Detection  Vol.4 No.1 , January 2016
Development of Simultaneous HPLC-Fluorescence Assay of Phenol and Chlorophenols in Tap Water after Pre-Column Derivatization with 3-Chlorocarbonyl-6,7-dimethoxy-1- methyl-2(1H)-quinoxalinone
Abstract: Chlorophenols (2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol and 2,4, 6-trichlorophenol) may be presented in natural waters or drinking water as a result of disinfection processes involving chlorination, or as contaminants derived from domestic products, industrial operations and agricultural chemicals. A previous HPLC-UV method for determination of phenol and five chlorophenols in tap water using 4-fluoro-7-nitro-2,1,3-benzoxadiaole as a UV labeling reagent shows limited sensitivity. Here, we present an improved HPLC-fluorescence detection method for simultaneous determination of phenol and the above chlorophenols in tap water after pre-column derivatization with 3-chlorocarbonyl-6,7-dimethoxy-1-methyl-2(1H)-quino- xalinone (DMEQ-COCl), using a short, narrow column (50 × 2.1 mm i.d., packed with 5 μm particles of C18 material) to improve the sensitivity. Standard samples containing the compounds are derivatized with DMEQ-COCl in borate buffer (pH 9.0) at room temperature for 3 mins. The response is linear in the concentration range of 0.01 - 0.05 to 0.5 mg/L with r2 values ≥0.9967 for all compounds. The lower limits of detection are 0.001 to 0.008 mg/L, and the coefficients of variation are less than 8.8%. The recovery values from tap water spiked with standard samples are satisfactory. The present method is suitable for examining whether or not tap water samples are contaminated with phenol and chlorophenols in excess of regulatory values.
Cite this paper: Higashi, Y. (2016) Development of Simultaneous HPLC-Fluorescence Assay of Phenol and Chlorophenols in Tap Water after Pre-Column Derivatization with 3-Chlorocarbonyl-6,7-dimethoxy-1- methyl-2(1H)-quinoxalinone. Detection, 4, 16-24. doi: 10.4236/detection.2016.41003.

[1]   World Health Organization (2006) Guidelines for Drinking-Water Quality Incorporating First Addendum. Vol. 1, 3rd Edition, WHO, 329-331.

[2]   Llompart, M., Lourido, M., Landin, P., García-Jares, C. and Cela, R. (2002) Optimization of a Derivatization-Solid- Phase Microextraction Method for the Analysis of Thirty Phenolic Pollutants in Water Samples. Journal of Chromatography A, 963, 137-148.

[3]   González-Toledo, E., Prat, M.D. and Alpendurada, M.F. (2001) Solid-Phase Microextraction Coupled to Liquid Chromatography for the Analysis of Phenolic Compounds in Water. Journal of Chromatography A, 923, 45-52.

[4]   Asan, A. and Isildak, I. (2003) Determination of Major Phenolic Compounds in Water by Reversed-Phase Liquid Chromatography after Pre-Column Derivatization with Benzoyl Chloride. Journal of Chromatography A, 988, 145- 149.

[5]   Farino, J., Norwitz, G., Boyko, W.J. and Keliher, P.N. (1981) Study of the Behaviour of Various Phenolic Compounds in the 4-Aminoantipyrine and Ultraviolet-Ratio Spectrophotometric Methods without and with Distillation. Talanta, 28, 705-708.

[6]   Rodriguez-Alcala, M., Yañez-Sedeño, P. and Diez, L.M. (1988) Determination of Pentachlorophenol by Flow-Injection Analysis with Spectrophotometric Detection.Talanta, 35, 601-604.

[7]   Ito, R., Kawaguchi, M., Honda, H., Koganei, Y., Okanouchi, N., Sakui, N., Saito, K. and Nakazawa, H. (2008) Hollow-Fiber-Supported Liquid Phase Microextraction with in Situ Derivatization and Gas Chromatography-Mass Spectrometry for Determination of Chlorophenols in Human Urine Samples. Journal of Chromatography B, 872, 63-67.

