Abstract
Trace metal composition of atmospheric aerosols provides clues as to emission sources and history of air masses. Atmospheric trace metal concentrations measured between 2011 and 2013 at puy de Dôme (1,465 m elevation, central France) are, on average, intermediate between low-altitude urban sites and Atlantic remote environment (115 ng/m3 Al, 0.55 ng/m3 Sr, 0.136 ng/m3 Ce, 1.34 ng/m3 Pb). Three main factors control trace metal variability: (1) the concentrations markedly decrease at night while the site is generally located in the free troposphere/nocturnal residual layer (average of 43 ng/m3 Al, 0.27 ng/m3 Sr, 0.052 ng/m3 Ce, 0.25 ng/m3 Pb during 2012 summer nights). The nocturnal depletion is greater for refractory crustal elements (Al, Fe, Ti and rare earth elements) than for B, Na and chalcophile/siderophile elements (e.g., Tl, In, Sb, Zn, Cd, Cu, Bi, Mo, Re, Pt and Pd), which probably partition into the gas phase and/or a fine mode fraction. (2) Cr, Ni, Mo, Ag, Pb and Pt record a greater influence of anthropogenic sources (combustion, iron/steel industry, and automobile exhaust catalysts) in winter, and/or in the continental air mass that most frequently influences the site during the cold season. (3) Air masses reaching the site have distinct trace element fingerprints depending on their origin. The African air has crustal like signatures (Al/Ti, La/Sm). The Atlantic air is enriched in B, Cu, Bi, Co, W, Re and Ag and depleted in Tl, Sb and Se relatively to Al. Continental air is enriched in Cr and Ni and depleted in Na. Local air (France) is enriched in chalcophile elements (Zn, Pb, Se, As, Sb, Tl) and to a lesser extent in alkalis and rare earth elements, likely due to limited activation and scavenging of primary particles during a short-history of transport.
Similar content being viewed by others
References
Aitken, J.: On the number of dust particles in the atmosphere. Nature 37, 428–430 (1988)
Allen, A.G., Nemitz, E., Shi, J.P., Harrison, R.M., Greenwood, J.C.: Size distributions of trace metals in atmospheric aerosols in the United Kingdom. Atmos Environ 35, 4581–4591 (2001)
Arimoto, R., Duce, R.A., Ray, B.J., Ellis, W.G., Cullen, J.D., Merrill, J.T.: Trace elements in the atmosphere over the North Atlantic. J Geophys Res 100, 1199–1213 (1995)
Asmi, E., Freney, E., Hervo, M., Picard, D., Rose, C., Colomb, A., Sellegri, K.: Aerosol cloud activation in summer and winter at puy-de-Dôme high altitude site in France. Atmos Chem Phys 12, 11589–11607 (2012)
Ayrault, S., Senhou, A., Moskura, M., Gaudry, A.: Atmospheric trace element concentrations in total suspended particles near Paris, France. Atmos Environ 44, 3700–3707 (2010)
Berg, T., Royset, O., Steinnes, E., Vadset, M.: Atmospheric trace element deposition: principal component analysis of ICP-MS data from moss samples. Environ Pollut 88, 67–77 (1995)
Berg, T., Ass, W., Pacyna, J., Uggerud, H.T., Vadset, M.: Atmospheric trace metal concentrations at Norwegian background sites during 25 years and its relation to European emissions. Atmos Environ 42, 7494–7501 (2008)
Boulon, J., Sellegri, K., Hervo, M., Picard, D., Pichon, J.M., Fréville, P., Laj, P.: Investigation of nucleation events vertical extent: a long term study at two different altitude sites. Atmos Chem Phys 11, 5625–5639 (2011)
Bourcier, L., Sellegri, K., Chausse, P., Pichon, J.M., Laj, P.: Seasonal variation of water-soluble inorganic component in size-segregated aerosol at the puy de Dôme station (1465 m a.s.l.), France. J Atmos Chem 69, 47–66 (2012)
Cattel, F.C.R., Scott, W.D.: Copper in aerosol particles produced by the Ocean. Science 202, 429–430 (1978)
Connan, O., Maro, D., Hébert, D., Roupsard, P., Goujon, R., Letellier, B., Le Cavelier, S.: Wet and dry deposition of particles associated metals (Cd, Pb, Zn, Ni, Hg) in a rural wetland site, Marais Vernier, France. Atmos Environ 67, 394–403 (2013)
