Advances in chemometric control of commercial diesel adulteration by kerosene using IR spectroscopy

• Published in: Analytical and bioanalytical chemistry Vol. 411; no. 11; pp. 2301 - 2315
• Main Authors: Moura, Heloise O. M. A., Câmara, Anne B. F., Santos, Marfran C. D., Morais, Camilo L. M., de Lima, Leomir A. S., Lima, Kássio M. G., de Carvalho, Luciene S.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01-04-2019; Springer; Springer Nature B.V
• Subjects: Aging; Algorithms; Analysis; Analytical Chemistry; Biochemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Chemometrics; Contamination; Control; Degradation; Degradation products; Diesel; Diesel fuels; Discriminant analysis; Economic conditions; Food Science; Genetic algorithms; Infrared spectroscopy; Kerosene; Laboratory Medicine; Least squares; Methods; Mixtures; Monitoring/Environmental Analysis; Physicochemical properties; Principal components analysis; Regression analysis; Research Paper; Screening; Shelf life; Spectra; Spectrum analysis; Stability analysis; Storage stability; Support vector machines; Multivariate analysis; Diesel fuel; Storage stability; Adulteration; Kerosene
• ISSN: 1618-2642; 1618-2650
• DOI: 10.1007/s00216-019-01671-y

Adulteration is a recurrent issue found in fuel screening. Commercial diesel contamination by kerosene is highly difficult to be detected via physicochemical methods applied in market. Although the contamination may affect diesel quality and storage stability, there is a lack of efficient methodologies for this evaluation. This paper assessed the use of IR spectroscopies (MIR and NIR) coupled with partial least squares (PLS) regression, support vector machine regression (SVR), and multivariate curve resolution with alternating least squares (MCR-ALS) calibration models for quantifying and identifying the presence of kerosene adulterant in commercial diesel. Moreover, principal component analysis (PCA), successive projections algorithm (SPA), and genetic algorithm (GA) tools coupled to linear discriminant analysis were used to observe the degradation behavior of 60 samples of pure and kerosene-added diesel fuel in different concentrations over 60 days of storage. Physicochemical properties of commercial diesel with 15% kerosene remained within conformity with Brazilian screening specifications; in addition, specified tests were not able to identify changes in the blends’ performance over time. By using multivariate classification, the samples of pure and contaminated fuel were accurately classified by aging level into two well-defined groups, and some spectral features related to fuel degradation products were detected. PLS and SVR were accurate to quantify kerosene in the 2.5–40% (
v
/
v
) range, reaching RMSEC < 2.59% and RMSEP < 5.56%, with high correlation between real and predicted concentrations. MCR-ALS with correlation constraint was able to identify and recover the spectral profile of commercial diesel and kerosene adulterant from the IR spectra of contaminated blends.