Speciation of Se, Fe and Zn in Human Milk Whey: The use of Instrumental Neutron Activation Analysis (INAA) to corroborate element profiles measured with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)

In human milk trace elements normally exist in a form which can easily be absorbed by the newborn infant. For investigations of the bioavailability of trace elements it is necessary to carry out a speciation analysis of the elements of interest. An independent analytical method has been used for the quality control of the shape of the element profiles obtained from the speciation analysis of Se, Fe and Zn in individual samples to human milk whey after chromatographic separation. For the element detection in the untreated milk fractions Instrumental Neutron Activation Analysis (INAA) was chosen as the reference method. Element distribution patterns have been obtained with Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) using on-line digestion of the fraction, reduction and hydride formation of Se (T-mode). Prior results are compared with those obtained by means of element detection in the untreated fractions (U-mode) with ICP-AES. The elution profiles of Se, Fe and Zn in human milk whey obtained by means of ICP-AES detection using the T-mode show good agreement with the distribution patterns obtained with INAA. Recoveries of 103% for Fe, 86% for Zn and 87% for Se were obtained. The element distribution patterns of Fe and Zn obtained with ICP-AES speciation using the T-mode also show good agreement with those obtained by means of ICP-AES using the U-mode.Dedicated to Professor Dr. Peter Brätter on the occasion of his 60th birthday.     

Trace element analysis of turkey vulture (Cathartes aura) feathers

Ten feather samples, including primary and secondary flight and tail feathers, were analysed for the trace element composition of vane and rachis structures using instrumental neutron activation analysis (INAA), inductively coupled plasma-mass spectrometry (ICP-MS), and cold vapour atomic absorption spectroscopy (CVAAS). Five environmentally significant elements, Cr, As, Se, Sb and Hg, were analysed by INAA and ICP-MS/CVAAS. A further seventeen elements were analysed by ICP-MS. The majority data obtained by INAA and ICP-MS/CVAAS were not statistically significantly different (p = 0.05), although the removal of isobaric interferences using dynamic reaction cell technology was essential to produce ICP-MS data that were consistent with INAA for Cr, As and Se. Significantly higher trace element concentrations were observed for vane relative to rachis for all elements, except Cu and Hg. These elements displayed vane/rachis ratios of 0.7 ± 0.2 and 1.0 ± 0.2, respectively. In general, vane and rachis subgroups afforded data that were consistent with a normal distribution, with RSDs in the range (12–83) % for INAA analyses. A total of 18 outliers were noted amongst the various feather, structure, element combinations, with 14 outliers being observed in the vane and/or rachis structures of the same tail feather. Given the significant differences in vane and rachis concentrations observed for many elements, the large RSDs reported for elements and the potential for outliers, the determination of environmental trace element burden using feathers is significantly enhanced by the analysis of multiple feathers using INAA.     

Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma/Mass Spectrometry (ICP-MS) for Trace Element Biomonitoring using Mosses

Two analytical methods - instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) - were used for the trace element analysis of naturally growing mosses for a heavy metal biomonitoring survey. The techniques were applied to reference mosses to evaluate the feasibility, analytical variability, detection limits and accuracy. These parameters were evaluated using 563 mosses sampled in the 1996 French survey. All the elements of interest in the European program "Atmospheric Heavy Metal Deposition in Europe - estimation based on moss analysis" (As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, V, Zn) were able to be determined by ICP-MS. INAA appeared suitable for the determination of As, Cr, Fe, Hg, V and Zn. The Cd, Cu, Ni and Pb concentrations determined by ICP-MS were preferred to the INAA results, because of increased feasibility or accuracy. The results provided by both methods on the French mosses were statistically compared for 14 elements. Significant linear correlation appeared for: Ba, Ce, Cs, La, Rb, Sm, Th and V. Among these eight elements, Ba, Cs, La and Sm concentrations determined by both methods exhibited a strong statistical similarity. The correlations obtained for As, Eu, Fe and Sb were not as strong and no correlation at all was observed for Co and Cr. These differences were attributed to instrumental factors (e.g. spectral interference occurred for both methods) or due to the sample preparation prior to ICP-MS. The consequences of such results on the regional trend evaluation of atmospheric heavy metal deposition were discussed.     