Duce, R.A., Hoffman, G.L., Zoller, W.H.: Atmospheric trace metals at remote northern and southern hemisphere sites: pollution or natural? Science 187, 59–61 (1975)
Fomba, K.W., Müller, K., van Pinxteren, D., Herrmann, H.: Aerosol size-resolved trace metal composition in remote northern tropical Atlantic marine environment: case study Cape Verde islands. Atmos Chem Phys 13, 4801–4814 (2013)
Freney, E.J., Sellegri, K., Canonaco, F., Boulon, J., Hervo, M., Weigel, R., Pichon, J.M., Clomb, A., Prévôt, A.S.H., Laj, P.: Seasonal variations in aerosol particle composition at the puy-de-Dôme research station in France. Atmos Chem Phys 11, 13047–13059 (2011)
Gelencsér, A., May, B., Simpson, D., Sanchez-Ochoa, A., Kasper-Giebl, A., Puxbaum, H., Caseiro, A., Pio, C., Legrand, M.: Source apportionment of PM2.5 aerosol over Europe: primary/secondary, natural/anthropogenic, and fossil/biogenic origin. J. Geophys. Res. 112, (2007). doi:10.1029/2006JD008094
Hammer, S., Wagenbach, D., Preunkert, S., Pio, C., Schlosser, C., Meinhardt, F.: Lead-210 observations within CARBOSOL: A diagnostic tool for assessing the spatiotemporal variability of related chemical aerosol species? J. Geophys. Res. 112, (2007). doi:10.1029/2006JD008065
Heimbürger, L.-E., Migon, C., Dufour, A., Chiffoleau, J.-F., Cossa, D.: Trace metal concentrations in the North-western Mediterranean atmospheric aerosol between 1986 and 2008: seasonal pattern and decadal trends. Sci Total Environ 408, 2629–2638 (2010)
Henne, S., Brunner, D., Folini, D., Solberg, S., Klausen, J., Buchmann, B.: Assessment of parameters describing representativeness of air quality in-situ measurement sites. Atmos Chem Phys 10, 3561–3581 (2010)
Ilyin, I., Rozovskaya, O., Travnikov, O., Varygina, M., Aas, W., Uggerud, H.T.,: Heavy metal transboundary pollution of the environment. EMEP Status report 2/2013, (June 2013)
Marx, S.K., Kamber, B.S., McGowan, H.A.: Scavenging of atmospheric trace metal pollutants by mineral dusts: Inter-regional transport of Australian trace metal pollution to New Zealand. Atmos Environ 42, 2460–2478 (2008)
Mbengue, S., Alleman, L.Y., Flament, P.: Size-distributed metallic elements in submicronic and ultrafine atmospheric particles from urban and industrial areas in northern France. Atmos Res 135–136, 35–37 (2014)
Migon, C., Robin, T., Dufour, A., Gentili, B.: Decrease of lead concentrations in the Western Mediterranean atmosphere during the last 20 years. Atmos Environ 42, 815–821 (2008)
Millner, T., Neugebauer, J.: Volatility of the oxides of tungsten and molybdenum in the presence of water vapour. Nature 163, 601–602 (1949)
Moreno, T., Querol, X., Castillo, S., Alastuey, A., Cuevas, E., Herrmann, L., Mounkaila, M., Elvira, J., Gibbons, W.: Geochemical variations in Aeolian mineral particles from the Sahara-Sahel dust corridor. Chemosphere 65, 261–270 (2006)
Pacyna, J.M., Pacyna, E.G.: An assessment of global and regional emissions of trace metals to the atmosphere from anthropogenic sources worldwide. Environ Rev 9, 269–298 (2001)
Pacyna, J., Pacyna, E., Ass, W.: Changes of emissions and atmospheric deposition of mercury, lead, and cadmium. Atmos Environ 43, 117–127 (2009)
Pio, C.A., Legrand, M., Oliviera, T., Afonso, J., Saontos, C., Caseiro, A., Fialho, P., Barata, F., Puxbaum, H., Sanchez-Ochoa, A., Kasper-Giebl, A., Gelencser, A., Preunkert, S., Schock, M.: Climatology of aerosol composition (organic versus inorganic) at nonurban sites on a west-east transect across Europe. J. Geophys. Res. 112, (2007). doi:10.1029/2006JD008038
Pöschl, U.: Atmospheric aerosols: composition, transformation, climate and health effects. Angew Chem Int Ed 44, 7520–7540 (2005)
Raes, F., Van Dingenen, R., Vignati, E., Wilson, J., Putaud, J.P., Seinfeld, J.H., Adams, P.: Formation and cycling of aerosols in the global troposphere. Atmos Environ 34, 4215–4240 (2000)
