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Exploring the impact of copper oxide nanoparticles on the biocontrol activity and plant growth promotion of Trichoderma asperellum 探讨氧化铜纳米颗粒对曲霉木霉生防活性及促进植株生长的影响
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-02-19 DOI: 10.1016/j.hazl.2025.100147
Claudia A. Ramírez-Valdespino , Marlyn Morales-García , Guillermo Herrera-Pérez , Yordan J. Romero-Contreras , Enrique García-Mireles , Joan Salas-Leiva , Susana González-Chávez , Socorro Tarango-Rivero , Erasmo Orrantia-Borunda
Agriculture is constantly in the search for new alternatives to control phytopathogens and improvement of plant growth. One of its main strategies is the use of biocontrollers, among them, Trichoderma genus stand out for their versatility and broad spectrum phytopatogenic fungi attacked. On the other hand, nanotechnology is positioning itself as an alternative to the use of agrochemicals, especially metal oxide nanoparticles, including ZnO, TiO2 and CuO. Recently, it has been seen that when Trichoderma is put in contact with nanoparticles, it increases its biocontrol and biostimulant activity. Therefore, in this work we performed the characterization of a T. asperellum strain, which was capable to grow in different concentrations of CuO nanoparticles, obtaining that, at 200 ppm, Trichoderma showed no changes in growth and no apparent stress. Moreover, the strain developed a higher biocontrol activity against two Fusarium oxysporum strains, but decreases with F. fujikuroi, as well as changes in the expression of genes associated to biocontrol. Finally, an enhance in alfalfa growth is reported. These results suggest that, at the tested concentrations, CuO-NPs do not interfere with the biocontrol activity of T. asperellum, providing the basis for the development of a bionanoformulation to control F. oxysporum and promotes alfalfa growth.
农业一直在不断寻找新的替代方法来控制植物病原体和改善植物生长。其主要策略之一是使用生物防治剂,其中木霉属以其多功能性和广谱的植物性真菌攻击而突出。另一方面,纳米技术将自己定位为农用化学品的替代品,特别是金属氧化物纳米粒子,包括ZnO、TiO2和CuO。最近,人们发现当木霉与纳米颗粒接触时,它的生物防治和生物刺激素活性增加。因此,在这项工作中,我们对一株能够在不同浓度的CuO纳米颗粒中生长的曲霉菌株进行了表征,结果表明,在200 ppm的浓度下,木霉的生长没有变化,也没有明显的胁迫。此外,该菌株对两种尖孢镰刀菌均有较高的生物防治活性,但对fujikuroi和生物防治相关基因表达的变化均有抑制作用。最后,报道了苜蓿生长的增强。这些结果表明,在测试浓度下,CuO-NPs不会干扰曲霉的生物防治活性,为开发防治尖孢镰刀菌和促进苜蓿生长的生物纳米制剂提供了基础。
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引用次数: 0
Sulfotransferases in mediating the chlorophenol metabolism: Metabolites identification and metabolic characterization 介导氯酚代谢的硫转移酶:代谢物鉴定和代谢特性
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-06-18 DOI: 10.1016/j.hazl.2025.100155
Kai Yang , Guoqiang qin , RuoYong Jia , Haoqian Zhang , Qiangqiang Gan , Shao-You Lu , Jian-Jun Liu , Zhong-Ze Fang
Chlorophenols (CPs) are persistent organic pollutants (POPs) widely detected in the natural environment. Sulfotransferases are a group of crucial phase II metabolic enzyme involved in the metabolism of endogenous and exogenous substances. This research aims to identify the metabolite and characterize the specific isoforms involved in the sulfonation of each CP. Recombinant enzyme assays and chemical inhibitors were used to characterize the primary SULT isoforms involved in the sulfonation of each CP. Our findings indicated that mono-sulfonate was identified in each incubation system. SULT1A1 predominated the sulfonation of monochlorophenol (MCP), SULT1A1, SULT1B1, and SULT1E1 emerged as the pivotal SULT isoforms mediating the sulfonation of 2,4-dichlorophenol (2,4-DCP), trichlorophenol (2,3,4-TCP), 2,4,6-trichlorophenol (2,4,6-TCP), and 3,4,5-trichlorophenol (3,4,5-TCP). Additionally, sulfonation of 2,4,5-trichlorophenol (2,4,5-TCP), 2,3,4,5-tetrachlorophenol (2,3,4,5-TECP), and 2,3,4,6-tetrachlorophenol (2,3,4,6-TECP) were primarily catalyzed by SULT1B1. Furthermore, SULT1B1 and SULT2A1 were the major isoforms involved in the sulfonation of 2,3,5,6-tetrachlorophenol (2,3,5,6-TECP) and pentachlorophenol (PCP). These results provide important insights into the metabolic elimination and toxicity of CPs from a novel perspective.
