Graphitic carbon nitride as sorbent for the emulsification-enhanced disposable pipette extraction of eight organochlorine pesticides prior to GC-MS analysis


Graphitic carbon nitride (g-C3N4) was explored as a sorbent for the emulsification-enhanced (EE) disposable pipette extraction (DPX) of eight organochlorine pesticides (OCPs) from environmental waters. The OCPs, including α-hexachlorocyclohexane, Aldrin, α-Chlordane, Dieldrin, 4,4′-dichlorodiphenyldichloroethylene, 4,4′-dichlorodiphenyldichloroethane, Heptachlor and Heptachlor epoxide (Isomer A), were analyzed by gas chromatography-mass spectrometry. The sorbent g-C3N4 was characterized by elemental analysis, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared and Raman spectroscopy. As a C-N analogue of graphite, g-C3N4 exhibits good water dispersibility and allows easy analyte recovery – a characteristic not commonly observed in carbon-based materials. When applied to DPX, g-C3N4 rapidly establishes strong interactions with the OCPs. Consequently, g-C3N4 displays superior extraction capability in comparison to six other commercial sorbents. An emulsification step prior to DPX was found to enhance the overall extraction efficiency by pre-concentrating the OCPs into the microdroplets of an organic solvent. The microdroplets were then adsorbed onto g-C3N4. Under the most favorable conditions, wide linear responses spanning over two to four orders of magnitudes are established. The limits of detection range between 2.4 ng·L−1 and 46.2 ng·L−1. The method is reproducible (relative standard deviations ≤ 7.4%) and enrichment factors are between 42 and 57. When applied to the analysis of lake and river water samples, EE-DPX-gas chromatography-mass spectrometry exhibits good resilience against matrix interferences. The relative recoveries range between 77.7% and 106.3%. In comparison to other sorbent-based extraction techniques reported for the analysis of OCPs in aqueous samples, EE-DPX utilizes the minimal amount of sample and solvent, and requires the shortest sample preparation time.

Schematic representation of the emulsification-enhanced disposable pipette extraction (DPX) of organochlorine pesticides (OCPs) using graphitic carbon nitride (g-C3N4) as sorbent. Emulsification and DPX work synergistically, thus allowing rapid dissolution of analytes into microdroplets of organic solvent, before being extracted by g-C3N4.

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  1. 1.

    Tang S, Chia GH, Chang Y, Lee HK (2014) Automated dispersive solid-phase extraction using dissolvable Fe3O4-layered double hydroxide core-shell microspheres as sorbent. Anal Chem 86(22):11070–11076.

  2. 2.

    Chen Z, Yu C, Xi J, Tang S, Bao T, Zhang J (2019) A hybrid material prepared by controlled growth of a covalent organic framework on amino-modified MIL-68 for pipette tip solid-phase extraction of sulfonamides prior to their determination by HPLC. Microchim Acta 186(6):393.

  3. 3.

    Tan SC, Lee HK (2019) A hydrogel composite prepared from alginate, an amino-functionalized metal-organic framework of type MIL-101(Cr), and magnetite nanoparticles for magnetic solid-phase extraction and UHPLC-MS/MS analysis of polar chlorophenoxy acid herbicides. Microchim Acta 186(8):545.

  4. 4.

    Guan H, Brewer WE, Garris ST, Craft C, Morgan SL (2010) Multiresidue analysis of pesticides in fruits and vegetables using disposable pipette extraction (DPX) and micro-luke method. J Agric Food Chem 58(10):5973–5981.

  5. 5.

    Xu N, Wang Y, Rong M, Ye Z, Deng Z, Chen X (2014) Facile preparation and applications of graphitic carbon nitride coating in solid-phase microextraction. J Chromatogr A 1364:53–58.

  6. 6.

    Ding X, Zhu J, Zhang Y, Xia Q, Bi W, Yang X, Yang J (2016) Separation and concentration of natural products by fast forced adsorption using well-dispersed velvet-like graphitic carbon nitride with response surface methodology optimisation. Talanta 154:119–126.

