Occurrence of N-nitrosamines in U.S. freshwater sediments near wastewater treatment plants

In the present study, 40 freshwater sediments collected near 14 wastewater treatment plants (WWTPs) across the United States were analyzed for eight N-nitrosamines by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Three N-nitrosamines were detected for the first time in freshwater sediments in units of ng/g dry weight at the specified detection frequency: N-nitrosodibutylamine (NDBA; 0.2–3.3; 58%), N-nitrosodiphenylamine (NDPhA; 0.2–4.7; 50%), and N-nitrosopyrrolidine (NPYR; 3.4–19.6; 18%). At least one N-nitrosamine was detected in 70% (28/40) of sediments analyzed. Non-detect values in units of ng/g dw were obtained for N-nitrosodimethylamine (NDMA; <10.2), N-nitrosomethylethylamine (NMEA; <1.7), N-nitrosodiethylamine (NDEA; <3.9), N-nitroso-di-n-propylamine (NDPA; <1.7), and N-nitrosopiperidine (NPIP; <3.6). Principal component analysis specifically points to two of multiple potential pathways explaining N-nitrosamine occurrences in sediment: NDBA and NDPhA were positively correlated with bulk water ammonia and pH levels, and NPYR with sediment content of organic carbon and iron. Interestingly, N-nitrosamine occurrences up- and downstream of WWTPs were statistically indistinguishable (p > 0.05). This is the first report on the occurrence of the carcinogenic N-nitrosamines NDBA, NDPhA, and NPYR in U.S. freshwater sediments. Discovery of this phenomenon warrants further research on the compounds’ origin, environmental persistence, aquatic toxicity, and risks posed.