New peat bog record of atmospheric lead pollution in Switzerland: Pb concentrations, enrichment factors, isotopic composition, and organolead species.

A peat core collected at Etang de la Gruère, an ombrotrophic bog in the Jura Mountains of Switzerland, was analyzed for organolead species (DEL, TEL, DML, and TML) using GC-MIP AES, Pb isotopes using TIMS, and total Pb using XRF and age-dated using 210Pb. The earliest occurrence of quantifiable alkyllead is found at a depth of 24 cm, which is dated at AD 1946 +/- 3; this finding is consistent with the introduction of leaded gasoline in Switzerland in 1947. The maximum concentration of alkyllead (2.89 ng/g) is found at 5 cm, which is dated at AD 1988 +/- 2. This same sample yielded 206Pb/207Pb = 1.1254, which is the least radiogenic value in the entire 2K core and comparable to the isotopic composition of Pb in leaded gasoline. The highest concentrations of DML (906 ng/g) and DEL (1906 ng/g) also were found in this sample. Total alkyllead never accounts for more than 0.02% of total Pb in any given sample. The spatial and temporal variations in organolead species is matched by the changes in the isotopic composition of Pb over the same interval. Despite this, the decline in anthropogenic Pb pre-dates the maximum in total alkyllead and minimum 206Pb/207Pb, indicating that atmospheric Pb emissions had already begun their decline prior to the introduction of unleaded gasoline. In fact the decline in anthropogenic Pb was probably in response to the introduction of legislation, first in Germany and later in the European Union, establishing a maximum allowable concentration of Pb in gasoline.

A new approach for quantifying cumulative, anthropogenic, atmospheric lead deposition using peat cores from bogs: Pb in eight Swiss peat bog profiles.

Peat cores taken from eight Swiss peatlands were used to calculate inventories of anthropogenic Pb using either Sc or Zr to quantify Pb derived from rock weathering. The shapes of the Pb/Sc and Pb/Zr profiles suggest that Pb was supplied exclusively by atmospheric deposition at all sites. At one of the sites (Etang de la Gruère), anthropogenic Pb was calculated using both Sc and Zr as the conservative reference element. Lithogenic Pb determined using Sc was twice that obtained using Zr, possibly because Zr resides only in zircons which are dense compared to pyroxene and amphibole which are the main Sc-bearing phases in the earth's crust. However, the inventory of 'natural' Pb (supplied almost entirely by soil dust) is dwarfed by the anthropogenic inventory such that anthropogenic Pb calculated using Sc and Zr agree to within 5%. The total amount of anthropogenic Pb accumulated in the bogs was calculated by simply adding the mass of anthropogenic Pb for each peat slice over the length of each core. Cumulative, anthropogenic Pb calculated in this way ranged from 1.0 to 9.7 g/m2 and showed pronounced regional differences: the site south of the Alps (Gola di Lago in Canton Ticino) with direct exposure to the heavily industrialized region of northern Italy received nearly 10 times more anthropogenic Pb as the sites in more remote alpine regions (Schöpfenwaldmoor in Canton Berne, and Mauntschas in Canton Grisons). The approach used here to calculate cumulative, anthropogenic, atmospheric Pb (CAAPb) is simple and robust, independent of the chronology of Pb deposition, and makes no assumptions about the immobility of Pb within the peat profile. Given the worldwide distribution of peat bogs, it should be possible to undertake continental and global inventories of atmospheric metal deposition, for both the natural and anthropogenic components of most trace metals of environmental interest.

An Energy-dispersive Miniprobe Multielement Analyzer (EMMA) for direct analysis of Pb and other trace elements in peats.

An Energy-dispersive Miniprobe Multielement Analyzer (EMMA) was designed and constructed for sensitive, rapid, and non-destructive analysis of trace elements (As, Cr, Cu, Fe, Ga, Ge, Hf, Mn, Ni, Pb, Rb, Se, Sr, Th, Y, U, Zn) in small (e.g. 50 microm) samples such as individual mineral grains from rocks. An alternative configuration of the EMMA instrument is described here for use with larger samples such as powders of coal, soil, sediments, and plant materials. To minimize heterogeneity problems, a larger X-ray beam size (0.1 x 6 mm) was used by installing a different collimator, and the sample holder rotated 25 times per minute. Using this approach, Rb, Sr, Cu, Zn and Pb were measured in peat samples collected from bogs in Switzerland and northern Scotland. The detection limit for Pb, for example, is approximately 0.3 microg/g which is one order of magnitude better than conventional XRF analyzers. For comparison, Pb was also measured in acid digests of the same samples using GFAAS. The Pb results obtained using EMMA are comparable to the GFAAS data for the continental peat samples. However, in the Cl-rich samples from the maritime bogs, the GFAAS signal was strongly suppressed, and an accurate comparison of the two methods was not possible. The EMMA technique, therefore, has three advantages over conventional GFAAS: first, no sample dissolution is required; second, several elements of interest are determined simultaneously; and third, the EMMA technique is not subject to matrix interferences.