Interreflection errors in Fourier transform spectroscopy: a preliminary appraisal

The presence of systematic ordinate errors in Fourier transform spectroscopy (FTS) is discussed, largely in terms of interreflection effects between the various interfaces of a two-beam interferometer and its adjacent optical components. Seven distinct categories of interreflection are specified and some consequences are noted. Certain types of optical filter are described which can be used diagnostically to distinguish between ordinate errors arising from interreflections and the intrinsic ordinate errors. The latter are those that remain when the interreflection effects have been removed by optical modifications. A strategy for achieving this is suggested. Finally, a theoretical model is being considered as a general way of handling a complicated problem.     

Intercomparison of industrial near-infrared diffuse reflectance measurements

An intercomparison of diffuse reflectance measurements in the near-infrared region was carried out. Fourteen participants from industry and academia measured a number of different reflectance standards, calibrated at the NPL, over the wavelength range from 800 to 2500 nm. Measurements were made in the integrating sphere geometries, i.e. specular included and specular excluded and in the 0/45 geometry. The results of the intercomparison are presented. The raw data results showed significant variations in the value of diffuse reflectance measured across industry, in excess of 80% difference from NPL reflectance values in some cases. Renormalisation of the data to the NPL near-infrared diffuse reflectance scale significantly improved the agreement in measured values between participants, most being within 5% of the NPL values. Integrating sphere errors were present in many of the instruments used.     

The development of gas standards and calibration techniques for measurements of vehicle, aircraft and industrial emissions, natural gas, occupational exposure and air quality

 The National Physical Laboratory (NPL) is involved in the dissemination of nationally traceable standards to which measurements of air quality, occupational exposure and air pollution source emissions, and natural gas analyses, can be referenced. This has required the development of national primary gas standards using absolute gravimetric and other techniques, and the development of dynamic calibration techniques for gaseous species which would be unstable in high-pressure cylinders. The methodology used for preparing gas standards gravimetrically is described, together with the rigorous quality assurance measurements and consistency checks which are used to demonstrate their accuracy and stability. The uncertainty budget assigned to these standards will also be summarised. NPL primary standards are used to certify traceable 'secondary' gas standards which are disseminated so as to ensure the accuracy of gas analysis measurements. Examples of the applications of these secondary standards are presented. The gas standards are employed in proficiency testing of industrial stack-testing organisations, and results of the initial rounds are presented. NPL gas standards are also now being used as the basis of the United Kingdom Environment Agency's new type-approval and certification scheme for continuous industrial stack-emission analysers. A recent important international initiative, in the field of gas analyses, is the agreement by national standards laboratories across the world to demonstrate the equivalence of their calibrations, by means of key comparisons between them. These worldwide key comparisons are complemented in Europe through the EUROMET initiative which seeks to establish the equivalence and comparability of calibration standards held at national standards laboratories across Europe. Examples of these intercomparisons are presented. Received: 23 March 2000 / Accepted: 18 August 2000     

Improvement of base-calling in multilane automated DNA sequencing by use of electrophoretic calibration standards, data linearization, and trace alignment

We present a new method for the linearization and alignment of data traces generated by multilane automated DNA sequencing instruments. Application of this method to data generated with the Visible Genetics Open Gene DNA sequencing system (using MicroCel 700 gel cassettes, with a 25 cm separation distance) allows read lengths of > 1,000 nucleotides to be routinely obtained with high confidence and > 97% accuracy. This represents an increase of 10-15% in average read length, relative to data from this system that have not been processed in the fashion described herein. Most importantly, the linearization and alignment method allows usable sequence to be obtained from a fraction of 10-15% of data sets which, because of original trace misalignment problems, would otherwise have to be discarded. Our method involves adding electrophoretic calibration standards to the DNA sequencing fragments. The calibration standards are labeled with a dye that differs spectrally from the dye attached to the sequencing fragments. The calibration standards are identical in all the lanes. Analysis of the mobilities of the calibration standards allows correction for both systematic and random variation of electrophoretic properties between gel lanes. We have successfully used this method with two-dye and three-dye DNA sequencing instruments.     

