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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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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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).

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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