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Direct solid sample analysis of geological samples with SS-GF-AAS and use of 3D calibration.

These results from direct solid-sample trace-element analysis, with 3D calibration, follow those of earlier publications. Cd, Cr, Cu, Ni, Pb, and Zn have been determined in complex inorganic powder samples, e.g. sediments, soils, rocks, and minerals. The measurements were performed with two SS-GF-AAS spectrometers which differ in the type of graphite furnace (transverse and longitudinal tube) and the background-correction technique (with and without the Zeeman system). The performance of the 3D calibration method was optimized by systematic investigation and the 2D- and 3D calibration techniques were compared. Another feature is the determination of confidence limits of the 3D calibration. This calibration error was calculated by the statistical bootstrap method. The results of calibration experiments and the precision and accuracy of the determination of trace elements in CRMs show that 3D calibration becomes increasingly essential as the refractory character of the analyte increases. Although there are large differences between the state of development and technical performance of the instruments used, 3D-calibration works with both SS-GF-AAS spectrometers.

Journal Article↗

Tackling calibration problems of spectroscopic analysis in high-throughput experimentation.

High-throughput experimentation and screening methods are changing work flows and creating new possibilities in biochemistry, organometallic chemistry, and catalysis. However, many high-throughput systems rely on off-line chromatography methods that shift the bottleneck to the analysis stage. On-line or at-line spectroscopic analysis is an attractive alternative. It is fast, noninvasive, and nondestructive and requires no sample handling. The disadvantage is that spectroscopic calibration is time-consuming and complex. Ideally, the calibration model should give reliable predictions while keeping the number of calibration samples to a minimum. In this paper, we employ the net analyte signal approach to build a calibration model for Fourier transform near-infrared measurements, using a minimum number of calibration samples based on blank samples. This approach fits very well to high-throughput setups. With this approach, we can reduce the number of calibration samples to the number of chemical components in the system. Thus, the question is no longer how many but which type of calibration samples should one include in the model to obtain reliable predictions. Various calibration models are tested using Monte Carlo simulations, and the results are compared with experimental data for palladium-catalyzed Heck cross-coupling.

Journal Article↗

European Prospective Investigation into Cancer and Nutrition (EPIC) calibration study: rationale, design and population characteristics.

The European Prospective Investigation into Cancer and Nutrition (EPIC), which covers a large cohort of half a million men and women from 23 European centres in 10 Western European countries, was designed to study the relationship between diet and the risk of chronic diseases, particularly cancer. Information on usual individual dietary intake was assessed using different validated dietary assessment methods across participating countries. In order to adjust for possible systematic over- or underestimation in dietary intake measurements and correct for attenuation bias in relative risk estimates, a calibration approach was developed. This approach involved an additional dietary assessment common across study populations to re-express individual dietary intakes according to the same reference scale. A single 24-hour diet recall was therefore collected, as the EPIC reference calibration method, from a stratified random sample of 36 900 subjects from the entire EPIC cohort, using a software program (EPIC-SOFT) specifically designed to standardise the dietary measurements across study populations. This paper describes the design and populations of the calibration sub-studies set up in the EPIC centres. In addition, to assess whether the calibration sub-samples were representative of the entire group of EPIC cohorts, a series of subjects' characteristics known possibly to influence dietary intakes was compared in both population groups. This was the first time that calibration sub-studies had been set up in a large multi-centre European study. These studies showed that, despite certain inherent methodological and logistic constraints, a study design such as this one works relatively well in practice. The average response in the calibration study was 78.3% and ranged from 46.5% to 92.5%. The calibration population differed slightly from the overall cohort but the differences were small for most characteristics and centres. The overall results suggest that, after adjustment for age, dietary intakes estimated from calibration samples can reasonably be interpreted as representative of the main cohorts in most of the EPIC centres.

Adult↗

The calibration of therapy level electron beam ionization chambers in terms of absorbed dose to water.

During 1998, NPL plans to introduce the world's first absorbed dose calibration service for electron beam radiotherapy. The service will be based on the primary standard graphite calorimeter, and will enable the direct calibration of electron ionization chambers, without reference to air kerma standards. This calibration is a two-step process. Firstly, a set of NACP-designed parallel-plate reference chambers have been calibrated against the calorimeter over the last few years. These chambers are then used to calibrate user chambers by direct comparison in a water phantom under standard conditions. This paper describes the calibration of the reference chambers against the calorimeter and the derivation of absorbed dose to water calibration factors (with an estimated uncertainty in this calibration of +/-1.50% at the 95% confidence level).

