Determination of aqueous fullerene aggregates in water by ultrasound-assisted dispersive liquid–liquid microextraction with liquid chromatography–atmospheric pressure photoionization-tandem mass spectrometry

A simple and solvent-minimized method for the determination of three aqueous fullerene aggregates (nC60, nC70, and aqueous [6,6]-phenyl C61 butyric acid methyl ester (nPCBM)) in water samples is described. The method involves the use of ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) coupled liquid chromatography–tandem mass spectrometry with atmospheric pressure photoionization (LC–APPI-MS/MS). The parameters affecting the extraction efficiency of the analytes from water samples were systematically investigated and the conditions optimized. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of 2-propanol (as a disperser solvent) and 10 μL of benzyl bromide (as an extraction solvent) into 10 mL of an aqueous solution (pH 10.0) containing 1% sodium chloride in a conical bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5000 rpm (10 min), the sedimented phase 5.0 μL was directly injected into the LC–APPI-MS/MS system. The limits of quantification (LOQs) were 150, 60 and 8 ng L−1 for nPCBM, nC60 and nC70, respectively. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 12% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 70 and 86%. A standard addition method was used to quantitate three aqueous fullerene aggregates, and the concentrations of these aqueous fullerene aggregates were determined to be in the range from n.d. to 130 ng L−1 in various environmental samples including municipal influent and effluent samples, industrial wastewater samples, and surface water samples.