电镜-能谱仪在柳树叶重金属污染研究中的应用

采用自然干燥、化学处理、冷冻处理3种方法制备待测样本,运用扫描电镜和透射电镜结合X射线能谱仪研究柳树叶肉组织对重金属的累积状况,并定位到栅栏组织的细胞壁,为定性定量以及定位分析组织细胞固定、转移重金属污染探索合适的制样方法.结果表明:(1)重金属Pb、Cu、Cd、Zn在柳树叶肉组织被检测到,并已进入到细胞壁内,同时定量结果显示污染越严重,重金属累积量越多,证明了柳树叶对重金属污染的吸收能力;(2)通过综合比较,认为冷冻处理的样本比较适合进行植物组织微区的元素定性定量以及定位分析,因此推测冷冻制样加冷冻电镜的方法将会最为理想.     

烟草制品及烟气中重金属检测方法的研究进展

从烟草制品及其烟气的前处理方法和检测方法两方面对烟草中重金属含量测定的研究进展进行了综述。重点介绍了湿法消解、微波消解、萃取和悬浮进样技术等样品前处理方法,以及原子光谱法、质谱法和液相色谱法等测定方法。列举了不同方法的灵敏度、准确性和适用范围,对各方法的优缺点进行了比较,并对烟草中重金属检测方法的发展进行了展望。     

土壤重金属污染来源及其解析研究进展

土壤重金属污染问题是环境和土壤科学研究者关注的热点问题。对土壤重金属污染物来源的鉴别是准确、有效控制和治理污染源的前提。根据近年来国内外对土壤重金属污染的相关研究报道,综述了土壤中污染物的工业、农业和交通因子三大主要来源,重点阐述了目前解析土壤重金属污染来源所运用的化学形态研究、剖面分布、同位素示踪、空间分析和多元统计等方法,并就存在的问题和今后的研究重点进行了总结。     

六氯丁二烯分析方法研究进展

六氯丁二烯是一种持久性有机污染物,于2015年和2017年分别被列入《斯德哥尔摩公约》附件A和附件C的受控污染物名单中。六氯丁二烯的来源、环境赋存和影响等研究对控制该新增受控持久性有机污染物污染具有重要意义,而灵敏可靠的六氯丁二烯分析方法是开展相关研究的前提和基础。近年来已有不少学者将六氯丁二烯作为分析目标物之一进行了检测或方法学研究。基于这些研究成果,该文综述了六氯丁二烯分析方法的研究进展,其中重点介绍了空气、水体、土壤、污泥、生物组织等多种介质中六氯丁二烯的样品前处理方法,并比较了各方法的优缺点,以期为该领域的进一步研究提供参考。空气中六氯丁二烯主要由泵抽气通过吸附管而采集,再经热脱附后进行仪器分析,检出限在ng/m³水平。也有研究应用聚氨酯泡沫被动采样器和吸附剂填充聚氨酯泡沫被动采样器采集大气中六氯丁二烯及其他污染物。基于吸附剂填充聚氨酯泡沫被动采样器的分析方法灵敏度较高,其对六氯丁二烯的检出限低至0.03 pg/m³。然而目前被动采样体积仅根据六氯丁二烯的log K_OA系数估算,未来仍需进一步实验校正。水体样品前处理通常也较简单,通过吹扫捕集、液-液萃取或固相萃取目标物后进行仪器分析。固相萃取法能够同步实现目标物的提取、净化和浓缩,在水样中六氯丁二烯分析方面具有明显优势。固相萃取柱类型以及干燥步骤中柱中残留水分去除率均会影响六氯丁二烯的回收率。灰尘、土壤、沉积物、污泥和生物组织等固体介质样品基质最为复杂,需联合多种方法进行前处理。固体样品中六氯丁二烯提取方法包括索氏提取,加速溶剂萃取和超声萃取,其中超声萃取法应用最为广泛。固体基质净化方面主要采用层析柱色谱法,多根净化柱联用或多层复合柱能够提升净化效果。仪器分析方面,六氯丁二烯主要采用气相色谱和质谱联用检测,高性能质谱检测器如串联质谱能够大大提高六氯丁二烯的检测灵敏度,具有较大的应用潜力。     

