Effects of milling on the metals analysis of soil samples containing metallic residues

Metallic residues are distributed heterogeneously onto small-arms range soils from projectile fragmentation upon impact with a target or berm backstop. Incremental Sampling Methodology (ISM) can address the spatially heterogeneous contamination of surface soils on small-arms ranges, but representative kilogram-sized ISM subsamples are affected by the range of metallic residue particle sizes in the sample. This study compares the precision and concentrations of metals in a small-arms range soil sample processed by a puck mill, ring and puck mill, ball mill, and mortar and pestle prior to analysis. The ball mill, puck mill, and puck and ring mill produced acceptable relative standard deviations of less than 15% for the anthropogenic metals of interest (Lead (Pb), Antimony (Sb), Copper (Cu), and Zinc (Zn)), with the ball mill exhibiting the greatest precision for Pb, Cu, and Zn. Precision by mortar and pestle, without milling, was considerably higher (40% to >100%) for anthropogenic metals. Median anthropogenic metal concentrations varied by more than 40% between milling methods, with the greatest concentrations produced by the puck mill, followed by the puck and ring mill and then the ball mill. Metal concentrations were also dependent on milling time, with concentrations stabilizing for the puck mill by 300 s but still increasing for the ball mill over 20 h. Differences in metal concentrations were not directly related to the surface area of the milled sample. Overall, the tested milling methods were successful in producing reproducible data for soils containing metallic residues. However, the effects of milling type and time on concentrations require consideration in environmental investigations.