Major and trace elements in soils in the Central Pyrenees: high altitude soils as a cumulative record of background atmospheric contamination over SW Europe

Abstract

High mountain soils constitute a long-term cumulative record of atmospherically deposited trace elements from both natural and anthropogenic sources. The main aims of this study were to determine the level of major and trace metals (Al, Ti, Mn, Fe, and Zr) of lithologic origin and airborne contaminating trace elements (Ni, Cu, Zn, As, Cd, and Pb) in soils in the Central Pyrenees as an indication of background contamination over SW Europe, to establish whether there is a spatial pattern of accumulation of trace elements in soils as a function of altitude, and to examine whether altitude-related physicochemical properties of soils affect the accumulation of major metals and trace elements. Major metals and trace elements were measured in "top" (i.e., first 10cm) and "bottom" (i.e., below 10cm) soil samples along an altitudinal transect (1,520-2,880ma.s.l.) in the Central Pyrenees. Total concentrations were determined by X-ray fluorescense spectrometry. Total major metal concentrations were analysed by conventional X-ray fluorescence spectrometry (XRF) with a Siemens SRS 303 instrument. Total trace element concentrations were determined with an energy-dispersive multielement miniprobe XRF analyser. Acid-extractable concentrations were measured by inductively coupled plasma after previous extraction with nitric acid and hydrogen peroxide in closed beakers. Acid-extractable major metal concentrations were measured by inductively coupled plasma (ICP)-Optic Emission Spectrometry with a Perkin Elmer 3200 RL Instrument. Acid-extractable trace element concentrations were determined by ICP-Mass Spectrometry with a Perkin Elmer ELAN 6000. Trace element concentration ranges were (in mgkg(-1), inventories in gm(-2) between parenthesis) <2-58 (0.5-6.6) for Ni, 6-30 (0.2-3.4) for Cu, 38-236 (1.6-32.4) for Zn, 6-209 (0.2-12.8) for As, 0.02-0.64 (<0.04) for Cd, and 28-94 (0.6-13.0) for Pb. These concentrations were, in general, comparable to those recorded in soils from other European mountainous areas and were in many cases above the threshold recommended for ecosystem protection by regional and European environmental authorities. The highest concentrations were found at lower altitudes, indicating an effect of local contamination up to ∼2,300ma.s.l. Only above this altitude can trace elements in soils be considered representative of a background, long-range atmospheric contamination. None of the storage capacity properties of soils examined were determinant of the differences in elemental concentrations along the altitudinal transect. At the upper altitude range, Ni, Cu, and Pb showed a approximately two- to fivefold increase over the average concentration of the local dominant lithology, reflecting the regional and global background of atmospheric contamination in the area.