Historic records of organic aerosols from a high Alpine glacier: implications of biomass burning, anthropogenic emissions, and dust transport

Abstract

Historic records of α-dicarbonyls (glyoxal, methylglyoxal), carboxylic acids (C6–C12 dicarboxylic acids, pinic acid, p-hydroxybenzoic acid, phthalic acid, 4-methylphthalic acid), and major ions (oxalate, formate, calcium) were determined with annual resolution in an ice core from Grenzgletscher in the southern Swiss Alps, covering the time period from 1942 to 1993. Measurements were conducted using ultra-high performance liquid chromatography (UHPLC) coupled to electrospray ionization high resolution mass spectrometry (ESI-HRMS). For the first time, long-term records of the carboxylic acids and dicarbonyls as well as their source apportionment are reported for Western Europe. Source assignment of the organic species present in the ice core was performed using principal component analysis. Our results suggest biomass burning, anthropogenic emissions, and transport of mineral dust to be the main parameters influencing the concentration of organic compounds. Ice core records of several highly correlated compounds (e.g. p-hydroxybenzoic acid, pinic acid, C7 and C8 dicarboxylic acids) can be related to the forest fire history in southern Switzerland. P-hydroxybenzoic acid was found to be the best organic fire tracer in the study area, revealing the highest correlation with the burned area from fires. Historical records of methylglyoxal, phthalic acid, and dicarboxylic acids C6, C10, and C12 are comparable with that of anthropogenic emissions of volatile organic compounds (VOCs). The small organic acids oxalic acid and formic acid are both highly correlated with calcium, suggesting their records to be affected by changing mineral dust transport to the drilling site.