Neutron activation analysis of human hair for environmental purposes

The possibility of using human hair as a monitor for the pollution of the environment with metals is discussed. Analyzed are 15 cases by means of Instrumental Neutron Activation Analysis. Elements Se, Cu, Ca, Na, Mn and S in Bulgarian hair are compared with those from other countries. Analyzed cases are divided into two groups: metal burdened and nonburdened. A difference in Na, Ca and Mn content in hair of both groups is observed. A value of Mn is outlined which indicates with a high probability the metal burden of a person.     

Preconcentration of mercury using duolite GT-73 in the analysis of water samples by inductively coupled plasma atomic emission spectrometry.

Duolite GT-73 resin was used for the preconcentration of Hg(II) from hydrochloric acid media as well as separation of the analyte from diversity of the co-existing metal ions (Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb and Zn) in off-line column operation. Due to the high affinity of the resin to the transition metals, Hg was adsorbed alongside with the foreign metals investigated. A complete release of the concomitant metals from the resin without the desorption of Hg was carried out using solutions of HCl and HNO3. A quantitative recovery of Hg was obtained by digestion of the resin using a H2SO4 and H2O2 mixture in an open-vessel system. An enrichment factor of 40 was achieved. The devised procedure was applied for the determination of Hg(II) in tap-water samples.     

Heavy metals assessment in the hair of street children by INAA method,Isfahan

The street children phenomenon is an increasing problem in most cities of the world including Isfahan, which is a fast growing town. The number of street children with the growth of the town is increased. It is therefore important to have baseline data on their health problems. Hair element analysis remains an important tool in the nutritional and environmental assessment of them. A measurement of the elemental concentration in recently-grown hair provides an integrated view of the element status in the follicular cells and their blood supply, unaffected by short term fluctuations in the nutrient intake of the subject. This study aimed to assess heavy metals concentrations in the hair of street children in Isfahan using neutron activation analysis method. The concentration of heavy metals (Cu, Cr, Fe, Hg, Mn, and Zn) of 17 Iranian street children (Isfahan) was examined. Data analysis found that different profiles of the concentrations of Cr, Hg, Mn, and Zn were seen in each sample. These results were discussed with reference to show of environmental effects.     

Radioactivation analysis of hair a means of biological monitoring of the environment

With the aim of indicating environmental pollution effects by heavy metals on humans using hair, nondestructive activation analysis was applied to 382 normal Japanese hair samples (background level). Elemental contents of hair could be determined for Ag, Al, As, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, I, K, La, Mg, Mn, Na, S, Sb, Sc, Se, Sm, Ti, V and Zn. As these elements in hair have wide concentration ranges, the differences in concentrations distribution between groups (sex, age, permanent treatment and regional difference) are discussed. A method for hair sampling is presented.     

Interactive effects of age and gender on levels of toxic and potentially toxic metals in children hair in different urban environments

Children growth and development may be affected by metal exposure. The objective of the present study was to investigate the interactive effects of age and gender on children hair toxic metal levels in urban environment of two Russian cities. A total of 2021 children living in Moscow and Novosibirsk aged 1–18 years old were examined. Hair Al, As, Cd, Hg, Ni, Pb and Sn levels were assessed using inductively-coupled plasma mass-spectrometry in dynamic reaction cell mode. Children from Novosibirsk were characterised by higher hair Al (37%), As (385%), Cd (127%), Hg (11%), Ni (23%), Pb (72%) and Sn (25%) in comparison to Moscow values. In the general cohort, boys had higher Al (13%), As (51%), Cd (65%), Pb (63%) and Sn (18%) levels, whereas hair Ni was higher in girls (17%). Further analysis demonstrated age-specific gender differences. In particular, only hair Ni and Cd levels were higher in male toddlers and pre-schoolers from Novosibirsk as compared to females. No gender difference was detected in Moscow. Maximal gender differences in hair metal levels were detected in adolescents for both locations. International Union of Pure and Applied Chemistry (IUPAC) reference values for all groups were also calculated. The overall reference limits for the studied children population were Al (1.335–3.340 µg/g), As (0.021–0.384 µg/g), Cd (0.000–1.389 µg/g), Hg (0.024–0.722 µg/g), Ni (0.076–0.701 µg/g), Pb (0.050–1.490 µg/g) and Sn (0.070–1.026 µg/g). Two-way ANOVA demonstrated significant effects of age, gender and age*gender interaction on hair metals in both cities. At the same time, the age-specific changes in hair metal content were more expressed in children from Novosibirsk, being exposed to higher metal pollution. The obtained data demonstrate that age, gender as well as the particular rate of pollution in each location should be taken into account during interpretation of hair test results.     

