Input variable selection and calibration data selection for storm water quality regression models.

PubMed

Sun, Siao; Bertrand-Krajewski, Jean-Luc

2013-01-01

Storm water quality models are useful tools in storm water management. Interest has been growing in analyzing existing data for developing models for urban storm water quality evaluations. It is important to select appropriate model inputs when many candidate explanatory variables are available. Model calibration and verification are essential steps in any storm water quality modeling. This study investigates input variable selection and calibration data selection in storm water quality regression models. The two selection problems are mutually interacted. A procedure is developed in order to fulfil the two selection tasks in order. The procedure firstly selects model input variables using a cross validation method. An appropriate number of variables are identified as model inputs to ensure that a model is neither overfitted nor underfitted. Based on the model input selection results, calibration data selection is studied. Uncertainty of model performances due to calibration data selection is investigated with a random selection method. An approach using the cluster method is applied in order to enhance model calibration practice based on the principle of selecting representative data for calibration. The comparison between results from the cluster selection method and random selection shows that the former can significantly improve performances of calibrated models. It is found that the information content in calibration data is important in addition to the size of calibration data.

Systematic review of statistical approaches to quantify, or correct for, measurement error in a continuous exposure in nutritional epidemiology.

PubMed

Bennett, Derrick A; Landry, Denise; Little, Julian; Minelli, Cosetta

2017-09-19

Several statistical approaches have been proposed to assess and correct for exposure measurement error. We aimed to provide a critical overview of the most common approaches used in nutritional epidemiology. MEDLINE, EMBASE, BIOSIS and CINAHL were searched for reports published in English up to May 2016 in order to ascertain studies that described methods aimed to quantify and/or correct for measurement error for a continuous exposure in nutritional epidemiology using a calibration study. We identified 126 studies, 43 of which described statistical methods and 83 that applied any of these methods to a real dataset. The statistical approaches in the eligible studies were grouped into: a) approaches to quantify the relationship between different dietary assessment instruments and "true intake", which were mostly based on correlation analysis and the method of triads; b) approaches to adjust point and interval estimates of diet-disease associations for measurement error, mostly based on regression calibration analysis and its extensions. Two approaches (multiple imputation and moment reconstruction) were identified that can deal with differential measurement error. For regression calibration, the most common approach to correct for measurement error used in nutritional epidemiology, it is crucial to ensure that its assumptions and requirements are fully met. Analyses that investigate the impact of departures from the classical measurement error model on regression calibration estimates can be helpful to researchers in interpreting their findings. With regard to the possible use of alternative methods when regression calibration is not appropriate, the choice of method should depend on the measurement error model assumed, the availability of suitable calibration study data and the potential for bias due to violation of the classical measurement error model assumptions. On the basis of this review, we provide some practical advice for the use of methods to assess and adjust for measurement error in nutritional epidemiology.

A graphical method to evaluate spectral preprocessing in multivariate regression calibrations: example with Savitzky-Golay filters and partial least squares regression.

PubMed

Delwiche, Stephen R; Reeves, James B

2010-01-01

In multivariate regression analysis of spectroscopy data, spectral preprocessing is often performed to reduce unwanted background information (offsets, sloped baselines) or accentuate absorption features in intrinsically overlapping bands. These procedures, also known as pretreatments, are commonly smoothing operations or derivatives. While such operations are often useful in reducing the number of latent variables of the actual decomposition and lowering residual error, they also run the risk of misleading the practitioner into accepting calibration equations that are poorly adapted to samples outside of the calibration. The current study developed a graphical method to examine this effect on partial least squares (PLS) regression calibrations of near-infrared (NIR) reflection spectra of ground wheat meal with two analytes, protein content and sodium dodecyl sulfate sedimentation (SDS) volume (an indicator of the quantity of the gluten proteins that contribute to strong doughs). These two properties were chosen because of their differing abilities to be modeled by NIR spectroscopy: excellent for protein content, fair for SDS sedimentation volume. To further demonstrate the potential pitfalls of preprocessing, an artificial component, a randomly generated value, was included in PLS regression trials. Savitzky-Golay (digital filter) smoothing, first-derivative, and second-derivative preprocess functions (5 to 25 centrally symmetric convolution points, derived from quadratic polynomials) were applied to PLS calibrations of 1 to 15 factors. The results demonstrated the danger of an over reliance on preprocessing when (1) the number of samples used in a multivariate calibration is low (<50), (2) the spectral response of the analyte is weak, and (3) the goodness of the calibration is based on the coefficient of determination (R(2)) rather than a term based on residual error. The graphical method has application to the evaluation of other preprocess functions and various types of spectroscopy data.

