IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143641

Graphene oxide nanoparticles (GO) (have promising properties for, electronics, energy, medicine, water purification, agriculture and food production industry. However, their potentially hazardous effects are still not satisfactorily recognized, so they are often included in the group of contaminants of emerging concern. Therefore, the aim of this investigation was to assess the potentially harmful effects of orally administered GO on the digestive enzyme activities of the house crickets Acheta domesticus. The activity of digestive enzymes was measured using the API®ZYM test and the results were compared in relation to the insect age group (Larvae, Adult Young and Adult Mature) and previous selection towards longevity (‘long living’ vs ‘wild’ strains). General analysis, encompassing all digestive enzymes simultaneously, as well as an analysis performed for individual enzyme subgroups, revealed that both factors and their interactions significantly modified the activity of digestive enzymes of A. domesticus. The most pronounced effect was connected with the age factor. The study revealed that the Adult Young age group was the most sensitive; in this group, the activity of digestive enzymes was, in general, decreased in comparison with the control group, while the remaining group did not respond to GO with a similar intensity. In turn, the inter-strain comparisons demonstrated different response patterns to the GO. The control enzymatic activity of the insects from long living’ strain was, in general, higher than in the ‘wild strain’; however, it was significantly decreased in the GO-exposed groups, while in the ‘wild’ strain, the activity remained relatively homogenous. Additionally, the tendency was more pronounced in Adult Young than in the remaining age groups. The potential toxicity of GO requires further investigation, mainly with a focus on the composition and functioning of gut microbiotas.

氧化石墨烯纳米粒子（GO）在电子、能源、医药、水净化、农业和食品生产等领域具有广阔的应用前景。然而，其潜在的有害影响仍未得到令人满意的认识，因此经常被列入新出现的污染物类别。因此，本研究旨在评估口服 GO 对家养蟋蟀（Acheta domesticus）消化酶活性的潜在有害影响。使用 API®ZYM 试验测量了消化酶的活性，并将结果与昆虫年龄组（幼虫、幼年成虫和成年成虫）和以前的长寿选择（"长寿 "品系与 "野生 "品系）进行了比较。同时对所有消化酶进行的总体分析以及对单个酶亚群进行的分析表明，这两个因素及其相互作用显著地改变了家蝇消化酶的活性。最明显的影响与年龄因素有关。研究表明，成年幼年组最为敏感；与对照组相比，该组消化酶的活性普遍下降，而其余组对 GO 的反应强度则不尽相同。反过来，菌株间的比较也显示出对 GO 的不同反应模式。一般来说，"长寿昆虫 "菌株的对照酶活性高于 "野生菌株"；然而，暴露于 GO 的菌株组的酶活性明显降低，而 "野生 "菌株的酶活性则保持相对稳定。此外，与其他年龄组相比，这种趋势在成年幼鼠中更为明显。GO 的潜在毒性需要进一步研究，主要侧重于肠道微生物群的组成和功能。

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引用次数: 0

Assessment of heavy metal contamination in groundwater and its implications for dental and public health 地下水重金属污染评估及其对牙科和公共卫生的影响。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143609

Groundwater contamination with heavy metals is a critical environmental issue, especially in regions heavily reliant on groundwater for drinking purpose. These metals can seep into groundwater from soil and rock weathering or through improper disposal of industrial waste and effluents. Access to safe drinking water is essential for maintaining public health. This study aimed to assess heavy metal contamination in groundwater and its implications for dental and public health. The objective of the study was to measure the concentration of the heavy metals in the dentine of extracted tooth of the study population. The study concurrently measured heavy metal concentrations in groundwater and tooth dentine samples, analyzing demographic profiles, heavy metal correlations, and underlying structures using Principal Component Analysis (PCA). The average level of heavy metals in the groundwater samples varied from 9.763 ± 3.362 μg/L for Cd to 3426.204 ± 875.264 μg/L for Fe. The mean concentrations (μg/g) in teeth dentine showed significant variations, with iron (Fe) ranging from 0.149 ± 0.03 μg/g in water purifiers to 4.62 ± 0.578 μg/g in local water sources. Similar variations were observed for other heavy metals across different water sources. Principal component analysis (PCA) revealed seven principal components, with the first two components explaining 96.1% of the total variance. The findings revealed varied concentrations of heavy metals across all water sources. Statistical analyses underscored the complex relationship between water sources and heavy metal contamination levels, highlighting the need for targeted interventions to improve water quality and mitigate health risks. The study highlights the urgent need for monitoring and mitigation efforts to ensure safe drinking water and mitigate health risks associated with heavy metal contamination.

