hyttinen, N., Herrmann, H., and Hansel, A.: First oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions, Commun. Chem., 2, 21, https://doi.org/10.1038/s42004-019-0120-9, 2019.
Birdsall, A. W., Andreoni, J. F., and Elrod, M. J.: Investigation of the Role of Bicyclic Peroxy Radicals in the Oxidation Mechanism of Toluene, J. Phys. Chem. A, 114, 10655–10663, https://doi.org/10.1021/jp105467e, 2010.
Calvert, J. G. and Calvert, J. G.: The mechanisms of atmospheric oxidation of aromatic hydrocarbons, Oxford University Press, Oxford, New York, 556 pp., https://doi.org/10.1093/oso/9780195146288.001.0001, 2002.
Cui, L., Wu, D., Wang, S., Xu, Q., Hu, R., and Hao, J.: Measurement report: Ambient volatile organic compound (VOC) pollution in urban Beijing: characteristics, sources, and implications for pollution control, Atmos. Chem. Phys., 22, 11931–11944, https://doi.org/10.5194/acp-22-11931-2022, 2022.
Ehn, M., Kleist, E., Junninen, H., Petäjä, T., Lönn, G., Schobesberger, S., Dal Maso, M., Trimborn, A., Kulmala, M., Worsnop, D. R., Wahner, A., Wildt, J., and Mentel, Th. F.: Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air, Atmos. Chem. Phys., 12, 5113–5127, https://doi.org/10.5194/acp-12-5113-2012, 2012.
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Dal Maso, M., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476, https://doi.org/10.1038/nature13032, 2014.
Elrod, M. J.: Kinetics Study of the Aromatic Bicyclic Peroxy Radical plus NO Reaction: Overall Rate Constant and Nitrate Product Yield Measurements, J. Phys. Chem. A, 115, 8125–8130, https://doi.org/10.1021/jp204308f, 2011.
Galloway, M. M., Huisman, A. J., Yee, L. D., Chan, A. W. H., Loza, C. L., Seinfeld, J. H., and Keutsch, F. N.: Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NOx conditions, Atmos. Chem. Phys., 11, 10779–10790, https://doi.org/10.5194/acp-11-10779-2011, 2011.
Garmash, O., Rissanen, M. P., Pullinen, I., Schmitt, S., Kausiala, O., Tillmann, R., Zhao, D., Percival, C., Bannan, T. J., Priestley, M., Hallquist, Å. M., Kleist, E., Kiendler-Scharr, A., Hallquist, M., Berndt, T., McFiggans, G., Wildt, J., Mentel, T. F., and Ehn, M.: Multi-generation OH oxidation as a source for highly oxygenated organic molecules from aromatics, Atmos. Chem. Phys., 20, 515–537, https://doi.org/10.5194/acp-20-515-2020, 2020.
Gomez Alvarez, E., Viidanoja, J., Muñoz, A., Wirtz, K., and Hjorth, J.: Experimental confirmation of the dicarbonyl route in the photo-oxidation of toluene and benzene, Environ. Sci. Technol., 41, 8362–8369, https://doi.org/10.1021/es0713274, 2007.
Hansel, A., Scholz, W., Mentler, B., Fischer, L., and Berndt, T.: Detection of RO2 radicals and other products from cyclohexene ozonolysis with NH
He, S. Y., Liu, Y., Song, M. D., Li, X., Lu, S. H., Chen, T. Z., Mu, Y. J., Lou, S. R., Shi, X. D., Qiu, X. H., Zhu, T., and Zhang, Y. H.: Insights into the Peroxide-Bicyclic Intermediate Pathway of Aromatic Photooxidation: Experimental Yields and NOx-Dependency of Ring-Opening and Ring-Retaining Products, Environ. Sci. Technol., 57, 20657–20668, https://doi.org/10.1021/acs.est.3c05304, 2023.
