Speciation, Distribution, Prediction, and Mobility of Lead in Urban Soils: A Multiscale Study

Lead (Pb), a trace metal notorious for its impacts on human health, has achieved worldwide environmental dispersal resulting from centuries of use by human society. The toxicity of Pb is governed largely by its mineral form, which is in turn controlled by pH, localized reactivity and soil processes that differ according to soil type, location and Pb source. Given the context of these localized dependencies, or site specificity, efforts to predict Pb toxicity and refine sustainable remediation techniques are most useful when Pb behavior is constrained and predicted within environments with homogeneous conditions, such as a single soil. I evaluated and predicted the behavior of Pb, a typical anthropogenic contaminant, within a single soil using bioaccessibility testing and predictive geospatial modeling to assess potential impacts and refine sustainable remediation methods. To test the hypothesis that Pb speciation is influenced by competitive sorption processes in soils, I investigated changes in mobility and speciation of Pb upon addition of amendments at multiple scales using flow-through column experiments, soil characterization and synchrotron-based x-ray techniques. Kriging and cokriging maps provided a successful estimation of background and total Pb, the latter incorporating housing age as a secondary variable to increase model accuracy, though efforts to automate detection of background Pb were complicated by approximation of building extents, and overall heterogeneity of soil Pb concentration gives high error. Acute Pb heterogeneity is observed at the scale of a single site among near-structure samples. At the city-scale, determination of bioaccessibility revealed that bioaccessible and total Pb are well-correlated, to the extent that bioaccessibility may be predicted for the soil underlying Burlington, VT; this information, combined with predictive blood lead level modeling and the CDC\u27s recent establishment of 5 μg kg-1 as a threshold for blood lead toxicity, enabled the establishment of a site-specific revised soil Pb limit of 360 mg kg-1, lower than the EPA\u27s general soil Pb threshold of 400 mg kg-1. Characterization of leached and unleached soil using scanning electron microscope energy dispersive spectroscopy (SEM-EDS) and microfocused x-ray techniques provided a first look at Pb paint species using synchrotron technologies. Pb was present within paint chips as hydrocerussite, but appeared to weather to anglesite over time. Pb also seemed to act as cation bridge, attracting clay minerals electrostatically and becoming incorporated into heterogeneous soil aggregates. Accessory paint elements are identified in soil and within paint chips and may further complicate these systems. Column experiments, at acidic pH, yielded little evidence of Pb mobility change in response to modification of competitive sorbents. Kinetics of Pb release were driven by pH, with Pb solubilizing at pH of ˜4.9 as column soil acidifies. This work provides evidence for changes in Pb speciation over time in urban soils impacted by Pb paint, and presents a framework for predictive risk analysis at a local site using experimental and modeling tools. Multiscale observations and analytical results can be used in future efforts to model and refine sustainable remediation solutions within a site-specific context