燃烧过程中碱/碱土金属对重金属迁移转化影响的研究进展

碱/碱土金属广泛存在于各种固体燃料中，在燃烧过程中碱/碱土金属与燃料中重金属及其他矿物发生复杂的物理化学反应，从而影响重金属的迁移和转化。本研究主要介绍了碱/碱土金属对As、Se、Pb和Cr四种重金属迁移转化的影响规律，包括碱金属和碱土金属对重金属迁移转化的影响，颗粒物团聚与黏结对重金属排放的影响三个方面。碱/碱土金属能够抑制重金属的挥发：碱金属与Cl元素的结合，降低了PbCl₂的生成；碱金属的存在有利于提升高岭土对Pb的吸附效率；碱/碱土金属可以与As和Se形成稳定的化合物。但同时需要注意碱/碱土金属与Cr的部分结合产物中，Cr以六价态存在，具有较高的毒性。碱/碱土金属对于团聚现象发生，分别起到了促进和抑制作用，适当含量的碱金属有利于减少重金属的释放。通过总结碱/碱土金属对重金属迁移转化的影响规律，以期为降低重金属的危害提供思路。     

Design of a portable luminescence bio-tool for on-site analysis of heavy metals in water samples

ABSTRACT

In this work, we report an innovative tool for heavy metal screening in water samples. This new chemiluminescent set-up screens the light generated from luminol oxidation by horseradish peroxidase (HRP) in the presence of hydrogen peroxide (H₂O₂). The pollutant concentrations in real water samples were calculated by studying the effect of metal ions on chemiluminescence signal. Owing to its simplicity, portability and low cost, this approach presents a real alternative to classical optical methods. It is constructed with simple materials: a black box containing a cuvette and a micro-camera. When the enzymatic reaction takes place, the luminescence is captured by the camera placed in upright position. The image can be saved automatically in a computer for further analysis using a MATLAB interface. The RGB diagram is then established to determine the analyte concentrations in the tested samples. This method was successfully applied for the determination of mercury (Hg), lead (Pb) and cadmium (Cd) in lake and field water samples. In these experiments, three concentrations of each analytes were tested (5, 25 and 50 µg/L). We noted a good proportionality between the analyte concentration and the chemiluminescent detection intensity. Detection of binary and tertiary combinations of heavy metals has been also investigated. The developed biosensor showed low detection limits for the tested heavy metals: 1, 0.7 and 0.02 for Hg²⁺, Pb²⁺ and Cd²⁺, respectively. Finally, excellent recoveries ranging from 98% to 104% were obtained for the HRP-inhibition assay.     

Heavy metals as toxicants in big cities

Heavy Metals (HMs) can exert detrimental effects on human health and on the environment. Their ecotoxicological properties are generally well known. As regards human toxicology, new aspects should be taken into consideration—gender and age dependence. The HMs chemical risk can be estimated and in this context, city demography data help to evaluate today's ecological situation (including HMs) and to predict the dynamics of future urbanization.As regards urban atmosphere, motor vehicles (Pb) and industry (V, Ni, Cr, Cd) exert the greatest influence; water, soil, vegetation also experience menace caused by HMs. Urban environments should be protected against contamination posed by HMs: the health status of big cities is dependent on adequate and safe supply of water. Vegetation plays a helpful role in reducing HM content in the atmosphere and the soil. Awareness of the inhabitants regarding the risks posed by HMs also counts as critical factor today. Ecoeducation at the beginning of the new century can be taken into consideration.     

Misused terms in analytical chemistry with emphasis on ultrasound application

A wide number of analytical terms have been applied erroneously for many years by analytical chemists, and they apply at present yet, by considering the time makes their use correct. The question is, may precedents validate the present use of incorrect scientific terms? Misused terms are found along the analytical process, starting with giving the name of the sample to the exiguous fraction of the original sample that reaches the detector or the high-resolution equipment after sample pretreatment and sample preparation. All the steps of the analytical process are considered in this article, with special emphasis on sample preparation and, within this, on the use of ultrasound, mainly for assisting extraction more unequivocally named as leaching or lixiviation. A call of attention in this respect is considered by the author to be of help to the analytical community.     

Analytical tools for urocanic acid determination in human samples: A review

Urocanic acid is a chromophore found in the skin that has been identified as an important immunosuppressant and carcinogenesis mediator through its photoisomerization from trans to cis form induced by ultraviolet radiation. Research on analytical methods that explore urocanic acid isomerization is indispensable to fully understand the deleterious effects mediated by this biomarker. In this context, the current relevant analytical methods for determination of these isomers in human samples are summarized in this review. The methods presented here are applicable to human samples collected by noninvasive methods (or minimally invasive), encompassing an array of analytical techniques, including high‐performance capillary electrophoresis, confocal Raman spectroscopy, gas chromatography, high‐performance liquid chromatography, and mass spectrometry, among others. Developed high‐performance liquid chromatography methods have proven to be advantageous, allowing noninvasive collections for in vivo analysis and the confocal Raman, specially, for real‐time analysis. Among all these methods, high‐performance liquid chromatography is the most investigated one with mass spectrometry or ultraviolet detector, and the mass spectrometry detector being the most studied in the last years, demonstrating high sensitivity, very low detection limits, and accurate identification, especially for clinical investigations.     

