Suitability of different containers for the sampling and storage of biogas and biomethane for the determination of the trace-level impurities – A review

The traceable and accurate measurement of biogas impurities is essential in order to robustly assess compliance with the specifications for biomethane being developed by CEN/TC408. An essential part of any procedure aiming to determinate the content of impurities is the sampling and the transfer of the sample to the laboratory. Key issues are the suitability of the sample container and minimising the losses of impurities during the sampling and analysis process. In this paper, we review the state-of-the-art in biogas sampling with the focus on trace impurities. Most of the vessel suitability studies reviewed focused on raw biogas. Many parameters need to be studied when assessing the suitability of vessels for sampling and storage, among them, permeation through the walls, leaks through the valves or physical leaks, sorption losses and adsorption effects to the vessel walls, chemical reactions and the expected initial concentration level. The majority of these studies looked at siloxanes, for which sampling bags, canisters, impingers and sorbents have been reported to be fit-for-purpose in most cases, albeit with some limitations. We conclude that the optimum method requires a combination of different vessels to cover the wide range of impurities commonly found in biogas, which have a wide range of boiling points, polarities, water solubilities, and reactivities. The effects from all the parts of the sampling line must be considered and precautions must be undertaken to minimize these effects. More practical suitability tests, preferably using traceable reference gas mixtures, are needed to understand the influence of the containers and the sampling line on sample properties and to reduce the uncertainty of the measurement.     

Sampling numbers and function spaces

We want to recover a continuous function using only its function values. Let us assume, that f is from the unit ball of some function space (for example a fractional Sobolev space or a Besov space) and the precision of the reconstruction is measured in the norm of another function space of this type. We describe the rate of convergence of the optimal sampling method (linear as well as nonlinear) in this setting.     

TDI CCD成像系统的研究

采用IL E2TDICCD作为传感器 ,与计算机构成了成像系统 ,并在计算机CRT上显示出图像。解决了CCD的时序电路及功率驱动电路设计问题。采用相关双采样技术滤除CCD输出信号复位噪声 ,提高了视频信号的信噪比。CCD的数据传送速度达到 10MHz ,行扫描速度达到 3.5kHz。     

Metrological estimation of sampling and sample preparation procedures as applied to analytical testing of technogenic origin raw material containing recoverable precious metal

 Different schemes of analytical testing including the sampling, sample preparation and sample analysis operations are considered as applied to a lot of raw material containing recoverable precious metal. The errors resulting from the step-by-step operations of the analytical testing are estimated. Sampling and sample preparation operations are found to be significant contributors to the total error of determination of the percentage and /or weight of a precious metal of interest in a lot. Some ways to diminish both the sampling error and the total error of the analytical testing procedure are recommended. Received: 28 December 1998 · Accepted: 22 February 1999     

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。     

A Sampling Theory for Compact Sets in Euclidean Space

We introduce a parameterized notion of feature size that interpolates between the minimum of the local feature size and the recently introduced weak feature size. Based on this notion of feature size, we propose sampling conditions that apply to noisy samplings of general compact sets in euclidean space. These conditions are sufficient to ensure the topological correctness of a reconstruction given by an offset of the sampling. Our approach also yields new stability results for medial axes, critical points, and critical values of distance functions. The authors were partially supported by DARPA under grant HR0011-05-1-0007 and by ANR under grant “Topologie, Géométrie Différentielle et Algorithmes.”     

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).     

The potential of Raman spectroscopy for characterisation of the fatty acid unsaturation of salmon

Raman spectroscopy has been evaluated for characterisation of the degree of fatty acid unsaturation (iodine value) of salmon (Salmo salar). The Norwegian Quality Cuts from 50 salmon samples were obtained, and the samples provided an iodine value range of 147.8-170.0 g I₂/100 g fat, reflecting a normal variation of farmed salmon. Raman measurements were performed both on different spots of the intact salmon muscle, on ground salmon samples as well as on oil extracts, and partial least squares regression (PLSR) was utilised for calibration. The oil spectra provided better iodine value predictions than the other data sets, and a correlation coefficient of 0.87 with a root mean square error of cross-validation of 2.5 g I₂/100 g fat was achieved using only one PLSR component. The ground samples provided comparable results, but at least two PLSR components were needed. Higher prediction errors were obtained from Raman spectra of intact salmon muscle, and this may partly be explained by sampling uncertainties in the relation between Raman measurements and reference analysis. All PLSR models obtained were based on chemically sound regression coefficients, and thus information regarding fatty acid unsaturation is readily available from Raman spectra even in systems with high contents of protein and water. The accuracy, the robustness and the low complexity of the PLSR models obtained suggest Raman spectroscopy as a promising method for rapid in-process control of the degree of unsaturation in salmon samples.     

光谱仪动态采样时间特性的研究

在实时传输的光谱仪数据采样中,通常存在采样时间间隔不等的现象,这使得实时传输光谱仪在一些特殊场合的应用受到较大的限制,如在预测能力更强,检测精度更高的动态光谱分析法中。而恰恰在动态光谱法等时间分辨光谱分析中对光谱信号的采样定时特性要求更高,时间间隔不等会直接影响光谱分析的结果,得到失真的结论。同时与一般采样所不同的是,光谱仪是一定时间的积分采样,这无形中增加了对光谱仪定时采样特性研究的难度。因此,巧妙地利用锯齿波的幅值与时间存在一线性编码的关系,对某一型号的光谱仪进行采样时间及采样时间间隔的测试与分析,测试表明采样时间与积分时间的设置相关,同时时间间隔与积分时间也息息相关,进一步探究了该型号光谱仪在不同积分时间下采样时间间隔波动的范围。研究对注重光谱时间特性的分析法提供积分时间选取的参考依据,同时也提出了一种评估动态时间特性的方法,有利于光谱的动态特性的评估与应用。     

无富集进样原子荧光光谱法测定地表水中的痕量汞

通过增大样品进样量的方式,样品进样量是标准进样量的10-100倍,降低了汞的检出限,从而达到了无富集直接进样测定地表水中痕量汞.其检出限为0.008μg/L;浓度为0.05μg/L和0.10μg/L左右的有证标准物质测定均值分别为0.0483μg/L和0.1016μg/L,加标回收率为92.3％和95.2％.灵敏度高,精密度好,能达到准确定量Ⅰ类和Ⅱ类地表水汞(0.05μg/L以下)的要求.对汉江湖北段水样进行测定,在较洁净的地表水分析中,氧化还原处理后与酸化水样测定结果差异不大,处理后水样结果略微增大.建议对较洁净的地表水样品将氧化还原预处理步骤省略掉,直接进样.