氢化物发生原子荧光光度法测定水中锑的不确定度评定

介绍了原子荧光光度法测定水中锑的不确定度评定方法,分析和识别在测定过程中的不确定度来源,较为全面地评定了测量不确定度,最后计算出测定结果的合成标准不确定度和扩展不确定度.结果表明,标准溶液配制过程和标准曲线拟合引起的不确定度是原子荧光光度法测定水中锑含量不确定度的主要来源.     

离子色谱法测定降水中部分阴离子含量的测量不确定度评定

通过对离子色谱法测定降水中F^-、Cl^-、NO3^-、SO4^2- 测量不确定度的分析，找出导致不确定度的因素。对测量不确定度进行计算和评定，结果表明，影响其测量不确定度的主要因素是标准曲线精密度。     

秩和检验法评价实验室间样品的考核

在实验室间质量控制考核中常用均值范围法对样品考核结果进行评价。它是将考核样品保证值的不确定度作适当展宽后,用以评价各实验室的测定结果,而它通常以精密度的标准偏差为度。不确定度的区间是反映测试结果的分布概率。因此,对有限次测量,甚至是一次测量的结果,使用概率分布的指标评价其“优”“良”与“及格”的等级是不适宜的,其评价方法只能对考核结果作出“合格”或“不合格”的判断。今在质控工作中,用秩和检验方法对一次质量考核中各参加实验室的考核结果列表计算以作评价。这种方法计算简便,对测定结果的分布要求也不严格…     

CFA1000连续流动分析系统测定水中总氮

通过绘制总氮的校准曲线,测定仪器的空白值、检出限和测定下限,并对仪器的A类不确定度进行评价,对比CFA1000连续流动分析系统与SKALAR SAN++型流动分析仪测定方法、国标法测定方法的分析结果。结果表明,在保证测定结果准确度和精密度的前提下,CFA1000连续流动分析系统具有较好的测试灵敏度。     

四种化学需氧量测定标准方法的比较

对国内外四种测定低浓度化学需氧量(COD)的方法进行了比对分析。从精密度、准确度、不确定度等方面对这四种方法进行了系统对比。结果表明,在测定低浓度COD的样品时,在准确度方面,除HJ/T399—2007[7]之外的其它三种方法中的任何一种都可以得到稳定可靠的回收率;在精密度方面,5220B.4b[3]和ISO15705—2002[4]的数据与标准文本中的参考数据具有一致性;在不确定度方面,四种方法相差不大,主要影响因素均为样品重复测定引起的不确定度;在方法间的差异及相关性上,采用HJ/T399—2007和其他三种方法得到的结果存在显著差异,而采用其它三种方法测定低浓度COD样品时,得到的结果没有显著差异,并且三种方法之间具有很好的相关性。在实际应用中,5220B.4b、ISO15705—2002和GB 11914—89的数据之间存在较大的随机极差。对比结果表明,5220B.4b、ISO15705—2002和GB11914—89具有可比性,得到的数据都可用。     

基于方法验证数据用Top-down方法评估测量不确定度

依据现有指南和规范,在分析方法标准验证实验和报告中,常常分别评估准确度和精密度。这容易导致以加标回收率表示的准确度数据缺乏良好精密度支持的现象。基于ISO 11352原理,首次提出在不增加实验室分析人员工作量的情况下,利用自上而下技术评估方法测量不确定度,即同时考虑准确度与精密度作为一个综合性指标评估方法性能。这是标准制修订时落实测量不确定度条文一条操作性强的技术路线。利用改进后的加标回收率计算结果评估方法准确度。5组方法验证实测数据表明,用测量不确定度这一综合性指标评估方法性能比分别用准确度和精密度指标更符合实际情况。他可引导实验室分析人员在设计和处理方法验证数据时,更加重视方法精密度。在修订HJ 168—2010时,建议增加测量不确定度这一综合性指标评估方法性能。     

X射线荧光光谱法测定土壤样品中铅的不确定度评定

用实例对X射线荧光光谱法测定土壤样品中铅的不确定度进行了评定.测量结果的不确定度由仪器综合稳定性、制样、标准物质、回归工作曲线、重复测量等所引入的不确定度分量组成.在对各个不确定度分量进行量化的基础上,通过合成得到测量结果的标准不确定度,再乘以95%置信概率下的扩展因子2,得到测量结果的扩展不确定度.     

