Temporal changes of inorganic ion deposition in the seasonal snow cover for the Austrian Alps (1983–2014)

Abstract

A long-term record of inorganic ion concentrations in wet and dry deposition sampled from snow packs at two high altitude glaciers was used to assess impacts of air pollution on remote sites in central Europe. Sampling points were located at Wurtenkees and Goldbergkees near the Sonnblick Observatory (3106 m above sea level), a background site for measuring the status of the atmosphere in Austria's Eastern Alps. Sampling was carried out every spring at the end of the winter accumulation period in the years 1983–2014. Concentrations of major ions (NH4+, SO42−, NO3−, Ca2+, Mg2+, K+, Na+ and Cl−) were determined using ion chromatography (IC) as well as atomic absorption spectroscopy (AAS) in the earlier years. Concentration of H+ was calculated via the measured pH of the samples.Trends in deposition and concentration were analysed for all major ions within the period from 1983 to 2014 using Kendall's tau rank correlation coefficient. From 1983 to 2014, total ion concentration declined ∼25%, i.e. solutions became ∼25% more dilute, indicating reduced acidic atmospheric deposition, even at high altitude in winter snow. SO42− and NO3− concentrations decreased significantly by 70% and 30%, respectively, accompanied by a 54% decrease of H+ concentrations. Ionic concentrations in snowpack were dominated by H+ and SO42− in the earliest decade measured, whereas they were dominated by Ca2+ by the most recent decade. SO42− and H+ depositions, i.e. concentrations multiplied by volume, also showed a significant decrease of more than 50% at both sites. This reflects the successful emission reductions of the precursor gases SO2 and NOx. Seasonal values with significantly elevated spring concentrations of NH4+, SO42− and H+ compared to fall snow reflects the beginning of vertical mixing during spring. All other ions do not show any seasonality. Source identification of the ions was performed using a principal component analysis (PCA). One anthropogenic cluster (SO42−, NO3− and NH4+) coming from road traffic or fossil fuel combustion and animal husbandry, one crustal cluster (Ca2+, Mg2+) originating from local geological input or Saharan dust events as well as one cluster of unknown origin with episodic character (Na+, K+ and Cl−) was found.