The complementary use of radioanalytical methods and trace analysis methods for the characterisation of environmental IAEA reference materials

The IAEA laboratories have access to both nuclear analytical methods and conventional instrumental methods for trace analysis for the characterisation of its environmental and biological reference materials. A technical concept integrating the homogeneity data, the recommended test portion mass and the uncertainty on the trace element concentrations is explored using a combination of INAA, XRF, ICP-MS, ICP-AES, and AAS. The above approach is illustrated by selected examples of reference materials currently under evaluation for their trace element content. They include some or all of the following elements Al, As, Br, Ca, Cd, Co, Cr, Cs, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sr, Th, U, Zn in environmental biomonitor organisms (lichen, algae) and air dust filters.     

Multi-element determination in earthworms with instrumental neutron activation analysis and inductively coupled plasma mass spectrometry: A comparison

Earthworms were collected from agricultural fields in Admont, Graz, Piber and Gumpenstein, Austria. Six earthworm samples were investigated with INAA and with ICP-MS in parallel for the element concentrations of As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Pb, Rb, Sb, Se and Zn. With both techniques 14 elements were analysed in a wide concentration range (ng/g to mg/g) GF-AAS and HG-AAS were used for verification of some element concentrations. A comparison of analytical results between INAA and ICP-MS was discussed. In general, good agreement between ICP-MS and INAA was obtained, the relative difference values of most of the elements are within ±20% range, however, a methodical error for the determination of Hg by ICP-MS was found.     

Trace elements in mussels (Mytilus Edulis) from coastal areas of the North Sea and the Baltic. Multielement analyses using instrumental neutron activation analysis

Samples of the mussel Mytilus edulis were collected from different sites of estuarine and coastal areas of the North Sea and the Baltic. The following elements were determined by INAA: Ca, Sc, Cr, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Cd, Sn, Cs, Ba, Ta, Eu, Tb, Yb, Hf, Au, Hg, Th. Multielement correlation analysis was used for the evaluation of the data. Differences in trace element patterns are found and described calculating trace element ratios. Regional differences in trace element concentrations are superimposed by typical seasonal variations, with highest concentration levels found in late winter and spring, and lowest in summer and autumn. With support of Deutsche Forschungsgemeinschaft     

电感耦合等离子体发射光谱法(ICP-AES)测定黑豆和红小豆中15种元素

采用ICP—AES法同时测定黑豆和红小豆中Na,Sn,Ca,Zn,Cu,Mg,Al,Fe,P,K,Si,Se,Ba,Mn,M015种元素含量,并对各元素进行了加标回收实验,黑豆和红小豆中各元素的平均回收率在93．11％～102．15％,相对标准偏（RSD）在0．83％0～2．8％,检出限介于0．11～14．09Fg／L。建立了简便、快速、准确和稳定的测定黑豆和红小豆中元素的测定方法。结果显示在黑豆和红小豆中K,Ca,P,Mg,Mn,Fe,Zn等常量元素和微量元素含量较高。红小豆中Ca,Mg,Fe,Zn等营养元素的含量较黑豆中的高。     

电感耦合等离子体原子发射光谱法测定马奶酒中的多种元素

电感耦合等离子体原子发射光谱法测定马奶酒中的多种元素嘎日迪,乌地（内蒙古师范大学化学系,配位化学研究所,呼和浩特,０１００２２）关键词电感耦合等离子体原子发射光谱,马奶酒,微量金属元素蒙古民族喜爱的传统饮料──马奶酒（蒙语“策格”）是用鲜马奶为原料发...     

