*Article* **Investigating Lead Bioavailability in a Former Shooting Range by Soil Microanalyses and Earthworms Tests**

**Carlo Porfido 1,\*, Concetta Eliana Gattullo 1, Ignazio Allegretta 1, Nunzio Fiorentino 2, Roberto Terzano 1, Massimo Fagnano 2 and Matteo Spagnuolo 1**


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> **Abstract:** Shooting ranges are among the major anthropogenic sources of Pb contamination in soils worldwide. Once they have reached the soil, bullet residues can have different fates according to the characteristics of the soil environment, leading to the formation of different Pb weathering products whose stability is crucial for Pb accessibility to soil biota. In this study, Pb availability in a former polluted shooting range was investigated with a combination of conventional soil analyses, X-ray microanalyses and assays with the bio-indicator earthworm *Eisenia andrei*. Chemical extractions evidenced a rather low mobility of soil Pb, while micro-X-ray fluorescence spectroscopy (μXRF) and scanning electron microscopy coupled with microanalysis (SEM-EDX) showed the formation of a weathering crust around Pb-containing bullet slivers dispersed within the soil. Such crusts consisted of a mixture of orthophosphates, including the highly insoluble Cl-pyromorphite. Furthermore, no acute toxicity effects and low Pb concentration values were measured in earthworm tissues (94.9 mg kg−1) and coelom fluids (794 μg <sup>L</sup>−1) after 28 days of exposure to the polluted soil. These results allow us to assume that most of the Pb in the shooting range soil underwent stabilization processes promoted by phosphatic fertilization. The soil was in fact used for agriculture after being dismissed for firing activities. Such a combined approach can be applied to study Pb bioavailability in other shooting ranges or, more generally, in soils heavily polluted with Pb.

> **Keywords:** firing ranges; *Eisenia andrei*; micro-X-ray fluorescence; SEM-EDX; Pb phosphates; pyromorphite
