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。     

微孔孔容和孔径标准物质的研制

选择商品化的13X分子筛颗粒作为微孔孔容和孔径标准物质候选材料,利用交叉缩分方法对标准物质样品进行分装;从分装后的标准物质样品中随机抽取样品来检验其均匀性、稳定性;采用国际公认的氩气物理吸附方法,通过与欧洲经济共同体IRMM标准物质BCR-704比较测量的方式对标准物质样品进行定值。结果表明,经均匀性、稳定性检验,所研制的微孔孔容和孔径标准物质GBW(E)130366具有良好的均匀性和稳定性(至少12个月);微孔孔容和孔径分别为0.242 cm3/g和0.668 nm;与国内外同类标准物质相比,GBW(E)130366填补了国内空白,其相对不确定度(3.3%和2.8%)达到国际同类标准物质的先进水平。     

纳米级氧化铝比表面积标准物质的均匀性和稳定性检验

标准物质是具有准确量值的测量标准,作为计量器具广泛应用于产品质量控制、设备校准、测试方法和质量仲裁等工作。对于标准物质而言,对其均匀性和稳定性的考察是非常重要的评定依据。本文以国家纳米科学中心研制的纳米级氧化铝比表面积标准物质为实例,对其均匀性和稳定性进行了检验。     

16种多环芳烃混合溶液标准样品研究

介绍了甲醇：二氯甲烷（V：V,1：1）中16种多环芳烃混合溶液标准样品的研制过程。该标准样品采用称量法制备,用气相色谱一质谱法进行均匀性检验和稳定性监测,对不确定度来源进行了全面评估,并与国际同类标准样品进行了量值比对分析。研究结果表明,该16种多环芳烃混合溶液标准样品均匀性和稳定性良好,量值准确可靠,可用于环境监测和科学研究工作。     

宽分布激光衍射用固体颗粒度标准物质的研制

研究制备出了宽分布激光衍射用固体颗粒度标准物质,填补了国内宽分布固体颗粒度标准物质的空白。采用高分辨力的扫描电子显微镜(SEM)绝对测量法对标准物质进行定值,标准值可溯源至国家长度基准。定值结果为D₅₀=41.5μm,扩展不确定度为1.76%(k=2)。采用单因素方差分析法和t检验法检验了样品的均匀性和稳定性。定值过程和均匀性、稳定性都符合国家级标准物质的要求。     

氯化钾电导率溶液标准物质的研制

介绍了氯化钾电导率溶液标准物质的研制方法,采用与一级标准物质比较定值的方法对该标准物质进行了定值,利用高精度电导率仪对定值结果进行了验证,同时对该标准物质进行了均匀性检验和稳定性考察。氯化钾电导率溶液标准物质的定值结果为1408μS/cm,扩展不确定度为:Urel=0.6%,k=2。其均匀性和稳定性检验结果表明,该标准物质符合国家二级标准物质的技术要求。     

气体吸附法测定低比表面积氧化铝粉体的比表面积

采用气体吸附法原理,以低比表面积氧化铝粉体标准物质为例,利用美国麦克仪器公司的ASAP2020比表面积和孔隙度分析仪测定其比表面积,通过改变测试条件分析各项参数值对测定结果的影响。结果表明:吸附系统"死体积"、样品用量和脱气条件等对测定结果都有比较明显的影响;对于低比表面积氧化铝粉体的理想测定条件为脱附温度250℃,脱附时间2h,样品用量2.5~3g。试验所得结果可为低比表面积粉体的比表面积准确测定提供参考。     

腹泻性贝类毒素基体标准物质的研制

为了保证小鼠生物法、荧光衍生法、质谱法等对腹泻性贝类毒素检测结果的准确、可靠和可比,以紫贻贝为基体,采用添加法研制了一种含腹泻性贝类毒素软海绵酸(OA)的冻干粉形式的贝类毒素基体标准物质.采用LC-MS/MS法,以多家定值的方式对标准物质中的OA进行定值.均匀性检验结果表明该样品均匀,短期稳定性和6个月的稳定性考察表明样品稳定性良好.经过对影响定值结果的称样量、定容、校准物、校准曲线等因素的考察,进行不确定度评定,标准物质中OA的含量及不确定度为2.96土0.50μgOA/g(k=2).该标准物质可以用于腹泻性贝类毒素检测过程的方法验证与质量控制等.     

