IDENTIFICATION OF PYROMORPHITE IN MINE-WASTE CONTAMINATED SOILS BY ATEM AND EXAFS

Calcium-rich pyromorphite [Pb-5(PO4)(3)Cl] has been positively identif ied as the major lead-bearing phase in mine-waste soils from the South Pennine Orefield, UK, by a combination of EXAFS spectroscopy, ATEM an d XRD. Evidence for a pyromorphite-like structure was provided by elec tron diffraction of individual Ca-rich, lead chlorophosphate grains in the soil using ATEM. Approximate unit-cell parameters derived from el ectron diffraction were used to identify peaks on the powder XRD trace obtained from the soil sample, allowing the cell parameters to be ref ined. The unit-cell parameters derived for the Ca-rich pyromorphite [a = 0.9789(7), c = 0.726(1) nm] are smaller than those reported for pur e end-member pyromorphite (a=0.998, c=0.733 nm; Baker, 1966) and are s ufficiently different to prevent positive identification by convention al XRD analysis. Lead absorption spectra and interatomic distances obt ained from EXAFS performed on bulk soils confirmed the predominance of pyromorphite-like structure. EXAFS is shown to be a useful tool in th e identification of soil minerals. It gives information about the loca l environment of one specific element in solids, be they crystalline o r amorphous, and is unaffected by the limited chemical substitution of Ca for Pb. The identification of impure Pb minerals in soil by techni ques other than XRD suggests that previous studies, based on XRD, may have underestimated the amount of soil Pb present as discrete Pb compo unds.