室内空气污染监测用氨标准样品研究

根据中国对室内空气污染监测的实际需要,介绍了室内空气污染监测用氨标准样品的研制方法,包括试剂的验证、均匀性和稳定性检验、分析定值和测定数据的统计检验等方面。氨标准样品采用重量法制备,用纳氏试剂分光光度法对样品进行均匀性和稳定性研究,并进行不确定度评估。研究结果表明,氨标准样品的均匀性良好,室温条件下可稳定18个月以上;在全面分析不确定度来源的基础上,定值结果为0.494 mg/L,不确定度小于3%。与美国同类标准物质进行比对分析,结果具有可比性。可用于氨测定的质量控制、分析方法评价以及实验室能力验证等方面。     

火焰原子吸收法测定水样铅含量的不确定度评定

实验室认可和资质认定都要求检测实验室具备评定测量不确定度的能力,现依据JJF1059-1999《测量不确定度评定与表示》,对火焰原子吸收法测定水样中铅含量进行不确定度评估,分析测定过程中不确定度来源,量化不确定度分量,求出合成不确定度和扩展不确定度,给出测定结果的表示式。     

氨氮精密度偏性试验浅析

精密度偏性试验是通过对影响分析测定的各种变异因素及回收率的全面分析,确定实验室测试结果的精密度和准确度。采用纳氏试剂分光光度法(HJ 535-2009)对水中氨氮进行了精密度偏性试验,对实验室监测数据的质量进行检验和评价。结果表明,该监测项目的各项检验指标均达到要求,质量控制图分布合理,加标回收率合格,整个分析过程均在质量控制范围内。     

Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

能量色散X射线荧光法快速测定生物质燃料中的磷含量

应用能量色散X射线荧光光谱法建立了生物质燃料中磷含量的快速测定方法。对比分析压片压力条件、基体效应和干扰元素,明确了能量色散X射线荧光光谱法的测试条件,通过加标回收率实验、标准样品测试、ICP-OES方法对比等获得实验结果。实验结果表明:能量色散X射线荧光光谱法用于生物质燃料样品的分析,标准工作曲线线性相关系数为0.998 3,方法检出限为0.4 mg/kg,平均加标回收率为98.1%,测定值的相对标准偏差为1.36%~4.92%,标准样品磷含量在标准值不确定度内,能量色散X射线荧光光谱法与行业标准ICP-OES方法的准确度和精密度不存在显著性差异,可应用于生物质中磷含量的环境监测。     

铬菁R分光光度法测定水和废水中痕量铍的方法评价

在方法研究的基础上 ,组织全国六个实验室对铬菁 R分光光度法测定水和废水中铍进行了方法验证。对统一标准样品、环境地表水、实际含铍废水进行了分析。以协作试验所得数据评价本方法的灵敏度、精密度、准确度和适用性     

基于便携式氢火焰离子化检测器法测定固定污染源废气中非甲烷总烃的研究

通过实验室和固定污染源废气现场比对测试,对便携式氢火焰离子化检测器法(催化氧化法和气相色谱法)测定非甲烷总烃的检出限、转化效率、精密度和准确度等性能指标开展研究。实验室测试结果表明,便携式氢火焰离子化检测器法测定非甲烷总烃的检出下限(0.3 mg/m^3)、转化效率(98.2%)、精密度(3.49%)、准确度(-2.38%)基本满足方法技术指标的要求,但是对于催化氧化法还需重点关注其转化效率。固定污染源废气现场比对测试结果表明,便携式氢火焰离子化检测器法与实验室方法测试结果的相对准确度(33.2%)、相对误差(-9.27%~23.7%)基本能满足测试方法的测试要求,趋势性也保持一致,适用于现场测试。     

The effect of absorbent grid preparation method on precision and accuracy of ambient nitrogen dioxide measurements using Palmes passive diffusion tubes

