XRF分析用合金标样的研制及在锌饼合金中的应用

在X-射线荧光光谱分析(XRF)用热镀锌合金标样的制备及数学校正方法研究的基础上,对锌合金标样的制备及应用进行了研究.经过锌饼合金生产控制分析及成品分析考核,表明研制的标样成分均匀,含量范围合格,方法准确,测定结果与化学法相符,为锌饼合金生产提供了一种简便、快速、准确的分析方法.     

铸造锡青铜光谱标样的研制

铸造锡青铜ZQSnD6-6-3、ZQSnD5-5-5,ZQ SnD3-11-4和ZQSnD3-8-6-1可用于制造摩擦条件下工作的耐磨、耐蚀零件,及海水、淡水、蒸汽压力不大于2.5MPa的管配件和阀门等.合金的化学成分对保证零配件的机械性能和寿命有着重要意义.在铸造锡青铜熔铸的炉前分析和产品化学成分分析中,采用化学湿法测定主成分锡、锌、铅、镍和杂质元素磷,摄谱法分析杂质元素铁、锑、铝和硅,在分析速度和准确度上难以满足炉前分析要求.生产上要求有一套适用于光电直读或X荧光光谱分析的块状标样,以便在几分钟内给出分析结果.但至今一套成分均匀的铸造锡青铜块状光谱分析标样,在国内外都是制备的难题.英国MBH公司曾经发行过一套(?)60mm,厚6mm蘑菇形铸造锡青铜块状标样,使用不方便.国内也曾经生产过一套锡青铜标样,仅供分析杂质元素铁、锑、硅和铝.在组织结构上是变形状态(挤压加工状态)与铸造状态有显著不同,与光谱分析标样和试样在组织结构一致的要求相悖.     

石油焦中硫含量二次标样的制备

本实验由两部分组成。第一部分内容主要是尝试制备用于测定石油焦中硫含量的二次标样,解决了因国内目前还没有石油焦中硫标样为分析带来的困难。还由于采用了二次标样,基本排除了基体对本方法测定结果的影响。本实验在尝试制备二次标样的过程中,用4种测试方法定值。首先对二次标样用方差法进行了均匀性检验。经检验合格后,用定值计算的数据统计方法(包括测定结果的离群值检验、数据分析正态性检验,各方法平均值间一致性检验和等精密度检验)进行定值。第二部分内容主要是使用所制备的二次标样,并用简单、快速的库仑滴定原理设计的快速定硫仪仪器分析替代了操作步骤复杂的管式炉法[1]来分析测定石油焦中硫含量。本方法具有操作简单、测定快速、结果准确及重复性好的优点。本方法基本满足了本公司铝工业用石油焦中硫含量的测定要求。本方法适用范围为0~2.0(m/m)%,方法标准偏差为1.2%。     

X射线荧光光谱法在稀土元素分析中的应用

本文研究了Ｘ射线荧光光谱在混合稀土氧化物和高纯稀土氧化物分析中的应用，并探讨了在常量分析中影响分析准确度和精密度的主要因素；样品及标样制备，基体效应校正方法在痕量分析中降低检测限的方法，选择最佳测量条件，降低背景，与分离富集手段相结合，取得满意的结果。     

直读光谱法测定铸铝115中硅铁镁锌铍

铝合金中化学成分测定常用比色法 [1,2 ]与滴定法 [1] ,这两种方法样品消耗量大 ,且需将样品转化成溶液 ,样品处理工作量大 ,预处理过程繁琐 ,耗时多 ,而且所用化学试剂多 ,化验成本偏高。光谱分析速度快 ,准确度高 ,单个样品从接样到报出结果所需时间不超过 1 0 min,是一种金属化学成分测定的快捷方法。但光谱分析对标准样品要求比较高 ,铸铝 1 1 5材料须分析硅、铁、镁、锌、铍五个元素 ,目前市场上的标样不能覆盖该材料 ,因此需要两套标样 ,本文采用ZLD1 0 1、LC4两套标样 ,用自制的控制试样 ,采取控样法分析铸铝 1 1 5样品 ,消除了因…     

X—射线荧光光谱测定甜瓜中矿质元素

报道了日本理学３０８０Ｅ３型Ｘ－射线荧光光谱仪在测定甜瓜样品旧和微量矿质元素中的的应用。以国家植物标准参考物质（ＧＢＷ）为校准标样，采用真空加热干燥法制备甜瓜样品，所得分析结果与ＩＣＰ－ＡＥＳ对照相吻合。     

钢中Si、Mn的电子探针定量分析与标样

采用特制的Fe-Si、Fe-Mn合金系列标样，用电子探针测定了钢或铁基合金中低含量的Si和Mn元素、与用纯元素作标样、经ZAF修正的结果相比较，提高了分析准确度．     

