Calibration Transfer Techniques Research Articles

Calibration transfer in temperature modulated gas sensor arrays

Shifts in working temperature are an important issue that prevents the successful transfer of calibration models from one chemical instrument to another. This effect is of special relevance when working with gas sensor arrays modulated in temperature. In this paper, we study the use of multivariate techniques to transfer the calibration model from a temperature modulated gas sensor array to another when a global change of temperature occurs. To do so, we built 12 identical master sensor arrays composed of three different types of commercial Figaro sensors and acquired a dataset of sensor responses to three pure substances (ethanol, acetone and butanone) dosed at 7 concentrations. The master arrays are then shifted in temperature (from −50 to 50°C, ΔT=10°C) and considered as slave arrays. Data correction is performed for an increasing number of transfer samples with 4 different calibration transfer techniques: Direct Standardization, Piece-wise Direct Standardization, Orthogonal Signal Correction and Generalized Least Squares Weighting. In order to evaluate the performance of the calibration transfer, we compare the Root Mean Square Error of Prediction (RMSEP) of master and slave arrays, for each instrument correction. Best results are obtained from Piece-wise Direct standardization, which exhibits the lower RMSEP values after correction for the smaller number of transfer samples.

Intercalibration of Microwave Radiometer Brightness Temperatures for the Global Precipitation Measurement Mission

A technique for comparing spaceborne microwave radiometer brightness temperatures (Tb) is described in the context of the upcoming National Aeronautics and Space Administration Global Precipitation Measurement (GPM) mission. The GPM mission strategy is to measure precipitation globally with high temporal resolution by using a constellation of satellite radiometers logically united by the GPM core satellite, which will be in a non-sun-synchronous medium inclination orbit. The usefulness of the combined product depends on the consistency of precipitation retrievals from the various microwave radiometers. The Tb calibration requirement to achieve such consistency demands first that Tb's from the individual radiometers be free of instrument and measurement artifacts and, second, that these self-consistent Tb's will be translated to a common standard (GPM core) for the unification of the precipitation retrieval. The intersatellite radiometric calibration technique described herein serves both the purposes by comparing individual radiometer observations to radiative transfer model (RTM) simulations (for “self-consistency” check) and by using a double-difference technique (to establish a linear calibration transfer function from one radiometer to another). This double-difference technique subtracts the RTM-simulated difference from the observed difference between a pair of radiometer Tb's. To establish a linear inter-radiometer calibration transfer function, comparisons at both the cold (ocean) and the warm (land) end of the Tb's are necessary so that, using these two points, slope and offset coefficients are determined. To this end, a simplified calibration transfer technique at the warm end (over the Amazon and Congo rain forest) is introduced. Finally, an error model is described that provides an estimate of the uncertainty of the radiometric bias estimate between comparison radiometer channels.

Use of synthetic wine for models transfer in wine analysis by HS-MS e-nose

A method to verify the feasibility of the calibration transfer technique in HS-MS wine analysis is proposed. PLS multivariate calibration models, whose elaboration and prediction quality are fully discussed, have been built for the quantitative determination of three of the most common volatiles found in wine aroma: ethyl hexanoate (EH), isoamyl acetate (IA) and 2-methyl butanol (MB). The method involves the use of a fortified synthetic wine to overcome the instability drawbacks related to the natural evolution of real wines. The results showed a decrease of the prediction error through the time for the three compounds when the calibration transfer is applied.

Content uniformity determination of pharmaceutical tablets using five near-infrared reflectance spectrometers: A process analytical technology (PAT) approach using robust multivariate calibration transfer algorithms

Near-infrared calibration models were developed for the determination of content uniformity of pharmaceutical tablets containing 29.4% drug load for two dosage strengths (X and Y). Both dosage strengths have a circular geometry and the only difference is the size and weight. Strength X samples weigh approximately 425 mg with a diameter of 12 mm while strength Y samples, weigh approximately 1700 mg with a diameter of 20 mm. Data used in this study were acquired from five NIR instruments manufactured by two different vendors. One of these spectrometers is a dispersive-based NIR system while the other four were Fourier transform (FT) based. The transferability of the optimized partial least-squares (PLS) calibration models developed on the primary instrument (A) located in a research facility was evaluated using spectral data acquired from secondary instruments B, C, D and E. Instruments B and E were located in the same research facility as spectrometer A while instruments C and D were located in a production facility 35 miles away. The same set of tablet samples were used to acquire spectral data from all instruments. This scenario mimics the conventional pharmaceutical technology transfer from research and development to production. Direct cross-instrument prediction without standardization was performed between the primary and each secondary instrument to evaluate the robustness of the primary instrument calibration model. For the strength Y samples, this approach was successful for data acquired on instruments B, C, and D producing root mean square error of prediction (RMSEP) of 1.05, 1.05, and 1.22%, respectively. However for instrument E data, this approach was not successful producing an RMSEP value of 3.40%. A similar deterioration was observed for the strength X samples, with RMSEP values of 2.78, 5.54, 3.40, and 5.78% corresponding to spectral data acquired on instruments B, C, D, and E, respectively. To minimize the effect of instrument variability, calibration transfer techniques such as piecewise direct standardization (PDS) and wavelet hybrid direct standardization (WHDS) were used. The PDS approach, the RMSEP values for strength X samples were lowered to 1.22, 1.12, 1.19, and 1.08% for instruments B, C, D, and E, respectively. Similar improvements were obtained using the WHDS approach with RMSEP values of 1.36, 1.42, 1.36, and 0.98% corresponding to instruments B, C, D, and E, respectively.

Transferência de calibração em métodos multivariados

Calibration transfer has received considerable attention in the recent literature. Several standardization methods have been proposed for transferring calibration models between equipments. The goal of this paper is to present a general revision of calibration transfer techniques. Basic concepts will be reviewed, as well as the main advantages and drawbacks of each technique. A case study based on a set of 80 NIR spectra of maize samples recorded on two different instruments is used to illustrate the main calibration transfer techniques (direct standardization, piecewise direct standardization, orthogonal signal correction and robust variable selection).

Process analytical technology case study, part III: Calibration monitoring and transfer

This is the third of a series of articles detailing the development of near-infrared spectroscopy methods for solid dosage form analysis. Experiments were conducted at the Duquesne University Center for Pharmaceutical Technology to develop a system for continuous calibration monitoring and formulate an appropriate strategy for calibration transfer. Indicators of high-flux noise (noise factor level) and wavelength uncertainty were developed. These measurements, in combination with Hotelling's T(2) and Q residual, are used to continuously monitor instrument performance and model relevance. Four calibration transfer techniques were compared. Three established techniques, finite impulse response filtering, generalized least squares weighting, and piecewise direct standardization were evaluated. A fourth technique, baseline subtraction, was the most effective for calibration transfer. Using as few as 15 transfer samples, predictive capability of the analytical method was maintained across multiple instruments and major instrument maintenance.