New human hair certified reference material for methylmercury and trace elements

 A new human hair certified reference material (NIES CRM No. 13) for mercury speciation and trace element analysis was prepared at the National Institute for Environmental Studies (NIES), Environmental Agency of Japan. Scalp hair from Japanese males, which is identical with the original material for the previous human hair CRM (NIES CRM No. 5), was used. Special attention was paid to reduce contamination from a grinding vessel during the preparation procedure. A newly-prepared ceramic/Teflon disc mill was used for cryogenic grinding of the hair. 1,000 bottles (3 g each) were produced after sieving and blending of the hair powder. Certified values for total mercury and methylmercury, as well as other trace elements of toxicological and nutritional significance (antimony, cadmium, copper, lead, selenium, and zinc), were determined based on analyses from extensive collaborations. Reference values for 12 elements (aluminium, arsenic, barium, calcium, cobalt, iron, magnesium, manganese, silver, sodium, sulfur and vanadium) were also given. Received: 8 February 1996/Accepted: 4 April 1996     

Characterization of NIES CRM No. 23 Tea Leaves II for the determination of multielements

A candidate environmental certified reference material (CRM) for the determination of multielements in tea leaves and materials of similar matrix, NIES CRM No. 23 Tea Leaves II, has been developed and characterized by the National Institute for Environmental Studies (NIES), Japan. The origin of the material was tea leaves, which were ground, sieved through a 106-μm mesh, homogenized, and then subdivided into amber glass bottles. The results of homogeneity and stability tests indicated that the material was sufficiently homogeneous and stable for use as a reference material. The property values of the material were statistically determined based on chemical analyses by a network of laboratories using a wide range of methods. Sixteen laboratories participated in the characterization, and nine certified values and five reference values were obtained. These property values of the candidate CRM, which are expressed as mass fractions, were close to the median and/or mean values of the mass fractions of elements in various tea products. The candidate CRM is appropriate for use in analytical quality control and in the evaluation of methods used in the analysis of tea and materials of similar matrix.     

Certified reference material for analytical quality assurance of minor and trace elements in food and related matrixes based on a typical Japanese diet: interlaboratory study

A Certified Reference Material (CRM) was prepared at the National Institute for Environmental Studies (NIES), Japan, in collaboration with the National Institute of Radiological Sciences (NIRS), Japan, for the analytical quality assurance of minor and trace elements in food and related matrixes. The starting material for the CRM was all food served in 29 households in Japan over two 3-day periods in 1997-1998, and thus the CRM represented a typical Japanese diet. All foods (meals, snacks, and beverages) were homogenized, freeze-dried, pulverized, blended, dispensed into 1,100 bottles, and sterilized. The within- and between-bottle homogeneity of the prepared CRM was satisfactory for most of the elements. The concentrations of 14 elements (Na, Mg, K, Ca, Mn, Cu, Zn, As, Se, Sr, Cd, Sn, Ba, and U) were certified based on a collaborative analysis involving NIES, NIRS, and 20 other laboratories. Reference values were given for the concentrations of 12 additional elements (P, Cl, Fe, Co, Ni, Br, Rb, Mo, I, Cs, Pb, and Th). The elements certified and those given reference values include minerals, essential trace elements, contaminant elements, and long-lived radionuclides. Thus, this CRM is of practical value in the quality assurance of element analysis of foods and diets in nutritional, environmental, and radiological research.     

Instrumental neutron activation analysis for quality assurance of a hair reference material for mercury speciation

Instrumental neutron activation analysis (INAA) has been employed in the investigation of mass balance for mercury species analysis in the analytical process. A new human hair reference material (IAEA-085) was analyzed for methylmercury using a solid/liquid extraction procedure, with samples of extracts, residues, and untreated samples being analyzed by INAA. The certified reference material NIES CRM No. 13, human hair, was analyzed in parallel. From the results obtained through the mass balance studies, it was found that the extraction procedure was quantitatively complete, and that there was no difference between the mass balance of Hg and the total Hg in the untreated materials.     

Certification for trace elements and methyl mercury mass fractions in IAEA-452 scallop (Pecten Maximus) sample

A marine certified reference material (CRM), IAEA-452, prepared with scallop (Pecten maximus) sample was recently produced by the International Atomic Energy Agency (IAEA) and certified for trace elements and methyl mercury (MeHg). The Scallop (Pecten maximus) sample is commonly found and consumed seafood and is also used as bio-indicators for trace metal contamination in marine pollution studies. This paper presents the sample preparation methodology, material homogeneity and stability studies, evaluation of certification campaign results, the assignment of property values and their associated uncertainty. The reference values and associated expanded uncertainty for 9 trace elements (As, Cd, Cr, Cu, Fe, Hg, Mn, Pb and Zn) and MeHg in scallop sample are established. The informative value for one more element (Ni) is also given. The new CRM can be used for the development and validation of analytical methods for determination of trace elements and methyl mercury in seafood and also for quality assurance/quality control purposes.     

