Evaluation of benzene residue in edible oils using Fourier transform infrared (FTIR) spectroscopy

  • Joshi, Ritu (Department of Biosystems Machinery Engineering, College of Agricultural and Life Science, Chungnam National University) ;
  • Cho, Byoung-Kwan (Department of Biosystems Machinery Engineering, College of Agricultural and Life Science, Chungnam National University) ;
  • Lohumi, Santosh (Department of Biosystems Machinery Engineering, College of Agricultural and Life Science, Chungnam National University) ;
  • Joshi, Rahul (Department of Biosystems Machinery Engineering, College of Agricultural and Life Science, Chungnam National University) ;
  • Lee, Jayoung (Department of Biosystems Machinery Engineering, College of Agricultural and Life Science, Chungnam National University) ;
  • Lee, Hoonsoo (Department of Biosystems Engineering, College of Agriculture, Life & Environment Science, Chungbuk National University) ;
  • Mo, Changyeun (Department of Biosystems Engineering, College of Agriculture and Life Sciences, Kangwon National University)
  • Received : 2018.11.13
  • Accepted : 2019.04.08
  • Published : 2019.06.01


The use of food grade hexane (FGH) for edible oil extraction is responsible for the presence of benzene in the crude oil. Benzene is a Group 1 carcinogen and could pose a serious threat to the health of consumer. However, its detection still depends on classical methods using chromatography which requires a rapid non-destructive detection method. Hence, the aim of this study was to investigate the feasibility of using Fourier transform infrared (FTIR) spectroscopy combined with multivariate analysis to detect and quantify the benzene residue in edible oil (sesame and cottonseed oil). Oil samples were adulterated with varying quantities of benzene, and their FTIR spectra were acquired with an attenuated total reflectance (ATR) method. Optimal variables for a partial least-squares regression (PLSR) model were selected using the variable importance in projection (VIP) and the selectivity ratio (SR) methods. The developed PLS models with whole variables and the VIP- and SR-selected variables were validated against an independent data set which resulted in $R^2$ values of 0.95, 0.96, and 0.95 and standard error of prediction (SEP) values of 38.5, 33.7, and 41.7 mg/L, respectively. The proposed technique of FTIR combined with multivariate analysis and variable selection methods can detect benzene residuals in edible oils with the advantages of being fast and simple and thus, can replace the conventional methods used for the same purpose.

CNNSA3_2019_v46n2_257_f0001.png 이미지

Fig. 1. Raw Fourier transform infrared (FTIR) spectra for pure sesame and cottonseed oil.

CNNSA3_2019_v46n2_257_f0002.png 이미지

Fig. 2. Principal component analysis (PCA) score plot for sesame oil (a) and cottonseed oil (b) after applying multiplicative scatter correction (MSC) preprocessing.

CNNSA3_2019_v46n2_257_f0003.png 이미지

Fig. 3. First three principal components loading plots from principal component analysis (PCA) for benzene-adulterated sesame oil (a), (b), (c) and the spectrum of pure benzene with variable importance in projection (VIP) and selectivity ratio (SR) for selected variables (d).

CNNSA3_2019_v46n2_257_f0004.png 이미지

Fig. 4. Regression plot of the actual versus calculated percentages of benzene in the validation set of the whole spectral region (a), VIP (b) and SR (c) variable selection methods. VIP, variable importance in projection; SR, selectivity ratio.

CNNSA3_2019_v46n2_257_f0006.png 이미지

Fig. 5. Beta coefcient plot from the PLSR (a), Residual plot for whole variables, PLS-VIP and PLS-SR method (b). PLSR, partial least squares regression; VIP, variable importance in projection; SR, selectivity ratio.

Table 1. Prediction results by partial least squares regression (PLSR), variable importance in projection (VIP), and selectivity ratio (SR) variable-selection methods for detecting pure and benzene-adulterated edible oils.

