Can the usual validation standard series for quantitative methods,ISO 5725, be also applied for qualitative methods?

Repeatability standard deviation, laboratory standard deviation, and reproducibility standard deviation for quantitative methods according to ISO 5725 series were recently proposed to estimate the precision of qualitative measurements, giving a presence/absence response. In this paper, it is shown that for qualitative methods, the reproducibility standard deviation across laboratories does not reflect the performance of the method as suggested. It is demonstrated that the benefit of the respective laboratory standard deviation is very limited. Alternative performance measures are introduced which are based on another approach also directly linked to ISO 5725. Thereby, meaningful information about the precision of qualitative test methods can be achieved.     

Interpretation of the measurement results near the detection limit in gamma-ray spectrometry using Bayesian statistics

The requirement that the true value of an activity cannot be negative is used for the transformation of raw observed values, which can be positive or negative, into the expected activity values. The probability distribution of the activity values is a truncated Gaussian distribution, and the expected value and the variance of the activity values are derived from the observed value and its standard deviation. It has been shown that the standard deviation of the activity values is smaller than the standard deviation of the observed value and that the ratio of the standard deviation of the activity values and the expected value is less than unity. Since the expected activity value is larger than the original observed value, and the standard deviation of the activity values is smaller than the standard deviation of the observed value, the additional information, that the activity cannot be negative, leads to an improvement in the result. However, since the expected activity value depends on the standard deviation of the observed value, conservatively assessed standard deviation lead to a bias of the expected activity values.     

Liquid chromatographic determination of maleic hydrazide in technical and formulated products: collaborative study

Fourteen collaborating laboratories assayed maleic hydrazide (MH), 6-hydroxypyridazin-3(2H)-one, in technical and formulated products by reversed-phase liquid chromatography (LC) with sulfanilic acid as an internal standard. The active MH in the samples (6 lots) ranged from 16% (expressed as the potassium salt) to 98% (MH in the technical). A small amount of 1 M KOH was added to the technical MH and analytical standards to create the potassium salt of the analyte which is soluble in water. Test samples and standards were extracted with water containing the internal standard before analysis by LC on a C8 column with an ion-pairing eluting solution and UV detection at 254 nm. The concentration of MH was calculated by comparing the peak area response ratios of the analyte and the internal standard with those in the analytical standard solution. Eleven laboratories weighed each test sample twice with single analysis. Three laboratories weighed each sample once and made duplicate injections on the LC system. The data were analyzed using the 11 laboratories' results. A second data analysis was done including all laboratory results using a Youden pair approach, selecting one of 2 duplicate assay values randomly for each laboratory and sample. In the first data analysis, the repeatability standard deviation ranged from 0.07 to 1.39%; reproducibility standard deviation ranged from 0.22 to 1.39%. In the second data analysis (using all laboratory data), repeatability standard deviation ranged from 0.09 to 0.86%; reproducibility standard deviation ranged from 0.22 to 1.31%.     

空白批内标准偏差和方法检出限的计算

环境分析化学中,尤其痕量分析时,方法检出限对于监测结果的报出很重要。检出限的确定常会涉及空白标准偏差的计算。通过对一典型案例剖析,指出一部分新制修订环境标准方法采用空白批间标准偏差计算检出限是不合理的。在求算检出限时应先判断批间是否存在显著性差异。     

Estimation of measurement uncertainty in food microbiology: The ISO approach

Given the current interest in measurement uncertainty (MU) in food microbiology, in particular for laboratory accreditation purposes, and the need to have harmonized reference documents specifically in that area at the international level, ISO is conducting works to meet this need. An ISO Technical Specification (ISO/TS 19036) is being prepared on MU estimation for quantitative determinations. A global approach has been chosen, based on the reproducibility standard deviation of the final result of the measurement process. Three possibilities are envisaged for the estimation of the reproducibility standard deviation, in a decreasing order of preference: The intra-laboratory standard deviation, the inter-laboratory standard deviation derived from method validation, and the inter-laboratory standard deviation derived from proficiency testing.The uncertainty of qualitative determinations is still under investigation, and will be covered by a separate ISO publication. Presented at AOAC Europe/Eurachem Symposium March 2005, Brussels, Belgium     

Propagation of uncertainties and systematic errors in the measurements of long-lasting heat flows using differential scanning calorimetry

