Sampling and Sample Homogeneity as Introductory Topics in Analytical Chemistry Undergraduate Courses

This work deals with the development of an experiment to evaluate the effect of sample characteristics on precision and accuracy of the sampling step. Parameters such as sample homogeneity, particle sizes, and sample mass were evaluated by analyzing the standard deviations (n = 3) obtained for Ca, Fe, Mg, Na, P, S, and Zn determinations in a breakfast cereal sample by inductively coupled plasma optical emission spectrometry. The proposed experiment can improve the assimilation of important concepts such as sampling, sample representativity, precision and accuracy by undergraduate students in analytical chemistry laboratory courses.     

Determination of Trace Elements in Biological Standard Reference Materials by Graphite Furnace Atomic Absorption Spectrometry with Solid and Slurry Sampling

Compared to conventional dissolution methods, solid and slurry sampling methods offer advantages which include speed, improved sensitivity, a reduced risk of contamination, and a reduced risk of analyte loss. Most successful graphite furnace atomic absorption spectrometry (GFAAS) results have been obtained by the use of modern furnace technology, which includes Zeeman background correction, platform atomization, and matrix modifiers. In this work, solid and slurry sampling were investigated for the determination of Ag, Cu, Fe, Mn, Pb, and Zn in biological National Institute of Standards and Technology (NIST) standard reference materials (SRMs) with the use of vintage (1980) GFAAS instrumentation, aqueous calibration, and deuterium arc background correction. Although reasonable accuracy was obtained with solid sampling, the relative standard deviation was between 13 and 53%, which was probably caused by the inability of the furnace to reproducibly vaporize the sample and the inability of deuterium arc background correction to account for the high background signals. Good accuracy and precision (3–13%) were obtained with slurry sampling, with the exception of the determination of copper in citrus leaves. This low result (three times below the certified value) and high precision (RSD = 31%) were probably caused by irreproducible atomization of the sample matrix.     

Linear quantification calibration of crystallinity based on a simple univariate analysis of binary chemical images by selecting a threshold to define the sampling depth in Raman mapping

It is common belief that in Raman mapping, the sampling depth from which Raman signal is collected originates from a probe laser spot size of approximately 1–5 µm³. Actually, the active pharmaceutical ingredient (API) crystals detected by mapping on the sample surface distribute from surface to over a few tens to hundreds of microns into the sample, as determined by z‐slices mapping in this context. It was also found that the score of API crystals detected in a chemical image decrease with their depth into the sample. Therefore, a larger threshold of the binary chemical images can be used to restrict the sampling depth and consequently eliminate the problem of ‘saturation’ by quantifying merely the amount of API crystals within a sampling volume equivalent to a smaller sampling depth rather than the overall detected crystalline API in the chemical images. Eventually, one single linear quantification calibration was established over the crystallinity from sub‐percent (<1%) to over 20% w/w of a model sample by using a simple univariate analysis of binary chemical images method. Copyright © 2013 John Wiley & Sons, Ltd.     

Current Status of Direct Solid Sampling for Electrothermal Atomic Absorption Spectrometry—A Critical Review of the Development between 1995 and 2005

Abstract

The literature about direct solid sampling (SS) and slurry sampling atomic absorption spectrometry (AAS) over the past decade has been surveyed critically. It became apparent that a very significant change had occurred, particularly in the relation between the two major techniques used for that purpose. In the 1990s, slurry sampling was typically considered the technique of choice, combining the significant advantages of the solid and the liquid sampling methods, at least in part because of the availability of a commercial accessory for automatic slurry sampling. The situation is completely inverted now, as the above accessory has been discontinued and rugged and reliable accessories for direct SS became available. Direct SS electrothermal (ET) AAS has been shown to provide the best limits of detection because of the absence of any dilution and a minimal risk of contamination. Calibration against aqueous standards appears to be feasible after careful program optimization. The absence of any significant sample handling makes SS ET AAS ideally suited for fast screening analyses. The introduction of high‐resolution continuum source AAS appears to open additional attractive features for SS ET AAS because of the significantly simplified optimization of furnace programs and the visibility of the spectral environment, which makes it easy to avoid spectral interferences. New calibration strategies make a “dilution” of samples unnecessary, which used to be one of the major limitations of SS ET AAS. Finally, direct SS analysis is an important contribution to clean chemistry, as practically no reagents are used.     

