Analytical and Bioanalytical Chemistry

, Volume 405, Issue 26, pp 8387–8395 | Cite as

Multi-walled carbon nanotubes as sorptive material for solventless in-tube microextraction (ITEX2)—a factorial design study

  • Thorsten Hüffer
  • Xochitli L. Osorio
  • Maik A. Jochmann
  • Beat Schilling
  • Torsten C. Schmidt
Research Paper


Multi-walled carbon nanotubes were evaluated as sorptive packing material for in-tube microextraction (ITEX2) in combination with GC-MS for the analysis of benzene, toluene, ethylbenzene, xylenes, and naphthalene in aqueous samples. For method development, a three-level full factorial design of experiment (DoE) was performed incorporating extraction temperature, number of extraction strokes, and extraction flow. The statistical analysis of method development showed that all considered extraction parameters significantly affected the extraction yield. Furthermore, it was shown that some factors significantly interacted with each other, which indicates the advantage of using DoE for method development. The thereby optimized ITEX2 protocol was validated regarding its linear dynamic range, method detection limit (MDL), and precision. The MDLs of investigated analytes ranged between 2 ng L−1 for naphthalene and 11 ng L−1 for p-xylene. The relatively low MDL obtained for naphthalene, despite its comparably low air–water partitioning, can be explained by its strong interaction with carbon nanotubes. All obtained MDLs are at least comparable to previous reports on microextraction techniques, emphasizing both the quality of ITEX2 and the highly promising sorbent characteristics of carbon nanotubes. Furthermore, the method was applied to three real samples, which demonstrated good recoveries of analytes from tap water, a bank filtrate, and an effluent from a wastewater treatment plant.


MWCNTs as sorptive material for ITEX2


Carbon nanotubes In-tube microextraction Design of experiment GC-MS VOCs Water samples 

Supplementary material

216_2013_7249_MOESM1_ESM.pdf (165 kb)
ESM 1(PDF 164 kb)


