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H-abstraction reactions occurring on electron ionization mass spectrometry (EI-MS) are a long-standing and crucial topic in MS research. Yet some critical relevant mechanisms are controversial and ambiguous, and information about the EI-induced H-abstraction reactions of halogenated organic compounds (HOCs) is completely in the dark. This study provides a systematic investigation of H-abstraction reactions of HOCs taking place on EI source using 13C6-hexachlorobenzene (13C6-HCB) and 13C6-hexabromobenzene (13C6-HBB) as exemplary compounds by gas chromatography high resolution mass spectrometry (GC-HRMS). The H-abstraction efficiencies were evaluated with the MS signal intensity ratios of ions with H-abstraction relative to the corresponding original ions (without H-abstraction). Ion source temperatures, EI energies and numbers of heavy isotope atoms (37Cl or 81Br) of isotopologues were investigated in terms of their effects on the H-abstraction efficiencies. The H-abstraction efficiencies of individual isotopologues generally decreased from the first to the last isotopologues of respective ions, and those of individual ions were different from each other, with the highest values of 0.017 and 0.444 for 13C6-HCB and 13C6-HBB, respectively. The overall H-abstraction efficiencies involving all measured ions of 13C6-HCB and 13C6-HBB were 0.004 and 0.128, respectively. EI energies and emission currents could impact the H-abstraction efficiencies. The H-abstraction reactions were inferred to belong to ion-molecule reactions. Some strategies were proposed for eliminating or alleviating the interference triggered by the H-abstraction reactions on EI-MS in identification of halogenated organic pollutants (HOPs). Our findings provide a better understanding for the EI-induced H-abstraction reactions of HOCs, and may benefit identification of HOPs in environmental analysis, especially for novel HOPs., Comment: 45 pages, 6 figures

This study investigated the consistency/inconsistency of carbon isotope compositions of chlorine-isotopologue pairs, e.g., 12C235Cl4 vs. 12C13C35Cl4, of individual organochlorines including two chloroethylenes, three polychlorinated biphenyls, methyl-triclosan and hexachlorobenzene. The raw carbon isotope ratios were measured by gas chromatography-high resolution mass spectrometry. Data simulations in terms of background subtraction, background addition, dual 13C-atoms substitution, deuterium substitution and hydrogen-transfer were conducted to confirm the validity of measured carbon isotope ratios and their differences. Inconsistent carbon isotope ratios derived from chlorine-isotopologue pairs of individual organochlorines were observed, and the isotopologues of each organochlorine were thus inferred to be non-randomly distributed. Mechanistic interpretation for these findings was tentatively proposed according to a basic principle in clumped-isotope geochemistry, reaction thermodynamics and kinetics, along with isotope effects occurring on electron ionization mass spectrometry. This study sheds light on the actual carbon isotope compositions of chlorine-isotopologue pairs of organochlorines, and yields new insights into the real distributions of carbon and chlorine isotopologues. The inconsistent carbon isotope compositions of chlorine-isotopologue pairs are anticipated to benefit the exploration of formation conditions and source identification of organochlorine pollutants., Comment: 27 pages, 4 figures

It has been reported that isotope fractionation can occur on gas chromatography (GC), yet little is known about concurrent dual-elements isotope fractionations on GC. Revelation of concurrent two-dimensional carbon and chlorine/bromine isotope fractionations of halogenated organic compounds (HOCs) on GC may be of important significance for compound-specific isotope analysis (CSIA). This study presents an in-depth investigation of the two-dimensional C and Cl/Br isotope fractionations of HOCs on GC using GC-double focus magnetic-sector high resolution mass spectrometry (GC-DFS-HRMS). The two-dimensional C and Cl/Br isotope fractionations of four organochlorines and four bromobenzenes on GC were simultaneously measured by GC-DFS-HRMS. The isotope fractionations were evaluated with isotope ratios, relative variations of isotope ratios and isotope fractionation extents. All the HOCs exhibited significant inverse C and Cl/Br isotope fractionations. The isotope fractionations were significant in both ends of chromatographic peaks, while the isotope ratios in center retention-time segments were the closest to comprehensive isotope ratios in the whole peaks. Significant correlations between C isotope fractionation and Cl/Br isotope fractionation were observed, indicating that the isotope fractionations might have strong relationships and/or be dominated by similar factors. Relevant mechanisms for the two-dimensional C and Cl/Br isotope fractionations were tentatively proposed on basis of a modified two-film model and the theories related to zero point energy. The results of this study gains new insights into concurrent two-dimensional isotope fractionation behaviors of HOCs during physical processes, and are conducive to CSIA studies involving C, Cl and Br for obtaining high-quality data, particularly to dual-elements CSIA of C and Cl/Br., Comment: 45 pages, 6 figures

