Non-linear and non-constant variance calibration curves in analysis of volatile organic compounds for testing of water by the purge-and-trap method coupled with gas chromatography/mass spectrometry.

Currently used operating conditions for analysing volatile organic compounds (VOCs) by purge-and-trap gas chromatography/mass spectrometry (GC/MS) produced non-linear calibration curves with non-uniform variance. Second-order polynomial models therefore had to be used in weighted regression analysis of measurements of replicates spiked at various concentrations. A transparent procedure based on a reported method of very low computational complexity allowed calculation of the parameters of second-order models, confidence bands of regression lines, prediction bands, and confidence intervals of discriminated analyte concentrations. Tolerance intervals were introduced for this last purpose. Critical, detection and quantification levels drawn from the calibration curves were compared with those calculated by the EPA method.