Environmental chemistry

环境化学
  • 文章类型: Journal Article
    可见光驱动的过氧化氢(H2O2)的光催化生产是目前将太阳能转化为化学能的新兴方法。总的来说,光催化生产H2O2的过程包括两个途径:水氧化反应(WOR)和氧还原反应(ORR)。然而,ORR的利用效率超过WOR,导致与天然水中低氧水平的差异,从而阻碍了它们的实际应用。在这里,我们报道了一种新型的供体-桥-受体(D-B-A)有机聚合物,通过Sonogashira-Hagihara偶联反应与四苯基乙烯(TPE)单元作为电子供体,乙炔(A)作为连接体,芘(P)部分作为电子受体。值得注意的是,所得的TPE-A-P表现出1.65%的显着太阳能到化学转化率和高BET比表面积(1132m2·g-1)。此外,即使在厌氧条件下,它显示出令人印象深刻的H2O2光合效率为1770μmolg-1h-1,超过了先前报道的绝大多数H2O2光合系统。出色的性能归因于电子和空穴的有效分离,随着足够的反应位点的存在促进了炔基电子桥的结合。该协议提出了一种通过水氧化反应产生H2O2的成功方法,标志着在自然环境中的实际应用取得了重大进展。
    The visible-light-driven photocatalytic production of hydrogen peroxide (H2O2) is currently an emerging approach for transforming solar energy into chemical energy. In general, the photocatalytic process for producing H2O2 includes two pathways: the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). However, the utilization efficiency of ORR surpasses that of WOR, leading to a discrepancy with the low oxygen levels in natural water and thereby impeding their practical application. Herein, we report a novel donor-bridge-acceptor (D-B-A) organic polymer conjugated by the Sonogashira-Hagihara coupling reaction with tetraphenylethene (TPE) units as the electron donors, acetylene (A) as the connectors and pyrene (P) moieties as the electron acceptors. Notably, the resulting TPE-A-P exhibits a remarkable solar-to-chemical conversion of 1.65% and a high BET-specific surface area (1132 m2·g-1). Furthermore, even under anaerobic conditions, it demonstrates an impressive H2O2 photosynthetic efficiency of 1770 μmol g-1 h-1, exceeding the vast majority of previously reported photosynthetic systems of H2O2. The outstanding performance is attributed to the effective separation of electrons and holes, along with the presence of sufficient reaction sites facilitated by the incorporation of alkynyl electronic bridges. This protocol presents a successful method for generating H2O2 via a water oxidation reaction, signifying a significant advancement towards practical applications in the natural environment.
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  • 文章类型: Journal Article
    被动采样器是采样水中亲水性微污染物的关键工具。两种主要方法解决了流体动力学的影响:(1)通过表征kw来确定特定地点的采样率(RS),水边界层(WBL)的传质系数,和(2)使用扩散材料减少WBL冲击以控制吸收。第一个需要校准数据,第二个仅使用易碎的扩散材料实现。这项研究评估了亲水性污染物通过聚四氟乙烯(PTFE;30µm厚)的转移,一种新的膜材料,具有比常用的聚醚砜(PES)更低的吸附。首次以类似Chemcatcher的配置组合,我们校准了44个微污染物的改良采样器,以提供RS-kw关系,用于原位RS测定(方法1)。微污染物在吸附剂上的积累比在PTFE上的积累多2000倍。基于PTFE的RS(0.027至0.300Lday-1)比先前报道的PES高2.5。膜性能测量(孔隙率,弯曲)表明积累主要受膜控制。外推法表明,使用较厚的PTFE膜(≥100µm)会在河流条件下将吸收控制完全转移到膜上(方法2)。这一发现可以实现基于污染物特性的RS预测,因此代表了被动采样的显著进步。
    Passive samplers are key tools to sample hydrophilic micropollutants in water. Two main approaches address the influence of hydrodynamics: (1) determining site-specific sampling rate (RS) by characterizing kw, the mass transfer coefficient of the water-boundary layer (WBL), and (2) reducing WBL impact using a diffusive material to control the uptake. The first requires calibration data and the second has only been achieved using fragile diffusive material. This study assesses the transfer of hydrophilic contaminants through polytetrafluoroethylene (PTFE; 30 µm thick), a new membrane material with lower sorption than commonly used polyethersulfone (PES). Combined for the first time in a Chemcatcher-like configuration, we calibrated the modified samplers for 44 micropollutants to provide RS - kw relationships for in-situ RS determination (approach 1). Micropollutants accumulated over 2000 times more on the sorbent than on PTFE. PTFE-based RS (0.027 to 0.300 L day-1) were 2.5 higher than previously reported with PES. Membrane property measurements (porosity, tortuosity) indicated that accumulation is primarily controlled by the membrane. Extrapolation indicated that using thicker PTFE membranes (≥ 100 µm) would shift uptake control entirely to the membrane in river conditions (approach 2). This finding could enable RS prediction based on contaminants properties, thus representing a significant advancement in passive sampling.