氯酚是一种广泛存在于自然环境中的持久性有机污染物。硫转移酶是一类重要的II期代谢酶,参与内源性和外源性物质的代谢。本研究旨在鉴定代谢物并表征参与每种CP磺化的特定亚型。重组酶测定和化学抑制剂用于表征参与每种CP磺化的主要SULT亚型。我们的研究结果表明,在每种培养体系中都鉴定出单磺酸盐。SULT1A1主导了单氯苯酚(MCP)的磺化,SULT1A1、SULT1B1和SULT1E1是SULT的关键同工异构体,介导了2,4-二氯苯酚(2,4- dcp)、三氯苯酚(2,3,4- tcp)、2,4,6-三氯苯酚(2,4,6- tcp)和3,4,5-三氯苯酚(3,4,5- tcp)的磺化。此外,2,4,5-三氯苯酚(2,4,5- tcp)、2,3,4,5-四氯苯酚(2,3,4,5- tecp)和2,3,4,6-四氯苯酚(2,3,4,6- tecp)的磺化反应主要由SULT1B1催化。此外,SULT1B1和SULT2A1是参与2,3,5,6-四氯酚(2,3,5,6- tecp)和五氯酚(PCP)磺化的主要亚型。这些结果为CPs的代谢消除和毒性提供了一个新的视角。
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引用次数: 0
Development of a silica gel chromatography-based cleanup method for quantification of polystyrene nanoplastics in tissue samples via pyrolysis–GC/MS 组织样品中聚苯乙烯纳米塑料的热解-气相色谱/质谱净化方法的建立
IF 8.1 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-10-25 DOI: 10.1016/j.hazl.2025.100166
Yurika Tokunaga , Kosuke Tanaka , Go Suzuki , Nami Shimizu , Yoshinori Ikenaka , Shouta M.M. Nakayama , Mayumi Ishizuka
Nanoplastics (NPs) are cause for increasing concern due to their ability to cross biological barriers, enhanced reactivity, and potentially greater toxicity than microplastics. However, their quantification in biological samples such as animal tissues remains challenging, primarily due to complex matrix interference and contamination risks. Reliable quantification of NPs in tissues is critical for understanding their bioavailability, bioaccumulation, and associated toxicological risks to animals, as well as their potential ecological risks. Here, we developed a simple yet robust method for quantifying polystyrene (PS) NPs in animal tissues using silica gel column chromatography coupled with pyrolysis–gas chromatography/mass spectrometry. Tissue samples were homogenized in dichloromethane (DCM) to extract and dissolve PS NPs in DCM and then subjected to alkaline digestion. The extract was subsequently purified using pre-heat-treated silica gel columns. The method showed high recovery rates (102.0 % and 91.2 % at 0.3 and 1.7 µg g⁻¹, respectively), with limits of detection and quantification of 3.0 ng and 7.8 ng, respectively. Validation with liver samples from Japanese quail orally exposed to 50 nm PS NPs revealed significantly elevated levels of PS NPs on Days 1 and 3 post-exposure (33.8 ± 1.5 and 34.1 ± 5.2 ng g⁻¹) compared to controls (13.2 ± 0.3 and 14.5 ± 2.0 ng g⁻¹) (p < 0.005). This method demonstrates effective removal of biological matrix components, enabling accurate and reproducible quantification of PS NPs in avian liver tissues. While the application to other biological samples will be explored in future studies, the method’s simplicity and minimal contamination make it a valuable tool for advancing risk assessments of NPs in biological systems.
