Identification and Quantitation of Volatile Organic Compounds from Oxidation of Linseed Oil

Solid phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) served to identify and quantitate the volatile organic compounds (VOCs) formed in the degradative oxidation of linseed oil. SPME involved experiments under nitrogen and oxygen atmosphere, two oil types (raw and boiled), and two different methods of sampling the head space to differentiate between the oxidation products and the oil impurities. Further experiments entailed the oxidation of neat linoleic and linolenic acids to assist with the development of a detailed reaction mechanism. The majority of the detected product species originated from the oxidation of linolenic compounds, which dominate the composition of linseed oil, while 2-propenal, pentanal, hexanal, 2,4-decadienal, and hexanoic acid, among others, were released from linoleic compounds. The concentration of hexanal (7-26), 2-pentenal (25-39), 1-penten-3-ol (3.1-4.8), trans,trans-2,4-heptadienal (33-50), trans,trans-2,4-decadienal (0.7-0.8), 3,5-octadien-2-one (2.5-6.2; relative area), ethanoic acid (137-195), and hexanoic acid (18-29) increased with the progress of oxidation; the numbers in the parentheses indicate initial and final concentration (ppm) of the species in the oil in 6 h experiments.

[1]  A. Lamola,et al.  REACTIVITY OF CHOLESTEROL AND SOME FATTY ACIDS TOWARD SINGLET OXYGEN , 1974, Photochemistry and photobiology.

[2]  E. Goicoechea,et al.  Formation of oxygenated α,β-unsaturated aldehydes and other toxic compounds in sunflower oil oxidation at room temperature in closed receptacles , 2008 .

[3]  H. H. Refsgaard,et al.  Modifications of proteins by polyunsaturated fatty acid peroxidation products. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[4]  Erik Uhde,et al.  Impact of reaction products from building materials and furnishings on indoor air quality—A review of recent advances in indoor chemistry , 2007 .

[5]  P. Chang,et al.  Headspace-solid phase microextraction (HS-SPME) analysis of oxidized volatiles from free fatty acids (FFA) and application for measuring hydrogen donating antioxidant activity , 2007 .

[6]  Ramón Aparicio,et al.  Changes in the Volatile Composition of Virgin Olive Oil during Oxidation: Flavors and Off-Flavors , 1997 .

[7]  K. Andersson,et al.  Drying of linseed oil paints: a laboratory study of aldehyde emissions , 2002 .

[8]  Pentti Kalliokoski,et al.  Reference values for structure emissions measured on site in new residential buildings in Finland , 2007 .

[9]  M. Gordon,et al.  Volatile oxidation compounds in a conjugated linoleic acid-rich oil , 2009 .

[10]  H. Jeleń,et al.  Application of headspace—solid phase microextraction and multivariate analysis for plant oils differentiation , 2003 .

[11]  Peder Wolkoff.  How to measure and evaluate volatile organic compound emissions from building products. A perspective. , 1999, The Science of the total environment.

[12]  F. Haghighat,et al.  Material emission rates: Literature review, and the impact of indoor air temperature and relative humidity , 1998 .

[13]  Per Axel Clausen,et al.  Sensory and chemical evaluation of odorous emissions from building products with and without linseed oil , 2007 .

[14]  Oscar Chiantore,et al.  Drying and oxidative degradation of linseed oil , 1999 .

[15]  J. Boff,et al.  Chemistry and Reaction of Singlet Oxygen in Foods. , 2002, Comprehensive reviews in food science and food safety.

[16]  M. Gordon,et al.  Solid phase microextraction of volatile oxidation compounds in oil-in-water emulsions , 2005 .

[17]  H. Rawls,et al.  A possible role for singlet oxygen in the initiation of fatty acid autoxidation , 1970 .

[18]  David B. Min,et al.  Mechanisms and Factors for Edible Oil Oxidation , 2006 .

[19]  S. Krist,et al.  Analysis of volatile compounds and triacylglycerol composition of fatty seed oil gained from flax and false flax , 2006 .

[20]  H. Jeleń,et al.  Headspace solid-phase microextraction use for the characterization of volatile compounds in vegetable oils of different sensory quality. , 2000, Journal of agricultural and food chemistry.

[21]  Jaehwan Lee,et al.  Analysis of volatile compounds from chlorophyll photosensitized linoleic acid by headspace solid-phase microextraction (HS-SPME) , 2010 .

[22]  Juita,et al.  Mechanism of Formation of Volatile Organic Compounds from Oxidation of Linseed Oil , 2012 .

[23]  A. Jiménez,et al.  Application of solid-phase microextraction to the analysis of volatile compounds in virgin olive oils. , 2004, Journal of chromatography. A.