  1. 1.
    Iijima S (1991) Helical microtubles of graphitic carbon. Nature 354:56–58CrossRefGoogle Scholar
  2. 2.
    Valcarcel M, Cardenas S, Simonet BM, Moliner-Martinez Y, Lucena R (2008) Carbon nanostructures as sorbent materials in analytical processes. TrAc Trends Anal Chem 27:34–43CrossRefGoogle Scholar
  3. 3.
    Mauter MS, Elimelech M (2008) Environmental applications of carbon-based nanomaterials. Environ Sci Technol 42:5843–5859CrossRefGoogle Scholar
  4. 4.
    Li QL, Yuan DX, Lin QM (2004) Evaluation of multi-walled carbon nanotubes as an adsorbent for trapping volatile organic compounds from environmental samples. J Chromatogr A 1026:283–288CrossRefGoogle Scholar
  5. 5.
    Feng X, Tian M, Li A, Zhao X, Zhang Y (2010) Multiwalled carbon nanotube coated on stainless steel wire for solid-phase microextraction of organochlorine pesticides in water. Anal Lett 43:2477–2486CrossRefGoogle Scholar
  6. 6.
    Merkoci A (2006) Carbon nanotubes in analytical sciences. Mikrochim Acta 152:157–174CrossRefGoogle Scholar
  7. 7.
    Perez-Lopez B, Merkoci A (2012) Carbon nanotubes and graphene in analytical sciences. Mikrochim Acta 179:1–16CrossRefGoogle Scholar
  8. 8.
    Hussain CM, Mitra S (2011) Micropreconcentration units based on carbon nanotubes (CNT). Anal Bioanal Chem 399:75–89CrossRefGoogle Scholar
  9. 9.
    Saridara C, Brukh R, Iqbal Z, Mitra S (2005) Preconcentration of volatile organics on self-assembled, carbon nanotubes in a microtrap. Anal Chem 77:1183–1187CrossRefGoogle Scholar
  10. 10.
    Cai YQ, Jiang GB, Liu JF, Zhou QX (2003) Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of bisphenol a, 4-n-nonylphenol, and 4-tert-octylphenol. Anal Chem 75:2517–2521CrossRefGoogle Scholar
  11. 11.
    Ravelo-Perez LM, Herrera-Herrera AV, Hernandez-Borges J, Rodriguez-Delgado MA (2010) Carbon nanotubes: solid-phase extraction. J Chromatogr A 1217:2618–2641CrossRefGoogle Scholar
  12. 12.
    Jiang RF, Zhu F, Luan TG, Tong YX, Liu H, Ouyang GF, Pawliszyn J (2009) Carbon nanotube-coated solid-phase microextraction metal fiber based on sol–gel technique. J Chromatogr A 1216:4641–4647CrossRefGoogle Scholar
  13. 13.
    Sarafraz-Yazdi A, Amiri A, Rounaghi G, Hosseini HE (2011) A novel solid-phase microextraction using coated fiber based sol–gel technique using poly(ethylene glycol) grafted multi-walled carbon nanotubes for determination of benzene, toluene, ethylbenzene and o-xylene in water samples with gas chromatography-flam ionization detector. J Chromatogr A 1218:5757–5764CrossRefGoogle Scholar
  14. 14.
    Maghsoudi S, Noroozian E (2012) HP-SPME of volatile polycyclic aromatic hydrocarbons from water using multiwalled carbon nanotubes coated on a steel fiber through electrophoretic deposition. Chromatographia 75:913–921CrossRefGoogle Scholar
  15. 15.
    Herrera-Herrera AV, Angel Gonzalez-Curbelo M, Hernandez-Borges J, Angel Rodriguez-Delgado M (2012) Carbon nanotubes applications in separation science: a review. Anal Chim Acta 734:1–30CrossRefGoogle Scholar
  16. 16.
    Berezkin VG, Makarov ED, Stolyarov BV (2003) Needle-type concentrator and its application to the determination of pollutants. J Chromatogr A 985:63–65CrossRefGoogle Scholar
  17. 17.
    Saito Y, Ueta I, Kotera K, Ogawa M, Wada H, Jinno K (2006) In-needle extraction device designed for gas chromatographic analysis of volatile organic compounds. J Chromatogr A 1106:190–195CrossRefGoogle Scholar
  18. 18.
    Eom IY, Niri VH, Pawliszyn J (2008) Development of a syringe pump assisted dynamic headspace sampling technique for needle trap device. J Chromatogr A 1196:10–14Google Scholar
  19. 19.
    Laaks J, Jochmann MA, Schilling B, Schmidt TC (2010) In-tube extraction of volatile organic compounds from aqueous samples: an economical alternative to purge and trap enrichment. Anal Chem 82:7641–7648CrossRefGoogle Scholar
  20. 20.
    Viinamaki J, Rasanen I, Vuori E, Ojanpera I (2011) Elevated formic acid concentrations in putrefied post-mortem blood and urine samples. Forensic Sci Int 208:42–46CrossRefGoogle Scholar
  21. 21.
    Niu LY, Bao JF, Zhao L, Zhang Y (2011) Odor properties and volatile compounds analysis of Torreya grandis aril extracts. J Essent Oil Res 23:1–6CrossRefGoogle Scholar
  22. 22.
    Socaci SA, Socaciu C, Tofană M, Raţi IV, Pintea A (2013) In-tube extraction and GC–MS analysis of volatile components from wild and cultivated sea buckthorn (Hippophae rhamnoides L. ssp. Carpatica) berry varieties and juice. Phytochem Anal. doi:10.1002/pca.24.13 Google Scholar
  23. 23.