黔产市售绿茶重金属的含量特征及健康风险评估

为研究黔产市售绿茶中重金属的含量分布特征及健康风险,以五个生产加工地的黔产市售绿茶为研究对象,分析其9种重金属(Pb、Cr、Cd、Hg、Cu、Zn、Mn、Ni和As)含量,利用美国环境保护署(USEPA)推荐的健康风险评价模型进行人体重金属的健康风险评价。结果表明,五种茶叶中Cr、Cd、Pb、Hg、Cu和As含量均低于国家限量标准。黔产市售绿茶的重金属浸出率大小次序为Zn>Mn>Hg>As>Cd>Pb>Cr>Cu>Ni。健康风险评价结果表明,五个产地的绿茶中重金属通过饮茶途径所产生的健康危害个人年风险大小次序为Cd>As>Mn>Ni>Cr>Hg>Pb>Zn>Cu,茶叶中重金属通过饮茶途径所产生的个人健康危害年风险总和为4.33×10-6~5.73×10-6 a-1,均低于USEPA和ICRP推荐的最大可接受风险水平,表明重金属引起的健康危害极小,其对暴露人群造成的健康危害可忽略不计,绿茶中重金属均处于安全范围内。     

Bioaccumulation of metals and induction of metallo‐ thioneins in selected tissues of common carp (Cyprinus carpio L.) co‐exposed to cadmium,mercury and lead

The concentrations of mercury (Hg), cadmium (Cd) and lead (Pb) at various exposure periods were determined in the gill, kidney, liver and muscle of common carp (Cyprinus carpio L.) co‐exposed to 1.0 µg ml^?1 each of Cd²⁺, Hg²⁺ and Pb²⁺ for up to 10 days. Metallothionein fractions (MTs) in these organs were characterized using the hyphenated technique of size‐exclusion chromatography (SEC) and inductively coupled plasma mass spectrometry (ICP‐MS). After 10 days of exposure, maximum toxic metal concentrations of Hg, Cd and Pb were 10.7 (gill), 0.145 (kidney) and 0.112 µg g^?1_dryweight (gill), respectively. The pattern of accumulation of Hg and Pb was in the order gill > kidney > liver > muscle. In the case of Cd, accumulation was in the order kidney > gill > liver > muscle. Cd and Hg binding MTs were significantly induced in the gill, kidney and liver of all the exposure groups in comparison with the control group (p < 0.05), and the amounts of them increased with the longer exposure time. Despite the higher intracellular Hg concentration and the stronger Hg? SH binding affinity, the amount of Cd‐binding MTs was much higher than that of Hg‐binding MTs. The results indicate that MT synthesis in these organs was clearly metal‐specific. MTs in gill may be used as a bio‐marker to detect the metal pollution caused by Hg and Cd. Zinc and copper binding MTs in the organs of the exposed fish were also increased. This may be due to the MTs' important role in the homeostatic regulation of essential metals and their protective role against the acute toxicity of non‐essential metals. Even though there was considerable accumulation of lead in the organs of the exposed fish, Pb‐binding MT synthesis was non‐significant. Copyright © 2006 John Wiley & Sons, Ltd.     

