Quantitation of Methanol & Acetaldehyde from Raw & Black Garlic by Headspace GC with PLOT Column

  • Authors

    • Chang-Hwan Oh
    2018-12-13
    https://doi.org/10.14419/ijet.v7i4.39.24378
  • Black garlic, Methanol, Acetaldehyde, Headspace sampling, GC-FID, PLOT column.
  • Background/Objectives: Black garlic is produced by heating a garlic at 60~70°C for a couple of weeks. Methanol and acetaldehyde are toxic chemicals that could be produced naturally from plant materials.

    Methods/Statistical analysis: Methanol and acetaldehyde contents in the raw and black garlic were measured. Manual static headspace (HS) sampling method was established and GC analysis with PLOT column was applied. Black garlic was prepared in a rice cooker at 60~70°C for three weeks followed by drying for two weeks. The ratio of water and mashed garlic for the preparation of the garlic extract was optimized.

    Findings: The optimum ratio between the garlic sample and water was 1:2 for the preparation of headspace liquid sample. The HS sample in the 20mL vial (containing 3 mL of garlic extract) was analyzed. Acetaldehyde detected as large amount comparing to methanol was almost gone in black garlic. It might be too volatile to survive in that harsh condition such as heating at 60~70°C for a couple of weeks. The analyzed methanol content in the black garlic was about 6 times higher than the raw garlic. That means the methanol derived from the pectin might be increased even at the relatively mild heating condition. If two weeks of the drying period was considered, actual amount of methanol occurred during the heating process might be higher than that. The naturally occurring methanol from the plant materials containing pectin is very popular in our dish. Moreover, the heating process is the essential part of cooking. Hazardous chemicals such as methanol are more likely to be present during common cooking processes.

    Improvements/Applications: The manual headspace sampling is very simple and easy to apply even without the expensive instruments specifically dedicated for the automatic headspace sampling. Moreover, the PLOT column is also a very efficient tool even without the concentration trap to decrease the peak width. The method could be applied in any laboratory if they have a GC-FID.

     

     

  • References

    1. [1] Corzo-Martinez M, Corzo N, Villamiel M. Biological properties of onions and garlic. Trends Food Sci Tech. 2007 Dec:18(12):609-25.

      [2] Lei M, Zhang Z, Liu R, Zhang M, Xu M, The physicochemical changes of black garlic during thermal processing. Adv J Food Sci Technol. 2015 Mar:7(9):712-5.

      [3] Wikipedia. Black garlic [Internet]. Wikimedia Foundation Inc.; [updated 2018 Aug 21; cited 2018 Sep 14]. Available from: https://en.wikipedia.org/wiki/Black_garlic

      [4] Ryu JH, Kang D. Physicochemical properties, biological activity, health benefits, and general limitations of aged black garlic: A review. Molecules. 2017 Jan:22(6):919. DOI:10.3390/molecules22060919.

      [5] Block E. The organosulfur chemistry of the genus Allium - Implications for the organic chemistry of sulfur. Angew Chem Int Ed Engl. 1992 Sep:31(9):1135-78.

      [6] Woo KS, Yoon HS, Lee YR, Lee JH, Kim DJ, Hong JT, Jeong HS. Characteristics and antioxidative activity of volatile compounds in heated garlic (Allium sativum), Food Sci Biotechnol. 2007 Oct:16(5):822-7.

      [7] Kim NY, Park MH, Jang EY, Lee JH. Volatile distribution in garlic (Allium sativum L.) by solid phase microextraction (SPME) with different processing conditions, Food Sci Biotechnol. 2011 Jun:20(3):775-82.

      [8] National Institute of Standards and Technology, NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Acetaldehyde. [Internet]: Washington: U.S. Department of Commerce; [updated 2017 Jun 21; cited 2018 Sep 14]. Available from: https://webbook.nist.gov/cgi/cbook.cgi?ID=C75070&Mask=2000#Gas-Chrom

      [9] National Institute of Standards and Technology. NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Acetaldehyde. [Internet]: Washington: U.S. Department of Commerce; [updated 2017 Jun 21; cited 2018 Sep 14]. Available from: https://webbook.nist.gov/cgi/cbook.cgi?ID=C67561&Units=SI&Mask=2000#Gas-Chrom

      [10] U.S. Environmental Protection Agency. Acetaldehyde, 75-07-0, Hazard Summary. [Internet]: Research Triangle Park, NC: c1992 [updated 2000 Jan; cited 2018 Sep 14]. Available from: https://www.epa.gov/sites/production/files/2016-09/documents/acetaldehyde.pdf

      [11] National Toxicology Program. Acetaldehyde, CAS No. 75-07-0, Report on Carcinogens, Fourteenth Edition. [Internet]. Durham: U.S. Department of Health and Human Services; [updated 2016 Nov 3; cited 2018 Sep 14]. Available from: https://ntp.niehs.nih.gov/ntp/roc/content/profiles/acetaldehyde.pdf

      [12] Wright AH, Delong JM, Arul J, Prange RK. The trend toward lower oxygen levels during apple (Malus domestica Borkh) storage – A review. J Hortic Sci Biotechnol. 2015 Nov:90(1):1-13.