He, S. Y., Liu, Y., Song, M. D., Li, X., Lou, S. R., Ye, C. S., Liu, Y. J., Liu, Y., Ye, J. R., Lu, S. H., Zhou, W. X., Qiu, X. H., Zhu, T., and Zeng, L. M.: Empirical Approach to Quantifying Sensitivity in Different Chemical Ionization Techniques for Organonitrates and Nitroaromatics Constrained by Ion-Molecule Reaction and Transmission Efficiency, Anal. Chem., 96, 16882–16890, https://doi.org/10.1021/acs.analchem.4c03751, 2024.
Hofzumahaus, A., Rohrer, F., Lu, K. D., Bohn, B., Brauers, T., Chang, C. C., Fuchs, H., Holland, F., Kita, K., Kondo, Y., Li, X., Lou, S. R., Shao, M., Zeng, L. M., Wahner, A., and Zhang, Y. H.: Amplified Trace Gas Removal in the Troposphere, Science, 324, 1702–1704, https://doi.org/10.1126/science.1164566, 2009.
Isaacman-VanWertz, G., Massoli, P., O'Brien, R., Lim, C., Franklin, J. P., Moss, J. A., Hunter, J. F., Nowak, J. B., Canagaratna, M. R., Misztal, P. K., Arata, C., Roscioli, J. R., Herndon, S. T., Onasch, T. B., Lambe, A. T., Jayne, J. T., Su, L. P., Knopf, D. A., Goldstein, A. H., Worsnop, D. R., and Kroll, J. H.: Chemical evolution of atmospheric organic carbon over multiple generations of oxidation, Nat. Chem., 10, 462–468, https://doi.org/10.1038/s41557-018-0002-2, 2018.
Iyer, S., Kumar, A., Savolainen, A., Barua, S., Daub, C., Pichelstorfer, L., Roldin, P., Garmash, O., Seal, P., Kurtén, T., and Rissanen, M.: Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics (vol 14, 4984, 2023), Nat. Commun., 14, 8303, https://doi.org/10.1038/s41467-023-44213-y, 2023.
Ji, Y., Huey, L. G., Tanner, D. J., Lee, Y. R., Veres, P. R., Neuman, J. A., Wang, Y., and Wang, X.: A vacuum ultraviolet ion source (VUV-IS) for iodide–chemical ionization mass spectrometry: a substitute for radioactive ion sources, Atmos. Meas. Tech., 13, 3683–3696, https://doi.org/10.5194/amt-13-3683-2020, 2020.
Ji, Y. M., Zhao, J., Terazono, H., Misawa, K., Levitt, N. P., Li, Y. X., Lin, Y., Peng, J. F., Wang, Y., Duan, L., Pan, B. W., Zhang, F., Feng, X. D., An, T. C., Marrero-Ortiz, W., Secrest, J., Zhang, A. L., Shibuya, K., Molina, M. J., and Zhang, R. Y.: Reassessing the atmospheric oxidation mechanism of toluene, P. Natl. Acad. Sci. USA, 114, 8169–8174, https://doi.org/10.1073/pnas.1705463114, 2017.
Klotz, B., Sorensen, S., Barnes, I., Becker, K. H., Etzkorn, T., Volkamer, R., Platt, U., Wirtz, K., and Martín-Reviejo, M.: Atmospheric oxidation of toluene in a large-volume outdoor photoreactor: In situ determination of ring-retaining product yields, J. Phys. Chem. A, 102, 10289–10299, https://doi.org/10.1021/jp982719n, 1998.
Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Kurtén, T., Worsnop, D. R., and Thornton, J. A.: An Iodide-Adduct High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic and Organic Compounds, Environ. Sci. Technol., 48, 6309–6317, https://doi.org/10.1021/es500362a, 2014.
Li, M., Zhang, Q., Zheng, B., Tong, D., Lei, Y., Liu, F., Hong, C., Kang, S., Yan, L., Zhang, Y., Bo, Y., Su, H., Cheng, Y., and He, K.: Persistent growth of anthropogenic non-methane volatile organic compound (NMVOC) emissions in China during 1990–2017: drivers, speciation and ozone formation potential, Atmos. Chem. Phys., 19, 8897–8913, https://doi.org/10.5194/acp-19-8897-2019, 2019.
