Changes in the occurrence of silver, gold, platinum, palladium and rhodium in Mont Blanc ice and snow since the 18th century
Introduction
Until now, investigations of the occurrence of heavy metals in Greenland, Antarctic or alpine snow and ice have been focused on a limited number of metals, especially Pb, Cd, Cu, Zn and Hg (see, e.g. Murozumi et al., 1969; Wolff and Suttie, 1994; Hong et al., 1994, Hong et al., 1996, Hong et al., 1997; Candelone et al., 1995; Boutron et al., 1998; Van de Velde et al., 1998; Wolff et al., 1999).
Various other heavy metals of high geochemical interest were, on the other hand, not considered in these studies. This is mainly because the available analytical techniques were not sensitive enough to allow for these other metals to be measured at the extremely low concentration levels at which they are present in snow and ice. The situation has changed recently with the availability of new ultra sensitive analytical techniques such as double focusing (high-resolution) inductively coupled plasma-mass spectrometry (DF-ICP-MS).
We present here comprehensive data on the occurrence of silver (Ag), gold (Au), platinum (Pt), palladium (Pd) and rhodium (Rh) in alpine ice and snow dating from the late 18th century to the early 1990s. They were obtained by analysing these metals in various sections of a 140 m snow/ice core drilled at a high-altitude location near the summit of Mont Blanc at the French/Italian border using DF-ICP-MS with microconcentric nebulisation (DF-ICP-MS-MN). These data allow the relative importance of natural and anthropogenic contributions of these metals to be assessed on a regional scale and their changes since the Industrial Revolution to be determined.
Section snippets
Field sampling
In June 1994, a 140 m snow/ice core (diameter 10 cm) was electromechanically drilled at an altitude of 4250 m on the East slope of Dôme du Goûter ∼1.5 km northwest of the summit of Mont Blanc in the French–Italian Alps (Van de Velde et al., 1998). The mean annual temperature and snow accumulation rate at the drilling site (45°50′N; 6°51′E) are −11°C and 3.5 m H2O yr−1, respectively (Vincent et al., 1997). The firn/ice transition occurs at a depth of ∼60 m.
Great precautions were taken in the field to
Character of the data
Ag, Au, Pt, Pd and Rh measured in the 74 depth intervals are listed in Table 1.
Measured concentrations range from 0.2 to 12 pg g−1 for Ag, 0.07–0.35 pg g−1 for Au, 0.08–0.62 pg g−1 for Pt, 0.5–10 pg g−1 for Pd and 0.01–0.39 pg g−1 for Rh. For Au, Pt, Pd and Rh, these are the first data to be published on alpine snow and ice fields. For Ag, on the other hand, Batifol and Boutron (1984) already published some data for surface snow collected at three locations in the Mont Blanc range. Their values ranged
Conclusions
This study has allowed to obtain one of the first time series of environmental contamination for Ag, Au, Pt, Pd and Rh in temperate areas. It will be interesting in the future to analyse other snow and ice cores taken at cold high altitude sites in the Alps and other mid-latitude mountain ranges especially in Asia and North and South America. It would however be important that these cores are drilled at locations where glaciological conditions allow to get longer time periods back to the
Acknowledgements
This work was supported in France by the Institut Universitaire de France, the Ministry of the Environment, the Agence de l'Environnement et de la Maı̂trise de l'Energie, the Institut National des Sciences de l'Univers, the Centre National de la Recherche Scientifique and the University Joseph Fourier of Grenoble. In Italy, this study was performed in the framework of the Projects on Environmental Contamination and Glaciology and Paleoclimatology of the Italian Antarctic National Research
References (36)
- et al.
Abundances of the elementsmeteoritic and solar
Geochimica Cosmochimica Acta
(1989) - et al.
Atmospheric heavy metals in high altitude surface snows from Mont Blanc, French Alps
Atmospheric Environment
(1984) - et al.
Aspects of rhodium marine chemistry
Marine Chemistry
(1993) - et al.
An improved method for decontaminating polar snow and ice cores for heavy metals analysis
Analitica Chimica Acta
(1994) - et al.
Platinum-group elements (Rh, Pt, Pd) and Au distribution in snow samples from the Kola Peninsula, NW Russia
Atmospheric Environment
(1999) - et al.
Changes in zinc and cadmium concentrations in Greenland ice during the past 7760 years
Atmospheric Environment
(1997) - et al.
Chemical concentrations of pollutant aerosols, terrestrial dusts and sea salts in Greenland and Antarctic snow strata
Geochimica Cosmochimica Acta
(1969) - et al.
Volatilization, transport and sublimation of metallic and non metallic elements in high temperature gases at Merapi volcano, Indonesia
Geochimica Cosmochimica Acta
(1987) - et al.
Seasonal variations of heavy metals in the 1960s Alpine icesources versus meteorological factors
Earth Planetary Science Letters
(1998) - et al.
Antarctic snow record of cadmium, copper, and zinc content during the twentieth century
Atmospheric Environment
(1999)
Trace elements in the atmosphere of American Samoaconcentrations and deposition to the tropical South Pacific
Journal of Geophysical Research
Trace element determination in Alpine snow and ice by Double Focusing Inductively Coupled Plasma Mass Spectrometry with Microconcentric Nebulization
Journal of Analytical Atomic Spectrometry
Rh, Pd and Pt determination in polar and alpine snow and ice by double focusing ICP-MS with micro concentric nebulisation
Analytical Chemistry
A clean laboratory for ultralow concentration heavy metals analysis
Fresenius Zeitschrift für Analytische Chemie
A forty year record of mercury in central Greenland snow
Geophysical Research Letters
Post Industrial Revolution changes in large-scale atmospheric pollution of the Northern Hemisphere by heavy metals as documented in Greenland snow and ice
Journal Geophysical Research
Luminous efficiency based on photographic observations of the Lost-City fireball and implications for the influx of interplanetary bodies onto Earth
Astronomy and Astrophysics
Etude de l'apport en métaux lourds issue de la métallurgie dans les neiges et glaces Alpines au cours des deux derniers siècles, Rapport de Maı̂trise de Géologie
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