Improved model for improving the inter-instrument agreement of spectrocolorimeters

A proposal by Robertson slightly modified by Berns and Petersen, to use spectral differences to predict systematic errors in spectrophotometers has found limited success in practical application. Porter suggested a way to improve the level of agreement between standardizing laboratories based on the Berns and Petersen method but suggested using derivatives calculated from piecewise polynomial splines. He did not know it at the time, but such a model was already in use. That model now has over five years of successful field testing and this paper discloses how the model was developed, the efficiency with which it can reduce systematic errors and the kinds of errors that cannot presently be corrected by computational comparison of reflectance or transmittance factor readings. For instruments of the same basic design, this model will produce a reduction of the systematic errors in colorimetric coordinates on the order of factors of 2–3. The magnitude of the initial color differences appears to be irrelevant. The corrective power of the model is limited by the numerical noise generated by the process of simulating analytical derivatives. We show that instruments with average color differences of 1.0 CIELAB unit can be reduced to a level of 0.5–0.3 units. Our testing has included a large variety of material samples including textiles, plastics, inks, paints and ceramics. Over 400 samples have been measured in proving this method. In addition, the model has been in place in industrial environments where multiple instruments of different manufacturer have been made to operate successfully from the same set of laboratory standards at reproducibility levels that rival those of national standards laboratories.     

火灾探测器滤光片校准方法

以紫外可见近红外分光光度计为计量标准器建立火灾探测器滤光片校准方法。火焰探测器紫外滤光片校准选择波长范围150~300 nm进行光谱扫描,测量滤光片在紫外区域的透射比;红外滤光片校准选择波长范围800~1 100 nm进行光谱扫描,测量滤光片在红外区域的透射比。线型光束感烟火灾探测器滤光片校准波长扫描范围设置为700~1 100 nm,取850~950 nm透射比平均值计算减光值。火焰探测器紫外滤光片校准结果为220,240,260,280 nm波长下的透射比,红外滤光片校准结果为850,900,950,1 000 nm波长下的透射比,不作合格性判定。线型光束感烟火灾探测器滤光片减光值标称值为0.4,0.9 d B时,误差不超过±0.1 d B;减光值标称值为10.0 d B时,误差不超过±1.0 d B。     

Sweeteners determination in table top formulations using FT-Raman spectrometry and chemometric analysis

A partial least squares (PLS) Fourier transform Raman spectrometry procedure based on the measurement of solid samples contained inside standard glass vials, has been developed for direct and reagent-free determination of sodium saccharin and sodium cyclamate in table top sweeteners. A classical 2² design for standards was used for calibration, but this system provides accuracy errors higher than 13% w/w for the analysis of samples containing glucose monohydrate. So, an extended model incorporating glucose monohydrate (2³ standards) was assayed for the determination of sodium saccharin and sodium cyclamate in all the samples. Mean centering spectra data pre-treatment has been employed to eliminate common spectral information and root mean square error of calibration (RMSEC) of 0.0064 and 0.0596 was obtained for sodium saccharin and sodium cyclamate, respectively. A mean accuracy error of the order of 1.1 and 1.9% w/w was achieved for sodium saccharin and sodium cyclamate, in the validation of the method using actual table top samples, being lower than those obtained using an external monoparametric calibration. FT-Raman provides a fast alternative to the chromatographic method for the determination of the sweeteners with a three times higher sampling throughput than that obtained in HPLC. On the other hand, FT-Raman offers an environmentally friendly methodology which eliminates the use of solvents. Furthermore, the stability of samples and standards into chromatographic standard glass vials allows their storage for future analysis thus avoiding completely the waste generation.     