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  • 文章类型: Journal Article
    社会和科学的进步导致了新的学习计划的形成,通常是多学科课程。此类课程的担保人和教师必须做好准备,以迅速适应学生的需求和要求,社会,就业市场,和商业领域,因为许多问题在项目生命的最初几年开始浮出水面。在这里,我们分享了自2019年以来在布尔诺的Masaryk大学教授的“环境与健康”学习计划中这样一个过程的经验,捷克共和国。学生和校友的反馈可以改善课程和组织。我们从三个角度展示了反馈循环:来自即时短期经验的反馈可以在一年内纳入,中期反馈循环可以在几年后显现,和长期的甚至几十年。虽然目前的学生通常只感知短期或中期问题,该计划的哲学和结构必须通过预测未来几十年的社会和商业需求来建立。这样的长期方面往往与学生的愿景背道而驰,但仍然必须考虑该计划对新申请人保持吸引力。平衡最初的愿景,准备和应用更改,处理各级反馈是成功学习计划的关键管理挑战。
    Societal and scientific progress has led to the formation of new study programs, often with multidisciplinary curricula. Guarantors and teachers of such programs must be prepared to quickly adapt to the needs and demands of students, society, the job market, and the commercial sphere since many issues start surfacing during the first years of the programs\' life. Here we share our experience with such a process in the study program \"Environment and Health\" taught since 2019 at Masaryk University in Brno, Czech Republic. Feedback from students and alumni allows for improvement of the curriculum and organization of the program. We show feedback loops from three perspectives: Feedback from immediate short-term experience can be incorporated within a year, medium-term feedback loops can manifest after several years, and long-term ones even decades. While current students usually perceive only short- or medium-term issues, the philosophy and structure of the program must be built by predicting societal and commercial needs in the following decades. Such long-term aspects are often counterintuitive to students\' vision, but still have to be considered for the program to remain attractive to new applicants. Balancing the original vision, preparing and applying changes, and dealing with feedback on all levels are key managerial challenges of successful study programs.
