Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma–atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.     

Proposition of a compensated pixelwise calibration for photonic infrared cameras and comparison to classic calibration procedures: Case of thermoelastic stress analysis

In this paper, we propose a compensated pixelwise calibration that integrates the effects of the camera housing temperature. The results of this calibration are compared on black body images to classic two points Non Uniformity Correction based calibrations, compensated or not. It is shown that the proposed approach leads to a significant improvement in the thermal resolution with a reduction in the mean error as well as the standard deviation. The approach is finally challenged on a real case measurement focusing on thermoelasticity. The gain in terms of accuracy measurement is highlighted by comparing the proposed calibration to classic calibrations and the scope of interest of this new calibration is discussed.     

A strategy for multivariate calibration based on modified single-index signal regression: Capturing explicit non-linearity and improving prediction accuracy

In this paper, a modified single-index signal regression (mSISR) method is proposed to construct a nonlinear and practical model with high-accuracy. The mSISR method defines the optimal penalty tuning parameter in P-spline signal regression (PSR) as initial tuning parameter and chooses the number of cycles based on minimizing root mean squared error of cross-validation (RMSECV). mSISR is superior to single-index signal regression (SISR) in terms of accuracy, computation time and convergency. And it can provide the character of the non-linearity between spectra and responses in a more precise manner than SISR. Two spectra data sets from basic research experiments, including plant chlorophyll nondestructive measurement and human blood glucose noninvasive measurement, are employed to illustrate the advantages of mSISR. The results indicate that the mSISR method (i) obtains the smooth and helpful regression coefficient vector, (ii) explicitly exhibits the type and amount of the non-linearity, (iii) can take advantage of nonlinear features of the signals to improve prediction performance and (iv) has distinct adaptability for the complex spectra model by comparing with other calibration methods. It is validated that mSISR is a promising nonlinear modeling strategy for multivariate calibration.     

An investigation of calibration materials for the measurement of metals in ambient particulate matter on filters by LA-ICP-MS

Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques.     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Review on the thickness measurement of ultrathin oxide films by mutual calibration method

Mutual calibration was suggested as a method to determine the absolute thickness of ultrathin oxide films. It was motivated from the large offset values in the reported thicknesses in the Consultative Committee for Amount of Substance (CCQM) pilot study P-38 for the thickness measurement of SiO₂ films on Si(100) and Si(111) substrates in 2004. Large offset values from 0.5 to 1.0 nm were reported in the thicknesses by ellipsometry, X-ray reflectometry (XRR), medium-energy ion scattering spectrometry (MEIS), Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), and transmission electron microscopy (TEM). However, the offset value for the thicknesses by X-ray photoelectron spectroscopy (XPS) was close to zero (−0.013 nm). From these results, the mutual calibration method was reported for the thickness measurement of SiO₂ films on Si(100) by combination of TEM and XPS. The mutual calibration method has been applied for the thickness measurements of hetero oxide films such as Al₂O₃ and HfO₂. Recently, the effect of surface contamination was reported to be critical to the thickness measurement of HfO₂ films by XPS. On the other hand, MEIS was proved to be a powerful zero offset method which is not affected by the surface contamination. As a result, the reference thicknesses in the CCQM pilot study P-190 for the thickness measurement of HfO₂ films on Si(100) substrate were determined by mutual calibration method from the average XRR data and MEIS analysis. Conclusively, the thicknesses of ultrathin oxide films can be traceably certified by mutual calibration method and most thickness measurement methods can be calibrated from the certified thicknesses.     

A two-point calibration method for quantifying organic binary mixtures using secondary ion mass spectrometry in the presence of matrix effects

Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′-bis(9-carbazolyl) biphenyl and tris(2-phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two-point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one-point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two-point calibration method could be of significant benefit to SIMS analysts.     

基于麻雀搜索算法结合深度前馈神经网络的近红外模型转移方法研究

该文提出了一种基于麻雀搜索算法结合深度前馈神经网络（SSA－DFN）的近红外光谱模型转移方法。使用深度前馈神经网络拟合不同仪器采集到的光谱之间的非线性函数映射,并将麻雀搜索算法用于网络各层连接权值和阈值的初始化,通过种群中个体位置的迭代更新,求得连接权值和阈值的最优初始值;通过多次调整深度前馈神经网络模型的超参数,使网络拟合效果趋于最优,最终确定转移函数。为验证方法的有效性,分别从烟叶近红外光谱谱图、主成分投影和预测结果的角度,将SSA－DFN方法与分段直接校正算法（PDS）、典型相关性分析算法（CCA）转移前后的效果进行了对比。结果表明SSA－DFN方法转移后的从机光谱与原主机光谱重合度最高,转移后主、从机总糖、烟碱含量的预测结果差异不显著,预测平均误差从8.32%、9.15%分别降至4.65%、4.82%,预测均方根误差（RMSEP）和决定系数（R2）等指标均优于PDS和CCA,取得了最佳的转移效果,可满足企业需求。结果表明该方法是一种有效的模型转移方法。     

基于非同步替代光谱定标的地表下垫面影响分析

对760nm附近的氧气吸收带,选用植被、枯萎植被、人工地物、沙地和雪地五种典型地表类型,基于模拟数据进行非同步替代光谱定标方法的误差分析,比较不同地表类型得到的光谱定标准确度,为高光谱成像仪的非同步替代光谱定标提供定标图像选择策略.结果表明:运用两种光谱匹配方法——光谱角度匹配和欧氏距离法得到的定标误差基本一致;730~800nm的地表反射率曲线标准差在0.05nm以内时,定标误差集中在±0.5nm范围内;人工地物类型中个别地物如橄榄绿光泽涂料和植被大面积覆盖的图像数据不适合用于非同步替代光谱定标.     

光栅投影相位法系统模型及标定方法

本文针对传统投影光栅相位法的光学三角法模型进行了改进,采用直入射光路并配合使用一种简便易行的标定方法,只需使用相移公式求取相位差,而不会引入与系统几何位置关系有关的量,简化了求取高度矩阵的要求。实验结果表明,新系统模型精度良好,测量误差为0.107 mm。采用该模型和标定方法可以克服传统方法系统模型的局限性,最大限度减少误差源并提高抗干扰性。