锑矿石化学物相分析方法精密度的确定与评估

长期以来化学物相分析方法的精密度一直没有得到科学的量化控制,实验室间的精密度更是缺少控制限要求。实验在建立我国具有代表性锑矿石化学物相分析方法的过程中,按照标准GB/T6379.2—2004《测量方法与结果的准确度(正确度与精密度)第2部分:确定标准测量方法重复性与再现性的基本方法》,通过配制6个水平的协作试验样品,选择Al_2O_3、TFe(以Fe_2O_3形式表示)、CaO、MgO、Sb、S等主量组分或元素进行均匀性检验,检验结果 F值均小于临界值4.39,表明试验样品是均匀的。组织8家实验室进行协作试验,获得锑总量和3个锑矿物相中的锑随质量分数(m)变化的重复性限(r)和再限性限(R),结果表明,在确定的矿石中总锑和各矿物相中锑的重复性限和再现性限中,总锑的重复性限和再现性限最小,均小于锑矿石各相态分析的重复性限和再现性限,化学物相分析方法重复性限和再现性限参数验证了化学物相分析误差主要来源于串相误差的基本特性。锑矿石化学物相的精密度为锑矿石化学物相分析标准方法的建立和质量控制提供了依据。     

Indirect and direct determination of the casein content of milk by Kjeldahl nitrogen analysis: collaborative study

The classic method for determination of milk casein is based on precipitation of casein at pH 4.6. Precipitated milk casein is removed by filtration and the nitrogen content of either the precipitate (direct casein method) or filtrate (noncasein nitrogen; NCN) is determined by Kjeldahl analysis. For the indirect casein method, milk total nitrogen (TN; Method 991.20) is also determined and casein is calculated as TN minus NCN. Ten laboratories tested 9 pairs of blind duplicate raw milk materials with a casein range of 2.42-3.05% by both the direct and indirect casein methods. Statistical performance expressed in protein equivalents (nitrogen x 6.38) with invalid and outlier data removed was as follows: NCN method (wt%), mean = 0.762, sr = 0.010, sR = 0.016, repeatability relative standard deviation (RSDr) = 1.287%, reproducibility relative standard deviation (RSDr) = 2.146%; indirect casein method (wt%), mean = 2.585, repeatability = 0.015, reproducibility = 0.022, RSDr = 0.560%, RSDR = 0.841; direct casein method (wt%), mean = 2.575, sr = 0.015, sR = 0.025, RSDr = 0.597%, RSDR = 0.988%. Method performance was acceptable and comparable to similar Kjeldahl methods for determining nitrogen content of milk (Methods 991.20, 991.21, 991.22, 991.23). The direct casein, indirect casein, and noncasein nitrogen methods have been adopted by AOAC INTERNATIONAL.     

氯化钙法分析土壤中重金属可提取态的精密度探讨

精密度是实验室进行质量控制的主要技术指标。目前,氯化钙法分析土壤中重金属可提取态的精密度控制指标尚未建立。采集制备5个水平土壤样品,分层随机抽取15瓶样品进行均匀性检验,分析结果采用单因素方差分析法评价,表明5批土壤样品均匀性良好。组织8家实验室开展了氯化钙法分析土壤中Cd、Cu、Ni、Zn等4种重金属可提取态的精密度试验,按照国标方法GB/T 6379.2—2004《测量方法与结果的准确度 第2部分:确定标准测量方法重复性与再现性的基本方法》进行统计分析,采用科克伦(Cochran)准则和格拉布斯(Grubbs)准则检验单元间试验数据精密度和平均值的一致性,评价了方法的重复性限(r)和再现性限(R)等精密度指标。其中Cd、Cu、Ni、Zn在0.143~7.69、0.40~24.7、0.32~2.55、3.09~181 mg/kg含量范围内,重复性限分别在0.013~0.32、0.04~1.4、0.02~0.11、0.18~7.8 mg/kg之间;再现性限分别在0.032~0.64、0.10~5.8、0.08~0.61、0.31~20 mg/kg之间。通过将重复性限和再现性限与其含量进行迭代回归统计分析,确定了分析方法重复性限和再现性限与含量的函数关系式,并进行了初步实验验证,为氯化钙法分析土壤中重金属可提取态的质量控制提供了科学依据,也为该标准方法的制订提供了数据支持。     

