Professional Documents
Culture Documents
Analytical Approaches For Free Fatty Acids Assessment in Oils and Fats
Analytical Approaches For Free Fatty Acids Assessment in Oils and Fats
Analytical Approaches For Free Fatty Acids Assessment in Oils and Fats
net/publication/262309052
Analytical Approaches for free fatty acids assessment in oils and fats
CITATIONS READS
22 2,969
5 authors, including:
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
Microwave-assisted synthesis of L-cysteine-capped nickel nanoparticles for catalytic reduction of 4-nitrophenol View project
All content following this page was uploaded by Aftab Kandhro on 10 November 2014.
Analytical
View Journal
Methods
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S.T.H. Sherazi, S.
A. Mahesar, A. Khaskheli, A. Kandhro and S. uddin, Anal. Methods, 2014, DOI: 10.1039/C4AY00344F.
www.rsc.org/methods
Published on 15 May 2014. Downloaded by Middle East Technical University
Page 1 of 29 Analytical Methods
Graphical Abstract
1
2
3
FFA Analysis
4
5
Methods
6
1
2
3
4 1 Analytical Approaches for free fatty acids assessment in oils and fats
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
24 titration method is still being used in most of the edible oil industries for the
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 25 determination of FFA. Due to lack of any comprehensive review on this very important
7
8 26 topic, we have made an attempt to present a review in order to discuss various available
9
10
27 methods with special emphasis on the instrumental methods due to their high sensitivity,
1
2
3
42 1. Introduction
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 43 Vegetable oils or fats are extracted from the oilseeds in the crude form. Various refining
7
8 44 stages such as degumming, neutralization, dewaxing, bleaching and deodorization are
9
10
45 followed to convert extracted crude oils to edible oils. During processing, a number of
1
2
3
65 (b) Spectroscopic methods
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
88 2. Discussion
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
111 the practical and health concerns of benzene, various authors used alternative to benzene
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
133 attention due to the complications in the analysis and incompatible values as compared to
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
156 The benefits of proposed method included the lack of toxic solvents, analysis at room
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
180 Good agreement was found between the standard non-aqueous titrimetry method and the
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 181 proposed method. The proposed method offers high sampling rate of 40–60 sample/h
7
8 182 and considerably low cost automated system that needs minimum human intervention
9
10
183 over long periods of time. Recently a visual and green titrimetric method was proposed
1
2
3
203 high sample throughput. Recently, Fedosov et al.,27 developed a novel microtitration
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 204 method for determining the FFA in small samples of oil (5–150 mg). The method was
7
8 205 based on the optical signal of pyranine (aqueous pK 7.3), which changed its absorbance
9
10
206 and fluorescence. All reactants were dissolved in a medium with universal solubility,
1
2
3
227 utilized by various authors30-34 to develop HPLC and FIA methods. The FIA system
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 228 coupled with voltammetric detection had high sensitivity, better reproducibility, low
7
8 229 solvent consumption and excellent throughput of 60 samples/h. Unfortunately this
9
10
230 technique did not receive much attention. Li et al.,35 proposed a new method using
1
2
3
251 2.2.3. pH-metric methods
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 252 In general the low polarity and high viscosity of oils have made it impractical to use pH
7
8 253 metric methods for the determination of FFA. Lapshina et al.,37 carried out pH metric
9
10
254 measurements by extracting FFA from oil into a polar solvent. In order to facilitate
1
2
3
274 2.3. Spectroscopic methods
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
296 After the above preliminary studies, a new procedure was reported for FFA in olive oil
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 297 based on attenuated total reflectance (ATR) FTIR spectroscopic measurements using
7
8 298 partial least-squares regression (PLSR).49 The developed method was applicable to
9
