低比表面积标准物质的研制

选择商品化的Al2O3颗粒作为低比表面积标准物质候选材料,利用交叉缩分方法对标准物质样品进行分装。经均匀性、稳定性(12个月)检验,标准物质样品具有良好的均匀性和稳定性。采用国际公认的氪气物理吸附BET方法,通过与德国BAM标准物质BAM-PM101比较测量的方式对标准物质样品进行定值(0.221 m2/g)。与国内外同类标准物质比较表明,研制的低比表面积标准物质GBW(E)130365填补了国内空白,其相对不确定度(5.9%)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。     

甲醇纯度国家一级标准物质的研制

介绍了甲醇纯度标准物质的研制方法,采用国际基准方法之一的凝固点下降法对该标准物质进行了定值,利用气相色谱法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.甲醇纯度标准物质定值结果为99.7%,扩展不确定度为0.3%.其均匀性和稳定性检验结果表明,该标准物质符合国家一级标准物质的技术要求.     

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。     

一种燃料热沉标准物质候选物的纯度定值及不确定度分析

一种多环烃化合物作为超声速飞行器用燃料热沉标准物质候选物,对于燃料的热沉准确计量具有十分重要的意义。通过采用质量平衡和核磁定量两种不同测量原理的方法,对这种热沉标准物质候选物的纯度进行了定值,并进行了不确定度分析和评定。在此过程中,采用气相色谱法(GC-FID)对候选物的分装样品进行了均匀性检验和稳定性考察。研究结果表明,标准物质候选物纯度均匀性良好,且在１年常规储存条件下(20 ℃,101.325kPa)具有良好的稳定性。标准物质候选物定值结果的标准值为99.42%, 扩展不确定度为0.84%(k=2)。     

水中硒成分分析标准物质研制

以高纯硒、高纯盐酸和三次纯化水为原料,在对高纯硒的纯度进行定值的基础上,采用重量—容量法制备了水中硒成分分析标准物质。分别采用F检验和直线拟合法对研制的标准物质进行均匀性检验和稳定性考察。结果表明,研制的水中硒成分分析标准物质具有很好的均匀性和短期、长期稳定性,标准值为1 000μg/m L,相对扩展不确定度U_(rel)=1%(k=2),采用电感耦合等离子体发射光谱法与国内同类标准物质比对,表明该标准物质量值准确且具有溯源性。     

2,3,4-三氯苯甲醚标准物质研制与定值

研制了2,3,4-三氯苯甲醚标准物质,介绍了其制备与定值方法。将制备的2,3,4-三氯苯甲醚标准物质分装成500瓶样品,随机抽取其中11瓶做均匀性检验,经F检验和t检验,结果表明在95%置信范围内样品均匀性良好。按短期与长期稳定性分别进行稳定性检验,结果表明在常温20℃下,2,3,4-三氯苯甲醚的稳定期不少于12月。采用液相色谱法和差示扫描量热法2种不同原理的方法对2,3,4-三氯苯甲醚标准物质纯度定值及不确定度评定,并采用液相色谱标准添加的方法确认了2,3,4-三氯苯甲醚标准物质中的主要杂质2,3,6-三氯苯甲醚。定值结果为99.56%± 0.40%（k=2）。     

氮中微量氧气体标准物质分析方法和定值方法的研究（下）

介绍了氮中微量氧标准气体的分析方法,给出了分析条件和方法的精密度,并对该标准气体配制的均匀性、稳定性的实验结果进行了分析与考察,对该气体标准物质的性能进行了评价。氧含量在(2~10)μmol/mol浓度范围气体标准物质定值不确定度<±2%;氧含量在(20~100)μmol/mol浓度范围气体标准物质定值不确定度<±1%,取得了国际的等效性。     

氮中微量氧气体标准物质分析方法和定值方法的研究 (上)

介绍了氮中微量氧标准气体的分析方法,给出了分析条件和方法的精密度,并对该标准气体配制的均匀性、稳定性的实验结果进行了分析与考察,对该气体标准物质的性能进行了评价。氧含量在(2~10)μmol/mol浓度范围气体标准物质定值不确定度<±2%;氧含量在(20~100)μmol/mol浓度范围气体标准物质定值不确定度<±1%,取得了国际的等效性。     

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)。     

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).     