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  • 文章类型: Journal Article
    我们审查的主要目标是系统地探索和比较农药检测中采用的最先进的方法,全球食品安全倡议的重要组成部分。发光纳米传感器领域的新方法,色谱,太赫兹光谱,和拉曼光谱进行了精确的讨论,快速,以及食品和农业生态样品中农药检测的通用策略。发光纳米传感器成为强大的工具,以其便携性和无与伦比的灵敏度和实时监控能力而著称。液相和气相色谱法与光谱检测器耦合,分析化学领域的中坚力量,因其精确而受到称赞,广泛的适用性,并在不同的监管环境中进行验证。太赫兹光谱提供了独特的优势,如非侵入性测试,深刻的渗透深度,和批量样品处理。同时,拉曼光谱以其无损性质脱颖而出,它甚至能够检测到痕量的农药,和样品制备的最低要求。在承认这些技术的成熟度和鲁棒性的同时,我们的审查强调了持续创新的重要性。这些方法的意义超出了它们目前的功能,强调他们应对不断变化的挑战的适应性。环境毒物化学2024;00:1-17。©2024作者WileyPeriodicalsLLC代表SETAC出版的环境毒理学和化学。
    The primary goal of our review was to systematically explore and compare the state-of-the-art methodologies employed in the detection of pesticides, a critical component of global food safety initiatives. New approach methods in the fields of luminescent nanosensors, chromatography, terahertz spectroscopy, and Raman spectroscopy are discussed as precise, rapid, and versatile strategies for pesticide detection in food items and agroecological samples. Luminescent nanosensors emerge as powerful tools, noted for their portability and unparalleled sensitivity and real-time monitoring capabilities. Liquid and gas chromatography coupled to spectroscopic detectors, stalwarts in the analytical chemistry field, are lauded for their precision, wide applicability, and validation in diverse regulatory environments. Terahertz spectroscopy offers unique advantages such as noninvasive testing, profound penetration depth, and bulk sample handling. Meanwhile, Raman spectroscopy stands out with its nondestructive nature, its ability to detect even trace amounts of pesticides, and its minimal requirement for sample preparation. While acknowledging the maturity and robustness of these techniques, our review underscores the importance of persistent innovation. These methodologies\' significance extends beyond their present functions, highlighting their adaptability to meet ever-evolving challenges. Environ Toxicol Chem 2024;43:1468-1484. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
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  • 文章类型: Journal Article
    全球氢氟碳化合物(HFC)制冷剂相下降的实施导致氢氟烯烃(HFO)作为低全球变暖潜能值(GWP)替代品的引入,考虑到他们的低大气寿命。然而,迄今为止,尚不完全清楚HFOs主要降解产物三氟乙醛(TFE)的长期大气命运,三氟乙酰氟(TFF),和三氟乙酸(TFA)。它特别涉及形成HFC-23的可能性,HFC-23是一种有效的全球变暖剂。虽然TFE的大气反应网络,TFF,TFA有相当的复杂性,相关的大气化学途径在文献中有很好的特点,能够对HFC-23的形成进行全面的危害评估,作为不同情况下的次要HFO分解产品。在基线情况下,HFO有效GWP的下限高于监管阈值。虽然进一步的研究对于完善气候风险评估至关重要,现有证据表明,与HFOs相关的气候危害不可忽视。
    The enforcement of a global hydrofluorocarbon (HFC) refrigerant phase down led to the introduction of hydrofluoroolefins (HFOs) as a low Global Warming Potential (GWP) substitute, given their low atmospheric lifetime. However, to this date it is not fully clear the long-term atmospheric fate of HFOs primary degradation products: trifluoro acetaldehyde (TFE), trifluoro acetyl fluoride (TFF), and trifluoroacetic acid (TFA). It particularly concerns the possibility of forming HFC-23, a potent global warming agent. Although the atmospheric reaction networks of TFE, TFF, and TFA have a fair level of complexity, the relevant atmospheric chemical pathways are well characterized in the literature, enabling a comprehensive hazard assessment of HFC-23 formation as a secondary HFO breakdown product in diverse scenarios. A lower bound of the HFOs effective GWP in a baseline scenario is found above regulatory thresholds. While further research is crucial to refine climate risk assessments, the existing evidence suggests a non-negligible climate hazard associated with HFOs.
