The determination of environmental and industrial exposure to heavy metals based on the quantitative isolation of metallothionein from human fluids, with application of covalent affinity chromatography with thiol-disulphide interchange gel as a solid-phase extraction support

The aim of this study was to present a new analytical method for the quantitative determination of metallothionein (MT) proteins in human body fluids and tissues, in order to determine the level of environmental and industrial exposure to heavy metals. For MT isolation, covalent affinity chromatography with thiol-disulphide inter-change (CAC-TDI) was applied. Fundamentals of indirect determination of the contents of metallothionein proteins were worked out through estimation of the quantities of metals bound with metallothionein protein and adsorbed on covalent affinity chromatography gel as on solid-phase extraction support during separating process. The (CAC-TDI) gel, specially prepared, was used as a solid phase extraction support (SPE) for preconcentration of Hg-thionein (Hg-Th), Cd-thionein (Cd-Th), Zn-thionein (Zn-Th) and Cu-thionein (Cu-Th) proteins and Hg, Cd, Zn and Cu bonded with MTs from water, human fluids such as: urine, human plasma, breast milk and tissues homogenates.     

Influence on elemental status by hip-endoprostheses

For many clinical purposes various artificial devices are applied, which contact human tissue and can thus cause adverse reactions between prosthetic surfaces and body components. Of the many materials applied for orthopaedic joint replacements the most common are cobalt-chromium-molybdenum alloys. In these cases considerable amounts of cobalt-chromium-molybdenum wear particles are released from the prostheses which have to be regarded as a cause of long-time problems for the patient.Since these particles are dissolved in body fluids of the surrounding area they are distributed in the whole body via blood. Elevated metal concentrations have been found in blood and urine of persons with endoprostheses. Partly the metals are excreted via urine, but to some extend they accumulate in different organs.Therefore this study dealt with the development of an analytical method for the determination of seven relevant trace elements, namely Al, Co, Cr, Mo, Nb, Ni, and Ti in nine kinds of human tissue (brain, heart, kidney, liver, lung, muscle, lymphatic nodes, spleen, body fat) starting with drawing of the sample, sample work up and finally analysis by means of atomic spectrometry. The optimized method was then applied to determine the metal contents in organs of persons (post mortem) with total hip replacements with metal on metal bearing surfaces. Comparison of the data obtained with those of persons without hip-endoprostheses shows that brain and lung are the main targets for elemental accumulation in persons with hip-endoprostheses. Mo and Nb represent the elements with the highest tendency to be accumulated.     

Determination of differential heavy metal and trace element accumulation in liver, gills, intestine and muscle of sterlet (Acipenser ruthenus) from the Danube River in Serbia by ICP-OES

The accumulation of heavy metals in fish has been extensively studied and well documented. However, the research has been mainly focused on the muscle tissue, while the distribution patterns among other tissues, such as liver and gills, have been mostly neglected. Within the present study, the concentrations of Ag, Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sr, Zn and Li in the muscle, gills, liver and intestine of the sterlet (Acipenser ruthenus) from the Danube River have been assessed by using the inductively-coupled plasma optical spectrometry. The analysis has revealed a high degree of differential accumulation of the studied heavy metals and trace elements in the tissues of the Danube sterlet. Liver appeared to be the main heavy metal storage tissue, while the lowest levels of analyzed metals were found in muscles. Heavy metal concentrations in the muscle were at acceptable levels for human consumption, except partly for cadmium. We conclude that, in order to enable a more efficient control of contaminants in fish products, there is an apparent need to resolve the problem of lack of legal limits for many metals in European legislation.     

Recent developments in assessment of bio-accessible trace metal fractions in airborne particulate matter: A review

In the last years a great deal of research has been focused on the determination of harmful trace metals such as Cd, Co, Cr, Cu, Ni or Pb in airborne particulate matter (APM). However, the commonly applied determination of total element concentrations in APM provides only an upper-end estimate of potential metal toxicity. For improved risk assessment it is important to determine bio-accessible concentrations instead of total metal contents. The present review gives an overview of analytical procedures reported for measurement of bio-accessible trace metal fractions in APM. The different approaches developed for extraction of soluble trace metals in APM are summarized. Furthermore the analytical techniques applied for accurate determination of dissolved trace metals in the presence of complex sample matrix are presented. Finally a compilation of published results for bio-accessible trace metals in APM is included.     

