Gas chromatography–mass spectrometry analysis of di- n-octyl disulfide in a straight oil metalworking fluid: : Application of differential permeation and Box–Cox transformation

Abstract

The aim of this study was to identify and quantify an unknown peak in the chromatogram of a very complex mixture, a straight oil metalworking fluid (MWF). The fraction that permeated through a thin nitrile polymer membrane had less mineral oil background than the original MWF did at the retention time of the unknown peak, thus facilitating identification by total ion current (TIC) gas chromatography–mass spectrometry (GC–MS). The peak proved to be di- n-octyl disulfide (DOD) through retention time and mass spectral comparisons. Quantitation of DOD was by extracted ion chromatogram analysis of the DOD molecular ion (mass-to-charge ratio ( m/ z) 290), and of the m/ z 71 ion for the internal standard, n-triacontane. Linear models of the area ratio ( y) of these two ions versus DOD concentration showed a systematic negative bias at low concentrations, a common occurrence in analysis. The linear model of y 0.8 (from Box–Cox power transformation) versus DOD concentration showed negligible bias from the lowest measured standard of 1.51 mg/L to the highest concentration tested at 75.5 mg/L. The intercept did not differ statistically from zero. The concentration of DOD in the MWF was then calculated to be 0.398 ± 0.034% (w/w) by the internal standard method, and 0.387 ± 0.036% (w/w) by the method of standard additions. These two results were not significantly different at p ≤ 0.05. The Box–Cox transformation is therefore recommended when the data for standards are non-linear.