Review on the application of upconversion nanomaterials in heavy metal detection

As a widespread element,heavy metals have a significant impact on human health and threaten human health.It is of great significance to develop analytical technologies that can detect heavy metal ions quickly and accurately.In comparison to conventional fluorescent materials such as organic dyes,quantum dot(QD)labels,and carbon quantum dots(CD),fluorescence detection technology utilizing lanthanide(Ln)ion-doped upconversion nanoparticles(UCNPs)stands out due to its distinctive attributes.These include a notably reduced autofluorescence background,enhanced tissue penetration capabilities,biocompatibility with cellular tissues,and minimal photodamage inflicted on biological samples.The utilization of this technology has garnered considerable attention across multiple fields.In the domain of heavy metal detection,traditional laboratory methods necessitate costly instrumentation and a fully equipped laboratory,involving intricate sample processing procedures and protracted detection periods,as well as a demand for skilled personnel.In contrast,the implementation of this material offers rapid and cost-effective detection,significantly mitigating the technical barriers for operators.Consequently,this represents an exceptional avenue to curtail expenses and broaden the scope of detection within the analytical process.This paper reviews the research progress of UCNPs in the detection of heavy metal ions,encompassing a brief elucidation of the luminescence principle of upconversion nanomaterials and commonly used detection principles.Additionally,it provides a detailed overview of the research status of several common non-metal ions and essential heavy metals.Furthermore,it summarizes the current focal points in UCNP detection and discusses the challenges and prospects associated with it.

Detection and Evaluation of Metals in Tea and Soils of Tea Gardens in Mingshan

[ Objective] The study aimed to detect and assess metal ions in tea and soil of tea gardens in Mingshan County. [ Method] Seven metals （ including Pb, Cr, Cu, Ca, Mn, Mg and Zn） in soil and tea samples of tea gardens in Mingshan were determined by atomic absorption spectrometry, and the pollution situation of the soil and tea by Pb, Cr and Cu were evaluated using the single factor pollution index and Nemerow pollu- tion index, finally the accumulation of heavy metals in different soils were analyzed by the enrichment factor. I-Result] There was little difference for the same heavy metals in various soils, but different heavy metals had very significant difference. The enrichment factors of metals needed by tea growing, such as Ca, Mn, Mg and Zn, were higher than heavy metals like Pb and Cr. In addition, soils and tea of the six tea gardens were not polluted by Pb, Cr and Cu, and both single factor pollution index and Nemerow pollution index were below 0.7. [ Condusion] The research could provide scientific references for preventing tea from being polluted by heavy metals.

THE STUDY ON NOVEL MICROELECTRODE ARRAY CHIPS FOR THE DETECTION OF HEAVY METALS IN WATER POLLUTION

Qualitative and quantitative analysis of trace heavy metals in aqueous environment are rapidly assuming significance along with the rapid development of industry.In this paper,gold microelectrode array(MEA)plated with mercury film was used for simultaneous voltammetric detection of zinc,cadmium,lead and copper ions in water.The electrochemical behavior and the actual surface area of the MEA were investigated by cyclic voltammetry in K_(3)[Fe(CN)_(6)].Electrochemical impedance spectrum(EIS)was utilized to examine the deposition of mercury on the electrode surface.Based on anodic stripping voltammetry,mercury film
Au MEA was applied to the detection of heavy metals in artificial analyte,where good calibrate linearity was obtained for cadmium,lead and copper ions,but with zinc exhibiting poor linearity.

