A study on the calibration characteristics of organic fatty acids designated as new offensive odorants by cryogenic trapping-thermal desorption technique

유기지방산 신규악취물질에 대한 저온농축 열탈착방식 (Thermal desorber)의 검량특성 연구

  • Received : 2009.09.11
  • Accepted : 2009.11.27
  • Published : 2009.12.25

Abstract

In this study, analytical methodology for several organic fatty acids (OFA: propionic acid (PA), butyric acid (BA), isovaleric acid (IA), and valeric acid (VA)) designated as new offensive odorants in Korea (as of year 2010) was investigated along with some odorous VOCs (styrene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, and isobutyl alcohol). For this purpose, working standards (WS) containing all of these 13 compounds were loaded into adsorption tube filled with Tenax TA, and analyzed by gas chromatography (GC) system thermal desorber interfaced with. The analytical sensitivities of organic fatty acids expressed in terms of detection limit (both in absolute mass (ng) and concentration (ppb)) were lower by 1.5-2 times than other compounds (PA: 0.24 ng (0.16 ppb), BA: 0.19 ng (0.11 ppb), IA: 0.15 ng (0.07 ppb), and VA: 0.28 ng (0.13 ppb)). The precision of BA, IA, and VA, if assessed in terms of relative standard error (RSE), maintained above 5%, while the precison of other compounds were below 5%. The reproducibility of analysis improved with the aid of internal standard calibration (PA: $1.1{\pm}0.4%$, BA: $10{\pm}0.46$, IA; $12{\pm}0.3%$, VA: $4{\pm}0.1%$), respectively. The results of this study showed that organic fatty acid can be analyzed using adsorption tube and thermal desorber in a more reliable way to replace alkali absorption method introduced in the odor prevention law of the Korea Ministry of Environment (KMOE).

Keywords

organic fatty acid;offensive odorants;thermal desorber;Tenax TA;internal standard

References

  1. 환경부, 악취방지법 (2005)
  2. L. Otten, M.T. Afzal, and D.M. Mainville, Biofiltration of odours: laboratory studies using butyric acid, Advances in Environmental Research, 8, 397-409 (2004) https://doi.org/10.1016/S1093-0191(02)00119-3
  3. Nagata, Y., 臭度及び嗅値について, 空氣淸淨, 41(2), 17-25(2003)
  4. I. G. Zenkevich and E. D. Makarov, Chromatographic quantitation at losses of analyte during sample preparation. Application of the modified method of double internal standard, J. Chromatography A, 1150, 117-123 (2007) https://doi.org/10.1016/j.chroma.2006.08.083
  5. W.-T. Chang, D.-L. Lin, and R. H. Liu, Isotopic analogs as internal standards for quantitative analyses by GC/MS-evaluation of cross-contribution to ions designated for the analyte and the isotopic internal standard, Forensic Science International, 121, 174-182(2001) https://doi.org/10.1016/S0379-0738(01)00396-6
  6. M. Abalos and J.M. Bayona, Application of gas chromatography coupled to chemical ionization mass spectrometry following headspace solid-phase microextraction for the determination of free volatile fatty acids in aqueous samples, J. Chromatography A, 891, 287-294(2000) https://doi.org/10.1016/S0021-9673(00)00655-5
  7. S.-I. Yun and Y. Ohta, Removal of volatile fatty acids with immobilized rhodococcus sp. B261, Bioresource Technology, 96, 41-46(2005) https://doi.org/10.1016/j.biortech.2004.03.006
  8. K. Wrobel, K. Wrobel, G.Cruz-Jimenez, and F. Angulo-Remero, Application of internal standard for micro extraction-spectrophotometric determination of copper in serum and in natural waters, Analytica Chimica Acta, 387, 217-224(1999) https://doi.org/10.1016/S0003-2670(99)00031-8
  9. A. Bories, J.-M. Guillot, Y. Sire, M. Couderc, S.-A. Lemaire, V. Kreim and J.-C. Roux, Prevention of volatile fatty acids production and limitation of odours from winery wastewaters by denitrification, Water Research, 41, 2987-2995(2007) https://doi.org/10.1016/j.watres.2007.03.022
  10. 김종보, 김태현, 김태화, 주도원, 임문순, On-line 열탈착기와 GC/FID를 이용한 환경대기 중 유기산 성분 (프로피온산, n-뷰티르산, n-발레르산, i-발레르산)들의 분석방법 연구, 한국냄새환경학회지, 7(4), 231-237(2008)
  11. A. Keshav, K.L. Wasewar, and S. Chand, Recovery of propionic acid from and aqueous stream by reactive extraction: effect of diluents, Desalination, 244, 12-23 (2009) https://doi.org/10.1016/j.desal.2008.04.032
  12. K.Y. Kono, 'Malodor Preventive Low: Editorial Supervision for Special Pollution Section of Air Preservation Department if the Ministry of Environment in Japan'. 13-35, Gyousei Inc., 1993
  13. L. Martensson, M. Magnusson, Y. Shen, and J. A. Jonsson, Air concentration of volatile organic acids in confined animal buildings-determination with ion chromatography, Agriculture, Ecosystem and Environment, 75, 101-108(1999) https://doi.org/10.1016/S0167-8809(99)00072-9
  14. C. Ibanez, Analysis of total propionic acid in feed using headspace solid-phase microextraction and gas chromatography, J. Chromatography A, 1017, 161-166(2003) https://doi.org/10.1016/j.chroma.2003.08.017
  15. G. Manni and F. Caron, Calibration and determination of volatile fatty acids in waste leachates by gas chromatography, J. Chromatography A, 690, 237-242(1995) https://doi.org/10.1016/0021-9673(94)01081-O
  16. P. Araujo, F. Couillard, E. Leirnes, K. Ask, A. Bokevoll and L. Froyland, Experimental design consideration s in quantification experiments by using the internal standard technique: Cholesterol determination by gas chromatography as a case study, J. Chromatography A, 1121, 99-105(2006) https://doi.org/10.1016/j.chroma.2006.03.119

Acknowledgement

Supported by : 한국학술진흥재단