Occurrence of contaminants of emerging concern in surface waters from Paraopeba River Basin in Brazil: seasonal changes and risk assessment

This study describes the application of gas chromatography coupled to mass spectrometry (GC-MS) to evaluate the occurrence of 12 CECs-contaminants of emerging concern (bisphenol A, diclofenac, 17 beta-estradiol, estriol, estrone, 17 alpha-ethinylestradiol, gemfibrozil, ibuprofen, naproxen, 4-nonylphenol, 4-octylphenol, and acetaminophen) in surface waters from Paraopeba River Basin, Minas Gerais State, Brazil. The analytical procedure was validated and applied to 60 surface water samples collected across four sampling campaigns along the upper and middle watershed. Methods for CECs determination involved sample filtration, and solid-phase extraction (SPE) with subsequent derivatization of the target compounds prior to their analysis by GC-MS. The LOQ varied from 3.6 to 14.4 ng/L and extraction recoveries ranged from 46.1 to 107.1% for the lowest spiked concentration level (10 ng/L). The results showed a profile of spatial distribution of compounds, as well as the influence of rainfall. Ibuprofen (1683.9 ng/L), bisphenol (1587.7 ng/L), and naproxen (938.4 ng/L) occurred in higher concentrations during the rainy season, whereas during the dry season, the concentrations of bisphenol (1057.7 ng/L), estriol (991.0 ng/L), and estrone (978.4 ng/L) were highlighted. The risk assessment of human exposure shows that for most contaminants, the concentration is well below the estimated thresholds for chronic toxicity from water intake. However, estradiol and 17 alpha-ethinylestradiol showed concentrations in the same order of magnitude as the guide values estimated for babies.