First determination of C60 and C70 fullerenes and N-methylfulleropyrrolidine C60 on the suspended material of wastewater effluents by liquid chromatography hybrid quadrupole linear ion trap tandem mass spectrometry

The increasing use and production of carbon-based nanoparticles demands for new analytical approaches able to achieve sensitivities in the low ng/L range in order to assess their presence in environmental samples. This paper describes development, optimization and validation of a novel method for the analysis of C60 and, C70 fullerenes and N-methylfulleropyrrolidine C60 in the environment. The method relies on ultrasonication extraction from suspended solids in wastewater, followed by liquid chromatography (LC) coupled to a hybrid triple quadrupole linear ion trap mass spectrometry (QqLIT-MS) for trace quantification. Recoveries obtained were generally higher than 60% for both surface water and wastewaters. The overall variability of the method was below 15%, for the three fullerenes and all tested matrices: ultra-pure water, surface water and wastewater. For the effluents of wastewater treatment plants the method quantification limits (MQL) ranged from 0.2 to 1 ng/L. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1% to 2% and from 5% to 9% for intra and inter-day analysis, respectively. The developed analytical method was applied to the analysis of fullerenes in the effluents of 22 wastewater treatment plants in Catalonia (NE of Spain). 50% of the analyzed samples contained fullerenes, nine of them in the μg/L concentration range. This work constitutes the first report on the occurrence of fullerenes in suspended solids of wastewater effluents highlighting the need of nanotechnologies residues assessment for risk evaluation of nanoparticles in the environment.