Comprehensive two-dimensional gas chromatography and chemometrics for the high-speed quantitative analysis of aromatic isomers in a jet fuel using the standard addition method and an objective retention time alignment algorithm
A high-speed quantitative analysis of aromatic isomers in a jet fuel sample is performed using comprehensive two-dimensional gas chromatography (GC x GC) and chemometrics. A GC x GC separation time of 2.8 min is achieved for three aromatic isomers in jet fuel, which is 5 times faster than a reference method in which a singlecolumn separation resolves two of the three isomers of interest. The high-speed GC x GC separation is more than 10 times faster than a recent GC x GC separation that fully resolves the three components of interest in gasoline. The high-speed GC x GC analysis of jet fuel is accomplished through short GC columns, high gas velocities, and partial chromatographic peak resolution followed by chemometric resolution of overlapped peaks. The standard addition method and an objective retention time alignment algorithm are used to correct for retention time variations prior to the chemometric data analysis. The standard addition method corrects for chemical matrix effects that cause analytes in complex samples to have peak shapes, widths, and retention times that differ considerably from those of calibration standards in pure solvents. The retention time alignment algorithm corrects for the relatively small retention time variations caused by fluctuating instrumental parameters such as flow rate and temperature. The use of data point interpolation in the retention time alignment algorithm results in a more accurate retention time correction then previously achieved. The generalized rank annihilation method (GRAM) is the chemometric technique used to resolve the overlapped GC x GC peaks. The correction of retention time variations allows for successful GRAM signal deconvolution. Using the retention time alignment algorithm, GRAM quantification accuracy and precision are improved by a factor of 4. The methodology used in this paper should be applicable to other comprehensive separation methods, such as two-dimensional liquid chromatography, liquid chromatography coupled with capillary electrophoresis, and liquid chromatography coupled with gas chromatography.
Fraga
CG
Center for Process Analytical Chemistry, Department of Chemistry, University of Washington, Seattle 98195-1700, USA.
Prazen
BJ
Synovec
RE