  7. 7.

    Huang J, Zhang X, Song H, Chen C, Han F, Wen C (2018) Protonated graphitic carbon nitride coated metal-organic frameworks with enhanced visible-light photocatalytic activity for contaminants degradation. Appl Surf Sci 441:85–98.

  8. 8.

    Nian Q, Wang X, Wang M, Zuo G (2019) A hybrid material composed of graphitic carbon nitride and magnetite (Fe3O4) for magnetic solid-phase extraction of trace levels of hydroxylated polycyclic aromatic hydrocarbons. Microchim Acta 186(8):497–505.

  9. 9.

    Marzi Khosrowshahi E, Matin AA (2019) A monolithic graphitic carbon nitride/polyethersulfone nanocomposite: an application of a mixed matrix membrane as a solid-phase microextraction fiber. Microchim Acta 186(10):679.

  10. 10.

    Grossi P, Olivares IR, de Freitas DR, Lancas FM (2008) A novel HS-SBSE system coupled with gas chromatography and mass spectrometry for the analysis of organochlorine pesticides in water samples. J Sep Sci 31(20):3630–3637.

  11. 11.

    World Health Organization (2017) Guidelines for drinking-water quality. Fourth Edition Incorporating the First Addendum

  12. 12.

    European Union (1998) EU Council directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. Off J Eur Commun L330:32–54

  13. 13.

    European Union (2006) Directive 2006/118/EC of the European parliament and of the council of 12 December 2006 on the protection of groundwater against pollution and deterioration. Off J Eur Commun L372:19–31

  14. 14.

    Huang Z, Chua PE, Lee HK (2015) Carbonized polydopamine as coating for solid-phase microextraction of organochlorine pesticides. J Chromatogr A 1399:8–17.

  15. 15.

    Brondi SHG, Spoljaric FC, Lanças FM (2005) Ultratraces analysis of organochlorine pesticides in drinking water by solid phase extraction coupled with large volume injection/gas chromatography/mass spectrometry. J Sep Sci 28(17):2243–2246.

  16. 16.

    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(16):2477–2486.

  17. 17.

    Li D, Zhu J, Wang M, Bi W, Huang X, Chen DD (2017) Extraction of trace polychlorinated biphenyls in environmental waters by well-dispersed velvet-like magnetic carbon nitride nanocomposites. J Chromatogr A 1491:27–35.

  18. 18.

    Wu T, Wang J, Liang W, Zang X, Wang C, Wu Q, Wang Z (2017) Single layer graphitic carbon nitride-modified graphene composite as a fiber coating for solid-phase microextraction of polycyclic aromatic hydrocarbons. Microchim Acta 184(7):2171–2180.

  19. 19.

    Luo YB, Yuan BF, Yu QW, Feng YQ (2012) Substrateless graphene fiber: a sorbent for solid-phase microextraction. J Chromatogr A 1268:9–15.

  20. 20.

    Y-p S, Ha W, Chen J, H-y Q, Y-p S (2016) Advances and applications of graphitic carbon nitride as sorbent in analytical chemistry for sample pretreatment: a review. Trends Anal Chem 84:12–21.

  21. 21.

    Fowkes FM (1964) Dispersion force contributions to surface and interfacial tensions, contact angles, and heats of immersion. In: Fowkes FM (ed) Contact angle, wettability, and adhesion, vol 43. American Chemical Society, pp 99–111.

  22. 22.

    Wang B, Wang H, Zhong X, Chai Y, Chen S, Yuan R (2016) A highly sensitive electrochemiluminescence biosensor for the detection of organophosphate pesticides based on cyclodextrin functionalized graphitic carbon nitride and enzyme inhibition. Chem Commun (Camb) 52(28):5049–5052.

  23. 23.

