Estimating the uncertainty from sampling in pollution crime investigation: The importance of metrology in the forensic interpretation of environmental data

The forensic interpretation of environmental analytical data is usually challenging due to the high geospatial variability of these data. The measurements' uncertainty includes contributions from the sampling and from the sample handling and preparation processes. These contributions are often disregarded in analytical techniques results' quality assurance. A pollution crime investigation case was used to carry out a methodology able to address these uncertainties in two different environmental compartments, freshwater sediments and landfill leachate. The methodology used to estimate the uncertainty was the duplicate method (that replicates predefined steps of the measurement procedure in order to assess its precision) and the parameters used to investigate the pollution were metals (Cr, Cu, Ni, and Zn) in the leachate, the suspect source, and in the sediment, the possible sink. The metal analysis results were compared to statutory limits and it was demonstrated that Cr and Ni concentrations in sediment samples exceeded the threshold levels at all sites downstream the pollution sources, considering the expanded uncertainty U of the measurements and a probability of contamination >0.975, at most sites. Cu and Zn concentrations were above the statutory limits at two sites, but the classification was inconclusive considering the uncertainties of the measurements. Metal analyses in leachate revealed that Cr concentrations were above the statutory limits with a probability of contamination >0.975 in all leachate ponds while the Cu, Ni and Zn probability of contamination was below 0.025. The results demonstrated that the estimation of the sampling uncertainty, which was the dominant component of the combined uncertainty, is required for a comprehensive interpretation of the environmental analyses results, particularly in forensic cases.