Occurrence and Distribution of Antibacterial Quaternary Ammonium Compounds in Chinese Estuaries Revealed by Machine Learning-Assisted Mass Spectrometric Analysis.

Antimicrobial resistance (AMR) undermines the United Nations Sustainable Development Goals of good health and well-being. Antibiotics are known to exacerbate AMR, but nonantibiotic antimicrobials, such as quaternary ammonium compounds (QACs), are now emerging as another significant driver of AMR. However, assessing the AMR risks of QACs in complex environmental matrices remains challenging due to the ambiguity in their chemical structures and antibacterial activity. By machine learning prediction and high-resolution mass spectrometric analysis, a list of antibacterial QACs (n = 856) from industrial chemical inventories is compiled, and it leads to the identification of 50 structurally diverse antibacterial QACs in sediments, including traditional hydrocarbon-based compounds and new subclasses that bear additional functional groups, such as choline, ester, betaine, aryl ether, and pyridine. Urban wastewater, aquaculture, and hospital discharges are the main factors influencing QAC distribution patterns in estuarine sediments. Toxic unit calculations and metagenomic analysis revealed that these QACs can influence antibiotic resistance genes (particularly sulfonamide resistance genes) through cross- and coresistances. The potential to influence the AMR is related to their environmental persistence. These results suggest that controlling the source, preventing the co-use of QACs and sulfonamides, and prioritizing control of highly persistent molecules will lead to global stewardship and sustainable use of QACs.

Occurrence and Ecological Risk of Alkylamine Triazines in Chinese Estuarine Sediments: An Emerging Class of Persistent, Mobile, and Toxic Substances.

Identifying persistent, mobile, and toxic (PMT) substances from synthetic chemicals is critical for chemical management and ecological risk assessment. Inspired by the triazine analogues (e.g., atrazine and melamine) in the original European Union's list of PMT substances, the occurrence and compositions of alkylamine triazines (AATs) in the estuarine sediments of main rivers along the eastern coast of China were comprehensively explored by an integrated strategy of target, suspect, and nontarget screening analysis. A total of 44 AATs were identified, of which 23 were confirmed by comparison with authentic standards. Among the remaining tentatively identified analogues, 18 were emerging pollutants not previously reported in the environment. Tri- and di-AATs were the dominant analogues, and varied geographic distributions of AATs were apparent in the investigated regions. Toxic unit calculations indicated that there were acute and chronic risks to algae from AATs on a large geographical scale, with the antifouling biocide cybutryne as a key driver. The assessment of physicochemical properties further revealed that more than half of the AATs could be categorized as potential PMT and very persistent and very mobile substances at the screening level. These results highlight that AATs are a class of PMT substances posing high ecological impacts on the aquatic environment and therefore require more attention.

Molecular characterization of diverse quinone analogs for discrimination of aerosol-bound persistent pyrolytic and photolytic radicals.

Aerosol-bound organic radicals, including environmentally persistent free radicals (EPFRs), are key components that affect climate, air quality, and human health. While putative structures have been proposed, the molecular characteristics of EPFRs remain unknown. Here, we report a surrogate method to characterize EPFRs in real ambient samples using mass spectrometry. The method identifies chemically relevant oxygenated polycyclic aromatic hydrocarbons (OxPAH) that interconvert with oxygen-centered EPFR (OC-EPFR). We found OxPAH compounds most relevant to OC-EPFRs are structurally rich and diverse quinones, whose diversity is strongly associated with OC-EPFR levels. Both atmospheric oxidation and combustion contributed to OC-EPFR formation. Redundancy analysis and photochemical aging model show pyrolytic sources generated more oxidized OC-EPFRs than photolytic sources. Our study reveals the detailed molecular characteristics of OC-EPFRs and shows that oxidation states can be used to identify the origins of OC-EPFRs, offering a way to track the development and evolution of aerosol particles in the environment.

An Integrated Workflow Assisted by In Silico Predictions To Expand the List of Priority Polycyclic Aromatic Compounds.

The limited information in existing mass spectral libraries hinders an accurate understanding of the composition, behavior, and toxicity of organic pollutants. In this study, a total of 350 polycyclic aromatic compounds (PACs) in 9 categories were successfully identified in fine particulate matter by gas chromatography high resolution mass spectrometry. Using mass spectra and retention indexes predicted by in silico tools as complementary information, the scope of chemical identification was efficiently expanded by 27%. In addition, quantitative structure-activity relationship models provided toxicity data for over 70% of PACs, facilitating a comprehensive health risk assessment. On the basis of extensive identification, the cumulative noncarcinogenic risk of PACs warranted attention. Meanwhile, the carcinogenic risk of 53 individual analogues was noteworthy. These findings suggest that there is a pressing need for an updated list of priority PACs for routine monitoring and toxicological research since legacy polycyclic aromatic hydrocarbons (PAHs) contributed modestly to the overall abundance (18%) and carcinogenic risk (8%). A toxicological priority index approach was applied for relative chemical ranking considering the environmental occurrence, fate, toxicity, and analytical availability. A list of 39 priority analogues was compiled, which predominantly consisted of high-molecular-weight PAHs and alkyl derivatives. These priority PACs further enhanced source interpretation, and the highest carcinogenic risk was attributed to coal combustion.

