Solid-phase extraction of organic compounds in atmospheric aerosol particles collected with the particle-into-liquid sampler and analysis by liquid chromatography–mass spectrometry

Abstract

Atmospheric aerosol particles, collected with the particle-into-liquid sampler at SMEARII station in Finland in mid-August 2007, were analysed for biogenic acids. The sample pretreatment method, comprising solid-phase extraction with anion exchange and hydrophilic–lipophilic balance materials, was optimized. Extraction efficiencies of solid-phase extraction from 10 and 20 ml samples were about 100%, with average relative standard deviation of 8.9%, in concentration range from 12.5 to 50 ng/ml of the acid. Extraction of aldehydes was less successful, with efficiencies from 69 to 163% and average 10% deviation. Pretreated samples were analysed by reversed phase high performance liquid chromatography with ion trap mass spectrometric detection. Limits of detection achieved for organic acids with the analytical procedure developed ranged from 9 to 27 μg/l of extracted sample, while limits of quantitation were from 31 to 90 μg/l. Oxidation with ozone was used for the preparation of the acid of β-caryophyllene (β-caryophyllinic acid), which was also studied in aerosol samples. MS 2 experiments were used to confirm the identification of trans-pinic, trans-pinonic and β-caryophyllinic acids. Azelaic, hexadecanoic, cis-pinonic, and cis- and trans-pinic acids were quantitated in the samples with use of authentic standards, while the concentrations of trans-pinonic and β-caryophyllinic acids were determined with cis-pinonic acid as surrogate. Also, the contribution of β-caryophyllene oxidation products to aerosol organic carbon was evaluated. Aldehydes could not be analysed in real samples due to the insufficient extraction. The particle-into-liquid sampler proved to be suitable for the collection of aerosol particles for the elucidation of daily and diurnal variation of selected species. The optimized sample pretreatment, together with the analysis method, offer a promising approach for the study of aerosol chemical composition, where artifact formation is minimal and time resolution is good.