Anodic stripping voltammetric determination of bismuth after solid-phase extraction using amberlite XAD-2 resin modified with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

A highly selective and sensitive anodic stripping differential pulse polarographic method has been developed for the determination of trace amount of bismuth in various samples after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex on amberlite XAD-2 resin in the pH range of 2.0-3.0. The retained analyte on the resin recovered with 10.0 ml of 2 M hydrochloric acid and bismuth is determined by anodic stripping differential pulse polarography. In this case, 0.15 μg of bismuth can be concentrated in the column from 1100 ml of aqueous sample, where its concentration is as low as 0.14 ng ml⁻¹ and the linearity is maintained in the concentration range 0.05-160 μg ml⁻¹ in final solution with a correlation coefficient of 0.999 and relative standard deviation of ±1.2%. Various parameters such as the effect of pH, flow rate, and interference of number of metal ions on the determination of bismuth have been studied in detail to optimize the conditions for determination of bismuth in standard alloys: Nippon Keikinzoku Kogyo (NKK CRM No. 916 aluminum alloy); (NKK CRM No. 1021 Al, Si, Cu, Zn alloy); and (NKK CRM No. 920 aluminum alloy), biological samples: National Institute for Environmental Studies (NIES, No. 5 human hair; NIES, No. 7 tea leaves) and water samples: (spring water, river water; Kerman water; and Shiraz water).     

Biological and environmental reference materials from the National Institute for Environmental Studies (Japan)

Biological reference materials for elemental speciation were prepared at the National Institute for Environmental Studies. A new human hair reference material, prepared by cryogenic grinding using a ceramic disc mill, is in the process of certification for methyl-Hg and trace elements. Hijiki seaweed reference material was prepared for As speciation studies, primarily for use in the analysis of As(V). Scallop tissue reference material will be certified for arsenobetaine.     

Development and certification of the new NIES CRM 28: urban aerosols for the determination of multielements

A new environmental certified reference material (CRM) for the determination of multielements in aerosol particulate matter has been developed and certified by the National Institute for Environmental Studies (NIES), Japan, based on analyses by a network of laboratories using a wide range of methods. The origin of the material was atmospheric particulate matter collected on filters in a central ventilating system in a building in Beijing city centre. The homogeneity and stability of this material were sufficient for its use as a reference material. Values for elemental mass fractions in the material were statistically determined based on the analytical results of the participating laboratories. Eighteen certified values and 14 reference values were obtained. The diameters, obtained from a micrographic image using image analysis software, of 99% of the particles were less than 10 μm, demonstrating that almost all the particles in the material could be classified as particles of 10 μm or less in aerodynamic diameter. The chemical composition and particle size distribution of this material were close to those of an authentic aerosol collected in Beijing. NIES CRM 28 is appropriate for use in analytical quality control and in the evaluation of methods used in the analysis of aerosols, particularly those collected in urban environments in northeast Asia Figure New NIES CRM 28 Urban Aerosols and photo micrograph of the material     

Determination of iron,cobalt, nickel,manganese, zinc,copper, cadmium and lead in human hair by inductively coupled plasma-atomic emission spectrometry

A method was standardized for the dissolution of hair samples and analysis was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES). Hair samples were brought into solution by using a mixture of nitric acid and hydrogen peroxide. Various parameters that influence the sample preparation, namely temperature, digestion time and ratio of acid mixture were studied and standardized. The optimized method has been employed to digest standard reference materials and hair samples of residents of India, collected from different age groups and sex, and analyzed for Fe, Co, Ni, Mn, Zn, Cu, Cd and Pb. The values agree for most of the metals with the data reported for human hair samples of residents of India. The NIES CRM Human Hair No. 5 and IAEA Reference Hair HH-1 certified reference materials were used in order to verify the accuracy of the method and the results were in excellent agreement with the certified values.     

Determination of total mercury in human hair and animal fur by combustion atomic absorption spectrometry

A commercially available mercury (Hg) analyzer based on sample combustion, gold amalgamation, and atomic absorption spectrometry (AAS) was evaluated for the direct determination of Hg in composites of human hair and individual samples of horse fur. Results for human hair reference material (NIES No. 13) were within the certified range. Analyses of “blind” samples from an international interlaboratory (n>16) comparison study produced results within 1S.D. of the consensus means. Precision (%R.S.D.) was found to be <5% and total analyses time per sample was <10 min. This study demonstrated that analyzers based on combustion-AAS are suitable for wide-scale monitoring of Hg in human hair and animal fur.     