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  • 文章类型: Journal Article
    现代社会的主要问题之一是不同有机物对水体的污染,无机,和污染细菌。寻找具有成本效益和高效的材料和方法用于水处理和环境修复是科学家们最重要的考虑因素之一。中空结构纳米材料,包括中空纤维膜,空心球,中空纳米盒,等。,已经显示出一种令人兴奋的废水精制方法的能力,包括膜技术,吸附,和光催化程序,由于其极高的比表面积,高孔隙率,独特的形态,和低密度。多样的中空纳米结构可以消除有机污染物,包括染料,抗生素,油/水乳液,杀虫剂,和其他酚类化合物,无机污染物,如重金属离子,盐,磷酸盐,溴酸盐,和其他离子,和细菌污染。这里,中空纳米结构的制造和改性的全面概述,水污染物分类,并且提供了具有比较态度的中空结构纳米材料在水处理领域的最新研究,表明这类纳米材料的特权和损害。最终,还提出了在炼油厂系统中使用中空纳米材料的未来前景以及扩大规模所面临的挑战。
    One of the major issues of modern society is water contamination with different organic, inorganic, and contaminants bacteria. Finding cost-effective and efficient materials and methods for water treatment and environment remediation is among the scientists\' most important considerations. Hollow-structured nanomaterials, including hollow fiber membranes, hollow spheres, hollow nanoboxes, etc., have shown an exciting capability for wastewater refinement approaches, including membrane technology, adsorption, and photocatalytic procedure due to their extremely high specific surface area, high porosity, unique morphology, and low density. Diverse hollow nanostructures could potentially eliminate organic contaminants, including dyes, antibiotics, oil/water emulsions, pesticides, and other phenolic compounds, inorganic pollutants, such as heavy metal ions, salts, phosphate, bromate, and other ions, and bacteria contaminations. Here, a comprehensive overview of hollow nanostructures\' fabrication and modification, water contaminant classification, and recent studies in the water treatment field using hollow-structured nanomaterials with a comparative attitude have been provided, indicating the privilege abd detriments of this class of nanomaterials. Eventually, the future outlook of employing hollow nanomaterials in water refinery systems and the upcoming challenges arising in scaling up are also propounded.
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  • 文章类型: Journal Article
    机器学习被用来为进一步评估硫辛烷(S8)的潜在提取提供数据,一种商业上有用的副产品,通过预测AMD水质数据集中的硫酸盐水平,从酸性矿山排水(AMD)。个体ML回归模型,即:线性回归(LR),最小绝对收缩和选择算子(LASSO),Ridge(RD),ElasticNet(EN),K-最近邻居(KNN),支持向量回归(SVR)决策树(DT)极端梯度提升(XGBoost),随机森林(RF),这些模型的多层感知器人工神经网络(MLP)和堆叠集成(SE-ML)组合已成功用于预测硫酸盐水平。在未处理的AMD上训练的SE-ML回归器堆叠了七个表现最佳的个体模型并将其馈送到LR元学习器模型,被发现是表现最佳的模型,其均方误差(MSE)为0.000011,平均绝对误差(MAE)为0.002617,R2为0.9997。温度(°C),总溶解固体(mg/L)和,重要的是,铁(mg/L)与硫酸盐(mg/L)高度相关,铁显示出强的正线性相关,表明黄铁矿氧化产生的溶解产物。合奏学习(装袋,升压和叠加)由于其组合的预测准确性而优于单个方法。令人惊讶的是,当将组合所有模型的SE-ML与仅组合性能最佳模型的SE-ML进行比较时,模型准确性仅有轻微差异,这表明在堆栈中包括表现不佳的模型对其预测性能没有不利影响.