A controlled experiment in ground water flow model calibration

USGS Publications Warehouse

Hill, M.C.; Cooley, R.L.; Pollock, D.W.

1998-01-01

Nonlinear regression was introduced to ground water modeling in the 1970s, but has been used very little to calibrate numerical models of complicated ground water systems. Apparently, nonlinear regression is thought by many to be incapable of addressing such complex problems. With what we believe to be the most complicated synthetic test case used for such a study, this work investigates using nonlinear regression in ground water model calibration. Results of the study fall into two categories. First, the study demonstrates how systematic use of a well designed nonlinear regression method can indicate the importance of different types of data and can lead to successive improvement of models and their parameterizations. Our method differs from previous methods presented in the ground water literature in that (1) weighting is more closely related to expected data errors than is usually the case; (2) defined diagnostic statistics allow for more effective evaluation of the available data, the model, and their interaction; and (3) prior information is used more cautiously. Second, our results challenge some commonly held beliefs about model calibration. For the test case considered, we show that (1) field measured values of hydraulic conductivity are not as directly applicable to models as their use in some geostatistical methods imply; (2) a unique model does not necessarily need to be identified to obtain accurate predictions; and (3) in the absence of obvious model bias, model error was normally distributed. The complexity of the test case involved implies that the methods used and conclusions drawn are likely to be powerful in practice.Nonlinear regression was introduced to ground water modeling in the 1970s, but has been used very little to calibrate numerical models of complicated ground water systems. Apparently, nonlinear regression is thought by many to be incapable of addressing such complex problems. With what we believe to be the most complicated synthetic test case used for such a study, this work investigates using nonlinear regression in ground water model calibration. Results of the study fall into two categories. First, the study demonstrates how systematic use of a well designed nonlinear regression method can indicate the importance of different types of data and can lead to successive improvement of models and their parameterizations. Our method differs from previous methods presented in the ground water literature in that (1) weighting is more closely related to expected data errors than is usually the case; (2) defined diagnostic statistics allow for more effective evaluation of the available data, the model, and their interaction; and (3) prior information is used more cautiously. Second, our results challenge some commonly held beliefs about model calibration. For the test case considered, we show that (1) field measured values of hydraulic conductivity are not as directly applicable to models as their use in some geostatistical methods imply; (2) a unique model does not necessarily need to be identified to obtain accurate predictions; and (3) in the absence of obvious model bias, model error was normally distributed. The complexity of the test case involved implies that the methods used and conclusions drawn are likely to be powerful in practice.

Linear regression analysis and its application to multivariate chromatographic calibration for the quantitative analysis of two-component mixtures.

PubMed

Dinç, Erdal; Ozdemir, Abdil

2005-01-01

Multivariate chromatographic calibration technique was developed for the quantitative analysis of binary mixtures enalapril maleate (EA) and hydrochlorothiazide (HCT) in tablets in the presence of losartan potassium (LST). The mathematical algorithm of multivariate chromatographic calibration technique is based on the use of the linear regression equations constructed using relationship between concentration and peak area at the five-wavelength set. The algorithm of this mathematical calibration model having a simple mathematical content was briefly described. This approach is a powerful mathematical tool for an optimum chromatographic multivariate calibration and elimination of fluctuations coming from instrumental and experimental conditions. This multivariate chromatographic calibration contains reduction of multivariate linear regression functions to univariate data set. The validation of model was carried out by analyzing various synthetic binary mixtures and using the standard addition technique. Developed calibration technique was applied to the analysis of the real pharmaceutical tablets containing EA and HCT. The obtained results were compared with those obtained by classical HPLC method. It was observed that the proposed multivariate chromatographic calibration gives better results than classical HPLC.

