Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring

Organosulfates of monoterpenes and isoprene, as well as their oxidation products have been identified in biogenic secondary organic aerosols (BSOA) from both laboratory and field studies. Organosulfates provide an interesting coupling between air pollution and formation of low-volatility BSOA.HPLC quadrupole time-of-flight mass spectrometry was used to study polar acidic monoterpene and isoprene oxidation products including pinic acid, pinonic and terpenylic acid along with organosulfates and nitrooxy organosulfates in aerosols from ambient air. The method was first validated by analysis of spiked quartz filters, which showed acceptable recoveries >74% for pinic acid, pinonic acid, camphor sulphonic acid and adipic acid. Acetonitrile was identified as a better solvent than methanol for extraction and analysis of pinonic acid and adipic acid, due to improved analytical sensitivity and prevention of methyl ester formation during sample extraction.PM1 (i.e, aerosols with an aerodynamic diameter ≤1 μm) were collected during spring 2008 in a forest in Denmark with mixed deciduous and coniferous trees. Average concentrations of the most abundant compounds were: pinic acid: 1.5 ng m−3, pinonic acid: 3.0 ng m−3, terpenylic acid: 0.8 ng m−3 and 3-methyl-1,2,3-butanetricarboxylic acid: 3.0 ng m−3.Organosulfates and nitrooxy organosulfates were identified in a majority of the daily samples and the highest levels were observed during a warm period in late spring. As a first approach, due to the lack of authentic standards, organosulfates and nitrooxy organosulfates were tentatively quantified based on the analytical response of camphor sulphonic acid. Generally the concentrations of organosulfates and nitrooxy organosulfates were lower than first generation oxidation products. The maximum concentration of a total of 10 organosulfates and nitrooxy organosulfates were found to be about three times lower than pinonic acid with a maximum concentration of 8 ng m−3.A correlation between total organosulfates (including nitrooxy organosulfates) and organic acids was observed with R2 = 0.89, indicating that the presence of organosulfates is closely connected to photochemical oxidation and aging of volatile organic compounds.

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► We study monoterpene and isoprene oxidation products incl. organosulfates in aerosols.
► Highest levels of organosulfates and nitrooxy organosulfates in a warm period.
► Total organosulfates correlate with total organic acids.