Determination of arsenic in scalp hair samples from exposed subjects using microwave-assisted digestion with and without enrichment based on cloud point extraction by electrothermal atomic absorption spectrometry

A simple and rapid cloud point extraction (CPE) procedure was applied for preconcentration of trace quantities of arsenic (As) in scalp hair samples. The samples were subjected to microwave-assisted digestion in a mixture of nitric acid and hydrogen peroxide (2 + 1, v/v) prior to preconcentration by CPE. The As in digested samples was complexed with ammonium pyrrolidine dithiocarbamate (APDC), and the resultant As-PDC complex was extracted by a nonionic surfactant, octylphenoxypolyethoxyethanol (Triton X-114). After centrifugation, the surfactant-rich phase was diluted with 0.1 M HNO3 in methanol and analyzed by electrothermal atomic absorption spectrometry. The experimental parameters, i.e., amount of APDC, concentration of Triton X-114, equilibrium temperature and time, were optimized. For validation of the proposed method, a certified reference material (CRM) of human hair (BCR 397) was used. No significant difference (P > 0.05) was observed between the experimental results and certified values of the CRM (paired t-test). The LOD and LOQ obtained under the optimal conditions were 0.025 and 0.083 microg/kg, respectively. The developed method was applied for the determination of As in scalp hair samples from male and female subjects of two villages of Khairpur Mir's, Pakistan.     

Microwave digestion of biological samples with tetramethylammonium hydroxide and ethylenediaminetetraacetic acid for element determination

A microwave-digestion system with a closed PTFE vessel was used to improve the leaching of inorganic constituents from biological samples with tetramethylammonium hydroxide (TMAH) and ethylenediaminetetraacetic acid (EDTA). The effects of microwave parameter settings and the quantities of TMAH and EDTA used on leaching efficiency were evaluated. This new digestion method has been applied to the standard reference materials NIST SRM 1577 B Bovine Liver 1515 Apple Leaves and NIES CRM No. 1 Pepperbush, No. 3 Chorella, No. 6 Mussel and No. 7 Tea Leaves. The major and minor elements in the digests were analyzed by flame atomic absorption spectrometry or graphite furnace atomic absorption spectrometry. Good agreement of the analytical results with the certified values was obtained.     

Radiochemical neutron-activation analysis of uncertified ultra-trace rare earth elements in two biological certified reference materials

Radiochemical neutron activation analysis (RNAA) has been used for the determination of eight rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) in two Chinese certified reference materials (CRM), GBW 08503 (wheat powder) and GBW 09101 (human hair). These determinations are important for possible certification of the above mentioned ultra-trace elements, so far not certified. A simple one-step (REE)F3 precipitation was used. Chemical yields were determined for all relevant elements by means of tracer experiments. The two CRM were also analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) to compare the merits and draw-backs of these two major trace analytical techniques for these particular elements. RNAA was proven to be a reliable technique for ultra-trace analysis, especially in the certification of some ultra-trace elements.     

NIES certified reference materials for arsenic speciation

 The National Institute for Environmental Studies (NIES) recently prepared two candidate certified reference materials (CRMs) for arsenicals to meet the growing demand for the quality assurance of arsenic speciation analysis. The NIES candidate CRM No. 14 Brown Alga was prepared from Hijiki seaweed for the certification of inorganic arsenic content, and No. 15 Scallop was prepared from adductor muscle of scallop for the certification of arsenobetaine content. The preparation of the candidate CRMs is briefly described. Cooperative analyses for total arsenic content of the candidate CRMs have been underway. The preliminary speciation analysis at NIES revealed difficulty in establishing suitable conditions for extracting arsenic species from the materials. Chromatograms of arsenic species by a high performance liquid chromatography-inductively coupled plasma mass spectrometric detection system are presented to provide information about arsenic species present in these candidate CRMs.     

NIES certified reference material for microcystins,hepatotoxic cyclic peptide toxins from cyanobacterial blooms in eutrophic water bodies

A certified reference material (CRM) for microcystins has been prepared by the National Institute for Environmental Studies (NIES). Microcystins are hepatotoxic cyclic peptides produced by cyanobacteria in eutrophic water bodies. At least seven microcystin variants were found by HPLC analysis of the NIES CRM, of which [Dha⁷]microcystin-RR and -LR were the major microcystins present. Because of the lack of available standards we determined the total microcystin concentration in the CRM by the MMPB method, and elucidated the structures of the main individual microcystin variants following their isolation. Analyses of NMR and MS spectra indicated that the remaining minor variants in the CRM were [D-Asp³, Dha⁷]microcystin-RR and -LR, and [Dha⁷]microcystin-YR, -ThTyrR, and -HilR. The CRM is valuable not only as a standard material for the quantitation of total microcystins but also for the identification of individual [Dha⁷]microcystin variants.     

