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Groundwater is the environmental compartment very often involved in the broader issues related to contaminated sites characterization and reclamation. It is not uncommon to find areas in which some substances directly linked to the petrographic composition of the aquifer reach high values exceeding the limits set by the regulations. These concentrations are defined as Natural Background Levels (NBL) and the need to quantify their real contribution, in areas subject to strong anthropogenic pressures, represents an emerging problem. Global statistical analyses and laboratory testing are proposed here to distinguish between the impacts of different forcing influencing water quality in hydrogeological systems. The study focus on the application of a methodology based on the Component Separation analysis for the NBL estimation of selected chemical species in potentially contaminated aquifers flowing in the proximity of landfill areas, and on the subsequent validation of the results through experimental studies of field samples. A site located in Calabria, Italy, and constituting a typical example of an aquifer which has been subjected to possible contact with the leachate produced by waste degradation is considered. The work is keyed to NBLs characterization of aluminum, iron and manganese and to the identification of their natural component for a proper environmental assessment of the site. Estimated NBLs are consistent with the geochemical composition of site samples. The adopted methodology can represent a useful instrument to distinguish effective anthropogenic contamination from natural conditions and to define realistic environmental clean-up goals., (Copyright © 2019 Elsevier Ltd. All rights reserved.)