The novel Outer Plug Standardization (OPS) calibration strategy applied in a new method for the high-throughput determination of Cl, NO and SO in rainwater samples.

This paper presents the Outer Plug Standardization - OPS, a novel technique as an alternative for the classic internal standardization using multiple injection in capillary zone electrophoresis is proposed herein. This technique was applied in a new method for the determination of chloride, nitrate and sulfate in rainwater samples. After the injection accuracy was tested and proved to be a minor error source (average 1.26% RSD), the OPS was applied and it improved the intra-day and inter-day precision of the analytical method by 32.5% and 24.7%, respectively. Using a capillary with effective length of 23.5 cm the electrophoretic separation of the three inorganic anions could be achieved in <1 min, with detection limits of 0.05, 0.09 and 0.11 mg L for chloride, nitrate and sulfate, respectively. Also, the statistical t-test was applied to the results obtained for 82 rainwater samples that were collected and analyzed applying both the method developed in this study and the official APHA 4140 method where no statistical difference was noted within a 95% confidence level.