Determination of Occurrence Characteristics of Heavy Metals in Soil and Water Environments in Tianshan Mountains,Central Asia

China has one of the fastest-growing economies in the world, but this economic development has important implications for environmental changes in this country. Our research was to quantify the presence of heavy metals in soil and water environments in the Tianshan Mountains region of China, associated with the economic development of this region. We used anomaly analysis, correlation analysis, and principal component analysis to assess the occurrence characteristics of heavy metals in this area. Results showed that Co, Cr, As, and Ni are more prevalent in water environments than in soil environments; in contrast, Cd, Zn, Pb, Hg, and Mn are more prevalent in soil samples than in water samples. This analysis grouped 10 heavy metals in soil and water environments into three principal components. In soil environments, the prevalence order was Co, Ni, Cr, As > Mn, Zn, Pb > Hg, Cd, Cu. In water environments, the order was Cu, Co, Ni, Cr, As > Hg, Mn, Zn > Cd, Pb. It is possible to distinguish between the natural and the anthropogenic sources of heavy metals in the Tianshan Mountains. With the current rapid economic development in the Tianshan Mountains, anthropogenic sources are playing principal roles in serious heavy metal accumulations in this region. This problem warrants immediate and widespread attention to prevent further deterioration of the soil and water environments.     

Multielement analysis of the hair of mining industry workers

Scalp hair samples were collected from 75 zinc mine workers at the Nakadatsu Mine in Fukui Prefecture and were subjected to instrumental neutron activation analysis for determination of Cu, Cl, Mn, Ca, Au, Br, As, Na, K, Hg, Zn and Co concentrations. For determination of Cd, atomic absorption spectrophotometry was applied to approximately a half of the samples. The results were compared with the data of inhabitants of Suginami Ward in the Tokyo Metropolitan Area. Excessive concentration in the mean values of Zn, Cu, Mn and Hg was observed in the hair of the miners as compared with the Suginami residents. On the other hand, the mean concentrations of K and Cl in the hair of the miners were lower than those of the Suginami inhabitants.     

Separation and preconcentration of trace amounts of several metals in magnesium metal and nitrate, with activated carbon as a collector

A method is described for the preconcentration and determination of traces of Hg, Ag, Cu, Fe, In, Mn, Pb, and Zn present as impurities in magnesium metal (1 g) and nitrate (100 g). After the metal sample has been dissolved in nitric acid (or the salt in water) and the pH adjusted to 8.1-9 (except for preconcentration of Hg, when pH 3 is used), the solution is filtered through a 2-cm paper coated with 50 mg of activated carbon. The trace metals are quantitatively adsorbed on the activated carbon and separated from the matrix. The rest of the procedure has already been described. The detection limits for the analysis of 1 g of Mg and 100 g of Mg(NO(3))(2).6H(2)O are 0.03-1.3 ppm and 0.00031-0.013 ppm respectively, for all the trace metals except Hg. The limit is 0.00001(4) ppm for Hg in 100 g of Mg(NO(3))(2).6H(2)O. The coefficient of variation is 4-33%, depending on the trace metal.     

Review on metal speciation analysis in cerebrospinal fluid-current methods and results: a review

