Multielement trace determination in high purity advanced ceramics and high purity metals

In the field of advanced ceramics two CRMs were developed in the last few years by the Federal Institute for Materials Research and Testing, one for silicon nitride and one for silicon carbide. Besides their application by industry they are appropriate to be used for the validation of special methods used for trace determination in accordance with high purity materials. This is demonstrated, for example, on ultrapure silicon carbide which was analysed by solid sampling electrothermal atomic absorption spectrometry (SS ET AAS). BAM is also certifying primary pure reference materials used as the National Standards for inorganic analysis in Germany. The crucial point of this project is the certification of the total purity of high purity materials, each representing one element of the periodic table. A variety of different analytical methods was necessary to determine the trace contents of metallic and non-metallic impurities from almost the whole periodic table in the high purity materials. The primary CRMs of copper, iron and molybdenum are used as examples to demonstrate the modus operandi, analytical effects observed by using high resolution ICP mass spectrometry (HR ICP-MS) and the results.     

Preparation of National CRMs of Active Compounds from Natural Products

According to the standard of GB/T1500.3-2008 and the guidelines of ISO/REMCO, the preparation of National Certified Reference Materials (CRMs) of active compounds was composed of the following two aspects: preparation and certification. This paper presents an example of the preparation of biochanin A to illustrate the preparation of National CRMs of active compounds from natural products. Firstly, the target compound was extracted and purified from crude materials. Then,its chemical structure was identified by UV spectrum, IR spectrum, ESI-MS, and NMR. The purity of the compound was determined by HPLC with the area normalization method. The certified value assessed by comparing the purity values from six independent qualified laboratories and the value of uncertainty were given. Thermal analysis, residual solvent, homogeneity testing and stability testing was tested in the process.     

血细胞计数分析用国家标准物质的研制

采用专用的白细胞、红细胞和血小板3类生物粒子合成模拟人的血液,按照国家一级标准物质研制规范制备血细胞计数标准物质,采用显微图像分析法为血细胞计数标准物质定值,对该血细胞计数标准物质的定值结果及不确定度评定、均匀性检验、稳定性检验过程进行分析,将该血细胞标准物质定值结果与国际参考方法的测定结果进行比对。结果证明:本血细胞计数标准物质适于血细胞分析仪的校准与计量检定。     

Development of Four Parabens Reference Materials Certified for Purity Mass Fraction by Mass Balance Approach

The need for pure organic reference materials for establishing traceability to the international system of units, validation of analytical methods and assuring quality of the measurement results has been increased recently. Mass balance approach was used for development of four reference materials from methyl, ethyl, propyl and butylparaben certified for purity mass fraction. The analyte mass fraction in each reference material was assigned by measurements of detectable impurity components include determination of organic, inorganic, water and volatile impurities by HPLC–DAD and GC–FID, IC, Karl Fisher and headspace, respectively. Assignment of certified purity was based on results from independent liquid and gas chromatographic methods. The certified purity values of methyl, ethyl, propyl, and butylparaben and their corresponding expanded uncertainties (k = 2.0) were found (998.48 ± 0.71), (997.80 ± 1.36), (998.20 ± 0.51) and (998.35 ± 0.89) mg/g, respectively. The prepared reference materials can be used as a measurement standard for analytical instruments and as a control sample for assuring quality of cosmetics, pharmaceutical and food products.     

Certification of Three Reference Materials for α- and γ-Tocopherol in Edible Oils

Tocopherols are important vegetable oil constituents, and their reliable quantitative analysis depends largely on the existence and quality of certified reference materials (CRMs) which provides traceability of the measurement results to the SI units. Since there is a lack of suitable CRMs in case of tocopherols analysis, three matrix reference materials from corn, peanut and soybean oils were certified for the content of α and γ-tocopherols. Homogeneity and stability of the prepared reference materials were studied and certification was done by two independent chromatographic analytical methods. The measurement results were statistically treated and the certified values of α and γ-tocopherol in corn, peanut and soybean oils were assigned and their associated expanded uncertainties were estimated as: 322.04 ± 8.62, 771.48 ± 15.31, 106.23 ± 5.19, 108.94 ± 9.72, 140.66 ± 5.93, 418.00 ± 14.36 mg/kg, respectively. These values were found useful for many food testing laboratories in validation of analytical methods and analytical quality control.     

