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Integrating automated machine learning and metabolic reprogramming for the identification of microplastic in soil: A case study on soybean. 整合自动机器学习和代谢重编程,识别土壤中的微塑料:大豆案例研究。
Pub Date : 2024-10-05 Epub Date: 2024-08-22 DOI: 10.1016/j.jhazmat.2024.135555
Zhimin Liu, Weijun Wang, Yibo Geng, Yuting Zhang, Xuan Gao, Junfeng Xu, Xiaolu Liu

The accumulation of polyethylene microplastic (PE-MPs) in soil can significantly impact plant quality and yield, as well as affect human health and food chain cycles. Therefore, developing rapid and effective detection methods is crucial. In this study, traditional machine learning (ML) and H2O automated machine learning (H2O AutoML) were utilized to offer a powerful framework for detecting PE-MPs (0.1 %, 1 %, and 2 % by dry soil weight) and the co-contamination of PE-MPs and fomesafen (a common herbicide) in soil. The development of the framework was based on the results of the metabolic reprogramming of soybean plants. Our study stated that traditional ML exhibits lower accuracy due to the challenges associated with optimizing complex parameters. H2O AutoML can accurately distinguish between clean soil and contaminated soil. Notably, H2O AutoML can detect PE-MPs as low as 0.1 % (with 100 % accuracy) and co-contamination of PE-MPs and fomesafen (with 90 % accuracy) in soil. The VIP and SHAP analyses of the H2O AutoML showed that PE-MPs and the co-contamination of PE-MPs and fomesafen significantly interfered with the antioxidant system and energy regulation of soybean. We hope this study can provide a reliable scientific basis for sustainable development of the environment.

聚乙烯微塑料(PE-MPs)在土壤中的积累会严重影响植物的质量和产量,也会影响人类健康和食物链循环。因此,开发快速有效的检测方法至关重要。本研究利用传统的机器学习(ML)和 H2O 自动机器学习(H2O AutoML)提供了一个强大的框架,用于检测土壤中的 PE-MPs(按土壤干重计算分别为 0.1%、1% 和 2%)以及 PE-MPs 和福美双(一种常见的除草剂)的共污染。该框架是根据大豆植物代谢重编程的结果制定的。我们的研究表明,由于优化复杂参数所面临的挑战,传统 ML 的准确度较低。H2O AutoML 可以准确区分清洁土壤和污染土壤。值得注意的是,H2O AutoML 可以检测出土壤中低至 0.1%的 PE-MPs(准确率为 100%),以及 PE-MPs 和福美沙芬的共污染(准确率为 90%)。H2O AutoML 的 VIP 和 SHAP 分析表明,PE-MPs 以及 PE-MPs 和福美双的共污染会显著干扰大豆的抗氧化系统和能量调节。我们希望这项研究能为环境的可持续发展提供可靠的科学依据。
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引用次数: 0
Efficient density functional theory directed identification of siderophores with increased selectivity towards indium and germanium. 以密度泛函理论为指导,高效识别对铟和锗具有更高选择性的苷元。
Pub Date : 2024-10-05 Epub Date: 2024-08-19 DOI: 10.1016/j.jhazmat.2024.135523
Christian Hintersatz, Satoru Tsushima, Tobias Kaufer, Jerome Kretzschmar, Angela Thewes, Katrin Pollmann, Rohan Jain

Siderophores are promising ligands for application in novel recycling and bioremediation technologies, as they can selectively complex a variety of metals. However, with over 250 known siderophores, the selection of suiting complexants in the wet lab is impractical. Thus, this study established a density functional theory (DFT) based approach to efficiently identify siderophores with increased selectivity towards target metals on the example of germanium and indium. Considering 239 structures, chemically similar siderophores were clustered, and their complexation reactions modeled utilizing DFT. The calculations revealed siderophores with, compared to the reference siderophore desferrioxamine B (DFOB), up to 128 % or 48 % higher selectivity for indium or germanium, respectively. Experimental validation of the method was conducted with fimsbactin A and agrobactin, demonstrating up to 40 % more selective indium binding and at least sevenfold better germanium binding than DFOB, respectively. The results generated in this study open the door for the utilization of siderophores in eco-friendly technologies for the recovery of many different critical metals from various industry waters and leachates or bioremediation approaches. This endeavor is greatly facilitated by applying the herein-created database of geometry-optimized siderophore structures as de novo modeling of the molecules can be omitted.

