Abstract
Methods to identify and quantify synthetic phenolic antioxidants, 3-tert-butyl-4-hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tert-butyl-hydroquinone (TBHQ) and propyl gallate (PG), in biodiesel samples by using reversed-phase liquid chromatography (LC) were developed. Using a C18 phase with LC and UV detection showed co-elution between BHT and fatty acid methyl esters (FAME) in the biodiesel sample, whereas an alkyl phenyl modified stationary phase resulted in good separation of all antioxidants from the fatty acid matrix, and allowed more accurate quantification of antioxidants in biodiesel samples. The latter column was applied for further study. Calibration curves for the four antioxidants were constructed, and the limit of detection estimated. Good calibration linearity was observed over the investigated concentration range of 10–80 ppm, with correlation coefficients (R2) ranging from 0.9986 to 0.9995 for all antioxidants. LOD values of 0.010, 0.015, 0.0125 and 0.030 ppm, and recoveries of 70 ± 2, 85 ± 2, 103 ± 2 and 92 ± 4% for PG, TBHQ, BHA and BHT at injected concentrations of 35 ppm were established, respectively. The method was applied for quantification of antioxidants in biodiesel without addition of spiked antioxidants, then for biodiesel spiked with the four antioxidants, and a commercial source of biodiesel with BHT addition. Identification of FAME in the biodiesel samples was performed by using an instrument capable of ultra-high performance LC hyphenated with an electrospray Orbitrap mass spectrometer (UHPLC–ESI-OrbitrapMS). The stability of antioxidants and FAME in different samples was then investigated. Total FAME C18 content decreased to 52 ± 4% w/w after 1 week, and 29 ± 6% w/w after 8 weeks in the test sample without antioxidants; FAME content and antioxidant composition were stable in the samples with antioxidants added, even after 8 weeks exposure to sunlight.
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Abbreviations
- BHA:
-
3-tert-Butyl-4-hydroxyanisole
- BHT:
-
Butylated hydroxytoluene
- ESI:
-
Electrospray ionisation
- LC:
-
Liquid chromatography
- MS:
-
Mass spectrometer
- PG:
-
Propyl gallate
- SPA:
-
Synthetic phenolic antioxidants
- TBHQ:
-
tert-Butyl-hydroquinone
- HPLC:
-
High-performance liquid chromatography
- UV:
-
Ultra-violet
References
Pullen J, Saeed K (2014) Factors affecting biodiesel engine performance and exhaust emissions—part I. Rev Energy 72:1–16
Goulart LA, Teixeira ARL, Ramalho DA, Terezo AJ, Castilho M (2014) Development of an analytical method for the determination of tert-butylhydroquinone in soybean biodiesel. Fuel 115:126–131
Ng J-H, Ng HK, Gan S (2010) Recent trends in policies, socioeconomy and future directions of the biodiesel industry. Clean Technol Environ Policy 12:213–238
Dunn RO (2008) Antioxidants for improving storage stability of biodiesel. Biofuels Bioprod Biorefin 2:304–318
Domingos AK, Saad EB, Vechiatto WWD, Wilhelm HM, Ramos LP (2007) The influence of BHA, BHT and TBHQ on the oxidation stability of soybean oil ethyl esters (biodiesel). J Braz Chem Soc 18:416–423
Tagliabue S, Gasparoli A, della Bella L, Bondioli P (2004) Quali-quantitative determination of synthetic antioxidants in biodiesel. Riv Ital Sostanze Gr LXXXI:37–40
da Silva YP, Dalmoro V, Ruiz YPM, Capeletti LB, Mendonça CRB, dos Santos JHZ, Piatnicki CMS (2014) Biodiesel water in oil microemulsions: ferrocene as a hydrophobic probe for direct analysis by differential pulse voltammetry at a Pt ultramicroelectrode. Anal Methods 6:9212–9219