    Machine learning was used to provide data for further evaluation of potential extraction of octathiocane (S8), a commercially useful by-product, from Acid Mine Drainage (AMD) by predicting sulphate levels in an AMD water quality dataset. Individual ML regressor models, namely: Linear Regression (LR), Least Absolute Shrinkage and Selection Operator (LASSO), Ridge (RD), Elastic Net (EN), K-Nearest Neighbours (KNN), Support Vector Regression (SVR), Decision Tree (DT), Extreme Gradient Boosting (XGBoost), Random Forest (RF), Multi-Layer Perceptron Artificial Neural Network (MLP) and Stacking Ensemble (SE-ML) combinations of these models were successfully used to predict sulphate levels. A SE-ML regressor trained on untreated AMD which stacked seven of the best-performing individual models and fed them to a LR meta-learner model was found to be the best-performing model with a Mean Squared Error (MSE) of 0.000011, Mean Absolute Error (MAE) of 0.002617 and R2 of 0.9997. Temperature (°C), Total Dissolved Solids (mg/L) and, importantly, iron (mg/L) were highly correlated to sulphate (mg/L) with iron showing a strong positive linear correlation that indicated dissolved products from pyrite oxidation. Ensemble learning (bagging, boosting and stacking) outperformed individual methods due to their combined predictive accuracies. Surprisingly, when comparing SE-ML that combined all models with SE-ML that combined only the best-performing models, there was only a slight difference in model accuracies which indicated that including bad-performing models in the stack had no adverse effect on its predictive performance.
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  • 文章类型: Journal Article
    明确土壤有机碳(SOC)的积累和分解对于理解陆地生态系统的碳循环至关重要。SOC富集和分解导致稳定碳同位素的分馏,一个受各种因素影响的复杂过程,包括微生物。然而,在早期土壤形成过程中的这种分馏过程和微生物的作用仍未得到充分探索。这项研究调查了腾格里沙漠稳定沙丘上最近形成的生物土壤结皮(BSC)的稳定碳同位素(δ13C)的相对组成,中国北方。在早期BSC发育过程中观察到δ13C的显着增加,可能是由蓝细菌直接固定二氧化碳驱动的。然而,BSC的δ13C值逐渐下降,接近原生植被下的土壤,可能与BSC内的微生物演替有关。这一发现强调了微生物对早期土壤碳周转的潜在影响,并强调了同位素示踪剂研究这一过程的有效性。
    Clarifying the accumulation and decomposition of soil organic carbon (SOC) is crucial for comprehending carbon cycling in terrestrial ecosystems. SOC enrichment and decomposition lead to the fractionation of stable carbon isotopes, a complex process influenced by various factors, including microbes. However, this fractionation process during early soil formation and the role of microorganisms remain poorly explored. This study investigated the relative composition of stable carbon isotopes (δ13C) of recently formed biological soil crusts (BSCs) on stabilized sand dunes in the Tengger Desert, Northern China. A notable increase in δ13C was observed during early BSC development, likely driven by cyanobacteria\'s direct fixation of CO2. Yet, δ13C values of BSCs gradually declined, approaching those of soils under native vegetation, probably linked to microbial succession within the BSCs. This finding highlights the potential microbial influence on early soil carbon turnover and underscores the effectiveness of isotope tracers for studying this process.
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  • 文章类型: Randomized Controlled Trial
    背景:全氟烷基和多氟烷基物质(PFAS)是耐热和耐污染的化学物质。他们坚持不懈,生物积累和传播无处不在。已经报道了人类暴露于高水平PFAS的许多热点。在人体中的一些小型观察研究表明,用阴离子交换树脂(AER)治疗可降低血清PFAS。这项首次临床对照交叉研究旨在评估AER是否降低高度暴露成年人的全氟辛烷磺酸(PFOS)。
    方法:在PFAS热点人群中进行了一项开放标签1:1随机治疗顺序交叉研究,分配给口服AER(胆甾胺4g,每日3次)或观察12周。主要纳入标准为血清PFOS>21ng/mL。主要终点是治疗和观察期之间血清PFOS水平的变化。
    结果:总计,纳入45名参与者,平均年龄为50岁(SD13)。血清全氟辛烷磺酸基线中位数为191ng/mL(IQR:129-229),治疗后平均为115ng/mL(95%CI:89-140),和4.3ng/mL在观察期对应的60%(95%CI:53-67;p<0.0001)。PFHxS,PFOA,PFNA和PFDA在治疗期间下降15%至44%。未报告严重不良事件。
    结论:口服AER可显著降低血清全氟辛烷磺酸浓度,这表明在高度暴露的成年人中,有可能采取增强全氟辛烷磺酸消除的治疗方法。
    BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are heat and stain resisting chemicals. They are persistent, bioaccumulating and spread ubiquitously. Many hotspots where humans are exposed to high levels of PFAS have been reported. A few small observational studies in humans suggest that treatment with an Anion Exchange Resin (AER) decreases serum PFAS. This first clinical controlled crossover study aimed to assess whether AER decreases perfluorooctanesulfonic acid (PFOS) in highly exposed adults.