嗜苷酸盐是很有希望应用于新型回收和生物修复技术的配体,因为它们可以选择性地络合各种金属。然而,目前已知的嗜苷酸盐有 250 多种,在湿实验室中选择合适的络合剂是不切实际的。因此,本研究以锗和铟为例,建立了一种基于密度泛函理论(DFT)的方法,以有效识别对目标金属具有更高选择性的络合剂。考虑到 239 种结构,对化学性质相似的嗜硒团进行了聚类,并利用 DFT 建立了它们的络合反应模型。计算结果表明,与参考苷元去铁胺 B(DFOB)相比,苷元对铟或锗的选择性分别高出 128% 或 48%。该方法通过菲姆巴坦 A 和农杆菌素进行了实验验证,结果表明与 DFOB 相比,铟的选择性结合率高达 40%,锗的结合率至少高出 7 倍。这项研究的结果为在生态友好型技术中利用嗜硒酸盐从各种工业用水和浸出液中回收多种不同的关键金属或采用生物修复方法打开了大门。由于可以省略对分子的重新建模,因此应用本研究创建的苷元结构几何优化数据库可以极大地促进这项工作。
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引用次数: 0
Novel visible-light activated photocatalytic ultrafiltration membrane for simultaneous separation and degradation of emerging contaminants. 用于同时分离和降解新兴污染物的新型可见光激活光催化超滤膜。
Pub Date : 2024-10-05 Epub Date: 2024-08-24 DOI: 10.1016/j.jhazmat.2024.135634
Ran Li, Zhidong Wei, Peng Li, Yangbo Qiu, Chengyi Wang, Chao Wang, Long-Fei Ren, Jiahui Shao, Yiliang He

Emerging contaminants (ECs) in secondary effluent of wastewater treatment plants (WWTPs) have received increasing attention due to their adverse effects on aquatic ecosystems and human health. Herein, visible-light responsive photocatalyst TM (TiO2 @NH2-MIL-101(Fe)) and resultant photocatalytic ultrafiltration (PUF, PVDF/TM) membrane were prepared to remove 32 typical compounds of antibiotics, 296 compounds of antibiotic resistance genes (ARGs), and their corresponding bacterial hosts. The construction of heterojunction photocatalyst promoted the electron transfer from NH2-MIL-101(Fe) to TiO2 and the formation of N-TiO2, enhancing visible-light (λ ≥ 420 nm) photocatalytic activity. With highly-hydrophilic surface and delicately-regulated pore structure, the initial water permeance of optimal PUF membrane significantly increased to 3912.2 L/m2/h at 1.0 bar. Meanwhile, membrane retention (via adsorption, electrostatic interaction, and steric hindrance) was improved due to the narrowed pore size, highly-negative surface charge and abundant functional groups. Additionally, hydroxyl radical (•OH) was the dominant active reactive oxygen species (ROS) for ECs degradation, and the narrowed pore structure could serve as microreactors to increase ROS concentration and reduce migration distance. Consequently, the removal efficiencies of antibiotics, bacteria and ARGs were 86.5 %, 91.4 % and 91.8 %, respectively. Overall, this novel visible-light-activated PUF membrane expands membrane application, and has great potential in ECs treatment.

由于对水生生态系统和人类健康的不利影响,污水处理厂(WWTPs)二级出水中的新污染物(ECs)日益受到关注。本文制备了可见光响应光催化剂TM(TiO2 @NH2-MIL-101(Fe))及其光催化超滤膜(PUF,PVDF/TM),用于去除32种典型的抗生素化合物、296种抗生素耐药基因(ARGs)化合物及其相应的细菌宿主。异质结光催化剂的构建促进了 NH2-MIL-101(Fe)向 TiO2 的电子转移和 N-TiO2 的形成,提高了可见光(λ ≥ 420 nm)下的光催化活性。最佳 PUF 膜具有高亲水性表面和微调的孔隙结构,在 1.0 巴的条件下,其初始透水量显著增加到 3912.2 L/m2/h。同时,由于孔径变窄、表面电荷呈高负值和功能基团丰富,膜的截留能力(通过吸附、静电作用和立体阻碍)也得到了改善。此外,羟基自由基(-OH)是降解 ECs 的主要活性氧(ROS),而狭窄的孔隙结构可作为微反应器,增加 ROS 浓度并缩短迁移距离。因此,抗生素、细菌和 ARGs 的去除率分别为 86.5%、91.4% 和 91.8%。总之,这种新型可见光激活 PUF 膜扩大了膜的应用范围,在治疗心血管疾病方面具有巨大潜力。
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引用次数: 0
Rainwater-borne H2O2 accelerates roxarsone degradation and reduces bioavailability of arsenic in paddy rice soils. 雨水中的 H2O2 可加速洛克沙砷的降解,降低砷在水稻田土壤中的生物利用率。
Pub Date : 2024-10-05 Epub Date: 2024-08-23 DOI: 10.1016/j.jhazmat.2024.135633
Kaiqing Fan, Liji Chen, Huashou Li, Jun Wei Lim, Chuxia Lin, Junhao Qin, Rongliang Qiu