地下水重金属污染是一个严重的环境问题，尤其是在严重依赖地下水作为饮用水的地区。这些金属可通过土壤和岩石风化或工业废物和污水的不当处置渗入地下水。获得安全的饮用水对维护公众健康至关重要。本研究旨在评估地下水中的重金属污染及其对牙齿和公众健康的影响。研究的目的是测量研究人群拔牙后牙本质中的重金属浓度。研究同时测量了地下水和牙齿牙本质样本中的重金属浓度，并使用主成分分析法（PCA）分析了人口统计学特征、重金属相关性和潜在结构。地下水样本中重金属的平均含量从镉的 9.763 ± 3.362 μg/L 到铁的 3426.204 ± 875.264 μg/L 不等。牙齿牙本质中的平均浓度（微克/克）变化很大，铁（Fe）从净水器中的 0.149 ± 0.03 微克/克到当地水源中的 4.62 ± 0.578 微克/克不等。其他重金属在不同水源中的含量也有类似变化。主成分分析（PCA）显示了七个主成分，前两个成分解释了总方差的 96.1%。研究结果表明，所有水源中的重金属浓度都很高。统计分析强调了水源与重金属污染水平之间的复杂关系，突出表明需要采取有针对性的干预措施来改善水质和降低健康风险。这项研究强调，迫切需要开展监测和缓解工作，以确保饮用水安全并减轻与重金属污染相关的健康风险。

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引用次数: 0

Development of an ion exchange process for ammonium removal and recovery from municipal wastewater using a metakaolin K-based geopolymer 利用偏高岭土 K 基土工聚合物开发用于去除和回收城市污水中氨的离子交换工艺。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143559

Ion exchange represents a promising process for ammonium removal from municipal wastewater (MWW), in order to recover it for fertilizer production. Previous studies on ammonium ion exchange neglected the assessment of process robustness and the optimization the desorption/recovery step. This study aimed at developing a continuous-flow process of ammonium removal/recovery based on a metakaolin K-based geopolymer, named G13. Process robustness was assessed by operating 7 adsorption/desorption cycles with two types of MWW. These tests resulted in satisfactory and constant performances: operating capacity at 40 mg_N L⁻¹ in the inlet = 12 mg_N g_{dry sorbent}⁻¹, bed volumes of treated MWW at the selected breakpoint = 199–226, ammonium adsorption yield = 88–91%. Empty bed contact time (EBCT) was decreased from 10 to 5 min without any reduction in performances. The NH₄⁺ adsorption process was effectively simulated by the Thomas model, allowing a model-based assessment of the effect of EBCT reductions on process performances. An innovative desorption procedure led to high ammonium recovery yields (86–100%) and to a desorbed product composed primarily of KNO₃ (54%_w) and NH₄NO₃ (39%_w), two salts largely used in commercial fertilizers. The energy consumption of ammonium removal/recovery with G13 resulted 0.027 kWh m⁻³_{treated WW}, with a relevant reduction in comparison to traditional nitrification/denitrification, whereas the operational cost resulted equal to 60–110% of the cost of the benchmark process. These results show that G13 is a promising material to recover ammonium in a circular economy approach.

离子交换是从城市污水（MWW）中去除铵，以便将其回收用于肥料生产的一种前景广阔的工艺。以往关于铵离子交换的研究忽视了对工艺稳健性的评估和解吸/回收步骤的优化。本研究旨在开发一种基于偏高岭土 K 基土工聚合物（名为 G13）的氨去除/回收连续流工艺。通过使用两种类型的 MWW 进行 7 个吸附/解吸循环，对工艺的稳健性进行了评估。这些测试的结果令人满意，而且性能稳定：入口处 40 mgN L-1 的运行能力 = 12 mgN gdry 吸附剂-1，选定断点处处理过的 MWW 的床体积 = 199 - 226，铵吸附率 = 88 - 91%。空床接触时间（EBCT）从 10 分钟减少到 5 分钟，但性能没有降低。托马斯模型有效地模拟了 NH4+ 的吸附过程，从而可以基于模型评估减少 EBCT 对工艺性能的影响。创新的解吸程序带来了很高的铵回收率（86 - 100%），解吸产物主要由 KNO3（54%w）和 NH4NO3（39%w）组成，这两种盐在商业化肥中使用量很大。使用 G13 去除/回收氨的能耗为 0.027 kWh m-3（处理过的 WW），与传统的硝化/反硝化工艺相比，能耗明显降低，而运行成本则相当于基准工艺成本的 60-110%。这些结果表明，在循环经济方法中，G13 是一种很有前景的氨回收材料。

