Per- and polyfluoroalkyl substances (PFAS) have been widely detected in global surface waters since the early 2000s. Here, we have compiled and analyzed the published data for perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs) in surface waters of coastal seas, the Great Lakes, and open oceans to examine temporal and geospatial trends. Mass discharges from major rivers were also estimated. A large number of measurements of individual PFAS have been made in these surface waters (29 500 values), with seven C4-C10 PFSAs and nine C4-C12 PFCAs accounting for 83% of all data. However, most results (85% for PFSAs; 80% for PFCAs) were for the coastal seas of Western Europe, China, Korea, and Japan, while results were limited for coastal North America and lacking for South America and Africa. Highest median concentrations of PFCAs and PFSAs were reported in the Bohai and Yellow Seas region of China as well as in the North and Baltic seas in Europe. Significant declines in median PFSAs and C7-C12 PFCAs were also observed for the period 2012-2018 in these same regions, and for 2004-2017 in the Great Lakes. Mass discharge estimates indicated continued substantial riverine emissions of long chain (C7-C12) PFCAs in the period 2015-2019 for the coastal seas of China and reductions in emissions for Western European rivers compared to earlier time periods.

Chlorinated paraffins (CPs) can be mixtures of nearly a half-million possible isomers. Despite the extensive use of CPs, their isomer composition and effects on the environment remain poorly understood. Here, we reveal the isomeric distributions of nine CP mixtures with single-chain lengths (C-14/15) and varying degrees of chlorination. The molar distribution of CnH2n+2-mClm in each mixture was determined using high-resolution mass spectrometry (MS). Next, the mixtures were analyzed by applying both one-dimensional H-1, C-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy. Due to substantially overlapping signals in the experimental NMR spectra, direct assignment of individual isomers was not possible. As such, a new NMR spectral matching approach that used massive NMR databases predicted by a neural network algorithm to provide the top 100 most likely structural matches was developed. The top 100 isomers appear to be an adequate representation of the overall mixture. Their modeled physicochemical and toxicity parameters agree with previous experimental results. Chlorines are not evenly distributed in any of the CP mixtures and show a general preference at the third carbon. The approach described here can play a key role in understanding of complex isomeric mixtures such as CPs that cannot be resolved by MS alone.