Contamination of rice by arsenic represents a significant human health risk. Roxarsone -bearing poultry manure is a major pollution source of arsenic to paddy soils. A mesocosm experiment plus a laboratory experiment was conducted to reveal the role of rainwater-borne H2O2 in the degradation of roxarsone in paddy rice soils. While roxarsone could be degraded via chemical oxidation by Fenton reaction-derived hydroxyl radical, microbially mediated decomposition was the major mechanism. The input of H2O2 into the paddy soils created a higher redox potential, which favored certain roxarsone-degrading and As(III)-oxidizing bacterial strains and disfavored certain As(V)-reducing bacterial strains. This was likely to be responsible for the enhanced roxarsone degradation and transformation of As(III) to As(V). Fenton-like reaction also tended to enhance the formation of Fe plaque on the root surface, which acted as a filter to retain As. The dominance of As(V) in porewater, combined with the filtering effect of Fe plaque significantly reduced the uptake of inorganic As by the rice plants and consequently its accumulation in the rice grains. The findings have implications for developing management strategies to minimize the negative impacts from the application of roxarsone-containing manure for fertilization of paddy rice soils.

砷污染水稻对人类健康构成重大威胁。含洛克沙砷的家禽粪便是稻田土壤中砷的主要污染源。为了揭示雨水携带的 H2O2 在稻田土壤中洛克沙砷降解过程中的作用,我们进行了中观宇宙实验和实验室实验。虽然洛克沙砷可以通过芬顿反应产生的羟基自由基进行化学氧化降解,但微生物介导的分解是主要机制。向稻田土壤中输入 H2O2 会产生较高的氧化还原电位,有利于某些洛克沙砷降解菌株和氧化 As(III)菌株,不利于某些还原 As(V)菌株。这很可能是罗沙松降解和 As(III) 转化为 As(V) 增强的原因。芬顿样反应还倾向于促进根表面铁斑块的形成,而铁斑块则起着过滤作用,可以截留 As。As(V) 在孔隙水中占主导地位,再加上铁斑的过滤作用,大大减少了水稻植株对无机砷的吸收,从而减少了无机砷在稻粒中的积累。这些发现有助于制定管理策略,最大限度地减少施用含洛克沙砷的粪肥对水稻田土壤的负面影响。
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引用次数: 0
A PM2.5 pollution-level adaptive air filtration system based on elastic filters for reducing energy consumption. 基于弹性过滤器的 PM2.5 污染级自适应空气过滤系统,可降低能耗。
Pub Date : 2024-10-05 Epub Date: 2024-08-15 DOI: 10.1016/j.jhazmat.2024.135546
Zhuolun Niu, Qiguang He, Chun Chen

Exacerbated by human activities and natural events, air pollution poses severe health risks, requiring effective control measures to ensure healthy living environments. Traditional filtration systems that employ high-efficiency particulate air (HEPA) filters are capable of effectively removing particulate matter (PM) in indoor environments. However, these systems often work without considering the fluctuations in air pollution levels, leading to high energy consumption. This study proposed a novel PM2.5 pollution-level adaptive air filtration system that combined elastic thermoplastic polyurethane (TPU) filters and an Internet of Things (IoT) system. The developed system can effectively adjust its filtration performance (i.e., pressure drop and PM2.5 filtration efficiency) in response to real-time air quality conditions by mechanically altering the structures of TPU filters. Furthermore, while operating in varied pollution conditions, the proposed system demonstrated remarkable reductions in pressure drop without notably compromising the pollution control capability. Finally, the energy consumption of the pollution-level adaptive air filtration system was estimated when applied in mechanical ventilation systems in different cities (Hong Kong, Beijing, and Xi'an) with various pollution conditions. The results revealed that, compared to a traditional fixed system, the annual energy consumption could be reduced by up to ∼26.4 % in Hong Kong.

