Application of time-of-flight aerosol mass spectrometry for the real-time measurement of particle-phase organic peroxides: an online redox derivatization–aerosol mass spectrometer (ORD-AMS)

Abstract

Aerosol mass spectrometers (AMS) are frequently applied in atmospheric aerosol research in connection with climate, environmental or health-related projects. This is also true for the measurement of the organic fraction of particulate matter, still the least understood group of components contributing to atmospheric aerosols. While quantification of the organic and/or inorganic aerosol fractions is feasible, more detailed information about individual organic compounds or compound classes can usually not be provided by AMS measurements. In this study, we present a new method to detect organic peroxides in the particle phase in real-time using an AMS. Peroxides (ROOR') are of high interest to the atmospheric aerosol community due to their potentially high mass contribution to SOA, their important role in new particle formation and their function as “reactive oxygen species” in aerosol–health-related topics. To do so, supersaturated gaseous triphenylphosphine (TPP) was continuously mixed with the aerosol flow of interest in a condensation/reaction volume in front of the AMS inlet. The formed triphenylphosphine oxide (TPPO) from the peroxide–TPP reaction was then detected by an aerosol mass spectrometer (AMS), enabling the semiquantitative determination of peroxide with a time resolution of 2 min. The method was tested with freshly formed and aged biogenic VOC and ozone SOA as well as in a short proof-of-principle study with ambient aerosol.