纳米塑料(NPs)由于其跨越生物屏障的能力、增强的反应性和潜在的比微塑料更大的毒性而引起越来越多的关注。然而,它们在生物样品(如动物组织)中的定量仍然具有挑战性,主要是由于复杂的基质干扰和污染风险。组织中NPs的可靠定量对于了解其生物利用度、生物蓄积、对动物的相关毒理学风险以及潜在的生态风险至关重要。在这里,我们开发了一种简单而可靠的方法来定量动物组织中的聚苯乙烯(PS) NPs,使用硅胶柱层析-热解-气相色谱/质谱联用。组织样品在二氯甲烷(DCM)中均质,提取并溶解PS NPs,然后进行碱性消化。提取液随后用预处理硅胶柱纯化。该方法在0.3和1.7 µg g⁻¹下的回收率分别为102.0 %和91.2 %,检测限分别为3.0 ng和7.8 ng。验证与肝脏样本日本鹌鹑口头暴露于50 nm PS NPs透露PS含量严重超标NPs在第1和3天接触后(33.8 ±  1.5和34.1±5.2  ng g⁻¹)相比,控制(13.2 ±  0.3和14.5±2.0  ng g⁻¹)(p & lt; 0.005)。该方法可有效去除生物基质成分,实现禽肝组织中PS NPs的准确、可重复性定量。虽然在其他生物样品中的应用将在未来的研究中探索,但该方法的简单性和最小的污染使其成为推进生物系统中NPs风险评估的有价值的工具。
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引用次数: 0
Parental BPA exposure disrupts offspring transcriptomic profiles and impairs embryonic lineage specification during zygotic genome activation 父母双酚a暴露破坏后代转录组谱和损害胚胎谱系规范在合子基因组激活
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-02-18 DOI: 10.1016/j.hazl.2025.100146
Yuequn Chen , Kusheng Wu , Wenlong Huang
Bisphenol A (BPA) is an endocrine-disrupting chemical known for its developmental toxicity. However, the impact of BPA on early embryonic development, particularly during zygotic genome activation (ZGA), remains underexplored. In this study, zebrafish embryos at 3.5 and 4.5 hours post-fertilization (hpf) were collected after 7-day parental exposure to 1.0 µM BPA for transcriptome sequencing. Transcriptomic data underwent differential gene expression functional enrichment and gene set enrichment analyses. Public single-cell transcriptome atlases of zebrafish embryos at different developmental stages (3.3, 4, and 4.8 hpf) were obtained to build signature matrices for digital cell type sorting of the bulk transcriptome using the CIBERSORTx algorithm. Results indicated that parental BPA exposure resulted in muted gene expression response, disturbed energy metabolism profile, and increased pro-inflammatory signatures during ZGA. Digital cell type deconvolution revealed altered cell composition, including deeper multilayer and enveloping layer cells and fewer margin cells. Furthermore, reductions in neural progenitor and heart primordium lineages, alongside expansions in primordial germ and mesendodermal lineages, potentially contribute to later-stage developmental abnormalities. This study elucidates the embryotoxic effects of BPA during the ZGA period, shedding light on the developmental perturbations from early-life exposure to this ubiquitous environmental contaminant.
双酚A (BPA)是一种内分泌干扰化学物质,以其发育毒性而闻名。然而,BPA对早期胚胎发育的影响,特别是在合子基因组激活(ZGA)期间,仍未得到充分研究。在本研究中,父母暴露于1.0 µM BPA 7天后,采集受精后3.5和4.5 小时(hpf)的斑马鱼胚胎进行转录组测序。转录组学数据进行了差异基因表达、功能富集和基因集富集分析。获取不同发育阶段(3.3、4和4.8 hpf)的斑马鱼胚胎的公开单细胞转录组图谱,利用CIBERSORTx算法构建标记矩阵,用于批量转录组的数字细胞类型分选。结果表明,父母双酚a暴露导致ZGA期间基因表达反应减弱,能量代谢谱紊乱,促炎特征增加。数字细胞类型反褶积显示细胞组成改变,包括多层和包络层细胞变深,边缘细胞变少。此外,神经祖细胞和心脏原基谱系的减少,以及原始生殖细胞和中胚层谱系的扩张,可能导致后期发育异常。本研究阐明了双酚a在ZGA时期的胚胎毒性作用,揭示了早期暴露于这种普遍存在的环境污染物对发育的干扰。
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引用次数: 0
Mesophilic compostability of polylactic acid and the associated microbiome as revealed by metagenomics 宏基因组学揭示的聚乳酸的中温堆肥性和相关微生物组
IF 8.1 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-08-06 DOI: 10.1016/j.hazl.2025.100161
Shu Wei Hsueh , Anya Callista Kurniadi , Tan S.M. Amelia , Chin-Fa Lee , Sebastian D. Fugmann , Shu Yuan Yang
Polylactic acid (PLA), the most popular bioplastic, has high sustainability potential as it is bio-sourced and also harbors biodegradability. A form of its biodegradability is via composting, and it was previously established that thermophilic temperatures are needed for PLA breakdown in composts. Here we report the development of composts that have overcome the high-temperature requirement for PLA composting. Our mesophilic composts exhibited clear PLA biodegradability, and this is due to specific biological activity enriched in our material. To investigate the nature of this mesophilic activity, we conducted metagenomics analysis to reveal the microbial composition and enzyme-coding potential associated with PLA biodegradation. These efforts revealed multiple enzyme subtypes with strong enrichment on PLA surfaces in our trained composts, and the top candidate was a type of hydro-lyase, an enzyme that can cleave ester bonds in the absence of water. Hydro-lyases represent a novel class of enzymes that could facilitate PLA degradation, and our results point to the model that the combinatorial action of multiple types of enzymes is what drives PLA biodegradation and how the temperature barrier for PLA composting is overcome.
