Lead in grass in the Scottish uplands: deposition or uptake?

If it is assumed that the Pb collected in grass samples is derived mainly from atmospheric deposition then grass samples can be used as a convenient and easily analysed monitor for Pb deposition, in particular to establish the isotopic composition of current deposition in remote locations. As some studies have demonstrated a strong correlation between soil and grass Pb concentrations, it was considered important to establish the proportion of soil Pb in the grasses used to monitor atmospheric deposition at upland locations in Scotland. Consideration of earlier studies provided evidence that very little, if any, Pb in grass was derived from soil. Lead isotope analysis, by thermal ionisation mass spectrometry, of grasses grown on soils spiked with enriched (207)Pb in the field situation allowed the relative contribution of atmospheric deposition and soil to the grass Pb to be calculated. In most cases, >80% of Pb in grass was derived from atmospheric deposition and in recent years this value was >90%. Recalculation of the (206)Pb/(207)Pb ratio in grass samples showed that there was very little error in the results, published previously, which were based on the assumption that all the Pb collected with grass was derived from the atmosphere. The trends established by measuring the (206)Pb/(207)Pb ratio in grasses were confirmed and remain valid.

Reproducibility of the BCR sequential extraction procedure in a long-term study of the association of heavy metals with soil components in an upland catchment in Scotland.

Humic iron podzol soils from three different plots at the Glensaugh Research Station, Aberdeenshire have been sampled on an annual basis since 1990 and analysed using both total digestion and the original BCR sequential extraction procedure. Particular care was required during the oxidation of these organic soils to prevent loss of material. The residue from the sequential extraction was analysed so that the values for total concentration derived from the total digestion and from the sum of the concentrations in the fractions of the extraction procedure could be compared. The comparison was good for all three soils indicating that not only did the sequential extraction give good recovery but that this was reproducible over a period of several years. The proportion of metals extractable at each step remained relatively constant thereby demonstrating the reproducibility of the procedure and the stability of the metals in the soils over the time scale of the sampling used. Whereas the total concentrations of Cr, Cu and Ni were highest in the soil from a roadside plot, this was not the case for Cd, Pb and Zn. In the case of Pb, concentrations in soils (0-25-cm depth) well away from the road were over 100 mg/kg and well above the expected background level. The distribution of metals between each of the extracted fractions varied not only between each metal but also between each of the three soils indicating that both metal and soil influenced the measured distribution. The distribution of Pb in the roadside soil was different from those in the other two soils and over 10% was extracted in the first, acetic acid soluble, fraction.

Origin of lead associated with different reactive phases in Scottish upland soils: an assessment made using sequential extraction and isotope analysis.

Soil samples (0-25 cm) have been taken annually since 1991 from three protected plots set up at an upland location at Glensaugh in Aberdeenshire, Scotland. The soils were analysed using the original BCR sequential extraction procedure and the lead isotopic composition was determined in each of the fractions, as well as the unfractionated soil using thermal ionisation mass spectrometry (TIMS). The lead concentrations in all the soils, including those well away from the road, were much higher than typical background values indicating that the whole area has been subject to deposition of anthropogenic lead. The distribution of lead between the different fractions was similar for the two non-roadside soils with most lead present in the oxidizable fraction. Although most lead in the roadside soil was also present in the oxidizable fraction, a substantial proportion (about 10%) was in the easily soluble fraction suggesting that roadside lead could be more mobile than lead in the other soils. Good reproducibility was obtained for the isotope analyses in all the fractions. The ratios calculated for the bulk soil from the ratios in the individual fractions agreed very closely with those measured directly in the unfractionated soil thereby demonstrating both reproducibilty and accuracy. The lowest (206)Pb/(207)Pb ratios were found in the roadside soil consistent with the recent deposition of petrol lead. The (206)Pb/(207)Pb ratios in all fractions of the other soils fell into a narrow band and it was necessary to use (204)Pb ratios to differentiate between lead in the extractable fractions and lead in the residual component. It is probable that lead in the non-roadside soils was deposited a considerable time ago and is characterised by a relatively high (206)Pb/(207)Pb ratio. Use of the (204)Pb ratios showed that the residual components in each of the three soils were isotopically distinct.