Three-dimensional calibration for routine analyses of bromide and nitrate ions as indicators of groundwater quality in coastal territories

Abstract

Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at different concentrations, ranging between 0.1 and 2 mM, were analyzed by means of ion chromatography. Splitting two partially merged chromatographic peaks and considering each resulting area as originating from a single species produces “measured” concentration values which differ from the nominal ones. Such a procedure generates errors (one per species) which can be written as a function of the above mentioned “measured” concentrations and which can be graphically represented by means of a surface in a three-dimensional (3D) space. In this way, “measured” concentrations of bromide and nitrate ions can be corrected by calculating the errors generated under the experimental conditions at which the chromatographic separation is performed. Notably, this is analogous with the two-dimensional (2D) calibration normally carried out for analytical purposes. Indeed, both methods allow estimation of the unknown concentration of species in solution by correlating the instrumental response with the concentration of standard solutions.