Zinc solubility and fractionation in cultivated calcareous soils irrigated with wastewater

Abstract

The solubility, lability and fractionation of zinc in a range of calcareous soils from Peshawar, Pakistan were studied (18 topsoils and 18 subsoils). The lability (E-value) of Zn was assessed as the fraction isotopically exchangeable with 70Zn2+; comparative extractions included 0.005M DTPA, 0.43M HNO3 and a Tessier-style sequential extraction procedure (SEP). Because of the extremely low concentration of labile Zn the E-value was determined in soils suspended in 0.0001M Na2-EDTA which provided reliable analytical conditions in which approximately 20% of the labile Zn was dissolved. On average, only 2.4% of soil Zn was isotopically exchangeable. This corresponded closely to Zn solubilised by extraction with 0.005 DTPA and by the carbonate extraction step (F1+F2) of the Tessier-style SEP. Crucially, although the majority of the soil CaCO3 was dissolved in F2 of the SEP, the DTPA dissolved only a very small proportion of the soil CaCO3. This suggests a superficial carbonate-bound form of labile Zn, accessible to extraction with DTPA and to isotopic exchange. Zinc solubility from soil suspended in 0.01M Ca(NO3)2 (PCO2 controlled at 0.03) was measured over three days. Following solution speciation using WHAM(VII) two simple solubility models were parameterised: a pH dependent ‘adsorption’ model based on the labile (isotopically exchangeable) Zn distribution coefficient (Kd) and an apparent solubility product (Ks) for ZnCO3. The distribution coefficient showed no pH-dependence and the solubility model provided the best fit to the free ion activity (Zn2+) data, although the apparent value of log10 Ks (5.1) was 2.8log units lower than that of the mineral smithsonite (ZnCO3).