水中阴离子表面活性剂的测量不确定度评定

简要介绍了测量不确定度的概念，运用《测量不确定度评定与表示》的技术规范，通过对阴离子表面活性剂的测定过程，分析了影响阴离子表面活性剂测量不确定度的因素，给出了相对标准不确定度分量，并具体阐明了测量不确定度的评定步骤，得出测量扩展不确定度的结果。     

地下水矿化度测定的不确定度评定

分析质量法测量地下水矿化度的测量不确定度来源，评定了地下水矿化度的测量不确定度，在各不确定度中，称量引入的不确定度较大。     

滴定法测定的不确定度评定——以EDTA法测定水中钙镁为例

用测量不确定度表示检测结果是当前国际上约定做法，然而如何对测量结果的不确定度进行合理评定，一直是困扰检测实验室的一个难题。作者依据测量不确定度的评定原则，通过实例，简要地阐述了滴定法测量不确定度评定方法，对环境检测领域测量不确定度的评定具有借鉴意义。     

水中氯化物测定的不确定度评定

根据硝酸银滴定法测定水中氯化物的含量，分析了该方法测量不确定度的来源，评定了水中氯化物的测量不确定度，在各不确定度中，以标准溶液配制与样品分析时滴定消耗的硝酸银体积引入的不确定度较大。     

原子吸收法测定水中铁的不确定度分析

通过对原子吸收法测定水中铁的不确定度的分析，找出了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以及仪器漂移。     

水质铜测定的不确定度评定

根据火焰原子吸收分光光度法测定水中铜的含量，分析了测量不确定度的主要来源，即标准曲线不确定度、标准溶液不确定度、测量重复性不确定度。计算得到水中铜的测定结果的合成不确定度为0．098mg／L，扩展不确定度为0．196mg/L。     

测量试样中的氮氧化物含量不确定度评定

以实际监测数据为例，详细描述测量试样中的NOx含量不确定度评定方法，包括不确定度源的分析，A类标准不确定度评定、B类标准不确定度评定、合成标准不确定度和扩展不确定度等，对不确定度的分量作了详尽的分析和计算。     

水中总磷测量的不确定度评定

采用钼酸铵分光光度法测定水中总磷的含量，分析该法测量不确定度的来源，评定水中总磷的测量不确定度。     

平皿计数法测定细菌总数的不确定度评定

根据细菌总数的测定方法,分析了该方法测量不确定度的来源,评定了水中细菌总数的测量不确定度。     

气相色谱-质谱法测定水中挥发性有机物的测量不确定度评定

根据测量不确定度评定与表示理论，采用气相色谱一质谱法测定水中挥发性有机物。以氯乙烯为例，通过计算和评定，得出当氯乙烯的测量结果为4．99μg／L时，取包含因子k=2（约95％置信概率），扩展不确定度U=0．96μg／L。该不确定度评定方法在实际工作中具有较强的实用价值。     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.     

Evaluation of the measurement uncertainty in automated long-term sampling of PCDD/PCDFs

Since the publication of the first version of European standard EN-1948 in 1996, long-term sampling equipment has been improved to a high standard for the sampling and analysis of polychlorodibenzo-p-dioxin (PCDD)/polychlorodibenzofuran (PCDF) emissions from industrial sources. The current automated PCDD/PCDF sampling systems enable to extend the measurement time from 6–8 h to 15–30 days in order to have data values better representative of the real pollutant emission of the plant in the long period. EN-1948:2006 is still the European technical reference standard for the determination of PCDD/PCDF from stationary source emissions. In this paper, a methodology to estimate the measurement uncertainty of long-term automated sampling is presented. The methodology has been tested on a set of high concentration sampling data resulting from a specific experience; it is proposed with the intent that it is to be applied on further similar studies and generalized. A comparison between short-term sampling data resulting from manual and automated parallel measurements has been considered also in order to verify the feasibility and usefulness of automated systems and to establish correlations between results of the two methods to use a manual method for calibration of automatic long-term one. The uncertainty components of the manual method are analyzed, following the requirements of EN-1948-3:2006, allowing to have a preliminary evaluation of the corresponding uncertainty components of the automated system. Then, a comparison between experimental data coming from parallel sampling campaigns carried out in short- and long-term sampling periods is realized. Long-term sampling is more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Automated sampling systems can assure very useful emission data both in short and long sampling periods. Despite this, due to the different application of the long-term sampling systems, the automated results could not be directly compared with manual results, not even in terms of measurement uncertainty. This investigation focuses on both uncertainty and repeatability of the automated sampling method. The standard 20988, developed by Internarional Organization of Standardization (ISO) can be used to estimate the measurement uncertainty. The results confirm that the uncertainties of manual and automated methods are comparable. At the same time, it is not appropriate to consider the manual method as a reference for the evaluation of the uncertainty of the automated sampling system, due to the high variability of both systems.     

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

An uncertainty analysis of mean flow velocity measurements used to quantify emissions from stationary sources

Point velocity measurements conducted by traversing a Pitot tube across the cross section of a flow conduit continue to be the standard practice for evaluating the accuracy of continuous flow-monitoring devices. Such velocity traverses were conducted in the exhaust duct of a reduced-scale analog of a stationary source, and mean flow velocity was computed using several common integration techniques. Sources of random and systematic measurement uncertainty were identified and applied in the uncertainty analysis. When applicable, the minimum requirements of the standard test methods were used to estimate measurement uncertainty due to random sources. Estimates of the systematic measurement uncertainty due to discretized measurements of the asymmetric flow field were determined by simulating point velocity traverse measurements in a flow distribution generated using computational fluid dynamics. For the evaluated flow system, estimates of relative expanded uncertainty for the mean flow velocity ranged from ±1.4% to ±9.3% and depended on the number of measurement locations and the method of integration.

Implications:Accurate flow measurements in smokestacks are critical for quantifying the levels of greenhouse gas emissions from fossil-fuel-burning power plants, the largest emitters of carbon dioxide. A systematic uncertainty analysis is necessary to evaluate the accuracy of these measurements. This study demonstrates such an analysis and its application to identify specific measurement components and procedures needing focused attention to improve the accuracy of mean flow velocity measurements in smokestacks.     

Receptor modeling of ambient particulate matter data using positive matrix factorization: review of existing methods

Methods for apportioning sources of ambient particulate matter (PM) using the positive matrix factorization (PMF) algorithm are reviewed. Numerous procedural decisions must be made and algorithmic parameters selected when analyzing PM data with PMF. However, few publications document enough of these details for readers to evaluate, reproduce, or compare results between different studies. For example, few studies document why some species were used and others not used in the modeling, how the number of factors was selected, or how much uncertainty exists in the solutions. More thorough documentation will aid the development of standard protocols for analyzing PM data with PMF and will reveal more clearly where research is needed to help future analysts select from the various possible procedures and parameters available in PMF. For example, research likely is needed to determine optimal approaches for handling data below detection limits, ways to apportion PM mass among sources identified by PMF, and ways to estimate uncertainties in the solution. The review closes with recommendations for documenting the methodological details of future PMF analyses.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 ± 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.