Development of an ammonium chloride-enhanced thermal-assisted-ESI LC-HRMS method for the characterization of chlorinated paraffins

Zheng, Li; Lian, Lushi; Nie, Jianxin; Song, Yue; Yan, Shuwen; Yin, Daqiang; Song, Weihua

doi:10.1016/j.envpol.2019.113303

Cited by 17 publications

(9 citation statements)

References 40 publications

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“…Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) modes have both been applied effectively for CP analysis by monitoring [M-H] -, [M+Cl] -, or other ions [10,24,25] . The postcolumn addition of dichloromethane to the mobile phase has been shown to favor the formation of [M+Cl]ions to enhance sensitivity and selectivity [21,26] , and the same effect was achieved more recently by Zheng et al [27] using a 0.05 mM NH 4 Cl buffered mobile phase. While dichloromethane addition has become widespread for LC-HRMS analysis, the use of NH 4 Cl as a mobile phase modifier [27] has not yet been widely applied for CP measurements.…”

Section: Introductionmentioning

confidence: 85%

Method validation and comparison of quantification strategies for analysis of chlorinated paraffins in indoor dust by liquid chromatography and high-resolution mass spectrometry

McGrath¹,

Poma²

2022

JEEA

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This paper describes the validation of a method for the simultaneous analysis of short-, medium-, and long-chained chlorinated paraffins (SCCPs, MCCPs, and LCCPs, respectively) in indoor dust by ultrasonic extraction and liquid chromatography quadrupole time-of-flight high-resolution mass spectrometry (LC-QTOF-HRMS). A series of spike and recovery experiments (n = 54) were conducted using CPs with varying carbon-chain lengths, chlorination degree, and concentrations. Technical standard mixtures of the SCCPs, MCCPs, and LCCPs were used to quantify spiking experiments by two commonly used calibration procedures: pattern deconvolution and chlorine-content calibration. The results quantified by pattern deconvolution meet the acceptability limits of the European Union Reference Laboratory (EURL) for all tests with trueness ranging from 72% to 141% and good precision represented by coefficients of variation (CVs) less than 15% in all experiments. The chlorine-content calibration also performed well overall, but on average overestimated concentrations for SCCPs and MCCPs by 32% and 25%, respectively, and did not meet the EURL’s trueness limits in all cases. CVs were below 18% for all results derived from the chlorine-content quantification. The final method was successfully applied to indoor dust samples from offices (n = 4), homes (n = 3), and a vehicle (n = 1) from Melbourne, Australia, with SCCPs (C10-13), MCCPs (C14-17), and LCCPs (C18-20) detected in all samples, up to 100, 240 and 190 μg/g, respectively. A preliminary human exposure assessment suggested that CP intake via dust may constitute a major pathway of exposure for populations in Melbourne, Australia.

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Section: Introductionmentioning

confidence: 85%

Method validation and comparison of quantification strategies for analysis of chlorinated paraffins in indoor dust by liquid chromatography and high-resolution mass spectrometry

McGrath¹,

Poma²

2022

JEEA

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“…The method for LC–HRMS identification of CPs has been reported in our previous study . In brief, ammonium chloride enhanced LC–HRMS was employed to quantify CPs in CDOM solutions.…”

Section: Methodsmentioning

confidence: 99%

“…The method for LC−HRMS identification of CPs has been reported in our previous study. 25 In brief, ammonium chloride enhanced LC−HRMS was employed to quantify CPs in CDOM solutions. The analytical instrument was a liquid chromatograph (G1290 Infinity II, Agilent, USA) coupled with quadrupole time-of-flight MS (G6545 QTOF, Agilent, USA).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Microheterogeneous Distribution of Hydroxyl Radicals in Illuminated Dissolved Organic Matter Solutions

Yan

Sun

Sha

et al. 2021

Environ. Sci. Technol.

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Hydroxyl radicals ( • OH) are important reactive species that are photochemically generated through solar irradiation of chromophoric dissolved organic matter (CDOM) in surface waters. However, the spatial distribution within the complex three-dimensional structure of CDOM has not been examined. In this study, we used a series of hydrophobic chlorinated paraffins as chemical probes to elucidate the microheterogeneous distribution of • OH in illuminated CDOM solutions. The steady-state concentration of • OH inside the CDOM microphase is 210 ± 31-fold higher than the concentration in the aqueous phase. Our results suggest that the most photochemically generated • OH are confined into the CDOM microphase. Thus, illuminated CDOM behaves as a natural microreactor for • OH-based oxidations. By including intra-CDOM • OH, the quantum yield of • OH for CDOM solutions was estimated to be 2.2 ± 0.5 × 10 −3 , which is 2 orders of magnitude greater than previously thought. The elevated concentrations of photogenerated • OH within the CDOM microphase may improve the understanding of hydrophobic pollutant degradation in aqueous environments. Moreover, our results also suggest that • OH oxidation may play more important roles in the phototransformation of CDOM than previously expected.

