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Influence of redox atmospheres on selenate retention by mackinawite, magnetite and pyrite 氧化还原气氛对镁铁石、磁铁矿和黄铁矿中硒酸盐截留的影响
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-24 DOI: 10.1016/j.jhazmat.2026.141869
Kaifeng Wang, Alejandro Fernandez Martinez, Nicolas Menguy, Laura Simonelli, Benoit Madé, Pierre Hénocq, Bin Ma, Laurent Charlet
Understanding the redox transformations of selenium (Se) under varying redox atmospheres is critical for predicting its environmental fate and optimizing Se removal from contaminated wastewater. However, the influence of redox atmospheres, specifically H2 and O2, on Se transformation mechanisms and the structural nature of the resulting Se(0) remains poorly understood. In this study, we investigated the interactions between aqueous selenate (Se(VI)) and Fe(II)-bearing minerals (pyrite, magnetite and mackinawite) under N2, H2 and air atmospheres, employing comprehensive characterizations on both aqueous and solid speciation. Our findings reveal that H2 and air atmospheres could enhance Se removal by pyrite but limit its removal by mackinawite, while magnetite shows no significant atmospheric influence on Se removal. Alongside Se removal, sorbed Se(VI) was transformed into distinct elemental Se depending on the mineral: trigonal γ-Se nanoneedles on magnetite, monoclinic β-Se on mackinawite, and nanosized amorphous Se(0) on pyrite. Moreover, H2 significantly lowered the solution redox potential, favoring the reduction of sorbed Se(VI) to Se(0) or FeSex. Overall, this work provides valuable insights for optimizing Se remediation and recovery strategies in Se-contaminated wastewater and improving understanding of Se behavior in diverse geochemical systems, including nuclear waste disposal repositories.
了解不同氧化还原气氛下硒(Se)的氧化还原转化对于预测其环境命运和优化污染废水中硒的去除至关重要。然而,氧化还原气氛,特别是H2和O2,对Se转化机制和Se(0)结构性质的影响仍然知之甚少。在这项研究中,我们研究了水硒酸盐(Se(VI))和含Fe(II)矿物(黄铁矿,磁铁矿和mackinawite)在N2, H2和空气气氛下的相互作用,并对水和固体形态进行了综合表征。研究结果表明,H2和空气气氛对黄铁矿脱除硒有促进作用,但对磁铁矿脱除硒有限制作用,而磁铁矿对脱除硒无明显影响。除Se外,吸附的Se(VI)根据不同的矿物转化为不同的元素Se:磁铁矿上的三角γ-Se纳米针,麦金石上的单斜β-Se纳米针,黄铁矿上的纳米无定形Se(0)。此外,H2显著降低了溶液氧化还原电位,有利于吸附的Se(VI)还原为Se(0)或FeSex。总的来说,这项工作为优化硒污染废水的硒修复和回收策略以及提高对包括核废料处置库在内的不同地球化学系统中硒行为的理解提供了有价值的见解。
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引用次数: 0
Buffering failure of the ratio of secondary to primary phases: Risk overestimation of soil heavy metals under alkaline conditions 次生与初级阶段的缓冲失效:碱性条件下土壤重金属的风险高估
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-23 DOI: 10.1016/j.jhazmat.2026.141844
Yingdong Wu, Zixin Zeng, Rong Teng, Junwei Yang, Jiang Yu, Hui Sun, Siwei Deng, Pengxinyue Huang, Jie Luo, Yi Wu, Xuetao Zhao
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引用次数: 0
Biofilm-mediated surface depolymerization of multiple synthetic polymers by mangrove-derived bacterial consortia 由红树林衍生的细菌联合体介导的多种合成聚合物的生物膜表面解聚
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141847
Sourav Bhattacharya, Prabhu Kolandhasamy, Abhishek Mandal, Rajendran Rajaram, Gopala Krishna Darbha
Plastic pollution persists across marine and terrestrial ecosystems largely due to the intrinsic resistance of synthetic polymers to biological attack. Despite growing evidence of microbial interactions with plastics, the mechanistic basis and extent of biofilm-mediated polymer deterioration remain poorly constrained. Here, we investigate the capacity of mangrove-derived bacterial consortia to initiate early-stage degradation of major synthetic polymers (PET, PS, LDPE, HDPE, and PP) under controlled laboratory conditions. Over a 120-day incubation under controlled laboratory conditions, consortium-exposed polymers exhibited differential mass loss, surface erosion, and mechanical weakening, with PS 20.14% and PET 8.33% showing the highest susceptibility. Integrated surface and molecular analyses using confocal laser scanning microscopy, atomic force microscopy, scanning electron microscopy energy dispersive X-ray spectroscopy, and Fourier-transform infrared spectroscopy revealed extensive biofilm formation, nanoscale pitting, oxidative functional group incorporation, and localized polymer chain modification. Tensile testing further demonstrated reductions in mechanical integrity consistent with surface-driven structural weakening. First-order kinetic fits were applied to gravimetric data to provide comparative, non-predictive estimates of degradation dynamics across polymer types. This study provides quantitative and mechanistic evidence that environmentally adapted microbial consortia can promote biofilm-driven surface depolymerization, highlighting mangrove sediments as underexplored reservoirs of plastic-interacting microbes. These findings advance current understanding of early-stage plastic biodegradation and inform future strategies for biotechnological intervention in microplastic-polluted environments.