Biophysical Phenomena↗

In vivo calibration of a femoral fixation device transducer for measuring anterior cruciate ligament graft tension: a study in an ovine model.

Toward developing a transducer for measuring in vivo tension in anterior cruciate ligament grafts in humans, the objectives of this study were to determine the following: (1) whether the calibration of a previously reported femoral fixation device transducer (FDT) (Ventura et al., 1998) is affected by the presence of the graft when implanted in the tibial metaphysis of an ovine model, (2) whether the FDT remains calibrated at 4 weeks postoperatively, and (3) whether the biological incorporation of the graft occurs prior to a change in the FDT calibration. The FDT was implanted in the hind limb of five sheep using an extra-articular procedure. Both the proximal common digital extensor tendon (i.e., graft) and a Teflon-coated wire were looped around the FDT inside a tunnel in the tibial metaphysis. The FDT was calibrated on three occasions using the loop of wire: once intraoperatively before graft insertion, once intraoperatively after graft insertion, and once postoperatively after the animals had been sacrificed at 4 weeks. Following sacrifice, the load transmitted to the FDT by the graft was also determined. The FDT exhibited linear calibration intraoperatively both before and after graft insertion with an average error relative to the calibration before insertion of the graft of -4.6 percent of full-scale load (150 N) and this average relative error was not significantly different from zero (p = 0.183). After 4 weeks of implantation, the average relative percent error was -5.0 percent and was not significantly different from zero (p = 0.434) indicating that the FDT remained calibrated in the in vivo environment. Because only 15 percent of the graft tension was transmitted to the FDT after 4 weeks, biological incorporation of the graft preceded the loss of calibration. In light of these findings, the FDT offers the capability of measuring the intra-articular ACL graft tension in vivo in animal models and possibly humans before the biological bond develops and also of monitoring the formation and maturation of the biological bond between a graft and bone tunnel.

Animals↗

Using reflectance models for color scanner calibration.

We examine the use of linear spectral reflectance models for calibrating a color scanner to generate device-independent CIE XYZ values from scanner vectors. Polynomial regression approaches to color scanner calibration use parameterized functions to approximate the calibration mapping over a set of training colors. These approaches can perform poorly if the parameterized functions do not accurately model the structure of the desired calibration mapping. Several studies have shown that linear reflectance models accurately characterize a wide range of materials. By viewing color scanner calibration as reflectance estimation, we can incorporate linear reflectance models into the calibration process. We show that in most cases linear models do not constrain the calibration problem sufficiently to allow exact recovery of X, Y, Z from a scanner vector obtained with three filters. By examining a series of methods that exploit information about reflectance functions, however, we show that reflectance information can be used to improve the accuracy of calibration over that of standard methods applied to the same set of inputs.

Journal Article↗

Effects of specific criteria and calibration on examiner reliability.

The purpose of this pilot study was to investigate the use of specific criteria and examiner calibration on the reliability of inexperienced examiners on dental sealant evaluations. Dental (N = 8) and dental hygiene (N = 8) students participated as examiners. The study objectives were to identify differences in calibrated and non-calibrated examiners, examiners calibrated by an expert or non-expert, and reliability between dental and dental hygiene student examiners. A criterion-referenced evaluation form was used to evaluate dental sealant end product on 20 teeth, twice by each examiner. Eight of 16 examiners participated in a one-hour calibration session between evaluations. The session consisted of a discussion of operational definitions, the evaluation procedure for dental sealants, and use of the criterion-referenced form. Intra- and interexaminer reliabilities were measured. There were no statistically significant differences (p less than .05) in intraexaminer reliability. Although calibration produced no significant increase in interexaminer reliability, the post-training reliability scores for the group calibrated by an expert decreased, and scores for the group calibrated by a non-expert increased. No significant difference was found in reliability between dental and dental hygiene student examiners.

Humans↗

Limitations of applicability of current calibration procedures for respiratory inductive plethysmography.

