A Historical Record of Heavy Metal Pollution in Alpine Snow and Ice

  • Carlo BarbanteEmail author
  • Jacopo Gabrieli
  • Paolo Gabrielli
  • Paul Vallelonga
  • Giulio Cozzi
  • Clara Turetta
  • Sungmin Hong
  • Kevin Rosman
  • Claude F. Boutron
  • Paolo Cescon


Heavy metals and trace elements are ubiquitous throughout the environment, some are essential for life (e.g., Fe), others are micronutrients (e.g., Se) and others are considered as toxic elements (e.g., Hg). Levels of these elements in the environment are determined by the local geochemistry and anthropogenic emissions, with implications for human and environmental health. Records from Alpine ice cores have demonstrated to be among the best tools in paleoenvironmental studies to reconstruct past emissions of heavy metals and persistent organic pollutants. From the comparison of trace element records in the snow and ice with the emission inventories compiled in recent years it is also possible to reconstruct the past trends in the emission of these compounds. We present here some trace elements records from the European Alps and in particular from the Mont Blanc and Monte Rosa regions. The study of levels of these elements in alpine regions allows us to begin to understand their biogeochemistry and their effects on a global and regional scale. However, without advances in clean working techniques and the outstanding improvement in instrument sensitivity that have occurred over the last two decades, none of these studies would have been possible.


Heavy Metal Lead Isotope Thermal Ionization Mass Spectrometry Heavy Metal Input Atmospheric Residence Time 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was supported in Italy by the Agenzia Regionale per la Prevenzione e Protezione Ambientale del Veneto (ARPAV) and by the Consorzio per l’Attuazione del Programma Nazionale delle Ricerche in Antartide, under projects on Environmental Contamination and Glaciology. In France it was supported by the Institut Universitaire de France, the Agence de l’Environnement et de la Maîtrise de l’Energie (ADEME), the Institut National des Sciences de l’Univers and the Université Joseph Fourier of Grenoble. In Korea it was supported by a research grant (PP09010) from the Korean Research Council of Fundamental Science & Technology. PV acknowledges the support of a European Union Marie Curie IIF Fellowship (Contract MIF1-CT-2006-039529).


  1. Anquetin, S., C. Guilbaud and J.P. Chollet, 1999a: Thermal valley inversion impact on the dispersion of a passive pollutant in a complex mountainous area. Atmos. Environ. 33, 3953–3959.CrossRefGoogle Scholar
  2. Anquetin, S., C. Guilbaud, K. Vinth Li and J.P. Chollet, 1999b: The formation and destruction of inversion layers within a deep valley. J. Appl. Meteorol. 37, 1547–1560.CrossRefGoogle Scholar
  3. Baltensperger, U., H.W. Gäggeler, D.T. Jost, M. Lugauer, M. Schwikowski, I. Weingartner and P. Seibert, 1997: Aerosol climatology at the high-alpine site Jungfraujoch. Switzerland J. Geophys. Res. 102, 19707–19715.CrossRefGoogle Scholar
  4. Barbante, C., K. van de Velde, G. Cozzi, G. Capodaglio, P. Cescon, F. Planchon, S. Hong, C. Ferrari and C.F. Boutron, 2001: Post-World War II uranium changes in dated Mont Blanc ice and snow. Environ. Sci. Technol. 35, 4026–4030.CrossRefGoogle Scholar
  5. Barbante, C., C.F. Boutron, A.L. Moreau, C. Ferrari, K. Van de Velde, G. Cozzi, C. Turetta and P. Cescon, 2002: Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s. J. Environ. Monit. 4, 960–966.CrossRefGoogle Scholar
