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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
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Volume 18, issue 15 | Copyright
Atmos. Chem. Phys., 18, 10973-10983, 2018
https://doi.org/10.5194/acp-18-10973-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 06 Aug 2018

Research article | 06 Aug 2018

Synthesis and characterisation of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol

Sarah S. Steimer1, Aurélie Delvaux1, Steven J. Campbell1, Peter J. Gallimore1, Peter Grice1, Duncan J. Howe1, Dominik Pitton2, Magda Claeys3, Thorsten Hoffmann2, and Markus Kalberer1 Sarah S. Steimer et al.
  • 1Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK
  • 2Institute of Inorganic and Analytical Chemistry, University of Mainz, 55128 Mainz, Germany
  • 3Department of Pharmaceutical Sciences, University of Antwerp, 2610 Antwerp, Belgium

Abstract. Peroxy acids were recently found to be involved in new particle formation in the atmosphere and could also substantially contribute towards particle toxicity. However, a lack of suitable analytical methods for the detection and characterisation of peroxy acids in the particle phase is currently hindering the quantitative investigation of their contribution to these important atmospheric processes. Further development of appropriate techniques and relevant standards is therefore urgently needed. In this study, we synthesised three peroxypinic acids, developed a liquid chromatography separation method and characterised them with tandem mass spectrometry. The observed fragmentation patterns clearly distinguish the different peroxypinic acids from both the acid and each other, showing several neutral losses previously already observed for other peroxy acids. Both monoperoxypinic acids were found to be present in secondary organic aerosol generated from ozonolysis of α-pinene in laboratory experiments. The yield of monoperoxypinic acid formation was not influenced by humidity. Monoperoxypinic acid quickly degrades on the filter, with about 60% lost within the first 5h. This fast degradation shows that time delays in traditional off-line analysis will likely lead to severe underestimates of peroxy compound concentrations in ambient particles.

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Aerosol particles are a major public health concern, but particle properties contributing to their toxicity are not well known. Oxidising components such as peroxy acids might contribute significantly to particle toxicity. However, there is a lack of analytical methods for their characterisation. We synthesized three peroxy acids, developed an analysis method and showed that degradation affects peracid yield, likely leading to underestimation of their concentration in conventional analyses.
Aerosol particles are a major public health concern, but particle properties contributing to...
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