Pb speciation versus TCLP release in army firing range soils.

A series of soil parameter and mineralogical investigative techniques were applied to assess the Pb speciation in four US Army firing range soils that presented significantly different Pb leaching regimes and soil characteristics. Soil gradation tests were complemented by total chemical analyses, X-ray powder diffraction (XRPD), Rietveld quantification, optical microscopy and scanning electron microscopy (SEM) analyses. The bulk geotechnical, mineralogical and chemical analyses pointed to two possible Pb retention mechanisms: precipitation as lead carbonate and sorption in the case of fine-grained soils. Lead speciation and mobility was further investigated by the toxicity characteristic leaching procedure (TCLP) and sequential extraction test (SET). As the TCLP Pb concentrations did not necessarily reflect the total Pb analysis of the soils, the Pb leachability ratio (TCLP/total) was found to be controlled by soil mineralogy and its response to changes in system pH. Geochemical modeling, using Visual MINTEQ, was employed to evaluate the mechanisms that controlled the observed TCLP Pb leaching behavior. It was found that lead carbonate precipitation/dissolution reactions controlled Pb TCLP leachability in all soils, while sorptive phenomena did not seem to play a role even in the case of fine-grained soils. More specifically, TCLP Pb leachability was controlled by the pH, the available Pb and the available carbonate in solution. This indicates that geochemical modeling strongly complimented TCLP Pb analyses. Thus, geochemical modeling is an important assessment tool to evaluate the magnitude of site-specific Pb-related environmental problems in firing range soils. Carbonation reactions, involving metallic Pb, that occur during the SET obscure its ability to reliably ascertain Pb speciation. More specifically, SET lumps the extractable Pb into predetermined phase categories that may not be truly representative of the actual soil mineralogy or dominant forms of Pb in the soil. A thorough geotechnical, mineralogical and chemical investigation of firing range soils, complemented by geochemical modeling, was therefore found to be a more reliable approach to evaluate Pb speciation and TCLP release in firing range soils.