Joint approximatediagonalization of eigenmatrices (JADE)as anew approachfor analysis of hyphenated and comprehensive two-dimensional gas chromatographic data

Hyphenated techniques combine separation and spectroscopic detection technique to exploit the advantages of bothand theyhave attractedattention of chemists to analyze complex mixtures. However, inadequate separation challenges still exist especially in theanalysis ofcomplex samples[1]. Therefore,two-dimensional chromatographic systems such as comprehensive two-dimensional gas chromatography-mass spectrometry(GC×GC-MS) have been proposed for the analysis of complexsamples due totheirhigherresolution and higherpeak capacity.However, oneof the main challenges in GC×GCisrelated to the difficulty of the analysis and interpretation of thehugeamount of data. Additionally,complete separation of all detectable components still cannotbe achieved.Therefore, the objective of the present work was development of joint approximatediagonalization of eigenmatrices (JADE) as a member of ICA family[2], for the analysisofGC-MSandGC×GC-MSdata.In this regard,simulatedGC-MSand GC×GC-MS data sets with different number of components, different degree of overlapandnoise levels were evaluated.Also, column-wise augmentation was used for GC-MS and GC×GC-MS dataarrangement before JADE analysis.The performance of JADE was evaluated in terms of statistical parametersof lack of fit (LOF), mutual information (MI) and Amari index[3]as well asanalytical figures of merit (AFOMs)obtained from calibration curves. In addition,the area of feasible solutions (AFS) was calculatedby two different approachesofMCR-BANDs and polygon inflation algorithm (fackpack). Furthermore, JADE performance was compared with multivariate curve resolution-alternation least squares (MCR-ALS) and other ICA algorithms of mean-field ICA (MFICA) and mutual information least dependent component analysis (MILCA).In all cases, JADE could successfully resolve the elution and spectral profiles in GC-MS and GC×GC-MSdata with acceptable statistical and calibration parameters andtheir solutions were in the AFS. To check the applicabilityof JADE in real cases, JADE was used for resolution and quantification of phenanthrene and anthracene in heavy fuel oil (HFO) analyzed by GC×GC-MS. Surprisingly, pure elution and spectral profiles of target compounds were properly resolved in the presenceof baseline and interferences using JADE. Once more, the performance of JADE was compared with MCR-ALS. On this matter, the MI values were 1.01 and 1.13 for resolved profiles by JADE and MCR-ALS, respectively. In addition, LOD values (μg/mL) were respectively 1.36 and 1.24 for phenanthrene and 1.26 and 1.09 for anthracene using MCR-ALS and JADE which showed outperformance of JADE over MCR-ALS.