聚乳酸(PLA)是最受欢迎的生物塑料,由于其生物来源和生物降解性,具有很高的可持续性潜力。其生物可降解性的一种形式是通过堆肥,并且以前已经确定需要嗜热温度才能在堆肥中分解聚乳酸。在这里,我们报告了堆肥的发展,克服了高温要求的聚乳酸堆肥。我们的中温堆肥表现出明显的聚乳酸生物降解性,这是由于我们的材料中富含特定的生物活性。为了研究这种中温活性的性质,我们进行了宏基因组学分析,以揭示与聚乳酸生物降解相关的微生物组成和酶编码潜力。这些努力揭示了多种酶亚型在我们训练的堆肥中PLA表面上有很强的富集,其中最可能的是一种水解酶,一种在没有水的情况下可以裂解酯键的酶。水解酶代表了一类可以促进PLA降解的新型酶,我们的研究结果表明,多种酶的组合作用是驱动PLA生物降解的原因,以及如何克服PLA堆肥的温度障碍。
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引用次数: 0
Per- and polyfluoroalkyl substances in rainfall runoff from an AFFF-impacted concrete pad: A field simulation study 受afff影响的混凝土垫块降雨径流中的全氟和多氟烷基物质:一项实地模拟研究
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2024-11-28 DOI: 10.1016/j.hazl.2024.100137
Phong K. Thai , Jeffrey T. McDonough , Trent A. Key , Anita Thapalia , Scott Porman , Pritesh Prasad , Stephanie Fiorenza , Hirozumi Watanabe , Craig M. Barnes , Jochen F. Mueller
Per- and polyfluoroalkyl substances (PFAS) retained within hardscape have been observed to leach over time in numerous laboratory studies. The aim of this study was to measure the release of key PFAS in rainfall runoff from a concrete pad impacted by historical AFFF use at the field-scale. Rainfall simulations were conducted on a 5 m2 (1 ×5 m) plot for 3 consecutive days. Runoff water was collected every 2 minutes and analyzed for 5 PFAS commonly associated with AFFF. Surface samples of the concrete were collected from the plot after the rainfall runoff experiment. Perfluorooctane sulfonate (PFOS) exhibited the highest concentrations within the concrete (up to ∼4000 μg kg−1) and runoff water (up to 500 μg L−1), followed by 6:2 fluorotelomer sulfonate (6:2 FTS). PFAS concentrations in runoff water were higher in the first sample and then decreased in the consecutive samples of each rainfall simulation. It is estimated that the percentage of the total PFAS mass within the surface of the concrete contributing to runoff samples ranged from 0.006 % (PFOS) to 0.031 % (PFHxA) per rainfall event. This suggests low but sustained PFAS leaching from AFFF-impacted concrete into runoff water. Our findings confirmed that concrete impacted by legacy use of AFFF is a likely secondary source of PFAS in runoff water and highlight some similarities and differences between laboratory- and field-scale rainfall simulations.
