An automated system for predicting detection limit and precision profile from a chromatogram

Abstract

This paper presents a basic model of an automated system for predicting the detection limit and precision profile (plot of relative standard deviation (RSD) of measurements against concentration) in chromatography. The fundamental assumption is that the major source of response errors at low sample concentrations is background noise and at high concentrations, it is the volumes injected into an HPLC system by a sample injector. The noise is approximated by the mixed random processes of the first order autoregressive process AR(1) and white noise. The research procedures are: (1) the description of the standard deviation (SD) of measurements in terms of the parameters of the mixed random processes; (2) the algorithm for the parameter estimation of the mixed processes from actual background noise; (3) the mathematical distinction between noise and signal in a chromatogram. When compounds are chromatographically separated, each obtained signal is given the detection limit and precision profile on laboratory-made software. A file of a chromatogram is the only requirement for the theoretical prediction of measurement uncertainty and therefore the repeated measurements of real samples can be dispensed with. The theoretically predicted RSDs are verified by comparing them with the statistical RSDs obtained by repeated measurements. Signal shapes on noise are illustrated at the detection limit and quantitation limit, the signal-to-noise ratios of which are close to the widely adopted values, 3 and 10, respectively.