Measurement report: Source apportionment of volatile organic compounds at the remote high-altitude Maïdo observatory

Abstract

We present a source apportionment study of a near-continuous 2-year dataset of volatile organic compounds (VOCs), recorded between October 2017 and November 2019 with a quadrupole-based high-sensitivity proton-transfer-reaction mass-spectrometry (hs-PTR-MS) instrument deployed at the Maïdo observatory (21.1ĝ gS, 55.4ĝ gE, 2160gm altitude). The observatory is located on La Réunion island in the southwest Indian Ocean. We discuss seasonal and diel profiles of six key VOC species unequivocally linked to specific sources - acetonitrile (CH3CN), isoprene (C5H8), isoprene oxidation products (Iox), benzene (C6H6), C8-aromatic compounds (C8H10), and dimethyl sulfide (DMS). The data are analyzed using the positive matrix factorization (PMF) method and back-trajectory calculations based on the Lagrangian mesoscale transport model FLEXPART-AROME to identify the impact of different sources on air masses sampled at the observatory. As opposed to the biomass burning tracer CH3CN, which does not exhibit a typical diel pattern consistently throughout the dataset, we identify pronounced diel profiles with a daytime maximum for the biogenic (C5H8 and Iox) and anthropogenic (C6H6, C8H10) tracers. The marine tracer DMS generally displays a daytime maximum except for the austral winter when the difference between daytime and nighttime mixing ratios vanishes. Four factors were identified by the PMF: background/biomass burning, anthropogenic, primary biogenic, and secondary biogenic. Despite human activity being concentrated in a few coastal areas, the PMF results indicate that the anthropogenic source factor is the dominant contributor to the VOC load (38g%), followed by the background/biomass burning source factor originating in the free troposphere (33g%), and by the primary (15g%) and secondary biogenic (14g%) source factors. FLEXPART-AROME simulations showed that the observatory was most sensitive to anthropogenic emissions west of Maïdo while the strongest biogenic contributions coincided with air masses passing over the northeastern part of La Réunion. At night, the observatory is often located in the free troposphere, while during the day, the measurements are influenced by mesoscale sources. Interquartile ranges of nighttime 30gmin average mixing ratios of methanol (CH3OH), CH3CN, acetaldehyde (CH3CHO), formic acid (HCOOH), acetone (CH3COCH3), acetic acid (CH3COOH), and methyl ethyl ketone (MEK), representative for the atmospheric composition of the free troposphere, were found to be 525-887, 79-110, 61-101, 172-335, 259-379, 64-164, and 11-21gpptv, respectively.