自动监测设备比对监测合格率统计方法的探讨

参照污染源达标率统计方法,得出自动监测设备比对监测的合格率统计方法,并具体介绍了企业单个项目合格率统计方法、区域单个项目合格率统计方法和区域综合合格率统计方法。     

环境检测领域能力验证工作的组织及评价方法

介绍了环境检测领域能力验证的基本情况和统计方法，以及当前国内外能力验证计划提供者采用的数据处理方法，分析了该领域能力验证的发展趋势。指出环境检测领域化学分析方面的能力验证计划一般采用参加者结果的中位值或稳健均值作为指定值，采用标准化四分位距或稳健标准偏差作为能力评定标准差，以 z比分数法评价参加者的能力。     

实验室间比对能力验证中的两种稳健统计技术探讨

对环境监测实验室能力验证中两种稳健数据统计技术以及z比分数评价准则进行了探讨,并介绍了如何使用Excel电子表格软件实现数据的统计处理。四分位数法和迭代法均可作为实验室比对能力验证的数据处理技术,相对于四分位数稳健统计方法,迭代法是一种更加温和且可靠的稳健统计方法,但不适用于分割水平设计的能力验证计划。     

A comparison of methods and materials for the analysis of leaded wipes

The purposes of this study are: (1) to determine whether proficiency analytical test (PAT) materials from the American Industrial Hygiene Association can be used to provide quality data for portable X-ray fluorescence analysis (XRF) of lead in dust wipe surface samples; (2) to provide data to determine whether the on-site analysis of field dust wipe samples by XRF and the laboratory method of inductively coupled plasma emission analysis (ICP) are comparable; and (3) to determine if differences exist between different wipe materials. Several wipes meet the ASTM E1792 performance requirements of lead background level less than 5 microg per wipe, be only one layer thick, yield recovery rates of 80- 120% from spiked samples, remain damp throughout the sampling procedure, and do not contain aloe. The wipes used in this study were Pace Wipes, which are used for the PAT materials, and, for the field samples, Palintest Wipes, which were supplied by the instrument manufacturer, and Ghost Wipes, which are popular because they digest in hot, concentrated acid, so that chemical analysis is simplified. Twenty PAT wipe samples were obtained from four different proficiency test rounds. Surface wipe samples were taken at three different locations representing different industry types. All samples were analyzed using a portable XRF spectrometer and by ICP. Strong linear relationships were found for the analysis of wipe samples by ICP and by portable XRF. For the PAT samples, the results from the ICP and XRF analysis were not statistically equivalent, which indicates a bias in the ICP analysis. The bias was not excessive, since all ICP analyses fell within the acceptable range for the proficiency samples. The good correlation between the proficiency sample reference values and the XRF determinations is not surprising considering similar proficiency samples were used to calibrate the instrument response. Users of this portable XRF analyzer could enroll in the proficiency test program as part of their quality assurance program. For field samples, the relationship was strongest for Palintest wipes, and the values found for all three industries could be combined. However, the results from the ICP and XRF analysis were not statistically equivalent using the correction factor in the calculation algorithm as supplied with the instrument, and a new coefficient was derived. The mean relative error for the XRF analysis versus the ICP analysis was greater than 25%, such that the method falls within the realm of screening procedures. For Ghost Wipe samples, the precision was different for different industries, and the results could not be pooled. Differences between the two wipe materials may be related to the number of folds required for analysis.     