[8]   Almeda, S., Nozal, L., Arce, L. and Valcárcel, M. (2007) Direct Determination of Chlorophenols Present in Liquid Samples by Using a Supported Liquid Membrane Coupled in-Line with Capillary Electrophoresis Equipment. Analytica Chimica Acta, 587, 97-103.

[9]   Tsukagoshi, K., Kameda, T., Yamamoto, M. and Nakajima, R. (2002) Separation and Determination of Phenolic Compounds by Capillary Electrophoresis with Chemiluminescence Detection. Journal of Chromatography A, 978, 213-220.

[10]   Suliman, F.E., Al-Kindi, S.S., Al-Kindy, S.M. and Al-Lawati, H.A. (2006) Analysis of Phenols in Water by High- Performance Liquid Chromatography Using Coumarin-6-Sulfonyl Chloride as a Fluorogenicprecolumn Label. Journal of Chromatography A, 1101, 179-184.

[11]   Ruiz-Jiménez, J. and de Castro, M.D.L. (2007) In-Column micro-High-Performance Liquid Chromatographic Concentration-Separation Prior to Ultraviolet Detection for the Determination of Chlorophenols in Water Samples. Journal of Chromatography A, 1174, 78-84.

[12]   Fattahi, N., Assadi, Y., Hosseini, M.R. and Jahromi, E.Z. (2007) Determination of Chlorophenols in Water Samples Using Simultaneous Dispersive Liquid-Liquid Microextraction and Derivatization Followed by Gas Chromatography-Electron-Capture Detection. Journal of Chromatography A, 1157, 23-29.

[13]   Wada, M., Kinoshita, S., Itayama, Y., Kuroda, N. and Nakashima, K. (1999) Sensitive High-Performance Liquid Chromatographic Determination with Fluorescence Detection of Phenol and Chlorophenols with 4-(4,5-Diphenyl-1H- imidazol-2-yl)benzoyl Chloride as a Labeling Reagent. Journal of Chromatography B, 721, 179-186.

[14]   Imai, K. (2003) Analytical Chemical Studies on High-Performance Recognition and Detection of Bio-Molecules in Life. Yakugaku Zasshi, 123, 901-917.

[15]   Higashi, Y., Nakamura, S., Matsumura, H. and Fujii, Y. (2006) Simultaneous Liquid Chromatographic Assay of Amantadine and Its Four Related Compounds in Phosphate-Buffered Saline Using 4-Fluoro-7-nitro-2,1,3-benzoxadia- zole as a Fluorescent Derivatization Reagent. Biomedical Chromatography, 20, 423-428.

[16]   Higashi, Y., Sakata, M. and Fujii, Y. (2007) Simultaneous Determination of the N-Dealkylated Metabolites of Four Butyrophenone-Type Agents in Rat Plasma by HPLC with Fluorescence Detection after Precolumn Derivatization with 4-Fluoro-7-nitro-2,1,3-benzoxadiazole. Journal of Liquid Chromatography & Related Technologies, 30, 2747-2754.

[17]   Fukushima, T., Kawai, J., Imai, K. and Toyo’oka, T. (2004) Simultaneous Determination of D- and L-Serine in Rat Brain Microdialysis Sample Using a Column-Switching HPLC with Fluorimetric Detection. Biomedical Chromatography, 18, 813-819.

[18]   Higashi, Y., Gao, R. and Fujii, Y. (2009) Determination of Fluoxetine and Norfluoxetine in Human Serum and Urine by HPLC Using a Cholester Column with Fluorescence Detection. Journal of Liquid Chromatography & Related Technologies, 32, 1141-1151.

[19]   Toyo’oka, T., Mantani, T. and Kato, M. (2003) Characterization of Labelling and De-Labelling Reagents for Detection and Recovery of Tyrosine Residue in Peptide. Biomedical Chromatography, 17, 133-142.

[20]   Higashi, Y. and Fujii, Y. (2009) HPLC-UV Analysis of Phenol and Chlorophenols in Water after Pre-Column Derivatization with 4-Fluoro-7-nitro-2,1,3-benzoxadiazole. Journal of Liquid Chromatography & Related Technologies, 32, 2372-2383.