Evaluation of an ultrasonic acid digestion procedure for total heavy metals determination in environmental and biological samples

In this study, a sample preparation method based on ultrasonic assisted acid digestion (UAD) has been evaluated for total heavy metals (Cd, Cr, Ni and Pb) determination in different environmental (soil, sediment and sewage sludge), and biological (fish muscles, vegetables and grains) samples, using electrothermal atomic absorption spectrometry (ETAAS). The investigated parameters influencing UAD such as presonication time, sonication time, temperature of ultrasonic bath, and different acid mixtures were fully optimized, whereas power was maintained constant at 100% of nominal power of ultrasonic bath. Six different sets of above parameters were applied on six certified reference materials (CRMs) having different matrices. The accuracy of the method was also tested by comparing the results with those obtained from conventional hot plate assisted acid digestion method on same CRMs. Analytical results for HMs by both methods showed no significant difference at 95% confidence limit (p<0.05). Recoveries of HMs ranging from 96.2% to 102% and 96.3% to 98.6% were obtained from biological and environmental samples, respectively. The average relative standard deviation of UAD method varied between 3.5% and 8.2%, depending on the analyte.     

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.     

Pore development process according to burn-off of activated carbon black with CO2 gas

Abstract

This study examined the pore development of carbon black according to burn-off (BO) ratio of carbon black activated in CO₂atmosphere. A horizontal tube furnace was charged with carbon black when the internal temperature reached 1000?°C, and activation time was adjusted to obtain BO ratios of 7.2%, 15.4%, 30.4%, 48.2%, 59.9%, and 83.2%. SEM observations showed that the primary particles of carbon black were aggregated, and varying BO ratios did not cause significant differences in shape and size. Carbon black was presumed to contain pores since the size of primary particles remained largely the same with varying BO ratios, and TEM observation revealed that pores existed within primary particles. The nitrogen adsorption isotherms were of type IV, which is characterized by a hysteresis loop. The specific surface area of raw carbon black was 61.4 m²/g, while that of BO at 83.2% increased 18.0 times to 1107.6 m²/g.     

获取优良分散性炭黑的表面硝酸氧化

为得到具有良好分散性的炭黑,考察其表面的化学性质,利用硝酸长时间氧化,用沉降度检测炭黑的分散性,并利用红外光谱、X射线光电子能谱及激光粒度仪检测其表面的物化性质.研究表明:硝酸氧化增加了炭黑的表面含氧量及炭黑的酸性,使炭黑的分散性得到了极大的提高;硝酸氧化在炭黑表面引进了羧基基团和羟基基团.     

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.     

Certified reference materials of trace elements in water

Measurement of trace elements is playing a vital role in industries and various sectors of science and technology including semiconductors, food, health and environmental sectors. In most of the cases a small error in measurement can vitiate all the measures taken for quality control and management. Many decisions regarding the suitability of material/products are based on the analysis. To reduce or eliminate the rejection rate of the products, accurate and reliable measurements are needed which can be achieved by the use of certified reference materials (CRMs). Their use in calibration of analytical equipments and validation of test methods ensures high quality in measurements and it provides traceability to the measurement data with national/international measurement systems (SI unit) also. In the present scenario of globalization of economy, use of certified reference materials (CRMs) in measurements is essential for global acceptance of products and test reports. Their use fulfil a mandatory requirement of international quality systems (ISO 9000, ISO/IEC standard 17025) including our national accreditation body, National Accreditation Board for Testing and Calibration Laboratories (NABL), World Trade Organization (WTO) etc. International manufacturers of CRMs are meeting most of the requirement of CRMs of the country. To meet the demand of CRMs indigenously, the National Physical Laboratory, India initiated a national programme on preparation and dissemination of certified reference materials.     

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.