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Environmental context There is growing concern that lead in the environment may cause adverse health effects in human populations. We investigated the combined use of isotopic abundance and isotopic dilution to show how the origins of soil Pb and soil characteristics affect lability. Soil pH and soil Pb content are the dominant controls on Pb lability; the lability of recent petrol-derived Pb is similar to that of other sources in urban soils but greater than geogenic Pb in rural roadside topsoils. Abstract Lability of lead in soils is influenced by both soil properties and source(s) of contamination. We investigated factors controlling Pb lability in soils from (i) land adjacent to a major rural road, (ii) a sewage processing farm and (iii) an archive of the geochemical survey of London. We measured isotopically exchangeable Pb (E-values; PbE), phase fractionation of Pb by a sequential extraction procedure (SEP) and inferred source apportionment from measured Pb isotopic ratios. Isotopic ratios (206Pb/207Pb and 208Pb/207Pb) of total soil Pb fell on a mixing line between those of petrol and UK coal or Pb ore. The main determinant of the isotopically exchangeable Pb fraction (%E-value) was soil pH: %E-values decreased with increasing pH. In rural roadside topsoils, there was also evidence that petrol-derived Pb remained more labile (35%) than Pb from soil parent material (27%). However, in biosolid-amended and London soils, %E-values were low (~25%), covered a restricted range and showed no clear evidence of source-dependent lability.

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Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables. Trace metal reactivity in urban soils depends on both soil properties and the original source material; the WHAM geochemical model predicts solubility using isotopically exchangeable metal as an input.