LAUSR

Abstract Despite the considerable advancements that occurred in the last years regarding the elucidation of bio-oils composition, quantitative studies still lack comprehensive investigation of matrix effects. In this context, matrix-matched calibration plays an important role in bio-oil analyses, due to the extremely complex nature of bio-oils, and the great diversity of functionalities displayed by the compounds comprising such matrices. In this study, for the first time, a systematic approach employing matrix-matched calibration is presented to evaluate the extent of matrix effect in bio-oil analysis and undoubted quantification of its components. A procedure using sequential liquid-liquid extraction (LLE) based on two approaches, organic solvent partitioning and pH-depended reactive extraction, was successfully employed to obtain a blank bio-oil matrix. In order to assess matrix effect, two types of external calibration were employed, namely, matrix-matched calibration and solvent calibration. The results highlighted the dependence of matrix effect on the quantitative analysis of the bio-oil by gas chromatography coupled to mass spectrometry detection. Sixteen analytes covering the main functionalities present in the bio-oil matrix were evaluated using authentic analytical standards, and most of these analytes displayed significant enhanced by the matrix presence. Additionally, improvements in peaks shape, as well as in linearity were observed when comparing matrix-matched to solvent calibration method. Beside the compensating for matrix effect, for obtaining an accurate quantification of bio-oil compounds, while compensating for matrix effect, it was developed and implemented a matrix-matched calibration method by comprehensive two-dimensional gas chromatography with quadrupole mass spectrometry detection (GC × GC/qMS). The proposed method showed adequate linearity (R2 > 0.98), precision (