苯系物溶液标准物质的研究

论述了苯系物溶液标准物质的研究工作 ,系统地介绍了标准物质原材料的选择、特性量值的测量方法、标准物质的制备方法、均匀性检验、稳定性考察以及定值测量。对样品的均匀性、测量的分散性及其他因素引入的不确定度分量分析和确定后 ,给出了整个测量过程不确定度的合成结果。对气相色谱法和液相色谱法所得到的实验结果进行了统计分析 ,其均匀性符合F检验和T检验 ,满足标准物质的技术规范。对苯系物溶液标准物质的稳定性进行了 2年的考察 ,证明该标准物质是稳定的 ,浓度值的不确定度为 2 8%。苯系物溶液标准物质已被批准为国家一级标准物质     

颗粒计数标准物质定值方法研究

为了探讨颗粒计数标准物质研究中缺乏操作性强、量值溯源可靠的颗粒计数标准物质定值方法等主要技术难点,本文中采用量值可溯源至长度基准的显微图象分析仪,配以血球计数板为球形乳胶颗粒计数标准物质定值,在确定标准值同时对于定值的不确定度进行了分析和研究。研究结果表明:采用这种方法的定值不确定度优于10%(k=2)。     

Development, validation, and application of a method for quantification of methylmercury in biological marine materials using gas chromatography atomic emission detection

A gas chromatographic method was developed for the quantification of alkylmercury species using microwave-induced plasma atomic emission detection (GC-AED). The column conditioning and analyte derivatization required for previous methods were found to be unnecessary for stable, accurate, and sensitive element-specific detection using GC-AED. Chromatographic and detection parameters such as stationary phase type, stationary phase film thickness, GC column dimensions, helium mobile phase column head pressure, detector makeup gas flow rate, and detector reagent gas type and flow rate were found to significantly affect analyte response. The detection limit for the optimized GC-AED conditions was 0.8 pg (0.1 pg/s) of methylmercury chloride (as mercury). A solid-liquid extraction procedure with preparative gel permeation chromatography cleanup and GC-AED analysis was used to quantify methylmercury in a variety of complex matrix marine materials. The methylmercury quantification method was validated with four marine certified reference materials (CRMs). The method was then applied to 13 standard reference materials, CRMs, and control materials for which no certified reference values for methylmercury have been determined. Four National Institute of Standards and Technology Standard Reference Materials and one control material, which were analyzed using the GC-AED method, were also analyzed by two other laboratories using independent methods to further validate the method.     

Development of Crude Oil Reference Material Certified for the Concentrations of Sulfur,Iron, Nickel,Vanadium and Magnesium

Crude oil quality and uses are largely affected by the presence of sulfur and some other elements. Controlling the risk associated with these elements in crude oil depends on their accurate determination which is crucially governed by the use of certified reference materials (CRMs). This paper describes the development of a natural-matrix reference material for quantification of sulfur, iron, nickel, vanadium and magnesium in crude oil. The crude oil was homogenized and bottled to prepare the candidate material. Homogeneity and stability of the prepared reference material were investigated and characterization of sulfur content was carried out using wavelength-dispersive X-ray fluorescence (WD-XRF) spectrometry and gravimetric methods. Meanwhile, characterization of iron, nickel, vanadium and magnesium content was carried out using atomic absorption spectrometry (AAS) and inductively coupled plasma-optical emission spectrometry (ICP-OES) techniques. Statistical evaluation of the data showed good homogeneity and stability of the candidate reference material. Sufficiently good agreement between methods of characterization was achieved which allowed certification. The certified values and their associated uncertainties were statistically derived using the approach of combining data from two or more independent analytical methods developed by National Institute for Standards and Technology (NIST, Gaithersburg, USA).     

