Study on the Derivatization Process Using N-O-bis-(trimethylsilyl)-trifluoroacetamide, N-(tert-butyldimethylsilyl)-N-methyltrifluoroace tamide, Trimethylsilydiazomethane for the Determination of Fecal Sterols by Gas Chromatography-Mass Spectrometry
Fecal sterol has been proposed as a chemical indicator
of human fecal pollution even when fecal coliform populations have
diminished due to water chlorination or toxic effects of industrial
effluents. This paper describes an improved derivatization procedure
for simultaneous determination of four fecal sterols including
coprostanol, epicholestanol, cholesterol and cholestanol using gas
chromatography-mass spectrometry (GC-MS), via optimization study
on silylation procedures using N-O-bis
(trimethylsilyl)-trifluoroacetamide (BSTFA), and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide
(MTBSTFA), which lead to the formation of trimethylsilyl (TMS) and
tert-butyldimethylsilyl (TBS) derivatives, respectively. Two
derivatization processes of injection-port derivatization and water bath
derivatization (60 oC, 1h) were inspected and compared. Furthermore,
the methylation procedure at 25 oC for 2h with
trimethylsilydiazomethane (TMSD) for fecal sterols analysis was also
studied. It was found that most of TMS derivatives demonstrated the
highest sensitivities, followed by methylated derivatives. For BSTFA
or MTBSTFA derivatization processes, the simple injection-port
derivatization process could achieve the same efficiency as that in the
tedious water bath derivatization procedure.
[1] P.D. Anderson, V.J. Daco, P. Shanahan, S.c. Chapra, M.E. Buzby, V.L.
Cunningham, B.M. Duplessie, E.P. Hayes, F.J. Masterocco, N.J. Papke,
J.C. Rader, J.H. Samuelian, B.W. Schwab, "Screening analysis of human
pharmaceutical compounds in U.S. surface waters," Environ. Sci.
Technol., vol. 38, pp. 838-849, 2004.
[2] P.D. Nichols, R. Leeming, M.S. Rayner, V. Latham, "Use of capillary gas
chromatography for measuring fecal-derived sterols. Application to storm
water, the sea-surface microlayer, beach grease, regional studies, and
distinguishing algal blooms and human and non-human sources of sewage
pollution," J Chromatogr. A., vol. 733, pp. 497-506, 1996.
[3] S.T. Glassmeyer, E.T. Furlong, D.W. Kolpin, J.D. Cahill, S.D. Zaugg,
S.L. Werner, M.T. Meyer, D.D. Kryak, "Transport of chemical and
microbial compounds from known wastewater discharges: potential for
use as indicators of human fecal contamination," Environ. Sci. Technol.,
vol. 39, pp. 5157-5169, 2005.
[4] P.G. Hatcher, P.A. McGillivary, "Sewage contamination in the New York
Bight. Coprostanol as an indicator," Environ. Sci. Technol., vol. 13, pp.
1225-1229, 1979.
[5] C. Pratt, J. Warnken, R. Leeming, J.M. Arthur, D.I. Grice, "Detection of
intermittent sewage pollution in a subtropical, oligotrophic,
semi-enclosed embayment system using sterol signatures in sediments,"
Environ. Sci. Technol., vol. 41, pp. 792-802, 2007.
[6] K.O. Isobe, M. Tarao, M.P. Zakaria, N.H. Chiem, L.Y. Minh, H. Takada,
"Quantitative application of fecal sterols using gas chromatography-Mass
Spectrometry to investigate fecal pollution in tropical waters: western
malaysia and mekong delta, vietnam," Environ. Sci. Technol., vol. 36, pp.
4497-4507, 2002.
[7] D. Pardasani, A. Mazumder, A.K. Gupta, P.K. Kanaujia, V. Tak, D.K.
Dubey, "Determination of hydrolytic degradation products of nerve
agents by injection port fluorination in gas chromatography/mass
spectrometry for the verification of the Chemical Weapons Convention ,"
Rapid. Commun. Mass. Spectrom, vol. 21, pp. 3109-3114, 2007.
[8] C.Y. Cheng, W.H. Ding, "Determination of acidic degradation products
of nonylphenol polyethoxylates by large-volume injection-port
derivatization and gas chromatography/mass spectrometry," Rapid.
Commun. Mass. Spectrom, vol. 21, pp. 1687-1690, 2007.