Certified sediment reference materials for trace element analysis from the National Metrology Institute of Japan (NMIJ)

Two types of sediment reference material (NMIJ 7302-a and 7303-a) for trace elements analysis have been prepared and certified by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original materials were collected from a bay near industrial activity in Kyushu (NMIJ CRM 7302-a; marine sediment) and from Lake Biwa (NMIJ CRM 7303-a; lake sediment). The sediment materials were air-dried, sieved, homogenized, packaged in 1000 glass bottles (60 g each), and radiation sterilized. Certification of these CRM for trace elements was conducted by NMIJ, where each element was determined by at least two independent analytical techniques. Isotope-dilution inductively coupled plasma mass spectrometry (ICP–MS) was applied for certification of all the elements except mono-nuclide elements such as As and Co. Other techniques such as ICP–MS with quadrupole mass spectrometry and sector-field mass spectrometry, inductively coupled plasma atomic emission spectrometry (ICP–AES), and atomic absorption spectrometry (AAS), were also used. Certified values have been provided for 14 elements (Sb, As, Cd, Cr, Co, Cu, Pb, Hg, Mo, Ni, Se, Ag, Sn, and Zn) in both CRM.     

Multielemental neutron activation analysis of fugitive dust particulates from cement factories in Central India

Knowledge of occurrence and concentration of trace elements in dust particulates from and around industrial establishments is essential to know the source of pollutants and atmosphere quality. Dust particulates from two cement factories in the central part of India were analyzed for 5 minor (Cl, Fe, K, Mg, Na) and 23 trace elements (Ag, As, Ba, Br, Cd, Co, Cr, Cs, Dy, Eu, Ga, Hf, Hg, La, Mn, Sb, Sc, Se, Sm, Sr, Th, W and Zn) by INAA and RNAA techniques. Significant differences have been observed for some toxic trace elements at different locations. Mn content is particularly high in all the dust particulates. Urban particulate (SRM 1648) and Coal fly ash (SRM 1633a) from NIST and Pond sediment (CRM No. 2) from NIES were also analyzed. The data have been analyzed and interpreted in terms of air quality at different locations inside the plant and two factories.     

Effect of ultrasound agitation on the release of heavy elements in Certified Reference Material of human hair (CRM BCR 397)

An ultrasonic-assisted leaching procedure was developed for the determination of heavy elements (As, Cu, Cd, Pb, and Zn) in Certified Reference Material of human hair (CRM 397) provided from the Community Bureau of Reference (BCR) of the Commission of the European Community. Concentrated nitric acid-30% hydrogen peroxide (2 + 1) was used for the leaching method. The effects of different factors on acid leaching of elements, such as presonication time (without ultrasonic stirring), sonication or exposure time to ultrasound, and temperature of the ultrasonic bath have been investigated. Optimum values of these parameters were selected for the maximum extraction of heavy metals from CRM BCR 397 and human scalp hair samples of normal healthy males. To check the validity of the proposed method, a wet acid digestion method was used to obtain the total elemental concentration in CRM BCR 397 and scalp hair samples. Cu and Zn in leachate and digests were measured by flame atomic absorption spectrometry using a conventional air/acetylene flame, while As, Cd, and Pd were determined by electrothermal atomic absorption spectrometry. Under optimized conditions, the recovery for Zn, Cd, Pd, As, and Cu was 98, 98.5, 97.5, 98.2, and 95%, respectively, of those obtained with the wet acid digestion method.     

Contents of arsenic, mercury and other trace elements in Napoleon's hair determined by INAA using the k0-method

Two samples of Napoleon's hair were received for determination of arsenic, mercury and other trace elements by INAA. Before sample irradiation, the hairs were washed following the IAEA washing procedure. Two standard reference materials of GBW09101 (human hair) and NIST/SRM1572 (citrus leaves) were analyzed along with Napoleon's hair for quality control. Standardization was conducted by applying the k ₀-method implemented in the program MULTINAA. The contents of arsenic and mercury as well as three additional elements chromium, antimony and zinc in Napoleon's hair are reported. Compared to the present normal levels, all of the determined elements in Napoleon's hair, except the mercury, are found to be irregular.