食品营养标签分析的标准物质研究

提高测量精确性可以保证食品营养标签提供食品营养可靠可知性和产品质量,是提高食品营养质量评价的重要手段。食品营养成分标准物质可保证测量有效性,是验证营养标签分析方法和实验室内分析的质量保证所必需的,对营养标签标准和标签法具有支持和推动作用。阐述了我国和美国食品营养分析标准物质,并介绍了美国AOAC作为发展一系列基于蛋白质、脂肪和碳水化合物的代表所有食品标签分析的标准物质的食品三角形模式图。     

An international evaluation of holmium oxide solution reference materials for wavelength calibration in molecular absorption spectrophotometry

Commercial spectrophotometers typically use absorption-based wavelength calibration reference materials to provide wavelength accuracy for their applications. Low-mass fractions of holmium oxide (Ho2O3) in dilute acidic aqueous solution and in glass matrixes have been favored for use as wavelength calibration materials on the basis of spectral coverage and absorption band shape. Both aqueous and glass Ho2O3 reference materials are available commercially and through various National Metrology Institutes (NMIs). Three NMIs of the North American Cooperation in Metrology (NORAMET) have evaluated the performance of Ho3-(aq)-based Certified Reference Materials (CRMs) under "routine" operating conditions using commercial instrumentation. The study was not intended to intercompare national wavelength scales but to demonstrate comparability of wavelength measurements among the participants and between two versions of the CRMs. It was also designed to acquire data from a variety of spectrophotometers for use in a NIST study of wavelength assignment algorithms and to provide a basis for a possible reassessment of NIST-certified Ho3+(aq) band locations. The resulting data show a substantial level of agreement among laboratories, instruments, CRM preparations, and peak-location algorithms. At the same time, it is demonstrated that the wavelength comparability of the five participating instruments can actually be improved by calibrating all of the instruments to the consensus Ho3+(aq) band locations. This finding supports the value of absorption-based wavelength standards for calibrating absorption spectrophotometers. Coupled with the demonstrated robustness of the band position values with respect to preparation and measurement conditions, it also supports the concept of extending the present approach to additional NMIs in order to certify properly prepared dilute acidic Ho2O3 solution as an intrinsic wavelength standard.     

碳黑比表面积标准物质的研制

选择商品化的碳黑作为比表面积标准物质候选材料,利用交叉缩分的方法对碳黑样品进行分装。经均匀性、稳定性(18个月)检验,碳黑标准物质样品具有良好的均匀性和稳定性。按照国际公认的氮气物理吸附BET方法,联合测量能力经确认过的8家实验室对碳黑标准物质样品进行定值(104.6、29.9、8.96 m2/g)。与国内外同类标准物质比较表明:研制的3种碳黑比表面积标准物质的相对不确定度(2.1%、2.3%和3.2%)达到国际同类标准物质的先进水平。     

粮食中营养成分标准物质制备技术

介绍粮食中营养成分基体标准物质的制备方法和流程,包括总的原则、成分设计、基体选择、物料采集、物料处理、成分初测、粉碎、筛分烘干过程、均匀性初检、分装、辐照灭菌、真空包装及储存。重点讨论和分析制备过程中应注意的细节以及为了保证均匀性和稳定性所采取的措施。     

Ultrasonic extraction and field-portable anodic stripping voltammetric measurement of lead in dust wipe samples

