Changes in the occurrence of silver, gold, platinum, palladium and rhodium in Mont Blanc ice and snow since the 18th century

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Abstract

Ag, Au, Pt, Pd and Rh have been measured at various depth intervals of a 140 m snow/ice core electromechanically drilled at an altitude of 4250 m in the French–Italian Alps. The measurements were made by double focusing ICP-MS with micro concentric nebulisation. It provides the first time series for these metals for the last two centuries. Observed 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. Since the 18th century, no clear increase is observed for Au and Pt. For Pd, Rh and especially Ag, however, concentrations are higher in the last decades than in ancient ice. From a qualitative review of the different possible natural and anthropogenic sources, it appears that volcanoes, mining and smelting activities, industry and waste incinerators could be significant sources of these metals in high-altitude Mont Blanc snow and ice. Pronounced seasonal variations in the concentrations of Pd, Rh and especially Ag are observed in ice dating from the 1960s. They are largely due to changes in the vertical structure of the regional troposphere during the year. For Au and Pt, on the other hand, there are no clear seasonal variations, which suggests that these two metals originate from distant sources.

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

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