Silyl Derivatization of Alkylphenols, Chlorophenols, and Bisphenol A for Simultaneous GC/MS Determination Donghao Li and Jongman Park* Department of Chemistry, Konkuk University, 1 Hwayangdong Gwangjingu, Seoul 143-701, Korea Jae-Ryoung Oh Korea Ocean Research and Development Institute, Ansan P.O. Box 29, Gyounggido 425-600, Korea A fast silyl derivatization technique for simultaneous GC/ MS analysis of alkylphenols, chlorophenols, and bis- phenol A was developed. The analytes were silylized with an excess amount of bis(trimethylsilyl)trifluoroacetamide (BSTFA) followed by hydrolysis of excess silyl reagent with water. Reaction rates of derivatization were studied in various solvents and found to be fastest in acetone. Derivatization reaction in acetone was completed quan- titatively within 1 5 s at room temperature while it took more than 1 h in other solvents studied. Similar results were obtained in mixed solvents with acetone if the content of acetone was higher than 6 0 % (v/ v). Since water- immiscible solvents such as dichloromethane or hexane are frequently used in the extraction of phenolic analytes in various sample matrixes, acetone can be added to the extracts in order to accelerate the reaction rate of deriva- tization. Stability of the derivatives in sample for long-term storage was ensured by hydrolyzing excess derivatizing reagent, BSTFA, with a spike of water followed by dehy- dration using anhydrous sodium sulfate. On the basis of the above results, a derivatizing treatment kit was de- signed to improve the convenience of analysis. It was possible to treat sample within several minutes success- fully by using the kit. So fast simultaneous determination of those anlaytes by GC/ MS was possible with improved convenience as well as sensitivity and reproducibility. Alkylphenol ethoxylates (APEs), chlorophenols (CPs), and bisphenol A (BPA) have been widely used in the preparation of detergents, wood preservatives, and polymeric materials for household and industrial applications. They have been discharged directly or indirectly to the environment and contaminated the atmosphere, water, and soil. APEs are degraded to alkylphenols (APs) during an aerobic or anaerobic waste treatment process or by microorganism 1 and photolysis 2 in nature. Although the APEs are less toxic to organisms, their metabolites 3,4 show high toxicity to organisms and fish. 5,6 So most countries have classified them as endocrine disrupter chemicals. 7-11 Numerous papers have been published about determination of APs, CPs, and BPA using various techniques. Some of the most frequently used methods for analysis of these are as follows: direct analysis using HPLC, 12-14 GC/ ECD, 15-17 LC/ MS, 18 GC/ MS, 19,20 and other techniques 21,22 or indirect analysis of the compounds using derivatization techniques such as methylation, 23 acetylation, 24,25 and silylation. 26-28 Methyl- ation and acetylation techniques are suitable for the analytes * To whom correspondence should be addressed: (phone) +82-2-450-3438; (fax) +82-3436-5382; (e-mail) jmpark@ kkucc.konkuk.ac.kr. (1) Giger, W.; Brunner, P. H.; Schaffner, C. Science 1984 , 225, 623-625. (2) Destaillats, H.; Hung, H.; Hoffmann, M. R. Environ. Sci. Technol. 2000 , 34, 311-317. (3) Nimrod, A. C.; Benson, W. H. Alkylphenols Alkylphenol Ethoxylates Rev. 1998 , 1, 75-101. (4) Ahel, M.; Giger, W.; Koch, M. Water Res. 1994 , 28, 1131-1142. (5) Tabira, Y.; Nakai, M.; Asai, D.; Yakabe, Y.; Tahara, Y.; Shimyozu, T.; Noguchi, M.; Takatsuki, M.; Shimohigashi, Y. Eur. J. Biochem. 1999 , 262, 240-245. (6) Gagne, F.; Pardos, M.; Blaise, C. Bull. Environ. Contam. Toxicol. 1999 , 62, 723-730. (7) Environmental estrogens and other hormones [online]. Available at http:/ / www.tmc.Tulane.edu/ ECME/ eehome/ . ( 8) Environmental Estrogens: Consequences to human health and wildlife; Medical Research Council: London, 1995. (9) World Wildlife Fund Canada [online]. Available at http:/ / www.wwfcan- ada.org/ hormone-disruptors/ , December 15, 1996. (10) Hosea, N. A.; Guengerich, F. P. Arch. Biochem. Biophys. 1998 , 353, 365- 373. (11) Harris, R. H.; Waring, R. H.; Kirk, C. J.; Hughes, P. J. J. Biol. Chem. 2000 , 275, 159-166. (12) Ahel, M.; Giger, W.; Schaffner, W. Water Res. 1994 , 28, 1143-1152. (13) Naylor, C. G.; Mieure, J. P.; Adams, W. J.; Weeks, J. A.; Cataldi, F. J.; Ogle, L. D.; Romano, R. R. Alkylphenols Alkylphenol Ethoxylates Rev. 1988 , 2, 32- 43. (14) Rudel, R. A.; Melly, S. J.; Geno, P. W.; Sun, G.; Brody, J. G. Environ. Sci. Technol. 1998 , 32, 861-869. (15) Bartels, P.; Ebeling, E.; Kramer, B.; Kruse, H.; Osius, N.; Vowinkel, K.; Wassermann, O.; Witten, J.; Zorn, C. Fresenius’ J. Anal. Chem. 1999 , 365, 458-464. (16) Buhr, A.; Genning, C.; Salthammer, C. Fresenius’ J. Anal. Chem. 2000 , 367, 73-78. (17) Machera, K.; Miliadis, G. E.; Anagnostopoulos, E.; Anastassiadou, P. Bull. Environ. Contam. Toxicol. 1997 , 59, 909-916. (18) Crescenzi, C.; Corcia, A. D.; Samperi, R.; Marcomini, A. Anal. Chem. 1995 , 67, 1797-1804. (19) Bhatt, B. D.; Prasad, J. V.; Kalpana, G.; Ali, S. J. Chromatogr. Sci. 1992 , 30, 203-210. (20) Blackburn, M. A.; Waldock, M. J. Water Res. 1995 , 29, 1623-1629. (21) Zemann, A.; Volgger, D. Anal. Chem. 1997 , 69, 3243-3250. (22) Wallingford, R. A. Anal. Chem. 1996 , 68, 2541-2548. (23) Field, J. A.; Reed, R. L. Environ. Sci. Technol. 1996 , 30, 3544-3550. (24) Croley, T. R.; Lynn, B. C., Jr. Rapid Commun. Mass Spectrom. 1998 , 12, 171-175. Anal. Chem. 2001, 73, 3089-3095 10.1021/ac001494l CCC: $20.00 © 2001 American Chemical Society Analytical Chemistry, Vol. 73, No. 13, July 1, 2001 3089 Published on Web 05/16/2001