Determination of Mercury in some TCMs (Traditional Chinese Medicines) by ICP-MS and Sepeciation of Mercury Species Using Ion-Exchange Chromatography

Cinnabar, composed mainly of HgS,is often used in Traditional Chinese Medicines as part of the active ingredients in formulated drugs to treat diseases such as epilepsy,sore throat. To gain understanding on the clinical efficacy, safety and toxicity of these TCMs, information regarding not only the total concentrations of the heavy metals, but also their different chemical species is necessary. Therefore, the development of sample treatment and analytical techniques for the accurate determination and speciation of heavy metals in TCM products are of critical importance. The dual objectives of this work are to:(1) develop a leaching procedure using simulated body fluids for bioavailability and toxicity studies, and (2) investigate the possibility of Cinnabar derived mercury to bind with other constitutes in Tian Wan Bu Xin Wan using a sequential extraction scheme.     

超积累植物富集机制研究方法进展

按照重金属由土壤到根经茎,最后转移至叶细胞的运输流程,概述了超积累植物对重金属离子的富集机制,详细描述了各步骤中重金属离子含量和形态分析方法,重点分析了微质子激发X荧光、扩展X-射线吸收精细结构(extended X-ray absorption fine structure,EXAFS)、X-射线吸收近边缘结构等分析手段在植物不同部位重金属离子含量和形态分析中的应用。     

Evaluation of the physiologically based extraction test as an indicator of metal toxicity in mussel tissue

In order to estimate the bioaccessibility of metals from mussel tissues, an in vitro physiologically based extraction test was applied to simulate the human gastrointestinal conditions. The samples were subjected to human body temperature, and Ag, Co, Cr, Cu, Mn, Ni, Pb and Sn were sequentially extracted with simulated gastric solution, followed by extraction with a simulated intestinal solution. Both gastric and intestinal extracted solutions and microwave-digested residue were analysed by ICP-MS. The procedure was applied to a certified reference material NIST 2977 (mussel tissue) to prove the accuracy of the method. Some mussel tissue samples from Northern Spain were subjected to this procedure to determine their metal content and their metal oral bioaccessibility.     

Voltammetric method for the determination of Zn,Cd, Pb,Cu and Ni in interstitial water

To determine heavy metals in interstitial water from Baltic sea sediments a sampling method with subsequent voltammetric determination is described. Copper, lead, zinc and cadmium are determined in the UV-digested samples of interstitial water by differential pulse anodic stripping voltammetry while nickel is determined by adsorption voltammetry. The determination of five metals in one sample in a wide concentrations range is possible using a low cost apparatus. The profiles of the metal concentrations in interstitial water of subsequent layers of sediments, sampled from Puck Bay, Gdańsk Bay, the Bornholm area and the S?upsk area are presented.     

食品中重金属元素检测方法研究进展

食品安全问题是直接关系到人民健康的重大民生问题。简要阐述了食品中重金属对人体的影响与危害,全面分析了重金属元素对食品的污染,从不同种类的食品,包括农作物(粮食、蔬菜、水果、食用菌、茶叶)、水产品、畜禽产品、食用油、食用酒精等方面,综述了近年来食品中重金属检测方法研究的进展。随着检测技术的不断发展进步,快速、灵敏、无损的多元素在线检测的方法必将在食品中重金属元素的测定方面得到广泛的应用。     

Multielemental determination in normal,benign, and cancerous tissues of the human brain

Although the metal content of the human body is only about 3%, metals are very important for human lives. Diseases occur when an excess or deficiency of in-vivo metals appear, when other metal pollutants enter the body, or when poisons or viruses enter into the metal ligand competition. Cancer is caused by carcinogens, which are substances capable of producing tumors in any test species at any dose level. This paper discusses the determination of some elements in diseased tissues of the human brain. As the elements present are mostly at micro- or nano-gram levels, the very sensitive technique of neutron activation analysis involving radiochemical separation has been employed. Substocihiometric estimations were carried out wherever possible. The radiochemical separation procedure includes a solvent extraction and precipitation technique. The elements estimated in the tissue samples are Cu, Au, As, Se, Hg, Co, Zn, Ca, Fe, P, Cr, Na, and K. The accuracy, precision, and radiochemical purity of the method have been discussed. Two samples and a standard can be analyzed in four days.     