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“…Various types of halogenated compounds (e.g., OCPs and BFRs) are determined in biotic samples using broadly applicable pretreatment procedures and subsequent group-specific instrumental analytical methods. , Gas chromatography (GC) coupled with mass spectrometry (MS) with different ion sources and corresponding parameters has been used for halogenated chemical analysis. , However, some halogenated compounds, such as long-chain chlorinated paraffins (LCCPs) and hexabromocyclododecanes (HBCDs), are not amenable to GC owing to their low vapor pressures and the tendency of their diastereomers to interconvert in the hot GC injectors. , Nevertheless, a recently developed method that couples chlorine ionization with liquid chromatography (LC)–MS offers the possibility of simultaneously scanning several polyhalogenated compounds as it involves the post-column addition of dichloromethane (DCM) coupled with LC–MS and enables the chlorine ionization of more than 200 CP congener groups . Compounds such as DPs and chlordane have also been chlorine-ionized using other mobile phase modifiers. ,, However, the chlorine-ionization efficiencies of the current methods are low. For example, very-short-chain chlorinated paraffins (vSCCPs) can only be analyzed by GC/high-resolution MS (GC–HRMS) .…”

Section: Introductionmentioning

confidence: 99%

“…For example, very-short-chain chlorinated paraffins (vSCCPs) can only be analyzed by GC/high-resolution MS (GC–HRMS) . In addition, the immiscibility of DCM and water can generate extremely high LC pressures, and current mobile phase modifiers either damage MS devices (due to these modifiers depositing inorganic salts) or produce high numbers of interference ions. ,, It is therefore necessary to develop an effective ionization method for use with HRMS to obtain extensive coverage and enable the sensitive screening of polyhalogenated compounds.…”

Section: Introductionmentioning

confidence: 99%

Tetraphenylphosphonium Chloride-Enhanced Ionization Coupled to Orbitrap Mass Spectrometry for Sensitive and Non-targeted Screening of Polyhalogenated Alkyl Compounds from Limited Serum

et al. 2022

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Although many types of halogenated compounds are known to bioaccumulate in humans, few are routinely biomonitored and many have remained uncharacterized in human exposome studies due to a lack of highsensitivity and high-resolution analytical methods. In this study, we discovered tetraphenylphosphonium chloride (Ph 4 PCl, 10 μM) as a simple additive to the mobile phase, which enhanced the ionizations of polyhalogenated alkyl compounds (such as organochlorinated pesticides [OCPs], chlorinated paraffins [CPs], dechlorane plus [DPs], and some brominated flame retardants [BFRs]) in the form [M + Cl] − and boosted mass spectrometry responses by an average of 1−3 orders of magnitude at a resolution of 140,000. Ph 4 PCl-enhanced ionization coupled with a halogenation-guided screening process was used to establish a sensitive and non-targeted method that required only single-step sample preparation and identified Cl-and/or bromine-containing alkyl compounds. The method enabled the identification of ∼700 polyhalogenated compounds from 200 μL of human serum, 240 of which were known compounds: 33 short-chain CPs, 52 median-chain CPs, 97 long-chain CPs, 22 very short-chain CPs (vSCCPs), 19 OCPs, 13 DPs, and 4 BFRs. We also identified 325 emerging contaminants (34 unsaturated CPs, 285 chlorinated fatty acid methyl esters [CFAMEs], and 6 chloro-bromo alkenes) and 130 new contaminants (114 oxygen-containing CPs, 2 hexachlorocyclohexane structural analogs, and 11 amino-containing and 3 nitrate-containing chlorinated compounds). The full scan results highlighted the dominance of CPs, CFAMEs, vSCCPs, and dichlorodiphenyltrichloroethanes in the serum samples. Ph 4 PCl-enhanced ionization enabled the sensitive and non-targeted identifications of polyhalogenated compounds in small volumes of biological fluid.

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Development of an ammonium chloride-enhanced thermal-assisted-ESI LC-HRMS method for the characterization of chlorinated paraffins

Cited by 17 publications

References 40 publications

Method validation and comparison of quantification strategies for analysis of chlorinated paraffins in indoor dust by liquid chromatography and high-resolution mass spectrometry

Method validation and comparison of quantification strategies for analysis of chlorinated paraffins in indoor dust by liquid chromatography and high-resolution mass spectrometry

Microheterogeneous Distribution of Hydroxyl Radicals in Illuminated Dissolved Organic Matter Solutions

Tetraphenylphosphonium Chloride-Enhanced Ionization Coupled to Orbitrap Mass Spectrometry for Sensitive and Non-targeted Screening of Polyhalogenated Alkyl Compounds from Limited Serum

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