Lopez-Hilfiker, F. D., Iyer, S., Mohr, C., Lee, B. H., D'Ambro, E. L., Kurtén, T., and Thornton, J. A.: Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts, Atmos. Meas. Tech., 9, 1505–1512, https://doi.org/10.5194/amt-9-1505-2016, 2016.
Molteni, U., Bianchi, F., Klein, F., El Haddad, I., Frege, C., Rossi, M. J., Dommen, J., and Baltensperger, U.: Formation of highly oxygenated organic molecules from aromatic compounds, Atmos. Chem. Phys., 18, 1909–1921, https://doi.org/10.5194/acp-18-1909-2018, 2018.
Nannoolal, Y., Rarey, J., and Ramjugernath, D.: Estimation of pure component properties. Part 4: Estimation of the saturated liquid viscosity of non-electrolyte organic compounds via group contributions and group interactions, Fluid Phase Equilibr., 281, 97–119, https://doi.org/10.1016/j.fluid.2009.02.016, 2009.
Nozière, B. and Hanson, D. R.: Speciated Monitoring of Gas-Phase Organic Peroxy Radicals by Chemical Ionization Mass Spectrometry: Cross-Reactions between CH3O2, CH3(CO)O2, (CH3)3CO2, and c-C6H11O2, J. Phys. Chem. A, 121, 8453–8464, https://doi.org/10.1021/acs.jpca.7b06456, 2017.
Orlando, J. J. and Tyndall, G. S.: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chem. Soc. Rev., 41, 8213–8213, 2012.
Pai, S. J., Heald, C. L., Pierce, J. R., Farina, S. C., Marais, E. A., Jimenez, J. L., Campuzano-Jost, P., Nault, B. A., Middlebrook, A. M., Coe, H., Shilling, J. E., Bahreini, R., Dingle, J. H., and Vu, K.: An evaluation of global organic aerosol schemes using airborne observations, Atmos. Chem. Phys., 20, 2637–2665, https://doi.org/10.5194/acp-20-2637-2020, 2020.
Pichelstorfer, L., Roldin, P., Rissanen, M., Hyttinen, N., Garmash, O., Xavier, C., Zhou, P., Clusius, P., Foreback, B., Almeida, T. G., Deng, C. J., Baykara, M., Kurten, T., and Boy, M.: Towards automated inclusion of autoxidation chemistry in models: from precursors to atmospheric implications, Environ. Sci.-Atmos., 4, 879–896, https://doi.org/10.1039/d4ea00054d, 2024.
Riipinen, I., Yli-Juuti, T., Pierce, J. R., Petäjä, T., Worsnop, D. R., Kulmala, M., and Donahue, N. M.: The contribution of organics to atmospheric nanoparticle growth, Nat. Geosci., 5, 453–458, https://doi.org/10.1038/ngeo1499, 2012.
Riva, M., Pospisilova, V., Frege, C., Perrier, S., Bansal, P., Jorga, S., Sturm, P., Thornton, J. A., Rohner, U., and Lopez-Hilfiker, F.: Evaluation of a reduced-pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species, Atmos. Meas. Tech., 17, 5887–5901, https://doi.org/10.5194/amt-17-5887-2024, 2024.
Smith, D. F., Kleindienst, T. E., and McIver, C. D.: Primary product distributions from the reaction of OH with p-, m-xylene, 1,2,4- and 1,3,5-trimethylbenzene, J. Atmos. Chem., 34, 339–364, https://doi.org/10.1023/A:1006277328628, 1999.
Song, M., He, S., Li, X., Liu, Y., Lou, S., Lu, S., Zeng, L., and Zhang, Y.: Optimizing the iodide-adduct chemical ionization mass spectrometry (CIMS) quantitative method for toluene oxidation intermediates: experimental insights into functional-group differences, Atmos. Meas. Tech., 17, 5113–5127, https://doi.org/10.5194/amt-17-5113-2024, 2024.
