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

Historic records of α-dicarbonyls (glyoxal, methylglyoxal), carboxylic acids (C6–C12 dicarboxylic acids, pinic acid, p-hydroxybenzoic acid, phthalic acid, 4-methylphthalic acid), and 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. Chemical analysis of the organic compounds was conducted using ultra-high-performance liquid chromatography (UHPLC) coupled to electrospray ionization high-resolution mass spectrometry (ESI-HRMS) for dicarbonyls and long-chain carboxylic acids and ion chromatography for short-chain carboxylates. Long-term records of the carboxylic acids and dicarbonyls, as well as their source apportionment, are reported for western Europe. This is the first study comprising long-term trends of dicarbonyls and long-chain dicarboxylic acids (C6–C12) in Alpine precipitation. 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, pimelic, and suberic 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 adipic acid, sebacic acid, and dodecanedioic acid 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.

10Be records of sediment cores from high northern latitudes

The 10Be records of four sediment cores forming a transect from the Norwegian Sea at 70°N (core 23059) via the Fram Strait (core 23235) to the Arctic Ocean at 86°N (cores 1533 and 1524) were measured at a high depth resolution. Although the material in all the cores was controlled by different sedimentological regimes, the 10Be records of these cores were superimposed by glacial/interglacial changes in the sedimentary environment. Core sections with high 10Be concentrations ( >1 * 10**9 at/g) are related to interglacial stages and core sections with low10Be concentrations ( <0.5 * 10**9 at/g) are related to glacial stages. Climatic transitions (e.g., Termination II, 5/6) are marked by drastic changes in the 10Be concentrations of up to one order of magnitude. The average 10Be concentrations for each climatic stage show an inverse relationship to their corresponding sedimentation rates, indicating that the 10Be records are the result of dilution with more or less terrigenous ice-rafted material. However, there are strong changes in the 10Be fluxes (e.g., Termination II) into the sediments which may also account for the observed oscillations. Most likely, both processes affected the 10Be records equally, amplifying the contrast between lower (glacials) and higher (interglacials) 10Be concentrations. The sharp contrast of high and low 10Be concentrations at climatic stage boundaries are an independent proxy for climatic and sedimentary change in the Nordic Seas and can be applied for stratigraphic dating (10Be stratigraphy) of sediment cores from the northern North Atlantic and the Arctic Ocean.