塑料污染在海洋和陆地生态系统中持续存在,很大程度上是由于合成聚合物对生物攻击的内在抵抗力。尽管越来越多的证据表明微生物与塑料相互作用,生物膜介导的聚合物恶化的机制基础和程度仍然很不清楚。在这里,我们研究了红树林衍生的细菌联合体在受控的实验室条件下启动主要合成聚合物(PET, PS, LDPE, HDPE和PP)的早期降解能力。在120天的受控实验室条件下,暴露在财团中的聚合物表现出不同的质量损失、表面侵蚀和机械弱化,PS 20.14%和PET 8.33%的敏感性最高。利用共聚焦激光扫描显微镜、原子力显微镜、扫描电子显微镜能量色散x射线能谱和傅里叶变换红外光谱对表面和分子进行综合分析,发现广泛的生物膜形成、纳米级点蚀、氧化官能团结合和局部聚合物链修饰。拉伸测试进一步证明了机械完整性的降低与表面驱动的结构弱化相一致。一阶动力学拟合应用于重量数据,以提供跨聚合物类型降解动力学的比较,非预测性估计。该研究提供了定量和机制证据,表明环境适应性微生物群落可以促进生物膜驱动的表面解聚,强调红树林沉积物是尚未开发的塑料相互作用微生物的储存库。这些发现促进了目前对早期塑料生物降解的理解,并为微塑料污染环境中生物技术干预的未来策略提供了信息。
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引用次数: 0
Sabatier-Optimized Co-incorporated CN Catalysts for Enhanced Elemental Mercury Oxidation via an O2-mediated Eley-Rideal mechanism sabatier优化的Co-incorporated CN催化剂通过o2介导的eley - ideal机制增强元素汞氧化
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141842
Haoyun Liu, Yile Zhai, Lingtao Zhou, Jinsong Zhou, Pei Li
Understanding the balance of oxygen activation and product desorption is a prerequisite for achieving high activity and durability in heterogeneous catalytic oxidation following the O2-mediated Eley-Rideal (E-R) mechanism. Using catalytic oxidation of gaseous elemental mercury (Hg0) from coal-fired flue gas as a probe, we establish a Sabatier relationship for O2-mediated E-R pathways over metal-incorporated graphitic carbon nitride (M-CN) catalysts. Density functional theory calculations reveal that the overall reaction rate is jointly limited by Hg-assisted O-O bond cleavage and the desorption of oxidized mercury species (HgO)x. Correlating catalytic activity with atomic oxygen adsorption energies identifies Co-CN as optimally positioned near the apex of the Sabatier volcano among ten M-CN catalysts. Guided by this mechanistic insight, a Co-CN catalyst is rationally synthesized via a novel stepwise strategy and exhibits near-complete Hg0 removal at 280 ºC, strong tolerance toward high SO2 concentrations, and a synergistic promotional effect of NO, while maintaining an Hg0 removal efficiency of 85.13% after eight thermal regeneration cycles, demonstrating excellent operational stability and recyclability. Long-term dynamic tests reveal that Co-CN reaches a stable balance between Hg0 oxidation and product desorption after ~15 h, delivering a Hg0 removal capacity of 0.94 mg∙g-1, superior to most reported carbon-based catalysts. Mechanistic validation confirms that Hg0 oxidation proceeds via surface-activated oxygen species on Co-N sites, while gradual accumulation of surface-bound (HgO)x and partial Co-N oxidation dictate long-term performance decay under oxygen-rich conditions. This work establishes a fundamental framework for designing Sabatier optimal catalysts in O2-mediated E-R models for environmental remediation.