Calibration and Data Analysis of the MC-130 Air Balance

NASA Technical Reports Server (NTRS)

Booth, Dennis; Ulbrich, N.

2012-01-01

Design, calibration, calibration analysis, and intended use of the MC-130 air balance are discussed. The MC-130 balance is an 8.0 inch diameter force balance that has two separate internal air flow systems and one external bellows system. The manual calibration of the balance consisted of a total of 1854 data points with both unpressurized and pressurized air flowing through the balance. A subset of 1160 data points was chosen for the calibration data analysis. The regression analysis of the subset was performed using two fundamentally different analysis approaches. First, the data analysis was performed using a recently developed extension of the Iterative Method. This approach fits gage outputs as a function of both applied balance loads and bellows pressures while still allowing the application of the iteration scheme that is used with the Iterative Method. Then, for comparison, the axial force was also analyzed using the Non-Iterative Method. This alternate approach directly fits loads as a function of measured gage outputs and bellows pressures and does not require a load iteration. The regression models used by both the extended Iterative and Non-Iterative Method were constructed such that they met a set of widely accepted statistical quality requirements. These requirements lead to reliable regression models and prevent overfitting of data because they ensure that no hidden near-linear dependencies between regression model terms exist and that only statistically significant terms are included. Finally, a comparison of the axial force residuals was performed. Overall, axial force estimates obtained from both methods show excellent agreement as the differences of the standard deviation of the axial force residuals are on the order of 0.001 % of the axial force capacity.

Hybrid PSO-ASVR-based method for data fitting in the calibration of infrared radiometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Sen; Li, Chengwei, E-mail: heikuanghit@163.com

2016-06-15

The present paper describes a hybrid particle swarm optimization-adaptive support vector regression (PSO-ASVR)-based method for data fitting in the calibration of infrared radiometer. The proposed hybrid PSO-ASVR-based method is based on PSO in combination with Adaptive Processing and Support Vector Regression (SVR). The optimization technique involves setting parameters in the ASVR fitting procedure, which significantly improves the fitting accuracy. However, its use in the calibration of infrared radiometer has not yet been widely explored. Bearing this in mind, the PSO-ASVR-based method, which is based on the statistical learning theory, is successfully used here to get the relationship between the radiationmore » of a standard source and the response of an infrared radiometer. Main advantages of this method are the flexible adjustment mechanism in data processing and the optimization mechanism in a kernel parameter setting of SVR. Numerical examples and applications to the calibration of infrared radiometer are performed to verify the performance of PSO-ASVR-based method compared to conventional data fitting methods.« less

Prediction models for clustered data: comparison of a random intercept and standard regression model

PubMed Central

2013-01-01

Background When study data are clustered, standard regression analysis is considered inappropriate and analytical techniques for clustered data need to be used. For prediction research in which the interest of predictor effects is on the patient level, random effect regression models are probably preferred over standard regression analysis. It is well known that the random effect parameter estimates and the standard logistic regression parameter estimates are different. Here, we compared random effect and standard logistic regression models for their ability to provide accurate predictions. Methods Using an empirical study on 1642 surgical patients at risk of postoperative nausea and vomiting, who were treated by one of 19 anesthesiologists (clusters), we developed prognostic models either with standard or random intercept logistic regression. External validity of these models was assessed in new patients from other anesthesiologists. We supported our results with simulation studies using intra-class correlation coefficients (ICC) of 5%, 15%, or 30%. Standard performance measures and measures adapted for the clustered data structure were estimated. Results The model developed with random effect analysis showed better discrimination than the standard approach, if the cluster effects were used for risk prediction (standard c-index of 0.69 versus 0.66). In the external validation set, both models showed similar discrimination (standard c-index 0.68 versus 0.67). The simulation study confirmed these results. For datasets with a high ICC (≥15%), model calibration was only adequate in external subjects, if the used performance measure assumed the same data structure as the model development method: standard calibration measures showed good calibration for the standard developed model, calibration measures adapting the clustered data structure showed good calibration for the prediction model with random intercept. Conclusion The models with random intercept discriminate better than the standard model only if the cluster effect is used for predictions. The prediction model with random intercept had good calibration within clusters. PMID:23414436

Regression calibration for models with two predictor variables measured with error and their interaction, using instrumental variables and longitudinal data.

