Archives of Pharmacal Research

, Volume 26, Issue 9, pp 697–705 | Cite as

Combined isobutoxycarbonylation andtert-butyldimethylsilylation for the GC/MS-SIM detection of alkylphenols, chlorophenols and bisphenol a in mackerel samples

  • Hyub KimEmail author
  • Jong-Ki Hong
  • Yong-Hwa Kim
  • Kyoung-Rae Kim


The alkylphenols, chlorophenols, and bisphenol A were determined by gas chromatography/mass spectrometry-selected ion monitoring (GC/MS-SIM) followed by two work-up methods for comparison: isobutoxycarbonyl (isoBOC) derivatization andtert-butyldimethylsilyl (TBDMS) derivatization. Eleven endocrine disrupting chemicals (EDCs) of phenols in biological samples were extracted with acetonitrile and then the acetonitrile layer underwent freezing filtration 60°C for 2 hours. Solid-phase extraction (SPE) was used with XAD-4 and subsequent conversion to isoBOC or TBDMS derivatives for sensitivity analysis with the GC/MS-SIM mode. For isoBOC derivatization and TBDMS derivatization the recoveries were 92.3~150.6% and 93.8~108.3%, the method detection limits (MDLs) of bisphenol A for SIM were 0.062 μg/kg and 0.010 μg/kg, and the SIM responses were linear with the correlation coefficient varying by 0.9755~0.9981 and 0.9908~0.9996, respectively. When these methods were applied to mackerel samples, the concentrations of the 11 phenol EDCs were below the MDL.

Key words

Endocrine disrupting chemicals Phenol isoBOC TBDMS Freezing filtration Method detection limits GC/MS-SIM 


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  1. Achii, G., Cellerino, G. P., dEril, G. M., and Bird, S., Simultaneous determination of 27 phenols and herbicides in water by high-performance liquid chromatography with multi-electrode electrochemical detection.J. Chromatogr. A, 697, 357–362 (1995).CrossRefGoogle Scholar
  2. Ahel, M., Giger, W., and Koch, M., Behavior of alkylphenol polyethoxylate surfactants in the aquatic environment-1. Occurrence and transformation in sewage treatment.Water Res., 28, 1131–1142 (1994).CrossRefGoogle Scholar
  3. Ahel, M., McEvoy, J., and Giger, W., Bioaccumulation of the lipophilic metabolites of nonionic surfactants in freshwater organisms.Environ. Pollut., 79, 243–248 (1993).PubMedCrossRefGoogle Scholar
  4. Boyd, Th. J., Identification and quantification of mono-, di- and trihydroxybenzenes (phenols) at trace concentrations in seawater by aqueous acetylation and gas chromato-graphicmass spectrometric analysis.J. Chromatogr., 662, 281–292 (1994).CrossRefGoogle Scholar
  5. Buchholz, K. D. and Pawlizyn, J., Optimization of solid-phase microextraction conditions for determination of phenols.Anal. Chem., 66, 160–167 (1994).CrossRefGoogle Scholar
  6. Cline, R. E., Todd, G. D., Ashley, D. L., Grainger, J., McCraw, J. M., Alley C. C., and Hill, R. H., Gas chromatographic and spectral properties of pentafluorobenzyl derivatives of 2,4-dichlorophenoxyacetic acid and Metabolite.J. Chromatogr. Sci., 28, 167–172 (1990).PubMedGoogle Scholar
  7. Ekelund, R., Bergman, A., Granmo, A. and Berggren, M., Bioaccumulation of 4-nonylphenol in marine animals a re-evaluation.Environ. Pollut., 64, 107–120 (1990).“EPA method 625, Base/neutrals and acids”; http://www.epa. gov/epaoswer/hazwaste/test17.PubMedCrossRefGoogle Scholar
  8. Heberer, T. and Stan, H. J., Detection of more than 50 substituted phenols as theirt-butyldimethylsilyl derivatives using gas chromatography-mass spectrometry.Anal, Chemical Acta, 341, 21–34 (1997).CrossRefGoogle Scholar
  9. Herterrich, R., Gas chromatographic determination of nitro-phenols in atmospheric liquid water and airborne particulates.J. Chromatogr., 549, 313–324 (1991).CrossRefGoogle Scholar
  10. Isobe, T., Takada, H., and Ogura, N., No. 32 Annual Meeting of Japan Society On Water Environment, Chiba, Tokyo, March, 17 (1998).Google Scholar
  11. Japan Environment Agency.Strategic Programs on Environmental; JEA: Tokyo, May 1998.Google Scholar
  12. Kim, K. R. and Kim, H., Gas chromatographic profiling and screening for phenols as isobutoxycarbonyl derivatives in aqueous samples.J. Chromatogr. A, 866, 87–96 (2000).PubMedCrossRefGoogle Scholar
  13. Lamprecht, G. and Huber, J. F. K., Ultra-trace analysis of phenols in water using high-performance liquid chromatography with on-line reaction detection.J. Chromatogr., 667, 47–57 (1994).CrossRefGoogle Scholar
  14. Lee, H. B. and Chau, S. Y., Analysis of pesticide residues by chemical derivatization, VII. Chromatographic properties of pentafluorobenzyl ether derivatives of thirty two phenols.J. Assoc. Off. Anal. Chem., 66(4), 1029–1038 (1983).Google Scholar
  15. Pocurull, E., Sánchez, G., Borrull F., and Marcé, R. M., Automated on-line trace enrichment and determination of phenolic compounds in environmental waters by high-performance liquid chromatography.J. Chromatogr. A, 696, 31–39 (1995).CrossRefGoogle Scholar
  16. Ruana, J., Urbe, I., and Burull, F., Determination of phenols at the ng/L level in drinking and river waters by liquid chromatography with UV and electrochemical detection.J. Chromatogr. A, 655, 217–226 (1993).PubMedCrossRefGoogle Scholar
  17. Street, H. V., Estimation and identification in blood plasma of paracetamol (N-Acetyl-p-Aminophenol) in the presence of barbiturates.J. Chromatogr., 109, 29–36 (1975).PubMedGoogle Scholar
  18. Tulp, M. T. M. and Hutzinger, O., Use of ethylesters deuteriomethyl ethers and cyclicn-butylboronates of hydroxy chlorobiphenyls in identification of polychlorinated biphenyls.J. Chromatogr., 139, 51–58 (1977).PubMedCrossRefGoogle Scholar
  19. Wahlberg, C., Renberg, L., and Wideqvist, U., Determination of nonylphenol and nonylphenol ethoxylates as their pentafluorobenzoates in water, sewage sludge and biota.Chemosphere, 20, 179–186 (1990).CrossRefGoogle Scholar
  20. Wennrich, L., Efer J., and Engewald, W., Gas chromatographic trace analysis of underivatized nitrophenols.Chromatographia, 41, 361–366 (1995).CrossRefGoogle Scholar

Copyright information

© The Pharmaceutical Society of Korea 2003

Authors and Affiliations

  • Hyub Kim
    • 1
    Email author
  • Jong-Ki Hong
    • 2
  • Yong-Hwa Kim
    • 3
  • Kyoung-Rae Kim
    • 4
  1. 1.Technology Innovation CenterSangju National UniversitySangjuKorea
  2. 2.Hazardous Substance Research TeamKorea Basic Science InstituteSeoulKorea
  3. 3.Korea Research Institute of Chemical TechnologyTaejeonKorea
  4. 4.College of PharmacySungkyunkwan UniversitySuwonKorea

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