Quantitative LC-ESI-MS Analysis for Pesticides in a Complex Environmental Matrix Using External and Internal Standards

Abstract

Quantitative liquid chromatography electrospray mass spectrometry (LC-MS) analysis for pesticides in a complex environmental matrix using external and internal standard calibration was investigated. Various approaches to introducing different internal standard compounds to address quantitative errors associated with signal suppression were also examined. The study involved the analysis of pesticides in wheat hay matrix samples using three kinds of internal standard compounds: deuterium labeled (D₃), carbon-13 (singly labeled), and structural analogs (derivatives) of the target analytes. Introduction of the internal standard by volumetric addition and direct post-column infusion were also studied and compared.

Isotopically labeled internal standards (i.e. D₃- ¹³C-) were found to be effective in correcting quantitative errors associated with signal suppression. The application of singly labeled ¹³C compounds may result in nonlinear calibration due to mass interference with the target analyte species. The interference may be compensated by using quadratic curve-fitting or subtraction of the interfering component. Although ineffective as volumetric internal standards, structural analogs can be effective in compensating for signal suppression when introduced into the LC effluent by continuous post-column infusion. Furthermore, the post-column introduction method allows the application of a single internal standard compound for the quantification of each analyte in a multi-component mixture.

The use of internal standards can be effectively incorporated into residue analysis development methods for pesticides in environmental matrices. High accuracy and reproducibility can be achieved while improving method efficiency by reducing the need for comprehensive sample clean-up.     

基于正交信号校正的秸秆青贮饲料粗蛋白近红外分析模型传递方法

探讨了基于不同数据预处理方法的正交信号校正在秸杆饲料近红外光谱模型传递中的应用.以141个秸杆青贮饲料样品为研究对象,以其粗蛋白含量为目标参数,研究了基于无处理、局部中心化、全局中心化和Z-score标准化预处理方法的正交信号校正,在源仪器(SPECTRUM ONE NTS)和目标仪器1(ANTA-RIS)与目标仪器2(FOSS 6500)之间的模型传递效果.实验表明:对于两台傅里叶变换型近红外光谱仪,采用局部中心化、全局中心化和Z-score标准化预处理方法的正交信号校正均可成功实现模型传递,其中局部中心化和全局中心化法的作用效果基本一致,且优于Z-score标准化法.对于傅立叶变换和光栅型近红外光谱仪,全局中心化的作用效果明显优于其它3组处理效果,且只有全局中心化预处理的正交信号校正传递后的模型可用于实际预测.     

A comparative study of the correction of systematic errors in the quantitation of pyrethroids in vegetables using calibration curves prepared using standards in pure solvent

A comparative study of two mathematical approaches was performed in order to correct systematic errors due to the presence of the unexpected interferences which appear when the quantitation of the analyte in real samples is carried out with calibration curves built using standards in pure solvent. These methods consisted in the establishment of different mathematical expressions which transform the concentration (Cs) obtained using calibration graphs built using pure solvent into the corrected concentration (C(M)) that should be obtained if the quantitation is carried out with calibration curves built using standards dissolved in blank matrix extracts. In the two approaches the correction is performed from the results of an intermediate precision study which was carried out using both calibration graphs (prepared using pure solvent and blank matrix extract). By using ANCOVA to compare the slope of both solvent-based and matrix-matched calibration graphs, matrix effect was found in the determination of deltamethrin in tomato and acrinathrin in tomato and pepper. In these cases, both approaches led to good results.     

Use of sol–gels as solid matrixes for laser-induced breakdown spectroscopy

Silicon, zirconium and aluminum sol–gels were investigated as suitable starting materials for tunable matrix calibration standards for laser-induced breakdown spectroscopy. A fast and simple preparation method was developed, using aluminum i-propoxide as the precursor in the sol–gel synthesis, which allows one to quickly prepare solid calibration standards offering very homogenous analyte distribution in the matrix, low optical spectral background, as well as reproducible behavior towards laser ablation and vaporization. The surface of the calibration targets and the morphology of the ablation craters were examined by optical and scanning electron microscopy, and the material ejection process was observed by shadowgraph imaging. Low μg/g detection limits and 4–15% relative standard deviation were measured by laser induced breakdown spectroscopy for Pb, Cr and Be used as internal standards.     