A few studies have suggested that the precision and accuracy of measurement of NO(2) by Palmes-type passive diffusion tube (PDT) are affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. Theses studies have been quite limited in extent and have tended to evaluate PDT accuracy as zero bias between PDT NO(2) value and the exposure-averaged NO(2) determined by co-located chemiluminescence analyser. This ignores the well-documented intrinsic systematic biases on PDT-derived NO(2), such as within-tube chemistry and exposure-duration nitrite loss, which may lead to non-zero bias values irrespective of effects of TEA absorbent preparation method on PDT accuracy. This paper reports on a statistical analysis of a large dataset comprising 680 duplicated PDT exposures spanning 146 separate exposure periods, spread over five urban exposure locations and a number of years. In each exposure period, PDTs prepared by between four and six different grid preparation methods were simultaneously compared. The preparation methods used combinations of the following: acetone or water as the TEA solvent; 20% or 50% as %TEA in the solution; and application of TEA solution by dipping grids for several minutes in the solution before drying and tube assembly, or by pipetting 50 microL of solution directly onto grids already placed in the PDT cap. These represent the range of preparation procedures typically used. Accuracy was evaluated as maximised nitrite capture within an exposure. Data were analysed by general linear modelling including examination of interaction between different aspects of grid preparation method. PDT precision and accuracy were both significantly better, on average, when the PDT grids were prepared by dipping in TEA solution, and neither solvent or %TEA used for the dipping solution were important. Where PDT preparation by pipetting TEA solution onto grids is to be used, better performance was obtained using 20% TEA in water. A systematic positive bias in PDT measure of NO(2), consistent with within-tube oxidation of NO to NO(2) and independent of preparation method, was again evident in this work.     

环境监测3种不确定度评定方法的比较——以水中化学需氧量的测定为例

利用环境监测实验室积累的数据,通过线性拟合法、GUM法和控制图法对水中化学需氧量的不确定度进行了评定。结果表明:3种不确定度评定方法的评定结果相似。在量化过程中存在两种主要不确定度评定的类型:一种是不确定度的正向传播,另一种是模型不确定度和参数不确定度的反向评定。GUM法明显是正向的不确定度,线性拟合法和控制图法是反向不确定度。GUM法应用复杂且烦琐,操作性差;相比,控制图法和线性拟合法更加简单实用,可代替GUM法来评估监测实验室的不确定度。     

Laboratory and field comparison of measurements obtained using the available diffusive samplers for ozone and nitrogen dioxide in ambient air

This study presents an evaluation of the extent of differences between measurements performed by O(3) and NO(2) diffusive samplers and by the reference methods for diffusive samplers commercially available. The tests were performed in an exposure chamber under extreme conditions of controlling factors and under field conditions. For NO(2), the results of the laboratory experiments showed that most of the diffusive samplers were affected by extreme exposure conditions. The agreement between the samplers and the reference method was better for the field tests than for the laboratory ones. The estimate of the uptake rate for the exposure conditions using a model equation improved the agreement between the diffusive samplers and the reference methods. The agreement between O(3) measured by the diffusive samplers and by the reference method was satisfactory for 1-week exposure. For 8-hour exposures, the diffusive samplers with high uptake rates quantified better the O(3) concentration than the samplers with low uptake rates. As for NO(2), the results of the O(3) field tests were in better agreement with the reference method than the ones of the laboratory tests. The field tests showed that the majority of diffusive samplers fulfils the 25% uncertainty requirement of the NO(2) European Directive and the 30% uncertainty requirement of the O(3) European Directive for 1-week exposure.     

碘量法测定水和废水中硫化物

设计制作了测定硫化物的酸化 -吹气 -吸收预处理装置 ,验证了装置对硫化物的回收效果 ,对分析条件进行了最佳选择 ,对干扰及消除情况进行了深入细致的研究 ,本方法的测量精密度和加标回收率均为良好 ,适用于含硫化物在0 .40 mg/L以上的水和废水的测定。     

Masonry fireplace emissions test method: Repeatability and sensitivity to fueling protocol

A test method for masonry fireplaces has been evaluated during testing on six masonry fireplace configurations. The method determines carbon monoxide and particulate matter emission rates (g/h) and factors (g/kg) and does not require weighing of the appliance to determine the timing of fuel loading.The intralaboratory repeatability of the test method has been determined from multiple tests on the six fireplaces. For the tested fireplaces, the ratio of the highest to lowest measured PM rate averaged 1.17 and in no case was greater than 1.32. The data suggest that some of the variation is due to differences in fuel properties.The influence of fueling protocol on emissions has also been studied. A modified fueling protocol, tested in large and small fireplaces, reduced CO and PM emission factors by roughly 40% and reduced CO and PM rates from 0 to 30%. For both of these fireplaces, emission rates were less sensitive to fueling protocol than emission factors.     

氮气中1,3-丁二烯气体标准样品的研制

采用重量法对氮气中1,3 -丁二烯气体标准样品的制备方法进行了研究.依据国际标准化组织(ISO)颁布的“6142气体分析-校准气体混合物的制备-重量法”的标准方法,对标准气体在重量法制备过程中的定值分析、不确定度来源、不确定度估算以及不确定度合成进行了阐述.制备的1,3 -丁二烯气体标准样品量值与同类标准样品量值具有可比性,能够满足环境有机污染物监测工作的需要.