Quantitative determination of Cu-thionein from human fluids with application of solid-phase extraction on covalent affinity chromatography with thiol-disulphide interchange support

The aim of our investigation was to carry out quantitative isolation of Cu-thionein (Cu-Th) in human body fluids (urine, plasma and breast milk) in order to determine the level of exposure to heavy metals. In the experiment covalent affinity chromatography with thiol-disulphide interchange gel (CAC-TDI) was used as a solid phase extraction (SPE) support for preconcentration of Cu-thionein (Cu-Th) protein and Cu bonded with MT from water and human fluids samples. The present paper is a continuation of early experiments on the quantitation of Hg-thionein (Hg-Th), Cd-thionein (Cd-Th) and Zn-thionein (Zn-Th) in human body fluids such as urine, plasma and breast milk.     

Simultaneous determination of traces of heavy metals by solid-phase spectrophotometry

A coupling sensitive solid phase spectrophotometric (SPS) procedure for determination of traces of heavy metals (Me-SPS) and multicomponent analysis by multiple linear regressions (MA), a simple methodology for simultaneous determination of metals in mixtures was inaugurated. The Me-SPS procedure is based on sorption of heavy metals on PAN-resin and direct absorbance measurements of colour product Me-PAN sorbed on a solid carrier in a 1-mm cell. This methodology (Me-SPS-MA) was checked by simultaneous determination of metals in synthetic mixtures with different compositions and contents of metals important in pharmaceutical practice: Zn, Pb, Cd, Cu, Co, and Ni. Good agreement between experimental and theoretical amounts of heavy metals is obtained from the recovery test (78.3–110.0%). The proposed method enables determination of particular metal ion at the ng mL⁻¹ level and it was successfully applied to the determination impurities from heavy metal traces in pharmaceutical substances (Cu in ascorbic acid, Pb in glucose, and Zn in insulin). The proposed procedure could be possible contribution to the development of pharmacopoeial methodology for a heavy metals test.     

海藻酸钠脱除重金属研究进展

重金属污染已成为全球性的环境问题,脱除重金属是治理重金属污染的主要途径。海藻酸钠(SA)本身无毒、性质稳定、价格低廉,具有较强的胶凝性、成膜性和络合能力,既可作为脱除重金属的吸附材料,又可作为脱除重金属的固定化载体,在重金属脱除中具有广泛的应用。本文重点综述了SA凝胶球、SA复合膜、SA纳米复合材料、SA分子印迹脱除重金属,以及SA作为单一固定化载体和复合固定化载体脱除重金属进展情况。展望了SA脱除重金属的应用前景。     

Bestimmung von Metallen in Flußschlämmen mit Hilfe der Röntgenfluorescenz. Bedeutung für die Praxis

The occurrence of metals in the sediments of the Rhine basin was investigated with the aid of X-ray fluorescence. In addition to trace metals such as zirconium, strontium and rubidium which are encountered in non-varying concentrations, the heavy metals copper, lead and, in particular, zinc were found to occur in concentrations that vary considerably from one region to the other. Concentrations beyond the normal background limits are due to influent waste water. Besides the easy determination of metal traces, X-ray fluorescence permits also deductions on the density and, consequently, the mineralogical composition of the sediments.     

Rare-earth element abundance in tissues and plasma of healthy subjects and patients by neutron activation analysis

In recent years much attention has been paid to the presence and role played by trace metals in human tissues and body fluids. Rare-earth element ions are known to have high affinity for calcium binding sites and to antagonize calcium-mediate biological response. The present paper describes an investigation on rare-earth elements abundance in tissue and endogenous plasma of apparently healthy subjects and patients affected by epicondylitis, at the elbow or by laryngeal carcinoma. Some rare-earth elements, namely La, Ce, Nd, Eu, Gd, Yb and Lu were determined by radiochemical neutron activation analysis. Results are presented and discussed as far as precision, accuracy and sensitivity are concerned. The obtained data indicate that rare-earth elements levels in plasma and tissues are significantly affected by the occurence of pathological conditions.     

