Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values.