Assessment of sampling and analytical uncertainty of trace element contents in arable field soils

Assessment of trace element contents in soils is required in Germany (and other countries) before sewage sludge application on arable soils. The reliability of measured element contents is affected by measurement uncertainty, which consists of components due to (1) sampling, (2) laboratory repeatability (intra-lab) and (3) reproducibility (between-lab). A complete characterization of average trace element contents in field soils should encompass the uncertainty of all these components. The objectives of this study were to elucidate the magnitude and relative proportions of uncertainty components for the metals As, B, Cd, Co, Cr, Mo, Ni, Pb, Tl and Zn in three arable fields of different field-scale heterogeneity, based on a collaborative trial (CT) (standardized procedure) and two sampling proficiency tests (PT) (individual sampling procedure). To obtain reference values and estimates of field-scale heterogeneity, a detailed reference sampling was conducted. Components of uncertainty (sampling person, sampling repetition, laboratory) were estimated by variance component analysis, whereas reproducibility uncertainty was estimated using results from numerous laboratory proficiency tests. Sampling uncertainty in general increased with field-scale heterogeneity; however, total uncertainty was mostly dominated by (total) laboratory uncertainty. Reproducibility analytical uncertainty was on average by a factor of about 3 higher than repeatability uncertainty. Therefore, analysis within one single laboratory and, for heterogeneous fields, a reduction of sampling uncertainty (for instance by larger numbers of sample increments and/or a denser coverage of the field area) would be most effective to reduce total uncertainty. On the other hand, when only intra-laboratory analytical uncertainty was considered, total sampling uncertainty on average prevailed over analytical uncertainty by a factor of 2. Both sampling and laboratory repeatability uncertainty were highly variable depending not only on the analyte but also on the field and the sampling trial. Comparison of PT with CT sampling suggests that standardization of sampling protocols reduces sampling uncertainty, especially for fields of low heterogeneity.     

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。     

便携式XRF测定仪在土壤检测中的应用及其影响因素

研究了便携式X射线荧光光谱仪(PXRF)的仪器性能,评估了其检出限、准确度及精密度,并和常规实验室检测方法比对进一步评估其性能,分析两者间的相关性和差异性。进一步探究了影响PXRF测定的2个最主要因素(土壤含水量和粒径)。结果表明:PXRF具备良好的仪器性能,8种元素的检出限为0.62～8.01 mg/kg,除Cd和Hg外,精密度均低于7%,准确度范围为-7.5%～11.1%。Pb、Cr、Cu、Zn、Ni、As的PXRF测定值与常规实验室方法测定值有良好的相关性,特别是Cu、Zn,相关系数可达0.873、0.832,而Cd和Hg的相关性则较弱。土壤含水量和土壤粒径会影响PXRF的测定性能,鲜样测定检测值普遍小于干样,0.15、2 mm粒径下检测值具有较强的相关性。研究旨在为PXRF的现场应用提供 参考,该方法可应用于初步监测和应急监测,实现土壤重金属元素的快速测定。     

便携式GC-MS测定气体样品中6种典型VOCs的不确定度评定

以便携式GC-MS测定气体样品中6种典型挥发性有机物(VOCs)组分(苯、1,1,2-三氯乙烷、四氯乙烯、乙苯、间二甲苯和1,3,5-三甲基苯)为例,应用不确定度理论,从检测过程和计算方法的角度分析了影响测量不确定度的各种因素:标准气体定值、标准气体稀释、工作曲线的非线性及重复性测定。对各测量不确定度分量进行计算和评定,同时采用稳健统计方法对测定结果进行准确度评价。结果表明:采用便携式GC-MS测定气体样品中VOCs不确定度的主要影响因素是标准气体定值和工作曲线的非线性,其次是重复性测定,标准气体稀释引入的不确定度较小。当VOCs组分含量为200 nmol/mol浓度水平时,测量扩展不确定度为14～17 nmol/mol,测量相对扩展不确定度为7.1%～9.2%(k=2,置信水平为95%),相对误差为1.5%～4.0%。     

Trace-level beryllium analysis in the laboratory and in the field: state of the art, challenges and opportunities