粉末标样的喷雾干燥制备新工艺

分析中所用标准样品(即标样)的制备,按其主体与杂质各自的存在形态来分,大体有固—固法、固—液法以及液—液法三种。前两法属于非均相配制体系,而后者为均相配制体系。由于标样中主体元素与各杂质元素的分布,要求高度的均匀。所以,液—液法均相配制体系,对标样的制备是最适宜的。     

X-射线荧光光谱测定甜瓜中矿质元素

报道了日本理学3080E3型X-射线荧光光谱仪在测定甜瓜样品常量和微量矿质元素中的应用。以国家植物标准参考物质(GBW)为校准标样,采用真空加热干燥法制备甜瓜样品,所得分析结果与ICP-AES对照相吻合。     

光谱标样定值的不确定度和标样的不均匀性

分析了目前国内发布的光谱标样的不均匀性，提出了要强调要调不均匀性的概念。为了能检出光谱标样的不均匀性，应该重新设计光谱标样的均匀性检验方案，同时应明确定义不均匀性的概念。     

小比表面标准物质的研制

本文报道了国内首创的用于评价固体材料比表而值测定准确度和校正比表面测定仪的小比表面标准物质SB2002的研制方法,包括材料的选择、制备及测试结果。用F和t检验法来检验分装前材料的均匀性,估计了分装后各瓶之间的不均匀性方差。由国内具权威性的九家实验室用不同类型仪器方法进行协作定值。数据经严密处理,得出了标准值及不确定度范围,并与国外同类标准物质作了比较。     

New NIST sediment SRM for inorganic analysis

NIST maintains a portfolio of more than 1300 standard reference materials (SRM), more than a third of these relating to measurements in the biological and environmental fields. As part of the continuous renewal and replacement efforts, a set of new marine sediments has been recently developed covering organic and inorganic determinations. This paper describes the steps taken in sample preparation, homogeneity assay, and analytical characterization and certification with specific emphasis on SRM 2702 inorganics in marine sediment. Neutron activation analysis showed the SRM to be highly homogeneous, opening the possibility for use with solid sampling techniques. The certificate provides certified mass fraction values for 25 elements, reference values for eight elements, and information values for 11 elements, covering most of the priority pollutants with small uncertainties of only several percent relative. The values were obtained by combining results from different laboratories and techniques using a Bayesian statistical model. An intercomparison carried out in field laboratories with the material before certification illustrates a high commutability of this SRM.Electronic Supplementary Material Supplementary material is available in the online version of this article at     

On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials

We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6–21% for pressed pellets and 3–21% for fused solids were obtained from n = 3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches.     

Recent developments in food-matrix Reference Materials at NIST

Since 1996, the National Institute of Standards and Technology (NIST) has developed several food-matrix Standard Reference Materials (SRMs) characterized for nutrient concentrations. These include SRM 1544 Fatty Acids and Cholesterol in a Frozen Diet Composite, SRM 1546 Meat Homogenate, SRM 1548a Typical Diet, SRM 1566b Oyster Tissue, SRM 1846 Infant Formula, and SRM 2383 Baby Food Composite. Three additional materials--SRM 1946 Lake Superior Fish Tissue, SRM 2384 Baking Chocolate, and SRM 2385 Spinach--are in preparation. NIST also recently assigned values for proximate (fat, protein, etc.), individual fatty acid, and total dietary fiber concentrations in a number of existing SRMs and reference materials (RMs) that previously had values assigned for their elemental composition. NIST has used several modes for assignment of analyte concentrations in the food-matrix RMs, including the use of data provided by collaborating laboratories, alone and in combination with NIST data. The use of data provided by collaborating food industry and contract laboratories for the analysis of food-matrix RMs has enabled NIST to provide assigned values for many analytes that NIST does not have the resources or analytical expertise to measure.     

Modifications to the NIST reference measurement procedure (RMP) for the determination of serum glucose by isotope dilution gas chromatography/mass spectrometry

The definitive method (DM), now known as the reference measurement procedure (RMP), for the analysis of glucose in serum was originally published in 1982 by the National Institute of Standards and Technology (NIST). Over the years the method has been subject to a number of modifications to adapt to newer technologies and simplify sample preparation. We discuss here an adaptation of the method associated with serum glucose measurements using a modified isotope dilution gas chromatography/mass spectrometry (ID-GC/MS) method. NIST has used this modified method to certify the concentrations of glucose in SRM 965b, Glucose in Frozen Human Serum, and SRM 1950, Metabolites in Human Plasma. Comparison of results from the revised method with certified values for existing Standard Reference Materials (SRMs) demonstrated that these modifications have not affected the quality of the measurements, giving both good precision and accuracy, while reducing the sample preparation time by a day and a half.     