Webster RL, Rawson PM, Evans DJ, Marriott PJ (2014) Synthetic phenolic antioxidants in conventional and alternatively-derived middle distillate fuels analysed by gas chromatography with triple quadrupole and quadrupole time of flight mass spectrometry. Energy Fuel 28:1097–1102
Kivevele T, Huan Z (2015) Influence of metal contaminants and antioxidant additives on storage stability of biodiesel produced from non-edible oils of Eastern Africa origin (Croton megalocarpus and Moringa oleifera oils). Fuel 158:530–537
Pereira GG, Alberici RM, Ferreira LL, Santos JM, Nascimento HL, Eberlin MN, Barrera-Arellano D (2015) A screening method to evaluate soybean oil-based biodiesel oxidative quality during its shelf life. J Am Oil Chem Soc 92:967–974
Rashed MM, Kalam MA, Masjuki HH, Rashedul HK, Ashraful AM, Shancita I, Ruhul AM (2015) Stability of biodiesel, its improvement and the effect of antioxidant treated blends on engine performance and emission. RSC Adv 5:36240–36261
Santos AGD, Souza LD, Caldeira VPS, Farias MF, Fernandes VJ Jr, Araujo AS (2014) Kinetic study and thermoxidative degradation of palm oil and biodiesel. Thermochim Acta 592:18–22
Yang Z, Hollebone BP, Wang Z, Yang C, Brown C, Landriault M (2014) Storage stability of commercially available biodiesels and their blends under different storage conditions. Fuel 115:366–377
Almeida JMS, Dornellas RM, Yotsumoto-Neto S, Ghisi M, Furtado JGC, Marques EP, Aucélio RQ, Marques ALB (2014) A simple electroanalytical procedure for the determination of calcium in biodiesel. Fuel 115:658–665
Chýlková J, Tomášková M, Mikysek T, Šelešovská R, Jehlička J (2012) Voltammetric determination of BHT antioxidant at gold electrode in biodiesel. Electroanalysis 24:1374–1379
Freitas HC, Almeida ES, Tormin TF, Richter EM, Munoz RAA (2015) Ultrasound-assisted digestion of biodiesel samples for determination of metals by stripping voltammetry. Anal Methods 7:7170–7176
Spudeit DA, Piovezan M, Dolzan MD, Vistuba JP, Azevedo MS, Vitali L, Oliveira MAL, Costa ACO, Micke GA (2013) Simultaneous determination of free and total glycerol in biodiesel by capillary electrophoresis using multiple short-end injection. Electrophoresis 34:3333–3340
Nogueira T, do Lago CL (2011) Determination of Ca, K, Mg, Na, sulfate, phosphate, formate, acetate, propionate, and glycerol in biodiesel by capillary electrophoresis with capacitively coupled contactless conductivity detection. Microchem J 99:267–272
Piovezan M, Costa ACO, Jager AV, de Oliveira MAL, Micke GA (2010) Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples. Anal Chim Acta 673:200–205
Okullo A, Ogwok P, Temu AK, Ntalikwa JW (2013) Gas chromatographic determination of glycerol and triglycerides in biodiesel from jatropha and castor vegetable oils. Adv Mater Res 824:436–443
Hirschegger L, Schober S, Mittelbach M (2014) Efficient and sensitive method for the quantification of saturated monoacylglycerols in biodiesel by gas chromatography–mass spectrometry. Eur J Lipid Sci Technol 116:89–96
Montpetit A, Tremblay AY (2016) A quantitative method of analysis for sterol glycosides in biodiesel and FAME using GC-FID. J Am Oil Chem Soc 93:479–487
Bezerra KS, Antoniosi Filho NR (2014) Gas chromatographic analysis of free steroids in biodiesel. Fuel 130:149–153
Farias AFF, Conceição MM, Cavalcanti EHS, Melo MAR, dos Santos IMG, de Souza AG (2016) Analysis of soybean biodiesel additive with different formulations of oils and fats. J Therm Anal Calorim 123:2121–2127
Ahmed MA, Khan I, Hashima J, Musharraf SG (2015) Sensitive determination of glycerol by derivatization using a HPLC-DAD method in biodiesel samples. Anal Methods 7:7805–7810