Control of workplace exposure to beryllium is a growing issue in the United States and other nations. As the health risks associated with low-level exposure to beryllium are better understood, the need increases for improved analytical techniques both in the laboratory and in the field. These techniques also require a greater degree of standardization to permit reliable comparison of data obtained from different locations and at different times. Analysis of low-level beryllium samples, in the form of air filters or surface wipes, is frequently required for workplace monitoring or to provide data to support decision-making on implementation of exposure controls. In the United States and the United Kingdom, the current permissible exposure level is 2 microg m(-3) (air) and the United States Department of Energy has implemented an action level of 0.2 microg m(-3) (air) and 0.2 microg/100 cm(2) (surface). These low-level samples present a number of analytical challenges, including (1) a lack of suitable standard reference materials, (2) unknown robustness of sample preparation techniques, (3) interferences during analysis, (4) sensitivity (sufficiently low detection limits), (5) specificity (beryllium speciation) and (6) data comparability among laboratories. Additionally, there is a need for portable, real-time (or near real-time) equipment for beryllium air monitoring and surface wipe analysis that is both laboratory-validated and field-validated in a manner that would be accepted by national and/or international standards organizations. This paper provides a review of the current analytical requirements for trace-level beryllium analysis for worker protection and also addresses issues that may change those requirements. The current analytical state of the art and relevant challenges facing the analytical community will be presented, followed by suggested criteria for real-time monitoring equipment. Recognizing and addressing these challenges will present opportunities for laboratories, research and development organizations, instrument manufacturers and others.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

New approaches for assessment of occupational exposure to metals using on-site measurements

Traditional assessment of occupational exposure to metals typically involves static or personal aerosol sampling on a membrane filter followed by a laboratory determination of the metal content on the filter sample. These techniques give results with high accuracy and low detection limits. However, they all have a drawback in that, since the samples have to be analysed in a laboratory, the results will usually be obtained days or weeks after the sampling took place. Today there is available a new generation of portable electronic micro-balances and instruments for metal analysis based on X-ray fluorescence. These instruments will make on-site measurements of metal exposure possible, which opens the way for new approaches for assessment of occupational exposure to metals. In combination with high-flow pumps, short-term sampling is possible, which allows monitoring of the exposure variation during a work shift as well as the exposure during individual work tasks of short duration. Screening measurements and emission measurements are other examples of monitoring that are facilitated using on-site determinations. Measure control monitoring can effectively be performed using on-site measurements and is an effective tool in the assessment of workplace improvements. On-site determinations can also form an effective and pedagogic tool showing workers how to perform specific tasks and demonstrating the effectiveness of different measures intended to improve their work environment. Other examples are the assessment of skin exposure using aerosol deposition on pads and screening of contamination using bulk samples.     

便携式智能移动终端在环境监测管理系统中的运用

介绍了将便携式智能移动终端引入现场环境监测管理系统的研究过程,依托部署在PDA上的嵌入式软件与通讯协议,将PDA与现场监测仪器直接连接并读取监测数据及结果,通过PDA上安装的无线CDMA模块,将实时的监测数据远程无线传输至指定的数据库内。实现了现场环境监测数据的无线实时传输与无纸化办公。     

便携式非分散红外烟气仪在高湿低硫锅炉烟气监测中的干扰和对策

简述了便携式非分散红外烟气分析仪在高湿低硫锅炉烟气监测中,存在采样流量、现场温度以及预处理装置反吹等方面的干扰因素。提出了在锅炉烟气监测中可采取控制采样流量、延长仪器预热时间、反吹预处理装置等措施,消除干扰,保证烟气监测的稳定准确。     

Spatial contaminant heterogeneity: quantification with scale of measurement at contrasting sites

Material within the terrestrial environment is rarely homogeneously distributed, either spatially or temporally. One consequence of heterogeneity is that uncertainty is usually generated in measurements that are taken with the aim of characterising the environment. For example, a measurement of analyte concentration within soil taken from one sampling location on contaminated land can vary substantially when compared against another sample taken at effectively the same nominal location. The measurement uncertainty arising from the heterogeneity can substantially limit the reliability of the interpretations made upon environmental investigations. The sampling uncertainty usually outweighs the analytical uncertainty from the laboratory, often by a factor of 20 or more. One approach to reducing the uncertainty is to design a more suitable sampling strategy. This might be achieved by predicting the degree of heterogeneity prior to the investigation, but this is often difficult to achieve accurately. Another approach, which was investigated here, is to actually characterise the heterogeneity prior to the main investigation using rapid and inexpensive technology, such as in situ measurement techniques. In situ portable X-ray fluorescence (PXRF) and X-ray microprobe (XMP) techniques were employed to test the feasibility of this approach. Two contrasting contaminated land sites were chosen to characterise the two-dimensional spatial heterogeneity of heavy metal contamination in topsoil at a range of scales (50 m to 0.001 m). The spatial heterogeneity of contaminants, expressed as relative standard deviations, was found to differ between the two sites by a factor of two, largely due to the mode of deposition of pollution. The study also indicated that the heterogeneity did not change systematically with the scale of measurement between sampling locations at either site.     

Interpretation of standard leaching test BS EN 12457-2: is your sample hazardous or inert?