Ionic liquids as a tool for determination of metals and organic compounds in food analysis

Ionic liquids (ILs) are non-molecular solvents, which are mainly characterized as possessing low melting points, low-to-negligible vapor pressures, and high thermal stability. Their unique solvation properties, coupled to the fact that they can be structurally tailored for specific applications, have increased study of ILs in many areas of fundamental and applied chemistry. Thus, ILs have successfully been utilized as novel solvents in different extraction and microextraction schemes in recent years, but mainly with environmental samples.Food samples are quite complicated matrices from an analytical point of view. They contain a large range of chemical substances, and sometimes they also have a high fat content. Even with the most advanced analytical techniques, food sampling and food-sample preparation prior to the analytical determination are labor-intensive and time-consuming, and normally require relatively large amounts of organic solvents.In this review, we summarize the most recent analytical developments aimed at employing ILs as a tool in food analysis. We discuss practical applications to determine metals and organic compounds in food samples of quite different natures, with special emphasis to the extraction step at which the IL is introduced, and the advantages of the IL-based methods developed over conventional extraction methods.     

Sensitive detection of heavy metals ions based on the calixarene derivatives-modified piezoelectric resonators: a review

Heavy-metal pollution is a foremost concern, as excessive heavy metals produce environmental contamination, and the accumulative effects of heavy metals pose a major hazard to human health. There is an urgent need for a fast, sensitive and effective method for detecting heavy metal cations in the environment. In recent years, using Quartz Crystal Microbalance (QCM) technique, significant progress was achieved in quantitative analysis by providing a new approach for determination of chemical content analysis. The objective aim of this review is to assess the research development of QCM applications in detection of heavy metal cations in natural water (or aqueous solution) and reflect the challenges and forthcoming point of view for QCM-based sensors for heavy-metal ions. A brief outline about the basic measurement methodologies and analytical techniques is given. To illustrate applications of the QCM techniques, the influence of the structural transformation resulting from polymer, macrocyclic ‘calixarenes’ and nanostructural coating on sensation will be discussed. Lastly, we summarise fields of applications and future forecast for the utilisation of functionalised QCM surface as a chemical sensor to study the interaction of heavy metal ions with calixarenes.     

A layered magnetic iron/iron oxide nanoscavenger for the analytical enrichment of ng-L concentration levels of heavy metals from water

Magnetically driven separation techniques have received considerable attention in recent decade because of their great potential application. In this study, we investigate the application of an unmodified layered magnetic Fe/Fe₂O₃ nanoscavenger for the analytical enrichment and determination of sub-parts per billion concentrations of Cd(II), Pb(II), Ni(II), Cr(VI) and As(V) from water samples. The synthesized nanoscavenger was characterized by BET, TGA, XRD and IR and the parameters influencing the extraction and recovery of the preconcentration process were assessed by atomic absorption spectrometry. The possible mechanism of the enrichment of heavy metals on Fe/Fe₂O₃ was proposed, which involved the dominant adsorption and reduction. The nanoscale size offers large surface area and high reactivity of sorption and reduction reactions. The obtained limits of detection for the metals studied were in the range of 20–125 ng L⁻¹ and the applicability of the nanomaterial was verified using a real sample matrix. The method is environmentally friendly as only 15 mg of nanoscavenger are used, no organic solvent is required for the extraction and the experiment is performed without the need for filtration or preparation of packed preconcentration columns.     

Some Aspects of the Mobility and Distribution of Toxic Heavy Metal Contaminants Insoil Profiles and River Sediments

Abstract

Investigations of the distribution and mobility of Pb, Ni, Cd and Hg have shown that Pb is strongly associated with humic substances in the top layer of soils and in river sediments, and that Pb shows the highest organophilicity. Ni is very organophilic, and Cd, somewhat less so. The hydrophilicity of Hg highly influences its movement in soil profiles and river sediments. The risk of contamination by these metals is characterized through the environment protection capacity (EPC_G) values which combine humus content and the quality and thickness of the humus layer in one parameter. The risk of contamination is highest at low EPC_G values. Increase of EPC_G decreases the risk of environmental contamination through binding of heavy metals to humic substances, decreasing their mobility.     