Kinetic isotope effects (KIEs) taking place in mass spectrometry (MS) can provide in-depth insights into the fragmental behaviors of compounds in MS. Yet the mechanisms of KIEs in collision-induced dissociation (CID) in tandem MS are unclear, and information about chlorine KIEs (Cl-KIEs) of organochlorines in MS is particularly scarce. This study investigated the Cl-KIEs of dichloromethane, trichloroethylene and tetrachloroethylene during CID using gas chromatography-electron ionization triple-quadrupole tandem MS. Cl-KIEs were measured with MS signal intensities, and their validity was confirmed in terms of chromatograms, crosstalk effects and background subtraction influences. All the organochlorines presented large inverse Cl-KIEs, showing the largest values of 0.492, 0.910 and 0.892 at the highest collision energy for dichloromethane, trichloroethylene and tetrachloroethylene, respectively. For dichloromethane, both intra-ion and inter-ion Cl-KIEs were studied, within the ranges of 0.492-1.020 and 0.614-1.026, respectively, showing both normal and inverse Cl-KIEs depending on collision energies. The observed Cl-KIEs generally declined with the increasing collision energies from 0-60 eV, but were inferred to be independent of MS signal intensities. The Cl-KIEs are dominated by critical energies at low internal energies, while controlled by rotational barriers (or looseness/tightness of transition states) at high internal energies. It is concluded that the Cl-KIEs may depend on critical energies, bond strengths, available internal energies, and transition state looseness/tightness. The findings of this study yield new insights into the fundamentals of Cl-KIEs of organochlorines during CID, and may be conducive to elucidating the mechanisms of KIEs in collision-induced and photo-induced reactions in the actual world., Comment: 37 pages, 6 figures

This study developed a method to measure compound-specific chlorine isotopologue distribution of organochlorines for source identification and apportionment. Complete chlorine isotopologues of individual model organochlorines were detected by gas chromatography-high resolution mass spectrometry (GC-HRMS). The measured relative abundances (RAmea), simulated relative abundances (RAsim), and relative variations between RAmea and RAsim (${\Delta}$RA) were obtained on basis of the detected MS signal intensities of individual isotopologues. The method has been partially validated in precision, injection-amount dependency and temporal drifts. The standard deviations (SDs) of RAmea of all istotopologues of perchlorethylene (PCE) and trichloroethylene (TCE) from different manufacturers were 0.002%-0.069%. The SDs of ${\Delta}$RA of the first three isotopologues of PCE and TCE from different manufacturers were 0.026%-0.155%. The ${\Delta}$RA and ${\Delta}$RA patterns of the standards of PCE and TCE from different manufacturers were able to be differentiated with statistical significance. The method has been successfully applied to an analogous case of source identification and apportionment for two trichlorodiphenyls that exhibited significant chlorine isotope fractionation on the GC-HRMS system. The results demonstrate that the ${\Delta}$RA in conjunction with isotope ratios can be applied to source identification and present high-validity identification outcomes. Moreover, the RAmea can be used to implement source apportionment for organochlorines from more sources with more reliable outcomes compared with the methods using isotope ratios only. This method opens a new way to perform fingerprinting analysis of compound-specific chlorine isotopologue distribution of organochlorines, and will be a promising high-performance approach in source delineation and apportionment for chlorinated organic compounds., Comment: 30 pages, 8 figures and 1 table

Compound-specific chlorine isotope analysis (CSIA-Cl) is a practicable and high-performance approach for quantification of transformation processes and pollution source apportionment of chlorinated organic compounds. This study developed a CSIA-Cl method for perchlorethylene (PCE) and trichloroethylene (TCE) using gas chromatography-double focus magnetic-sector high resolution mass spectrometry (GC-DFS-HRMS) with a bracketing injection mode. The achieved highest precision for PCE was 0.021% (standard deviation of isotope ratios), and that for TCE was 0.025%. When one standard was used as the external isotopic standard for another of the same analyte, the lowest standard deviations of relative isotope-ratio variations ({\delta}37Cl') between the two corresponding standards were 0.064% and 0.080% for PCE and TCE, respectively. As a result, the critical {\delta}37Cl' for differentiating two isotope ratios are 0.26% and 0.32% for PCE and TCE, respectively, which are comparable with those in some reported studies using GC-quadrupole MS (GC-qMS). The lower limit of detection for CSIA-Cl of PCE was 0.1 ug/mL (0.1 ng on column), and that for TCE was determined to be 1.0 ug/mL (1.0 ng on column). Two isotope ratio calculation schemes, i.e., a scheme using complete molecular-ion isotopologues and another one using a pair of neighboring isotopologues, were evaluated in terms of precision and accuracy. The complete-isotopologue scheme showed evidently higher precision and was deduced to be more competent to reflect trueness in comparison with the isotopologue-pair scheme. The CSIA-Cl method developed in this study will be conducive to future studies concerning transformation processes and source apportionment of PCE and TCE, and light the ways to method development of CSIA-Cl for more organochlorines., Comment: 9 pages, 4 figures,1 table