了解氧活化和产物脱附的平衡是在o2介导的E-R机制下实现高活性和耐用的非均相催化氧化的先决条件。以燃煤烟气中气态单质汞(Hg0)的催化氧化为探针,我们建立了金属掺杂石墨氮化碳(M-CN)催化剂上o2介导的E-R途径的Sabatier关系。密度泛函理论计算表明,总体反应速率受hg辅助O-O键裂解和氧化汞(HgO)x解吸的共同限制。将催化活性与氧原子吸附能进行对比,发现在10种M-CN催化剂中,Co-CN位于Sabatier火山顶端附近。在此机理的指导下,通过一种新的分步合成策略合理地合成了Co-CN催化剂,该催化剂在280℃下几乎完全去除Hg0,对高SO2浓度具有较强的耐受性,并具有NO的协同促进作用,同时在8次热再生循环后仍保持85.13%的Hg0去除效率,表现出优异的操作稳定性和可回收性。长期动态测试表明,在~15 h后,Co-CN在Hg0氧化和产物脱附之间达到稳定的平衡,其Hg0去除率为0.94 mg∙g-1,优于大多数报道的碳基催化剂。机制验证证实,在富氧条件下,Hg0氧化通过Co-N位点上的表面活性氧进行,而表面结合(HgO)x的逐渐积累和部分Co-N氧化决定了长期的性能衰减。本研究为设计用于环境修复的o2介导E-R模型中的Sabatier最佳催化剂建立了基本框架。
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引用次数: 0
From technical HCH residues to industrial relevant vicinal dichlorinated compounds: Electrochemical chlorine transfer as a strategy for waste valorisation 从技术性六氯环己烷残留物到工业相关的邻二氯化合物:作为废物增值策略的电化学氯转移
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141851
Simon Horsinka, Dominik Weis, Philipp Beeskow, Till Langner, Jörg Sauer, Siegfried R. Waldvogel
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引用次数: 0
Enhancing the Mycoremediation Potential: The Multifaceted Role of Fulvic Acid in Polystyrene Microplastics Degradation by Phanerochaete chrysosporium 增强霉菌修复潜力:黄孢平革菌降解聚苯乙烯微塑料中黄腐酸的多方面作用
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141848
Zelin Hou, Yongkang Wu, Yang Liu, Ningjia Dong, Yu Mao, Hong Liang, Dawen Gao
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引用次数: 0
Biochar-enhanced alternating current-microbial remediation of petroleum-contaminated soil: extracellular polymeric substances-mediated electron transfer pathway 生物炭增强的交流电-微生物修复石油污染土壤:胞外聚合物物质介导的电子转移途径
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141849
Shuang Zhou, Huan He, Ying Huang, Xiaoxia Yang, Wenqian Gu, Al-Anazi Abdulaziz, Bin Huang, Xuejun Pan
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引用次数: 0
Descriptor-guided unlocking of efficient nitrate-to-ammonia electroreduction on copper-based single-atom alloys 描述符引导解锁铜基单原子合金上有效的硝酸盐到氨电还原
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141852
Denglei Gao, Dayi Guo, Zunlong Hu, Xiaofei Zhang, Huanrong Liu, Linjie Wang, Bowen Liu, Xiuying Zhang, Jiahao Liu, Wei Wang, Zhongjing Lu
The electrocatalytic nitrate reduction reaction (e-NO3-RR) is an effective way to address nitrate pollution and offers an attractive strategy for ammonia synthesis under mild conditions. However, the identification of novel catalysts via computational guidance remains a central challenge in this field. Herein, a series of single-atom transition-metals (TMs)-alloyed copper-based single-atom alloys (SAAs) were used as model catalysts (TM1-Cu(111)) for e-NO3-RR. Among them, three TM1-Cu(111) catalysts (TM = Ti, Zr, and Nb) had outstanding catalytic activity, with low limiting potentials of −0.20, −0.39, and −0.32 V, respectively. Furthermore, these candidates effectively suppressed the hydrogen evolution reaction and demonstrated excellent thermodynamic stability. To clarify the activity trend of e-NO3-RR on Cu-based SAAs, the adsorption strength of the NO intermediate was identified as an effective descriptor. This work provides computational guidance for the rational design of high-performance e-NO3-RR catalysts.
