Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Solventless Microextraction Techniques for Determination of Trihalomethanes by Gas Chromatography in Drinking Water


Three different solventless sample preparation techniques based on microextraction, membrane extraction, and headspace extraction have been developed and optimized for determination of trihalomethanes in drinking water by gas chromatography electron capture detector and mass spectrometry detection. The techniques employed were headspace (HS) solid-phase microextraction, hollow fiber liquid-phase microextraction (HFLPME) and HS extraction. All techniques used were optimized with different experimental designs in order to select the most relevant variables which significantly affect the different processes. The different analytical figures of merit such as limit of detection (LOD), limit of quantification, reproducibility, accuracy, and linear dynamic range were obtained. The new HFLPME method applied used a hollow fiber membrane of polypropylene and the optimized variables were extraction time, extraction temperature, and salting-out effect. The software MODDE 6.0 was used and its design was one central composite on face with a total of 17 runs. The best conditions for the HFLPME were 20 min, 40°C, and 10% NaCl, respectively. The LODs ranged from 0.018 μg·L−1 (for CHClBr2) to 0.049 μg·L−1 (for CHBr3), being this technique the most sensitive one among those studied. Finally, after having optimized the sample preparation techniques and chromatographic conditions, several water samples were taken in two different water treatment plants in Spain (Zaragoza) and Colombia (Viterbo, Caldas). The results obtained are shown and discussed.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4


  1. US EPA (1995). EPA method 551.1, Rev. 1.0.

  2. Antoniou, C. V., Koukouraki, E. E., & Diamadopoulos, E. (2006). Determination of chlorinated volatile organic compounds in water and municipal wastewater using headspace–solid phase microextraction–gas chromatography. Journal of Chromatography A, 1132(1–2), 310–314.

  3. Bahri, M., & Driss, M. R. (2010). Development of solid-phase microextraction for the determination of trihalomethanes in drinking water from Bizerte, Tunisia. Desalination, 250(1), 414–417.

  4. Caro, J., Serrano, A., & Gallego, M. (2007). Direct screening and confirmation of priority volatile organic pollutants in drinking water. Journal of Chromatography. A, 1138(1–2), 244–250.

  5. Cho, D., Kong, S., & Oh, S. (2003). Analysis of trihalomethanes in drinking water using headspace-SPME technique with gas chromatography. Water Research, 37(2), 402–408.

  6. Culea, M., Iordache, A., Cozar, O., & Ristoiu, D. (2009). Trihalomethanes analysis in drinking water. Journal of Environmental Protection and Ecology, 10(2), 342–350.

  7. Di Gioia, M. L., Leggio, A., Le Pera, A., Liguori, A., Napoli, A., & Siciliano, C. (2004). SPE-GC-MS analysis of chloroform in drinking water. Chromatographia, 60(5/6), 319–322.

  8. Dickenson, E. R. V., Summers, R. S., Croue, J., & Gallard, H. (2008). Haloacetic acid and trihalomethane formation from the chlorination and bromination of aliphatic β-Dicarbonyl acid model compounds. Environmental Science and Technology, 42(9), 3226–3233.

  9. Ikem, A. (2010). Measurement of volatile organic compounds in bottled and tap waters by purge and trap GC-MS: are drinking water types different? Journal of Food Composition and Analysis, 23(1), 70–77.

  10. Ivahnenko, T. & Zogorski, J. S. (2006). Sources and occurrence of chloroform and other trihalomethanes in drinking-water supply wells in the United States, 1986–2001. US Geological Survey Scientific Investigations Report, 13.

  11. Joll, C. A., Alessandrino, M. J., & Heitz, A. (2010). Disinfection by-products from halogenation of aqueous solutions of terpenoids. Water Research, 44(1), 232–242.

  12. Lara-Gonzalo, A., Sánchez-Uría, J. E., Segovia-García, E., & Sanz-Medel, A. (2008). Critical comparison of automated purge and trap and solid-phase microextraction for routine determination of volatile organic compounds in drinking waters by GC–MS. Talanta, 74(5), 1455–1462.

  13. Leivadara, S. V., Nikolaou, A. D., & Lekkas, T. D. (2008). Determination of organic compounds in bottled waters. Food Chemistry, 108(1), 277–286.

  14. Nakamura, S., & Daishima, S. (2005). Simultaneous determination of 22 volatile organic compounds, methyl-tert-butyl ether, 1,4-dioxane, 2-methylisoborneol and geosmin in water by headspace solid phase microextraction-gas chromatography–mass spectrometry. Analytica Chimica Acta, 548(1–2), 79–85.

