Multi-walled carbon nanotubes as efficient solid-phase extraction materials of organophosphorus pesticides from apple, grape, orange and pineapple fruit juices

Multi-walled carbon nanotubes (MWCNTs) have been used for the first time as solid-phase extraction (SPE) sorbents for the extraction of eight organophosphorus pesticides (i.e. ethoprophos, diazinon, chlorpyriphos-methyl, fenitrothion, malathion, chlorpyriphos, fenamiphos and buprofezin) from different commercial fruit juices (i.e. apple, grape, orange and pineapple). The developed method, which involves SPE and direct gas chromatography with nitrogen phosphorus detection analysis, is very fast, simple and cheap: only 1:1 dilution with Milli-Q water and pH adjustment to 6.0 of 10 mL of juice is necessary prior to a quick MWCNTs-SPE procedure that used only 40 mg of stationary phase (MWCNTs of 10–15 nm o.d., 2–6 nm i.d. and 0.1–10 μm length). Mean recovery values were above 73% for all the pesticides and fruit juices (between 77 and 101% for apple juice, 75 and 103% for grape juice, 73 and 103% for orange juice and 73 and 93% for pineapple juice) with a relative standard deviation (RSD) lower than 8.5% in all cases. Matrix matched calibration was carried out for each sample matrix since statistical differences between the calibration curves constructed is pure solvent and in the reconstructed juice extracts were found. Limits of detection ranged between 1.85 and 7.32 μg/L (which also represents LODs between 1.85 and 7.34 μg/kg) well below the European Union maximum residue limits for the raw fruits. The proposed method, which is demonstrated to be quick, cheap, accurate and highly selective, was also applied to the analysis of this group of pesticides in several commercial juices in which none of the selected pesticides were found.