在许多实验室研究中,已观察到保留在硬景观中的全氟烷基和多氟烷基物质(PFAS)随着时间的推移会浸出。本研究的目的是在农田尺度上测量受历史AFFF使用影响的混凝土垫块降雨径流中关键PFAS的释放。在5 m2 (1 ×5 m)样地连续3天进行降雨模拟。每2 分钟收集一次径流水,并分析与AFFF相关的5种PFAS。雨水径流试验后,在小区内采集混凝土表面试样。全氟辛烷磺酸(PFOS)在混凝土中的浓度最高(高达~ 4000 μg kg−1),径流水中的浓度最高(高达500 μg L−1),其次是6:2氟端聚体磺酸(6:2 FTS)。径流水中PFAS浓度在第一个样品中较高,在每个降雨模拟的连续样品中依次下降。据估计,每次降雨事件中,混凝土表面总PFAS质量对径流样品的贡献百分比从0.006 % (PFOS)到0.031 % (PFHxA)不等。这表明受afff影响的混凝土中低但持续的PFAS浸出到径流水中。我们的研究结果证实,受AFFF遗留使用影响的混凝土可能是径流水中PFAS的次要来源,并强调了实验室和现场尺度降雨模拟之间的一些异同。
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引用次数: 0
No traces of emerging and priority organic pollutants in the muscles of Procambarus clarkii suggest the feasibility of its regulated and sustainable control from uncontaminated environments 在克氏原螯虾的肌肉中没有新出现的和优先存在的有机污染物的痕迹,这表明在未受污染的环境中对其进行调控和可持续控制是可行的
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2024-12-30 DOI: 10.1016/j.hazl.2024.100140
Dario Savoca , Vincenzo Arizza , Gaetano Cammilleri , Leonardo Cerasino , Antonella Maccotta , Federico Marrone , Licia Pantano , Nico Salmaso , Francesco Paolo Faraone
A monitoring of organic contaminants in the muscles of the Procambarus clarkii and environmental samples of water and sediment was conducted in three Sicilian wetlands (Italy). The substances investigated in the biological samples were per- and polyfluoroalkyl substances (PFAS), phthalic acid esters (PAEs), pesticides, antibiotics, and microcystins (MCs), all of which were below the detection limit. Given that the Louisiana red swamp crayfish is considered a bioaccumulator, the results of this study indicate that these environments are not significantly contaminated by the selected pollutants. Furthermore, the study suggests the potential uses of the edible portions of this alien species. Despite P. clarkii cannot be marketed in several countries, including Italy, it is possible that the animal biomass obtained in the frame of the monitoring, control and eradication activities carried out by local authorities, could be exploited for various purposes, such as food, feed and biotechnology. This would reduce the costs associated with disposal and make these activities more sustainable in the long term, thereby contributing to the preservation of ecosystems that are currently threatened by this invasive species.
在意大利西西里的三个湿地对克氏原螯虾(Procambarus clarkii)肌肉中的有机污染物以及水和沉积物环境样本进行了监测。生物样品中检测的物质有全氟烷基和多氟烷基物质(PFAS)、邻苯二甲酸酯(PAEs)、农药、抗生素和微囊藻毒素(MCs),均低于检测限。考虑到路易斯安那州的红沼泽小龙虾被认为是一种生物蓄积器,本研究的结果表明,这些环境没有受到所选污染物的显著污染。此外,该研究还提出了这种外来物种可食用部分的潜在用途。尽管克拉氏杆菌不能在包括意大利在内的一些国家销售,但在地方当局开展的监测、控制和根除活动中获得的动物生物量有可能被用于各种目的,如食品、饲料和生物技术。这将减少与处理相关的成本,并使这些活动在长期内更具可持续性,从而有助于保护目前受到这种入侵物种威胁的生态系统。
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引用次数: 0
A dual approach using UV irradiation and subcritical water extraction for enhanced PLA waste degradation in a bioaugmented food composter 采用紫外照射和亚临界水萃取的双重方法在生物增强食物堆肥中增强聚乳酸废物的降解
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-06-05 DOI: 10.1016/j.hazl.2025.100154
Christian Adi Pratama , Avnish Nitin Mistry , Saowaluk Krainara , Patamavadee Treeson , Nattapong Tuntiwiwattanapun , Nichakorn Khondee , Luthfia Dwi Rachmani , Ekawan Luepromchai
Polylactic acid (PLA) ranks among the most extensively produced bioplastics, raising waste management concerns globally. This study explored dual pretreatment strategies, specifically photolysis by Ultraviolet-C (UVC) and hydrolysis by subcritical water extraction (SWE), for PLA waste treatment. UVC irradiation reduced the mechanical strength and viscosity average molecular weight (Mv) of PLA, but the effects were more significant in thin PLA films than in thick PLA beverage cups. Thus, the PLA cups were selected for SWE treatment, which reduced their Mv from 190,000 to 5300. The pulverized SWE-treated PLA was later used for inducing protease and esterase in PLA-degrading bacterial consortium EAc. This active inoculum was applied as a bioaugmentation agent in a food composter for degrading UVC-treated PLA cups with food waste. PLA weight loss in the bioaugmented food composter (42 %) after 56 days was greater than the naturally attenuated composter (1 %). The residual PLA in the final bioaugmented compost had a relatively smaller size and lower Mv with prominent surface erosion. In addition, the 16S rRNA gene amplicon sequencing revealed that the bioaugmentation promoted bacterial diversity and community interactions. Conclusively, PLA waste can be treated by UVC irradiation followed by composting with food waste using an active EAc inoculum.