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引用次数: 0

A synthetic bacterial community engineered from Miscanthus floridulus roots enhances ammonia nitrogen removal in ionic rare earth mine tailings 从花叶茜根中提取的合成细菌群落可提高离子型稀土矿尾矿中氨氮的去除率。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143650

Ammonium sulfate, as the primary leaching agent, has caused significant nitrogen pollution in rare earth elements (REEs) mining areas. Phytoremediation is a promising remediation method, relying on the synergistic relationships between plants and their root-associated microbiome. Nevertheless, harnessing the microbiome to accelerate nitrogen transformation and absorption by plants is challenging. Here, we investigated the composition, activities and culturable fraction of the root bacterial microbiome of the pioneer plant Miscanthus floridulus grown in a REEs tailing soil containing a high ammonia nitrogen (AN) concentration at 344.35 mg kg⁻¹. Based on this, we constructed a simplified synthetic microbial community (SynCom) derived from the roots of M. floridulus, possessing nitrification and denitrification capabilities, to help REEs mine plants efficiently convert pollutant AN into nutrients, thereby enhancing plant growth and AN removal. This SynCom, consisting of 10 bacterial strains, included species of the genera Burkholderia (5) Paraburkholderia (1), Curtobacterium (1), Leifsonia (1) and Sinomonas (2). As a result, this SynCom alone achieved a significant reduction of 24.8% in AN content in tailing soil. When the SynCom inoculated with plants, the reduction in AN was even more significant (32.6%), surpassing the reduction achieved solely by plants (25.5%). Moreover, live SynCom inoculation significantly increased shoot and root biomass by 39.8% and 49.7%, respectively, compared to dead SynCom inoculation. These results indicate that the reduction in AN can be attributed to the SynCom's nitrification and denitrification capabilities, as well as its ability to enhance plant nitrogen absorption by stimulating their growth. Notably, seven nitrifying and denitrifying strains of the SynCom are particularly enriched, suggesting that plant roots selectively recruit nitrogen cycle-related bacteria to accelerate nitrogen transformation and absorption. These results provide a practical solution for harnessing the synergistic relationships between plants and their root microbiome in environmental remediation efforts.

硫酸铵作为主要的浸出剂，对稀土元素（REEs）矿区造成了严重的氮污染。植物修复是一种很有前景的修复方法，它依赖于植物与其根部相关微生物群之间的协同关系。然而，利用微生物群加速植物的氮转化和吸收是一项挑战。在这里，我们研究了生长在氨氮（AN）浓度高达 344.35 毫克/千克的稀土尾矿土壤中的先锋植物花叶木（Miscanthus floridulus）根部细菌微生物组的组成、活性和可培养部分。在此基础上，我们构建了一个简化的合成微生物群落（SynCom），该群落来自花叶木的根部，具有硝化和反硝化能力，可帮助稀土尾矿植物有效地将污染物氨氮转化为养分，从而促进植物生长和氨氮去除。该 SynCom 由 10 个细菌菌株组成，包括 Burkholderia 属（5 个）、Paraburkholderia 属（1 个）、Curtobacterium 属（1 个）、Leifsonia 属（1 个）和 Sinomonas 属（2 个）。结果，仅这种 SynCom 就使尾矿土壤中的 AN 含量显著降低了 24.8%。当 SynCom 与植物一起接种时，AN 的降低幅度更大（32.6%），超过了仅靠植物实现的降低幅度（25.5%）。此外，与接种死的 SynCom 相比，接种活的 SynCom 能显著增加芽和根的生物量，分别增加 39.8% 和 49.7%。这些结果表明，AN 的减少可归因于 SynCom 的硝化和反硝化能力，以及它通过刺激植物生长来提高植物氮吸收的能力。值得注意的是，SynCom 的七种硝化和反硝化菌株特别丰富，这表明植物根系会选择性地招募与氮循环相关的细菌，以加速氮的转化和吸收。这些结果为在环境修复工作中利用植物与其根部微生物群之间的协同关系提供了一个实用的解决方案。