由于人类活动和自然事件的加剧,空气污染带来了严重的健康风险,需要采取有效的控制措施来确保健康的生活环境。采用高效空气微粒(HEPA)过滤器的传统过滤系统能够有效去除室内环境中的微粒物质(PM)。然而,这些系统在工作时往往没有考虑空气污染水平的波动,从而导致高能耗。本研究提出了一种新型 PM2.5 污染水平自适应空气过滤系统,该系统结合了弹性热塑性聚氨酯(TPU)过滤器和物联网(IoT)系统。所开发的系统可通过机械改变热塑性聚氨酯过滤器的结构,有效调节其过滤性能(即压降和 PM2.5 过滤效率),以应对实时空气质量条件。此外,在不同的污染条件下运行时,所提出的系统在不明显影响污染控制能力的情况下显著降低了压降。最后,在不同城市(香港、北京和西安)的不同污染条件下,对污染级别自适应空气过滤系统应用于机械通风系统的能耗进行了估算。结果表明,与传统的固定系统相比,香港每年的能耗最多可减少 26.4%。
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引用次数: 0
Transfer of heavy metals along the food chain: A review on the pest control performance of insect natural enemies under heavy metal stress. 重金属沿食物链的转移:重金属胁迫下昆虫天敌的害虫控制性能综述。
Pub Date : 2024-10-05 Epub Date: 2024-08-22 DOI: 10.1016/j.jhazmat.2024.135587
Zhe Zhang, Hongfei Wu, Aoying Zhang, Mingtao Tan, Shanchun Yan, Dun Jiang

Heavy metal contamination represents a critical global environmental concern. The movement of heavy metals through the food chain inevitably subjects insect natural enemies to heavy metal stress, leading to various adverse effects. This review assesses the risks posed by heavy metal exposure to insect natural enemies, evaluates how such exposure impacts their pest control efficacy, and investigates the mechanisms affecting their fitness. Heavy metals transfer and accumulate from soil to plants, then to herbivorous insects, and ultimately to their natural enemies, impeding growth, development, and reproduction of insect natural enemies. Typically, diminished growth and reproduction directly compromise the pest control efficacy of these natural enemies. Nonetheless, within tolerable limits, increased feeding may occur as these natural enemies strive to meet the energy demands for detoxification, potentially enhancing their pest control capabilities. The production of reactive oxygen species and oxidative damage caused by heavy metals in insect natural enemies, combined with disrupted energy metabolism in host insects, are key factors contributing to the reduced fitness of insect natural enemies. In summary, heavy metal pollution emerges as a significant abiotic factor adversely impacting the pest control performance of these beneficial insects.

重金属污染是一个严重的全球环境问题。重金属在食物链中的移动不可避免地会使昆虫天敌受到重金属胁迫,从而导致各种不利影响。本综述评估了昆虫天敌暴露于重金属所带来的风险,评价了这种暴露如何影响它们的害虫控制功效,并研究了影响其适应性的机制。重金属从土壤转移和积累到植物,然后转移到食草昆虫,最终转移到天敌,阻碍昆虫天敌的生长、发育和繁殖。通常情况下,生长和繁殖能力的下降会直接影响这些天敌的害虫控制效果。不过,在可容忍的范围内,这些天敌可能会增加摄食量,以满足解毒的能量需求,从而增强其害虫控制能力。昆虫天敌体内重金属产生的活性氧和氧化损伤,加上寄主昆虫体内能量代谢紊乱,是导致昆虫天敌体能下降的关键因素。总之,重金属污染是影响这些益虫害虫控制性能的一个重要非生物因素。
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引用次数: 0
Biotransformation of 6:2/4:2 fluorotelomer alcohols by Dietzia aurantiaca J3: Enzymes and proteomics. Dietzia aurantiaca J3 对 6:2/4:2 氟代醇的生物转化:酶和蛋白质组学。
Pub Date : 2024-10-05 Epub Date: 2024-08-13 DOI: 10.1016/j.jhazmat.2024.135510
Shefali Bhardwaj, Matthew Lee, Denis O'Carroll, James McDonald, Keith Osborne, Stuart Khan, Russell Pickford, Nicholas Coleman, Casey O'Farrell, Sarah Richards, Michael J Manefield

