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     

Development of clenbuterol reference materials: lyophilized bovine eye samples free of clenbuterol (CRM 673) and containing clenbuterol (CRM 674)

The certification by inter-laboratory testing of two candidate reference materials (RMs) for the mass concentration of the anabolic agent clenbuterol in bovine eye material is described: RM 674 with ca 10 microg clenbuterol per kg of eye matrix and RM 673 clenbuterol-free eye matrix as the negative control (<0.50 microg kg(-1)). Both candidate RMs were certified by eleven EU laboratories, and sixty-six accepted replicate measurements were included in the "Certification Study". The precision of the measurement process was assessed by calculation of the standard variation determined within each laboratory during the certification step. The study was performed according to the "Guidelines for the production and certification of BCR reference materials" and to "ISO guide 31, 33, and 35". The certified clenbuterol mass concentration for clenbuterol-free eye material CRM 673 (calculated on the basis of clenbuterol as the free base) was <0.50 microg kg(-1). The corresponding concentration for clenbuterol-containing eye material CRM 674 was 9.42 +/- 0.88 microg kg(-1). These certified values are very close to the desired target concentration of <0.5 microg kg(-1) and ca 10 microg kg(-1). This study has demonstrated that successful certification of clenbuterol-containing and clenbuterol-free bovine eye materials is possible.     

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.     

Development of reference materials for paralytic shellfish poisoning toxins

A project was undertaken to develop mussel reference materials that were certified for their mass fractions of saxitoxin and decarbamoyl-saxitoxin. Fifteen laboratories from various European countries participated. Three of these had major responsibility for substantial parts of the work and overall coordination of the project. The project involved 4 main activities: (1) procurement and characterization of calibrants; (2) improvement of analytical methodology; (3) preparation of reference materials, including homogeneity and stability studies; (4) 2 interlaboratory studies and a certification exercise. The joint activities resulted in 3 homogeneous and stable reference materials: 2 lyophilized mussel materials with and without naturally incurred paralytic shellfish poisoning (PSP) toxins, and a saxitoxin enrichment solution. The reference materials were certified with respect to their saxitoxin and decarbamoyl-saxitoxin content. The lyophilized mussel material with PSP toxins (CRM 542) contained <0.07 mg saxitoxin x 2HCl/kg and 1.59 +/- 0.20 mg decarbamoyl-saxitoxin x 2HCl/kg. The lyophilized mussel material without PSP toxins (CRM 543) contained <0.07 mg saxitoxin x 2HCl/kg and <0.04 mg decarbamoyl-saxitoxin x 2HCl/kg. The certified value of the saxitoxin mass fraction in the saxitoxin enrichment solution (CRM 663) was 9.8 +/- 1.2 microg/g.     

Development of a certified reference material (NMIJ CRM 7505-a) for the determination of trace elements in tea leaves

A certified reference material (CRM) for trace elements in tea leaves has been developed in National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder (<90 μm) after frozen pulverization of washed and dried fresh tea leaves from a tea plant farm in Shizuoka Prefecture, Japan. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), high-resolution (HR-) ICP-MS, isotope-dilution (ID-) ICP-MS, inductively coupled plasma optical emission spectrometry (ICP-OES), graphite-furnace atomic-absorption spectrometry (GF-AAS) and flame atomic-absorption spectrometry (FAAS). Property values were provided for 19 elements (Ca, K, Mg, P, Al, B, Ba, Cd, Cu, Fe, Li, Mn, Na, Ni, Pb, Rb, Sr, Zn and Co) and informative values for 18 elements (Ti, V, Cr, Y, and all of the lanthanides, except for Pm whose isotopes are exclusively radioactive). The concentration ranges of property values and informative values were from 1.59% (mass) of K to 0.0139 mg kg(-1) of Cd and from 0.6 mg kg(-1) of Ti to 0.0014 mg kg(-1) of Lu, respectively. Combined relatively standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, analytical methods, characterization, calibration standard, and dry-mass correction factor. The range of the relative combined standard uncertainties was from 1.5% of Mg and K to 4.1% of Cd.     