PubMed

Strand, Matthew; Sillau, Stefan; Grunwald, Gary K; Rabinovitch, Nathan

2014-02-10

Regression calibration provides a way to obtain unbiased estimators of fixed effects in regression models when one or more predictors are measured with error. Recent development of measurement error methods has focused on models that include interaction terms between measured-with-error predictors, and separately, methods for estimation in models that account for correlated data. In this work, we derive explicit and novel forms of regression calibration estimators and associated asymptotic variances for longitudinal models that include interaction terms, when data from instrumental and unbiased surrogate variables are available but not the actual predictors of interest. The longitudinal data are fit using linear mixed models that contain random intercepts and account for serial correlation and unequally spaced observations. The motivating application involves a longitudinal study of exposure to two pollutants (predictors) - outdoor fine particulate matter and cigarette smoke - and their association in interactive form with levels of a biomarker of inflammation, leukotriene E4 (LTE 4 , outcome) in asthmatic children. Because the exposure concentrations could not be directly observed, we used measurements from a fixed outdoor monitor and urinary cotinine concentrations as instrumental variables, and we used concentrations of fine ambient particulate matter and cigarette smoke measured with error by personal monitors as unbiased surrogate variables. We applied the derived regression calibration methods to estimate coefficients of the unobserved predictors and their interaction, allowing for direct comparison of toxicity of the different pollutants. We used simulations to verify accuracy of inferential methods based on asymptotic theory. Copyright © 2013 John Wiley & Sons, Ltd.

[New method of mixed gas infrared spectrum analysis based on SVM].

PubMed

Bai, Peng; Xie, Wen-Jun; Liu, Jun-Hua

2007-07-01

A new method of infrared spectrum analysis based on support vector machine (SVM) for mixture gas was proposed. The kernel function in SVM was used to map the seriously overlapping absorption spectrum into high-dimensional space, and after transformation, the high-dimensional data could be processed in the original space, so the regression calibration model was established, then the regression calibration model with was applied to analyze the concentration of component gas. Meanwhile it was proved that the regression calibration model with SVM also could be used for component recognition of mixture gas. The method was applied to the analysis of different data samples. Some factors such as scan interval, range of the wavelength, kernel function and penalty coefficient C that affect the model were discussed. Experimental results show that the component concentration maximal Mean AE is 0.132%, and the component recognition accuracy is higher than 94%. The problems of overlapping absorption spectrum, using the same method for qualitative and quantitative analysis, and limit number of training sample, were solved. The method could be used in other mixture gas infrared spectrum analyses, promising theoretic and application values.

Improving regression-model-based streamwater constituent load estimates derived from serially correlated data

USGS Publications Warehouse

Aulenbach, Brent T.

2013-01-01

A regression-model based approach is a commonly used, efficient method for estimating streamwater constituent load when there is a relationship between streamwater constituent concentration and continuous variables such as streamwater discharge, season and time. A subsetting experiment using a 30-year dataset of daily suspended sediment observations from the Mississippi River at Thebes, Illinois, was performed to determine optimal sampling frequency, model calibration period length, and regression model methodology, as well as to determine the effect of serial correlation of model residuals on load estimate precision. Two regression-based methods were used to estimate streamwater loads, the Adjusted Maximum Likelihood Estimator (AMLE), and the composite method, a hybrid load estimation approach. While both methods accurately and precisely estimated loads at the model’s calibration period time scale, precisions were progressively worse at shorter reporting periods, from annually to monthly. Serial correlation in model residuals resulted in observed AMLE precision to be significantly worse than the model calculated standard errors of prediction. The composite method effectively improved upon AMLE loads for shorter reporting periods, but required a sampling interval of at least 15-days or shorter, when the serial correlations in the observed load residuals were greater than 0.15. AMLE precision was better at shorter sampling intervals and when using the shortest model calibration periods, such that the regression models better fit the temporal changes in the concentration–discharge relationship. The models with the largest errors typically had poor high flow sampling coverage resulting in unrepresentative models. Increasing sampling frequency and/or targeted high flow sampling are more efficient approaches to ensure sufficient sampling and to avoid poorly performing models, than increasing calibration period length.

