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Post 17th-Century Changes of European PAH Emissions Recorded in High-Altitude Alpine Snow and Ice

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Department of Environmental Sciences, University Ca’ Foscari of Venice, Dorsoduro 2137, 30123 Venice, Italy, Environmental Protection Agency of Veneto (ARPAV), Belluno Department, via Tomea 5, 32100 Belluno, Italy, Institute for the Dynamics of Environmental Processes - CNR, University of Venice, Dorsoduro 2137, 30123 Venice, Italy, Paul Scherrer Institut (PSI), 5232 Villigen, Switzerland, Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland, Oeschger Centre for Climate Change Research, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland, and Laboratoire de Glaciologie et Geophysique de l’Environnement, BP 96, 38402 Saint Martin D’Herez Cedex, France
* Corresponding author phone: +39 041 2348942; fax: +39 041 2348549; e-mail: [email protected]
†Department of Environmental Sciences, University Ca’ Foscari of Venice.
‡Environmental Protection Agency of Veneto (ARPAV).
§Institute for the Dynamics of Environmental Processes - CNR, University of Venice.
∥Present address: Centre for Ice and Climate, Niels Bohr Institute, University of Copenhagen, 2100 Copenhagen, Denmark.
⊥Present address: School of Earth Sciences and Byrd Polar Research Center, Ohio State University, 43210 Columbus, OH.
#Paul Scherrer Institut (PSI).
∇Department of Chemistry and Biochemistry, University of Bern.
○Oeschger Centre for Climate Change Research, University of Bern.
◆Laboratoire de Glaciologie et Geophysique de l’Environnement.
Cite this: Environ. Sci. Technol. 2010, 44, 9, 3260–3266
Publication Date (Web):April 14, 2010
Copyright © 2010 American Chemical Society

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    The occurrence of organic pollutants in European Alpine snow/ice has been reconstructed over the past three centuries using a new online extraction method for polycyclic aromatic hydrocarbons (PAH) followed by liquid chromatographic determination. The meltwater flow from a continuous ice core melting system was split into two aliquots, with one aliquot directed to an inductively coupled plasma quadrupole mass spectrometer for continuous trace elements determinations and the second introduced into a solid phase C18 (SPE) cartridge for semicontinuous PAH extraction. The depth resolution for PAH extractions ranged from 40 to 70 cm, and corresponds to 0.7−5 years per sample. The concentrations of 11 PAH were determined in dated snow/ice samples to reconstruct the atmospheric concentration of these compounds in Europe for the last 300 years. The PAH pattern is dominated by phenanthrene (Phe), fluoranthene (Fla), and pyrene (Pyr), which represent 60−80% of the total PAH mass. Before 1875 the sum of PAH concentration (ΣPAH) was very low with total mean concentrations less than 2 ng/kg and 0.08 ng/kg for the heavier compounds (ΣPAH*, more than four aromatic rings). During the first phase of the industrial revolution (1770−1830) the PAH deposition showed a weak increase which became much greater from the start of the second phase of the industrial revolution at the end of 19th Century. In the 1920s, economic recession in Europe decreased PAH emissions until the 1930s when they increased again and reached a maximum concentration of 32 ng/kg from 1945 to 1955. From 1955 to 1975 the PAH concentrations decreased significantly, reflecting improvements in emission controls especially from major point sources, while from 1975 to 2003 they rose to levels equivalent to those in 1910. The Fla/(Fla+Pyr) ratio is often used for source assignment and here indicates an increase in the relative contribution of gasoline and diesel combustion with respect to coal and wood burning from 1860 to the 1980s. This trend was reversed during the last two decades.

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    Additional detail regarding the sampling site, Colle Gnifetti core chronology, melter system and continuous flow analysis design, reproducibility tests and concentrations of individual PAH. This material is available free of charge via the Internet at

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