实验室能力验证中的分割水平检测样品与稳健统计技术

论述了分割水平检测样品和稳健统计技术在对实验室能力验证活动中的应用,并对导致CNAL T040水中金属元素检测能力验证计划中部分结果异常的原因进行了分析。     

The quality of fiber counts using improved slides with relocatable fields

A parameter based on discrepancies between reported fibers and verified fibers of relocatable slides is shown to be effective in monitoring the quality of airborne fiber counts. Analysts report only the fibers in each field examined. The verified fibers were determined by two experienced analysts, and are here considered as a "true" value. Most of the verified fibers were confirmed by the reported fibers, and the disputed fibers or fiber counting errors were all located and accounted for. In this study, reference (REF) slides were manufactured from proficiency analytical test (PAT) filter samples from the American Industrial Hygiene Association containing chrysotile or amosite. The slides were made using coverglasses bearing a grid pattern to allow accurate re-examinations. These coverglasses are an improved version of those used in previous studies. Seventy-four out of 85 amosite results and 51 out of 60 chrysotile results of REF slides were within their PAT proficiency ranges. When all reported fibers were normalized against their respective verified fibers, the average fiber count was over-estimated for amosite by 38.3% and under-estimated for chrysotile by 30.4%. The error from counting short fibers (sizing-extra) was 82.6% of the extra fibers and accounted for the 38% over-estimation of amosite fibers. For chrysotile fibers, sizing-extra errors were 74.0% of the extra fibers, but by far the larger errors were oversight-missing errors, which were 96.7% of the missing fibers and accounted for the 30% under-estimation of the chrysotile fibers. The discrepancies were found to be linearly related to counting errors as had been noted in a previous study, giving further weight to a proposed score, calculated from the discrepancy parameter (SigmaD(+) + |SigmaD(-)|)/VF(total), for evaluating the proficiencies of analysts. If a proficiency score =60 is selected, 48 out of 85 amosite results and 17 out of 60 chrysotile results satisfied this criterion in this study. The number of fiber counting errors in this study was larger than could be expected by PAT proficiency criteria. It may be useful to complement existing proficiency test programs with these REF slides. At the end of each proficiency testing round, detailed reports of discrepancies can be provided to participants so that they can improve on their skills in searching and sizing fibers and minimize their counting errors. In addition, the internal quality control program of each laboratory could include counting REF slides regularly by all analysts with control charts of (SigmaD(+)/VF(total)), (SigmaD(-)/VF(total)), (SigmaD(+) + |SigmaD(-)|)/VF(total) and RF(total)/VF(total) maintained to monitor errors, proficiencies and intercounter variations. Ten percent of relocatable slides of routine samples could also be recounted to monitor intracounter variation.     

中国环境空气苯系物类挥发性有机物监测能力现状分析

为了解和评价中国环境空气挥发性有机物(VOCs)的监测能力和技术水平,以量化的手段评估环境空气VOCs监测数据质量,促进实验室质量管理水平提升,笔者以环境空气VOCs中的苯系物为代表,组织31个省、自治区、直辖市216家各级各类生态环境检验检测机构开展了实验室比对,利用稳健统计技术分析评价实验结果。结果表明:环境空气苯系物类VOCs比对结果的整体合格率为68.5%,省级站、地市级以上站、社会化检测机构合格率分别为86.7%、75.4%和46.9%。可见现阶段中国环境空气苯系物类VOCs整体检测能力仍有提升的空间,社会化机构的检测技术水平尚待提升。建议地方部门加强对环境空气VOCs监测的技术培训,尽快提高VOCs监测技术水平,保障VOCs监测数据质量,同时强化对社会化检测机构的监督管理,督促其提升服务水平。     

A proficiency testing scheme for aromatic hydrocarbons in air by the manual thermal desorption-GC method: a comparison of laboratory performance with the uncertainty requirements of the European Union Ambient Air Directive