聚乳酸(PLA)是生产最广泛的生物塑料之一,引起了全球对废物管理的关注。本研究探索了双预处理策略,即紫外- c光解(UVC)和亚临界水萃取(SWE)水解处理PLA废物。UVC辐照降低了聚乳酸的机械强度和粘度平均分子量(Mv),但对聚乳酸薄膜的影响比对聚乳酸饮料杯的影响更显著。因此,选择PLA杯进行SWE处理,将其Mv从190,000降低到5300。将经sw处理的聚乳酸粉碎后,在聚乳酸降解细菌联合体EAc中诱导蛋白酶和酯酶。该活性接种物作为生物增强剂应用于食物堆肥机中,用于降解uvc处理的聚乳酸杯和食物垃圾。生物增强食物堆肥56 d后PLA失重(42. %)大于自然减重(1 %)。最终生物增强堆肥中残余聚乳酸体积相对较小,Mv较低,表面侵蚀明显。此外,16S rRNA基因扩增子测序显示,生物增强促进了细菌多样性和群落相互作用。综上所述,聚乳酸废物可以通过UVC照射处理,然后使用活性EAc接种物与食物垃圾一起堆肥。
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引用次数: 0
Substantially underestimated PFAS pollution in diverse Ghana’s land-use types revealed by a refined TOP assay 在加纳不同土地使用类型的PFAS污染被大大低估了,通过改进的TOP分析揭示
IF 8.1 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-10-23 DOI: 10.1016/j.hazl.2025.100165
Liang Zhao , Junjie Zhang , Shivani Kubendraraj , Susana Villa Gonzalez , Murat V. Ardelan , K. Avarachen Mathew , Emmanuel Ansah , Millicent Kwawu , Christopher Gordon , Alexandros G. Asimakopoulos , Bo Yuan
Per- and polyfluoroalkyl substances (PFAS) research in developing countries has largely focused on imported sources such as e-waste, but contributions from local land-use activities remain poorly understood. This study selected Ghana as a model to investigate PFAS contamination in sediments from riverine ecosystems across four land-use types: mining, municipal & electronic waste, and agriculture. In addition to conventional target analysis, we refined the direct total oxidizable precursor (dTOP) assay by applying direct oxidation to sediments, with the highest PFAS yields achieved using an eightfold increase in oxidizing agents. Target PFAS concentrations were relatively low, likely reflecting the impact of global regulations, but post-dTOP concentrations increased by 239–65,400 % across all sites, ranging from 0.603 to 476 ng/g. Over 99 % of detected PFAS were attributed to previously untargeted precursors, emphasizing the iceberg nature of PFAS contamination, where routine methods capture only a small visible fraction. Mining and agricultural areas showed higher PFAS levels than the e-waste zone, suggesting that locally driven sources are dominant contributors. The tailored dTOP approach proved essential in revealing these hidden PFAS burdens, highlighting the need for broader monitoring frameworks to inform environmental risk assessment and sustainable land-use management in developing regions.
