Effect of injection matrix concentration on peak shape and separation efficiency in ion chromatography

In HPLC, injection of solvents that differ from the eluent can result in peak broadening due to solvent strength mismatch or viscous fingering. Broadened, distorted or even split analyte peaks may result. Past studies of this injection-induced peak distortion in reversed phase (RPLC) and hydrophilic interaction (HILIC) liquid chromatography have led to the conclusion that the sample should be injected in the eluent or a weaker solvent. However, there have been no studies of injection-induced peak distortion in ion chromatography (IC). To address this, injection-induced effects were studied for six inorganic anions (F−, Cl−, NO2−, Br−, NO3− and SO42−) on a Dionex AS23 IC column using a HCO3−/CO32− eluent. The VanMiddlesworth-Dorsey injection sensitivity parameter (s) showed that IC of anions has much greater tolerance to the injection matrix (HCO3−/CO32− herein) mismatch than RPLC or HILIC. Even when the injection contained a ten-fold greater concentration of HCO3−/CO32− than the eluent, the peak shapes and separation efficiencies of six analyte ions did not change significantly. At more than ten-fold greater matrix concentrations, analyte anions that elute near the system peak of the matrix were distorted, and in the extreme cases exhibited a small secondary peak on the analyte peak front. These studies better guide the degree of dilution needed prior to IC analysis of anions.