Fullerenes for aromatic and non-aromatic N-nitrosamines discrimination

The detection of N-nitrosamines (NAms) in water supplies is an environmental and public health issue because many NAms are classified as probable human carcinogens. Non-aromatic (aliphatic and cyclic) NAms are more toxic than aromatic ones as their maximum admissible concentration is limited in drinking water (20–2000 ng L−1). From that premise, a simple and novel method to discriminate between both fractions of NAms according to their toxicity was proposed. An automatic solid-phase extraction unit containing two sequential sorbent columns was constructed. A sample volume of 25 mL was passed through a C60 fullerene column in which only the aromatic fraction was retained, and the effluent was then passed through a Merck LiChrolut EN column where the non-aromatic fraction was retained. Following elution of the non-aromatic NAms with 150 μL of ethyl acetate–acetonitrile (9:1), 1 μL of the extract was injected into a GC/MS. A comparative study of C60 and C70 fullerenes and nanotubes revealed C60 fullerene to be the best choice to selectively retain the aromatic fraction. The method exhibits a linear range of 15–20,000 ng L−1; limits of detection of 4–15 ng L−1; and an RSD of ∼5%. Recoveries throughout the whole method were between 95% and 102% for six non-aromatic NAms spiked into several types of waters. Our study demonstrates that a simple and fast SPE system (10 min per sample) with a customary GC–MS instrument permits the quantification of these amines in complex matrices with considerable sensitivity and selectivity.