Detection and Analysis of Heavy Metal Pollution in Part Poultry Farms in Eastern China

Heavy metal contents of water, feed and manure samples in part poultry farms in Eastern China were investigated. In the survey, 49 samples were col- lected including 16 water samples, 24 feed samples and 9 manure samples. The Samples were processed by microwave digestion, the contents of copper （Cu）, zinc （Zn）, plumbum （Pb）, cadmium （Cd） and chromium （Cr） were detected by atomic absorption spectrometry, the contents of arsenic （As） and mercury （Hg） were detected by inductively coupled plasma mass spectrometry（1CP-MS）. The Sesults showed that the contents of Cu, Zn, Pb, As, Cd and Cr in water samples were very low, which reached The Standard of Class 111 Water Quality according to Environmental Quality Standard for Surface Water. The contents of Cr and As in part feed samples exceeded National Hygienical Standard, and the exceeding standard rates of Cr and As reached 33.3% and 8.3%, the highest contents of Cr and As were 622.5 mg/kg and 5.8 mg/kg respectively. The contents of all the metals in manures were in the range of the standard except Cu. The study suggested that heavy metal pollution existed in a few poultry farms, the contents of Cu, Cr and As in feeds should be controlled.

Improved sensitivity on detection of Cu and Cr in liquids using glow discharge technology assisted with LIBS

Laser-induced breakdown spectroscopy-assisted glow discharge(LIBS-GD)for analysis of elements in liquid was proposed,and it was applied to detect heavy metals in highly sensitive mixed solutions of Cu and Cr.During the experiments of GD and LIBS-GD,the experimental parameters have been optimized and the optimal voltage is 450 V,laser energy is 60 mJ,and the delay time is 4000 ns.Furthermore,the calibration curves of Cu and Cr under GD and LIBS-GD experiments have been established,and the limits of detection(LODs)of Cu and Cr were obtained with the method of GD and LIBS-GD,respectively.The LOD of Cu decreased from3.37(GD)to 0.16 mg l(LIBS-GD),and Cr decreased from 3.15 to 0.34 mg l.The results prove that the capability of elemental detection under LIBS-GD has improved compared with the GD method.Therefore,LIBS-GD is expected to be developed into a highly sensitive method for sewage detection.

Determination of Some Heavy-metal-ions Using a Sulfur Ion Modified BZ Oscillating System

A highly sensitive method is developed for the determination of trace amounts of some heavy metal ions in aqueous solution based on the classical Belousov-Zhabotinskii （BZ） oscillating chemical system. Introducing of S^2- ion makes the new oscillating system Ce（SO4）2 - KBrO3 - CH2（COOH）2 - Na2S - H2SO4 have to a high sensitivity for some heavy metal ions such as Ag^＋, Pb^2＋, Hg^2＋, Cd^2＋, Cu^2＋and Bi^3＋ with detection limits down to 10^-12 mol·L^- 1

Sources, distribution, behavior, and detection techniques of microplastics in soil: A review

In recent years, the problem of environmental pollution caused by microplastics has attracted widespread attention. This paper reviews the latest research progress in terms of the source, content and distribution characteristics, harm, and detection technology of soil microplastics by referring to the relevant literature on soil microplastics worldwide. It concludes that:(1) Existing studies worldwide have detected the presence of microplastics in soil, water, and atmosphere, and the use of agricultural films, sewage sludge,and other man-made activities are the main sources of microplastics in soil;(2) microplastics can adsorb heavy metals, persistent organic pollutants and antibiotics in soil, change the physical and chemical properties of soil. This will result in composite pollution and harm to the ecosystem;(3) microplastics in soil not only can destroy the activity of key soil microorganisms, but also enter the body of crops and soil animals, affecting normal growth of crops and soil animals, and further threaten human health;(4) at present, there is no unified operating standard for the sampling, processing, and detection process of microplastics. Analysis methods such as visual inspection, spectroscopy, and thermal analysis have both advantages and disadvantages, and emerging detection technologies require urgent development.Microplastics have become a new pollutant in soil and their distribution characteristics are closely related to human activities. They pollute the environment and threaten human health through the food chain.Although related research on soil microplastics has just begun, it will become the focus of research in the future.