    Zapata J, Mateo-Vivaracho L, Lopez R, Ferreira V (2012) Automated and quantitative headspace in-tube extraction for the accurate determination of highly volatile compounds from wines and beers. J Chromatogr A 1230:1–7CrossRefGoogle Scholar
  24. 24.
    Zapata J, Lopez R, Herrero P, Ferreira V (2012) Multiple automated headspace in-tube extraction for the accurate analysis of relevant wine aroma compounds and for the estimation of their relative liquid–gas transfer rates. J Chromatogr A 1266:1–9CrossRefGoogle Scholar
  25. 25.
    Hibbert DB (2012) Experimental design in chromatography: a tutorial review. J Chromatogr B 910:2–13CrossRefGoogle Scholar
  26. 26.
    Harvey D (2000) Modern analytical chemistry. McGraw-Hill, ColumbusGoogle Scholar
  27. 27.
    Kamphoff M, Thiele T, Kunz B (2007) Influence of different extraction parameters on a solid-phase dynamic extraction for the gas chromatographic determination of d-limonene degradation products by using a fractional factorial design. J AOAC Int 90:1623–1627Google Scholar
  28. 28.
    Gaujac A, Emidio ES, Navickiene S, Costa Ferreira SL, Dorea HS (2008) Multivariate optimization of a solid phase microextraction-headspace procedure for the determination of benzene, toluene, ethylbenzene and xylenes in effluent samples from a waste treatment plant. J Chromatogr A 1203:99–104CrossRefGoogle Scholar
  29. 29.
    Zuazagoitia D, Millan E, Garcia R (2007) A screening method for polycyclic aromatic hydrocarbons determination in water by headspace SPME with GC-FID. Chromatographia 66:773–777CrossRefGoogle Scholar
  30. 30.
    Corporation SR Interactive PhysProp Database Demo (2013) Accessed 13 Jan 2013
  31. 31.
    Staudinger J, Roberts PV (2001) A critical compilation of Henry’s law constant temperature dependence relations for organic compounds in dilute aqueous solutions. Chemosphere 44:561–576CrossRefGoogle Scholar
  32. 32.
    Jochmann MA, Yuan X, Schmidt TC (2007) Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction. Anal Bioanal Chem 387:2163–2174CrossRefGoogle Scholar
  33. 33.
    Diaz E, Ordonez S, Vega A (2007) Adsorption of volatile organic compounds onto carbon nanotubes, carbon nanofibers, and high-surface-area graphites. J Colloid Interface Sci 305:7–16CrossRefGoogle Scholar
  34. 34.
    Jochmann MA, Yuan X, Schilling B, Schmidt TC (2008) In-tube extraction for enrichment of volatile organic hydrocarbons from aqueous samples. J Chromatogr A 1179:96–105CrossRefGoogle Scholar
  35. 35.
    Zhang ZY, Pawliszyn J (1993) Headspace solid-phase microextraction. Anal Chem 65:1843–1852CrossRefGoogle Scholar
  36. 36.
    Goss KU (2004) Comment on “Influence of soot carbon on the soil-air partitioning of polycyclic aromatic hydrocarbon”. Environ Sci Technol 38:1622–1623CrossRefGoogle Scholar
  37. 37.
    Glaser JA, Foerst DL, Mckee GD, Quave SA, Budde WL (1981) Trace analyses for wastewaters—method detection limit, a new performance criterion for chemical analysis, is defined as that concentration of the analyte that can be detected at a specific confidence level. Both theory and applications are discussed for reliable wastewater analyses of priority pollutants. Environ Sci Technol 15:1427–1435CrossRefGoogle Scholar
  38. 38.
    Pan B, Xing BS (2008) Adsorption mechanisms of organic chemicals on carbon nanotubes. Environ Sci Technol 42:9005–9013CrossRefGoogle Scholar
  39. 39.
    Adamson AW (1990) Physical chemistry of surfaces. Wiley, New YorkGoogle Scholar
  40. 40.
    Abraham MH, Andonian-Haftvan J, Whiting GS, Leo A, Taft RS (1994) Hydrogen bonding. Part 34. The factors that influence the solubility of gases and vapor in water at 298 K, and a new method for its determination. J Chem Soc Perkin Trans 2(8):1777–1791Google Scholar
  41. 41.
    Kah M, Zhang X, Jonker MTO, Hofmann T (2011) Measuring and modelling adsorption of PAHs to carbon nanotubes over a six order of magnitude wide concentration range. Environ Sci Technol 45:6011–6017CrossRefGoogle Scholar
  42. 42.
    Yang K, Zhu LZ, Xing BS (2006) Adsorption of polycyclic aromatic hydrocarbons by carbon nanomaterials. Environ Sci Technol 40:1855–1861CrossRefGoogle Scholar
  43. 43.
    The Council of the European Union (1998) Off J Euro Communities 41:32–54Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Thorsten Hüffer
    • 1
  • Xochitli L. Osorio
    • 1
  • Maik A. Jochmann
    • 1
  • Beat Schilling
    • 2
  • Torsten C. Schmidt
    • 1
    • 3
  1. 1.Instrumental Analytical ChemistryUniversity of Duisburg-EssenEssenGermany
  2. 2.BGB Analytik GmbHBoecktenSwitzerland
  3. 3.Centre for Water and Environmental Research (ZWU)University of Duisburg-EssenEssenGermany

Personalised recommendations