  6. Barbante, C., M. Schwikowski, T. Döring, H.W. Gäggeler, U. Schotterer, L. Tobler, K. van de Velde, C. Ferrari, G. Cozzi, A. Turetta, K. Rosman, M. Bolshov, G. Capodaglio, P. Cescon and C. Boutron, 2004: Historical record of European emissions of heavy metals to the atmosphere since the 1650s from Alpine snow/ice cores drilled near Monte Rosa. Environ. Sci. Tech. 38, 4085–4090.CrossRefGoogle Scholar
  7. Böhm, R., I. Auer, M. Brunetti, M. Maugeri, T. Nanni and W. Schöner, 2001: Regional temperature variability in the European Alps: 1760–1998 from homogenized instrumental time series. Int. J. Climatol. 21, 1779–1801.CrossRefGoogle Scholar
  8. Bollhöfer, A. and K.J.R. Rosman, 2000: Isotopic source signatures for atmospheric lead: the Southern Hemisphere. Geochim. Cosmochim. Acta 64, 3251–3262.CrossRefGoogle Scholar
  9. Bollhöfer, A. and K.J.R. Rosman, 2001a: Isotopic source signatures for atmospheric lead: The Northern Hemisphere. Geochimica et Cosmochimica Acta 65, 1727–1740.CrossRefGoogle Scholar
  10. Bollhöfer, A. and K.J.R. Rosman, 2001b: Lead isotopic ratios in European atmospheric aerosols. Phys. Chem. Earth Part B: Hydrol. Oceans Atmos. 26, 835–838.CrossRefGoogle Scholar
  11. Boutron, C.F., U. Görlach, J.P. Candelone, M.A. Bolshov and R.J. Delmas, 1991: Decrease in anthropogenic lead, cadmium and zinc in Greenland snows since the late 1960s. Nature 353, 153–156.CrossRefGoogle Scholar
  12. Candelone, J.P., S. Hong, C. Pellone and C.F. Boutron, 1995: Post-Industrial Revolution changes in large-scale atmospheric pollution of the northern hemisphere by heavy metals as documented in central Greenland snow and ice. J. Geophys. Res. 100, 16605–16616.CrossRefGoogle Scholar
  13. Capodaglio, G., C. Barbante and P. Cescon, 2001: Anthropogenic lead in Antarctic sea water. In: S. Caroli, P. Cescon, D. Walton (Eds.), Environmental Contamination in Antarctica: A Challenge to Analytical Chemistry, Elsevier, Amsterdam, 107–154.CrossRefGoogle Scholar
  14. Chen, J.H., R.L. Edwards and G.J. Wasserburg, 1986: 238U, 234U and 232Th in seawater. Earth Planet. Sci. Lett. 80, 241–256.CrossRefGoogle Scholar
  15. Dansgaard, W., S.J. Johnsen, J. Moller, and C.C.J. Langway, 1969: One thousand centuries of climatic record from camp century on the Greenland ice sheet. Science 166, 377–381.CrossRefGoogle Scholar
  16. Donat, J.R. and K.W. Bruland, 1995: Trace elements in the oceans. In: B. Salbu, E. Steines (Eds.), Trace Elements in Natural Waters, CRC Press, Boca Raton, 247–280.Google Scholar
  17. Döscher, A., H.W. Gäggeler, U. Schotterer and M. Schwikowski, 1995: A 130 years deposition record of sulfate, nitrate and chloride from a high-alpine glacier. Water Air Soil Pollut. 85, 603–609.CrossRefGoogle Scholar
  18. Döscher, A., H.W. Gaggeler, U. Shotterer and M. Schwikowski, 1996: A historical record of ammonium concentrations from a glacier in the Alps. Geophys. Res. Lett. 23, 20, 2741–2744.CrossRefGoogle Scholar
  19. EPICA community members, 2004: Eight glacial cycles from an Antarctic ice core. Nature 429, 623–628.CrossRefGoogle Scholar
  20. Federal Standard 209, USA 1988: Airborne Particulate Cleanliness Classes in Cleanrooms and Clean Zones.Google Scholar
  21. Flegal, A.R., H. Maring and S. Niemeyer, 1993: Anthropogenic lead in Antarctic sea water. Nature 365, 242–244.CrossRefGoogle Scholar
