Equilibrium solubility and dissolution rate of the lead phosphate chloropyromorphite

Phosphate addition to lead-contaminated soils can immobilize lead in situ through the formation of lead phosphate minerals such as chloropyromorphite (Pb5(PO4)3Cl). The long-term stability of lead immobilized in lead phosphate precipitates depends on the equilibrium solubility and dissolution rates of the lead phosphate solids. The equilibrium solubility and dissolution kinetics of chloropyromorphite were quantified in a series of batch and flow-through reactors. Both equilibrium solubility and dissolution rates were strongly affected by pH. Synthetic chloropyromorphite was more soluble than was predicted using a widely cited solubility product for pure chloropyromorphite, an observation that is consistent with several other recent studies. A trace amount of a more soluble lead solid, such as lead hydroxide, in chloropyromorphite could significantly increase dissolved Pb at neutral pH. The pH-dependence of the dissolution rate was examined in flow-through experiments. A dissolution rate law with a single rate constant for synthetic chloropyromorphite and a constant reaction order of 0.65 with respect to [H+] has been determined. The slow dissolution rate of chloropyromorphite relative to other lead minerals and its low solubility can result in its long-term stability in soils.