Fedosov SN, Fernandes NA, Firdaus MY (2014) Analysis of oil–biodiesel samples by high performance liquid chromatography using the normal phase column of new generation and the evaporative light scattering detector. J Chromatogr A 1326:56–62
Haagenson DM, Perleberg JR, Wiesenborn DP (2014) Fractionation of canola biodiesel sediment for quantification of steryl glucosides with HPLC/ELSD. J Am Oil Chem Soc 91:497–502
Allen SJ, Ott LS (2012) HPLC method for rapidly following biodiesel fuel transesterification reaction progress using a core-shell column. Anal Bioanal Chem 404:267–272
Carvalho MS, Mendonça MA, Pinho DMM, Resck IS, Suarez PAZ (2012) Chromatographic analyses of fatty acid methyl esters by HPLC-UV and GC-FID. J Braz Chem Soc 23:763–769
Brandão LFP, Braga JWB, Suarez PAZ (2012) Determination of vegetable oils and fats adulterants in diesel oil by high performance liquid chromatography and multivariate methods. J Chromatogr A 1225: 150–157
Guo L, Xie M-Y, Yan A-P, Wan Y-Q, Wu Y-M (2006) Simultaneous determination of five synthetic antioxidants in edible vegetable oil by GC–MS. Anal Bioanal Chem 386:1881–1887
Ding M, Zou J (2012) Rapid micropreparation procedure for the gas chromatographic-mass spectrometric determination of BHT, BHA and TBHQ in edible oils. Food Chem 131:1051–1055
Marriott PJ, Chin S-T, Maikhunthod B, Schmarr H-G, Bieri S (2012) Multidimensional gas chromatography. TrAC Trends Anal Chem 34:1–21
Mogollon NGS, Ribeiro FADL, Lopez MM, Hantao LW, Poppi RJ, Augusto F (2013) Quantitative analysis of biodiesel in blends of biodiesel and conventional diesel by comprehensive two-dimensional gas chromatography and multivariate curve resolution. Anal Chim Acta 796:130–136
O’Neil GW, Culler AR, Williams JR, Burlow NP, Gilbert GJ, Carmichael CA, Nelson RK, Swarthout RF, Reddy CM (2015) Production of jet fuel range hydrocarbons as a coproduct of algal biodiesel by butenolysis of long-chain alkenones. Energy Fuel 29:922–930
Jiang M, Kulsing C, Nolvachai Y, Marriott PJ (2015) Two-dimensional retention indices improve component identification in comprehensive two-dimensional gas chromatography of saffron. Anal Chem 87:5753–5761
Nolvachai Y, Marriott PJ (2013) GC for flavonoids analysis: past, current and prospective trends. J Sep Sci 36:20–36
Gao X, Williams SJ, Woodman OL, Marriott PJ (2010) Comprehensive two-dimensional gas chromatography, retention indices and time-of-flight mass spectra of flavonoids and chalcones. J Chromatogr A 1217:8317–8326
Holčapek M, Jandera P, Fischer J, Prokeš B (1999) Analytical monitoring of the production of biodiesel by high-performance liquid chromatography with various detection methods. J Chromatogr A 858:13–31
Knothe G (2007) Some aspects of biodiesel oxidative stability. Fuel Process Technol 88:669–677
Acknowledgements
PJM acknowledges the Australian Research Council for a Discovery Outstanding Researcher Award; DP130100217. MC acknowledges CAPES Foundation for financial support. The authors acknowledge Agilent Technologies and ThermoFisher Scientific for provision of support for some of the facilities used in this study.
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Casagrande, M., Kulsing, C., Althakafy, J.T. et al. Direct Analysis of Synthetic Phenolic Antioxidants, and Fatty Acid Methyl Ester Stability in Biodiesel by Liquid Chromatography and High-Resolution Mass Spectrometry. Chromatographia 82, 271–278 (2019). https://doi.org/10.1007/s10337-018-3681-3
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DOI: https://doi.org/10.1007/s10337-018-3681-3