硫酸亚铁铵滴定法测定铁矿石中钒含量国家标准研究

通过对硫酸亚铁铵滴定法测定铁矿石中钒含量方法的研究,对原国家标准GB／T6730．32—1986进行修订,新国标增加了碳酸钠一硼酸混合熔剂熔融分解试样,优化了指示剂校正和空白测定及铬干扰的消除方法,同时进行了精密度试验,用精密度（重复性限和再现性限）代替了原标准的允许差。     

应用能力验证结果评定火花源原子发射光谱法测定低合金钢中镍的方法精密度研究

应用能力验证结果,研究一种分析方法精密度的评定方法。利用6个轮次能力验证中,采用火花源原子发射光谱法(SS-AES)测定不同含量水平的低合金钢中Ni含量的结果数据,对方法的精密度进行评定,建立了重复性限r和再现性限R的拟合计算公式。采用组内相关系数(ICC)法,对拟合公式计算结果与国家标准中的精密度公式计算结果的一致性进行了评价,重复性限r和再现性限R的组内相关系数分别为ICC_r =0.99,ICC_R=0.94,表明拟合公式信度良好,拟合公式与国家标准方法的精密度公式非常一致。     

实验室测量结果的评价

为了正确、合理评价分析方法和测试数据,依据分析测试的测量参数、分析方法的精密度参数（重复性限和再现性限）以及实验室间共同试验数据,用数理统计方法论证测量结果的精密度和正确度,给出了实验室测量结果精密度和正确度检验的方法。试验数据的统计结果可作为分析方法的选择、分析测试数据精度和正确度的评定、实验室内和实验室间测试数据的比对、标准物质定值分析数据评定的判据。所提出的检验方法建立在数理统计和共同试验数据的基础上,有很好的可靠性和实用性。     

火花源原子发射光谱仪分析低合金钢中碳的重复性和再现性研究

研究了火花源原子发射光谱仪分析低合金钢中碳的重复性和再现性.实验采用低合金钢标准样品在5台光谱仪上测试含碳量.采用统计方法分析了测试数据,剔除异常数据后计算了质量水平(m)、重复性(r)和再现性(R),并在此基础上建立了r-m,R-m的回归方程.将该方法得到的重复性和再现性结果与国内外的标准进行了比较,同时说明重复性和再现性的应用.通过分析发现碳的重复性优于国家标准,劣于JIS标准,碳的再现性与标准相比还有差距.     

辉光放电原子发射光谱法测定钢铁表面纳米尺度薄膜厚度的重复性和再现性

以辉光放电原子发射光谱法测定钢铁表面纳米尺度薄膜的厚度为例进行了膜厚测定的多家实验室共同试验。对共同试验的结果进行了计算,得到相应的重复性和再现性数据,得出膜厚与重复性之间的关系为:lgr=0.018 3+0.459 6 lgm;膜厚与再现性之间的关系为:lgR=0.140 9+0.485 lgm。并对共同试验中出现的准确度问题——薄膜的密度和最小光源稳定时间进行了讨论。     

电感耦合等离子体原子发射光谱法测定高硫铜磁铁矿中硫

铜磁铁矿作为冶炼铜和铁的重要原料,有害元素硫含量较高。试样经逆王水消解、氢氟酸挥硅和高氯酸进一步氧化后,在硝酸体系中,选择S 182.034nm为分析谱线,使用铁基体匹配的标准溶液系列绘制校准曲线消除基体效应的影响,使用电感耦合等离子体原子发射光谱法(ICP-AES)测定高硫铜磁铁矿中硫。硫质量浓度为0.10~150μg/mL时与其发射光谱强度呈良好的线性关系,线性相关系数为0.9998;方法检出限为0.0135%。实验方法用于测定5个含量水平高硫铜磁铁矿样品中硫,测定结果的相对标准偏差(RSD,n=11)为2.1%~3.7%,与高频燃烧红外吸收法的测定结果没有显著性差异。方法的重复性标准差为S_r=0.0135x+0.0143,重复性限为r=0.0379x+0.0396,再现性标准差为S_R=0.0232x+0.0137,再现性限为R=0.0653x+0.0383。     