Repeatability of calibration of the respiratory inductive plethysmograph and its stability with time were investigated in young healthy subjects. Eight were submitted to sequential runs of calibration-validation by simultaneous equation (SEM) and least squares methods (LSM) (30 in all): in five subjects, after an initial acceptable calibration, accuracy and precision were repeatedly checked over three hours (a total of 50 trials). Although mean errors for the whole sample seemed acceptably low (7.6%, SD 7.0 for SEM; 7.3%, SD 7.3 for LSM), a marked inconsistency of apparently comparable calibrations and a wide variability of results along but independently of the time in steady conditions (ranging up to 30%) were discovered. An analysis of factors interfering with the response of the equipment was made. The unreliability of the current calibration procedure was related to the fact that in most cases the calibration line derived by the change-in-posture technique, as currently applied, may not be adequately representative of the full range of relationships between the participant variables, as they occur in the selected posture. To overcome this difficulty, two suggestions are made: a) prolong the calibration procedure so as to use more data points, and b) investigate alternative procedures of calibration in any one position.

Adult↗

Thromboplastin calibration. Experience of the Dutch reference laboratory for anticoagulant control.

Standardization of the thromboplastin most commonly used for anticoagulant control in The Netherlands has been achieved by the Dutch Reference Laboratory for Anticoagulant Control. The system established for control indicates the performance characteristics of each batch of thromboplastin in patients relative to a national calibration batch. Calibration constants were assessed according to an ICTH/ICSH proposal and with a reproducibility of approximately 2% (CV). With the use of a given calibration constant of the International Reference Preparation of Thromboplastin (1.0) and after assessment of the calibration constant of the National Reference Preparation in international terms (0.93), the accuracy of calibration with the various modifications of the calibration procedure is of the order of magnitude of 3% (CV). On the basis of the calibration protocol, physicians will be provided with correlation tables containing, for their convenience, prothrombin (thromboplastin) times in terms of the reference thromboplastin (uniform, i.e., batch-independent, prothrombin times), conventional prothrombin activity (percentages), and in due course with International Calibrated Ratios. With this approach current practice in the prescription of oral anticoagulants will be maintained. Opportunity is given, however, to aim at internationally proposed therapeutically optimal target values.

Blood Coagulation Tests↗

Calibrated user-friendly reverse transcriptase-PCR assay: quantitation of epidermal growth factor receptor mRNA.

We report a competitive reverse transcriptase-PCR (RT-PCR) assay and a calibrated user-friendly RT-PCR assay (CURT-PCR) for epidermal growth factor receptor (EGFR) mRNA. A calibrator was prepared from isolated rat liver RNA, and the amount of EGFR mRNA was determined by competitive RT-PCR. In CURT-PCR, a calibration curve was developed by plotting the ratio between the amount of PCR product originating from the calibrator and the RNA internal standard vs the amount of EGFR mRNA present in the calibrator. A fixed amount of RNA internal standard was coamplified with the EGFR mRNA present in the calibrator or in the sample, using the same primer set. The primers were chosen in regions of the EGFR mRNA that show 100% homology between human, rat, and mouse. The amount of EGFR in the unknown samples was calculated from the calibration curve based on the ratio between PCR product originating from the sample and the corresponding RNA internal standard. Competitive RT-PCR and CURT-PCR were used for rat liver samples from 21 different animals. Comparable results were obtained by the two methods. The imprecision of the CURT-PCR method was 8% (n = 20), and the imprecision of the traditional competitive RT-PCR was 16% (n = 17). We conclude that the CURT-PCR method developed is suitable for routine applications such as quantitation of EGFR expression in tumor biopsies. The imprecision is relatively low. Furthermore, the use of a calibration curve makes it possible to analyze a large number of samples in one analytical run and to accept or reject the results according to existing rules for quality assurance.

Animals↗

Fermentation process tracking through enhanced spectral calibration modeling.

The FDA process analytical technology (PAT) initiative will materialize in a significant increase in the number of installations of spectroscopic instrumentation. However, to attain the greatest benefit from the data generated, there is a need for calibration procedures that extract the maximum information content. For example, in fermentation processes, the interpretation of the resulting spectra is challenging as a consequence of the large number of wavelengths recorded, the underlying correlation structure that is evident between the wavelengths and the impact of the measurement environment. Approaches to the development of calibration models have been based on the application of partial least squares (PLS) either to the full spectral signature or to a subset of wavelengths. This paper presents a new approach to calibration modeling that combines a wavelength selection procedure, spectral window selection (SWS), where windows of wavelengths are automatically selected which are subsequently used as the basis of the calibration model. However, due to the non-uniqueness of the windows selected when the algorithm is executed repeatedly, multiple models are constructed and these are then combined using stacking thereby increasing the robustness of the final calibration model. The methodology is applied to data generated during the monitoring of broth concentrations in an industrial fermentation process from on-line near-infrared (NIR) and mid-infrared (MIR) spectrometers. It is shown that the proposed calibration modeling procedure outperforms traditional calibration procedures, as well as enabling the identification of the critical regions of the spectra with regard to the fermentation process.