Rauch, S., Hemond, H.F., Barbante, C., Owari, M., Morrison, G.M., Peucker-Ehrenbrink, B., Wass, B.: Importance of automobile exhaust catalyst emission for the deposition of Platinum, Palladium, and Rhodium in the Northern Hemisphere. Environ Sci Technol 39, 8156–8162 (2005)
Reimann, C., de Caritat, P.: Distinguishing between natural and anthropogenic sources for elements in the environment: regional geochemical surveys versus enrichment factors. Sci Total Environ 337, 91–107 (2005)
Rose, C., Boulon, J., Hervo, M., Holmgren, H., Asmi, E., Ramonet, M., Laj, P., Sellegri, K.: Long-term observations of cluster ion concentration, sources and sinks in clear sky conditions at the high-altitude site of the Puy de Dôme, France. Atmos Chem Phys 13, 11573–11594 (2013)
Roy, S., Négrel, P.: A Pb isotope and trace element study of rainwater from the Massif Central (France). Sci Total Environ 277, 225–239 (2001)
Rudnick, R.L., Gao, S.: Composition of the continental crust. Treatise Geochem 3, 1–64 (2003)
Salvador, P., Artinano, B., Pio, C., Afonso, J., Legrand, M., Puxbaum, H., Hammer, S.: Evaluation of aerosol sources at European high altitude background sites with trajectory statistical analysis methods. Atmos Environ 44, 2316–2329 (2010)
Seeker, W.M.R.: Waste combustion. Twenty-third international symposium on Combustion/The combustion institute, pp. 867–885 (1990).
Song, F., Gao, Y.: Size distributions of trace elements associated with ambient particulate matter in the affinity of a major highway in the New Jersey- New York metropolitan area. Atmos Environ 45, 6714–6723 (2011)
Symonds, R.B., Reed, M.H., Rose, W.I.: Origin, speciation, and fluxes of trace-element gases at Augustine volcano, Alaska: insight into magma degassing and fumarolic processes. Geochim Cosmochim Acta 56, 633–657 (1992)
Travnikov, O., Ilyin, I., Rozovskaya, O., Varygina, M., Aas, W., Uggerud, H.T., Mareckova, K., Wankmueller, R.: Long-term changes of heavy metal transboundary pollution of the environment (1990–2010). EMEP Status report 2/2012, (June 2012)
Venzac, H., Sellegri, K., Villani, P., Picard, D., Laj, P.: Seasonal variation of aerosol size distributions in the free troposphere and residual layer at the puy de Dôme station, France. Atmos Chem Phys 9, 1465–1478 (2009)
Weisel, C.P., Duce, R.A., Fasching, J.L., Heaton, R.W.: Estimates of the transport of trace metals from the ocean to the atmosphere. J Geophys Res 89, 11607–11618 (1984)
Witt, M., Baker, A.R., Jickells, T.D.: Atmospheric trace metals over the Atlantic and South Indian Oceans: investigation of metal concentrations and lead isotope ratios in coastal and remote marine aerosols. Atmos Environ 40, 5435–5451 (2006)
Wood, S.A.: Thermodynamic calculations of the volatility of the platinum group elements (PGE): the PGE content of fluids at magmatic temperatures. Geochim Cosmochim Acta 51, 3041–3050 (1987)
Zoller, W.H., Gladney, E.S., Duce, R.A.: Atmospheric concentrations and sources of trace metals at the South Pole. Science 183, 198–200 (1974)
Acknowledgments
This paper benefited from the constructive comments of two anonymous reviewers. Thanks to E. Atlas (Editor) who handled this manuscript. C. Bosq is thanked for technical assistance in the clean room. This work benefited from financial support from the Observatoire de Physique du Globe de Clermont Ferrand, the French Government Laboratory of Excellence initiative n°ANR-10-LABX-0006, the Région Auvergne and the European Regional Development Funds. This is Laboratory of Excellence ClerVolc contribution number 119.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Supplementary Table A
(XLS 114 kb)
Supplementary Figure A
(GIF 284 kb)
Rights and permissions
About this article
Cite this article
Vlastelic, I., Suchorski, K., Sellegri, K. et al. The trace metal signature of atmospheric aerosols sampled at a European regional background site (puy de Dôme, France). J Atmos Chem 71, 195–212 (2014). https://doi.org/10.1007/s10874-014-9290-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10874-014-9290-0