TC11钛合金光谱分析标准物质的研制

研制了TC11钛合金光谱分析标准物质,采用合理的熔炼和锻造工艺保证了标准物质的均匀性．经方差法和极差法检验,各元素均匀性良好。采用9家权威实验室协作定值,确定的标准值准确可靠,与国内外同类标准物质比对,结果表明,该套标准物质达到了同类标准物质国际先进水平。     

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.     

微波溶样ICP-MS直接测定茶叶中15种痕量稀土元素

本文报道用ＨＮＯ３－Ｈ２Ｏ２微波溶样，不经分离富集，用标准加入ＩＣＰ－ＭＳ法，直接测定茶叶中１５种痕量稀土元素．对微波溶样和等离子体质谱测定条件进行了优化选择．在最佳实验条件下，用本法测定了国家一级茶叶标准物质ＧＢＷ０７６０５中的单一稀土元素，测得值与标准值很好吻合     

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.     

Preparation and certification of a fish oil natural matrix reference material for organochlorine pesticides

The mass fractions of six organochlorine pesticides in a fish oil certified reference material (CRM) have been determined using multiple methods of analysis. Fish oil was extracted from the filet of Tilapia fish collected from the River Nile, and this CRM was recently issued by the National Institute of Standards (NIS). It can be used as natural matrix CRM for organochlorine pesticides determination in fish and for marine environmental measurement purposes. The analytical methods used are described, and the obtained results were combined to calculate the mass fractions of the six detected organochlorine pesticides and their associated uncertainty values. It has been concluded that mass fractions of four pesticides are certified values. These are 1,1-(dichloroethylidene)bis[4-chlorobenzene](4,4′-DDE), 1,1-(2,2,-dichloroethylidene)bis[4-chlorobenzene] (4,4′-DDD), 1-chloro-2-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene (2,4′-DDT) and 1,1-(2,2,2-trichloroethylidene)bis[4-chlorobenzene] (4,4′-DDT). Meanwhile, mass fractions of two pesticides were reference values. These are heptachlor and 1-chloro-2-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene (2,4′-DDD).     

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.     

A new certified reference material for benzene measurement in air on a sorbent tube: development and proficiency testing

A certified matrix reference material (CRM) for the measurement of benzene in ambient air has been developed at Laboratoire National de Métrologie et d’Essais. The production of these CRMs was conducted using a gravimetric method fully traceable to the International System of Units. The CRMs were prepared by sampling an accurate mass of a gaseous primary reference material of benzene, using a high-precision laminar flowmeter and a mass flow controller, with a PerkinElmer sampler filled with Carbopack™ X sorbent. The relative standard deviations obtained for the preparation of a batch of 20 tubes loaded with 500 ng of benzene were below 0.2%. Each CRM is considered independent from the others and with its own certified value and an expanded uncertainty estimated to be within 0.5%, lower than the uncertainties of benzene CRMs already available worldwide. The stability of these materials was also established up to 12 months. These CRMs were implemented during proficiency testing, to evaluate the analytical performances of seven French laboratories involved in benzene air monitoring.     

Traceability of measurement results in chemistry: a case study of certification of three new pharmaceutical reference materials

This paper compares the results of the studies carried out with three new candidate certified reference materials (CRM) of captopril, metronidazole, and sodium diclofenac, which are the first CRMs of these active pharmaceutical ingredients (APIs) reported in the literature. The studies were carried out according to the ISO Guides 34: 2009 and 35: 2006 and included the determination of organic, inorganic, and volatile impurities mass fractions, evaluation of homogeneity and stability under transport and storage conditions, calculation of API mass fractions by mass balance, cross-checking of obtained results, and estimation of measurement uncertainties. The certified property values and corresponding expanded uncertainties, obtained from the combined standard uncertainties multiplied by the coverage factor (k?=?2), for a confidence level of 95?%, were (995.65?±?0.93) mg/g for captopril, (998.87?±?0.15) mg/g for metronidazole, and (999.76?±?0.10) mg/g for sodium diclofenac. These new CRMs are intended to be used in assay and tests methods, including equipment calibration, method validation, as well as assignment of traceable property values and corresponding uncertainties to non-certified reference materials, with the objective to ensure metrological traceability of measurement results to the International System of Units, as well as results accuracy and comparability.     

