环境化学开放性实验设计:重金属污染土壤的化学淋洗*

介绍了一个开放性环境化学实验。该实验以被重金属污染的土壤为研究对象,分别使用稀盐酸、乙二胺四乙酸、氯化钙为淋洗剂,对其进行化学淋洗修复。通过电感耦合等离子体光谱仪分析比较修复前后土壤中铅、镉的含量,用以帮助学生加深理解配合/螯合作用、酸-碱反应、离子交换反应、胶体的性质、土壤重金属形态、土壤性质与组成等相关环境化学知识。实验所用的土壤样品由学生自选,不同类型土壤的理化性质影响淋洗效果,从而增加了实验结果的不确定性。本实验贴近学科前沿且联系工程实际,可激发学生独立思考和探索精神,提高学生的科研能力与解决复杂问题的能力。     

凝聚态化学研究中的动力学振动光谱理论与技术

化学变化的本质是化学键的形成与断裂。凝聚态化学的主要特征是分子内的物理与化学过程与周围环境之间的动态相互作用和动力学耦合,不仅会影响化学键形成与断裂的化学反应平衡与反应速率,还会改变化学反应的走向。动力学振动光谱技术是探测凝聚态体相中与表面上各种微观分子细节最为有力的当代谱学表征技术之一。与脉冲核磁技术类似,科学家们使用一组精心设计的激光脉冲在凝聚态体系中激发复杂的光学响应,所产生的信号中包含了比传统吸收光谱丰富得多的反应机理、分子与溶液结构、分子运动、电荷与能量传递等微观信息。近年来,各种动力学振动光谱被运用于凝聚态化学的各个领域,尤其是在溶液态和表界面态领域,获得了一系列突破性进展,并且处于不断发展的过程之中。在本文中,我们将回顾及展望动力学振动光谱技术的基本概念、实验方法和理论框架,以及它们在凝聚态及表面态化学中的重要应用。     

Real‐Time Atomic‐Scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction

By using in situ aberration‐corrected environmental transmission electron microscopy, for the first time at atomic level, the dynamic evolution of the Cu surface is captured during CO oxidation. Under reaction conditions, the Cu surface is activated, typically involving 2–3 atomic layers with the formation of a reversible metastable phase that only exists during catalytic reactions. The distinctive role of CO and O₂ in the surface activation is revealed, which features CO exposure to lead to surface roughening and consequently formation of low‐coordinated Cu atoms, while O₂ exposure induces a quasi‐crystalline CuOx phase. Supported by DFT calculations, it is shown that crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.     

Organophosphate esters by GC–MS: An optimized method for aquatic risk assessment

Organophosphate esters used as flame retardants and plasticizers are ubiquitous contaminants in surface waters. Many studies indicate that these compounds are neurotoxicants, endocrine disruptors, and may affect reproduction and development of aquatic organisms. Thus, analytical methods that allow accurate quantification of these contaminants at environmentally relevant concentrations are desirable for risk assessment studies. In this study, a method based on solid phase extraction and gas chromatography coupled to mass spectrometry was developed for determination of organophosphate esters in river water extracts. Multivariate optimization was used to determine the best conditions for injection of larger volumes of sample in a Programmable Temperature Vaporization inlet. Furthermore, the matrix effect on the instrumental response was evaluated and compensated by association of extraction‐blank‐matched calibration and isotopically labeled focus standards. The method quantification limits ranged from 0.009 to 0.11 µg/L, staying below the predicted non‐effect concentration for the aquatic compartment for all analytes, which is a requisite for using in risk assessment studies. The method was applied to freshwater samples collected in rivers from the Sao Paulo State, Brazil, and eight out of the ten target organophosphate esters were quantified, being tris(2‐chloroisopropyl) phosphate and tris(phenyl) phosphate the most frequently detected compounds.     

pH electrodes based on iridium oxide films for marine monitoring

The pH is an important parameter that affects the growth and development of marine organisms, environmental changes, and industrial and agricultural production processes. Nowadays, important trends in pH detection and analysis are higher stability, adaptation to extreme environmental conditions, miniaturization, portability, and digital intelligence. Several studies have focused on the application of the iridium oxide film (IROF) pH electrodes in water quality monitoring and physiological analysis. The central aim of this work was to review the preparation techniques of the IROF pH electrodes and to expand their application in the field of marine monitoring. The studied methods include electrochemical deposition, electrochemical growth, sputtering deposition, heat treatment, and novel preparation methods. The IROF pH electrodes prepared via these methods are more sensitive, have a wider pH measurement ranges, and can be miniaturized further than traditional glass and pH photometer. Hence, in environmental analysis, combining IROF pH electrodes with wireless technology for the physiological and biochemical analysis of marine organisms, seawater, and sediment pore water is an important development tendency.     