    Guan H, Brewer WE, Garris ST, Morgan SL (2010) Disposable pipette extraction for the analysis of pesticides in fruit and vegetables using gas chromatography/mass spectrometry. J Chromatogr A 1217(12):1867–1874.

  24. 24.

    Zhang Y, Lee HK (2012) Application of ultrasound-assisted emulsification microextraction based on applying low-density organic solvent for the determination of organochlorine pesticides in water samples. J Chromatogr A 1252:67–73.

  25. 25.

    Han Q, Wang Z, Xia J, Xia L, Chen S, Zhang X, Ding M (2013) Graphene as an efficient sorbent for the SPE of organochlorine pesticides in water samples coupled with GC-MS. J Sep Sci 36(21–22):3586–3591.

  26. 26.

    Gülbakan B, Uzun C, Çelikbıçak Ö, Güven O, Salih B (2008) Solid phase extraction of organochlorine pesticides with modified poly (styrene-divinylbenzene) microbeads using home-made solid phase extraction syringes. React Funct Polym 68(2):580–593.

  27. 27.

    Mehdinia A (2014) Preconcentration and determination of organochlorine pesticides in seawater samples using polyaniline/polypyrrole-cellulose nanocomposite-based solid phase extraction and gas chromatography-electron capture detection. J Braz Chem Soc 25(11):2048–2053.

  28. 28.

    Zhang S, Du Z, Li G (2013) Metal-organic framework-199/graphite oxide hybrid composites coated solid-phase microextraction fibers coupled with gas chromatography for determination of organochlorine pesticides from complicated samples. Talanta 115:32–39.

  29. 29.

    Zhou Q, Huang Y, Xiao J, Xie G (2011) Micro-solid phase equilibrium extraction with highly ordered TiO2 nanotube arrays: a new approach for the enrichment and measurement of organochlorine pesticides at trace level in environmental water samples. Anal Bioanal Chem 400(1):205–212.

  30. 30.

    Taghani A, Goudarzi N, Bagherian G (2016) Application of multiwalled carbon nanotubes for the preconcentration and determination of organochlorine pesticides in water samples by gas chromatography with mass spectrometry. J Sep Sci 39(21):4219–4226.

  31. 31.

    Doyle MP, Siegfried B, Dellaria JF Jr (1977) Alkyl nitrite-metal halide deamination reactions. 2. Substitutive deamination of arylamines by alkyl nitrites and copper(II) halides. A direct and remarkably efficient conversion of arylamines to aryl halides. J Org Chem 42(14):2426–2431.

  32. 32.

    Brewer WE (2003) Disposable pipette extraction. US Patent 6566145 B2,

  33. 33.

    Mastrianni KR, Metavarayuth K, Brewer WE, Wang Q (2018) Analysis of 10 β-agonists in pork meat using automated dispersive pipette extraction and LC-MS/MS. J Chromatogr B Analyt Technol Biomed Life Sci 1084:64–68.

  34. 34.

    Ibrahim WA, Nodeh HR, Sanagi MM (2016) Graphene-based materials as solid phase extraction sorbent for trace metal ions, organic compounds, and biological sample preparation. Crit Rev Anal Chem 46(4):267–283.

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The authors thankfully acknowledge the National University of Singapore (NUS) for the support provided throughout the duration of this research (Grant No. 143-000-023-001). S.C. Tan is grateful to the NUS Graduate School for Integrative Sciences and Engineering for a scholarship award.

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Correspondence to Hian Kee Lee.

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Tan, S.C., Lee, H.K. Graphitic carbon nitride as sorbent for the emulsification-enhanced disposable pipette extraction of eight organochlorine pesticides prior to GC-MS analysis. Microchim Acta 187, 129 (2020) doi:10.1007/s00604-019-4107-0

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  • Bulk material
  • g-C3N4
  • Sample preparation
  • Microextraction
  • Sorbent-based extraction
  • Large volume injection
  • Gas chromatography-mass spectrometry
  • Halogenated compounds
  • Environmental water analysis