Chlorine and Bromine Isotope Fractionation of Halogenated Organic Pollutants on Gas Chromatography Columns

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 figure

A penalty ADMM with quantized communication for distributed optimization over multi-agent systems

summary:In this paper, we design a distributed penalty ADMM algorithm with quantized communication to solve distributed convex optimization problems over multi-agent systems. Firstly, we introduce a quantization scheme that reduces the bandwidth limitation of multi-agent systems without requiring an encoder or decoder, unlike existing quantized algorithms. This scheme also minimizes the computation burden. Moreover, with the aid of the quantization design, we propose a quantized penalty ADMM to obtain the suboptimal solution. Furthermore, the proposed algorithm converges to the suboptimal solution with an $O(\frac{1}{k})$ convergence rate for general convex objective functions, and with an R-linear rate for strongly convex objective functions