Biomass-derived carbon nanospheres decorated by manganese oxide nanosheets, intercalated into polypyrrole, as an inside-needle capillary adsorption trap sorbent for the analysis of linear alkylbenzenes

Carbon nanospheres (CNSs) were derived hydrothermally from biomass (orange peels) and decorated by manganese dioxide (MnO₂) nanosheets. The MnO₂/CNSs nanocomposite was intercalated into polypyrrole (PPy) during flow-through in-situ electropolymerization of pyrrole on the surface of the inner wall of a stainless-steel needle to prepare an inside-needle capillary adsorption trap (INCAT) device. The surface morphology, thermogravimetric behavior, sorption characteristics, and structure of the MnO₂/CNSs@PPy nanocomposite were characterized using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX), nitrogen physisorption by the Brunauer-Emmett-Teller (BET) method, dynamic light scattering (DLS) size distribution, and Fourier-transform infrared spectrometry (FT-IR). The INCAT device was coupled with GC-FID and applied for dynamic headspace analysis of linear alkyl benzenes (LABs) in wastewater samples. The effective experimental variables on the extraction efficiency was optimized using a central composite design (CCD) based on response surface methodology (RSM). Under the optimal conditions, the limits of detection (LODs) were in the range of 0.5–1.0 ng mL⁻¹. The calibration plots were linear over the range of 0.01–10 μg mL⁻¹. The relative standard deviations (RSDs%) for intra-day, inter-day, and inter-INCAT precision were calculated 5.3–8.3%, 9.4–13.5%, and 13.6–16.9%, respectively. The developed technique was employed successfully for the analysis of LABs in water and wastewater samples with average recovery values ranging from 92 to 109%. A single INCAT device was used more than 90 times without significant change in its extraction capability.