脂质组学及其分析方法

脂质组学的研究属于生命科学的范畴,与人类的健康密切相关。目前,脂质组学已成为代谢组学最重要的分支之一,且是一个非常活跃的研究领域,尤其在研究疾病方面的重要性已经引起了科学界的广泛关注。该文简要介绍了脂质组学的研究内容,重点评述了脂质组学分析方法,包括样品处理、轮廓分析、目标分析、成像分析以及数据处理。最后提出了脂质组学分析技术和方法的展望。     

Semi-Automated Determination of Heavy Metals in Autopsy Tissue Using Robot-Assisted Sample Preparation and ICP-MS

The endoprosthetic care of hip and knee joints introduces multiple materials into the human body. Metal containing implant surfaces release degradation products such as particulate wear and corrosion debris, metal-protein complexes, free metallic ions, inorganic metal salts or oxides. Depending on the material composition of the prostheses, a systemic exposure occurs and may result in increasing metal concentrations in body fluids and tissues especially in the case of malfunctions of the arthroplasty components. High concentrations of Cr, Co, Ni, Ti and Al affect multiple organs such as thyroid, heart, lung and cranial nerves and may lead to metallosis, intoxications, poly-neuropathy, retinopathy, cardiomyopathy and the formation of localized pseudo tumors. The determination of the concentration of metals in body fluids and tissues can be used for predicting failure of hip or knee replacements to prevent subsequent severe intoxications. A semi-automated robot-assisted measurement system is presented for the determination of heavy metals in human tissue samples using inductively coupled plasma mass spectrometry (ICP-MS). The manual and automated measurement processes were similarly validated using certified reference material and the results are compared and discussed. The automation system was successfully applied in the determination of heavy metals in human tissue; the first results are presented.     

梅州农村饮用水重金属元素监测与分析

对梅州农村饮用水中的重金属元素进行了监测和分析，选择Fe，Mn，Zn，Cu，Ag，Pb，Cd七种元素为检测指标。从实验结果来看，Cu，Ag，Cd含量低，未超标；Fe，Mn，Zn，Pb有超标现象：按其危害程度，Pb，Mn的超标是急需解决的问题。     

Honey as an environmental indicator: Effect of sample preparation on trace element determination by ICP-AES

Trace element concentrations in honey collected from a wide area can be used as an environmental indicator, but sample preparation methods prior to analysis can have large effects on the results. The efficiency and reproducibility of sample preparation methods (dilution, ashing and digestion) for simultaneous multi-element analysis have been compared for 13 elements. Digestion in a PTFE bomb was found to be the most reliable method.     

紫外分光光度法测定地龙中重金属的含量

为地龙重金属限量标准提供依据,采用紫外分光光度法测定了地龙中重金属的含量,分析波长为273 nm.结果表明,赤子爱胜蚓的重金属含量为13.04 μg/g,线性范围0～50 μg,平均加样回收率为99.42%.该法简便、快速、重现性好,能在一次操作中测出中药中大部分重金属的含量.     

Optimization of sample preparation using statistical methods: spectrophotometric determination of Fe and Co in pharmaceutical samples

This work presents alternatives for Fe and Co determination in pharmaceutical samples using flow analysis. The first procedure describes Fe extraction in mineral/vitamin complexes. The best conditions were reached when HNO₃ concentration and volume, sample mass and shaking time were 1.0 mol l⁻¹, 5 ml, 25 mg and 10 min. Three mineral/vitamin complexes of known concentrations (ranging from 12 to 32 g kg⁻¹) were analyzed (10 authentic replicates for each) and recoveries of around 100% were obtained when compared with a well-established mineralization procedure employing concentrated HNO₃ and H₂O₂ (30% w/v). The second work part shows the employment of Tiron and H₂O₂ reaction for Co determination in a drug for inappetence. The results (352±18.7 mg kg⁻¹) were compared with those using Electrothermal Atomic Absorption Spectrometry—ETAAS (346±15.7 mg kg⁻¹). The proposed method showed detection and quantification limits of 0.20 and 0.70 μg l⁻¹, respectively. Both procedures for Fe and Co determination presented time, reagent and effort reduction.     

Green analytical chemistry in sample preparation for determination of trace organic pollutants

The principles of green chemistry are applied to not only chemical engineering and synthesis, but also increasingly analytical chemistry. We describe environment-friendly analytical techniques applied to isolate and to enrich trace organic pollutants from solid and aqueous samples. Amounts of organic solvents used in analytical laboratories are reduced by applying solventless extraction, extraction using other types of solvent, assisted solvent extraction and miniaturized analytical systems.