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引用次数: 0

Research on intensive nitrogen removal of municipal sewage by mainstream anaerobic ammonia oxidation process 利用主流厌氧氨氧化工艺对城市污水进行强化脱氮的研究。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143622

The anaerobic ammonia oxidation (anammox) process is a pivotal nitrogen removal technique, playing a significant role in the field of wastewater treatment. The paper commences by delineating the merits of the anammox process in comparison to conventional nitrification-denitrification techniques. Subsequently, it delves into the characteristics of different sludge morphologies process of the behavior of anammox bacteria and their reactions to environmental factors. Revising the issues associated with managing urban sewage in mainstream areas., it discusses the issues faced by the anammox process under reduced nitrogen loads, such as restricted activity due to decreased the levels of ammonia nitrogen and nitrite concentrations, as well as the impact of environmental factors like low temperature, organic matter, and sulfur ions. Following this, a comprehensive review of various types of coupled anammox processes is provided, highlighting the advantages and characteristics of partial nitrification (PN), partial denitrification (PD), methane-dependent nitrite/nitrate reduction (DAMO), sulfur-driven autotrophic denitrification (SAD), iron ammonia oxidation (feammox) and algae photoautotrophy coupling techniques, emphasizing their significance in system stability and resource utilization efficiency. Future research directions include exploring the applicability of the anammox process under various temperature conditions and addressing NO₃⁻-N issues in effluent. The findings from these studies will offer valuable insights for further enhancing the optimization of the anammox process in mainstream urban wastewater treatment.

厌氧氨氧化（anammox）工艺是一种关键的脱氮技术，在废水处理领域发挥着重要作用。本文首先阐述了厌氧氨氧化工艺与传统硝化-反硝化技术相比的优点。随后，论文深入探讨了不同污泥形态的特征、厌氧细菌的行为过程及其对环境因素的反应。在修订与主流地区城市污水管理相关的问题时，它讨论了在氮负荷减少的情况下厌氧菌过程所面临的问题，如由于氨氮和亚硝酸盐浓度水平降低而导致的活性受限，以及低温、有机物和硫离子等环境因素的影响。随后，对各种类型的耦合氨氧化过程进行了全面回顾，重点介绍了部分硝化（PN）、部分反硝化（PD）、甲烷依赖性亚硝酸盐/硝酸盐还原（DAMO）、硫驱动自养反硝化（SAD）、铁氨氧化（feammox）和藻类光自养耦合技术的优势和特点，强调了它们在系统稳定性和资源利用效率方面的重要意义。未来的研究方向包括探索氨氧化工艺在各种温度条件下的适用性，以及解决污水中的 NO3-N 问题。这些研究结果将为进一步优化主流城市污水处理中的氨氧化工艺提供有价值的见解。

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引用次数: 0

Exposure of young German adults to the anti-dandruff agent climbazole from 2002 to 2022: Analysis of specific biomarkers in urinary samples 2002 年至 2022 年德国年轻成年人接触去屑剂康拜唑的情况：尿液样本中特定生物标志物的分析。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143611

The fungicide climbazole is mainly used as an anti-dandruff (AD) agent in cosmetics, such as shampoos or other hair care products. Consequently, an exposure of the general population seems likely because many people suffer from dandruff. We have analyzed urine samples from the German Environmental Specimen Bank (ESB) for two specific climbazole biomarkers, namely (OH)₂-climbazole and cx–OH–climbazole, in samples collected in the years 2002, 2007, 2012, 2017 and 2022. (OH)₂-Climbazole was determined diastereoselectively, hence three analytes are discussed ((OH)₂-climbazole 1, (OH)₂-climbazole 2 and cx–OH–climbazole). The study population consisted of 300 students (150 male, 150 female) aged between 20 and 29 at the time of sampling from Halle/Saale in Germany. Most samples under scrutiny did not contain any climbazole metabolites in levels above the limit of quantification (LOQ, 0.5 μg/L for either analyte), only in 16 samples at least one analyte could be quantitated. Even the sample with the highest metabolite concentrations (10.23 μg/L (OH)₂-climbazole and 2.53 μg/L cx–OH–climbazole) barely reached the urinary concentrations found in an excretion kinetics study after the typical application of a climbazole-containing shampoo in three volunteers. As a result, estimated daily intakes (max. 1.8 μg/kg bw/d) lay below the subchronic NOAEL (15 mg/kg bw/d) and NOEL (5 mg/kg bw/d) by a factor of more than 8300 and 2700, respectively. The evaluation of the climbazole burden of the general population gives valuable insights for the authorities on the effect of legal restrictions.