Dust wipe samples were subjected to ultrasonic extraction (UE) in diluted nitric acid, and then analyzed for lead content using field-portable anodic stripping voltammetry (ASV). Recoveries of lead were determined from wipe materials which were spiked with certified reference materials (CRMs) containing known quantities of lead. Four different wipe materials and four different CRMs were tested, with and without filtration of aliquots of sample extract through 0.45 microm hydrophilic polytetrafluoroethylene filters. The CRMs consisted of paint, soil, particulate, and dust matrices. Wipe materials were chosen from those which have been found to meet the performance aspects of an ASTM standard specification. UE/ASV experiments were carried out in accordance with newly published ASTM procedures for on-site extraction and electroanalysis. Recoveries were found to vary for different wipe materials and CRMs. For several CRMs, quantitative (80--120%) recoveries for UE/ASV were observed for one wipe material whether filtration was used or not, while other wipe materials required filtration for quantitative recovery. In the case of one wipe material which contained detergents, quantitative recoveries could not be achieved whether filtration was used or not. The total analysis time for a sample set of 6--12 samples was 60--90 min, including extraction time and sample manipulation. The results of this work have provided information on the choice of wipe materials that can be used for quantitative lead measurements by UE/ASV in materials that are representative of sources of lead in surface dust.     

Evaluation of Measurement Uncertainty for Absolute Flatness Measurement by Using Fizeau Interferometer with Phase-Shifting Capability

It is important to precisely measure flatness of the optical flats, as many industries use these as reference standards to ensure the quality of precision measurements and fabricated components. This paper describes identification of sources of error and measurement uncertainty evaluation for three flat test. Three flat test is used for absolute flatness measurement of optical flats, with the help of Fizeau interferometer (VerifireXP/D, with phase shift interferometry) established recently at National Physical Laboratory, India (NPL-I). The absolute profile of reference flat with higher accuracy can be determined using liquid level reference but liquid flat reference is more difficult to realize practically. Therefore three flat test is frequently adopted in standard interferometric measurements and traceability of this test can also be established by using a traceable laser head. This paper describes three flat method in detail along with observations and evaluation of measurement uncertainty as per ISO GUM is also done. Factors contributing to uncertainty of measurement of surface flatness have been indentified and detailed evaluation of uncertainty in measurements has been reported here.     

Lubricant Oils as a Certified Reference Material for Cleveland Open Cup Flash Point Testers

The flash point is an important indicator for the flammability of the liquid materials and also in the development of safe practices for handling and storage of these materials. The production of certified reference materials is essential to guarantee the performance of the flash point measurement apparatus so that it can be trusted and acceptable for its intended use. In this work lubricant oils of high molecular weight hydrocarbons (HM1, and HM2) were tested as certified reference materials in accordance with ISO guide 34 and 35 by using the high flash point temperature detector Cleveland-open cup as per ASTM D-92. The selected oils were tested for uncertified properties like pour point, viscosity, cloud point, density, and total acid number. The thermal analysis techniques DSC, and TGA were used to ensure the thermal stability of the lubricant oils and its ability to be used as high temperature flash point reference material. The certified value of the flash point temperature was assigned upon evaluation of the data acquired in an inter-laboratory comparison involving expert laboratories using the same measurement method. The certified values of the candidate reference materials with expanded uncertainty (coverage factor K = 2, approximate 95% confidence level) calculated using the results of the characterization, calibration (organizer lab), homogeneity, and stability assessment were 232 ± 9 °C for HM1, and 242 ± 10 °C for HM2.     

Production,characterization and development of standards for biodiesel — A review

Biodiesel is being promoted worldwide as a supplement and alternative automotive fuel for petroleum diesel in spite of several technological, economical and social barriers. This has provided an impetus for new research to overcome these deterrents in its production, to establish its quality criteria (standards), and to develop superior analytical methods for quality control and quality assessment of biodiesel in production and entire distribution chain until consumed by end user. The present review paper briefly covers the production, characterization and standardization of biodiesel, having relevance to the preparation of certified reference materials (CRMs) of biodiesel.     