      [13] U.S. Environmental Protection Agency. Environmental Criteria and Assessment Office, Health Assessment Document for Acetaldehyde. OHEA Review ECAO-R-056 HERO 69104. [Internet]: Research Triangle Park, NC: [updated 1991 Apr; cited 2018 Sep 14]. Available from: https://hero.epa.gov/hero/index.cfm/reference/details/reference_id/69104

      [14] U.S. Office of Environmental Health Hazard Assessment. Proposition 65 Interpretive guideline No. 2012-01 Consumption of methanol resulting from pectin that occurs naturally in fruits and vegetables. [Internet]. California: California Environmental Protection Agency (US); [updated 2012 March; cited 2018 Sep 14]. Available from: https://oehha.ca.gov/media/downloads/proposition-65/chemicals/ig12001methanol.pdf

      [15] Lund ED, Kirkland CL and Shaw EW. Methanol, ethanol and acetaldehyde contents of citrus products. J Agric Food Chem. 1981 Mar:29(2):361-6.

      [16] Adams A. Quantification of aspartame in diet sodas [dissertation]. [Monmouth (OR)]: Western Oregon University; 2016. 61 p.

      [17] European Food Safety Authority (EFSA). EFSA Panel on Food Additives and Nutrient Sources added to Food. Scientific Opinion on the re-evaluation of aspartame (E 951) as a food additive. EFSA J [Internet]. 2013 [cited 2018 Sep 14]; 11(12):3496:1-263. doi:10.2903/j.efsa.2013.3496. Available from: http://www.europarl.europa.eu/meetdocs/2009_2014/documents/envi/dv/envi20131216_efsa-aspartame_/envi20131216_efsa-aspartame_en.pdf

      [18] Dorokhov YL, Shindyapina AV, Sheshukova EV, Komarova TV. Metabolic methanol: Molecular pathways and physiological roles. Physiol Rev. 2015 Apr:95:603-44.

      [19] Diaz JV, Anthon GE, Barrett DM. Nonenzymatic degradation of citrus pectin and pectate during prolonged heating: Effects of pH, temperature, and degree of methyl esterification, J Agric Food Chem. 2007 Jun:55(13):5131-6.

      [20] Massiot P, Perron V, Baron A, Drilleau JF. Release of methanol and depolymerization of highly methyl esterified apple pectin with an endopolygalacturonase from Aspergillus niger and Pectin methylesterases from A. niger or from Orange, LWT-Food Sci Technol. 1997 Nov:30(7):697-702.

      [21] Sharma VK, Jadhav RK, Rao GJ, Saraf AK, Chandra H. High performance liquid chromatographic determination of alcohols with reference to body distribution of methanol. Forensic Sci Int. 1991 Sep:50(2):255-61.

      [22] Parpinello GP, Versari A. A simple high-performance liquid chromatography method for the analysis of glucose, glycerol, and methanol in a bioprocess, J Chromatogr Sci. 2000 Jun:38(6):259-61.

      [23] Vogel M, Büldt A, Karst U. Hydrazine reagents as derivatizing agents in environmental analysis - a critical review. Fresenius J Anal Chem. 2000 Apr:366(8):781–91.

      [24] Guan X, Rubin E, Anni H. An optimized method for the measurement of acetaldehyde by high-performance liquid chromatography. Alcohol Clin Exp Res. 2012 Mar:36(3):398–405. DOI:10.1111/j.1530-0277.2011.01612.x.

      [25] Oh CH, Lee YJ, Min SH. Estimation of methanol exposure level via alcoholic beverage consumed by Jecheon citizen, South Korea. Korean J Food & Nutr. 2013 Mar:26(1):44-50. Korean.

      [26] Schmarr HG, Wacker M, Mathes M. Isotopic separation of acetaldehyde and methanol from their deuterated isotopologues on a porous layer open tubular column allows quantification by stable isotope dilution without mass spectrometric detection. J Chromatogr A. 2017 Jan:1481(20):111-15.

      [27] Zeeuw J, Majors RE. The development and applications of PLOT columns in gas-solid chromatography. LCGC. 2010 Oct:28(10):848-64.

      [28] Oh CH. Volatile profile comparison for the Astragali Radix according to drying methods, Indian J Sci Technol. 2015 Oct:8(26):1-7. DOI: 10.17485/ijst/2015/v8i26/80761.

      [29] Uebelacker M, Lachenmeier DW. Quantitative determination of acetaldehyde in foods using automated digestion with simulated gastric fluid followed by headspace gas chromatography. J Autom Methods Manag Chem. 2011 Jun:907317. DOI:10.1155/2011/907317

      [30] Possner D, Zimmer T, Kurbel P, Dietrich H. Methanol contents of fruit juices and smoothies in comparison to fruits and a simple method for the determination thereof. Deut Lebensm Rundsch. 2014 Feb:110(2):65-9.


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    Oh, C.-H. (2018). Quantitation of Methanol & Acetaldehyde from Raw & Black Garlic by Headspace GC with PLOT Column. International Journal of Engineering & Technology, 7(4.39), 571-575. https://doi.org/10.14419/ijet.v7i4.39.24378