RATIO OF SEQUENTIAL CHROMATOGRAMS FOR QUANTITATIVE-ANALYSIS AND PEAK DECONVOLUTION - APPLICATION TO STANDARD ADDITION METHOD AND PROCESS MONITORING

This paper describes a new technique for data analysis in chromatography, based on taking the point-by-point ratio of sequential chromatograms that have been base line corrected. This ratio chromatogram provides a robust means for the identification and the quantitation of analytes. In addition, the appearance of an interferent is made highly visible, even when it coelutes with desired analytes. For quantitative analysis, the region of the ratio chromatogram corresponding to the pure elution of an analyte is identified and is used to calculate a ratio value equal to the ratio of concentrations of the analyte in sequential injections. For the ratio value calculation, a variance-weighted average is used, which compensates for the varying signal-to-noise ratio. This ratio value, or equivalently the percent change in concentration, is the basis of a chromatographic standard addition method and an algorithm to monitor analyte concentration in a process stream. In the case of overlapped peaks, a spiking procedure is used to calculate both the original concentration of an analyte and its signal contribution to the original chromatogram. Thus, quantitation and curve resolution may be performed simultaneously, without peak modeling or curve fitting. These concepts are demonstrated by using data from ion chromatography, but the technique should be applicable to all chromatographic techniques. In a preliminary evaluation for overlapped peaks (resolution = 0.87), the mean percent change for 10 replicates was accurate to within 1% of the true change; thus, the technique is not biased. The within-run standard deviation was conservatively a 4% concentration change. A simulation of reduced resolution suggested that concentration changes could be estimated for a resolution as low as 0.1. © 1990, American Chemical Society. All rights reserved.