Detection and quantification of Pb and Cr in oysters using laser-induced breakdown spectroscopy

The quantitative determination of heavy metals in aquatic products is of great importance for food security issues.Laser-induced breakdown spectroscopy(LIBS)has been used in a variety of foodstuff analysis,but is still limited by its low sensitivity when targeting trace heavy metals.In this work,we compare three sample enrichment methods,namely drying,carbonization,and ashing,for increasing detection sensitivity by LIBS analysis for Pb and Cr in oyster samples.The results demonstrate that carbonization can remove a significant amount of the contributions of organic elements C,H,N and O;meanwhile,the signals of the metallic elements such as Cu,Pb,Sr,Ca,Cr and Mg are enhanced by3–6 times after carbonization,and further enhanced by 5–9 times after ashing.Such enhancement is not only due to the more concentrated metallic elements in the sample compared to the dried ones,but also the unifying of the matter in carbonized and ashed samples from which higher plasma temperature and electron density are observed.This condition favors the detection of trace elements.According to the calibration curves with univariate and multivariate analysis,the ashing method is considered to be the best choice.The limits of detection of the ashing method are 0.52 mg kg-1 for Pb and0.08 mg kg-1 for Cr,which can detect the presence of heavy metals in the oysters exceeding the maximum limits of Pb and Cr required by the Chinese national standard.This method provides a promising application for the heavy metal contamination monitoring in the aquatic product industry.

Trends of Laboratory-Detected Heavy Metals in Children: Solutions for Heavy Metal Contamination in Infant Food Products

In 2019, an investigation by the U.S. House of Representatives revealed major infant food conglomerates had products with high levels of arsenic, lead, cadmium, and mercury, posing concerns for infants’ vulnerability to the neurotoxic effects of these metals. Trends of laboratory-detected heavy metals were analyzed in children aged zero to five from 1999-2020, providing insights on heavy metal contamination in infant food products. Utilizing National Health and Nutrition Examination Survey (NHANES) data, mean heavy metal levels in children were calculated, considering gender, race, and income-to-poverty ratio as proxies for assessing associations with increasing heavy metal rates in infant food. Findings indicated an overall decrease in mean concentrations over time, though remaining elevated. Black children exhibited higher lead levels than the overall average, while the Asian subgroup displayed higher levels of total blood mercury and cadmium levels. Lack of internal standards in regulatory bodies, particularly the FDA, exacerbates the issue, with no legally enforceable guidelines or strict maximum levels for heavy metals in infant foods. Urgent FDA interventions are needed, addressing contamination at the sources of raw materials, implementing transparent and extensive product testing, and comprehensive manufacturer labeling to inform consumers about elevated heavy metal levels in infant products.

Electrochemical Sensing of Heavy Metal Ions based on Monodisperse Single-crystal Fe_3O_4 Microspheres

Single-crystal Fe_3 O_4 with monodisperse microspheres structure has been used for individual electrochemical detection of heavy metal ions. Morphology and structure of the as-prepared Fe_3 O_4 microspheres were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD). Meanwhile the electrochemical properties of the Fe_3 O_4 microspheres modified glass carbon electrodes(GCE) were characterized by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS), and the enhanced electrochemical response in stripping voltammetry for individual detection of Pb(Ⅱ), Hg(Ⅱ), Cu(Ⅱ), and Cd(Ⅱ) was evaluated using square wave anodic stripping voltammetry(SWASV). With high specific surface area and excellent catalytic activity toward heavy metal ions, the as-prepared monodisperse and single-crystal Fe_3 O_4 microspheres show a preferable sensing sensitivity(22.2 μA/μM) and limit of detection(0.0699 μM) toward Pb(Ⅱ). Furthermore, the electrochemical sensor of Fe_3 O_4 microspheres exhibits excellent stability and it also offers potential practical applicability for the determination of heavy metal ions in real water samples. This study provides a potential simple and low cost iron oxide for the construction of sensitive electrochemical sensors applied to monitor and control the pollution of toxic metal ions.