杀真菌剂克霉唑主要用作化妆品（如洗发水或其他护发产品）中的去屑剂。因此，由于很多人都患有头皮屑，普通人群似乎也有可能接触到这种物质。我们对德国环境样本库（ESB）的尿样进行了分析，以检测 2002、2007、2012、2017 和 2022 年收集的样本中的两种特定攀唑生物标志物，即 (OH)2-climbazole 和 cx-OH-climbazole。(OH)2-climbazole是非对映选择性测定的，因此讨论了三种分析物（(OH)2-climbazole 1、(OH)2-climbazole 2和cx-OH-climbazole）。研究对象包括来自德国哈勒/萨勒的 300 名学生（150 名男生，150 名女生），采样时他们的年龄在 20 至 29 岁之间。大部分受检样本中的任何一种康美唑代谢物含量均未超过定量限（LOQ，任何一种分析物的定量限均为 0.5 微克/升），只有 16 个样本中至少有一种分析物可以定量。即使是代谢物浓度最高的样本（10.23 μg/L (OH)2-climbazole 和 2.53 μg/L cx-OH-climbazole），也几乎没有达到在对三名志愿者使用含攀唑的洗发水后进行的排泄动力学研究中发现的尿液浓度。因此，估计的日摄入量（最大 1.8 μg/kg体重/天）低于亚慢性无观测不良效应水平（15 mg/kg体重/天）和无观测不良效应水平（5 mg/kg体重/天），分别低于 8300 和 2700 倍以上。对普通人群的爬唑负荷进行评估，为有关当局了解法律限制的效果提供了宝贵的信息。

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引用次数: 0

Dual function of sea grapes (Caulerpa racemosa) as phytoremediator for palm oil mill effluent and as ornamental fish feed formulation 海葡萄（Caulerpa racemosa）作为棕榈油厂污水植物修复剂和观赏鱼饲料配方的双重功能。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143668

Phytoremediation is a promising technology for treating Palm Oil Mill Effluent (POME). Moreover, phytoremediators have the potential for various aplication, including as feedstock. Hence, this study aims to elucidate the ability of sea grapes (Caulerpa racemosa) in remediating POME and evaluate their suitability as ornamental fish feed. Results showed that application of sea grapes effectively decreased the COD, TSS, phosphate (PO₄³⁻), and nitrate (NO₃⁻) levels in POME. Sea grapes maintained in POME with a concentration of 12.5% had the highest reduction rate and growth performance. Moreover, sea grapes biomass from the remediation process can be utilized as feed material for ornamental fish, as indicated by increasing skin coloration of fish. For the first time, this study provides sustainable options for managing POME using sea grapes and suggests sea grapes as a potential fish feed formulation for ornamental fish.

植物修复是处理棕榈油厂废水（POME）的一项前景广阔的技术。此外，植物修复剂还具有多种应用潜力，包括用作原料。因此，本研究旨在阐明海葡萄（Caulerpa racemosa）修复 POME 的能力，并评估其作为观赏鱼饲料的适宜性。结果表明，施用海葡萄可有效降低 POME 中的 COD、TSS、磷酸盐（PO43-）和硝酸盐（NO3-）水平。海葡萄在 POME 中的浓度为 12.5%，其降低率和生长性能最高。此外，修复过程中产生的海葡萄生物质可用作观赏鱼的饲料原料，其表现为鱼的皮肤颜色增加。这项研究首次提供了利用海葡萄管理 POME 的可持续方案，并建议将海葡萄作为观赏鱼的潜在鱼饲料配方。