CNNSA3_2019_v46n2_257_t0001.png 이미지


Supported by : Korea Institute of Planning and Evaluation for Technology in Food, Agriculture, Forestry and Fisheries(IPET)


  1. Aksoy M, Dincol K, Erdem S, Dincol G. 1972. Acute leukaemia due to chronic exposure to benzene. The American Journal of Medicine 52:160-166.
  2. Aksoy M, Erdem S, Dincol G. 1974. Leukaemia in shoe workers exposed chronically to benzene. Blood 44:837-841.
  3. Anderssen E, Dyrstad K, Westad F, Martens H. 2006. Reducing over-optimism in variable selection by cross-model validation. Chemometrics and Intelligent Laboratory System 84:69-74.
  4. Ami D, Mereghetti P, Doglia SM. 2000. Multivariate analysis for Fourier transform infrared spectra of complex biological systems and processes. Multivariate Analysis in Management, Engineering and the Sciences, IntechOpen, 2013:189-220.
  5. Aprea E, Biasioli F, Carlin S, Mark TD, Gasperi F. 2008. Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry. International Journal of Mass Spectrometry 275:117-121.
  6. Atkinson R, Boissard C, Cao X, Chandler J, Crump DR, Davies TJ, Delaney M, Derwent RG, Dollard GJ, Duckham SC, Dumitrean P, Field RA, Hewitt CN, Jones BMR, Midgley PM, Murlis J, Nason PD, Passant NR, Watkins D. 1995. Volatile organic compounds in the atmosphere. Environmental Science and Technology 4 Hester RE and Harrison RM eds. Royal Society of Chemistry, London, UK.
  7. Budowski P, Markely KS. 1951. The chemical and physiological properties of sesame oil. Chemical Reviews 48:125-151.
  8. Che Man YB, Setiowaty G. 1999. Determination of anisidine value in thermally oxidized palm olein by Fourier transform infrared spectroscopy. Journal of the American Oil Chemist's Society 76:243-247.
  9. Che Man YB, Mirghani MES. 2000. Rapid method for determining moisture content in crude palm oil by Fourier transform infrared spectroscopy. Journal of the American Oil Chemist's Society 77:631-637.
  10. Chen ZP, Morris J, Martin E. 2006. Extracting chemical information from spectral data with multiplicative light scattering effects by optical path-length estimation and correction. Analytical Chemistry 78:7674-7681.
  11. Cho JH, Lee D, Park JH, Kim K, Lee IB. 2002. Optimal approach for classification of acute leukemia subtypes based on gene expression data. Biotechnology Progress 18:847-854.
  12. Chong IG, Jun CH. 2005. Performance of some variable selection methods when multicollinearity is present. Chemometrics and Intelligent Laboratory Systems 78:103-112.
  13. Dowd MK, Boykin DL, Meredith WR, Campbell Jr BT, Bourland FM, Gannaway JR, Glass KM, Zhang J. 2010. Breeding and genetics: Fatty acid profiles of cottonseed genotypes from the national cotton variety trials. Journal of Cotton Science 14:64-73.
  14. Farres M, Platikano S, Tsakovski S, Tauler R. 2015. Comparison of the variable importance in projection (VIP) and of the selectivity ratio (SR) methods for variable selection and interpretation. Journal of Chemometrics 29:528-536.
  15. Flores G, Ruiz Del Castillo ML, Herraiz M, Blanch GP. 2006. Study of the adulteration of olive oil with hazelnut oil by on-line coupled high performance liquid chromatographic and gas chromatographic analysis of filbertone. Food Chemistry 97:742-749.
  16. Geladi P, McDougall D, Martens H. 1985. Linearization and scatter-correction for near-infrared reflectance spectra of meat. Applied Spectroscopy 39:491-500.
  17. Goodarcre R, York EV, Heald JK, Scott IM. 2003. Chemometric discrimination of unfractionated plant extracts analyzed by electrospray mass spectrometry. Phytochemistry 62:859-863.
  18. Hong SJ, Lee AY, Han YH, Park JM, So JD, Kim GS. 2018. Rancidity prediction of soybean oil by using near infrared spectroscopy techniques. Journal of Biosystems Engineering 43:219-228.