Per- and polyfluoroalkyl substances (PFAS) are recalcitrant synthetic organohalides known to negatively impact human health. Short-chain fluorotelomer alcohols are considered the precursor of various perfluorocarboxylic acids (PFCAs) in the environment. Their ongoing production and widespread detection motivate investigations of their biological transformation. Dietzia aurantiaca strain J3 was isolated from PFAS-contaminated landfill leachate using 6:2 fluorotelomer sulphonate (6:2 FTS) as a sulphur source. Resting cell experiments were used to test if strain J3 could transform fluorotelomer alcohols (6:2 and 4:2 FTOH). Strain J3 transformed fluorotelomer alcohols into PFCAs, polyfluorocarboxylic acids and transient intermediates. Over 6 days, 80 % and 58 % of 6:2 FTOH (0.1 mM) and 4:2 FTOH (0.12 mM) were degraded with 6.4 % and 14 % fluoride recovery respectively. Fluorotelomer unsaturated carboxylic acid (6:2 FTUCA) was the most abundant metabolite, accounting for 21 to 30 mol% of 6:2 FTOH (0.015 mM) applied on day zero. Glutathione (GSH) conjugates of 6:2/4:2 FTOH and 5:3 FTCA adducts were also structurally identified. Proteomics studies conducted to identify enzymes in the biotransformation pathway have revealed the role of various enzymes involved in β oxidation. This is the first report of 6:2/4:2 FTOH glutathione conjugates and 5:3 FTCA adducts in prokaryotes, and the first study to explore the biotransformation of 4:2 FTOH by pure bacterial strain.

全氟烷基和多氟烷基物质(PFAS)是一种难降解的合成有机卤化物,已知会对人类健康产生负面影响。短链氟代醇被认为是环境中各种全氟羧酸(PFCAs)的前体。它们的持续生产和广泛检测促使人们对其生物转化进行研究。以 6:2 氟代苯磺酸酯(6:2 FTS)为硫源,从受 PFAS 污染的垃圾填埋场渗滤液中分离出 Dietzia aurantiaca 菌株 J3。静止细胞实验用于检测菌株 J3 能否转化氟代醇(6:2 和 4:2 FTOH)。菌株 J3 将氟代醇转化为全氟羧酸、多氟羧酸和瞬时中间产物。6 天内,6:2 FTOH(0.1 mM)和 4:2 FTOH(0.12 mM)分别降解了 80% 和 58%,氟回收率分别为 6.4% 和 14%。氟代不饱和羧酸(6:2 FTUCA)是最丰富的代谢物,占第零天施用的 6:2 FTOH(0.015 mM)的 21 至 30 摩尔%。还从结构上确定了 6:2/4:2 FTOH 和 5:3 FTCA 加合物的谷胱甘肽(GSH)共轭物。为确定生物转化途径中的酶而进行的蛋白质组学研究揭示了参与 β 氧化的各种酶的作用。这是首次报道原核生物中的 6:2/4:2 FTOH 谷胱甘肽共轭物和 5:3 FTCA 加合物,也是首次探讨纯细菌菌株对 4:2 FTOH 的生物转化的研究。
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引用次数: 0
Polystyrene nanoplastics significantly facilitate largemouth bass ranavirus infection of host cells. 聚苯乙烯纳米塑料大大促进了大口鲈鱼匐茎病毒对宿主细胞的感染。
Pub Date : 2024-10-05 Epub Date: 2024-08-23 DOI: 10.1016/j.jhazmat.2024.135597
Linyong Zhi, Guimei Zhang, Zhen Li, Fang Chen, Qiwei Qin, Youhua Huang, Xiaohong Huang, Jun Wang

