Abstract
A novel method for the quantitative determination of chlorinated paraffins (CPs) was developed using bromide-anion attachment atmospheric-pressure chemical ionization mass spectrometry (APCI-MS). Bromoform was used to enhance ionization of CPs. Near exclusive formation of stable bromide adduct ions ([M + Br]−) enabled accurate detection of individual CP congener groups (CnClm) with only a moderate-resolution quadrupole time-of-flight mass spectrometer. Furthermore, the method was free from interference commonly observed with chloride-anion attachment methods (e.g., decomposition ions [M + Cl – HCl]−) that require deconvolution. Together with a CnClm-response-factor algorithm for quantifying short-chain CPs and a CnClm-pattern-reconstruction algorithm for quantifying medium- and long-chain CPs, method applicability was demonstrated on biota and sediment samples. These data were generated significantly faster and with improved selectivity and sensitivity versus those of conventional measurements by chloride...
Highlights
Chlorinated paraffins (CPs) represent a diverse mixture of polychlorinated straight-chain alkanes (CnH2n+2−mClm, where n = 6−38)[1,2] commonly used as plasticizers, flame retardants, and metal cutting fluids
SCCPs were added to the Stockholm Convention on persistent organic pollutants (POPs) in 2017;4 production of alternatives such as MCCPs and LCCPs is expected to increase.[5]
Recent studies have reported on the global occurrence of SCCPs, MCCPs, and LCCPs in sewage sludge,[6,7] soil,[8] sediment cores,[9] wildlife,[10,11] indoor environments,[12−15] human blood and tissue,[16,17] and mothers’ milk,[18,19] highlighting the need to characterize health risks associated with CPs
Summary
Simultaneous analysis of SCCPs, MCCPs, and LCCPs is commonly performed using direct liquid injection chloride-anion attachment atmospheric-pressure chemical ionization mass spectrometry (Cl-anion attachment APCI-MS) using chloroform or dichloromethane.[20,21]. Accurate determination of individual CnClm groups requires either a MS resolution of >50000 (e.g., Orbitrap25) or deconvolution of mass spectra obtained from a moderate-resolution mass spectrometer,[26] which is time-consuming for hundreds of CnClm groups per analyte.[15]. Another option for distinguishing individual CnClm groups involves formation of heterohalogen CP adduct ions, for example, by introducing a halogen other than chlorine into the ion source. The method improves the sensitivity and selectivity relative to those of conventional methods and takes less time for data processing because of a lack of signal overlap
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