Analysis of Haloacetic Acids in Drinking Water by Direct Derivatization and Headspace-SPME Technique with GC-MS

Handspace Solid Phase Microextraction 방법에 의한 HAAs 분석에 관한 연구

  • 조덕희 (성남시 상하수도사업소 정수과)
  • Received : 2004.07.20
  • Accepted : 2004.09.30
  • Published : 2004.10.15

Abstract

In many drinking water treatment plants, chlorination process is one of the main techniques used for the disinfection of water. This disinfecting treatment leads to the formation of haloacetic acid (HAAs). In this study, headspace solid-phase microextraction (HS-SPME) was studied as a possible alternative to liquid-liquid extraction for the analysis of HAAs in drinking water. The method involves direct derivatization of the acids to their methyl esters without methyl tert-butyl ether (MTBE) extraction, followed by HS-SPME with a $2cm-50/30{\mu}m$ divinylbenzene/carboxen/polydimethylsiloxane fiber. The effects of experimental parameters such as selection of SPME fiber, the volume of sulphuric acid and methanol, derivatization temperature and time, the addition of salts, extraction temperature and time, and desorption time on the analysis were investigated. Analytical parameters such as linearity, repeatability and limit of detection were also evaluated. The $2cm-50/30{\mu}m$-divinylbenzene/carboxen/polydimethylsiloxane fiber, sulphuric acid of 1ml, methanol of 3ml, derivatization temperature of $50^{\circ}C$ derivatization time of 2hrs, sodium chloride salt of 10g, extraction time of 30 minutes, extraction temperature of $20^{\circ}C$ and desorption time of 1 minute at $260^{\circ}C$ were selected as the optimal experimental conditions for the analysis of HAAs. The linearities ($r^2$), relative standard deviations (%RSD) and limits of detection (LOD) for HAAs were 0.9978~0.9991, 1.1~9.8% and $0.05{\sim}0.2{\mu}g/l$, respectively.

Keywords

References

  1. Banal F. A., AI-RRub F. A. and Simandl J. (1999) Experimental study of the salt effect in vapor/liquid equilibria using headspace gas chromatography, Chemical Engineering Technology, 22, pp. 761-765
  2. Benanou D., Acobas F. and Sztajnbok P. (1998) Analysis of haloacetic acids in water by a novel technique: simultaneous extraction derivatization, Water Research, 32, pp. 2798-2806
  3. Bull R. J. and Kopfler F. C. (1991) Formation and occurrence of disinfectant by-products. In Health Effects of disinfectants and by-products, Denver, CO, AWWA Research Foundation, pp. 55-103
  4. Cancho B., Ventura F. and Galceran M. T. (2001) Determination of aldehydes in drinking water using pentafluorobenzylhydroxylamine derivatization and solid-phase microextraction. J. Chromatography A, 943, pp. 1-13
  5. Cho Deok-Hee and Oh Seong-Geun (2001) Analysis of Trihalomethanes in Drinking Water by Headspace-Solid Phase Microexreaction Method, Journal of the Korean Society of Water and Wastewater, 15 (4), pp. 302-308
  6. Cho Deok-Hee, and Oh Seong-Geun (2003) Analysis of Di-and Trichlroroacetic acids in Drinking Water using Headspac-SPME Technique with GC-MS, Journal of the Korean Society of Water and Wastewater, 17 (6), pp. 821-826
  7. Cho Deok-Hee, Kong Sung-Ho and Oh Seong-Geun (2003) Analysis of trihalomethanes in drinking water using headspace-SPME technique with gas chromatography, Water Research, 37, pp. 402-408
  8. Clesceri L. S., Greenberg A E. and Eaton A D. (1998) Standard Methods for Examination of Water and wastewater, 20th ed., APHA, AWWA and WEF. Washington, DC
  9. Dalvi A. G. L., Al-Rasheed R. and Javeed M. A. (2000) Haloacetic acids(HAAs) formation in desalination processes from disinfectants. Desalination, 129, pp. 261-271
  10. Doong Ruey-An and Liao Pei-Lin (2001) Determination of organochlorine pesticides and their metabolites in soil samples using headspace solid-phase microextraction. J. Chromatography A, 918, pp. 177-188
  11. Jia M., Zhang H. and Min D. (1998) Optimization of solid-phase microextraction analysis for headspace flavor compounds of orange juice. J. Agricultural Food and Chemistry, 46, pp. 2744-2747
  12. Liompart M., Li K. and Fingas M. (1999) Headspace solid phase microextraction (HSSPME) for the determination of volatile and semivolatile pollutants in soils. Talanta, 48, pp. 451-459
  13. Nilsson T., Pelusio F., Montanarella L., Larsen B., Facchetti S. and Madsen J. (1995) An evaluation of solid-phase microextraction for analysis of volatile organic compounds in drinking water. J. High Resolut. Chromatography, 18, pp. 617-624
  14. Norin H. and Renberg L. (1980) Determination of trihalomethanes (THMs) in water using high efficiency solvent extraction. Water Research, 14, pp. 1397-1402
  15. Popp P., Bauer C., Moder M. and Paschke A. (2000) Determination of polycyclic aromatic hydrocarbons in waste water by off-line coupling of solid-phase microextraction with column liquid chromatography. J. Chromatography A, 897, pp. 153-159
  16. Sarrion M. N., Santos F. J. and Galceran M. T. (1999) Solid-phase microextraction coupled with gas chromatography-ion trap mass spectrometry for the analysis of haloacetic acids in water, J. Chromatography A, 859, pp. 159-171
  17. Stack M. A., Fitzgerald G., O'Connell S. and James K. J. (2000) Measurement of trihalomethanes in potable and recreational waters using solid phase micro extraction with gas chromatography-mass spectrometry. Chemosphere, 41, pp. 1821-1226
  18. US EPA (1992) Method 552.1: determination of haloacetic acids and dalapon in drinking water by ion exchange liquid-solid extraction and gas chromatography with an electron capture detector. Environmental Monitoring and System Laboratory, Cincinnati, OH
  19. US EPA (1995) Method 552.2: determination of haloacetic acids and dalapon in drinking water by liquid-liquid extraction, derivatization and gas chromatography with an electron capture detector. Environmental Monitoring and System Laboratory, Cincinnati, OH
  20. US EPA (1998) National primary drinking water regulations; disinfectants and disinfection by-products; final rule. Federal Register, 63(241), pp.69390-69476
  21. Watson S. B., Brownlee B., Satchwill T. and Hargesheimer E. E. (2000) Quantitative analysis of trace level of Geosmin and MlB in source and drinking water using headspace SPME. Water Research, 34(10), pp. 2818-2828 https://doi.org/10.1016/S0043-1354(00)00027-0
  22. WHO (1996) Guidelines for drinking water quality, Health criteria and other supporting information. Geneva: World Health Organization
  23. Zhang Z. and Pawliszyn J. (1995) Quantitative extraction using an interally cooled solid phase microextraction device. Analytical Chemistry, 67, pp. 34-43