中红外光谱透射比标准物质研制

采用物化性质稳定的单晶硅作为基质,以直流磁控溅射方式轻蒸镀不同厚度的镍、铬混合膜层,实现了中红外波段(500~4000 cm^–1)不同透射比标准物质的研制。研制的中红外光谱透射比标准物质其透射比标称值分别为10%和50%,扩展不确定度优于0.008(k=2)。该标准物质具有量值稳定、光谱平坦等特点,可用于各类傅里叶变换红外光谱设备的透射比校准。     

傅里叶变换近红外光谱法快速检测人血清生化成分

应用傅里叶变换近红外光谱透射技术结合偏最小二乘法(PLS)建立了人血清中7种生化成分的定标模型,利用内部交叉验证和自动优化功能对定标模型进行了优化,确定了最优建模参数。模型对人血清中总胆固醇、甘油三酯、总蛋白、白蛋白、载脂蛋白B、低密度脂蛋白胆固醇、葡萄糖定标样品集的预测值与化学值的相关系数r分别为0.9011、0.9593、0.9249、0.761、0.8831、0.5191、0 9148,预测校正标准误差RMSECV分别为15mg/dL,21.6mg/dL,2 66g/L,3 96g/L,0.091g/L,16.2mg/dL,0.49mmol/L。     

Instrumental dead-time and its relationship with matrix corrections in x-ray fluorescence analysis

The relationship between instrumental dead-time and the self-absorption coefficients, α_ii, in x.r.f. matrix correction by means of influence coefficients, is not generally recognized but has important analytical consequences- Systematic errors of the order of 1% (relative) for any analyte result from experimental uncertainties in instrumental dead-time. Such errors are applied unevenly across a given range of concentration because the error depends on the calibration standards and on the instrumental conditions used. Refinement of the instrumental dead-time value and other calibration parameters to conform with influence coefficients determined elsewhere assumes exact knowledge of dead-time of the instrument used originally, and quite similar excitation conditions and spectrometer geometry for the two instruments. Though these qualifications may not be met, adjustment of any of the parameters (dead-time, reference concentration, background concentration, self-absorption and other influence coefficients) can be easily achieved.     

Rapid and mobile determination of alcoholic strength in wine,beer and spirits using a flow-through infrared sensor

Background  

Ever since Gay-Lussac's time, the alcoholic strength by volume (% vol) has been determined by using densimetric measurements. The typical reference procedure involves distillation followed by pycnometry, which is comparably labour-intensive and therefore expensive. At present, infrared (IR) spectroscopy in combination with multivariate regression is widely applied as a screening procedure, which allows one to determine alcoholic strength in less than 2 min without any sample preparation. The disadvantage is the relatively large investment for Fourier transform (FT) IR or near-IR instruments, and the need for matrix-dependent calibration. In this study, we apply a much simpler device consisting of a patented multiple-beam infrared sensor in combination with a flow-through cell for automated alcohol analysis, which is available in a portable version that allows for on-site measurements.     

Determination of colorimetric uncertainties in the spectrophotometric measurement of colour

A method for the determination of colorimetric uncertainties has been developed in order to meet the requirements for accreditation by the UK accreditation service (UKAS), which include a statement of uncertainty for all certified quantities. The values of the principal sources of spectrophotometric uncertainty are first determined and are used to calculate corresponding components of colorimetric uncertainty using a simple model. The components of uncertainty analysed are 100% level (diffuse reflectance), photometric non-linearity, dark level and wavelength error. Bandwidth error is not significant for NPL surface colour standards because a small bandwidth is always used.

The gloss trap error and specular beam error are determined and corrected so that only the uncertainties after correction need be considered. These can be treated as components of dark level uncertainty. The uncertainties are determined for the following colour data: x, y, Y, u′, v′, L^*, a^* and b^* for the CIE 10° Standard Observer and the CIE Standard Illuminant D₆₅ for three geometries: specular included, specular excluded and 0°/45°. These are now quoted routinely on NPL certificates for ceramic colour standards, white and black ceramic tile standards and Russian opal standards.     

