Estimation of the age of a weathered mixture of volatile organic compounds Original Research Article

The ability to predict the amount of time that a light petroleum mixture has been weathered could have many applications, such as aiding forensic investigators in determining the cause and intent of a fire. In our study, an evaporation chamber that permits control of airflow and temperature was constructed and used to weather a model nine-component hydrocarbon mixture. The composition of the mixture was monitored over time by gas chromatography and a variety of chemometric models were explored, including partial least squares (PLS), nonlinear PLS (PolyPLS) and locally weighted regression (LWR or loess). A hierarchical application of multivariate techniques was able to predict the time for which a sample had been exposed to evaporative weathering. A classification model based on partial least squares discriminant analysis (PLS-DA) could predict whether a sample was relatively fresh (< 12 h exposure time) or highly weathered (>20 h exposure time). Subsequent regression models for these individual classes were evaluated for accuracy using the root mean square error of prediction (RMSEP). Prior to regression model calculation, y-gradient generalized least squares weighting (GLSW) was used to preprocess the data by removing variance from the X-block, which was orthogonal to the Y-block. LWR was found to be the most successful regression method, whereby fresh samples could be predicted to within 40 min of exposure and highly weathered samples predicted to within 5.6 h. These results suggest that our hierarchical chemometric approach may also allow us to estimate the age of more complicated light petroleum mixtures, such as gasoline.