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     

Analysis of a copper alloy: Comité Consultatif pour la Quantite de Matière (CCQM) pilot study P76 international intercomparison

The capabilities of National Metrology Institutes (NMIs) and selected outside “expert” laboratories of determining the mass fractions of the main and minor elements Cu, Pb, Sn, Fe, and Ni in a lead-containing brass were assessed. This pilot study P76 was organized as an activity of the Inorganic Analysis Working Group of CCQM and was piloted by the Federal Institute for Materials Research and Testing (BAM). In total 12 laboratories (four NMIs and eight outside labs) submitted results, some of them more than one set of results per element. The laboratories were free to choose any analytical method they wanted to use for the analysis. Consequently various methods of measurement were employed: inductively coupled plasma optical emission spectrometry (ICP–OES), inductively coupled plasma mass spectrometry (ICP–MS), instrumental neutron-activation analysis (INAA), titrimetry, flame atomic-absorption spectrometry (FAAS), spectrophotometry (MAS), electrogravimetry, and gravimetric analysis. After testing for homogeneity within BAM, a certified reference material of lead-containing brass was used as test sample without informing the participants about the source of the material. The agreement of the results for all elements investigated was acceptable and mean values calculated from the results of all participants were close to the certified mass fractions of the CRM used as test sample. No statistically significant differences between the results of the NMIs and those of the non-NMIs could be observed.     

A new Antarctic certified reference material for trace elements: Adamussium colbecki

The certification of a new reference material for trace elements based on the Antarctic bivalve Adamussium colbecki is reported. This certified reference material (CRM), labelled IRMM 813, was produced in the frame of the Italian National Program for Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). About 40 kg of the scallop were collected at Terra Nova Bay (Ross Sea). The raw material was freeze-dried, jet-milled and homogenized so as to make it suitable for certification. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. Homogeneity and short- and long-term stability were preliminarily investigated so as to assess the suitability of the freeze-dried mass as a candidate CRM. The candidate material was found to be fit for purpose, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign. Eighteen laboratories from twelve countries accepted to participate in the certification project which thus could be successfully completed.     

Ti-6Al-4V钛合金光谱分析标准物质的研制

采用真空自耗电极电弧炉与凝壳炉复合熔炼工艺,以及交互式镦拔均匀化变形加工技术,制备了Ti-6Al-4V钛合金光谱分析标准物质。采用方差法和极差法进行均匀性检验,结果表明,Al、V、Fe、Si、C5种元素的均匀性良好。经多家协同定值,确定的标准值准确可靠。经多种光电直读光谱仪应用表明,本套标准物质成线性良好。本套标准物质的均匀性、成线性、标准值及不确定度达到国际同类标准样品的先进水平。     

Production of certified reference materials for mycotoxins: IRMM’s view on the assessment of uncertainties

Analytical difficulty and the economic importance of controlling mycotoxin levels in food and feed led the Community Bureau of Reference (BCR) to prepare a series of certified reference materials (CRM) for various mycotoxins. Because of the wide acceptance of these CRM and the need to ensure the comparability and traceability of measurements in the future it is necessary to prepare and certify new batches of mycotoxin reference materials (RM). In the following text two different approaches for evaluation of the characterisation uncertainty of CRM will be compared using the certification of aflatoxin M₁ (AfM₁) in milk powder as an example. The conventional approach is based on evaluation of characterisation exercise data; the alternative approach is based on measurement uncertainties of the employed analytical methods. Because laboratories are using totally different approaches to estimate the measurement uncertainties, combination of the uncertainties obtained from the participating laboratories was not recommended. Therefore, a new integrated approach for assessment of the measurement uncertainties of the analytical methods on the basis of additional data collected during the characterisation exercise will be described. The conventional approach was found to be the most appropriate and economical approach to evaluate the characterisation uncertainty as a characterisation exercise must be performed anyway to establish the property values of candidate (C)RM, irrespective of whether or not reliable measurement uncertainties can be provided by the laboratories. An integrated approach for assessment of measurement uncertainties based on additional characterisation data as applied here to enable use of an uncertainty-based approach provides more information but is too time-consuming and cost-intensive to become common practice.     