电感耦合等离子体原子发射光谱法(ICP-AES)测定黄禾和谷子中15种元素

提出了用电感耦合等离子体原子发射光谱法对通辽地区产黄禾和谷子中Na,Ca,Sn,Cu,Zn,Al,Mg,Fe,P,Si,K,Ba,Se,Mo,Mn 15种元素含量同时进行测定的方法,并对各元素作了加标回收实验,黄禾和谷子中各元素的平均回收率为96.67%~104.00%,相对标准偏差RSD均小于5%。方法简便、快速、准确地测定了黄禾和谷子中的元素。结果显示,在黄禾和谷子中K,P,Mg含量高,谷子中Ca,Mg,Fe,Zn和Mn的含量较黄禾中的高。黄禾和谷子中富含丰富的Na,Ca,Zn,Fe等元素,从微量元素角度看谷子中对身体有益的元素较黄禾高。     

Multielement analytical procedure coupling INAA, ICP-MS and ICP-AES: Application to the determination of major and trace elements in sediment samples of the Bouregreg river (Morocco)

Instrumental neutron activation analysis (INAA), inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) were used for the determination of major and trace elements in sediment samples of the Bouregreg river (Morocco). The reliability of the results was checked, by using IAEA Soil-7 certified reference material. Results obtained by the three techniques were compared to control digestions efficiencies. A general good agreement was found between INAA and both ICP-MS and ICP-AES after alkaline fusion (ICPf). The ICP-MS technique used after acid attack (ICPa) was satisfactory for a few elements. A principal component analysis (PCA) has been used for analyzing the variability of concentrations, and defining the most influential sites with respect to the general variation trends. Three groups of elements could be distinguished. For these groups a normalization of concentrations to the central element concentration (that means Mn, Si or Al) is proposed.     

Element content and element correlations in Chinese human liver

The amounts of the 19 elements As, Br, Ca, Cd, Ce, Co, Cr, Cs, Fe, K, La, Mo, Na, Rb, Sb, Sc, Se, Sm, and Zn in 92 lyophilized autopsy human liver samples from normal subjects have been analyzed by instrumental neutron-activation analysis (INAA). For intercomparison and quality control ten samples were independently analyzed in two institutes, the Institute of High Energy Physics in China and the Joef Stefan Institute in Slovenia. Most of the element contents determined by the two institutes were in quite good agreement, even though different experimental conditions were applied, indicating the reliability of the analytical results. Analysis of the chemical species of mercury present in the ten liver samples was also performed in Slovenia. Possible differences between the element content of male and female liver samples were studied by means of Students t-test, but significant differences were found only for Ce, Co, Fe, La, Mo, and Zn. The results obtained were also compared with those reported from other areas of the world; no appreciable differences were observed. Correlation among the various elements in the human liver samples was studied using multivariate statistics. It was found that there was relatively close correlation between some elements, for example As–Fe, Ca–Fe, Cd–Co, Cd–Zn, Mo–Zn, Co–Se, Cs–Rb, Br–Rb, Sc–Sm, La–Sm, La–Ce, etc.; these correlations could be rationally explained by the similarity of the electronic structures of the elements and/or their physiological functions in the human body.     

Determination of trace amounts of cadmium, cobalt, chromium, iron, molybdenum, nickel, selenium, titanium, vanadium and zinc in blood and milk by neutron activation analysis

The concentrations of Cd, Co, Cr, Fe, Mo, Ni, Se, Ti, V and Zn in biological fluids, human blood serum and market milk were determined by neutron activation analysis, with enrichment by coprecipitation. The pre-concentration of these trace elements was accomplished by converting the dissolved trace metal ions into their pyrrolidinedithiocarbamate (1-pyrrolidinecarbodithioate) chelates, followed by coprecipitation with a metal carrier such as Ni, Pb or Bi. The coprecipitation was carried out prior to irradiation for the short-lived nuclides (V, Ti and Se) and after irradiation for the other elements. The validity of the method was checked using certified biological reference materials; the concentrations of trace elements found by the proposed method agreed well with the published certified data. The limits of detection for Cd, Co, Cr, Fe, Mo, Ni, Se (obtained through the long-lived isotope 75Se) and Zn under the present experimental conditions were found to be 5, 5, 10, 520, 5, 70, 10 and 150 ng, respectively, for 5 ml of biological liquor. The limits of detection for Ti and V obtained (through their short-lived radionuclides 51Ti and 52V, respectively) were found to be 180 and 1.4 ng, respectively, for 50 ml of market milk, or 70 and 0.7 ng for 1 ml of blood serum.     