Calibration↗

C-arm calibration--is it really necessary?

C-arm fluoroscopy is modelled as a perspective projection, the parameters of which are estimated through a calibration procedure. It has been universally accepted that precise intra-procedural calibration is a prerequisite for accurate quantitative C-arm fluoroscopy guidance. Calibration, however, significantly adds to system complexity, which is a major impediment to clinical practice. We challenge the status quo by questioning the assumption that precise intra-procedural calibration is really necessary. We derived theoretical bounds for the sensitivity of 3D measurements to mis-calibration. Experimental results corroborated the theory in that mis-calibration in the focal spot by as much as 50 mm still allows for tracking with an accuracy of 0.5 mm in translation and 0.65 degrees in rotation, and such mis-calibration does not impose any additional error on the reconstruction of small objects.

Algorithms↗

A novel phantom-less spatial and temporal ultrasound calibration method.

This paper introduces a novel method for ultrasound calibration for both spatial and temporal parameters. The main advantage of this method is that it does not require a phantom, which is usually expensive to fabricate. Furthermore, the method does not require extensive image processing. For spatial calibration, we solve an optimization problem established by a set of equations that relate the orientations of a line (i.e., calibration pointer) to the intersection points appearing in the ultrasound image. The line orientation is provided through calibration of both ends of the calibration pointer. Temporal calibration is achieved by processing of the captured pointer orientations and the corresponding image positions of intersection along with the timing information. The effectiveness of the unified method for both spatial and temporal calibration is apparent from the quality of the 3D reconstructions of a known object.

Algorithms↗

Refractive indices for volatile anesthetic gases: equipment and method for calibrating vaporizers and monitors.

OBJECTIVE: The objective of our study was to establish the refractive indices and the virial coefficients of the volatile anesthetic vapors. These indices and coefficients will allow refractometry to be used by manufacturers to produce accurate calibration, without requiring expensive high-precision calibration gases. METHODS: We used a precision refractometer to measure the refractive indices for five volatile anesthetic vapors. We prepared our calibration gases by mixing a gravimetrically calibrated amount of liquid agent with a constant gas flow. RESULTS: The refractive indices for the volatile anesthetic vapors are 1,603.2 for halothane, 1,540.4 for enflurane, 1,563.3 for isoflurane, 1,538.3 for sevoflurane, and 1,211.7 for desflurane. The maximum theoretical error in our measurements, due to all sensors and all uncertainty in our measurement of apparatus and physical constants, is +/- 0.56% of the reading (+/- 0.70% for desflurane). CONCLUSIONS: If refractometry replaced calibration gases in cylinders, as a calibration standard, manufacturers might avoid errors that now occur because calibration gases manufactured by numerous companies seem to differ. We propose that our values serve as an interim database.

Anesthesia, Inhalation↗

European semi-anthropomorphic spine phantom for the calibration of bone densitometers: assessment of precision, stability and accuracy. The European Quantitation of Osteoporosis Study Group.