  19. Hori R, Sugiyama J. 2002. A combined FT-IR microscopy and principal component analysis on softwood cell walls. Carbohydrate Polymers 52:449-453.
  20. Jomtib N, Prommuak C, Goto M, Sasaki M, Shotipruk A. 2011. Effect of co-solvents on transesterification of refined palm oil in supercritical methanol. Engineering Journal 15:49-58.
  21. Jung SY, Park CS. 2015. Variable selection with nonconcave penalty function on reduced-rank regression. Communications for Statistical Applications and Methods 22:41-54.
  22. Kupper L, Heise HM, Lampen P, Davies AN, McIntyre P. 2001. Authentication and quantification of extra virgin olive oils by attenuated total reflectance infrared spectroscopy using silver halide fiber probes and partial least-squares calibration. Applied Spectroscopy 55:563-570.
  23. Kutner M, Nachtsheim CJ, Neter J, Li W. 2008. Applied linear statistical models (5th ed.). Journal of American Statistical Association 103:880-880.
  24. Kvalheim OM, Karstang TV. 1989. Interpretation of latent-variable regression models. Chemometrics and Intelligent Laboratory System 7:39-51.
  25. Lai YW, Kemsley EK, Wilson RH. 1995. Quantitative analysis of potential adulterants of extra virgin olive oil using infrared spectroscopy. Food Chemistry 53:95-98.
  26. Lazraq A, Cleroux R, Gauchi JP. 2003. Selecting both latent and explanatory variables in the PLS1 regression model. Chemometrics and Intelligent Laboratory Systems 66:117-126.
  27. Lerma-Garcia MJ, Ramis-Ramos G, Herrero-Martinez JM, Simo-Alfonso EF. 2010. Authentication of extra virgin olive oils by Fourier transform infrared spectroscopy. Food Chemistry 118:78-83.
  28. Liang P, Wang H, Chen C, Ge F, Liu D, Li S, Han B, Xiong X, Zhao S. 2013. The use of Fourier transform infrared spectroscopy for quantification of adulteration in virgin walnut oil. Journal of Spectroscopy 2013.
  29. Lim JG, Kim GY, Mo CY, Oh KM, Kim GS, Yoo HC, Ham HH, Kim YT, Kim SM, Kim MS. 2017. Rapid and nondestructive discrimination of Fusarium Asiaticum and Fusarium Graminearum in hulled barley (Hordeum vulgare L.) using near-infrared spectroscopy. Journal of Biosystems Engineering 42:301-313.
  30. Lohumi S, Lee S, Cho BK. 2015. Optimal variable selection for Fourier transform infrared spectroscopic analysis of starch-adulterated garlic powder. Sensors and Actuators B 216:622-658.
  31. Marigheto NA, Kemsley EK, Defernez M, Wilson RH. 1998. A comparison of mid-infrared and Raman spectroscopies for the authentication of edible oils. Journal of the American Oil Chemist's Society 75:987-992.
  32. Masohan A, Parsad G, Khanna MK, Chopra SK, Rawat BS, Garg MO. 2000. Estimation of trace amounts of benzene in solvent-extracted vegetable oils and oil seed cakes. Analyst 125:1687-1689.
  33. McMullin D, Mizaikoff B, Krska R. 2015. Advancements in IR spectroscopic approaches for the determination of fungal derived contaminations in food crops. Analytical and Bioanalytical Chemistry 407:653-660.
  34. Mo C, Lim J, Kwon SW, Lim DK, Kim MS, Kim G, Kang J, Kwon KD, Cho BK. 2017. Hyperspectral imaging and partial least square discriminant analysis for geographical origin discrimination of white rice. Journal of Biosystems Engineering 42:293-300.
  35. Muick L, Norgaad L, Englesen S, Bro R, Andersson C. 1998. Chemometrics in food science-a demonstration of the feasibility of a highly exploratory, inductive evaluation strategy of fundamental scientific significance. Chemometrics and Intelligent Laboratory System 14:31-60.
  36. Ning XF, Gong YJ, Chen YL, Li H. 2018. Construction of a ginsenoside content-predicting model based on hyperspectral imaging. Journal of Biosystems Engineering 43:369-378.