氮中43组分TO-14VOCs标准气体的研制

研制了浓度约为1×10~(-6)(mol/mol)氮中43组分TO-14 VOCs标准气体[GBW(E)062376]。该标准气体根据GB/T 5274严格按照配制气体标准物质的基本方法称量法制备及定值。利用研究开发的气质联用法对其进行了均匀性和稳定性检验。还将其与国际公认的同类标准气体进行了比对,并经国内最具权威性部门中国计量科学研究院进行检测验证。     

3-硝基-1,2,4-三唑-5-酮标准物质的制备

介绍了3-硝基-1,2,4-三唑-5-酮(NTO)标准物质的制备方法。以工业品NTO为基体,经热过滤除去机械杂质、重结晶、低沸点溶剂煮洗、真空干燥等步骤,制备出均匀、稳定的NTO标准物质。使用液相色谱测试主体成分含量,对制备的标准物质进行了均匀性初检,并进行均匀性、稳定性评价研究。研究结果表明,NTO标准物质纯度达到99.91%,均匀性良好,稳定性在一年以上,达到了标准物质的技术指标要求。     

Species-specific GC/ICP-IDMS for trimethyllead determinations in biological and environmental samples

An accurate and sensitive species-specific isotope dilution GC/ICPMS method was developed for the determination of trimethyllead (Me3Pb+) in biological and environmental samples. A trimethyllead spike was synthesized from 206Pb-enriched metallic lead by reaction of lead halide with methyllithium and subsequent formation of trimethyllead iodide. The isotopic composition of the spike solution was determined by GC/ICPMS after derivatization with tetraethylborate, and its concentration was determined by reverse isotope dilution analysis. The species-specific GC/ICP-IDMS method was validated by reference material CRM 605 (urban dust) certified for Me3Pb+. The method was also applied to determine the Me3Pb+ content in six biological reference materials (DORM 2, CRM 278, CRM 422, CRM 463, CRM 477, MURST-ISS-A2) and one sediment reference material (CRM 580) for which no certified values of this species exist. The Me3Pb+ concentrations in the biological reference materials vary in the range of 0.3-17 ng g(-1) (as Pb) except for the Antarctic Krill (MURST-ISS-A2), where the concentration was less than the detection limit of 0.09 ng g(-1), which was also found for the sediment. Up to 20% of total lead was methylated in the biological reference materials, whereas much higher methylation fractions were found for mercury. The method was also applied to seafood samples purchased from a supermarket with Me3Pb+ concentrations in the limited range of 0.3-0.7 ng g(-1). On the contrary, the portion of methylated lead in these samples varied over more than 2 orders of magnitude from 0.02 to 7.5%.     

多孔和高分散材料比表面积、孔结构标准物质研究进展

多孔和高分散材料比表面积、孔结构标准物质在相应仪器设备的校准、分析方法的确认、产品质量的控制等方面具有重要的作用。本文中简述了物理吸附法、压汞法测量多孔和高分散材料比表面积、孔结构的基本原理以及国内外相应分析测量标准的现状,重点讨论了国外多孔和高分散材料物理吸附法和压汞法比表面积、孔结构标准物质的研究现状,指出了我国相应标准物质研制存在的不足以及今后应努力的方向。     

Octadecyl immobilized surface for precipitate collection with a renewable microcolumn in a lab-on-valve coupled to an electrothermal atomic absorption spectrometer for ultratrace cadmium determination

Octadecyl immobilized surface was, for the first time, proved to be a superb precipitate-collecting medium. Surface charge effect was assumed to dominate the adsorption of cadmium hydroxide precipitate, facilitated by electrostatic interaction between the negatively charged C18 bead surface and positively charged cadmium hydroxide clusters. Residual silanol groups on the C18-immobilized silica surface did not contribute to precipitate adsorption. A novel procedure for ultratrace cadmium preconcentration was proposed by incorporating a renewable microcolumn in a lab-on-valve system. Cd(OH)(2) precipitate was adsorbed onto the C18 surface, which was afterward eluted with 20 microL of nitric acid (1%) and quantified with detection by electrothermal atomic absorption spectrometry. An enrichment factor of 28 and a limit of detection of 1.7 ng L(-1), along with a sampling frequency of 13 h(-1) were obtained with a sample consumption of 600 microL within the concentration range of 0.01-0.2 microg L(-1), achieving a precision of 2.1% RSD at the 0.05 microg L(-1) level. The enrichment factor was further enhanced to 44 by increasing the sample volume to 1200 microL. The procedure was validated by analyzing cadmium in three certified reference materials, that is, river sediment (CRM 320), sea lettuce (CRM 279), and frozen cattle blood (GBW 09140). Good agreement between the obtained results and the certified values was achieved.     

