Sampling and metrology

The result of a measurement refers in principle only to the amount of substance actually contributing to the analytical signal. However, an appropriate definition of the measurand must include a specification of the system for which the result of the measurement should apply. All systems being inherently heterogeneous, representativity assumes importance for the metrological quality of a measurement, and the process needed to ascertain representativity is sampling. The contribution from this characteristic must be included when expressing the uncertainty of the reported value of the measurand. Representative sampling of systems that are infinite or non-uniform was developed by Pierre Gy in his Theory of Sampling. Finite systems can achieve uniformity by mechanical treatment and mixing; the heterogeneity of these systems can be characterized by a sampling constant, expressed in units of weight, for each particular species being determined. Examples of the contribution of sampling to the uncertainty of analytical results are discussed for some biological materials. Presented at the 2nd International Conference on Metrology – Trends and Applications in Calibration and Testing Laboratories, November 4–6, 2003, Eilat, Israel.     

Designing a contaminated soil sampling strategy for human health risk assessment

Human health risk assessment is a site-based approach used to identify the potential health hazards which are induced by an old site contamination. For a proper evaluation of the daily doses of contaminants to which people will be exposed given the future occupation of the site, both a characterization and a quantification of soil pollution are needed. Such information can be provided by soil sampling. Thus the choice of the location, the number, depth and type of soil samples is very important and ought to follow a well-defined strategy. A review of contaminated site sampling practices in Europe and North America could not identify any completely formalized sampling strategy for human health risk assessment. On the contrary there are several approaches which can be roughly classified into two categories: a systematic sampling scheme over the whole site, on the one hand, and a sampling design driven by an initial knowledge of the contamination sources and fitted to the suspected pollution pattern, on the other. The first approach provides a complete coverage of the site but it may be rather expensive and entail useless sampling. The performance of the second depends on the quality of prior information. Actually both methods can be combined as explained hereafter. In view of the specificity of each site, the requirements of health risk assessment and the time and cost constraints, it seems difficult to work out a typical soil sampling strategy suitable for all sites. However, some recommendations can be made according to the site dimensions, the nature, degree and heterogeneity of contamination, and the (future) use of the site. The scientist should thus rely on a thorough examination of all available information (site history, geology and hydrogeology, soil properties, contaminants behaviour , etc.) to delimit contaminated areas as homogeneous as possible and then distribute the sampling points (e.g.using a sampling grid). They should also take the potential exposure paths into account in order to define the areas and soil strata to be sampled as a priority. Statistical and geostatistical tools can be helpful for formulating a sampling strategy as well as for interpreting the collected data. Received: 7 December 2001 Accepted: 24 February 2002     

Study of parameters associated with the determination of cadmium in lake sediments by slurry sampling electrothermal atomic absorption spectrometry

Cadmium concentration in lake sediments is determined by suspending the solid samples in a solution containing 5% (v/v) concentrated nitric acid and 0.1% (v/v) Triton X-100. Three modifiers were tested for the direct determination. The furnace temperature programmes and appropriate amount for each modifier were optimised to get the highest signal and the best separation between the atomic and background signals. The drying stage is performed by programming a 400 °C temperature, a ramp time of 25 s and hold time of 10 s on the power supply of the atomiser. No ashing step is used and platform atomisation is carried out at 2200 °C. W–Rh permanent modifier combined with conventional modifier by delivering 10 μl of 0.50% (w/v) NH₄H₂PO₄ solution was the best chemical modifier for cadmium determination. This modifier also acts as a liquid medium for the slurry, thus simplifying the procedure. Calibration is performed using aqueous standards in the 1–5 μg l⁻¹ range. The optimised method gave a limit of detection of 0.56 ng ml⁻¹, characteristic mass of 10.1±0.8 pg for aqueous standard, 9.6±0.7 pg for slurry samples containing different Cd concentrations and good precision (7.6–5.2%). The method was validated by analysing four certified reference lake sediment materials: LKSD-1, LKSD-2, LKSD-3 and LKSD-4; satisfactory recoveries were obtained (90.0–96.3%) and no statistical differences were observed between the experimental and the certified cadmium concentration. The developed methodology was used to determine cadmium in three ‘real’ sediment samples from lakes in the area of Wielkopolski National Park, Poland.     

The raised-cosine wavelets in computerized tomography

In Computerized Tomography (CT), an image must be recovered from its sampled projections in the form of values of the Radon transform. In this work a method of recovering the image is based on the properties of the raised-cosine wavelet. This wavelet has a closed form which allows for certain precomputations and avoids convolution. The rate of convergence of the resulting algorithm to the image density function is found under suitable hypotheses. This algorithm is then tested on the standard Shepp–Logan     

The U.S. Department of Energy (DOE) Sampling and Analytical Chemistry Guide: Doe Methods for Evaluating Environmental and Waste Management Samples

Abstract

DOE Methods for Evaluating Environmental and Waste Management Samples (DOE Methods) is a guidance/methods document to support sampling and analysis activities at DOE sites. DOE Methods is intended to supplement existing guidance documents (e.g., EPA's Test Methods for Evaluating Solid Waste, SW-846), which generally apply to low-level or nonradioactive samples. DOE Methods targets the complexities of DOE radioactive mixed waste and environmental samples. The document contains quality assurance (QA), quality control (QC), safety, sampling, organic analysis, inorganic analysis, and radioanalytical guidance as well as sampling and analytical methods. An addendum is distributed every six months (April and October) with updated guidance and additional methods.

