Aqueous solubility of Pb at equilibrium with hydroxypyromorphite over a range of phosphate concentrations

Abstract

Hydroxypyromorphite (HPM) is a low-solubility Pb phosphate mineral that has the potential to limit solubility and bioavailability of Pb in soils and water. Because of reported uncertainty regarding the solubility product of this important mineral, we re-evaluated the solubility of Pb and activity of the free Pb²⁺ ion in aqueous suspensions of microcrystalline HPM equilibrated up to 30 days over a wide range of added soluble phosphate. A small addition of phosphate (0.1 mM) reduced Pb solubility as measured by ICP-OES, but greater phosphate additions (up to 50 mM) had no further effect in lowering HPM solubility. However, free Pb²⁺ ion activity measured by ion-selective electrode progressively decreased from about 10^−6.5 with no added phosphate to 10⁻⁹ as soluble phosphate was increased. The effect of soluble phosphate in lowering Pb²⁺ activity is attributed to inhibited dissolution of HPM as well as increased Pb²⁺-phosphate ion pair formation in solution at higher solution concentrations of phosphate. Measurement of the ion activity products (IAP) of the solutions at equilibrium with HPM gave highly variable IAP values that were sensitive to pH and were generally not consistent with the reported solubility product of this mineral. The high variability of the IAPs for solutions with variable pH and phosphate concentrations indicates that dissolution–precipitation reactions of HPM are not described by a constant solubility product at equilibrium, possibly because of the incongruent dissolution behavior of this mineral at near-neutral pH.