Electrothermal atomic absorption spectrometric determination of total and hexavalent chromium in atmospheric aerosols

A method was developed which allow separate determination of Cr(VI) and total Cr from the same minute sample of atmospheric aerosols. Cr(VI) was leached was with 0.1M Na(2)CO(3) and the total Cr concentrations were determined after acid digestion. The method was validated by the analysis of certified reference materials, CRM 545, Mess-3 and Pacs-2 with good agreement between certified and found values. Cr concentrations in air samples taken around the chromium smelter show concentrations that exceed the maximum allowed levels in 8h with higher values closer to the smelter. The limit of detection (LOD) of the method for Cr(VI) determination in air samples was found to be 0.2 ng m(-3), i.e. lower than offered by the commonly preferred spectrophotometric and colorimetric techniques.     

Development and evaluation of a candidate reference measurement procedure for the determination of progesterone in human serum using isotope-dilution liquid chromatography/tandem mass spectrometry

Progesterone is a steroid hormone that is involved in regulating female reproductive processes. Its concentration in blood is measured to determine ovarian function. A candidate reference measurement procedure for progesterone in human serum involving isotope dilution coupled with liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been developed and critically evaluated. The progesterone along with its internal standard (progesterone-13C2) was extracted from the serum matrix using liquid-liquid extraction prior to reversed-phase LC/MS/MS. The accuracy of the measurement was evaluated by a comparison of results of this method on a lyophilized human serum reference material for progesterone [Certified Reference Material (CRM) 347] with the certified values determined by gas chromatography/mass spectrometry (GC/MS) reference methods and by a recovery study for the added progesterone. The results of this method for progesterone agreed with the certified value within the uncertainty of the measurements for the CRM 347. The recovery of the added progesterone ranged from 100.1 to 100.9%. This method was applied to the determination of progesterone in frozen serum samples from three individual female donors with the progesterone concentrations ranging from 0.151 to 24.42 ng/g. Excellent reproducibility was obtained with within-set coefficients of variation (CVs) ranging from 0.1 to 1.4%, and between-set CVs ranging from 0.3 to 0.5%. Excellent linearity was also obtained with correlation coefficients of all linear regression lines (measured intensity ratios vs mass ratios) ranging from 0.9998 to 1.0000. The detection limit at a signal-to-noise ratio of approximately 3 was 1.8 pg of progesterone. This well-characterized LC/MS/MS method for serum progesterone, 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 progesterone can be compared and that will serve as a standard of higher order for measurement traceability.     

Problems Involved in Using Improper Calibration CRMs in Geochemical Analyses: A Case Study on Mafic Rocks of Boggulakonda Pluton, East of Cuddapah Basin, India

The performance and response of two commonly used certified reference materials (CRMs) for mafic rocks MRG-1 (CANMET, Canada) and JGb-1 (Geological Survey of Japan), both gabbroic in composition, are evaluated for a set of mafic plutonic rocks (gabbros) from Boggulakonda (BK) occurring to the east of Proterozoic Cuddapah Basin, South India. In this study, quadrupole-inductively coupled plasma mass spectrometry was used to generate trace and rare earth element (REE) data using MRG-1 and JGb-1 as calibration standards separately for a comparative study. It is found that the two CRMs show highly variable major, minor and trace element compositions except ΣREE. When used for BK gabbros, JGb-1 has yielded better results than MRG-1 with respect to trace elements (HFS elements Nb and Ta in specific), whereas a good agreement was observed between both CRMs for REE concentrations when compared with certified data. The Nb–Ta element distribution patterns for BK gabbros in the spidergrams plotted using JGb-1 as CRM show relatively prominent and pronounced negatively spiking anomalies with reference to Th, whereas using MRG-1 as calibration CRM yielded unresolved and unclear Nb–Ta anomalies in the present study. The geochemistry (major, minor and trace) of MRG-1 is different when compared to that of JGb-1. Probably this is reason for the disparity in the results obtained by inductively coupled plasma mass spectrometry on mafic plutonic rocks. The study conducted on the BK gabbros, reveals better and reliable results using JGb-1 as CRM. This study also reveals the importance of using proper CRM for calibration having closely matching trace and REE concentrations in addition to major and minor elements, for obtaining reliable data in geological samples.     

异辛烷热值标准物质

采用国家固体燃烧热基准,即电能标定的等温式氧弹热量计,为异辛烷热值标准物质定值。通过电能标定热量计的热容量,使热值结果溯源到温度、电流、时间和质量等国际单位上。采用自制的聚乙烯胶囊盛装异辛烷,避免了样品挥发引入的质量测量和不完全燃烧的系统误差。异辛烷热值标准物质在标准状态下的高位发热量为47777 J/g,扩展不确定度为52 J/g（扩展因子k=2）。     

河流沉积物环境放射性标准物质的研制

研制出一种天然基质的河流沉积物环境放射性标准物质。由多个实验室用多种准确可靠的方法对其中９种天然的和人工的放射性核素进行了定值。介绍样品制备、均匀性及稳定性检验、核素定值方法和定值结果。