DOE Methods provides a vehicle for technology transfer within the environmental restoration (ER) and waste management (WM) (collectively known as EM) community. As DOE Methods evolves, its usefulness and applicability are anticipated to grow to meet the demands of the DOE/EM mission. At the present time, DOE Methods contains methods and guidance information supplied by DOE sites. Because the EM activities in DOE are not unique to the United States, the international environmental community could benefit from the information gathered for the DOE program. This information could provide additional resources for their EM activities.     

用极值频率法分析数字全息的记录条件

根据全息理论,通过分析全息图光栅结构的极值频率,利用抽样定理以及频谱分离条件,分析了离轴菲涅耳全息的记录条件,得到了不同于以往文献的最小记录距离及参考光源设置表达式,并做了计算机模拟验证.结果表明：用该方法推得的离轴菲涅耳全息最小记录距离和参考光设置表达式是正确的.只有同时满足抽样条件和频谱分离条件,才能得到高质量的再现像.     

大气气溶胶中有机碳和元素碳监测方法的进展

本文主要介绍和评述了近10年来大气气溶胶中的有机碳和元素碳的采样和分析技术的进展,引用参考文献41篇。     

高纯四氯化锗测试样品的采集和制备方法研究

针对光纤级高纯四氯化锗(99.999999%)中痕量含氢杂质吸收峰红外透过率检测(FTIR)用试样的采集,以及痕量金属杂质的电感耦合等离子体质谱法(ICP-MS)测定用试样的制备方法进行了系统研究。设计开发了用于检测痕量含氢杂质吸收峰红外透过率的样品采集实验装置,实现了含氢杂质(如—OH、—CH、HCl等)吸收峰的红外透过率在线连续测试,试样采集过程全密闭进行,避免了采样过程的二次污染,采样过程流程简短,操作简便;实验优选了在制备ICP-MS法测定痕量金属杂质用的试样过程中消除四氯化锗基体干扰、防止砷等易挥发杂质损失以及防止样品处理过程污染试样的制样方法,实现了试样制备过程二次污染源的有效控制,制样过程试剂消耗量少,制备时间短,待测元素无损失。     

Determination of hydrogen sulfide and volatile thiols in air samples by mercury probe derivatization coupled with liquid chromatography-atomic fluorescence spectrometry

A new procedure is proposed for the sampling and storage of hydrogen sulphide (H₂S) and volatile thiols (methanethiol or methyl mercaptan, ethanethiol and propanethiol) for their determination by liquid chromatography. The sampling procedure is based on the trapping/pre-concentration of the analytes in alkaline aqueous solution containing an organic mercurial probe p-hydroxymercurybenzoate, HO-Hg-C₆H₄-COO⁻ (PHMB), where they are derivatized to stable PHMB complexes based on mercury-sulfur covalent bonds. PHMB complexes are separated on a C₁₈ reverse phase column, allowing their determination by liquid chromatography coupled with sequential non-selective UV-vis (DAD) and mercury specific (chemical vapor generation atomic fluorescence spectrometry, CVGAFS) on-line detectors. PHMB complexes, S(PHMB)₂CH₃S-PHMB, C₂H₅S-PHMB and C₃H₇S-PHMB, are stable alt least for 12 h at room temperature and for 3 months if stored frozen (−20 °C).The best analytical figures of merits in the optimized conditions were obtained by CVGAFS detection, with detection limits (LODc) of 9.7 μg L⁻¹ for H₂S, 13.7 μg L⁻¹ for CH₃SH, 17.7 μg L⁻¹ for C₂H₅SH and 21.7 μg L⁻¹ for C₃H₇SH in the trapping solution in form of RS-PHMB complexes, the relative standard deviation (R.S.D.) ranging between 1.0 and 1.5%, and a linear dynamic range (LDR) between 10 and 9700 μg L⁻¹. Conventional UV absorbance detectors tuned at 254 nm can be employed as well with comparable R.S.D. and LDR, but with LODc one order of magnitude higher than AFS detector and lower specificity. The sampling procedure followed by LC-DAD-CVGAFS analysis has been validated, as example, for H₂S determination by a certified gas permeation tube as a source of 3.071 ± 0.154 μg min⁻¹ of H₂S, giving a recovery of 99.8 ± 7% and it has been applied to the determination of sulfur compounds in real gas samples (biogas and the air of a plant for fractional distillation of crude oil).     

Passive sampling and/or extraction techniques in environmental analysis: a review

The current state-of-the-art of passive sampling and/or extraction methods for long-term monitoring of pollutants in different environmental compartments is discussed in this review. Passive dosimeters that have been successfully used to monitor organic and inorganic contaminants in air, water, sediments, and soil are presented. The application of new approaches to the determination of pollutants at the sampling stage is discussed. The main milestones in the development of passive techniques for sampling and/or extraction of analytes, and in biomonitors used in environmental analysis, are summarized in this review. Passive samplers and biomonitors are compared.