MOFs基微流控电化学芯片对多种重金属离子的实时在线检测

将具有丰富微孔的ZIF-8金属有机框架和电化学技术对金属离子的富集作用与微流控器件对溶液流动的可控性相结合,构建了一种新型传感器,实现了高通量、实时和快速检测环境中的多种金属离子污染物.研制的ZIF-8-Nafion/ITO基微流控电化学传感器对Cd^(2+),Pb^(2+)及Hg^(2+)离子在0.1~100μmol/L的浓度范围内具有良好的线性关系,检出限分别为0.055,0.0025及0.0016μmol/L(S/N=3).该微流控芯片对于样品的需求量少,可降低对能源的消耗;同时由聚二甲基硅氧烷拓印的微流控器件还有望实现柔性电极的功能,对便携式电化学柔性器件在生物和环境样品的集成化和自动化检测具有重要意义.

Sign Response Mechanism of TCA Self-assembled Fluorescence Probe for Cu^2＋ Detection： FRET Evidence by DFT

A new type of self-assembled molecule ON-OFF fluorescence probe for toxic transition metal ions, made up of thiacalix[4]arene, micelle and fluorescence group, has been studied by DFT/TDDFT method combined with experiment spectra. Since the mechanism of the optical quenching signal response of such self-assembled micelle probe has always been a controversial issue of uncertainty, the spatial construction and geometric structures of the functional units of probe in the Cu2＋ ion detecting process were calculated and the mechanism was investigated by the molecular transition orbital pairs method to explore the origination of ON-OFF fluorescence sign response. The results presented that the signal response mechanism of the micelle probe is ascribed to F？rster resonance energy transfer（FRET） which provides new sights different from most of the conclusions by the related research work reported.

Systematic and long-term technical validity of toxicity determination and early warning of heavy metal pollution based on an automatic water-toxicity-determination-system

Water toxicity determination with electrochemically active bacteria(EAB)shows promise for providing early warnings for heavy metal pollution in water.However,thus far,only idealized tests with a few types of heavy metals have been conducted.In this study,an automatic water-toxicitydetermination system with high technical maturity was established,and the toxicological properties of common heavy metals were systematically assessed.The results demonstrated that the common heavy metals linearly inhibited EAB currents in the range of 0.1 mg/L to 0.5 mg/L.The toxicity ranking of the tested heavy metals was Pb^(2+)>Tl^(3+)>Cu^(2+)>Cd^(2+)>Zn^(2+)>Ni^(2+)>Hg^(2+)>As^(3+).The toxicity interaction mainly exhibited an antagonistic effect in binary heavy metal mixtures.The system can accurately determine surface water toxicity and rapidly monitor heavy metal pollution,with good repeatability and a long lifetime.Overall,this study demonstrates that EAB are capable of long-term(>60 d)surface water quality monitoring and on-site early warning of heavy metal pollution.

基于Android的便携式水质电化学检测系统的研究

为实现水质重金属现场检测,设计一种基于Android的便携式水质电化学检测系统。该系统基于三电极体系电化学检测原理,以STM32单片机为主控芯片,结合外围的恒电位电路和控制软件,实现了电化学计时电流法检测。借助Android智能设备在人机交互方面的优势,在Android平台上开发出APP应用软件,通过蓝牙实现与传感器的通信并实时显示检测数据,简化了复杂的电化学检测分析过程,满足了用户的操作需求。该系统对水质重金属离子Cr^(6+)进行了初步检测,检测线性范围为5~2 000μg/L,符合地表Ⅰ~Ⅴ类水质Cr^6+检测标准。结果表明,与电化学工作站测试数据相比,该系统测试误差小于4.85%,适用于野外现场自动检测分析。

双金属MOF衍生ZnCo多孔碳骨架电化学分析Hg(Ⅱ)的研究

以Zn/Co-ZIF为前驱体制备了高比表面积、高石墨化程度和均匀N掺杂的双金属MOF衍生ZnCo多孔碳骨架。采用扫描电镜(SEM)、透射电镜(TEM)和能谱(EDS)对其形貌和元素组成进行了表征,并利用X射线衍射(XRD)和X射线光电子能谱(XPS)对其物相和元素价态进行研究。利用ZnCo多孔碳骨架复合材料修饰电极构建电化学传感器,采用方波阳极溶出伏安法分析水环境中的Hg(Ⅱ),新型传感器表现为宽的检测范围,较好的灵敏度、线性程度和检测限。