引用次数: 0

Molecular mechanisms of iron nanominerals formation in fungal extracellular polymeric substances (EPS) layers during fungus-mineral interactions 真菌与矿物相互作用过程中真菌胞外聚合物质（EPS）层中纳米铁矿物形成的分子机制。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143660

Extracellular polymeric substances (EPS), which envelop on fungal hyphae surface, interact strongly with minerals and play a crucial role in the formation of nanoscale minerals during biomineralization in nature environments. However, it remains poorly understood about the molecular mechanisms of nanominerals (i.e., iron nanominerals) formation in fungal EPS halos during fungus-mineral interactions. This process is vital because fungi typically grow attached to various mineral surfaces in nature. According to the changes of thickness of the fungal cell and EPS layers during the Trichoderma guizhouense NJAU 4742 and hematite cultivation experiments, we found that fungal biomineralization could trigger the formation of EPS layers. Fe-dominated nanominerals, aromatic C (283-286.1 eV), alkyl C (287.6-288.3 eV), and carboxylic C (288.4-289.1 eV) were the dominant chemical groups on the EPS layers, as determined by nanoscale secondary ion mass spectrometry (NanoSIMS), high-resolution transmission electron microscope (HRTEM), and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Further, evidence from Fe K-edge X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) spectra indicated that oxygen vacancy (O_V) was formed on the Fe-dominated nanomineral surface during fungus-mineral interactions, which played an important role in catalyzing H₂O₂ decomposition and HO∗ production. Taken together, the intrinsic peroxidase-like activity by reactive oxygen species (ROS) could modulate the Fe-dominated nanominerals formation in EPS layers to newly form a physical barrier between the cell and the external environments around hyphae, providing novel insights into the effects of ROS-mediated fungal-mineral interactions on fungal nutrient recycling, attenuation of contaminants, and biological control in nature environments.

包裹在真菌菌丝表面的胞外高分子物质（EPS）与矿物质有强烈的相互作用，在自然环境中的生物矿化过程中对纳米级矿物质的形成起着至关重要的作用。然而，人们对真菌与矿物相互作用过程中真菌 EPS 光晕形成纳米矿物（即纳米铁矿物）的分子机制仍然知之甚少。这一过程至关重要，因为在自然界中，真菌通常会附着在各种矿物表面生长。根据本研究中贵州毛霉 NJAU 4742 和赤铁矿培养实验中真菌细胞层和 EPS 层厚度的变化，我们发现真菌生物矿化可引发 EPS 层的形成。通过纳米尺度二次离子质谱（NanoSIMS）、高分辨率透射电子显微镜（HRTEM）和碳1s近缘X射线吸收精细结构（NEXAFS）光谱测定，EPS层上的主要化学基团是以铁为主的纳米矿物、芳香族C（283-286.1 eV）、烷基C（287.6-288.3 eV）和羧基C（288.4-289.1 eV）。此外，来自铁 K 边 X 射线吸收近边结构（XANES）和 X 射线光电子能谱（XPS）光谱的证据表明，在真菌与矿物相互作用的过程中，以铁为主的纳米矿物表面形成了氧空位（OV），在催化 H2O2 分解和 HO* 生成方面发挥了重要作用。综上所述，活性氧（ROS）固有的过氧化物酶样活性可调节 EPS 层中以铁为主的纳米矿物的形成，在菌丝周围新形成细胞与外部环境之间的物理屏障，为研究 ROS 介导的真菌与矿物相互作用对自然环境中真菌营养循环、污染物衰减和生物控制的影响提供了新的见解。

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引用次数: 0

Integration of Fe-MOF-laccase-magnetic biochar: From Rational Designing of a biocatalyst to aflatoxin B1 decontamination of peanut oil Fe-MOF-漆酶-磁性生物炭的整合：从合理设计生物催化剂到花生油中黄曲霉毒素 B1 的净化。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143424