[9] A. Shareef, M.J. Angove, J.D. Wells, "Optimization of silylation using
N-methyl-N-(trimethylsilyl)-trifluoroacetamide,
N,O-bis-(trimethylsilyl)-trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the
determination of the estrogens estrone and 17╬▒-ethinylestradiolby gas
chromatography-mass spectrometry," J Chromatogr. A., vol. 1108, pp.
121-128, 2006.
[10] L.Z. Yu, M.J.M. Wells, "Establishing the feasibility of coupled
solid-phase extraction-solid-phase derivatization for acidic herbicides," J
Chromatogr. A., vol. 1143, pp. 16-25, 2007.
[11] T. Gunnar, K. Ariniemi, P. Lillsunde, "Determination of 14
benzodiazepines and hydroxyl metabolites, zaleplon and zolpidem as
tert-butyldimethylsilyl derivatives compared with other common
silylating reagents in whole blood by gas chromatography-mass
spectrometry," J Chromatogr. B., vol. 818, pp. 175-189, 2005.
[12] A. Shareef, C.J. Parnis, M.J. Angove, J.D. Wells, B.B. Johnson,
"Suitability of N,O-bis(trimethylsilyl)trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide as derivatization
reagents for the determination of estrogens estrone and
17╬▒-ethinylestradiol by gas chromatography-mass spectrometry," J
Chromatogr. A., vol. 1026, pp. 295-300, 2004.
[13] A. Shareef, M.J. Angove, J.D. Wells, "Optimization of silylation using
N-methyl-N-(trimethylsilyl)-trifluoroacetamide,
N,O-bis(trimethylsilyl)trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the
determination of estrogens estrone and 17╬▒-ethinylestradiol by gas
chromatography-mass spectrometry," J Chromatogr. A., vol. 1108, pp.
121-128, 2006.
[14] T. Niino, T. Ishibashi, T. Itho, S. Sakai, H. Ishiwata, T. Yamada, S.
Onodera, "Simultaneous determination of phthalate di- and monoesters in
poly(vinylchloride) products and human saliva by gas
chromatography-mass spectrometry," J Chromatogr. B., vol. 780, pp.
35-44, 2002.
[1] P.D. Anderson, V.J. Daco, P. Shanahan, S.c. Chapra, M.E. Buzby, V.L.
Cunningham, B.M. Duplessie, E.P. Hayes, F.J. Masterocco, N.J. Papke,
J.C. Rader, J.H. Samuelian, B.W. Schwab, "Screening analysis of human
pharmaceutical compounds in U.S. surface waters," Environ. Sci.
Technol., vol. 38, pp. 838-849, 2004.
[2] P.D. Nichols, R. Leeming, M.S. Rayner, V. Latham, "Use of capillary gas
chromatography for measuring fecal-derived sterols. Application to storm
water, the sea-surface microlayer, beach grease, regional studies, and
distinguishing algal blooms and human and non-human sources of sewage
pollution," J Chromatogr. A., vol. 733, pp. 497-506, 1996.
[3] S.T. Glassmeyer, E.T. Furlong, D.W. Kolpin, J.D. Cahill, S.D. Zaugg,
S.L. Werner, M.T. Meyer, D.D. Kryak, "Transport of chemical and
microbial compounds from known wastewater discharges: potential for
use as indicators of human fecal contamination," Environ. Sci. Technol.,
vol. 39, pp. 5157-5169, 2005.
[4] P.G. Hatcher, P.A. McGillivary, "Sewage contamination in the New York
Bight. Coprostanol as an indicator," Environ. Sci. Technol., vol. 13, pp.
1225-1229, 1979.
[5] C. Pratt, J. Warnken, R. Leeming, J.M. Arthur, D.I. Grice, "Detection of
intermittent sewage pollution in a subtropical, oligotrophic,
semi-enclosed embayment system using sterol signatures in sediments,"
Environ. Sci. Technol., vol. 41, pp. 792-802, 2007.
[6] K.O. Isobe, M. Tarao, M.P. Zakaria, N.H. Chiem, L.Y. Minh, H. Takada,
"Quantitative application of fecal sterols using gas chromatography-Mass
Spectrometry to investigate fecal pollution in tropical waters: western
malaysia and mekong delta, vietnam," Environ. Sci. Technol., vol. 36, pp.
4497-4507, 2002.
[7] D. Pardasani, A. Mazumder, A.K. Gupta, P.K. Kanaujia, V. Tak, D.K.