Elemental Quantification in Intradermal Tattoo-Inks by Means of Total Reflection X-Ray Fluorescence

This work describes the application of a detailed set of TXRF evaluations to the elemental content of assorted tattoo inks, on the market of the city of Concepcion, Chile. We applied TXRF as a screening method for determining the composition in 3 sets of tattoo inks, in order to establish, from an inorganic point of view, the composition and purity of the samples, evaluating their elemental innocuousness. The analyzed 48 products were freely acquired from on line suppliers. All of them were analyzed by external standard quantification, but in order to inter-compare the results, a 15% of the samples were acidly digested and then quantified by the internal standard method. In the samples we determined: 1) their inorganic quantitative composition and, 2) the possible presence of elements which are potential health hazards. In this study few anomalies were found: 1) The high presence Ti of and W in few samples, 2) Arsenic was found in four of them, and 3) A trace detection of a rare earth element in a particular product. The products studied are almost freely imported from a world open marked, so the questions about their innocuousness could affect not only to the Chilean society.

纳米材料在食品重金属离子快速检测中的应用研究进展

纳米材料因具有比表面积大、良好稳定性、特殊的结构、易于修饰、良好的生物相容性等优点,已被广泛应用于食品中重金属离子检测领域。文章重点综述了碳纳米管、石墨烯、碳量子点、金属有机骨架、纳米酶等纳米材料在食品中重金属离子检测方面的研究与应用现状,并展望了纳米材料在食品中重金属离子检测领域面临的挑战和应用前景。

便携式激光诱导击穿光谱仪测定土壤中重金属

土壤重金属污染对农作物生长和人体健康都有严重危害,现场快速检测对土壤重金属污染调查、应急监测具有重要意义。采用自主研发的土壤重金属激光诱导击穿光谱现场快速检测仪对矿区周边土壤进行现场检测分析,以835个不同基质土壤的光谱数据建立定标数据库,通过支持向量机建立回归模型对土壤重金属元素含量进行定量反演。现场检测获取的全波段光谱波动在15%以内,Cd、Cr、Cu、Ni、Pb和Zn等6种元素光谱强度相对标准偏差平均值为6.31%。将检测结果与实验室电感耦合等离子体质谱法分析对比,6种元素的皮尔逊相关系数r在0.8501~0.9829,检测结果80%以上处于±30%相对误差区间分布。对比结果表明自主研发的土壤重金属激光诱导击穿光谱现场检测仪可以满足现场快速检测需求。

微波消解-电感耦合等离子体质谱法测定有机肥中镉、砷、汞、铅、铬含量

采用电感耦合等离子体质谱法(ICP-MS)测定,比较湿法消解30 min,湿法消解至近干和微波消解等不同前处理方法对有机肥料中镉、砷、汞、铅、铬元素的提取效果,建立了一种基于ICP-MS测定有机肥料多种重金属元素含量的方法。结果表明:湿法消解至近干和微波消解法对有机肥多元素成分分析标准物质(RMH-F001)中5项重金属含量的测试结果均满足标准要求,方法定量值、标准值偏差分别低于6.3%、5.7%;硝酸/过氧化氢体系-微波消解处理下,样品结果稳定性最佳,相对标准偏差为0.8%~6.8%,相对偏差为1.1%~9.0%,相对相差为2.2%~18.0%,加标回收率为99.4%~102.9%。硝酸/过氧化氢体系-微波消解-ICP-MS法可作为有机肥中5项重金属统一化测定的常规方法。

重金属检查与有害元素测定虚拟仿真实验设计

为解决中药重金属检查与有害元素测定实验长期存在的易受实验环境制约、实验周期长、环节多、实验成本高等问题,教学团队运用虚拟仿真技术构建了“重金属的检查与有害元素测定虚拟仿真实验”。该实验涵盖了重金属检查与有害元素测定所需的化学分析和仪器分析操作方法,帮助学生加强对实验原理和注意事项的理解。