  37. Park MK, Yoo JH, Lee JB, Im GJ, Kim DH, Kim W-II. 2013. Detection of heavy metal content in sesame oil samples grown in Korea using microwave-assisted acid digestion. Journal of Food Hygiene and Safety 28:45-49.
  38. Qin J, Kim MS, Chao K, Cho BK. 2017. Raman chemical imaging technology for food and agricultural application. Journal of Biosystems Engineering 42:170-189.
  39. Rajalahti T, Arneberg R, Berven F, Myhr KM, Ulvik RJ, Kvalheim OM. 2009a. Biomarker discovery in mass spectral profiles by means of selectivity ratio plot. Chemometrics and Intelligent Laboratory System 95:35-48.
  40. Rajalahti T, Arneberg R, Kroksveen AC, Berle M, Myhr KM, Kvalheim OM. 2009b. Discriminating variable test and selectivity ratio plot: Quantitative tools for interpretation and variable (biomarker) selection in complex spectral or chromatographic profiles. Analytical Chemistry 81:2581-2590.
  41. Richardson M. 2009. Principal component analysis. pp. 1-23. Accessed in on 1 September 2018
  42. Rinnan A, Norgaard L, van den Berg F, Thygesen J, Bro R, Engelsen SB. 2009. Data pre-processing. Infrared Spectroscopy for Food Quality Analysis and Control Edited by Da-Wen Sun. Elsevier Inc., Amsterdam, Netherlands.
  43. Rohman A, Man YBC. 2010. Fourier transform infrared (FTIR) spectroscopy for analysis of extra virgin olive oil adulterated with palm oil. Food Research International 43:886-892.
  44. Rusak DA, Brown LM, Martin SD. 2003. Classification of vegetable oils by principal component analysis of FTIR spectra. Journal of Chemical Education 80:541-543.
  45. Sanchez AB, Budziak D, Martendal E, Carasek E. 2012. Determination of benzene in beverages by solid-phase micro-extraction and gas chromatography. Scientia Chromatographic 4:209-216.
  46. Saxena DK, Sharma S, Sambi S. 2011. Comparative extraction of cottonseed oil by n-hexane and ethanol. Journal of Engineering and Applied Sciences 6:84-89.
  47. Setiowaty G, Che Man YB, Jinap S, Moh MH. 2000. Quantitative determination of peroxide value in thermally oxidized palm olein by Fourier transform infrared spectroscopy. Phytochemical Analysis 11:74-78.
  48. Stevens JP. 2009. Applied multivariate statistics for the social sciences (5th ed.). Routledge, New York, USA.
  49. Styarini DO, Zaus O, Hamim N. 2011. Validation and uncertainty estimation of analytical method for determination of benzene in beverages. Eurasian Journal of Analytical Chemistry 6:159-172.
  50. Tapp HS, Defernez M, Kemsley EK. 2003. FTIR spectroscopy and multivariate analysis can distinguish geographical origin of extra virgin olive oil. Journal of Agricultural and Food Chemistry 51:6110-6115.
  51. Van de Voort FR, Sedman J, Emo G, Ismail AA. 1992. Rapid and direct iodine value and saponification number determination of fats and oils by attenuated total reflectance/Fourier transform infrared spectroscopy. Journal of American Oil Chemist's Society 69:118-1123.
  52. Vigliani EC, Saita G. 1964. Benzene and leukaemia. The New England Journal of Medicine 271:872-876.
  53. Vigliani EC. 1976. Leukaemia associated with benzene exposure. Annals of the New York Academy of Sciences 271:143-151.
  54. Vinci RM, Jacxsens L, Loco JV. 2012. Assessment of human exposure to benzene through foods from the Belgian market. Chemosphere 88:1001-1007.
  55. Wang YL, Bollard ME, Keun H, Antti H, Beckonert O, Ebbels TM, Lindon JC, Holmes E, Tang HR, Nicholson JK. 2003. Spectral editing and pattern recognition methods applied to high-resolution magic-angle spinning H-1 nuclear magnetic resonance spectroscopy of liver tissues. Analytical Biochemistry 322:26-32.
  56. Yang CC, Novell CG, Marin DP, Ginel JEG, Varo AG, Cho HJ, Kim MS. 2015. Differentiate of beef and fish meals in animal feeds using chemometrics and analytic models. Journal of Biosystems Engineering 40:153-158.