Dechlorinated fragmental ions of organochlorines can be commonly found on electron ionization-mass spectrometry (EI-MS). Yet it is still unclear whether multiple dechlorination reactions taking place in EI-MS are concerted or stepwise. This study investigated the concertedness of the multiple dechlorination reactions of perchlorethylene (PCE) in EI-MS in light of the observed chlorine isotope effects during different dechlorination reactions along with the detected MS signal intensities. The fluctuant isotope ratios among different ions revealed that the observed multiple dechlorinated reactions in the EI-DFS-HRMS were stepwise. And the changing trends of isotope ratios of the ions detected by EI-qMS might suggest that the observed multiple dechlorination reactions in this MS were concerted. Mechanisms for these concerted/stepwise multiple dechlorination reactions are tentatively interpreted. Besides the evidence of isotope effects, according to the quasi-equilibrium theory, the MS signal intensities also suggested that the multiple dechlorination reactions in the EI-HRMS were likely stepwise, while those in the EI-qMS might be concerted. The distance from the ionization region to the mass analyzer entrance in an MS may be a critical factor affecting the dechlorination reactions of ions flying over this distance. This distance in the EI-qMS is significantly shorter than that in the EI-HRMS. Thus, the main detected ions in the EI-qMS might be generated during the ionization and in-source fragmentation processes, while the main ions detected in the EI-HRMS might be produced during the fragmentation of precursor ions flying over the distance. We deduce that the main dechlorination reactions in the ionization region were concerted, while those taking place during the flight of precursor ions over the distance from the ionization region to the mass analyzer entrance were stepwise., Comment: 26 pages, four figures

Compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) has become a useful approach for degradation pathway investigation and source appointment of halogenated organic pollutants (HOPs). CSIA-Cl/Br is usually conducted by gas chromatography-mass spectrometry (GC-MS), which could be negatively impacted by chlorine and bromine isotope fractionation of HOPs on GC columns. In this study, 31 organochlorines and 4 organobromines were systematically investigated in terms of Cl/Br isotope fractionation on GC columns using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). On-column chlorine/bromine isotope fractionation behaviors of the HOPs were explored, presenting various isotope fractionation modes and extents. Twenty-nine HOPs exhibited inverse isotope fractionation, and only polychlorinated biphenyl-138 (PCB-138) and PCB-153 presented normal isotope fractionation. And no observable isotope fractionation was found for the rest four HOPs, i.e., PCB-101, 1,2,3,7,8-pentachlorodibenzofuran, PCB-180 and 2,3,7,8-tetrachlorodibenzofuran. The isotope fractionation extents of different HOPs varied from below the observable threshold (0.50%) to 7.31% (PCB-18). The mechanisms of the on-column chlorine/bromine isotope fractionation were tentatively interpreted with the Craig-Gordon model and a modified two-film model. Inverse isotope effects and normal isotope effects might contribute to the total isotope effects together and thus determine the isotope fractionation directions and extents. Proposals derived from the main results of this study for CSIA-Cl/Br research were provided for improving the precision and accuracy of CSIA-Cl/Br results. The findings of this study will shed light on the development of CSIA-Cl/Br methods using GC-MS techniques, and help to implement the research using CSIA-Cl/Br to investigate the environmental behaviors and pollution sources of HOPs., Comment: 30 pages, 5 figures

Revelation of chlorine and bromine isotope fractionation of halogenated organic compounds (HOCs) in electron ionization mass spectrometry (EI-MS) is crucial for compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) using gas chromatography EI-MS (GC-EI-MS). This study systematically investigated chlorine/bromine isotope fractionation in EI-MS of HOCs including 12 organochlorines and 5 organobromines using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Chlorine/bromine isotope fractionation behaviors of the HOCs in EI-MS showed varied isotope fractionation patterns and extents depending on compounds. Besides, isotope fractionation patterns and extents varied at different EI energies, demonstrating potential impacts of EI energy on the chlorine/bromine isotope fractionation. Hypotheses of inter-ion and intra-ion isotope fractionations were applied to interpreting the isotope fractionation behaviors. The inter-ion and intra-ion isotope fractionations counteractively contributed to the apparent isotope ratio for a certain dehalogenated product ion. The isotope fractionation mechanisms were tentatively elucidated on basis of the quasi-equilibrium theory. In the light of the findings of this study, isotope ratio evaluation scheme using complete molecular ions and the EI source with sufficient stable EI energies may be helpful to achieve optimal precision and accuracy of CSIA-Cl/Br data. The method and results of this study can help to predict isotope fractionation of HOCs during dehalogenation processes and further to reveal the dehalogenation pathways., Comment: 32 pages, 6 figures