系列液体和固体水分标准物质的研制

针对水分检测领域对标准物质的需要,研制了系列水分标准物质,包括4种液体水分标准物质,量值覆盖范围为0.139~47.6 mg/g,不确定度范围为0.012~1.1 mg/g;还包括3种含结晶水化合物水分标准物质,量值覆盖范围为50.7~156.3 mg/g,不确定度范围为0.6~1.3 mg/g,以及3种混合物水分标准物质,量值覆盖范围为0.142~9.90 mg/g,不确定度范围为0.013~0.20 mg/g。该系列液体和固体水分标准物质,适用于卡尔·费休库仑法和容量法水分仪的校准和检定,以及水分测量方法的验证,能够保障我国水分检测的量值准确和等效一致。     

Development and evaluation of a reference measurement procedure for the determination of estradiol-17beta in human serum using isotope-dilution liquid chromatography-tandem mass spectrometry

Estradiol is the most potent natural estrogen and is derived from the ovaries. Its concentration in blood is measured to determine ovarian function. A reference measurement procedure for estradiol in serum involving isotope-dilution coupled with liquid chromatography-tandem mass spectrometry (LC/MS/MS) has been developed and critically evaluated. A deuterated estradiol (estradiol-d3) was used as an internal standard. The estradiol and its internal standard were extracted from serum matrix using solid-phase extractions and derivatized with dansyl chloride prior to reversed-phase LC/MS/MS. The accuracy of the measurement was evaluated by a comparison of results of this reference method on lyophilized human serum reference materials for estradiol [Certified Reference Materials (CRMs) 576, 577, and 578] with the certified values determined by gas chromatography/mass spectrometry (GC/MS) reference methods and by a recovery study for the added estradiol. The results of this method for estradiol agreed with the certified values within the uncertainty of the measurements for the three CRMs. The recovery of the added estradiol ranged from 100.7 to 101.8%. This method was applied to the determination of estradiol in frozen serum samples from three individual female donors. Excellent reproducibility was obtained with within-set coefficient of variations (CVs) ranging from 0.6 to 2.2% and between-set CVs ranging from 0.2 to 0.4%. Excellent linearity was also obtained, with correlation coefficients of all linear regression lines (measured intensity ratios vs mass ratios) ranging from 0.998 to 1.000. The detection limit at a signal-to-noise ratio of approximately 3 was 0.6 pg of estradiol (or 1 ng/L, as expressed as a concentration). This well-characterized LC/MS/MS method for serum estradiol, which demonstrates good accuracy and precision, low susceptibility to interferences, and comparability with GC/MS reference methods, qualifies as a reference measurement procedure that can be used to provide an accuracy base to which routine methods for estradiol can be compared and that will serve as a standard of higher order for measurement traceability.     

Determination of methylmercury and butyltin compounds in marine biota and sediments using microwave-assisted acid extraction,solid-phase microextraction,and gas chromatography with microwave-induced plasma atomic emission spectrometric detection

A method is described for the determination of methylmercury and butyltin compounds in marine sediment and tissue using microwave-assisted acid extraction or digestion and solid-phase microextraction (SPME) followed by analysis using gas chromatography with microwave-induced plasma atomic emission spectrometric detection (GC-MIP-AES). Using the SPME-GC-MIP-AES method, enrichment factors for methylmercury and butyltin compounds of 50-100 were achieved, as compared to the typical hexane extraction, and measurements in marine tissue and sediment matrixes were possible at 1-2 microg/kg (methylmercury) and 10-100 ng/kg (butyltins). The SPME-GC-MIP-AES method was validated using several marine sediment and tissue matrix certified reference materials (CRMs) with certified values for methylmercury and butyltin compounds. The SPME-GC-MIP-AES method was used to measure methylmercury in four marine tissue CRMs ranging from oyster tissue at 13.0 +/- 1.0 microg/kg to fish tissue at 397 +/- 13 microg/kg (as Hg dry mass). Results from the SPME-GC-MIP-AES method were used in conjunction with results from other techniques to assign certified values for methylmercury in oyster, mussel, and fish tissue CRMs. Mono-, di-, and tributyltin were measured in three sediment CRMs at concentration levels of (0.08 +/- 0.03)-(0.35 +/- 0.05) mg/kg (as Sn dry mass).