The large number of patients suffering from neurodegenerative diseases like Alzheimer's disease and Parkinson's disease motivates many research groups worldwide to investigate pathogenic factors and molecular mechanisms of these diseases. Recent studies and reviews indicate that metals are involved in these neurodegenerative processes in case their homeostasis in the brain is disturbed. Important is that the focus of these recent studies is on essential metals like Fe, Cu, Zn and Mn, but not on the well-known neurotoxic metals like Hg and Pb. Key issues for understanding metal induced neurotoxic effects are the transport processes across the neural barriers, the metal binding forms (species) and their interactions with neuronal structures. Total metal concentrations in cerebrospinal fluid were published in several studies for controls and patients, but the amount of reliable data sets is not yet sufficient for clear definition of normal and elevated levels. The need for more detailed information on metal species in CSF is highlighted in this review. However, studies on element speciation analysis, that means identification and quantification of the various binding forms of metals in cerebrospinal fluid, are rare. The major reasons therefore are difficulties in accessing cerebrospinal fluid samples, the non-covalent nature of many metal species of interest and their rather low concentrations. In spite of this, several applications demonstrate the potential of hyphenated techniques as additional diagnostic tools for cerebrospinal fluid analysis. This review shows the importance of trace element analysis and more specifically of element speciation in cerebrospinal fluid for an improved understanding of pathologic mechanisms promoting neuro-degeneration. Respective analytical techniques are also highlighted. Additionally, biochemical assays for selected high molecular mass metal species are summarized and critically discussed. Moreover additional potential techniques like direct non-invasive methods as well as mathematical modelling approaches are considered. Data on total concentrations of numerous elements in CSF as well as speciation information of elements such as Al, As, Ca, Cd, Cu, Fe, Mg, Mn, Hg, Pb, Se and Zn in CSF are summarized.     

Sorption of trace metals on human hair and application for cadmium and lead pre-concentration with flame atomic absorption determination

Human hair shavings were characterized as a sorbent for trace metals. At pH 7.0 metal sorption follows the order Pb(II)>Cd(II)>Cr(VI)>Fe(III)>Cu(II)>Ni(II)>Mn(VI). Metal recovery is quantitative for Pb and Cd after 30 min of equilibration. Recovery of other metals is less quantitative and varies with pH. For example, while Cu is best recovered at pH 5, Ni and Mn are sorbed optimally in the basic pH region. Sorbed metals can be washed off the sorbent with 0.5 mol L(-1) strong mineral acids or more completely with 0.1 mol L(-1) ethylenediaminetetraacetic acid (EDTA). Typical sorption isotherms were obtained for Cd and Pb with sorption capacities of 39 and 26 micromol g(-1), respectively.Hair sorbent was used for 40-fold pre-concentration of Cd and Pb from treated wastewater samples followed by flame atomic absorption spectroscopic (FAAS) determination. Comparison of the data obtained for lead and cadmium by the proposed pre-concentration method with that by graphite furnace atomic absorption spectroscopy (GFAAS) showed 79 to 86% recovery and comparable analytical precision. Common cations and anions at the levels normally present in natural water do not interfere in the proposed pre-concentration-FAAS method.     

An intercomparison exercise for trace metal monitoring in oxygen-rich and anoxic Baltic waters

Seawater samples for a laboratory intercomparison of trace metal concentrations (Mn, Fe, Ni, Cu, Cd, Pb) in the dissolved (<0.4 μm filtered) and particle-bound phases as well as total and reactive Hg were collected in the Gotland Basin, a region in the Baltic Sea with trace metal gradients in the halocline and the redox boundary. Two laboratories took part in this exercise, each laboratory analysing samples from two vertical profiles collected using ”clean” sampling techniques. The hydrographic and hydrochemical situation was determined to characterise the water column and help interpret the results. An estimation of the conformity of the two laboratories was performed by comparing the results with international intercalibration exercises and certified reference materials. For all metals the characteristic vertical distribution and the concentration range of the data were comparable to other results published for the region. The concentration differences in the amount contents of Mn, Fe, Ni, Cu, Cd, Pb and Hg determined between both laboratories were better than the confidence intervals given by an ICES (International Council for the Exploration of the Sea) international comparison exercise for Baltic waters. Differences for Ni in the anoxic water body are attributed to the sulphidic matrix and their influence on the different methods used by the laboratories. For Pb and Hg the concentrations were near the detection limit of our methods, low level contamination was possibly responsible for the concentration differences. Small differences for dissolved Mn were attributed to different sampling techniques. We conclude that sampling and sample handling are still weak links in the trace metal analysis of anoxic seawater and that the analytical methods we used for this exercise are satisfactory for the accurate determination of Cd, Cu, Pb, Mn, Fe, and also for studying biogeochemical cycling of these trace metals in oxygen-rich and anoxic water bodies. Received: 8 February 2001 Accepted: 8 August 2001     

胶州湾表层沉积物重金属分布特征及污染评价

为评价胶州湾跨海大桥的建设对其沉积物中重金属分布的影响,于2009年7月采集了黄海胶州湾11个站位的表层沉积物,测定了沉积物中的重金属含量.结果显示,胶州湾沉积物重金属污染程度较低,Hg、Cu、Pb、Zn、Cd、Ni、Co、Mn 8种重金属的平均含量分别为0.031、19.05、12.7、51.14、0.055、17....     