  15. Nerin, C., Salafranca, J., Aznar, M., & Batlle, R. (2009). Critical review on recent developments in solventless techniques for extraction of analytes. Analytical and Bioanalytical Chemistry, 393(3), 809–833.

  16. Nikolaou, A. D., Lekkas, T. D., Golfinopoulos, S. K., & Kostopoulou, M. N. (2002). Application of different analytical methods for determination of volatile chlorination by-products in drinking water. Talanta, 56(4), 717–726.

  17. Pérez Pavón, J. L., Herrero Martín, S., García Pinto, C., & Moreno Cordero, B. (2008). Determination of trihalomethanes in water samples: a review. Analytica Chimica Acta, 629(1–2), 6–23.

  18. Pezo, D., Salafranca, J., & Nerín, C. (2007). Development of an automatic multiple dynamic hollow fibre liquid-phase microextraction procedure for specific migration analysis of new active food packagings containing essential oils. Journal of Chromatography. A, 1174(1–2), 85–94.

  19. Rodríguez, A., Pedersen-Bjergaard, S., Rasmussen, K. E., & Nerín, C. (2008). Selective three-phase liquid phase microextraction of acidic compounds from foodstuff simulants. Journal of Chromatography. A, 1198–1199, 38–44.

  20. Ruiz-Bevia, F., Fernandez-Torres, M. J., & Blasco-Alemany, M. P. (2009). Purge efficiency in the determination of trihalomethanes in water by purge-and-trap gas chromatography. Analytica Chimica Acta, 632(2), 304–314.

  21. Sa, C. S. A., Boaventura, R. A. R., & Pereira, I. B. (2011). Analysis of trihalomethanes in water and air from indoor swimming pools using HS-SPME/GC/ECD. Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances Environmental Engineering, 46(4), 355–363.

  22. Salafranca, J., Domeno, C., Fernandez, C., & Nerin, C. (2003). Experimental design applied to the determination of several contaminants in Duero River by solid-phase microextraction. Analytica Chimica Acta, 477(2), 257–267.

  23. Salafranca, J., Pezo, D., & Nerín, C. (2009). Assessment of specific migration to aqueous simulants of a new active food packaging containing essential oils by means of an automatic multiple dynamic hollow fibre liquid phase microextraction system. Journal of Chromatography. A, 1216(18), 3731–3739.

  24. San Juan, P. M., Carrillo, J. D., & Tena, M. T. (2007). Fibre selection based on an overall analytical feature comparison for the solid-phase microextraction of trihalomethanes from drinking water. Journal of Chromatography. A, 1139(1), 27–35.

  25. Serrano, A., & Gallego, M. (2007). Rapid determination of total trihalomethanes index in drinking water. Journal of Chromatography. A, 1154(1–2), 26–33.

  26. Sun, A., Chen, W., Lin, T., & Xu, Q. (2010). Application of the response surface method for optimization of headspace liquid phase microextraction of trihalomethanes in drinking water. Clean: Soil, Air, Water, 38(4), 353–360.

  27. Tor, A., & Aydin, M. E. (2006). Application of liquid-phase microextraction to the analysis of trihalomethanes in water. Analytica Chimica Acta, 575(1), 138–143.

  28. Vora-adisak, N., & Varanusupakul, P. (2006). A simple supported liquid hollow fiber membrane microextraction for sample preparation of trihalomethanes in water samples. Journal of Chromatography. A, 1121(2), 236–241.

  29. Zoccolillo, L., Amendola, L., Cafaro, C., & Insogna, S. (2005). Improved analysis of volatile halogenated hydrocarbons in water by purge-and-trap with gas chromatography and mass spectrometric detection. Journal of Chromatography. A, 1077(2), 181–187.

Download references


The authors are grateful for the financial support provided by EMPOCALDAS and Vicerrectoria de Investigaciones y Postgrados of Caldas University, and help obtained from EL MIRADOR and Zaragoza’s water treatment plants to take freely the water samples. Financial support was received by Gobierno de Aragón (Spain), Grupo GUIA, Grupo consolidado de Investigación T-10.

Author information

Correspondence to Cristina Nerin.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Rosero, M.M., Aguirre, M., Pezo, D. et al. Solventless Microextraction Techniques for Determination of Trihalomethanes by Gas Chromatography in Drinking Water. Water Air Soil Pollut 223, 667–678 (2012).

Download citation


  • Microextraction
  • THMs
  • Drinking water
  • GC-ECD
  • GC-MS
  • Water disinfection