Results from the measurement of the heat of reaction of hydrothermal carbonization by power compensated differential scanning calorimetry exhibited a comparably high experimental standard deviation of around 10?C20%. The reasons for this standard deviation have been investigated and are being presented in this article. The zeroline deviation and its repeatability showed a decisive influence on the measurements due to the length of the thermal effects (several hours) and the experimental setup (high thermal capacity due to pressure capsules and hydrothermal conditions, type of calorimeter). It was quantified by reference runs and compensated mathematically. In addition, conceptual issues due to the propagation of uncertainty by sum operations are derived. There is an optimum peak length after which the uncertainty rises due to this uncertainty propagation. This optimum is at a signal level within the noise level. However, the contribution of this uncertainty showed little significance compared to the zeroline deviation and thus could be neglected. Results from hydrothermal carbonization of glucose show a mean value of 1060?J/g_daf with a standard deviation of 14% for the presented experimental setup. These values include compensations of systematic errors, including the zeroline deviation, baseline correction, leakage, and transient effects, which are discussed in detail.     

Detection limits and goodness-of-fit measures for the two-component model of chemical analytical error

The utility of analytical chemistry measurements in most applications is dependent on an assessment of measurement error. This paper demonstrates the use of a two-component error model in setting limits of detection and related concepts and introduces two goodness-of-fit statistics for assessing the appropriateness of the model for the data at hand. The model is applicable to analytical methods in which high concentrations are measured with approximately constant relative standard deviation. At low levels, the relative standard deviation cannot stay constant, since this implies vanishingly small absolute standard deviation. The two-component model has approximately constant standard deviation near zero concentration, and approximately constant relative standard deviation at high concentrations, a pattern that is frequently observed in practice. Here we discuss several important applications of the model to environmental monitoring and also introduce two goodness-of-fit statistics, to ascertain whether the data exhibit the error structure assumed by the model, as well as to look for problems with experimental design.     

Gene analysis of multiple oral bacteria by the polymerase chain reaction coupled with capillary polymer electrophoresis

Capillary polymer electrophoresis is identified as a promising technology for the analysis of DNA from bacteria, virus and cell samples. In this paper, we propose an innovative capillary polymer electrophoresis protocol for the quantification of polymerase chain reaction products. The internal standard method was modified and applied to capillary polymer electrophoresis. The precision of our modified internal standard protocol was evaluated by measuring the relative standard deviation of intermediate capillary polymer electrophoresis experiments. Results showed that the relative standard deviation was reduced from 12.4–15.1 to 0.6–2.3%. Linear regression tests were also implemented to validate our protocol. The modified internal standard method showed good linearity and robust properties. Finally, the ease of our method was illustrated by analyzing a real clinical oral sample using a one‐run capillary polymer electrophoresis experiment.     

Interlaboratory studies of highly permeable thin‐film composite polyamide nanofiltration membrane

The aim of this paper is to survey interlaboratory studies of performance data to produce highly permeable thin‐film composite (TFC) polyamide nanofiltration (NF) membrane in the form of flat sheet at bench scale. TFC polyamide NF membranes were fabricated via interfacial polymerization of 1,3‐phenylenediamine and trimesoyl chloride on porous polyethersulfone (PES) membrane. The NF membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross‐flow filtration. The AFM and SEM analyses indicated that a rough and dense film was formed on the PES support membrane. The permeability and NaCl rejection of the NF membrane prepared at the presence of camphor sulfonic acid as pH regulator and triethylamine as accelerator in the aqueous solution were 21 l m^?2 h^?1 and 70%, respectively. In order to estimate the repeatability and reproducibility standard deviations, the development of an interlaboratory study was conducted by measurements of permeation flux and salt rejection of the synthesized membranes. Repeatability standard deviation of the permeation flux data for the membrane based on optimum formulation was 1.99, and reproducibility standard deviation was 3.55. Also based on this trend, repeatability standard deviation of the salt rejection data was 1.57, and reproducibility standard deviation was 4.11. The American Society for Testing and Materials standard E691‐05 was used for data validation of the repeatability and reproducibility standard deviations and consistency statistics. Copyright © 2011 John Wiley & Sons, Ltd.     