A slag sample from a lead refiner has been obtained and given to two analytical laboratories to determine the release of trace elements from the sample according to BS EN 12457-2. Samples analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert material; samples of the same material analysed by the other laboratory failed waste acceptance criteria and were classified as hazardous. It was found that the sample preparation procedure is the critical step in the leaching analysis and that the effects of particle size on leachability should be taken into account when using this standard. The purpose of this paper is to open a debate on designing a better defined standard leaching test and making current waste acceptance criteria more flexible.     

Sampling and analysis for radon-222 dissolved in ground water and surface water

Radon-222 is a naturally occurring radioactive gas in the uranium-238 decay series that has traditionally been called, simply, radon. The lung cancer risks associated with the inhalation of radon decay products have been well documented by epidemiological studies on populations of uranium miners.The realization that radon is a public health hazard has raised the need for sampling and analytical guidelines for field personnel. Several sampling and analytical methods are being used to document radon concentrations in ground water and surface water worldwide but no convenient, single set of guidelines is available. Three different sampling and analytical methods-bubbler, liquid scintillation, and field screening-are discussed in this paper. The bubbler and liquid scintillation methods have high accuracy and precision, and small analytical method detection limits of 0.2 and 10 pCi/l (picocuries per liter), respectively. The field screening method generally is used as a qualitative reconnaissance tool.     

Quality assurance in measuring the elemental composition of the alga Fucus vesiculosus

Algae are increasingly used for the purpose of environmental biomonitoring, for instance in the long-term program of the Federal Environmental Specimen Bank of Germany. Therefore, for the studies presented here, freeze-dried samples of Fucus vesiculosus collected from the North Sea shores were analyzed for a broad range of elements by instrumental neutron activation analysis (INAA), while inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) were carried out on digests. The entire analytical procedures, including field sampling, cleaning of material, sample handling, determination of blanks and instrumental parameters, are described. Certified reference materials analyzed in parallel with real samples and intermethod comparisons were used for assuring the accuracy of the analytical data. Reproducibility of INAA measurements was between 4 and 6% depending on the element considered. Possible sources of uncertainty and variation of the contaminant origins are discussed. Boundary conditions for the performance of algae sampling within environmental monitoring programs and the application of this marine bioindicator for the purpose of controlling time-dependent and local differences in element patterns are presented.     

固体废物氰化物总量和浸出毒性测定方法的比较

中国现行的固体废物氰化物总量和氰化物浸出毒性的分析方法存在缺陷，不便于广泛指导监测工作，笔者优化了固体废物氰化物测定的前处理方法，明确了固体废物氰化物总量、氰化物浸出毒性测定时的样品粒径、浸提方法和消解方法，建立了容量法、分光光度法、流动注射法测定固体废物氰化物总量和浸出毒性的方法，并与标准方法（离子色谱法）进行比较。实验结果表明：容量法、分光光度法、流动注射法测定结果与离子色谱法无显著差异，3种方法测定固体废物氰化物总量加标回收率为80.5%~102%，平行样测定相对标准偏差为3.0%~6.9%，3种方法测定固体废物氰化物浸出毒性加标回收率为80.1%~107%，平行样测定相对标准偏差为7.8%~9.5%，3种方法测定结果精密度和准确度良好，均能够满足固体废物氰化物总量和氰化物浸出毒性的测定要求。其中容量法、分光光度法由于其仪器设备简单、操作简便，可用于突发环境事件应急监测等情况下固体废物氰化物的测定。但容量法检出限较高，不能满足评价标准较低的分析测试工作要求，离子色谱法、分光光度法和流动注射法检出限均能满足一般分析测试要求。     

Remote in situ voltammetric techniques to characterize the biogeochemical cycling of trace metals in aquatic systems

The contamination of aquatic ecosystems by natural and anthropogenic metals has lead to a need to better characterize their impact in the environment. To a large extent, the fate and the (eco)toxicity of these elements in aquatic systems are related to their chemical speciation, which may vary continuously in space and time. Detailed measurements of the fraction of specific metal species or groups of homologous metal species and their variation as a function of the bio-physicochemical conditions of the natural media are thus of prime importance. To determine these metal fractions as well as redox chemical species regulating their distribution (dissolved oxygen, sulfides, iron and manganese oxides), new analytical tools capable of performing in situ, real-time monitoring in both water columns and sediments with minimum perturbation of the media are required. This paper reviews the challenges associated with metal speciation studies, and the progress made with state of the art voltammetric techniques to measure the speciation of metals in situ. More specifically, it summarizes the specific conceptual, analytical, and technical criteria that must be considered and/or fulfilled to develop rugged, field deployable, non-perturbing sensors and probes. Strategies used to satisfy these criteria are presented by describing the up-to-date most advanced voltammetric sensors, mini-/micro-integrated analytical systems, and submersible equipments developed for in situ measurements of trace metals and main redox species in aquatic systems. The spatial and temporal resolutions achieved by these news tools represent a significant advantage over traditional laboratory techniques, while simultaneously remaining cost effective. The application of these tools to aquatic systems is illustrated by several examples of unattended and remote in situ monitoring and/or profiling in water columns and sediments.     