Time-resolved monitoring of heavy-metal intoxication in single hair by laser ablation ICP–DRCMS

The potential of laser ablation inductively coupled plasma mass spectrometry for the time-resolved analysis of heavy-metal intoxication in human bodies by analysis of hair is demonstrated. As application, we analyzed forensic samples from one individual after Hg intake and from one treated with a Pt-containing cytostatic remedy. Single hairs were analyzed from the hair root to the tip by laser ablation ICP–MS with a spatial resolution of 20 μm (corresponding to approx. 2 h growth of the hair). Sulfur was used as internal standard and was analyzed by using oxygen as reaction gas in the dynamic reaction cell of the ICP–DRCMS. The detection limits for Hg and Pt were found to be 0.3 μg g^–1 and 0.5 ng g⁻¹, respectively. Standard uncertainties for the quantification results were 10% for Hg and approximately 15 % for Pt. The analyzed hair samples reflected the forensic evidence in both cases. A significant increase of Hg concentration, by a factor of 50, at the time of HgO administration could be shown, and variation of Pt in the hair strands could be used to monitor the time and relative amount of Pt intake by the patient. The investigations also revealed that the concentrations in the outer and the inner parts of the hair varied similarly with time, even though the concentration in the core of the hair is approximately 0.25 that at the surface for both Pt and Hg.     

Monitoring trace elements in selected organs of Antarctic penguin (Pygoscelis adeliae) by plasma-based techniques

A study was undertaken to evaluate the content and distribution of eight key elements, namely, As, Cd, Co, Cu, Hg, Mn, Pb and Se in liver, kidney and muscle of chick individuals of Adélie penguin (Pygoscelis adeliae). Samples were collected during the 2002/2003 austral summer season campaign around Jubany Station (Argentine scientific station), Potter Cove, King George Island. Solutions of organs were prepared by acid-assisted microwave (MW) digestion by employing HNO₃ and H₂0₂. Instrumental techniques selected to analyze the different tissues were inductively coupled plasma optical emission spectroscopy (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS). A wide range of elements retention capacity among the different organs was observed and the ranges ascertained are as follows (in μg g^− 1): As, 0.5 (liver)-0.8 (muscle); Cd, < 0.07 (muscle)-3.4 (kidney); Co, 0.07 (liver)-0.7 (muscle); Cu, 0.6 (muscle)-18 (liver); Hg, 0.2 (kidney)-2.7 (liver); Mn, 1.5 (muscle)-10 (liver); Pb, 0.1 (muscle)-2.0 (liver); Se, 3.0 (muscle)-8.4 (liver). The observed trend in metal accumulation in the three organs of chick penguins was in the order Cu > Mn > Se ? As > Co > Pb ? Cd > Hg. Levels of metals and metalloids were, in general terms, higher in liver that is a specific target organ for metal accumulation. This study aimed at contributing to the establishment of base-line data on potential pollutants of ecotoxicological interest in the Antarctic ecosystem.     