液液萃取-GC-MS法测定水中硝基苯质量控制指标研究

采用液液萃取–气相色谱–质谱法测定水中硝基苯,通过统计全国多家实验室的测定数据,对平行样测定结果相对偏差、空白加标回收率、样品加标回收率、空白加标回收率相对偏差及样品加标回收率相对偏差5个质控指标进行分析,得出质控指标评价标准。在概率P,γ均为0.90时,平行样测定结果允许最大相对偏差应控制在11.0%;当空白加标浓度为0.2～30μg/L时,回收率控制范围为59%～113%;当样品未检出、加标浓度在0.25～50μg/L时,样品加标回收率控制范围为56%～110%;空白加标、样品加标回收率最大相对偏差应分别控制在10.0%和11.1%。在概率P和γ均为0.95时,平行样测定结果允许最大相对偏差应控制在13.5%;当空白加标浓度为0.2～30μg/L时,回收率的控制范围为50%～122%;当样品未检出、加标浓度在0.25～50μg/L时,样品加标回收率控制范围为49%～117%;空白加标、样品加标回收率最大相对偏差应分别控制在12.6%和14.6%。     

The performance-characteristics of analytical methods-II

Statements on the errors of analytical results are an important aspect of characterizing the performance of analytical methods. The general nature of random and systematic errors is briefly discussed, and methods of numerically defining the former are considered. It is suggested that the standard deviation of analytical results be used exclusively as the quantitative measure of precision within the context of performance-characteristics. Techniques for, and precautions to be observed in, estimating standard deviation are critically discussed. On this basis, general principles are proposed that should be observed whenever possible in experimental tests to estimate standard deviation.     

Determination of uranium in electro-refined plutonium by a combined ion-exchange and x-ray fluorescence technique

Uranium is separated from plutonium by adsorption on an anion-exchange resin from a concentrated hydrochloric acid solution and is eluted from the resin, collected on a disc of cation-exchange paper, and determined by X-ray fluorescence. The lower limit of detection is 2mug of uranium, and 50mug may be determined with a recovery of 98% and a standard deviation of 3.2mug. In plutonium metal, 19ppm of uranium were found, with a standard deviation of 2 ppm (6 results).     

A new approach to the statistical treatment of 2D-maps in proteomics using fuzzy logic

A new approach to the statistical treatment of 2D-maps has been developed. This method is based on the use of fuzzy logic and allows to take into consideration the typical low reproducibility of 2D-maps. In this approach the signal corresponding to the presence of proteins on the 2D-maps is substituted with probability functions, centred on the signal itself. The standard deviation of the bidimensional gaussian probability function employed to blur the signal allows to assign different uncertainties to the two electrophoretic dimensions. The effect of changing the standard deviation and the digitalisation resolution are investigated.     

A comparative study of some nuclear methods for235U/238U isotopic ratios determination

In the present work, a comparative study is made among nuclear methods for²³⁵U/²³⁸U ratios determination: activation analysis followed by high-resolution gamma-ray spectrometry, delayed neutron counting, passive gamma-ray and alpha spectrometry. Activation analysis followed by high-resolution gamma-ray spectrometry yielded a relative standard deviation down to 0.1% and a relative error of about 1% for standards of uranium enriched to 14%. Passive gamma-ray spectrometry using Ge(Li) detectors yielded a relative error down to 0.1% for enriched uranium and values even lower for the standard deviation. Passive gamma-ray spectrometry using Low Energy Photon Detector (LEPD) yielded a precision of 0.2% and a still better accuracy for enriched standards. In the case of alpha spectrometry, a relative error down to 0.5% and a precision of about 1% were obtained, also for enriched uranium standards. Delayed neutron counting allowed a relative standard deviation of about 7% and a relative error of about 2%, for standards of depleted uranium.     

Comparison of an instrumental and modified Kjeldahl technique for determination of nitrogen in niobium and tantalum alloys

Results obtained for the determination of nitrogen in two tantalum alloys and six niobium alloys by modified Kjeldahl and Leco TC-30 nitrogen—oxygen determinator are compared. In the 5–25 ppm range, for tantalum alloys, the relative standard deviation was 3–9% by the Kjeldahl procedure and 9–11% by the instrumental technique. In the range 30–80 ppm, for niobium alloys, the relative standard deviation was 2–8% by the Kjeldahl procedure and 5–7% by the instrumental technique.     