    METHODS: An open label 1:1 randomized treatment sequence crossover study with allocation to oral AER (cholestyramine 4 g three times daily) or observation for 12 weeks was conducted among citizens from a PFAS hotspot. Main inclusion criteria was serum PFOS > 21 ng/mL. Primary endpoint was change in serum PFOS levels between treatment and observational period.
    RESULTS: In total, 45 participants were included with a mean age of 50 years (SD 13). Serum PFOS baseline median was 191 ng/mL (IQR: 129-229) and decreased with a mean of 115 ng/mL (95 % CI: 89-140) on treatment, and 4.3 ng/mL in observation period corresponding to a decrease of 60 % (95 % CI: 53-67; p < 0.0001). PFHxS, PFOA, PFNA and PFDA decreased during treatment between 15 and 44 %. No serious adverse events were reported.
    CONCLUSIONS: Oral treatment with AER significantly lowered serum PFOS concentrations suggesting a possible treatment for enhancing elimination of PFOS in highly exposed adults.
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  • 文章类型: Journal Article
    环境中的塑料废物问题要求开发新的聚合物材料,专门设计用于在其生命周期结束时易于回收。在这里,开发了包括一系列带有蒽二聚体单元的项链状聚二甲基硅氧烷的绿色聚合物体系。该聚合物具有低的环境影响并且易于回收。Further,其灵活性和玻璃化转变温度易于控制。这些项链状无机聚合物是通过光聚合(二聚)蒽封端的低聚二甲基硅氧烷单体合成的。本工作的一个关键成就是通过热解聚从聚合物中成功地化学回收单体。使单体-聚合物回收。通过使用碱性催化剂进行平衡聚合,具有受控分布链长的单体由具有恒定链长的单体合成。由这些无规单体合成的项链状聚合物具有无定形结构并容易形成透明膜。可以通过控制蒽二聚物之间的聚二甲基硅氧烷的平均链长来调节聚合物的热和机械性能。这项研究提出了一种具有广泛应用的聚合物材料的合成和循环利用方法,包括塑料和弹性体。
    The problem of plastic waste in the environment calls for the development of new polymeric materials designed specifically for easy recycling at the end of their life cycle. Herein, a green polymer system comprising a series of necklace-shaped polydimethylsiloxanes bearing anthracene dimer units is developed. The polymers have low environmental impact and are easily recycled. Further, their flexibility and glass transition temperatures are easy to control. These necklace-shaped inorganic polymers are synthesized by photopolymerizing (dimerizing) anthracene-terminated oligo-dimethylsiloxane monomers. A key achievement of the present work is the successful chemical recovery of the monomers from the polymers through thermal depolymerization, enabling monomer-polymer recycling. By applying equilibrium polymerization with base catalysts, monomers with a controlled distributed chain length are synthesized from monomers with a constant chain length. The necklace-shaped polymers synthesized from these randomized monomers have amorphous structures and readily form transparent films. It is possible to modulate the thermal and mechanical properties of the polymers by controlling the average chain length of the polydimethylsiloxane between the anthracene dimers. This investigation presents a method for the synthesis and cyclic utilization of polymer materials with a wide range of applications, including plastics and elastomers.
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