Effective Pre-Concentration and Analysis of Heavy Metals Using Ligand Step Gradient Focusing in Combination with Isotachophoresis

A capillary electrophoretic method for the pre-concentration of metals based on selective focusing of metal chelates with subsequent online ITP analysis was developed and verified. The selected ions of heavy metals (Pb²⁺ and Cd²⁺) were subjected to pre-concentration from the mixture and analysed. Focusing of the metals was carried out in a ligand step gradient, which was created by the addition of a convenient ligand agent to the regular stationary pH step gradient. The metal ions were continuously dosed into the column, where they were selectively trapped (with the exception of Na⁺) on the stationary ligand step gradient in the form of non-moving zones of citrate complexes with an effective charge of zero. After a detectable amount of analyte was accumulated, the dosing was stopped and the accumulated zones were mobilized to the analytical column, where they were analysed by the ITP method with conductivity or photometric detection. The electrolyte systems for the dosing (mode IEF), mobilizing (mode MBE), and analytical steps (mode ITP) were developed and tested. The cLOD was decreased by approximately two orders of magnitude using an acceptable dosing time of 25 min.     

肿瘤和微量元素的关系

采用量子共振检测仪测定了２５例恶性肿瘤患者、２５例良性肿瘤者和２５例无肿瘤人头发中Ｚｎ、Ｃｕ、Ｍｎ、Ｓｅ的含量。结果表明,恶性肿瘤患者头发中的锌含量明显高于良性肿瘤患者（Ｐ〈０．００１）和无肿瘤人（Ｐ〈０．００１）,而Ｓｅ、Ｍｎ、Ｃｕ的含量明显低于良性肿瘤患者和无肿瘤人（Ｐ〈０．００１）。恶性肿瘤患者锌含量过高,而Ｓｅ、Ｍｎ、Ｃｕ含量过低,所以高锌是诱发癌症的危险因素,也是诱发良好肿瘤的因素,而Ｓ     

Several modified piezoelectric quartz crystals for determination of omethoate

A chromatographic method for the determination of transition metals in human hair samples is described. The method involves the separation of Cu, Pb, Zn, Ni, Co, Cd and Mn in a C18 column coated with sodium hexadecane-sulfonate (SHS) and spectrophotometric detection (520 nm) after post-column reaction of the eluted metals with 4-(2-pyridylazo)-resorcinol (PAR). The eluent was a 100 mM tartrate solution adjusted to pH 3.1 with a 2 M sodium hydroxide solution (flow-rate=1.0 ml min(-1)). A good separation of the eluted metals (specially for Cu/Pb and Zn/Ni) has been achieved. The detection limits, expressed as mug l(-1), were 2.2 (Cu), 8.0 (Pb), 2.8 (Zn), 1.5 (Ni), 1.5 (Co), 12.0 (Cd), and 1.4 (Mn). A microwave-assisted closed vessel acid digestion procedure with HNO(3)+HClO(4) (4+1 ml) was used for the hair samples solubilisation. Nineteen hair samples were analysed with the proposed method. The results were in good agreement with those obtained by atomic absorption spectrometry (AAS).     

Voltammetry as an Alternative Tool for Trace Metal Detection in Peloid Marine Sediments

Here was demonstrated for the first time a possible application of abrasive stripping voltammetry in the direct measurement of trace metals in anoxic, sulfidic marine sediments (peloid mud) from a small and shallow (0.2–1 m) marine lagoon in Central Dalmatia, Croatia. Trace amounts of sample compounds are transferred to the graphite electrode surface and electrochemical reduction or oxidation processes are followed by the cyclic voltammetry in seawater or 0.55 M NaCl as electrolyte. After a preelectrolysis at potentials ranging from ?1.0 to ?1.5 V (vs. SCE) a well‐defined anodic stripping peak corresponding to the oxidation of metal deposits generated at deposition potentials is obtained around ?0.74 V (vs. SCE). The same samples were studied by anodic stripping voltammetry at the Hg electrode and inductively coupled plasma‐mass spectrometer (ICP‐MS). ICP‐MS showed higher concentrations of trace metals such as Al, Fe, Mo, Mn. A relatively high concentration of reduced sulfur species (RSS) (10^?3 M) is determined electrochemically in porewater of the peloid mud, indicating that the magnitude of metal enrichment in the sediments is probably controlled by precipitation with sulfide.