The distribution of elemental species of chromium (Cr) in potentially-contaminated soil samples warrants investigation due to the differing mobilities and toxicities of trivalent [Cr(III)] and hexavalent chromium [(Cr(VI)]. In addition, the possibility of species interconversions requires the implementation of robust methods that can correct for changes at the point of sampling, extraction and analysis. This work presents the application of speciated isotope dilution mass spectrometry (SIDMS) to accurately quantify Cr(VI) in agricultural soils within close proximity to a mine tailings dam in the Copperbelt Province of Zambia. Interpolated plots of total Cr, produced from data collected through a nested sampling design, were used to optimise the sampling across the spatial domain. Extraction of Cr(VI) was undertaken using a microwave assisted reaction system (80 °C for 5 min) with 50 mM EDTA, to complex Cr(III) and reduce the likelihood of oxidation during the extraction. Isotopically-enriched