Speciation Analysis of Mercury in Aquatic Environment

Abstract

This review considers methods for mercury speciation with low limits of detection that can be applied to real aquatic environmental samples (waters, sediments, biological tissues). Special attention is given to the necessity of clean sampling procedures and the proper storage of the samples. In this review, different extraction techniques for sediments and biological tissues are considered. The performance of different separation techniques, like liquid chromatography and off‐line and on‐line gas chromatography, are compared for their environmental applications.     

A statistical method for characterizing the noise in nonlinearly reconstructed images from undersampled MR data: The POCS example

The projection-onto-convex-sets (POCS) algorithm is a powerful tool for reconstructing high-resolution images from undersampled k-space data. It is a nonlinear iterative method that attempts to estimate values for missing data. The convergence of the algorithm and its other deterministic properties are well established, but relatively little is known about how noise in the source data influences noise in the final reconstructed image. In this paper, we present an experimental treatment of the statistical properties in POCS and investigate 12 stochastic models for its noise distribution beside its nonlinear point spread functions. Statistical results show that as the ratio of the missing k-space data increases, the noise distribution in POCS images is no longer Rayleigh as with conventional linear Fourier reconstruction. Instead, the probability density function for the noise is well approximated by a lognormal distribution. For small missing data ratios, however, the noise remains Rayleigh distributed. Preliminary results show that in the presence of noise, POCS images are often dominated by POCS-enhanced noise rather than POCS-induced artifacts. Implicit in this work is the presentation of a general statistical method that can be used to assess the noise properties in other nonlinear reconstruction algorithms.     

层状介质上时空展源瞬变电磁响应的计算方法研究

在瞬变电磁法的实际应用中,由于发射回线和发射波形的不规则性而导致其发射源成为时空展源. 展源效应的忽略会造成正反演和数据解释的差错,因此开展展源效应的研究对于瞬变电磁法的实际应用具有重要的意义. 对于空间展源,本文以磁偶极子的响应为基响应,应用有源空间的互易定理和第二类曲线积分,提出了一种可基于发射回线数值坐标求取任意形状发射回线响应的计算方法. 同时对于时间展源,以阶跃波形的响应为基响应,对阶跃响应的特性进行了分析,提出了一种对发射信号进行非均匀采样的高效时间域计算方法,解决了对数采样的基响应与高密度采样的发射波形之间进行常规卷积时所面临的时间与精度之间的矛盾. 通过对层状大地上展源响应的模拟仿真和对比验证显示了本文所提出方法的正确性. 最后本文考察了几种常见时空展源在常规近似前后响应的差别,并给出了相关结论. 关键词： 分层介质 展射电源 互易定理 非均匀采样     

高分辨宽测绘带星载合成孔径雷达频域重构算法

针对传统星载合成孔径雷达(SAR)系统高分辨率和宽测绘带之间的矛盾,采用方位向偏置相位中心结合距离向波束扫描（ScanSAR）模式实现同时高分辨宽测绘带SAR成像,并针对雷达脉冲发射频率、平台速度和天线尺寸不满足严格约束条件导致的方位向非均匀采样提出了频域重构算法。该算法可以实现精确频谱重构,并且极大地提高了系统设计和参数选择的灵活性。五扫六通道SAR系统的频域重构算法的仿真结果显示成对回波抑制达60 dB以上,方位模糊比达-23 dB,证明了该算法的有效性。     

基于中位数排序集抽样的非参数估计

本文提出中位数排序集抽样下总体中位数的非参数估计,证明了这种估计具有强相合性和渐近正态性,并系统验证了新估计量的功效一致优于排序集抽样下和简单随机抽样下总体中位数的估计量。最后,我们对针叶树的一组真实数据进行了实际应用。