  22. Gabrieli, J., 2008: Trace elements and Polycyclic Aromatic Hydrocarbons (PAHs) in snow and ice sampled at Colle Gnifetti, Monte Rosa (4450 m), during the last 10,000 years: environmental and climatic implications, Venice and Grenoble, p. 176.Google Scholar
  23. Gabrielli, P., C. Barbante, J.M.C. Plane, A. Varga, S. Hong, G. Cozzi, V. Gaspari, F.A.M. Planchon, W. Cairns, C. Ferrari, P. Crutzen, P. Cescon and C.F. Boutron, 2004: Meteoric smoke fallout over the Holocene epoch revealed by iridium and platinum in Greenland ice. Nature 432, 1011–1014.CrossRefGoogle Scholar
  24. Hong, S., J.P. Candelone, C.C. Patterson and C.F. Boutron, 1994: Greenland ice evidence of hemispheric lead pollution two millennia ago by Greek and Roman civilizations. Science 265, 1841–1843.CrossRefGoogle Scholar
  25. Hong, S., J.P. Candelone, M. Soutif and C.F. Boutron, 1996: A reconstruction of changes in copper production and copper emissions to the atmosphere during the past 7000 years. Sci. Total Environ. 188, 183–193.CrossRefGoogle Scholar
  26. Hunter, K.A., 1997: Chemistry of the sea-surface microlayer. In: P.S. Liss and R.A. Duce (Eds.), The Sea Surface and Global Change, Cambridge University Press, Cambridge, 287–319.CrossRefGoogle Scholar
  27. Jenk, T.M., S. Szidat, M. Schwikowski, H.W. Gaeggeler, S. Brutsch, L. Wacker, H.-A. Synal and M. Saurer, 2006: Radiocarbon analysis in an Alpine ice core: Record of anthropogenic and biogenic contributions to carbonaceous aerosols in the past (1650–1940). Atmos. Chem. Phys. 6, 5381–5390.CrossRefGoogle Scholar
  28. Jenk, T.M., S. Szidat, D. Bolius, M. Sigl, H.W. Gäggeler, L. Wacker, M. Ruff, C. Barbante, C.F. Boutron and M. Schwikowski, 2009: A novel radiocarbon dating technique applied to an ice core from the Alps indicating late Pleistocene ages. J. Geophys. Res. 114, D14305, doi:10.1029/2009JD011860CrossRefGoogle Scholar
  29. Lugauer, M., U. Baltensperger, M. Furger, H.W. Gaggeler, D.T. Jost, M. Schwikowski and H. Wanner, 1998: Aerosol transport to the high Alpine sites Jungfraujoch (3454 m asl) and Colle Gnifetti (4452 m asl). Tellus 50B, 76–92.Google Scholar
  30. Martinez Cortizas, A., X. Pontevedra Pombal, E. Garcia Rodeja, J.C. Nóvoa Muñoz and W. Shotyk, 1999: Mercury in a Spanish peat bog: Archive of climate change and atmospheric metal deposition. Science 284, 939–942.CrossRefGoogle Scholar
  31. McLennan, S.M., 2001: Relationships between the trace element composition of sedimentary rocks and upper continental crust. Geochem. Geophys. Geosyst. 2, doi:10.1029/2000GC000109.Google Scholar
  32. Nriagu, J.O., 1989: A global assessment of natural sources of atmospheric trace metals. Nature 338, 47–49.CrossRefGoogle Scholar
  33. Nriagu, J.O., 1990a: The rise and fall of leaded gasoline. Sci. Total Environ. 92, 12–38.CrossRefGoogle Scholar
  34. Nriagu, J.O., 1990b: Global metal pollution. Environment 32, 7–11.CrossRefGoogle Scholar
  35. Nriagu, J.O., 1996: A history of global metal pollution. Science 272, 223–224.CrossRefGoogle Scholar
  36. Nriagu, J.O. and J.M. Pacyna, 1988: Quantitative assessment of worldwide contamination of air, water and soils by trace metals. Nature 333, 134–139.CrossRefGoogle Scholar
  37. Olendrzynski, K., S. Anderberg, J. Bartnicki, J.M. Pacyna and W. Stigliani, 1996: Atmospheric emissions and depositions of cadmium, lead, and zinc in Europe during the period 1955–1987. Environ. Rev. 4, 300–320.CrossRefGoogle Scholar