Development and certification of reference materials for residues of organochlorine and organophosphorus pesticides in beef fat ACSL CRM 1 and 2

Beef fat samples were prepared and tested as candidate reference materials for organochlorine and organophosphorus pesticides. The CRMs consisted of beef fat spiked with pesticide solutions. One sample (ACSL CRM 1) was prepared containing close to 0.2 mg/kg of each of the organochlorine pesticides dieldrin and heptachlor epoxide. A second sample (ACSL CRM 2) was prepared containing close to 0.8 mg/kg of each of the organophosphorus pesticides diazinon, chlorpyrifos and ethion. The spiking levels and homogeneity of the materials were verified. The coefficients of variation of 5 analyses carried out to test between-jar homogeneity for each reference material were dieldrin, 3.5%; heptachlor epoxide, 1.1%; diazinon, 2.1%; chlorpyrifos, 1.2% and ethion, 3.1%. No instability in any of these compounds was detected over a twelve month period. The candidate reference materials were found to be suitable for certification by interlaboratory testing. The certification process was based on a two-stage nested design described in ISO Guide 35. Analysis of results reported by collaborating laboratories provided an assessment of the homogeneity of the reference materials. The certified values together with their upper and lower 95% confidence limits are: ACSL CRM 1*Dieldrin*0.199 mg/kg **(0.188, **0.210 mg/kg) *Heptachlor epoxide*0.194 mg/kg **(0.176, **0.212 mg/kg) ACSL CRM 2*Diazinon*0.805 mg/kg **(0.755, **0.855 mg/kg) *Chlorpyrifos*0.790 mg/kg **(0.728, **0.852 mg/kg) *Ethion*0.813 mg/kg **(0.746, **0.879 mg/kg). A certificate for each material was prepared according to the guidelines set out in ISO Guide 31. Received: 25 April 1997 / Revised: 19 August 1997 / Accepted: 28 August 1997     

Development and certification of reference materials for residues of organochlorine and organophosphorus pesticides in beef fat ACSL CRM 1 and 2

Beef fat samples were prepared and tested as candidate reference materials for organochlorine and organophosphorus pesticides. The CRMs consisted of beef fat spiked with pesticide solutions. One sample (ACSL CRM 1) was prepared containing close to 0.2 mg/kg of each of the organochlorine pesticides dieldrin and heptachlor epoxide. A second sample (ACSL CRM 2) was prepared containing close to 0.8 mg/kg of each of the organophosphorus pesticides diazinon, chlorpyrifos and ethion. The spiking levels and homogeneity of the materials were verified. The coefficients of variation of 5 analyses carried out to test between-jar homogeneity for each reference material were dieldrin, 3.5%; heptachlor epoxide, 1.1%; diazinon, 2.1%; chlorpyrifos, 1.2% and ethion, 3.1%. No instability in any of these compounds was detected over a twelve month period. The candidate reference materials were found to be suitable for certification by interlaboratory testing. The certification process was based on a two-stage nested design described in ISO Guide 35. Analysis of results reported by collaborating laboratories provided an assessment of the homogeneity of the reference materials. The certified values together with their upper and lower 95% confidence limits are: ACSL CRM 1*Dieldrin*0.199 mg/kg **(0.188, **0.210 mg/kg) *Heptachlor epoxide*0.194 mg/kg **(0.176, **0.212 mg/kg) ACSL CRM 2*Diazinon*0.805 mg/kg **(0.755, **0.855 mg/kg) *Chlorpyrifos*0.790 mg/kg **(0.728, **0.852 mg/kg) *Ethion*0.813 mg/kg **(0.746, **0.879 mg/kg). A certificate for each material was prepared according to the guidelines set out in ISO Guide 31.