Dubey, "Determination of hydrolytic degradation products of nerve
agents by injection port fluorination in gas chromatography/mass
spectrometry for the verification of the Chemical Weapons Convention ,"
Rapid. Commun. Mass. Spectrom, vol. 21, pp. 3109-3114, 2007.
[8] C.Y. Cheng, W.H. Ding, "Determination of acidic degradation products
of nonylphenol polyethoxylates by large-volume injection-port
derivatization and gas chromatography/mass spectrometry," Rapid.
Commun. Mass. Spectrom, vol. 21, pp. 1687-1690, 2007.
[9] A. Shareef, M.J. Angove, J.D. Wells, "Optimization of silylation using
N-methyl-N-(trimethylsilyl)-trifluoroacetamide,
N,O-bis-(trimethylsilyl)-trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the
determination of the estrogens estrone and 17╬▒-ethinylestradiolby gas
chromatography-mass spectrometry," J Chromatogr. A., vol. 1108, pp.
121-128, 2006.
[10] L.Z. Yu, M.J.M. Wells, "Establishing the feasibility of coupled
solid-phase extraction-solid-phase derivatization for acidic herbicides," J
Chromatogr. A., vol. 1143, pp. 16-25, 2007.
[11] T. Gunnar, K. Ariniemi, P. Lillsunde, "Determination of 14
benzodiazepines and hydroxyl metabolites, zaleplon and zolpidem as
tert-butyldimethylsilyl derivatives compared with other common
silylating reagents in whole blood by gas chromatography-mass
spectrometry," J Chromatogr. B., vol. 818, pp. 175-189, 2005.
[12] A. Shareef, C.J. Parnis, M.J. Angove, J.D. Wells, B.B. Johnson,
"Suitability of N,O-bis(trimethylsilyl)trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide as derivatization
reagents for the determination of estrogens estrone and
17╬▒-ethinylestradiol by gas chromatography-mass spectrometry," J
Chromatogr. A., vol. 1026, pp. 295-300, 2004.
[13] A. Shareef, M.J. Angove, J.D. Wells, "Optimization of silylation using
N-methyl-N-(trimethylsilyl)-trifluoroacetamide,
N,O-bis(trimethylsilyl)trifluoroacetamide and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the
determination of estrogens estrone and 17╬▒-ethinylestradiol by gas
chromatography-mass spectrometry," J Chromatogr. A., vol. 1108, pp.
121-128, 2006.
[14] T. Niino, T. Ishibashi, T. Itho, S. Sakai, H. Ishiwata, T. Yamada, S.
Onodera, "Simultaneous determination of phthalate di- and monoesters in
poly(vinylchloride) products and human saliva by gas
chromatography-mass spectrometry," J Chromatogr. B., vol. 780, pp.
35-44, 2002.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:49468", author = "Jingming Wu and Ruikang Hu and Junqi Yue and Zhaoguang Yang and Lifeng Zhang", title = "Study on the Derivatization Process Using N-O-bis-(trimethylsilyl)-trifluoroacetamide, N-(tert-butyldimethylsilyl)-N-methyltrifluoroace tamide, Trimethylsilydiazomethane for the Determination of Fecal Sterols by Gas Chromatography-Mass Spectrometry", abstract = "Fecal sterol has been proposed as a chemical indicator
of human fecal pollution even when fecal coliform populations have
diminished due to water chlorination or toxic effects of industrial
effluents. This paper describes an improved derivatization procedure
for simultaneous determination of four fecal sterols including
coprostanol, epicholestanol, cholesterol and cholestanol using gas
chromatography-mass spectrometry (GC-MS), via optimization study
on silylation procedures using N-O-bis
(trimethylsilyl)-trifluoroacetamide (BSTFA), and
N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide
(MTBSTFA), which lead to the formation of trimethylsilyl (TMS) and
tert-butyldimethylsilyl (TBS) derivatives, respectively. Two
derivatization processes of injection-port derivatization and water bath
derivatization (60 oC, 1h) were inspected and compared. Furthermore,
the methylation procedure at 25 oC for 2h with
trimethylsilydiazomethane (TMSD) for fecal sterols analysis was also
studied. It was found that most of TMS derivatives demonstrated the
highest sensitivities, followed by methylated derivatives. For BSTFA
or MTBSTFA derivatization processes, the simple injection-port
derivatization process could achieve the same efficiency as that in the
tedious water bath derivatization procedure.", keywords = "Fecal Sterols, Methylation, Silylation, BSTFA, MTBSTFA, TMSD, GC-MS.", volume = "4", number = "1", pages = "1-4", }