Enzymatic degradation of aflatoxins in food commodities has gained significant attention. However, enzyme denaturation in organic media discourages their direct use in oils to remove aflatoxins. For that, enzymes are immobilized or encapsulated for improved stability and reusability under unfavorable conditions. We sandwiched the laccase between a carrier and an outer protective layer. We used spent-mushroom-substrate (SMS) derived porous magnetic biochar as the laccase carrier and coated it with an iron MOF to create a biocomposite, Fe-BTC@Lac@FB. The immobilized laccase demonstrated enhanced chemical, thermal, and storage stability and proficient reusability. Fe-BTC@Lac@FB exhibited 11 times enhanced aflatoxin B₁ (AFB₁) degradation compared to free laccase (FL). In addition, thermally inactivated Fe-BTC@Lac@FB could adsorb 11.2 mg/g of AFB₁ from peanut oil. Multi-aflatoxin removal also proved promising, while Fe-BTC@Lac@FB could retain >85 % of AFB₁ removal efficacy after five reusability cycles. Fe-BTC@Lac@FB treatment did not affect peanut oil quality as indicated by different oil quality parameters and proved essentially non-cytotoxic. All these aspects helped recognize Fe-BTC@Lac@FB as an excellent laccase-carrying material with exceptionally higher stability, activity, and reusability.

酶法降解食品中的黄曲霉毒素已受到广泛关注。然而，酶在有机介质中变性，不利于直接用于油类中去除黄曲霉毒素。为此，需要对酶进行固定或封装，以提高其稳定性和在不利条件下的重复使用性。我们将漆酶夹在载体和外保护层之间。我们使用废蘑菇基质（SMS）衍生的多孔磁性生物炭作为漆酶载体，并在其上涂覆铁MOF，从而创建了一种生物复合材料--Fe-BTC@Lac@FB。固定化的漆酶具有更高的化学、热和贮存稳定性以及良好的重复使用性。与游离漆酶（FL）相比，Fe-BTC@Lac@FB 对黄曲霉毒素 B1（AFB1）的降解能力提高了 11 倍。此外，热失活的 Fe-BTC@Lac@FB 能从花生油中吸附 11.2 mg/g 的 AFB1。事实证明，Fe-BTC@Lac@FB 对多种黄曲霉毒素也有很好的去除效果，经过五个重复使用周期后，Fe-BTC@Lac@FB 对 AFB1 的去除率仍大于 85%。从不同的油质参数来看，Fe-BTC@Lac@FB 处理不会影响花生油的质量，而且基本上没有细胞毒性。所有这些方面都表明，Fe-BTC@Lac@FB 是一种具有极高稳定性、活性和可重复使用性的优秀漆包线杆菌载体材料。

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引用次数: 0

Mechanism of UV photodegradation of fluoroquinolone antibiotic ciprofloxacin in aqueous solutions 氟喹诺酮类抗生素环丙沙星在水溶液中的紫外线光降解机理。

IF 8.1 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Chemosphere

Pub Date : 2024-11-01 DOI: 10.1016/j.chemosphere.2024.143643

Mechanism of direct UV photolysis of the zwitterionic and anionic forms of the quinolone antibiotic ciprofloxacin (CIP) was revealed by combination of nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. For both forms, the main intermediate is a dissociative triplet state, which loses a fluorine ion to form a triplet carbocation; subsequent solvent attack of the latter leads to the formation of products of hydroxylation both the aromatic ring and the piperazyl substituent. Correspondingly, the quantum yield of photolysis of both CIP forms does not depend on the excitation wavelength, but depends on the concentration of dissolved oxygen. Secondary photolysis leads to a number of products of oxidation of the aromatic system, as well as oxidation, opening and full destruction of the piperazinyl substituent. The results obtained may be important for understanding the fate of quinolone antibiotics in UVC disinfection processes and in natural waters under the action of sunlight.

通过结合纳秒激光闪烁光解、稳态光解以及高分辨率液相色谱-质谱和 DFT 量子化学计算，揭示了喹诺酮类抗生素环丙沙星 (CIP) 齐聚物和阴离子形式的直接紫外光解机理。这两种形式的主要中间体都是离解三重态，失去一个氟离子后形成三重碳位；后者随后受到溶剂侵蚀，形成芳香环和哌嗪取代基的羟基化产物。相应地，两种 CIP 形式的光解量子产率并不取决于激发波长，而是取决于溶解氧的浓度。二次光解会产生多种芳香系统氧化产物，以及哌嗪基取代基的氧化、开放和完全破坏。所获得的结果可能对了解喹诺酮类抗生素在紫外线消毒过程中以及在阳光作用下在自然水体中的命运具有重要意义。

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