Improved Regression Analysis of Temperature-Dependent Strain-Gage Balance Calibration Data

NASA Technical Reports Server (NTRS)

Ulbrich, N.

2015-01-01

An improved approach is discussed that may be used to directly include first and second order temperature effects in the load prediction algorithm of a wind tunnel strain-gage balance. The improved approach was designed for the Iterative Method that fits strain-gage outputs as a function of calibration loads and uses a load iteration scheme during the wind tunnel test to predict loads from measured gage outputs. The improved approach assumes that the strain-gage balance is at a constant uniform temperature when it is calibrated and used. First, the method introduces a new independent variable for the regression analysis of the balance calibration data. The new variable is designed as the difference between the uniform temperature of the balance and a global reference temperature. This reference temperature should be the primary calibration temperature of the balance so that, if needed, a tare load iteration can be performed. Then, two temperature{dependent terms are included in the regression models of the gage outputs. They are the temperature difference itself and the square of the temperature difference. Simulated temperature{dependent data obtained from Triumph Aerospace's 2013 calibration of NASA's ARC-30K five component semi{span balance is used to illustrate the application of the improved approach.

Incorporating Measurement Error from Modeled Air Pollution Exposures into Epidemiological Analyses.

PubMed

Samoli, Evangelia; Butland, Barbara K

2017-12-01

Outdoor air pollution exposures used in epidemiological studies are commonly predicted from spatiotemporal models incorporating limited measurements, temporal factors, geographic information system variables, and/or satellite data. Measurement error in these exposure estimates leads to imprecise estimation of health effects and their standard errors. We reviewed methods for measurement error correction that have been applied in epidemiological studies that use model-derived air pollution data. We identified seven cohort studies and one panel study that have employed measurement error correction methods. These methods included regression calibration, risk set regression calibration, regression calibration with instrumental variables, the simulation extrapolation approach (SIMEX), and methods under the non-parametric or parameter bootstrap. Corrections resulted in small increases in the absolute magnitude of the health effect estimate and its standard error under most scenarios. Limited application of measurement error correction methods in air pollution studies may be attributed to the absence of exposure validation data and the methodological complexity of the proposed methods. Future epidemiological studies should consider in their design phase the requirements for the measurement error correction method to be later applied, while methodological advances are needed under the multi-pollutants setting.

Using structural equation modeling to construct calibration equations relating PM2.5 mass concentration samplers to the federal reference method sampler

NASA Astrophysics Data System (ADS)

Bilonick, Richard A.; Connell, Daniel P.; Talbott, Evelyn O.; Rager, Judith R.; Xue, Tao

