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Relative abundances of chlorine and carbon isotopologues of individual organochlorines (e.g. polychlorinated organic pollutants) are generally recognised to comply with stochastic distribution, and thus can be calculated by the binomial theorem. As a result, carbon isotope ratios derived from different chlorine-isotopologue pairs, e.g. 12C235Cl4 vs. 12C13C35Cl4, should be consistent. Yet this recognition may not exactly reflect the reality. This study investigated the consistency/inconsistency of carbon isotope compositions of chlorine-isotopologue pairs 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, along with measurements at different injection concentrations 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 in electron ionisation 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. [ABSTRACT FROM AUTHOR]

• A nontarget analysis method for alkylamides by GC-PCI-Q-Orbitrap-HRMS was developed. • An algorithm for screening and anchoring quasi-molecular ions was developed and used. • Characterization of alkylamides in 2 sockets and an electric fan was accomplished. • In all 36 alkylamides were identified and their relative contents were revealed. • Occurrence characteristics of alkylamides in the electrical products were sketched. Alkylamides are used as plastic additives in various materials and products, potentially posing risks to human health and the environment. Besides reported alkylamides in plastics, many unknown alkylamides may exist in various plastics, which are needing identification and characterization. This study performed nontarget analysis of alkylamides in electrical product plastics by gas chromatography-positive chemical ionization high-resolution mass spectrometry in full scan mode and an in-house developed data-processing algorithm. The algorithm was based on exact mass discrepancies and signal intensities of specific fragment and adduct ions of alkylamides, and was able to efficiently screen and anchor quasi-molecular ions. As a whole, 36 alkylamides were identified, of which 7 were found in all the plastics and 14 were observed in ≥ 2 plastics. The content distributions were elucidated with normalized abundances of quasi-molecular ions of alkylamides. Oleamide showed chromatographic peaks with the highest abundances in individual samples and was the most abundant alkylamide in all the plastics, of which the normalized abundances accounted for 57.42–70.06% of the total abundances of all alkylamides. Besides, (2E)-2-hexenamide, palmitamide and stearamide showed relatively high abundances, of which the relative abundances were 6.99–25.79%. The high abundances together with predicted environmental behaviors and toxicities indicate that alkylamides in plastics are worthy of further in-depth research. The nontarget analysis method including the instrumental analysis and data-processing algorithm can be applied to identification and characterization of alkylamides in more diverse matrices. In addition, the analysis results for the first time provide knowledge about the specific characteristics and relative content distributions of alkylamides in electrical product plastics from a comprehensive perspective. [ABSTRACT FROM AUTHOR]

A reliable method was proposed for the simultaneous determination of five fluoroquinolones (FQs) and two tetracyclines (TCs) in sewage sludge using ultrasonic-assisted extraction (USE) followed by SPE cleanup and high-performance liquid chromatography-mass spectrometry (HPLC-MS)/MS analysis with electrospray ionisation (ESI) in a positive mode. The USE conditions (e.g. extraction solvent, pH, and extraction cycles) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) parameters were optimised. Quantification was performed by internal standard calibration in multiple reaction monitoring mode. Recoveries of the antibacterials ranged from 41 to 123%, with relative standard deviations within 17%. The sample-based limits of quantification were 10–63 ng g−1 dry weight (dw) for FQs (ciprofloxacin, enrofloxacin, lomefloxacin, norfloxacin, and ofloxacin) and 250–500 ng g−1 dw for TCs (tetracycline and oxytetracycline). The method was applied to determine the antibacterials in sewage sludge and sediment samples were collected from the Pearl River Delta, China. Ciprofloxacin, norfloxacin, and ofloxacin were frequently detected, ranging from 1052 to 17740 ng g−1 dw in dewatered sludge samples, 585–3545 ng g−1 dw in untreated solids, and 98–258 ng g−1 dw in an urban stream sediment sample, respectively. Lomefloxacin and enrofloxacin were also occasionally detected. [ABSTRACT FROM AUTHOR]