基于尺度不变特征变换筛选稳定特征波长的近红外光谱模型传递方法

该研究利用一维尺度不变特征变换(SIFT)算法寻找烟叶近红外光谱(Near infrared spectroscopy,NIRS)的稳定特征波长,根据样品精密度测试光谱筛选的波长计算重现率和重现度,采用L_9(3~3)正交表优化SIFT算法中的相关参数,使重现率和重现度尽可能高。基于优化的参数和主机上10个代表性样品的光谱,筛选出10个稳定特征波长集合,以这些波长集合并集的光谱响应为自变量,采用偏最小二乘(PLS)方法构建烟叶总植物碱NIRS模型(简称SIFT-PLS)。该模型直接传递到3台从机后,对3台从机样品总植物碱的平均相对预测误差(MRE)均满足小于6%的企业内控要求,而全光谱模型(WW-PLS)直接转移后仅1台从机的MRE满足要求,经分段直接校正(PDS)方法校正从机光谱后,WW-PLS模型也仅对1台从机的MRE小于6%。采用SIFT算法筛选稳定特征波长建立的NIRS模型可在3台从机直接共享,无需转移集,不需对从机光谱或光谱模型进行校正,实现了真正意义的无标样NIRS模型的直接转移。     

Data fusion in multivariate calibration transfer

We report the use of stacked partial least-squares regression and stacked dual-domain regression analysis with four commonly used techniques for calibration transfer to improve predictive performance from transferred multivariate calibration models. The predictive performance from three conventional calibration transfer methods, piecewise direct standardization (PDS), orthogonal signal correction (OSC) and model updating (MUP), requiring standards measured on both instruments, was significantly improved from data fusion either by stacking of wavelet scales or by stacking of spectral intervals, as demonstrated by transfer of calibrations developed on near-infrared spectra of synthetic gasoline. Stacking did not produce as significant an improvement for calibration transfer using a finite impulse response (FIR) filter, but application of SPLS regression to FIR-transferred spectra improves predictive performance of the transferred model.     

Determination of amylose content in starch using Raman spectroscopy and multivariate calibration analysis

Fourier transform Raman spectroscopy and chemometric tools have been used for exploratory analysis of pure corn and cassava starch samples and mixtures of both starches, as well as for the quantification of amylose content in corn and cassava starch samples. The exploratory analysis using principal component analysis shows that two natural groups of similar samples can be obtained, according to the amylose content, and consequently the botanical origins. The Raman band at 480 cm^?1, assigned to the ring vibration of starches, has the major contribution to the separation of the corn and cassava starch samples. This region was used as a marker to identify the presence of starch in different samples, as well as to characterize amylose and amylopectin. Two calibration models were developed based on partial least squares regression involving pure corn and cassava, and a third model with both starch samples was also built; the results were compared with the results of the standard colorimetric method. The samples were separated into two groups of calibration and validation by employing the Kennard-Stone algorithm and the optimum number of latent variables was chosen by the root mean square error of cross-validation obtained from the calibration set by internal validation (leave one out). The performance of each model was evaluated by the root mean square errors of calibration and prediction, and the results obtained indicate that Fourier transform Raman spectroscopy can be used for rapid determination of apparent amylose in starch samples with prediction errors similar to those of the standard method.

The effect of the physical matrix on accurate measurements using fixed volume analytical techniques

In order to perform high accuracy analytical measurements most analytical techniques require some form of calibration using standards of the same quantity as that being measured. The highest accuracy calibration standards are those prepared by mass (gravimetrically) as opposed to by volume (volumetrically). The use of gravimetrically prepared standards to calibrate analytical techniques that rely on fixed volume injections can cause systematic errors, even when the analytical technique does not suffer from a chemical matrix interference. The origin of these errors is explained and is demonstrated experimentally for the analysis of sulphate in synthetic seawater samples, and the measurement of the anionic content of particulate matter following extraction with water and wetting agents; where average measurement biases of +2.7 and -3.2%, respectively, were observed. Proposals are offered for methods to overcome this 'physical matrix effect'.