Lead Solubility and Mineral Structures of Coprecipitated Lead/Calcium Oxalates

Low-molecular-weight organic acids such as oxalate, which are ubiquitous in the environment, can control the solubility and bioavailability of toxic metals such as Pb in soils and water by influencing complexation and precipitation reactions. Here, we investigated Pb solubility in relation to Pb-oxalate precipitation at pH 5.0 in the absence and presence of calcium (Ca), a common cation in environmental matrices. At Pb mole fractions less than 0.10, sequestration of Pb into Ca oxalate to form a solid solution substantially lowered Pb solubility relative to that of pure Pb oxalate to an extent inversely proportional to the Pb mole fraction. Small Pb/Ca solid-solution distribution coefficients at these low mole ratios was largely attributed to the stronger complexation of Pb compared to Ca with oxalate to form soluble metal-oxalate complexes, which in turn limited Pb incorporation into the Ca-oxalate crystal lattice. Characterization of the Pb/Ca-oxalate coprecipitates by X-ray diffraction, optical microscopy, and Fourier transform infrared spectroscopy revealed that the whewellite (Ca-oxalate monohydrate) structure was destabilized by substitution of small amounts of Pb into the lattice, and thus, the formation of the Ca-oxalate dihydrate (weddellite) was favored over the monohydrate. At Pb mole fractions above 0.20, discrete crystallites of Pb oxalate were identified. These new findings imply that Pb/Ca-oxalate coprecipitates in the presence of Ca could reduce the solubility of Pb in Pb-contaminated acid soils.