电催化硝酸还原反应(e-NO3-RR)是解决硝酸盐污染的有效途径,为温和条件下合成氨提供了一种有吸引力的策略。然而,通过计算指导识别新型催化剂仍然是该领域的核心挑战。本文采用一系列单原子过渡金属(tm)合金铜基单原子合金(SAAs)作为e-NO3-RR的模型催化剂(TM1-Cu(111))。其中,TM1-Cu(111)催化剂TM = Ti、Zr和Nb具有较好的催化活性,其下限电位分别为- 0.20、- 0.39和- 0.32 V。此外,这些候选物有效地抑制了析氢反应,并表现出良好的热力学稳定性。为了明确e-NO3-RR在cu基SAAs上的活性趋势,鉴定了NO中间体的吸附强度作为有效描述符。该工作为合理设计高性能e-NO3-RR催化剂提供了计算指导。
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引用次数: 0
Mechanistic insights into the degradation of trans-ferulic acid by hydroxyl and sulfate radicals in UV/H2O2 and UV/PDS systems: A computational study 在UV/H2O2和UV/PDS系统中羟基和硫酸盐自由基降解反式阿魏酸的机理:一项计算研究
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141853
Qingliang Dai, Bo Wei, Huaqing Liu, Ruo tong Zhao, Zexuan Li, Xiaoqiang Cao, Jian Zhang
Trans-Ferulic acid (FA), a prevalent and ecotoxic phenolic pollutant, requires effective remediation strategies. While advanced oxidation processes (AOPs) employing •OH and SO4- are widely used for phenolic degradation, their efficiency is highly substrate-dependent. This hinders the accurate prediction of FA degradation, stemming from an insufficient mechanistic understanding of the atomic-level differences between the two radicals. In this study, we employed density functional theory (DFT) calculations and kinetic simulations to elucidate the origins of their divergent reactivity. The results show that radical adduct formation (RAF) overwhelmingly dominates the initial reaction flux (>98%) for both radicals. Notably, OH and SO4- exhibit distinct site selectivity, with •OH attacking the electron-rich aromatic C2 position and SO4- preferring the sterically accessible side-chain C9 site. This difference in selectivity and intrinsic reactivity results in a second-order rate constant for •OH (8.01 × 109 M-1 s-1 at 298 K) that is an order of magnitude higher than that for SO4- (2.31 × 108 M-1 s-1 at 298 K). Kinetic simulations further reveal that at low oxidant dosages (8–60 μM), the UV/H2O2 system achieves higher degradation efficiency relative to UV/PDS, whereas at higher dosages and across a broad pH range, the UV/PDS process maintains more stable performance due to reversible SO4-/•OH interconversion. Toxicity predictions indicate that FA degradation generally reduces ecological risk, although certain epoxidized intermediates retain residual toxicity. These mechanistic insights provide a foundation for rational optimization of radical-driven oxidation systems for phenolic pollutants.