Recent applications of atomic spectroscopy coupled with magnetic solid-phase extraction techniques for heavy metal determination in environmental samples: A review

Atomic spectroscopy is the most popular approach to determine the presence of heavy metals in the environment. Heavy metals are potentially toxic and have various negative effects on many living organisms, including humans. With the rapid increase in the variety of industries and human activities, large amounts of heavy metals are released into the atmosphere, water, and soil. Heavy metal analysis of environmental samples is very important for determining the exposure limits. Environmental samples are highly complex matrices, and various sample preparation techniques have been developed for the extraction of heavy metals from them, including magnetic solid-phase extraction (MSPE). The use of MSPE in heavy metal analysis has recently gained significant attention owing to a number of advantages. MSPE technique overcomes main issues such as phase separation, handling, and column packing. The use of magnetic adsorbents in sample preparation has grown over the past few years, making MSPE a promising technique for sample preparation. The objective of this review article is to provide the latest applications of MSPE coupled with atomic spectroscopy for heavy metal determination in environmental samples. In addition, new magnetic adsorbents and their analytical merits are emphasized.     

Development of reference materials for the analysis of acid-extractable metals in sludge

The development of reference materials to verify the determination of metals in sludge is described. Effluents from domestic and industrial treatment facilities were dried, size-reduced and homogenized. Multiple aliquots of each material were analyzed in two different government laboratories to determine reference values for the acid-extractable concentrations of more than 15 metals. These acid-extractable concentrations are distinct from total metal values. Different sample preparation and instrumental methods, along with internal quality assurance protocols, were used to confirm the results. The data show good agreement for most metals in the domestic material. Reference values for the leachable concentrations of several toxic metals and major constituents will become part of the Certificate of Analysis for Standard Reference Material (SRM) 2781 issued by the National Institute of Standards and Technology (NIST). Data for the candidate industrial sludge reference material are also presented and discussed.     

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.     

Extended specificity studies of mRNA assays used to infer human organ tissues and body fluids

Messenger RNA (mRNA) profiling is a technique increasingly applied for the forensic identification of body fluids and skin. More recently, an mRNA‐based organ typing assay was developed which allows for the inference of brain, lung, liver, skeletal muscle, heart, kidney, and skin tissue. When applying this organ typing system in forensic casework for the presence of animal, rather than human, tissue is an alternative scenario to be proposed, for instance that bullets carry cell material from a hunting event. Even though mRNA profiling systems are commonly in silico designed to be primate specific, physical testing against other animal species is generally limited. In this study, human specificity of the organ tissue inferring system was assessed against organ tissue RNAs of various animals. Results confirm human specificity of the system, especially when utilizing interpretation rules considering multiple markers per cell type. Besides, we cross‐tested our organ and body fluid mRNA assays against the target types covered by the other assay. Marker expression in the nontarget organ tissues and body fluids was observed to a limited extent, which emphasizes the importance of involving the case‐specific context of the forensic samples in deciding which mRNA profiling assay to use and when for interpreting results.     

一种便携快速测量水中铅和镉含量的仪器-ANDalyze

快速测量污染水中重金属元素含量对于监测野外突发污染至关重要.建立了使用以生物酶（DNA酶）为原理的便捷仪器快速测定污染水中铅（Pb）和镉（Cd）元素含量的方法.使用生物酶传感器对标准溶液进行测量,根据溶液推荐和测量浓度之间的线性关系对仪器进行校准后,可测量的质量浓度范围:Pb为2~100 μg/L,Cd为0.1~1.0 mg/L.仪器可以在3~5 min内方便快速完成重金属的现场测量,使用DNA酶可以快速获得污染水中的微量金属元素含量,有利于野外重金属污染的即时测量.