A sensitive and reliable liquid chromatographic-tandem mass spectrometric method for enantiomeric determination of five chiral azole antifungals (econazole, ketoconazole, miconazole, tebuconazole, and propiconazole) in wastewater and sludge has been established and validated. An isotope-labeled internal standard was used for quantification. Recovery of the individual enantiomers was usually in the range of 77-102 % for wastewater and 71-95 % for sludge, with relative standard deviations within 20 %. No significant difference ( p > 0.05) was observed between recovery of pairs of enantiomers of the chiral azole antifungals except for those of tebuconazole. Method quantification limits for individual enantiomers were 0.3-10 ng L and 3-29 ng g dry weight for wastewater and sludge, respectively. The method was used to investigate the enantiomeric composition of the azole pharmaceuticals in wastewater and sludge samples from a sewage treatment plant in China. Enantiomers of miconazole, ketoconazole, and econazole were widely detected. The results showed that the azole antifungals in wastewater and sludge were generally racemic or marginally non-racemic. The method is a useful tool for investigation of the enantiomeric occurrence, behavior, and fate of the chiral azole antifungals in the environment. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Dechlorination reactions of organochlorines can commonly take place in fragmentation on electron ionization mass spectrometry (EI-MS) and collision-induced dissociation (CID) on electron ionization tandem mass spectrometry (EI-MS/MS), possibly accompanied with chlorine isotope effects. However, it remains unclear whether characteristics of chlorine isotope effects of individual organochlorines occurring on different types of mass spectrometers are similar or different. Revelation of characteristics of chlorine isotope effects on different mass spectrometers may help to elucidate mechanisms of dechlorination reactions and fragmental pathways of organochlorines. This study investigated the characteristics of chlorine isotope effects of two model organochlorines, i.e., tetrachloroethylene and trichloroethylene, during fragmentation/CID on EI-double focusing magnetic-sector high resolution MS (EI-HRMS), EI-quadrupole MS (EI-qMS) and EI-triple-quadrupole MS/MS (EI-MS/MS) that were all coupled with gas chromatography (GC). The patterns of chlorine isotope ratios measured by different instruments were different, showing different characteristics of chlorine isotope effects. On EI-HRMS, both normal and inverse chlorine isotope effects were observed; while on EI-qMS, only normal isotope effects were found, and on EI-MS/MS merely inverse isotope effects were discovered. On EI-HRMS and EI-qMS, inter-ion and intra-ion chlorine kinetic isotope effects (Cl-KIEs) might participate in isotope fractionation processes and contribute to inverse inter-ion and normal intra-ion isotope effects, respectively, and the dominant isotope effects determined the direction of observed (apparent) isotope effects. On EI-MS/MS, both inter-ion and intra-ion Cl-KIEs were inverse at high collision energies (including 30 and 45 eV) and contributed to normal inter-ion and inverse intra-ion isotope effects, respectively, and the inverse intra-ion isotope effects were the dominant, leading to the inverse apparent isotope effects in all dechlorination reactions. Particularly, the chlorine isotope ratios measured by EI-qMS exponentially decreased with the increasing Cl atoms of ions, implying that the intra-ion isotope effects rose as broken C–Cl bonds increased. Moreover, fundamentals of chlorine isotope effects in the stepwise multibond dechlorination reactions were revealed with the aid of density functional theory calculations. The different measurement timescales and geometries of the mass spectrometers and the difference in EI-induced fragmentation and CID might result in the different characteristics of chlorine isotope effects. This study may be conducive to elucidating isotope fractionation behaviors and fragmental pathways of organochlorines on EI-MS(/MS), and provides new insights into the mechanisms of dechlorination reactions losing multiple chlorine atoms. Image 1 • Chlorine isotope effects of 2 organochlorines on 3 types of EI-MS were investigated. • Stepwise dechlorination reactions led to varied Cl isotope effects on each EI-MS. • Different characteristics of Cl isotope effects on the 3 types of EI-MS were found. • Different timescales, geometries and fragmental modes might cause the characteristics. • Inter-ion and intra-ion Cl-KIEs essentially determined the observed isotope effects. [ABSTRACT FROM AUTHOR]