Quantification of Short-Chain Chlorinated Paraffins by Deuterodechlorination Combined with Gas Chromatography–Mass Spectrometry

Abstract

Analysis of short-chain chlorinated paraffins (SCCPs) is extremely difficult because of their complex compositions with thousands of isomers and homologues. A novel analytical method, deuterodechlorination combined with high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS), was developed. A protocol is applied in the deuterodechlorination of SCCPs with LiAlD4, and the formed deuterated n-alkanes of different alkane chains can be distinguished readily from each other on the basis of their retention time and fragment mass ([M](+)) by HRGC-HRMS. An internal standard quantification of individual SCCP congeners was achieved, in which branched C10-CPs and branched C12-CPs were used as the extraction and reaction internal standards, respectively. A maximum factor of 1.26 of the target SCCP concentrations were determined by this method, and the relative standard deviations for quantification of total SCCPs were within 10%. This method was applied to determine the congener compositions of SCCPs in commercial chlorinated paraffins and environmental and biota samples after method validation. Low-chlorinated SCCP congeners (Cl1-4) were found to account for 32.4%-62.4% of the total SCCPs. The present method provides an attractive perspective for further studies on the toxicological and environmental characteristics of SCCPs.

Chlorines Are Not Evenly Substituted in Chlorinated Paraffins: A Predicted NMR Pattern Matching Framework for Isomeric Discrimination in Complex Contaminant Mixtures

“…This trend of congener group distribution in a CP mixture is consistent with previous studies. 29 , 33 The calculated degrees of chlorination of the C 14/15 CP mixtures agree with the manufacturer-reported values ( r 2 > 0.99) with the absolute deviation ranging from −0.22% Cl to 0.06% Cl ( Table S1 ). In addition, C 14 Cl 15 was found in the C 14 60.14% Cl mixture.…”

“… 31 The quantification performance was evaluated by the CP mixture’s degree of chlorination calculated on the basis of the congener group distribution. 32 , 33 For detailed instrumental settings and response factor calculation, see the Supporting Information and Figure S1 .…”

Chlorinated paraffins in hinges of kitchen appliances

“…Apart from two samples with chlorine contents of < 51%, this range was close to the %Cl content determined for the 52% Cl MCCP mixture (54.3% Cl). CP-52 formulations have been shown to contain highly varying amounts of SCCPs (Gao et al, 2012(Gao et al, , 2016Li et al, 2018;Sprengel & Vetter, 2020). Low shares of SCCPs (i.e., 4% and 8%, respectively) were previously detected in two CP-52 products, mainly consisting of MCCPs (Sprengel & Vetter, 2020).…”

Developments and interlaboratory study of the analysis of short-chain chlorinated paraffins

“…In 2016 Gao et al [26] developed a method for which the calculated concentration depends less on the distribution profile of SCCP congeners in the standards. This method also enabled the detection of SCCPs with Cl 1e4 and acquires information on both carbon chain length and chlorine distribution.…”