2015-02-01

The objective of this study was to remove systematic bias among fine particulate matter (PM2.5) mass concentration measurements made by different types of samplers used in the Pittsburgh Aerosol Research and Inhalation Epidemiology Study (PARIES). PARIES is a retrospective epidemiology study that aims to provide a comprehensive analysis of the associations between air quality and human health effects in the Pittsburgh, Pennsylvania, region from 1999 to 2008. Calibration was needed in order to minimize the amount of systematic error in PM2.5 exposure estimation as a result of including data from 97 different PM2.5 samplers at 47 monitoring sites. Ordinary regression often has been used for calibrating air quality measurements from pairs of measurement devices; however, this is only appropriate when one of the two devices (the "independent" variable) is free from random error, which is rarely the case. A group of methods known as "errors-in-variables" (e.g., Deming regression, reduced major axis regression) has been developed to handle calibration between two devices when both are subject to random error, but these methods require information on the relative sizes of the random errors for each device, which typically cannot be obtained from the observed data. When data from more than two devices (or repeats of the same device) are available, the additional information is not used to inform the calibration. A more general approach that often has been overlooked is the use of a measurement error structural equation model (SEM) that allows the simultaneous comparison of three or more devices (or repeats). The theoretical underpinnings of all of these approaches to calibration are described, and the pros and cons of each are discussed. In particular, it is shown that both ordinary regression (when used for calibration) and Deming regression are particular examples of SEMs but with substantial deficiencies. To illustrate the use of SEMs, the 7865 daily average PM2.5 mass concentration measurements made by seven collocated samplers at an urban monitoring site in Pittsburgh, Pennsylvania, were used. These samplers, which included three federal reference method (FRM) samplers, three speciation samplers, and a tapered element oscillating microbalance (TEOM), operated at various times during the 10-year PARIES study period. Because TEOM measurements are known to depend on temperature, the constructed SEM provided calibration equations relating the TEOM to the FRM and speciation samplers as a function of ambient temperature. It was shown that TEOM imprecision and TEOM bias (relative to the FRM) both decreased as temperature increased. It also was shown that the temperature dependency for bias was non-linear and followed a sigmoidal (logistic) pattern. The speciation samplers exhibited only small bias relative to the FRM samplers, although the FRM samplers were shown to be substantially more precise than both the TEOM and the speciation samplers. Comparison of the SEM results to pairwise simple linear regression results showed that the regression results can differ substantially from the correctly-derived calibration equations, especially if the less-precise device is used as the independent variable in the regression.

Load estimator (LOADEST): a FORTRAN program for estimating constituent loads in streams and rivers

USGS Publications Warehouse

Runkel, Robert L.; Crawford, Charles G.; Cohn, Timothy A.

2004-01-01

LOAD ESTimator (LOADEST) is a FORTRAN program for estimating constituent loads in streams and rivers. Given a time series of streamflow, additional data variables, and constituent concentration, LOADEST assists the user in developing a regression model for the estimation of constituent load (calibration). Explanatory variables within the regression model include various functions of streamflow, decimal time, and additional user-specified data variables. The formulated regression model then is used to estimate loads over a user-specified time interval (estimation). Mean load estimates, standard errors, and 95 percent confidence intervals are developed on a monthly and(or) seasonal basis. The calibration and estimation procedures within LOADEST are based on three statistical estimation methods. The first two methods, Adjusted Maximum Likelihood Estimation (AMLE) and Maximum Likelihood Estimation (MLE), are appropriate when the calibration model errors (residuals) are normally distributed. Of the two, AMLE is the method of choice when the calibration data set (time series of streamflow, additional data variables, and concentration) contains censored data. The third method, Least Absolute Deviation (LAD), is an alternative to maximum likelihood estimation when the residuals are not normally distributed. LOADEST output includes diagnostic tests and warnings to assist the user in determining the appropriate estimation method and in interpreting the estimated loads. This report describes the development and application of LOADEST. Sections of the report describe estimation theory, input/output specifications, sample applications, and installation instructions.

Domain-Invariant Partial-Least-Squares Regression.

PubMed

Nikzad-Langerodi, Ramin; Zellinger, Werner; Lughofer, Edwin; Saminger-Platz, Susanne

2018-05-11

Multivariate calibration models often fail to extrapolate beyond the calibration samples because of changes associated with the instrumental response, environmental condition, or sample matrix. Most of the current methods used to adapt a source calibration model to a target domain exclusively apply to calibration transfer between similar analytical devices, while generic methods for calibration-model adaptation are largely missing. To fill this gap, we here introduce domain-invariant partial-least-squares (di-PLS) regression, which extends ordinary PLS by a domain regularizer in order to align the source and target distributions in the latent-variable space. We show that a domain-invariant weight vector can be derived in closed form, which allows the integration of (partially) labeled data from the source and target domains as well as entirely unlabeled data from the latter. We test our approach on a simulated data set where the aim is to desensitize a source calibration model to an unknown interfering agent in the target domain (i.e., unsupervised model adaptation). In addition, we demonstrate unsupervised, semisupervised, and supervised model adaptation by di-PLS on two real-world near-infrared (NIR) spectroscopic data sets.