Trace element determination in high-purity aluminum clad samples by k 0-based internal monostandard instrumental neutron activation analysis

The k₀-based internal monostandard instrumental neutron activation analysis (IM-INAA) method was applied for quantification of trace impurities in seven high purity aluminum samples used as fuel cladding in a research reactor. Samples along with BCS CRM 182 (Si–Al alloy) were irradiated in high flux reactor neutrons for 10–15 h. In situ detection efficiency, needed in concentration calculation ratio by IM-INAA, was obtained using gamma rays of activation products produced in the samples. Elemental concentration ratios obtained with respect to Fe (used as internal monostandard) were converted to absolute concentrations by determining concentration of Fe by relative method of NAA. Concentrations of ten trace elements (Sc, Cr, Co, Zn, Ga, La, Ce, Sm, W and Hf) including major element Fe were determined in this work. The method used is non-destructive in nature and does not need multielement standards. Results of IM-INAA were compared with those obtained by relative method of INAA and inductively coupled plasma atomic emission spectrometry (ICP-AES). Details of methodologies and results obtained by all methods are discussed and compared in the paper.     

Determination of trace elements in high purity copper by INAA, GFAAS and ICP/AES

Trace impurity elements in high purity copper metal (4 mine class) put on the market were analyzed by Instrumental Neutron Activation Analysis (INAA) and the results compared with those from Graphite Furnace Atomic Absorption Spectrophotometry (GFAAS) and Inductively Coupled Plasma Atomic Emission Spectrophotometry (ICP-AES). The sample irradiation was done at the irradiation facilities (thermal neutron flux, 5·10¹² n·cm⁻²·s⁻¹) of the TRIGA Mark-III research reactor in the Korea Atomic Energy Research Institute. Four unalloyed copper standards (NIST SRM # 393, 394, 395 and 398) were used to identify the accuracy and precision of the analytical procedure. The homogeneity of samples was assessed by means of the elements such as Ag, As, Co, Sb, Se and Zn. The analytical results of INAA, GFAAS and ICP-AES were in good agreement within expected uncertainties each other and showed the possibility of using them for the analytical quality control.     

Studies of kidney stones using INAA,EDXRF and XRD techniques

Four kidney stones collected from patients being treated in the Advance Urology Centre of PGIMR, Chandigarh were characterized using instrumental neutron activation analysis (INAA), energy dispersive X-ray fluorescence (EDXRF) and X-ray diffraction (XRD) techniques. For INAA, samples were irradiated in tray rod facility of Dhruva reactor, Mumbai and pneumatic fast transfer system of KAMINI reactor, IGCAR, Kalpakkam. Radioactive assay was carried out using HPGe detector coupled to 8k channel analyzer. Elements determined in the samples by INAA are Zn, Sr, Co, Fe, Cr, Sc, Se, Na and Mn. EDXRF was used for the quantification of Ca. XRD patterns showed that three of the kidney stones are calcium oxalate stone and the other one is uric acid stone. The concentrations of trace elements in general were found to be higher in calcium oxalate stones and positive correlation was observed in the concentrations of Ca with Sr and Zn.     

Nutritional and Environmental Properties of Algal Products Used in Healthy Diet by INAA and ICP-AES

Spirulina platensis alga sampled in the Caribbean Sea and seven other commercial algal products available on the Italian market of different origin and aspect, have been analyzed by instrumental neutron activation analysis (INAA) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). By neutron irradiation and -ray spectrometry (INAA), as many as 20 elements could be measured instrumentally without any chemical treatment. Cu, Mg, Mn and Pb were determined after dissolution of the sample by ICP-AES. The cross-checking of the data, specifically by comparing those of Ca, Cr, Fe and Zn, obtained by the two techniques was found to be in good agreement. Special attention from analytical and nutritional point of view has been devoted to the toxic metals. The measurements have been carried out employing the reference algal material prepared by International Atomic Energy Agency (IAEA).     

