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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
© Author(s) 2017. This work is distributed under
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Research article
07 Nov 2017
Review status
This discussion paper is a preprint. A revision of the manuscript is under review for the journal Atmospheric Chemistry and Physics (ACP).
Online gas and particle phase measurements of organosulfates, organosulfonates and nitrooxyorganosulfates in Beijing utilizing a FIGAERO ToF-CIMS
Michael Le Breton1, Yujue Wang2, Åsa M. Hallquist3, Ravi Kant Pathak1, Jing Zheng2, Yudong Yang2, Dongjie Shang2, Marianne Glasius4, Thomas J. Bannan5, Qianyun Liu6, Chak K. Chan7, Carl J. Percival8, Wenfei Zhu9, Shengrong Lou9, David Topping5, Yuchen Wang6, Jianzhen Yu6, Keding Lu2, Song Guo2, Min Hu2, and Mattias Hallquist1 1Department of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg, Sweden
2State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, China
3IVL Swedish Environmental Research Institute, Gothenburg, Sweden
4Department of Chemistry and iNANO, Aarhus University, 8000 Aarhus C, Denmark
5Centre for Atmospheric Science, School of Earth, Atmospheric and Environmental Science, University of Manchester, Manchester, UK
6Division of Environment and Sustainability, The Hong Kong University of Science and Technology, Clearwater Bay, Kowloon, Hong Kong
7School of Energy and Environment, City University of Hong Kong, Hong Kong
8Jet Propulsion laboratory, Pasadena, California, USA
9Shanghai Academy of Environmental Sciences, Shanghai 200233, China
Abstract. A Time of Flight Chemical Ionisation Mass spectrometer (CIMS) utilizing the Fast Inlet for Gas and AEROsol (FIGAERO) was deployed at a regional site 40 km north west of Beijing and successfully identified and measured 17 sulfur containing organics (SCOs = organo/nitrooxyorgano sulfates and sulfonates) with biogenic and anthropogenic precursors. The SCOs were quantified using laboratory synthesized standards of lactic acid sulfate and nitrophenol organosulfate (NP OS). The mean total (of the 17 identified by CIMS) SCO particle mass concentration was 207 ± 106 ng m−3 and had a maxima of 542 ng m−3, although contributed to only 2 ± 2.8 % of the organic aerosol (OA). SCO contribution to submicron mass (PM1) indicates a dominant secondary production of SCO due to the low contribution of SCOs to PM1 during periods of high mass loading. The CIMS identified a persistent gas phase presence of SCOs in the ambient air, which was further supported by post campaign vapour pressure measurements of NP OS. An increase in RH appeared to promote partitioning to the particle phase whereas higher temperatures favored higher gas phase concentrations. On average 12 % of the total SCOs were observed in the gas phase with C10H16NSO7 having just 5 % and IEPOX OS having 44 % on average in the gas phase.

Biogenic emissions contributed to only 19 % of total SCOs detected. C10H16NSO7, an alpha-pinene derived SCO, representing the highest fraction (10 %) followed by an isoprene-derived SCO. Anthropogenic SCOs with PAH and aromatic precursors dominated the SCO mass loading (51 % total SCOs) with C11H11SO7, derived from methyl napthalene oxidation, contributing to 40 ng m−3 and 0.3 % of the OA mass. Biomass burning was also identified as a potential anthropogenic and biogenic source of SCOs, based on nitrophenol (NP) and acetonitrile time series via secondary production of NP OS.

Gas and particle phase measurements of glycolic acid suggest that partitioning towards the particle phase promotes glycolic acid sulfate production, contrary to the current formation mechanism suggested in the literature. Highly oxidised multifunctional organic compounds (HOMS) and RO2 radical diurnal profiles, as measured by the iodide ToF-CIMS, are similar to that of total SCOs, supporting results that indicate HOMS are able to play a role in SCO production. Anthropogenic related SCOs correlated well with benzene, although their abundance depended highly on the photochemical age of the air mass, tracked using the ratio between pinonic acid and its oxidation product, acting as a qualitative photochemical clock. The HSO4.H2SO4 cluster measured by the CIMS was utilized as a qualitative marker for acidity and provides further evidence that the production rate of total SCOs is efficient in highly acidic aerosols with high SO42− and organic content. This dependency becomes more complex when observing individual SCOs due to variability of specific VOC precursors.

Citation: Le Breton, M., Wang, Y., Hallquist, Å. M., Pathak, R. K., Zheng, J., Yang, Y., Shang, D., Glasius, M., Bannan, T. J., Liu, Q., Chan, C. K., Percival, C. J., Zhu, W., Lou, S., Topping, D., Wang, Y., Yu, J., Lu, K., Guo, S., Hu, M., and Hallquist, M.: Online gas and particle phase measurements of organosulfates, organosulfonates and nitrooxyorganosulfates in Beijing utilizing a FIGAERO ToF-CIMS, Atmos. Chem. Phys. Discuss.,, in review, 2017.
Michael Le Breton et al.
Michael Le Breton et al.
Michael Le Breton et al.


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Short summary
This paper utilises a chemical ionisation mass spectrometer measuring gas and particle phase organosulfates (OS) simultaneously during a field campaign in Beijing, China, and highlights how high time frequency online measurements enable detailed analysis of dominant production mechanisms. We find that high aerosol acidity, organic precursor concentration and relative humidity promote the production of OS. The thermogram desorptions reveal the potential for semi volatile gas phase OS.
This paper utilises a chemical ionisation mass spectrometer measuring gas and particle phase...