Probing Ag nanoparticle surface oxidation in contact with (in)organics: an X‐ray scattering and fluorescence yield approach

Characterizing interfacial reactions is a crucial part of understanding the behavior of nanoparticles in nature and for unlocking their functional potential. Here, an advanced nanostructure characterization approach to study the corrosion processes of silver nanoparticles (Ag‐Nps), currently the most highly produced nanoparticle for nanotechnology, is presented. Corrosion of Ag‐Nps under aqueous conditions, in particular in the presence of organic matter and halide species common to many natural environments, is of particular importance because the release of toxic Ag⁺ from oxidation/dissolution of Ag‐Nps may strongly impact ecosystems. In this context, Ag‐Nps capped with polyvinolpyrrolidone (PVP) in contact with a simple proxy of organic matter in natural waters [polyacrylic acid (PAA) and Cl^? in solution] has been investigated. A combination of synchrotron‐based X‐ray standing‐wave fluorescence yield‐ and X‐ray diffraction‐based experiments on a sample consisting of an approximately single‐particle layer of Ag‐Nps deposited on a silicon substrate and coated by a thin film of PAA containing Cl revealed the formation of a stable AgCl corrosion product despite the presence of potential surface stabilizers (PVP and PAA). Diffusion and precipitation processes at the Ag‐Nps–PAA interface were characterized with a high spatial resolution using this new approach.     

Determination of low level nitrite and nitrate in biological, food and environmental samples by gas chromatography-mass spectrometry and liquid chromatography with fluorescence detection

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography with fluorescence detection (LC-FL) methods have been proposed for the determination of low level nitrite and nitrate in biological, food and environmental samples. The methods include derivatization of aqueous nitrite with 2,3-diaminonaphthalene (DAN), enzymatic reduction of nitrate to nitrite, extraction with toluene and chromatographic analyses of highly fluorescent 2,3-naphthotriazole (NAT) derivative of nitrite by using GC-MS in selected-ion-monitoring (SIM) mode and LC-FL. Nitrite and nitrate ions in solid samples were extracted with 0.5 M aqueous NaOH by sonication. The recoveries of nitrite and nitrate ions based on GC-MS and LC-FL results were 98.40% and 98.10% and the precision of these methods, as indicated by the relative standard deviations (RSDs) were 1.00% for nitrite and 1.20% for nitrate, respectively. The limits of detection of the GC-MS in SIM mode and LC-FL methods based on S/N = 3 were 0.02 and 0.29 pg/ml for nitrite and 0.03 and 0.30 pg/ml for nitrate, respectively.     

Regression analysis of right-censored failure time data with missing censoring indicators

This paper discusses regression analysis of right-censored failure time data when censoring indicators are missing for some subjects. Several methods have been developed for the analysis under different situations and especially, Goetghebeur and Ryan considered the situation where both the failure time and the censoring time follow the proportional hazards models marginally and developed an estimating equation approach. One limitation of their approach is that the two baseline hazard functions were assumed to be proportional to each other. We consider the same problem and present an efficient estimation procedure for regression parameters that does not require the proportionality assumption. An EM algorithm is developed and the method is evaluated by a simulation study, which indicates that the proposed methodology performs well for practical situations. An illustrative example is provided.     

浊点萃取-石墨炉原子吸收光谱法测定环境样品中的镉

建立了浊点萃取分离富集石墨炉原子吸收光谱法测定环境样品中痕量镉的方法.浊点萃取选择8-羟基喹啉为螯合剂,Triton X-100为表面活性剂.在pH 8～9、0.01%8-羟基喹啉和0.2%-Triton X-100、80 ℃水浴20 min的优化条件下,所建立方法的检出限为2.5 ng/L; 加标回收率为94.6%～106.2%; 对样品溶液进行富集的富集因子为17.利用该方法分别测定了2个实际水样和2个国家标准参考物质中的总镉含量,结果令人满意.