Use of INAA,PGAA, and RNAA to determine 30 elements for certification of an SRM: Tomato Leaves, 157a

Analyses for certification have been made for the determination of 30 elements in the National Institute of Standards and Technology (NIST) Tomato Leaves renewal reference material, SRM 1573a. Three of the analytical techniques used were instrumental neutron activation analysis (INAA), radiochemical neutron activation analysis (RNAA), and prompt gamma activation analysis (PGAA). These techniques provided data on 19 elements by INAA, 10 elements by PGAA, and 7 elements by RNAA, with some overlap between techniques. For example, INAA was able to obtain overall analytical uncerainties (at the 95% confidence level) averaging ±2.2% for major and minor constituents (Ca, Mg, K), ±3.3% for constituents from 1 to 1000 g/g (Na, Fe, Al, Mn, Ba, Zn, Rb, La, Cr), and ±6.4% for elements between 10 and 1000 ng/g (Co, V, Se, Th, Sc, Sb), using sample dry weights of approximately 150 mg. These analyses represent the most extensive use to date of nuclear analytical techniques in the certification of a trace element SRM at NIST.     

Comparison of instrumental neutron activation analysis of geological materials with other multielement techniques

Results obtained for 12 elements in approximately 1600 rocks by instrumental neutron activation analysis (INAA) are compared with those obtained by ICP emission spectrometry (ICP-ES), XRF, and atomic-absorption spectrometry (AAS). Sample duplicates and two controls are used to evaluate the precison of the methods investigated. Application of a method (Maximum Likelihood Functional Relationship) to determine and quantify rotational and translational bias is demonstrated. The elements Na, Fe, Ba, Co, Cr, La, Ni and Rb can be determined in rocks by INAA with sufficient sensitivity and precision, whereas the determination of Ag, Yb, Zn and Zr suffers from inadequate sensitivity. Good agreement is seen in the results for Na (by INAA, ICP-ES and XRF) and AG (INAA and AAS). A significant positive bias (13% or less) is evident in the comparison of results by INAA and ICP-ES or XRF for Cr, Ba, Ni and Fe over a wide range of concentration. A similar trend, though less significant, is observed for the elements Yb, Rb, La and Co; the upper limit of concentration for satisfactory determination is within a decade of the highest detection limit for these elements. Rotational and translational bias is evident for Zn in the comparison of data obtained by INAA and ICP-ES, the results by INAA being appreciably lower above about 400 ppm Zn.     

白族长寿地区硬果仁中19种元素的测定分析

用电感耦合等离子体发射光谱法（ICP－AES）,对云南省白族长寿区的葵花子仁、麻子仁和核桃仁中的Ca、Mg、P、S、Na、AI、B、Fe、Zn、Cu、Mo、Sr、Mn、Cr、Se、Ge、Cd、Pb、As等19种元素进行了测定分析。结果表明,3种硬果仁中含有丰富的人体必需的Ca、Mg、P、S、Na、Fe、Zn、Mn、Se、Cu、Cr、Sr、Mo等有益元素,且P、Mg、S、Ca、Na、Zn、Mn、Fe、Se的含量较高。这些生命元素在3种硬果仁中的含量存在差异。有害元素Cd、Pb均未检出,核桃仁中As含量较高。硬果仁中富含这些生命元素是该地区老人健康长寿的一个重要原因。     

Application of tandem calibration for the direct analysis of copper by inductively coupled plasma atomic emission spectrometry (ICP-AES)

A procedure has been proposed for the direct ICP-AES analysis of solid copper samples using spark sampling. Calibration curves have been obtained using multi-element reference solutions of analytes (MES). The internal standards are spectral lines of copper with the energy parameters (excitation and ionization potentials) similar to those of analytes. Standard Reference Material (SRM) of copper have been used for the estimation of performance characteristics. The absence of significant differences between the found and certified concentrations of analytes has been shown. The developed procedure of ICP-AES analysis of solid copper samples with spark sampling and calibration using MES provides the determination of up to 14 elements: Ag, As, Au, Cd, Fe, Mn, Ni, P, Pb, Pt, Sb, Se, Sn, Te, and Zn in the concentration range from n × 10^?3 to n × 10^?1 wt %.