The Workplace Analysis Scheme for Proficiency (WASP) is a proficiency testing scheme for the analysis of occupational hygiene and environmental air samples and is operated in the UK by the Health and Safety Laboratory. Since 1997, WASP has offered samples of benzene, toluene and m-xylene, at environmental levels on Tenax, and has about 35 laboratories participating, mostly from industry, local government and consultancy organisations in the UK. The results reported cover the first 10 rounds of the environmental analytes (1997-1999) and demonstrate the important role of proficiency testing in assessing the quality of laboratory performance. Estimates are obtained for within-laboratory precision and the total variability at each analyte level. The estimates of within-laboratory precision suggest that laboratories have more difficulty analysing toluene and m-xylene than benzene. Linear relationships for the reproducibility relative standard deviation (RSDT) with loading level are evident for the analytes at occupational levels. At environmental levels, the relationship between loading level and reproducibility is much less well defined. The standard deviation for the proficiency testing assessment for all three analytes at the environmental level is 14%, as derived from the benzene data. Expanded uncertainty estimates (k = 1.96), for the analysis of samples since the scheme started, are obtained from the average total variance, and are 27% for benzene, 39% for toluene and 36% for m-xylene. Although the linear trend of performance against round number was not significant at the 95% level of confidence (p = 0.23 for benzene, p = 0.3 for toluene and p = 0.32 for m-xylene), there was a general improvement in RSDT from 26-34% to about 8-13% 10 rounds later. Currently, for a laboratory to meet one of the data quality objectives in the Ambient Air Directive (indicative measurement of benzene, expanded uncertainty +/- 30% or less), it would have to achieve a level of analytical performance to satisfy the category 1 (best performance) limit of better than +/- 8.8%. In the last proficiency testing round, discussed in this paper, only 58% of laboratories obtained performance scores that indicated that they were able to consistently achieve this level of performance.     

土壤重金属分析方法间检测结果一致性判断方法——数据对t值检验法的改进与完善

不同分析方法测定结果间的比较,或者说如何判断两种分析方法测定结果的一致性,是检测实验室经常遇到的实际问题。其应用场景包括方法标准验证实验、新方法与经典方法间的比对,特别是在缺少标准样品、测试数据不满足t值检验的条件下,选用合适的判据尤其重要。以采用单波长激发型能量色散X射线荧光光谱法、电感耦合等离子体质谱法、波长色散X射线荧光光谱法测定土壤和水系沉积物样品中Cd、As、Pb、Cu、Zn、Ni、Cr、Co、V、Mn、Mo、Sb等重金属含量所得数据为例,探讨了《环境监测分析方法标准制订技术导则》(HJ 168—2020)附录B中规定的"数据对t值检验法"的不足及改进办法,即用数据对相对偏差和再现性限合格率作为判据,判断分析方法测定结果的一致性。对一组验证样品分别用两种分析方法进行了测定,在数据对t值检验的基础上,取各元素测定结果的相对偏差与相关限值进行比较,或者取两者的差值与基准分析方法标准规定的再现性限进行比较,利用合格率大小协助判断了两分析方法测定结果的一致性。研究结果表明,此方法符合日常质控技术规范中关于精密度的规定,实用性强,是一条将数理统计原理与专业知识相结合的合理技术路线。     

采用能力验证数据评估环境监测结果测量不确定度

测量不确定度评估是实验室检测能力的体现,能力验证是实验室质量控制的有效方法,对环境监测领域实验室采用能力验证数据进行测量结果不确定度评估方法进行了研究。依据Nordtest准则,根据实验室内再现性标准差和测量偏倚,评估了重铬酸钾法测定水中质量浓度为100 mg/L的化学需氧量测量结果的相对不确定度为6.00%。该评估方法避免了ISO GUM评定方法自下而上不确定度评估过程的繁琐,还充分考虑了实验室内外误差的来源,能够促进环境监测结果不确定度评定的一致性。     

美国环境实验室认证体系概况

通过对美国环境实验室认定现用标准(2003 NELAC Standard)的研究,介绍了美国现行使用的环境实验室认定过程中能力验证、实地评估、认定程序、质量体系和认证机构认可5个部分的方法、程序、评定模式、组织管理等内容,对我国开展环境监测实验室的资质认定工作具有一定的借鉴作用.     

