Protein-affinity guided identification of chlorinated paraffin components as ubiquitous chemicals

Chlorinated paraffins (CPs) have been extensively examined to identify their components. Short-chain CPs with a carbon number of 10-13 have been strictly restricted or banned due to their addition to the list of Persistent Organic Pollutants in the world. However, more constituents with potential toxicities in these complicated mixtures are still unclear. In the present study, a purification method based on the protein affinity of thyroid hormone-related proteins (transthyretin and thyroid receptor) was established. The protein-based affinity extraction coupled with high-throughput scanning successfully discover a new group of chlorinated compounds (CP(O₂)) in commercial CP mixtures. The CP(O₂)s were purified from the commercial mixtures and identified to be chlorinated fatty acid methyl esters (CFAMEs) with a carbon chain length of 17-19 and 3-11 chlorines by a combination of liquid-liquid extraction, hydrolysis, Fourier transform infrared spectrometry and Orbitrap mass spectrometry. The newly identified CFAMEs were found to be ubiquitous in the environmental matrices, and concentration ratios of ∑CFAMEs/∑CPs ranged from 0.01 to 35 in air, soil and food samples. CFAMEs were also detected in blood samples of general populations, and accumulated in humans through dietary uptake. CFAMEs can compete with T4 for binding TTR with higher potencies than CPs, possibly leading to disruptions of thyroid hormone homeostasis.