Application of a gaseous-burst agitation technique to the development of spectral plates

The performance of a gaseous-burst agitation development technique built on the basis of Kodak's recommendations was compared to that of development by other techniques, namely by vibration—turbulence, hand rocked dish, no agitation and laminar flow techniques. In the course of the experiments the standard deviations of blackening of uniformly exposed spectral plates and the variations of the γ-values obtained by the different methods were compared. A low standard deviation and a high value of γ can be achieved simultaneously by providing a turbulent flow of and intermittent agitation in the developer. Such agitation can be obtained using the vibration—turbulence and the gaseous-burst methods. These techniques make possible a considerable reduction in standard deviation in the determination of the logarithm of light intensity.     

马尿酸及乙酰苯胺燃烧能的测定

设计并建立一台精密转动弹热量计,能在恒温和绝热两种模式下操作.测量数据的采集由在线微机自动完成,测量结果通过适当的程序计算.用量热标准物质NBS39i苯甲酸标定其能当量,偏差约为±0.006%.马尿酸及乙酰苯胺的燃烧能测定值分别为-(23542.7±0.9)J/g和-(31245.8±2.4)J/g(平均值和标准偏差).不确定度为总标准偏差的2倍,分别为±4.5J/g和±7.5J/g.结果与推荐值一致.还讨论了这两个化合物作为低含氮量量热参考物质的性质.     

Eichfunktion und analysenfehler in der spektrochemischen Analytik—I. Regression bei konstanter standardabweichung für die meßgröße

For spectrochemical analyses, calibration is a basic operation generally necessary for quantitative determinations. It yields the calibration function and by inversion the analytical function which is not directly accessible.—In the following, a scheme is developed in order to find-according to different methods of analysis-the respective suitable calibration function: it should give an expectable standard deviation as small as possible for the estimated content, it should, if possible, be linear and it should be applicable in a range of content as large as possible. The condition of Part I of this paper is the constant standard deviation for the measuring quantity in this range.-The scheme is examined by five analytical examples: for trace analyses (OES-ICP and AAS) the simple relationship between the intensity I and the concentration c is linear anyhow and yields a constant absolute standard deviation not dependent on the trace content. For analyses over a large range of concentration, a double-logarithmic transformation leads to linearity and constant relative standard deviation (OES with Laser). If physical matrix effects are existing, for example in surface analysis (ISS) the ‘binary-ratio method’ is recommended; in this case, the relative standard deviation is proportional to (1 - c). For XRF of main and additional components, the non-linear regression of the equation of Beattie and Brissey is to be realized with √I-values.     

Sequential testing as an efficient screening method for interferences in routine analysis as applied to atomic-absorption spectrometry with flame and graphite furnace atomization

Reliable standardization is a serious problem for most analytical methods. In spite of extensive work on interferences, the results are not suited for prediction of gross errors in any particular case. This paper is intended to show the power of sequential testing in practical atomic-absorption spectrometric analyses for the efficient detection of interferences causing changes in sensitivity; this test is carried out by comparing the sensitivity of the standard with the sensitivity for the sample, as determined by the difference between the signals for the spiked and unspiked samples. The simple computations can be carried out instantly and experimentation is terminated as soon as a conclusion can be drawn. The major advantage over the traditional tests lies in the smaller number of independent measurements, requiring less time and sample. Three separate cases are discussed: with the mean sensitivity of the standard known and the deviation expected to occur in one direction only (single-sided alternative hypothesis); with the standard deviation of the determination known and the deviation possibly occurring in both directions (double-sided alternative hypothesis); and with the mean and the standard deviation unknown but estimated during the test (sequential t-test). It is shown that assumptions about the normal distribution of the data do not impose serious restrictions in practical AAS work.     

Exact mass measurements using a 7 tesla fourier transform ion cyclotron resonance mass spectrometer in a good laboratory practices-regulated environment

Fourier transform ion cyclotron resonance mass spectrometry has been found to produce reliable exact mass measurements using two different internal calibration methods. For these measurements, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) were utilized both individually and in tandem. For internal calibration with a co-dissolved polyethylene glycol standard, measurements of 41 compounds resulted in an average absolute mass determination error of 0.7 ppm, with a standard deviation of 0.9 ppm. For comparison, internal calibration was effected through the simultaneous use of ESI and MALDI, with the former being used for the introduction of analyte ions and the latter for formation of polymethylmethacrylate calibrant ions. This technique led to mass measurements with an average absolute error of 0.8 ppm and a standard deviation of 1.0 ppm. In addition, exact mass measurements of tandem mass spectrometry fragment ions were made for 35 compounds using external calibration with a single internal mass standard. The observed average absolute error was 0.7 ppm with a standard deviation of 1.0 ppm.