电感耦合等离子体原子发射光谱法测定高硫铜磁铁矿中硫

铜磁铁矿作为冶炼铜和铁的重要原料,有害元素硫含量较高。试样经逆王水消解、氢氟酸挥硅和高氯酸进一步氧化后,在硝酸体系中,选择S 182.034nm为分析谱线,使用铁基体匹配的标准溶液系列绘制校准曲线消除基体效应的影响,使用电感耦合等离子体原子发射光谱法(ICP-AES)测定高硫铜磁铁矿中硫。硫质量浓度为0.10~150μg/mL时与其发射光谱强度呈良好的线性关系,线性相关系数为0.9998;方法检出限为0.0135%。实验方法用于测定5个含量水平高硫铜磁铁矿样品中硫,测定结果的相对标准偏差(RSD,n=11)为2.1%~3.7%,与高频燃烧红外吸收法的测定结果没有显著性差异。方法的重复性标准差为S_r=0.0135x+0.0143,重复性限为r=0.0379x+0.0396,再现性标准差为S_R=0.0232x+0.0137,再现性限为R=0.0653x+0.0383。     

Cardiovascular anatomy and physiology in the female

A flow-injection analysis method for the determination of albumin tannate in tablets is reported. After optimization of the variables involved, the method has been characterized and validated in terms of calibration using three procedures: repeatability and reproducibility; ruggedness; and selectivity. Finally, it has been applied to real samples (tablets).     

S400G中硫含量检测的不确定度评定

测量不确定度是反映被测量值的分散性、与测量结果相联系的参数,是对测量结果质量的定量表征。结合宝钢特钢检测中心炼钢炉前分析作业区的生产实际,依照国标GB/T 20123—2006,运用高频燃烧红外吸收法对S400G中硫含量进行分析,对样品的测量重复性分量、校正时测量变动性分量进行了A类不确定度评定,对标准物质硫含量分量、称量引起的分量、仪器显示分辨率的分量分别进行了B类不确定度评定,明确了评定过程所需参数的数据采集和计算方法。结果表明,采用高频燃烧红外吸收法的检测可信度较高,同时也为其他钢种的高硫含量测量评定提供了参考依据。     

Peptide separation in normal phase liquid chromatography

A new method is established for separating peptides in normal phase liquid chromatography using TSK gel Amide-80, carbamoyl groups bonded to a silica gel matrix, and an acetonitrile-water solution containing 0.1% trifluoroacetic acid. Peptide retention time increased with acetonitrile concentration in the initial eluent. Hydrophilic peptides with no retention in a reversed phase column were retained and separated in the present method. Separation selectivities in the present and reversed phase methods differed significantly. Two-dimensional separation of protein digest using reversed and normal phases was conducted, taking advantage of the differences in selectivities. All peptides obtained from the digest could be separated completely. The present method is useful for separating peptide mixtures in conjunction with reversed phase liquid chromatography. Peptide recovery from the Amide-80 column exceeded 80%, as with the reversed phase column, and repeatability and reproducibility were satisfactory.     

"Aggrecanase" activity is implicated in tumour necrosis factor alpha mediated cartilage aggrecan breakdown but is not detected by an in vitro assay

An accurate analysis of the morphological changes which take place during pathological processes of the posterior pole is important for a correct diagnosis and therapeutic approach. The purpose of the study was to determine the intraobserver and interobserver reproducibility of the Image-net system 100 (Topcon, Japan) to take measurements on the retina. The program 'Linear/Areal Measurement functions' of Image-net system 100 which is an image digitalization technique, was tested. Twelve patients were consecutively selected from the patients of the Retina Center of the Department of Ophthalmology, University of Genoa. Three images of each eye were taken from each subject and only the best image was used in this study. The intraobserver and interobserver reproducibility of both the distance between two pre-set points (linear measurement), and the perimeter and area of preselected retinal zones were calculated. The repeatability (or intraobserver reproducibility) of the linear sizes was measured by the coefficient of variation and ranged from 0.32% to 7.38%, while the interobserver reproducibility ranged from 0.46% to 5.22%. The repeatability and reproducibility of the perimeters ranged from 0.72% to 9.63% and from 0.6% to 5.7%, respectively, while the repeatability and reproducibility of the areas ranged from 0.72% to 9.63% and from 0.6% to 5.7%, respectively. Although the results were quite good, the quality of the image of the fundus and the number of observers influenced the coefficient of variation; furthermore, the anatomy of the areas to be measured and the computer 'mouse' could increase the value of the coefficient of variation.     