Song, M. D., Liu, Y., Li, X., and Lu, S. H.: Advances on Atmospheric Oxidation Mechanism of Typical Aromatic Hydrocarbons, Acta Chim. Sinica, 79, 1214–1231, https://doi.org/10.6023/A21050224, 2021.
Tuazon, E. C., Macleod, H., Atkinson, R., and Carter, W. P. L.: Alpha-Dicarbonyl Yields from the Nox-Air Photooxidations of a Series of Aromatic-Hydrocarbons in Air, Environ. Sci. Technol., 20, 383–387, https://doi.org/10.1021/es00146a010, 1986.
Wang, L. H., Wang, Y. W., Yang, G., Li, Y. Y., Liu, Y. L., Lu, Y. Q., Yao, L., and Wang, L.: Measurements of Atmospheric HO2 Radicals Using Br-CIMS with Elimination of Potential Interferences from Ambient Peroxynitric Acid, Anal. Chem., 96, 13792–13800, https://doi.org/10.1021/acs.analchem.4c01184, 2024a.
Wang, S. N., Riva, M., Yan, C., Ehn, M., and Wang, L. M.: Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene: A Combined Theoretical and Experimental Study, Environ. Sci. Technol., 52, 12255–12264, https://doi.org/10.1021/acs.est.8b02783, 2018.
Wang, Y., Li, C., Zhang, Y., Li, Y., Yang, G., Yang, X., Wu, Y., Yao, L., Zhang, H., and Wang, L.: Secondary reactions of aromatics-derived oxygenated organic molecules lead to plentiful highly oxygenated organic molecules within an intraday OH exposure, Atmos. Chem. Phys., 24, 7961–7981, https://doi.org/10.5194/acp-24-7961-2024, 2024b.
Watne, Å. K., Psichoudaki, M., Ljungström, E., Le Breton, M., Hallquist, M., Jerksjö, M., Fallgren, H., Jutterström, S., and Hallquist, Å. M.: Fresh and Oxidized Emissions from In-Use Transit Buses Running on Diesel, Biodiesel, and CNG, Environ. Sci. Technol., 52, 7720–7728, https://doi.org/10.1021/acs.est.8b01394, 2018.
Whalley, L. K., Edwards, P. M., Furneaux, K. L., Goddard, A., Ingham, T., Evans, M. J., Stone, D., Hopkins, J. R., Jones, C. E., Karunaharan, A., Lee, J. D., Lewis, A. C., Monks, P. S., Moller, S. J., and Heard, D. E.: Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest, Atmos. Chem. Phys., 11, 7223–7233, https://doi.org/10.5194/acp-11-7223-2011, 2011.
Wu, R. R. and Xie, S. D.: Spatial Distribution of Ozone Formation in China Derived from Emissions of Speciated Volatile Organic Compounds, Environ. Sci. Technol., 51, 2574–2583, https://doi.org/10.1021/acs.est.6b03634, 2017.
Wu, R. R., Pan, S. S., Li, Y., and Wang, L. M.: Atmospheric Oxidation Mechanism of Toluene, J. Phys. Chem. A, 118, 4533–4547, https://doi.org/10.1021/jp500077f, 2014.
Wu, X. Q., Huang, C., Niu, S. Y., and Zhang, F.: New theoretical insights into the reaction kinetics of toluene and hydroxyl radicals, Phys. Chem. Chem. Phys., 22, 22279–22288, https://doi.org/10.1039/d0cp02984j, 2020.
Xu, L., Moller, K. H., Crounse, J. D., Kjaergaard, H. G., and Wennberg, P. O.: New Insights into the Radical Chemistry and Product Distribution in the OH-Initiated Oxidation of Benzene, Environ. Sci. Technol., 54, 13467–13477, https://doi.org/10.1021/acs.est.0c04780, 2020.