Metal diffusion properties of a Nafion-coated porous membrane in an aquatic passive sampler system

A cellulose acetate membrane, positioned in a passive sampler system, was coated with the perfluorinated polymer Nafion. Aqueous metal transport through the membrane and the Nafion film was investigated. The Nafion-coated membrane prevents the transport of metals bound to natural organic material to the receiving phase in the passive sampler, while copper associated with small synthetic ligands pass through the Nafion film. Increasing thickness of the Nafion film decreases the metal uptake rate to the receiving phase in the passive sampler and increases the response time. A decreased response time for the passive sampler would provide a better estimation of rapid changes in concentration, particularly for dynamic aquatic systems such as urban runoff. Limited biofouling protection with the Nafion coating was demonstrated by growth inhibition of natural periphyton communities on glass surfaces.     

浅谈环境监测化学测量结果的计量溯源性

确保测量结果的计量溯源性是保障数据有效性的基本要求。为此,国家明确提出要建立健全国家生态环境监测量值溯源体系。化学测量是环境监测工作中最常用的一种测量方式。由于基体、浓度等的影响往往比较复杂,如何确保环境监测化学测量结果的计量溯源性成为环境监测领域的重要研究内容。通过总结建立环境监测化学测量结果计量溯源性的途径,对环境监测分析方法标准、国家环境标准样品、环境检测能力验证等在保证环境监测化学测量结果计量溯源性中的作用进行了分析,以期为环境监测化学测量结果计量溯源性的建立提供参考。     

浅谈授权签字人对环境监测数据报告的审核

根据计量认证和中国实验室国家认可工作中对授权签字人能力的考核以及通过认证／认可的实验室对授权签字人赋予的职责和权利,针对目前环境管理、环境执法以及社会公众对环境监测数据不断增长的需要,结合监测数据报告审核的体会,探讨了授权签字人在环境监测数据报告审核中应采取的审核程序与方法及重点关注的问题。     

VPT511BF-SY多孔流速仪在烟气流量在线监测中的应用

针对目前国内基于单个探头的单点在线测试烟气流量与参比方法监测比对合格率不高的问题,提出一种新颖的基于平均差压皮托管法的多孔流速仪,通过对不同的安装位置及安装数量的多孔烟气流速仪的烟气在线流量监测结果与手工监测结果进行比对,验证在适当位置安装一定数量的多孔烟气流速仪可以确保与手工监测比对结果满足要求。     

Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.     

第三方环境检测机构发展现状与展望

介绍了我国第三方环境检测行业的现状,指出了存在的问题,分析了我国第三方环境检测行业发展趋势,并对完善我国第三方环境检测行业发展提出了健全机制,建立资质、能力验证、市场监管,全面的实验室比对,限制服务范围,创建高端品牌化第三方环境检测实验室的建议.     

Reference materials for the monitoring of the aquatic environment--a review with special emphasis on organic priority pollutants

During recent years, the awareness of quality assurance and quality control in environmental analyses has constantly increased, especially due to the implementation of new guidelines and regulations at both the national and international level. Achieving comparable results by using certified reference materials is one of the primary concerns of the scientific community. As a result, there is a growing demand for certified reference materials to cover different matrices and pollutants. Moreover, these CRMs should be in close relationship to the determinants and target concentrations required by environmental bodies and European Directives as well. Supplementary information to this paper presents an inventory of reference materials available on the market from different suppliers against the priority pollutants listed in the Water Framework Directive. These CRMs cover matrices such as water, sediment and biota. The use of CRMs in relationship to appropriate analytical methods and relevant determinants is discussed and the need for matrix-CRMs, particularly for organic pollutants is emphasised. The use of proficiency testing schemes as an alternative for the lack of appropriate CRMs and future trends in the production of CRMs within the BCR framework are also discussed.     

应用稳健马氏距离评价实验室间比对能力考核

基于稳健马氏距离的多元统计算法，综合评价了全国环境监测系统96个实验室4种有机氯农药监测能力考核的结果，从中筛选出25个考核结果存在异常的实验室。将多元统计结果与稳健Z比分数结果进行比较，发现基于稳健马氏距离筛选出的异常实验室其稳健Z比分数结果也存在一定的问题。同时简单介绍了稳健马氏距离及其相关的异常值筛选的算法原理，并详细介绍了其基于R语言的实现过程。