10
299 samples of different categories of olive oil with analysis time of 5 min/sample. Che Man
1
2
3
319 checked by comparison to a conventional AOCS titrimetric procedure. Yu et al.,56-57
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 320 reported a new approach for the automated determination of FFA in edible oils using
7
8 321 spectral reconstitution (SR) technique. The data obtained by this technique was accurate
9
10
322 and reproducible. The developed automated method was capable of analysing ~90
1
2
3
342 saponification was reported.59 The method was automatable, and capable of analyzing
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 343 about 60 samples/h. Later on a sensitive and rapid methodology for the quantification of
7
8 344 a low levels (<0.005%) of FFA in edible oils was described using sodium hydrogen
9
10
345 cyanamide (NaHNCN) to convert FFA to their carboxylate salts.60-61 The feasibility of
1
2
3
365 After the initial work of Frankel et al.,64 there was no any further work carried out on NIR
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 366 for ten years. Majority of the methods were developed on mid IR range. In 1997, a direct
7
8 367 method for the determination of FFA in fish oil was reported.65 PLS and multiple linear
9
10
368 regression (MLR) was used for calibration and described that first derivative
1
2
3
387 A novel method was developed for the estimation of FFA content directly in high-oleic
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 388 sunflower seeds.68 For the calibration a sample set of different varieties from the harvest
7
8 389 of 2004 and 2005 was used. The developed NIR spectroscopic calibration was calculated
9
10
390 with a modified PLS algorithm, standard normal variate (SNV), detrend scatter correction
1
2
3
411 2.3.3. Raman spectrometry
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 412 Fourier transform (FT) Raman spectrometry in combination with PLS regression
7
8 413 was used for direct reagent-free determination of FFA content in olive oils and olives.
9
10
414 Oils were directly investigated in a simple flow cell, while olives were measured in a
1
2
3
435 tuna (Thunnus alalunga) using high-resolution l3C NMR spectroscopy.75 FFA carbonyl
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 436 resonances were detected at the lower field of the 13C NMR carbonyl region and used for
7
8 437 its quantitative determination. NMR data agreed with those obtained using UV
9
10
438 spectrophotometry, showed that NMR is a suitable method to follow lipolytic alterations.
1
2
3
459 determination of FFA in edible oils using an automated thermometric titration with KOH
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 460 in isopropanol as titrant.82 The end point was indicated by the strongly exothermic base-
7
8 461 catalyzed reaction between acetone and chloroform. The procedure was accurate,
9
10
462 sensitive, easy to use, fast, and highly reproducible but did not get much attention.
1
2
3
482 Conflict of Interest
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
4 503 References
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 504 1. R. D. O’Brien, Fats and Oils: Formulating and Processing for Applications,
7
8
9 505 Technomic Publishing Company, Lancaster, PA, 1998.
10
506 2. Official Methods and Recommended Practice of the American Oil Chemists
1
2
3
526 15. Z. Zhi, A. Rios and M. Valcarcel, Anal. Chim. Acta, 1996, 318, 187–194.
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 527 16. P. Linares, M. D. Luque de castro and M. Valcarcel, Anal. Chim. Acta, 1989,
7
8 528 225, 431–436.
9
10
529 17. P. G. Nouros, A. G. Constantinos and M. G. Polissiou, Anal. Chim. Acta, 1997,
1
2
3
549 34. A. Kotani, F. Kusu and K. Takamura, Anal. Chim. Acta, 2002, 465, 199–206.
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6
7
550 35. S. G. Li, H. Zhang and W. T. Xue, Eur. J. Lipid Sci. Technol., 2007, 109, 1088–
8
9 551 1094.
10
1
2
3
571 47. A. C. Lanser, G. R, List, R. K. Holloway and T. L. Mounts, J. Am. Oil Chem.
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
1
2
3
594 59. A. Al-Alawi, F. R. van de Voort and J. Sedman, J. Am. Oil Chem. Soc., 2004, 81,
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.
6 595 441–446.
7
8 596 60. A. Al-Alawi, F. R. van de Voort and J. Sedman, Spectrosc. Lett., 2005, 38, 389–
9
10
597 403.
1
2
3
617 72. X. Yu, J. Zhang, Q. Li, C. Xu and J. Gao, Trans. Chinese Soc. Agric. Machin.,
4
5
Published on 15 May 2014. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2014 19:09:24.