Differentiation of wood-derived vanillin from synthetic vanillin in distillates using gas chromatography/combustion/isotope ratio mass spectrometry for δ13C analysis

Katryna A. van Leeuwen, Paul D. Prenzler, Danielle Ryan, Mauro Paolini, Federica Camin

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3 Citations (Scopus)

Abstract

Rationale: Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ13C values, the δ13C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). Methods: The δ13C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ13C values of vanillin and to compare them with values for other sources of vanillin. Results: δ13C values were determined for: natural vanillin extracts (−21.0 to −19.3‰, 16 samples); vanillin ex-lignin (−28.2‰, 1 sample); and synthetic vanillin (−32.6 to −29.3‰, 7 samples). Seventeen tannin samples were found to have δ13C values of −29.5 to −26.7‰, which were significantly different (p < 0.05) from those of the natural and synthetic vanillins. The vanillin δ13C values measured in distillates (−28.9 to −25.7‰) were mainly in the tannin range, although one spirit (−32.5‰) was found to contain synthetic vanillin. Conclusions: The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ13C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates.

Original languageEnglish
Pages (from-to)311-318
Number of pages8
JournalRapid Communications in Mass Spectrometry
Volume32
Issue number4
Early online dateNov 2017
DOIs
Publication statusPublished - 28 Feb 2018

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Isotopes
Gas chromatography
Mass spectrometry
Wood
Tannins
vanillin
Lignin
Flavors
Methylene Chloride
Ether
Dilution
Ethanol

Cite this

@article{40c7d3d364d34694af4119e6be067a7e,
title = "Differentiation of wood-derived vanillin from synthetic vanillin in distillates using gas chromatography/combustion/isotope ratio mass spectrometry for δ13C analysis",
abstract = "Rationale: Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ13C values, the δ13C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). Methods: The δ13C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ13C values of vanillin and to compare them with values for other sources of vanillin. Results: δ13C values were determined for: natural vanillin extracts (−21.0 to −19.3‰, 16 samples); vanillin ex-lignin (−28.2‰, 1 sample); and synthetic vanillin (−32.6 to −29.3‰, 7 samples). Seventeen tannin samples were found to have δ13C values of −29.5 to −26.7‰, which were significantly different (p < 0.05) from those of the natural and synthetic vanillins. The vanillin δ13C values measured in distillates (−28.9 to −25.7‰) were mainly in the tannin range, although one spirit (−32.5‰) was found to contain synthetic vanillin. Conclusions: The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ13C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates.",
author = "{van Leeuwen}, {Katryna A.} and Prenzler, {Paul D.} and Danielle Ryan and Mauro Paolini and Federica Camin",
year = "2018",
month = "2",
day = "28",
doi = "10.1002/rcm.8031",
language = "English",
volume = "32",
pages = "311--318",
journal = "Rapid Communications in Mass Spectrometry",
issn = "0951-4198",
publisher = "John Wiley & Sons",
number = "4",

}

TY - JOUR

T1 - Differentiation of wood-derived vanillin from synthetic vanillin in distillates using gas chromatography/combustion/isotope ratio mass spectrometry for δ13C analysis

AU - van Leeuwen, Katryna A.

AU - Prenzler, Paul D.

AU - Ryan, Danielle

AU - Paolini, Mauro

AU - Camin, Federica

PY - 2018/2/28

Y1 - 2018/2/28

N2 - Rationale: Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ13C values, the δ13C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). Methods: The δ13C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ13C values of vanillin and to compare them with values for other sources of vanillin. Results: δ13C values were determined for: natural vanillin extracts (−21.0 to −19.3‰, 16 samples); vanillin ex-lignin (−28.2‰, 1 sample); and synthetic vanillin (−32.6 to −29.3‰, 7 samples). Seventeen tannin samples were found to have δ13C values of −29.5 to −26.7‰, which were significantly different (p < 0.05) from those of the natural and synthetic vanillins. The vanillin δ13C values measured in distillates (−28.9 to −25.7‰) were mainly in the tannin range, although one spirit (−32.5‰) was found to contain synthetic vanillin. Conclusions: The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ13C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates.

AB - Rationale: Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ13C values, the δ13C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). Methods: The δ13C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ13C values of vanillin and to compare them with values for other sources of vanillin. Results: δ13C values were determined for: natural vanillin extracts (−21.0 to −19.3‰, 16 samples); vanillin ex-lignin (−28.2‰, 1 sample); and synthetic vanillin (−32.6 to −29.3‰, 7 samples). Seventeen tannin samples were found to have δ13C values of −29.5 to −26.7‰, which were significantly different (p < 0.05) from those of the natural and synthetic vanillins. The vanillin δ13C values measured in distillates (−28.9 to −25.7‰) were mainly in the tannin range, although one spirit (−32.5‰) was found to contain synthetic vanillin. Conclusions: The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ13C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates.

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U2 - 10.1002/rcm.8031

DO - 10.1002/rcm.8031

M3 - Article

VL - 32

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SN - 0951-4198

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