Yang, X. P., Li, Y., Ma, X. F., Tan, Z. F., Lu, K. D., and Zhang, Y. H.: Unclassical Radical Generation Mechanisms in the Troposphere: A Review, Environ. Sci. Technol., 58, 15888–15909, https://doi.org/10.1021/acs.est.4c00742, 2024a.
Yang, X. P., Wang, H. C., Lu, K. D., Ma, X. F., Tan, Z. F., Long, B., Chen, X. R., Li, C. M., Zhai, T. Y., Li, Y., Qu, K., Xia, Y., Zhang, Y. Q., Li, X., Chen, S. Y., Dong, H. B., Zeng, L. M., and Zhang, Y. H.: Reactive aldehyde chemistry explains the missing source of hydroxyl radicals, Nat. Commun., 15, https://doi.org/10.1038/s41467-024-45885-w, 2024b.
Yang, Y. D., Shao, M., Wang, X. M., Nölscher, A. C., Kessel, S., Guenther, A., and Williams, J.: Towards a quantitative understanding of total OH reactivity: A review, Atmos. Environ., 134, 147–161, https://doi.org/10.1016/j.atmosenv.2016.03.010, 2016.
Yu, Y., Guo, S., Wang, H., Shen, R. Z., Zhu, W. F., Tan, R., Song, K., Zhang, Z. R., Li, S. D., Chen, Y. F., and Hu, M.: Importance of Semivolatile/Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Chinese Domestic Cooking Emissions, Environ. Sci. Tech. Let., 9, 507–512, https://doi.org/10.1021/acs.estlett.2c00207, 2022.
Zaytsev, A., Koss, A. R., Breitenlechner, M., Krechmer, J. E., Nihill, K. J., Lim, C. Y., Rowe, J. C., Cox, J. L., Moss, J., Roscioli, J. R., Canagaratna, M. R., Worsnop, D. R., Kroll, J. H., and Keutsch, F. N.: Mechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions, Atmos. Chem. Phys., 19, 15117–15129, https://doi.org/10.5194/acp-19-15117-2019, 2019.
Zaytsev, A., Breitenlechner, M., Novelli, A., Fuchs, H., Knopf, D. A., Kroll, J. H., and Keutsch, F. N.: Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase, Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, 2021.
Zhang, H. X., Chen, C. R., Yan, W. J., Wu, N. N., Bo, Y., Zhang, Q., and He, K. B.: Characteristics and sources of non-methane VOCs and their roles in SOA formation during autumn in a central Chinese city, Sci. Total Environ., 782, 146802, https://doi.org/10.1016/j.scitotenv.2021.146802, 2021.
Zhang, X., Schwantes, R. H., McVay, R. C., Lignell, H., Coggon, M. M., Flagan, R. C., and Seinfeld, J. H.: Vapor wall deposition in Teflon chambers, Atmos. Chem. Phys., 15, 4197–4214, https://doi.org/10.5194/acp-15-4197-2015, 2015.
Zhao, Y., Thornton, J. A., and Pye, H. O. T.: Quantitative constraints on autoxidation and dimer formation from direct probing of monoterpene-derived peroxy radical chemistry, P. Natl. Acad. Sci. USA, 115, 12142–12147, https://doi.org/10.1073/pnas.1812147115, 2018.
Zhu, J., Wang, S., Wang, H., Jing, S., Lou, S., Saiz-Lopez, A., and Zhou, B.: Observationally constrained modeling of atmospheric oxidation capacity and photochemical reactivity in Shanghai, China, Atmos. Chem. Phys., 20, 1217–1232, https://doi.org/10.5194/acp-20-1217-2020, 2020.
Short summary
We developed a method for speciated and quantitative measurement of peroxy radicals formed during the breakdown of aromatic hydrocarbons. These measurements revealed missing reaction pathways in current chemical mechanisms. Our findings help improve predictions of air quality and deepen understanding of chemical processes in the atmosphere.
We developed a method for speciated and quantitative measurement of peroxy radicals formed...
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