Pressurized liquid extraction of organochlorine pesticides from certified solid materials

In order to propose a versatile method to use in laboratories devoted to environmental analysis, a scheme for the determination of organochlorine pesticides from different solid matrices is evaluated. Pressurized liquid extraction is chosen as the sample preparation technique, followed by the purification of the extract by means of solid-phase extraction with Envi-carb cartridge (100 m(2)/g). Finally, the extracts are analyzed by programmed temperature vaporization (PTV)-gas chromatography (GC)-electron-capture detection and PTV-GC-mass spectrometry. The suitability of the method for the analysis of different matrices is determined by the extraction and analysis of four certified reference materials of solid matrices: CRM 804-050 (soil), SRM 1941b (organics in marine sediment), SRM 1944 (New York/New Jersey waterway sediment) and SRM 1649a (Urban Dust). Good statistical concordance between the results obtained and the certified or reference concentration are observed for most of the analyzed pesticides.     

Use of neutron activation analysis for the characterization of single-wall carbon nanotube materials

Instrumental neutron activation analysis (INAA) and prompt gamma neutron activation analysis (PGAA) were used to characterize a variety of single-wall carbon nanotube (SWCNT) materials from different principal production processes, as well as a material containing SWCNTs together with other carbon species, catalyst residues, and trace element contaminants to be issued by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. INAA proved to be well suited for the direct determination of catalyst and contaminant trace elements requiring only minimal sample preparation. PGAA complemented the INAA data in particular with determinations of the light elements. Carbon and hydrogen results provided information on the materials purity and storage properties. Strategies for the quality assurance of the measurements in these new materials were developed. INAA and PGAA data were provided for the value assignment of mass fractions of catalyst and trace elements in the candidate SRM and a systematic overview was obtained of the catalyst and trace element contaminants associated with each of the major production routes.     

Direct determination of polycyclic aromatic hydrocarbons in solid matrices using laser desorption/laser photoionization ion trap mass spectrometry

The development and characterization of a new instrument for solid sampling which couples IR laser desorption followed by UV laser photo-ionization and analysis using an ion trap mass spectrometer has been investigated. For calibration, a new type of solid sample preparation involving activated charcoal as the solid substrate was used. This solid sample provided a steady signal for several thousand laser shots, which allowed optimization of the experimental procedure. It was found that both the IR and UV intensity and the delay between them play an important role in both the magnitude and type of signals observed. A method of gas phase accumulation with multiple laser shots was examined. Finally, this technique was demonstrated to be effective in providing direct qualitative information for N.I.S.T. SRM 1944 river sediment sample with no sample pre-treatment.     

On the certification of cadmium at trace and ultratrace levels in standard reference materials using ID ICP-MS

Analytical methods used for the isotope dilution inductively coupled plasma mass spectrometric (ID-ICP-MS) measurement of Cd at μg kg⁻¹ and sub-μg kg⁻¹ levels are described and applied to the certification of new dietary supplement, blood, and serum Standard Reference Materials (SRMs). The materials are: SRM 3240 Ephedra sinica Stapf Aerial Parts, SRM 3241 Ephedra sinica Stapf Native Extract, SRM 3243 Ephedra-Containing Solid Oral Dosage Form, SRM 3244 Ephedra-Containing Protein Powder, SRM 966 Toxic Metals in Bovine Blood, Level 1 (L1) and Level 2 (L2), and SRM 1598a Animal Serum. The concentration of Cd in the materials ranges from 120 μg kg⁻¹ down to 0.03 μg kg⁻¹. At these levels, the factors that most influence the accuracy of the ICP-MS data are the procedure blank and spectral and nonspectral interferences. Nonspectral interference, caused by the high concentration of dissolved solids in the matrices investigated, resulted in signal suppression. Matrix separation was used to enhance signal intensity and to reduce spectral interference for the accurate determination of Cd in SRM 1598a and SRM 3244. Chromatographic separation procedures using Chelex for SRM 1598a and anion exchange for SRM 3244 were optimized to achieve the desired separation characteristics without substantially increasing the procedure blank. Sensitivity for the determination of Cd in serum was additionally enhanced through the use of desolvation nebulization. We determined that separations were not required for the accurate ICP-MS determination of Cd in SRM 3240, SRM 3241, SRM 3243, and SRM 966 L2 under optimized analysis conditions. These samples were diluted to a minimum volume and introduced to the ICP-MS via low flow (40–100 μL/min) microconcentric nebulizers. SRM 966 L1 was also analyzed directly, but results were highly variable. The ID-ICP-MS sample preparation and ratio measurement protocols described here resulted in total expanded uncertainties of less than 1% for the determination of 90.85 μg kg⁻¹ Cd in SRM 3240, and less than 10% total expanded uncertainty for the determination of 0.0468 μg kg⁻¹ Cd in SRM 1598a.