Monodisperse lignin fractions as standards in size-exclusion analysis: Comparison with polystyrene standards

The difficulty of preparing monodisperse lignin fractions on a large scale is a limiting factor in many applications. The present paper addresses this problem by examining the properties and size-exclusion behavior of lignin isolated by the acetosolv pulping process from post-extraction crushed sugarcane bagasse. The isolated lignin was subjected to a solvent pretreatment, followed by preparative gel permeation chromatography fractionation. The fractions were analyzed by high-performance size-exclusion chromatography (HPSEC) and these samples showed a great decrease in polydispersity, compared to the original acetosolv lignin. Several fractions of very low polydispersity, close to unity, were employed as calibration curve standards in HPSEC analysis. This original analytical approach allowed calibration with these lignin fractions to be compared with the polystyrene standards that are universally employed for lignin molecular mass determination. This led to a noteworthy result, namely that the lignin fractions and polystyrene standards showed very similar behavior over a large range of molecular masses in a typical HPSEC analysis of acetosolv lignin.     

EQUINOX55型遥感傅里叶变换红外光谱系统的校正

利用遥感傅 里叶变换红外发射光谱，对红外辐射源的绝对光谱能量分布和热气体浓度进行测量时，首先必须对测得的红外辐射源的发射光谱强度进行校正，为此，需用已知温度的标准绝对黑体对系统进行校正，本文考察了黑体温度对EQUINOX55型遥感傅里叶变换红外光谱的响应函数的影响。结果表明，仪器响应函数随着温度的升高而增加，但当温度比较高时，仪器响应函数曲线变化趋小。     

Linearity of calibration curves: use and misuse of the correlation coefficient

The correlation coefficient is commonly used to evaluate the degree of linear association between two variables. However, it can be shown that a correlation coefficient very close to one might also be obtained for a clear curved relationship. Other statistical tests, like the Lack-of-fit and Mandel’s fitting test thus appear more suitable for the validation of the linear calibration model. A number of cadmium calibration curves from atomic absorption spectroscopy were assessed for their linearity. All the investigated calibration curves were characterized by a high correlation coefficient (r >0.997) and low quality coefficient (QC <5%), but the straight-line model was systematically rejected at the 95% confidence level on the basis of the Lack-of-fit and Mandel’s fitting test. Furthermore, significantly different results were achieved between a linear regression model (LRM) and a quadratic regression (QRM) model in forecasting values for mid-scale calibration standards. The results obtained with the QRM did not differ significantly from the theoretically expected value, while those obtained with the LRM were systematically biased. It was concluded that a straight-line model with a high correlation coefficient, but with a lack-of-fit, yields significantly less accurate results than its curvilinear alternative. Received: 15 January 2002 Accepted: 18 April 2002     

Calibration uncertainty

Methods recommended by the International Standardization Organisation and Eurachem are not satisfactory for the correct estimation of calibration uncertainty. A novel approach is introduced and tested on actual calibration data for the determination of Pb by ICP-AES. The improved calibration uncertainty was verified from independent measurements of the same sample by demonstrating statistical control of analytical results and the absence of bias. The proposed method takes into account uncertainties of the measurement, as well as of the amount of calibrant. It is applicable to all types of calibration data, including cases where linearity can be assumed only over a limited range. Received: 25 August 2001 Accepted: 21 December 2001     

Limits of determination and calibration in HPLC

Summary In HPLC calibration the expressions lowest calibration limit and determination limit are defined in statistical terms. The lowest calibration limit is the minimum mass in the measured series of calibration points. It is calculated from the confidence interval of the inverse of the calibration function as the lowest mass limit that may be differentiated from zero mass with a preset probability of error. If the calculated lowest calibration limit is lower than the actual data, points at lower concentration may be measured. The determination limit is the smallest concentration of an analysis that is differentiated from the concentration zero or an apparent blind value in the calibration curve with a given probability of error.Using two different UV-detectors (variable wavelength and photodiode-array) the lowest calibration limit is experimentally evaluated and compared with specific data for the detectors.Dedicated to Prof. Dr. E. Bayer, Tübingen on ocassion of his 60th birthday.     