  38. Pacyna, J.M., 1984: Estimation of the atmospheric emissions of trace elements from anthropogenic sources in Europe. Atmos. Environ. 18, 41–50.CrossRefGoogle Scholar
  39. Pacyna, J.M., 1996: Atmospheric Emissions of Heavy Metals for Europe (Improvements, Updates, Historical Data and Projections), International Institute for Applied Systems Analysis, Laxenburg, Hagan, Norway, 1996.Google Scholar
  40. Pacyna, J.M. and E.G. Pacyna, 2001: An assessment of global and regional emissions of trace metals to the atmosphere from anthropogenic sources worldwide. Environ. Rev. 9, 269–298.CrossRefGoogle Scholar
  41. Pacyna, J.M., A. Semb and J. Hanssen, 1984: Emission and long-range transport of trace elements in Europe. Tellus 36B, 163–178.CrossRefGoogle Scholar
  42. Planchon, F.A.M., C.F. Boutron, C. Barbante, E.W. Wolff, G. Cozzi, V. Gaspari, C.P. Ferrari and P. Cescon, 2001: Ultrasensitive determination of heavy metals at the sub-picogram per gram level in ultraclean Antarctic snow samples by inductively coupled plasma sector field mass spectrometry. Anal. Chim. Acta 450, 193–205.CrossRefGoogle Scholar
  43. Preunkert, S., M. Legrand and D. Wagenbach, 2001: Sulfate trends in a Col du Dôme (French Alps) ice core: A record of anthropogenic sulfate levels in the European midtroposphere over the twentieth century. J. Geophys. Res. 106, 31991–32004.CrossRefGoogle Scholar
  44. Rampino, M.R. and S. Self, 1992: Volcanic winter and accelerated glaciation following the Toba super-eruption. Nature 359, 50–52.CrossRefGoogle Scholar
  45. Raynaud, D., T. Blunier, Y. Ono and R.J. Delmas, 2003: Paleoclimate, Global Change and the Future. Springer Verlag, Berlin, pp. 13–33.Google Scholar
  46. Renberg, I., M.W. Persson and O. Emteryd, 1994: Pre-industrial atmospheric lead contamination detected in Swedish lake sediments. Nature 368, 323–326.CrossRefGoogle Scholar
  47. Rosman, K.J.R. and D. Walton (Eds.), 2001: Environmental Contamination in Antarctica: A Challenge to Analytical Chemistry, Elsevier, Amsterdam, 87–106.Google Scholar
  48. Rosman, K.J.R., C. Ly, K. Van de Velde and C.F. Boutron, 2000: A two century record of lead isotopes in high altitude Alpine snow and ice. Earth Planet. Sci. Lett. 176, 413–424.CrossRefGoogle Scholar
  49. Rudnick, R.L. and D.M. Fountain, 1995: Nature and composition of the continental crust: A lower crustal perspective. Rev. Geophys. 33, 267–309.CrossRefGoogle Scholar
  50. Schwikowski, M., A. Döscher, H.W. Gäggeler and U. Shotterer, 1999: Anthropogenic versus natural sources of atmospheric sulphate from an Alpine ice core. Tellus 51B, 938–951.Google Scholar
  51. Schwikowski, M., C. Barbante, T. Döring, H.W. Gäggeler, C. Boutron, U. Schotterer, L. Tobler, K. van de Velde, C. Ferrari, G. Cozzi, K. Rosman and P. Cescon, 2004: Post-17th-century changes of European lead emissions recorded in high-altitude Alpine snow and ice. Environ. Sci. Technol. 38, 957–964.CrossRefGoogle Scholar
  52. Shotyk, W., 1996: Peat bog archives of atmospheric metal deposition: geochemical evaluation of peat profiles, natural variations in metal concentrations, and metal enrichment factors. Environ. Rev. 4, 149–183.CrossRefGoogle Scholar
  53. Shotyk, W., D. Weiss, P.G. Appleby, A.K. Cheburkin, R. Frei, M. Gloor, J.D. Kramers, S. Reese and W.O. van der Knapp, 1998: History of atmospheric lead deposition since 12,370 14 C yr BP from a peat bog, Jura mountains, Switzerland. Science 281, 1635–1640.CrossRefGoogle Scholar
