Formation mechanisms of carcinogenic N-nitrosamines from dissolved organic matter derived from nitrogen-containing microplastics during chloramine disinfection

The high occurrence of microplastics (MPs) in water treatment facilities may complicate the source-control of disinfection by-products. Herein, we reported that the carcinogenic N-nitrosamines, such as N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA), were generated during monochloramine disinfection of water in which nitrogen-containing microplastics (N-MPs, such as polyamide and polyacrylonitrile) were present. The precursors of NDMA and NDEA were mainly derived from the dissolved organic matter released from N-MPs (N-MP-DOM), which were characteristic of a significantly higher proportion of polar and non-cationic fractions, favouring the N-nitrosamine formation. The results of excitation-emission-matrix spectra and orbitrap-mass spectrometry indicated that the polar components were mainly CHON and highly hydrogen-saturated molecules (H/C ≥ 1.5) (such as protein-like substrates), which are potential precursors of N-nitrosamines. Further mass difference network analysis revealed that the reactions of amine and nitro/nitroso groups in the precursors made predominant contribution to the generation of N-nitrosamines. Two potent NDMA precursors bearing a (CH₃)₂N–R structure were identified based on the diagnostic fragments (e.g., 45.0578 Da and m/z 58.0651) and in silico fragmentation tool (MetFrag 2.2) in MS² spectra. Our findings provide valuable insights into understanding the potential risks of N-MPs due to monochloramine disinfection in water treatment systems.