A Novel Method for Profiling and Quantifying Short- and Medium-Chain Chlorinated Paraffins in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography–Electron Capture Negative Ionization High-Resolution Time-of-Flight Mass Spectrometry

Chlorinated paraffins (CPs) are complex technical mixtures containing thousands of isomers. Analyzing CPs in environmental matrices is extremely challenging. CPs have broad, unresolved profiles when analyzed by one-dimensional gas chromatography (GC). Comprehensive two-dimensional GC (GC×GC) can separate CPs with a high degree of orthogonality. A novel method for simultaneously profiling and quantifying short- and medium-chain CPs, using GC×GC coupled with electron capture negative ionization high-resolution time-of-flight mass spectrometry, was developed. The method allowed 48 CP formula congener groups to be analyzed highly selectively in one injection through accurate mass measurements of the [M – Cl]⁻ ions in full scan mode. The correlation coefficients (<i>R</i>²) for the linear calibration curves for different chlorine contents were 0.982 for short-chain CPs and 0.945 for medium-chain CPs. The method was successfully used to determine CPs in sediment and fish samples. By using this method, with enhanced chromatographic separation and high mass resolution, interferences between CP congeners and other organohalogen compounds, such as toxaphene, are minimized. New compounds, with the formulas C₉H₁₄Cl₆ and C₉H₁₃Cl₇, were found in sediment and biological samples for the first time. The method was shown to be a powerful tool for the analysis of CPs in environmental samples

Human Exposure to Short- and Medium-Chain Chlorinated Paraffins via Mothers’ Milk in Chinese Urban Population

Chlorinated paraffins (CPs) are high production volume synthetic chemicals, found ubiquitously in various environmental matrices. However, little information is available on CP contamination in mothers’ milk. In this study, 1370 urban mothers’ milk samples were collected from 12 Chinese provinces in 2007 and 16 provinces in 2011. CP geographical distribution and congener group profiles were studied to assess the CP levels and figure out the source of exposure in humans. Twenty-eight pooled samples were analyzed for 48 short-chain CP (SCCP) and medium-chain CP (MCCP) congener groups using the GC × GC-ECNI-HRTOFMS method. The median concentrations of SCCPs were 681 and 733 ng/g lipid in 2007 and 2011, respectively; median concentrations of MCCPs were 60.4 and 64.3 ng/g lipid in 2007 and 2011, respectively. Variations of more than 2 orders of magnitude in CP exposure levels were found between different provinces. The levels of CPs increased from 2007 to 2011, which indicates that CP production and use may be an important exposure source. This is the first global comprehensive and large-scale investigation of CPs in mothers’ milk, and it lays foundations for improving our understanding of the metabolism of CPs in humans. The high CP concentrations found in Chinese mothers’ milk should raise concern about potential toxic effects in both mothers and breastfeeding infants