Electrical calibration and testing of calorimeters with simulated, time-variable reaction power

For calorimetric investigations where the reconstruction of the real heat-flow rate during the experiment is required, the usual electrical calibration with constant power is often not sufficient. However, the use of a chemical calibration is limited by the number of suitable and certified reactions showing a known dynamics of the heat-flow rate. Therefore, a computer controlled electrical calibration unit was developed capable of duplicating any simulated reaction power-time curve in the calorimetric cell. The calibration unit consists of a universal simulation software with an interface to a programmable precision current supply connected to the calibration heater inside the calorimetric vessel. The reliability of the electrical calibration was proved with a continuous titration calorimeter using different recommended test reactions (TRIS+HCl, dilution of aqueous KCl, NaCl and urea solutions).

In order to test the electrical calibration procedure in the dynamic mode the heat-flow rate of a first-order equilibrium reaction during a continuous titration experiment was simulated. It is demonstrated that the combination of simulation software and electrical calibration hardware provides a very close adaptation of calibration and experiment, allows a more reliable estimation of experimental uncertainties, simplifies the verification of complex data analysis procedures and opens up new possibilities for the optimization of experimental parameters.     

Evaluation of measurement uncertainty for thermometers with calibration equations

The method recommended by Eurachem did not mention the effect of adequateness of calibration equations on the measurement uncertainty. In this work, the sources of measurement uncertainty for two types of thermometer were evaluated. Three calibration equations were adopted to compare its predictive performance. These sources of combined uncertainty include predicted values of calibration equation, nonlinearity and repeatability, reference source, and resolution source. The uncertainty analysis shows that the predicted uncertainly of calibration equations is the main source for two types of thermometer. No significant difference of the uncertainty was found between the classical method and the inverse method. However, the calculation procedure of the inverse method was simpler and easier than that of the classical method.     

Update on the activities of the National Cooperation for Laboratory Accreditation

 The efforts to form a laboratory accreditation cooperation in the United States and North America are described, including activities of the Laboratory Accreditation Working Group and the interim board of the National Cooperation for Laboratory Accreditation. The vision, mission, and guiding principles developed by the two groups are presented, along with the operational documents, such as bylaws, the recognition document, guidance documents and the quality manual drafted by the interim board. Received: 8 June 1998 · Accepted: 16 June 1998     

Multivariate calibration of spectral data using dual-domain regression analysis

To date, few efforts have been made to take simultaneous advantage of the local nature of spectral data in both the time and frequency domains in a single regression model. We describe here the use of a novel chemometrics algorithm using the wavelet transform. We call the algorithm dual-domain regression, as the regression step defines a weighted model in the time-domain based on the contributions of parallel, frequency-domain models made from wavelet coefficients reflecting different scales. In principle, any regression method can be used, and implementation of the algorithm using partial least squares regression and principal component regression are reported here. The performance of the models produced from the algorithm is generally superior to that of regular partial least squares (PLS) or principal component regression (PCR) models applied to data restricted to a single domain. Dual-domain PLS and PCR algorithms are applied to near infrared (NIR) spectral datasets of Cargill corn samples and sets of spectra collected on batch chemical reactions run in different reactors to illustrate the improved robustness of the modeling.     

Conformity assessment and metrology: update on the state of affairs

A couple of years ago, ISO CASCO launched a major project of transforming all the existing ISO Guides on conformity assessment to a comprehensive series of ISO standards 17000 being now in various stages of development. As the concept of traceability underpinning all measurements has been a basic mission of metrology, a number of these standards have a direct bearing on metrology. The series is logically based on a definition standard, ISO 17000, giving, among others, a guidance which activities fall under conformity assessment. The fact that calibration does not, might have important consequences which must yet be assessed. A controversial discussion on some issues has been in progress concerning ISO 17011 on accreditation bodies which touches both on national metrology institutes (NMIs) with an accreditation function and on calibration labs at large. ISO 17040 on peer review could be used with an advantage to support mutual recognition arrangements among a limited number of bodies of a specialized expertise (e.g., CIPM MRA among NMIs under the Metre Convention). ISO 17025 has been the most important standard for the metrology community and has undergone a major overhaul taking on board the uncovered requirements from ISO 9001:2000. In general, the paper will give an update on the developments outlined above and discuss the consequences and further steps from the viewpoint of metrology.