Organosulfates and organic acids in Arctic aerosols: speciation, annual variation and concentration levels

Abstract

Abstract. Sources, composition and occurrence of secondary organic aerosols (SOA) in the Arctic were investigated at Zeppelin Mountain, Svalbard, and Station Nord, northeast Greenland, during the full annual cycle of 2008 and 2010 respectively. We focused on the speciation of three types of SOA tracers: organic acids, organosulfates and nitrooxy organosulfates from both anthropogenic and biogenic precursors, here presenting organosulfate concentrations and compositions during a full annual cycle and chemical speciation of organosulfates in Arctic aerosols for the first time. Aerosol samples were analysed using High Performance Liquid Chromatography coupled to a quadrupole Time-of-Flight mass spectrometer (HPLC-q-TOF-MS). A total of 11 organic acids (terpenylic acid, benzoic acid, phthalic acid, pinic acid, suberic acid, azelaic acid, adipic acid, pimelic acid, pinonic acid, diaterpenylic acid acetate (DTAA) and 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA)), 12 organosulfates and one nitrooxy organosulfate were identified at the two sites. Six out of the 12 organosulfates are reported for the first time. Concentrations of organosulfates follow a distinct annual pattern at Station Nord, where high concentration were observed in late winter and early spring, with a mean total concentration of 47 (±14) ng m−3, accounting for 7 (±2)% of total organic matter, contrary to a considerably lower organosulfate mean concentration of 2 (±3) ng m−3 (accounting for 1 (±1)% of total organic matter) observed during the rest of the year. The organic acids followed the same temporal trend as the organosulfates at Station Nord; however the variations in organic acid concentrations were less pronounced, with a total mean organic acid concentration of 11.5 (±4) ng m−3 (accounting for 1.7 (±0.6)% of total organic matter) in late winter and early spring, and 2.2 (±1) ng m−3 (accounting for 0.9 (±0.4)% of total organic matter) during the rest of the year. At Zeppelin Mountain, organosulfate and organic acid concentrations remained relatively constant during most of the year at amean concentration of 15 (±4) ng m−3 (accounting for 4 (±1)% of total organic matter) and 3.9 (±1) ng m−3 (accounting for 1.1 (±0.1)% of total organic matter) respectively. However during four weeks of spring remarkably higher concentrations of total organosulfates (23–36 ng m−3) and total organic acids (7–10 ng m−3) were observed. The periods of observed elevated organosulfate and organic acid concentration at Station Nord and at Zeppelin Mountain coincided with the Arctic Haze period. Furthermore, backwards air mass trajectories indicated northern Eurasia as the main source region of the Arctic haze aerosols at both sites. Periods with air mass transport from Russia to Zeppelin Mountain were associated with a doubled number of detected organosulfate species compared with periods of air mass transport from the Arctic Ocean, Scandinavia and Greenland. Our analysis showed the presence of organosulfates and organic acids of both biogenic and anthropogenic origin throughout the year at both Arctic sites. As the formation of organosulfates binds inorganic sulfate, their presence may possibly affect the formation and lifetime of clouds in the Arctic atmosphere.