A comparison of sonically derived and traditional cephalometric values

The roentgenocephalometric technique is the standard used by orthodontists to assess skeletal, dental, and soft-tissue relationships. However, this technique exposes patients to radiation, preventing orthodontists from taking frequent cephalograms to assess growth and to monitor treatment. Recently, the Dolphin Imaging Company developed the DigiGraph, a nonradiographic cephalometric method that uses sound waves and mathematical algorithms, and consequently does not expose patients to radiation. But the DigiGraph's accuracy as a cephalometric alternative has not been adequately investigated. The purpose of this study was to compare the values obtained by traditional cephalometrics with those obtained by the DigiGraph technique for 30 well-known measurements, and then to assess the repeatability (intraobserver comparison) and reproducibility (interobserver comparison) for both techniques. Eighteen of the 30 measurements had mean differences that were statistically significant (p > .0067). Regression plots generally illustrate low correlations for the measurements, although Ricketts' esthetic line (upper and lower lip) and Steiner's soft-tissue convexity reveal strong linear relationships between the two methods. Additionally, the radiographically generated measurements showed greater repeatability and reproducibility.     

MSA在钢的化学成分分析中的应用

介绍了测量系统和测量系统分析(MSA)的概念及意义,重点阐述了开展测量系统的重复性和再现性分析的步骤和方法,以钢中磷元素成分分析的测量系统的重复性和再现性分析为例,介绍了运用Minitab软件对钢中化学成分分析系统进行测量系统分析的新方法及应用。     

火焰原子吸收光谱法测定红土镍矿中铜含量

The laterite nickel ore sample was decomposed with hydrochloric acid, nitric acid, hydrofluoric acid and perchloric acid. Then, in diluted nitric acid medium, the content of copper was determined on flame atomic absorption spectrometry at 324.8 nm. The background was deducted with deuterium lamp. Under optimized experimental conditions, the absorbance is linear with copper concentration in the range of 0.50-2.50 mg/L. The limit of determination was 0.057 mg/L. The recoveries obtained by standard addition method range from 91% to 103%.Copper content range from 0.01% to 0.50%, the equation of repeatability and reproducibility are r=0.114 8m+0.003 2 and R=0.130 0 m+0.007 4. This method was applicable for the determination of laterite nickel ore with copper content of 0.01%-0.50%.     

High performance liquid chromatographic method for the determination of lobenzarit disodium in a sustained release tablet formulation

A rapid and simple high performance liquid chromatographic method is described and validated for the determination of lobenzarit disodium (CAS 64808-48-6) in a sustained release tablet formulation. The calibration graph was linear over the range 20-105 micrograms/ml. The sensitivity (discriminator capacity) was 2.079 micrograms/ml. The coefficient of variations for repeatability and reproducibility were less than 1.60% and 1.30%, respectively. The accuracy of the method did not depend on lobenzarit concentration in tablets. The mean recovery was found to be 100.62%. The method was selective, even when degradation products were present.     

火试金重量法测定载金炭中的金量

建立了样品焙烧处理一火试金重量法测定载金炭中的金量;经过了一系列条件实验,分别确定了称样量范围、焙烧温度、配料、熔样温度、分金时间、分金酸度及金银质量比例等最佳实验条件。在最佳实验条件下,该方法加入标准物质的回收率为99．85％-100．1％,与原子吸收光谱法对比,体现了更好的重复性和再现性。在载金炭交易中,该方法被推荐为仲裁分析方法。     

Morphometric assessment of enamel demineralisation from photographs

OBJECTIVES: To investigate the validity and reproducibility of a method of morphometric assessment of enamel demineralisation. METHODS: An in vitro investigation was carried out on 22 human teeth. One investigator coated the crowns of the teeth with an acid-resistant varnish, leaving a small window on the buccal surface. This was incrementally occluded by varnish over a 14-day period, during which the teeth were placed in a demineralising gel at pH 4.5. After varnish removal, a second investigator blindly quantitated the demineralised area by three methods of examination; direct visual, microscopic and from photographs. The microscopic and photographic measurements were carried out using a morphometric assessment with a 121-dot array. Photographs and assessments were repeated after 1 week. The readings were analysed using the kappa statistic, the limits of agreement and the coefficient of repeatability. RESULTS: Photographic assessments demonstrated excellent agreement for grid positioning (kappa > 0.81) and substantial agreement for reading reproducibility (kappa = 0.61-0.80). The coefficients of repeatability were found to be the same for repeat readings of the same slide and the repeated slides (5.0 mm2). They were higher for the microscopic technique (6.8 mm2) and for the direct visual technique (7.8 mm2). The limits of agreement are presented graphically. CONCLUSIONS: The photographic technique used was a reproducible method of measuring artificial enamel demineralisation. Measurement from photographs was more reproducible than direct measurement with the naked eye. Subjectiveness of the index leads to most variation and more objective means of assessing enamel demineralisation need to be found.