Novel pollutants nanoplastics (NPs) are widely distributed in aquatic environments and may pose a health threat to aquatic organisms. Notably, the contribution of NPs to the occurrence of viral diseases in aquatic animals remains largely uncertain. In this study, the effects of polystyrene nanoplastics (PS-NPs) on Largemouth bass ranavirus (LMBV)-infected MsF cells were investigated. MsF cells took up PS-NPs in a time- and dose-dependent manner and significantly affect cell viability at an exposure concentration of 500 μg/mL. Western blot and qPCR assays indicated that exposure to PS-NPs accelerated LMBV replication in MsF cells. PS-NPs act synergistically with LMBV to disrupt the cellular antioxidant system, as evidenced by increased ROS production and decreased mRNA levels of antioxidant-associated genes. Furthermore, PS-NPs was found to exacerbate LMBV-induced inflammatory responses, as demonstrated by disturbed expression of inflammation-related factors. In addition, our results suggest that PS-NPs reduce IFN production by inhibiting the expression of molecules related to the cGAS-STING signaling pathway, thereby promoting viral replication. Collectively, our findings suggest the potential threat of NPs to infectious diseases caused by freshwater fish viruses and provide new insights for fish disease prevention and control.

新型污染物纳米塑料(NPs)广泛分布于水生环境中,可能对水生生物的健康构成威胁。值得注意的是,纳米塑料对水生动物病毒性疾病发生的影响在很大程度上仍不确定。本研究调查了聚苯乙烯纳米塑料(PS-NPs)对大口鲈鱼匐茎病毒(LMBV)感染的 MsF 细胞的影响。MsF 细胞对 PS-NPs 的吸收具有时间和剂量依赖性,当接触浓度为 500 μg/mL 时,PS-NPs 会显著影响细胞活力。Western 印迹和 qPCR 检测表明,暴露于 PS-NPs 会加速 LMBV 在 MsF 细胞中的复制。PS-NPs 与 LMBV 协同作用,破坏细胞的抗氧化系统,ROS 生成增加和抗氧化相关基因的 mRNA 水平降低就是证明。此外,PS-NPs 还会加剧 LMBV 诱导的炎症反应,这表现在炎症相关因子的表达紊乱。此外,我们的研究结果表明,PS-NPs 通过抑制与 cGAS-STING 信号通路相关的分子的表达来减少 IFN 的产生,从而促进病毒的复制。总之,我们的研究结果表明了 NPs 对淡水鱼病毒引起的传染性疾病的潜在威胁,并为鱼类疾病的预防和控制提供了新的见解。
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引用次数: 0
Cadmium stress alleviates lipid accumulation caused by chiral penthiopyrad through regulating endoplasmic reticulum stress and mitochondrial dysfunction in zebrafish liver. 镉胁迫通过调节斑马鱼肝脏的内质网胁迫和线粒体功能障碍,缓解手性吡噻菌胺引起的脂质积累。
Pub Date : 2024-10-05 Epub Date: 2024-08-17 DOI: 10.1016/j.jhazmat.2024.135560
Xinquan Wang, Weixuan Di, Zhiwei Wang, Peipei Qi, Zhenzhen Liu, Huiyu Zhao, Wei Ding, Shanshan Di

The coexistence of cadmium (Cd) can potentiate (synergism) or reduce (antagonism) the pesticide effects on organisms, which may change with chiral pesticide enantiomers. Previous studies have reported the toxic effects of chiral penthiopyrad on lipid metabolism in zebrafish (Danio rerio) liver. The Cd effects and toxic mechanism on lipid accumulation were investigated from the perspective of endoplasmic reticulum (ER) stress and mitochondrial dysfunction. The coexistence of Cd increased the concentrations of penthiopyrad and its metabolites in zebrafish. Penthiopyrad exposure exhibited significant effects on lipid metabolism and mitochondrial function-related indicators, which were verified by lipid droplets and mitochondrial damage in subcellular structures. Moreover, penthiopyrad activated the genes of ER unfolded protein reaction (UPR) and Ca2+ permeable channels, and S-penthiopyrad exhibited more serious effects on ER stress with ER hyperplasia than R-penthiopyrad. As a mitochondrial uncoupler, the coexistence of Cd could decrease lipid accumulation by alleviating ER stress and mitochondrial dysfunction, and these effects were the most significant for R-penthiopyrad. There were antagonistic effects between Cd and penthiopyrad, which could reduce the damage caused by penthiopyrad in zebrafish, thus increasing the bioaccumulation of penthiopyrad in zebrafish. These findings highlighted the importance and necessity of evaluating the ecological risks of metal-chiral pesticide mixtures.