发展中国家对全氟和多氟烷基物质的研究主要集中在电子废物等进口来源,但对当地土地利用活动的贡献仍然知之甚少。本研究选择加纳作为模型,调查河流生态系统沉积物中的PFAS污染,涉及四种土地利用类型:采矿、市政和电子废物以及农业。除了传统的目标分析外,我们还通过对沉积物进行直接氧化来改进直接总可氧化前体(dTOP)测定,在氧化剂增加8倍的情况下,PFAS产量最高。目标PFAS浓度相对较低,可能反映了全球法规的影响,但所有站点的dtop后浓度增加了239-65,400 %,范围从0.603到476 ng/g。超过99% %的检测到的PFAS归因于以前未靶向的前体,强调了PFAS污染的冰山性质,常规方法只能捕获一小部分可见的部分。矿区和农业区的PFAS水平高于电子废物区,表明当地驱动的来源是主要贡献者。事实证明,量身定制的dTOP方法对于揭示这些隐藏的PFAS负担至关重要,强调需要建立更广泛的监测框架,为发展中地区的环境风险评估和可持续土地利用管理提供信息。
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引用次数: 0
Development of a fluorophilic ion-exchange material with dual binding mechanism for solid-phase extraction of PFAS 具有双结合机制的亲氟离子交换材料固相萃取PFAS的研制
IF 6.6 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2025-11-01 Epub Date: 2025-07-13 DOI: 10.1016/j.hazl.2025.100158
Johanna Freilinger , Jan O. Back , Raphael Plangger , Herwig Schottenberger , Christian W. Huck , Marco Rupprich , Rania Bakry
Per- and polyfluoroalkyl substances (PFAS) are persistent contaminants for which authorities worldwide have imposed limits on drinking water, groundwater and surface water. This has created challenges in PFAS detection, leading to an urgent need for reliable and selective solid-phase extraction (SPE) materials for PFAS analysis. In addressing this demand, we have tailored highly crosslinked copolymers containing 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinylimidazolium chloride as a comonomer with ethylene dimethacrylate in various molar ratios. For ionic fluorosurfactants, these copolymers feature a dual binding mechanism that synergistically combines fluorophilic interactions and electrostatic attraction, enhancing selectivity and efficiency. The adsorption behavior of short- and long-chain PFAS and their recoveries were evaluated and compared to commercial SPE cartridges. Characterization revealed the highest ion-exchange capacity (412.7 ± 22 µeq g−1) for a monomer-to-crosslinker ratio of 2:1. The dynamic adsorption capacities for various PFAS ranged from 15.2 to 306 g−1. Recovery experiments consistently demonstrated high PFAS recoveries (98.8–121.6 %), while enrichment studies from wastewater confirmed its robustness in complex environmental matrices (recoveries: 90.8–99.2 %). Additionally, reusability experiments showed consistent recoveries over five cycles (recoveries: 90.34–108.0 %). The findings underscore the potential of this innovative polyelectrolyte as a selective, regenerable, and efficient alternative to conventional SPE materials, qualifying it as a superior candidate for PFAS analysis.
全氟烷基和多氟烷基物质(PFAS)是持久性污染物,世界各地的主管部门对饮用水、地下水和地表水实施了限制。这给PFAS检测带来了挑战,导致迫切需要可靠和选择性的固相萃取(SPE)材料进行PFAS分析。为了满足这一需求,我们定制了高度交联的共聚物,其中含有3-(1H,1H,2H,2H-全氟辛基)-1-乙烯基咪唑氯作为共聚体,以不同的摩尔比与二甲基丙烯酸乙烯酯。对于离子氟表面活性剂,这些共聚物具有双重结合机制,将亲氟相互作用和静电吸引协同结合,提高了选择性和效率。对短链PFAS和长链PFAS的吸附性能和回收率进行了评价,并与商用固相萃取筒进行了比较。表征表明,当单体与交联剂的比例为2:1时,离子交换容量最高(412.7 ± 22µeq g−1)。不同PFAS的动态吸附量为15.2 ~ 306 g−1。回收实验一致证明了PFAS的高回收率(98.8-121.6 %),而废水富集研究证实了其在复杂环境基质中的稳健性(回收率:90.8-99.2 %)。此外,可重用性实验表明,在5个循环中,回收率一致(回收率:90.34-108.0 %)。这些发现强调了这种创新的聚电解质作为传统SPE材料的选择性、可再生和高效替代品的潜力,使其成为PFAS分析的优越候选者。
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Journal of hazardous materials letters
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