Up to now it has not been possible to reliably cross-calibrate dual-energy X-ray absorptiometry (DXA) densitometry equipment made by different manufacturers so that a measurement made on an individual subject can be expressed in the units used with a different type of machine. Manufacturers have adopted various procedures for edge detection and calibration, producing various normal ranges which are specific to each individual manufacturer's brand of machine. In this study we have used the recently described European Spine Phantom (ESP, prototype version), which contains three semi-anthropomorphic "vertebrae" of different densities made of stimulated cortical and trabecular bone, to calibrate a range of DXA densitometers and quantitative computed tomography (QCT) equipment used in the measurement of trabecular bone density of the lumbar vertebrae. Three brands of QCT equipment and three brands of DXA equipment were assessed. Repeat measurements were made to assess machine stability. With the large majority of machines which proved stable, mean values were obtained for the measured low, medium and high density vertebrae respectively. In the case of the QCT equipment these means were for the trabecular bone density, and in the case of the DXA equipment for vertebral body bone density in the posteroanterior projection. All DXA machines overestimated the projected area of the vertebral bodies by incorporating variable amounts of transverse process. In general, the QCT equipment gave measured values which were close to the specified values for trabecular density, but there were substantial differences from the specified values in the results provided by the three DXA brands. For the QCT and Norland DXA machines (posteroanterior view), the relationships between specified densities and observed densities were found to be linear, whereas for the other DXA equipment (posteroanterior view), slightly curvilinear, exponential fits were found to be necessary to fit the plots of observed versus specified densities. From these plots, individual calibration equations were derived for each machine studied. For optimal cross-calibration, it was found to be necessary to use an individual calibration equation for each machine. This study has shown that it is possible to cross-calibrate DXA as well as QCT equipment for the measurement of axial bone density. This will be of considerable benefit for large-scale epidemiological studies as well as for multi-site clinical studies depending on bone densitometry.

Absorptiometry, Photon↗

Molecular clock calibrations and metazoan divergence dates.

It has recently been argued that living metazoans diverged over 800 million years ago, based on evidence from 22 nuclear genes for such a deep divergence between vertebrates and arthropods (Gu 1998). Two "internal" calibration points were used. However, only one fossil divergence date (the mammal-bird split) was directly used to calibrate the molecular clock. The second calibration point (the primate-rodent split) was based on molecular estimates that were ultimately also calibrated by the same mammal-bird split. However, the first tetrapods that can be assigned with confidence to either the mammal (synapsid) lineage or the bird (diapsid) lineage are approximately 288 million years old, while the first mammals that can be assigned with confidence to either the primate or the rodent lineages are 65 million years old, or 85 million years old if ferungulates are part of the primate lineage and zhelestids are accepted as ferungulate relatives. Recalibration of the protein data using these fossil dates indicates that metazoans diverged between 791 and 528 million years ago, a result broadly consistent with the palaeontological documentation of the "Cambrian explosion." The third, "external" calibration point (the metazoan-fungal divergence) was similarly problematic, since it was based on a controversial molecular study (which in turn used fossil dates including the mammal-bird split); direct use of fossils for this calibration point gives the absurd dating of 455 million years for metazoan divergences. Similar calibration problems affect another recent study (Wang et al. 1999), which proposes divergences for metazoans of 1000 million years or more: recalibrations of their clock again yields much more recent dates, some consistent with a "Cambrian explosion" scenario. Molecular clock studies have persuasively argued for the imperfection of the fossil record but have rarely acknowledged that their inferences are also directly based on this same record.

Animals↗

Evaluation of three calibration methods to compensate matrix effects in environmental analysis with LC-ESI-MS.

In quantitative analysis of environmental samples using high-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS) one of the major problems is the suppression or, less frequently, the enhancement of the analyte signals in the presence of matrix components. Standard addition is the most suitable method for compensating matrix effects, but it is time-consuming and laborious. In this study we compare the potential of three calibration approaches to compensate matrix effects that occurred when seven analytes (naphthalene sulfonates) were quantified in time series samples of waters with different matrices (untreated and treated industrial wastewater). The data obtained by external calibration, internal calibration with one standard, and external sample calibration (corresponding to matrix-matched calibration) were compared with those obtained by standard addition. None of the three approaches were suitable for a sample series of highly loaded, untreated wastewater with highly variable matrix. For less heavily loaded and less variable samples (treated wastewater effluents), the external sample calibration provided reasonable results for most analytes with deviations mostly below 25% as compared to standard addition. External sample calibration can be suitable to compensate matrix effects from moderately loaded samples with more uniform matrices, but it is recommended to verify this for each sample series against the standard addition approach.

Calibration↗

Test and calibration processes for microcalorimeters, with special reference to heat conduction instruments used with aqueous systems.

Calorimeters are normally calibrated by use of electrical heaters, but the calibration values derived may not always be representative for the chemical or biological process investigated. It is therefore important to have available chemical test processes by which the electrical calibration values can be controlled. In some cases, electrical calibration should be replaced by chemical calibrations. With particular reference to needs in work with thermophile heat conduction microcalorimeters, a number of test and calibration processes are presented. Some calibration problems for various types of reaction vessel are discussed.

1-Propanol↗