  54. Thompson, L.G., T. Yao and M.E. Davis, 1997: Tropical climate instability: The last glacial cycle from a Qinghai-Tibetan ice core. Science 276, 1821–1825.CrossRefGoogle Scholar
  55. Tylecote, R.F., 1992: A History of Metallurgy. The Institute of Materials, London.Google Scholar
  56. van de Velde, K., C. Boutron, C. Ferrari, T. Bellomi, C. Barbante, S. Rudnev and M. Bolshov, 1998: Seasonal variations of heavy metals in the 1960s Alpine ice: sources versus meteorological factors. Earth Planet. Sci. Lett. 164, 521–533.CrossRefGoogle Scholar
  57. van de Velde, K., C. Ferrari, C. Barbante, I. Moret, T. Bellomi, S. Hong and C.F. Boutron, 1999: A 200 year record of atmospheric cobalt, chromium, molybdenum, and antimony in high altitude Alpine firn and ice. Environ. Sci. Technol. 33, 3495–3501.CrossRefGoogle Scholar
  58. van de Velde, K., C.F. Boutron, C. Ferrari, R.J. Delmas, C. Barbante and T. Bellomi, 2000: A two hundred years record of atmospheric cadmium, copper and zinc concentrations in high altitude snow and ice from the French-Italian Alps. Geophys. Res. Lett. 27, 249–252.CrossRefGoogle Scholar
  59. Wedepohl, K.H., 1995: The composition of the continental crust. Geochim. Cosmochim. Acta 59, 1217–1232.CrossRefGoogle Scholar
  60. Westerlund, S. and P. Öhman, 1991: Cadmium, copper, cobalt, nickel, lead, and zinc in the water column of the Weddell Sea, Antarctica. Geochim. Cosmochim. Acta 55, 2127–2146.CrossRefGoogle Scholar
  61. Wolff, E.W., H. Fischer, F. Fundel, U. Ruth, B. Twarloh, G.C. Littot, R. Mulvaney, R. Rothlisberger, M. de Angelis, C.F. Boutron, M.E. Hansson, U. Jonsell, M.A. Hutterli, F. Lambert, P. Kaufmann, B. Stauffer, T. Stocker, J.P. Steffensen, M. Bigler, M.L. Siggaard-Andersen, R. Udisti, S. Becagli, E. Castellano, M. Severi, D. Wagenbach, C. Barbante, P. Gabrielli and V. Gaspari, 2006: Southern Ocean sea-ice extent, productivity and iron flux over the past eight glacial cycles. Nature 440, 491–496CrossRefGoogle Scholar
  62. Yoshiyuki, N., 1999: A fresh look at element distribution in the North Pacific. EOS Trans. Am. Geophys. Union 78, 21, 221–221.Google Scholar
  63. Zreda-Gostynska, G. and P.R. Kyle, 1997: Volcanic gas emissions from Mount Erebus and their impact on the Antarctic environment. J. Geophys. Res. 102, 15039–15055.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  • Carlo Barbante
    • 1
    • 2
    Email author
  • Jacopo Gabrieli
    • 1
    • 2
  • Paolo Gabrielli
    • 2
    • 3
  • Paul Vallelonga
    • 2
    • 4
  • Giulio Cozzi
    • 2
  • Clara Turetta
    • 2
  • Sungmin Hong
    • 5
  • Kevin Rosman
    • 6
  • Claude F. Boutron
    • 7
    • 8
  • Paolo Cescon
    • 1
    • 2
  1. 1.Department of Environmental SciencesUniversity Ca’Foscari of VeniceVeniceItaly
  2. 2.Institute for the Dynamics of Environmental ProcessesUniversity Ca’Foscari of VeniceVeniceItaly
  3. 3.Byrd Polar Research CenterOhio State UniversityColumbusUSA
  4. 4.Centre for Ice and Climate, Niels Bohr InstituteUniversity of CopenhagenCopenhagenDenmark
  5. 5.Korea Polar Research InstituteSongdo-dong, Yeonsu-gu, IncheonSouth Korea
  6. 6.Department of Imaging and Applied PhysicsCurtin University of TechnologyPerthAustralia
  7. 7.Laboratoire de Glaciologie et Géophysique de l’EnvironnementUniversity Josef Fourier GrenobleSaint Martin d′HèresFrance
  8. 8.Unité de Formation et de Recherche de Physique et Observatoire des Sciences de l’UniversUniversité Joseph Fourier de GrenobleSaint Martin d’ HèresFrance

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