镉(Cd)的共存会增强(协同)或降低(拮抗)农药对生物的影响,这可能会随手性农药对映体的变化而改变。以往的研究曾报道过手性戊硫磷对斑马鱼(Danio rerio)肝脏脂质代谢的毒性作用。本研究从内质网(ER)应激和线粒体功能障碍的角度研究了镉对脂质积累的影响和毒性机制。镉的共存增加了斑马鱼体内倍硫磷及其代谢物的浓度。暴露于苯噻菌胺会对脂质代谢和线粒体功能相关指标产生显著影响,亚细胞结构中的脂滴和线粒体损伤证实了这一点。此外,苯噻菌胺还激活了ER未折叠蛋白反应(UPR)基因和Ca2+通透性通道,S-苯噻菌胺对ER应激的影响比R-苯噻菌胺更严重,并伴有ER增生。作为线粒体解偶联剂,镉的共存可通过缓解ER应激和线粒体功能障碍来减少脂质积累,而这些效应对R-苯噻菌胺的影响最为显著。镉与苯噻菌胺之间存在拮抗作用,可以减轻苯噻菌胺对斑马鱼的伤害,从而增加苯噻菌胺在斑马鱼体内的生物累积。这些发现凸显了评估金属手性农药混合物生态风险的重要性和必要性。
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引用次数: 0
Challenging established norms: The unanticipated role of alcohols in UV/PDS radical quenching. 挑战既定规范:醇类在 UV/PDS 自由基淬灭中的意外作用。
Pub Date : 2024-10-05 Epub Date: 2024-08-23 DOI: 10.1016/j.jhazmat.2024.135502
Boqiang Li, Baiyang Chen, Zongsu Wei

UV/peroxydisulfate (UV/PDS) process is known to be highly efficient for degrading micropollutants from water by generating sulfate (SO4•-) and hydroxyl radicals (HO). Reliable analyses of short-lived SO4•- and HO are therefore critical for understanding reaction mechanisms and optimizing operating conditions. Currently, alcohols are commonly used as quenchers to distinguish radicals based on the assumption that they exclusively react with target radicals without other influences. However, this study for the first time reveals a series of unexpected effects that challenge this conventional wisdom because: 1) adding alcohols altered the decomposition rates of PDS by replacing the reactions between SO4•- and HO with PDS by the reactions between secondary reactive species and PDS; and 2) SO4•- preferably reacted with alcohols to generate nonnegligible level of hydrogen peroxide (H2O2) under oxygen-rich conditions, which subsequently led to indirect formation of HO. Additionally, the formation of H2O2 was substantially impacted by the types of alcohols, dosages, dissolved oxygen, and solution pH. Using probe tests as tools, we found that the actual SO4•- levels after dosing alcohols were only slightly different from assumed/expected levels, whereas the actually HO levels were 43.7, 3364.9, and 12.5 times higher than assumed/expected conditions for samples dosed with methanol, iso-propanol, and tert-butanol, respectively. These unanticipated effects thus suggest that cautions are needed when using alcohols to qualitative and quantitative determine HO and SO4•- in UV/PDS process.

众所周知,紫外线/过氧化二硫酸盐(UV/PDS)工艺可通过产生硫酸盐(SO4--)和羟基自由基(HO--)高效降解水中的微污染物。因此,对短寿命 SO4-- 和 HO- 的可靠分析对于了解反应机制和优化操作条件至关重要。目前,醇类通常被用作区分自由基的淬灭剂,其假设是醇类只与目标自由基发生反应而不受其他影响。然而,本研究首次揭示了一系列意想不到的效果,挑战了这一传统观点,因为1) 加入醇类改变了 PDS 的分解率,将 SO4--和 HO- 与 PDS 的反应改为次生反应物与 PDS 的反应;以及 2) 在富氧条件下,SO4--最好与醇类反应生成不可忽略的过氧化氢(H2O2),随后间接形成 HO-。此外,醇的种类、剂量、溶解氧和溶液 pH 对 H2O2 的形成有很大影响。以探针测试为工具,我们发现在添加酒精后,SO4--的实际水平与假定/预期水平仅略有不同,而添加甲醇、异丙醇和叔丁醇的样品中,HO-的实际水平分别比假定/预期条件高出 43.7、3364.9 和 12.5 倍。因此,这些意想不到的影响表明,在 UV/PDS 过程中使用醇类来定性和定量测定 HO- 和 SO4--时需要谨慎。
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Journal of hazardous materials
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