反式阿魏酸(FA)是一种普遍存在的生态毒性酚类污染物,需要有效的修复策略。虽然采用•OH和SO4•-的高级氧化工艺(AOPs)广泛用于酚类降解,但其效率高度依赖于底物。这阻碍了FA降解的准确预测,这源于对两种自由基之间原子水平差异的机制理解不足。在这项研究中,我们采用密度泛函理论(DFT)计算和动力学模拟来阐明它们的发散反应性的起源。结果表明,自由基加合物形成(RAF)压倒性地主导了两种自由基的初始反应通量(>98%)。值得注意的是,•OH和SO4•-表现出明显的位点选择性,•OH攻击富含电子的芳香C2位点,而SO4•-更倾向于立体可达侧链C9位点。这种选择性和本征反应性的差异导致•OH的二级速率常数(在298 K时为8.01 × 109 M-1 s-1)比SO4•-(在298 K时为2.31 × 108 M-1 s-1)高一个数量级。动力学模拟进一步表明,在低氧化剂量(8-60 μM)下,UV/H2O2体系相对于UV/PDS具有更高的降解效率,而在较高的氧化剂量和较宽的pH范围内,UV/PDS过程由于SO4•-/•OH可逆相互转化而保持更稳定的性能。毒性预测表明,尽管某些环氧化中间体保留残留毒性,但FA降解通常会降低生态风险。这些机制的见解为酚类污染物自由基驱动氧化系统的合理优化提供了基础。
{"title":"Mechanistic insights into the degradation of trans-ferulic acid by hydroxyl and sulfate radicals in UV/H2O2 and UV/PDS systems: A computational study","authors":"Qingliang Dai, Bo Wei, Huaqing Liu, Ruo tong Zhao, Zexuan Li, Xiaoqiang Cao, Jian Zhang","doi":"10.1016/j.jhazmat.2026.141853","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2026.141853","url":null,"abstract":"Trans-Ferulic acid (FA), a prevalent and ecotoxic phenolic pollutant, requires effective remediation strategies. While advanced oxidation processes (AOPs) employing •OH and SO<sub>4</sub>•<sup>-</sup> are widely used for phenolic degradation, their efficiency is highly substrate-dependent. This hinders the accurate prediction of FA degradation, stemming from an insufficient mechanistic understanding of the atomic-level differences between the two radicals. In this study, we employed density functional theory (DFT) calculations and kinetic simulations to elucidate the origins of their divergent reactivity. The results show that radical adduct formation (RAF) overwhelmingly dominates the initial reaction flux (&gt;98%) for both radicals. Notably, <strong>•</strong>OH and SO<sub>4</sub>•<sup>-</sup> exhibit distinct site selectivity, with •OH attacking the electron-rich aromatic C2 position and SO<sub>4</sub>•<sup>-</sup> preferring the sterically accessible side-chain C9 site. This difference in selectivity and intrinsic reactivity results in a second-order rate constant for •OH (8.01 × 10<sup>9<!-- --> </sup>M<sup>-1</sup> s<sup>-1</sup> at 298<!-- --> <!-- -->K) that is an order of magnitude higher than that for SO<sub>4</sub>•<sup>-</sup> (2.31 × 10<sup>8<!-- --> </sup>M<sup>-1</sup> s<sup>-1</sup> at 298<!-- --> <!-- -->K). Kinetic simulations further reveal that at low oxidant dosages (8–60<!-- --> <!-- -->μM), the UV/H<sub>2</sub>O<sub>2</sub> system achieves higher degradation efficiency relative to UV/PDS, whereas at higher dosages and across a broad pH range, the UV/PDS process maintains more stable performance due to reversible SO<sub>4</sub>•<sup>-</sup>/•OH interconversion. Toxicity predictions indicate that FA degradation generally reduces ecological risk, although certain epoxidized intermediates retain residual toxicity. These mechanistic insights provide a foundation for rational optimization of radical-driven oxidation systems for phenolic pollutants.","PeriodicalId":361,"journal":{"name":"Journal of Hazardous Materials","volume":"15 1","pages":""},"PeriodicalIF":13.6,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147493119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Kinetics and Mechanism of Nonradical Disinfection of Escherichia coli by Activation of Peroxides with N-Doped Carbonaceous Materials n掺杂碳质材料活化过氧化物对大肠杆菌非根治消毒的动力学及机理
IF 13.6 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-03-22 DOI: 10.1016/j.jhazmat.2026.141840
Xinyi Tang, Yan Wang, Xiumei Chen, Wei Kong, Xue He, Yi Yang
{"title":"Kinetics and Mechanism of Nonradical Disinfection of Escherichia coli by Activation of Peroxides with N-Doped Carbonaceous Materials","authors":"Xinyi Tang, Yan Wang, Xiumei Chen, Wei Kong, Xue He, Yi Yang","doi":"10.1016/j.jhazmat.2026.141840","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2026.141840","url":null,"abstract":"","PeriodicalId":361,"journal":{"name":"Journal of Hazardous Materials","volume":"46 1","pages":""},"PeriodicalIF":13.6,"publicationDate":"2026-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Journal of Hazardous Materials
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