Optimization of sampling for the determination of mean radium-226 concentration in surface soil

There are thousands of properties in the United States on which the soil has been contaminated to some degree with uranium mill tailings. An effort is now underway by the United States Department of Energy to identify sites contaminated with tailings and to perform remedial action when ²²⁶Ra levels exceed current guidelines. Because of the large number of sites involved, it is imperative that sample collection be performed in a cost-effective manner. In this paper we describe the results of a study in which we compared the efficiencies of different methods of sample collection in order to determine an optimal method for estimating the mean ²²⁶Ra concentration in soil. The study involved a field experiment in which extensive sampling was performed on sites known to be contaminated with uranium tailings. The experiment was designed to identify the advantages and limitations of composite sampling, the relative merits of random and uniformly spaced sample collection, the use of field gamma measurements for supplementing and reducing soil sample collection, and practical levels of accuracy and precision that can be obtained. Conclusions regarding gamma measurements are unique to ²²⁶Ra contamination. On the other hand, conclusions concerning composite sampling and random versus uniformly spaced sampling may depend primarily on the way the contamination was spread by man and hence may not be unique to ²²⁶Ra.Research sponsored by the Department of Remedial Action Projects, Office of Terminal Waste Disposal, U. S. Department of Energy under contract DE-AC05-84OR21400 with the Martin Marietta Energy Systems, Inc.ORNL—Grand Junction Office, Grand Junction, Colorado.     

便携式XRF在污染地块土壤金属元素调查中的应用

研究了便携式X荧光光谱仪（PXRF）测定土壤中砷、铅、铬、铜、锌和镍的性能，评估其检出限、精密度和准确度，探索了土壤水分和粒径对测定结果的影响程度，并与常规实验室分析方法测定结果进行比对。结果表明，PXRF测定土壤中砷、铅、铬、铜、锌和镍的检出限为5~15mg/kg，标准物质测定结果的相对标准偏差（RSD）≤8.6%，相对误差在±15%以内。随着土壤水分含量的增加，各金属元素测定结果均呈下降趋势，而RSD有上升趋势。土壤粒径对测定结果的影响较小，随着土壤粒径减少，各金属元素测定结果的RSD略有下降趋势。PXRF可以简单、快速地测定多种重金属元素，适用于污染地块重金属元素的现场实时监测。     

A new method for detecting individual trees in aerial LiDAR point clouds using absolute height maxima

Data acquired from aerial laser scanner systems are increasingly used for detecting individual trees in operational inventories. In conventional analyses, tree detection is often performed on raster models that use local height maxima filters; an option that is likely to accumulate important errors. In order to reduce errors and improve the detection of individual trees, a new method is proposed that uses an Absolute Height Maxima (AHM) filter applied on the original point clouds obtained from Aerial Laser Scanning (ALS). ALS point clouds at a density of 2 to 4 points per square meter were acquired over forest stands in Hyrcanian forests. In the new method, false trees and commission errors were automatically found and excluded. To evaluate the efficiency of this new method, 121 sample trees in the field were located, with a DGPS and a mapping camera. The height and crown radius of the sample trees were also measured. The field-surveyed variables were compared to the closest detected tree, with an overall detection accuracy of 75.2%. The initial results of this analysis allowed us to hypothesize that a higher detection of tree may be expected with larger densities.     

环境监测实验室认可中应关注的若干问题

对《检测和校准实验室能力认可准则》（简称《准则》）实施中关于有效性评价实施不到位、关注实验室法律文本的法律性、把握不符合项的实施准确性、实验室CNAS能力验证、测量不确定度政策落实不到位等问题进行了探讨。指出，应从环境监测实验室管理实际出发，深刻理解《准则》的管理要求和作用，以《准则》规范实验室行为，不断改进和完善实验室管理体系建设，确保管理体系持续有效运行。     

电感耦合等离子体发射光谱法（ICP-AES)与火焰原子吸收法（AAS）测定水中铁、锰方法对比

采用电感耦合等离子体发射光谱法、火焰原子吸收法测定水中的铁、锰，优化了测定条件。结果表明，两种方法检Ⅲ限均较低，准确度高，精密度好，具有很强的可比性。