Determination of isoprene-derived secondary organic aerosol tracers (2-methyltetrols) by HPAEC-PAD: Results from size-resolved aerosols in a tropical rainforest

Abstract

Secondary organic aerosol (SOA) formed from oxidation of isoprene, the most abundant nonmethane hydrocarbon in the atmosphere, has been estimated to contribute significantly to the global aerosol burden. Measurement of isoprene-derived SOA molecular markers has become an effective method for the investigation of biogenic aerosol contributions in the atmosphere. The primary goals of this work are to present a new method based on high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) to quantify diastereoisomeric 2-methyltetrols (2-methylerythritol and 2-methylthreitol), marker compounds of isoprene-derived SOA, and thus to obtain better understanding regarding their abundance and size distribution specifically in a rainforest area. The 2-methyltetrol data, along with water-soluble inorganic ion concentrations, were obtained from size-segregated samples collected at a tropical rainforest site in South China during the period from May to June, 2010. The concentrations of 2-methyltetrols from selected samples measured by HPAEC-PAD showed good agreement with those measured by GC/MS. Overall, the HPAEC-PAD method provides a simple and fast, yet selective and sensitive, alternative to GC/MS for 2-methyltetrol determination, allowing for more efficient analysis of large sample numbers. The size distributions of 2-methylerythritol and 2-methylthreitol both exhibited a unimodal pattern, peaking in the particle size range of 0.44–1.0 μm, where their average concentrations were 11.7 and 4.2 ng m−3, respectively. A strong correlation between 2-methylerythritol and 2-methylthreitol was observed among the entire set of size-segregated samples, indicating their photochemical origin and similar formation mechanism regardless of particle sizes. Compared to the results obtained from previous chamber studies, the similar isomeric fraction of 2-methyltetrols obtained in this study and other field studies confirms their formation through photooxidation of isoprene.