Dynamic monitoring of self-assembly by confining conformational changes of butterfly-motion-based molecules.

A simple dynamic monitoring strategy for chiral self-assembly is achieved by confining the bent-to-planar evolution observed in N,N'-diphenyl-dihydrodibenzo[a,c]phenazine derivatives (DPAC-R/S-GLD). Besides, this approach provides a facile pathway to fabricate architectures with circularly polarized luminescence (CPL) properties.

Occurrence and Temporal Trends of Benzotriazole UV Stabilizers in Mollusks (2010-2018) from the Chinese Bohai Sea Revealed by Target, Suspect, and Nontarget Screening Analysis.

Benzotriazole UV stabilizers (BZT-UVs), including 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole (UV-328) that is currently under consideration for listing under the Stockholm Convention, are applied in many commodities and industrial products. However, limited information is available on the interannual variation of their environmental occurrence. In this study, an all-in-one strategy combining target, suspect, and nontarget screening analysis was established to comprehensively explore the temporal trends of BZT-UVs in mollusks collected from the Chinese Bohai Sea between 2010 and 2018. Significant residue levels of the target analytes were determined with a maximum total concentration of 6.4 × 103 ng/g dry weight. 2-(2-Hydroxy-3-tert-butyl-5-methyl-phenyl)-5-chloro-benzotriazole (UV-326), 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole (UV-327), and 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P) were the predominant analogues, and UV-328 was the most frequently detected BZT-UV with a detection frequency (DF) of 87%. Whereas five biotransformation products and six impurity-like BZT-UVs were tentatively identified, their low DFs and semi-quantified concentrations suggest that the targeted analytes were the predominant BZT-UVs in the investigated area. A gradual decrease in the total concentrations of BZT-UVs was observed, accompanied by downward trends of the abundant compounds (e.g., UV-326 and UV-P). Consequently, the relative abundance of UV-327 increased because of its consistent environmental presence. These results suggest that continuous monitoring and risk assessment of BZT-UVs other than UV-328 are of importance in China.

Cooperative Effect of ZIF-67-Derived Hollow NiCo-LDH and MoS2 on Enhancing the Flame Retardancy of Thermoplastic Polyurethane.

In this work, a novel three-dimensional (3D) hollow nickel-cobalt layered double hydroxide (NiCo-LDH) was synthesized using zeolitic imidazole framework-67 (ZIF-67) as a template, and then utilized to functionalize molybdenum disulfide (NiCo-LDH/MoS2) via electrostatic force. Flame retardant thermoplastic polyurethane (TPU) composites were prepared by the melt blending method. Compared to pure TPU, NiCo-LDH/MoS2 filled TPU composite was endowed with a decrease of 30.9% and 55.7% of the peak heat release rate (PHRR) and the peak smoke production rate (PSPR), respectively. Furthermore, the addition of NiCo-LDH/MoS2 can significantly improve the thermal stability and char yield of the TPU composite. The catalytic carbonization effect and dilution effect of NiCo-LDH, and the barrier effect of MoS2 nanosheets enable TPU composites with excellent flame retardancy and toxic gas suppression ability.

Synthesis of 3D Hollow Layered Double Hydroxide-Molybdenum Disulfide Hybrid Materials and Their Application in Flame Retardant Thermoplastic Polyurethane.

The development of high-performance thermoplastic polyurethane (TPU) with high flame retardancy and low toxicity has always been the focus of its research. In this paper, the novel 3D hollow layered double hydroxide/molybdenum disulfide (LDH/MoS2) hybrid materials were synthesized by hydrothermal method using the MIL-88A as in situ sacrificial template and MoS2 as synergistic flame retardant. Among all TPU composites, the peak heat release rate, total heat release rate, and total smoke release rate of TPU/NiFeTb-LDH/MoS2 were reduced by 50.9%, 18.2%, and 35.8% compared with pure TPU, respectively. The results of the thermogravimetric infrared analysis demonstrated that the contents of combustible volatiles (hydrocarbons) and toxic volatiles (CO and HCN) emitted from TPU/LDH/MoS2 were significantly reduced, indicating that LDH/MoS2 hybrid materials can dramatically enhance the fire safety of TPU composites. Combined with the analysis of carbon residues and thermal stability of TPU composites, the enhanced flame retardancy and smoke suppression performances are primarily attributed to the catalytic carbonization of LDH and the physical barrier effect of MoS2.