Linear regression analysis for comparing two measurers or methods of measurement: but which regression?

PubMed

Ludbrook, John

2010-07-01

1. There are two reasons for wanting to compare measurers or methods of measurement. One is to calibrate one method or measurer against another; the other is to detect bias. Fixed bias is present when one method gives higher (or lower) values across the whole range of measurement. Proportional bias is present when one method gives values that diverge progressively from those of the other. 2. Linear regression analysis is a popular method for comparing methods of measurement, but the familiar ordinary least squares (OLS) method is rarely acceptable. The OLS method requires that the x values are fixed by the design of the study, whereas it is usual that both y and x values are free to vary and are subject to error. In this case, special regression techniques must be used. 3. Clinical chemists favour techniques such as major axis regression ('Deming's method'), the Passing-Bablok method or the bivariate least median squares method. Other disciplines, such as allometry, astronomy, biology, econometrics, fisheries research, genetics, geology, physics and sports science, have their own preferences. 4. Many Monte Carlo simulations have been performed to try to decide which technique is best, but the results are almost uninterpretable. 5. I suggest that pharmacologists and physiologists should use ordinary least products regression analysis (geometric mean regression, reduced major axis regression): it is versatile, can be used for calibration or to detect bias and can be executed by hand-held calculator or by using the loss function in popular, general-purpose, statistical software.

Sensitivity of regression calibration to non-perfect validation data with application to the Norwegian Women and Cancer Study.

PubMed

Buonaccorsi, John P; Dalen, Ingvild; Laake, Petter; Hjartåker, Anette; Engeset, Dagrun; Thoresen, Magne

2015-04-15

Measurement error occurs when we observe error-prone surrogates, rather than true values. It is common in observational studies and especially so in epidemiology, in nutritional epidemiology in particular. Correcting for measurement error has become common, and regression calibration is the most popular way to account for measurement error in continuous covariates. We consider its use in the context where there are validation data, which are used to calibrate the true values given the observed covariates. We allow for the case that the true value itself may not be observed in the validation data, but instead, a so-called reference measure is observed. The regression calibration method relies on certain assumptions.This paper examines possible biases in regression calibration estimators when some of these assumptions are violated. More specifically, we allow for the fact that (i) the reference measure may not necessarily be an 'alloyed gold standard' (i.e., unbiased) for the true value; (ii) there may be correlated random subject effects contributing to the surrogate and reference measures in the validation data; and (iii) the calibration model itself may not be the same in the validation study as in the main study; that is, it is not transportable. We expand on previous work to provide a general result, which characterizes potential bias in the regression calibration estimators as a result of any combination of the violations aforementioned. We then illustrate some of the general results with data from the Norwegian Women and Cancer Study. Copyright © 2015 John Wiley & Sons, Ltd.

Use of partial least squares regression for the multivariate calibration of hazardous air pollutants in open-path FT-IR spectrometry

NASA Astrophysics Data System (ADS)

Hart, Brian K.; Griffiths, Peter R.

1998-06-01

Partial least squares (PLS) regression has been evaluated as a robust calibration technique for over 100 hazardous air pollutants (HAPs) measured by open path Fourier transform infrared (OP/FT-IR) spectrometry. PLS has the advantage over the current recommended calibration method of classical least squares (CLS), in that it can look at the whole useable spectrum (700-1300 cm-1, 2000-2150 cm-1, and 2400-3000 cm-1), and detect several analytes simultaneously. Up to one hundred HAPs synthetically added to OP/FT-IR backgrounds have been simultaneously calibrated and detected using PLS. PLS also has the advantage in requiring less preprocessing of spectra than that which is required in CLS calibration schemes, allowing PLS to provide user independent real-time analysis of OP/FT-IR spectra.

The Detection and Quantification of Adulteration in Ground Roasted Asian Palm Civet Coffee Using Near-Infrared Spectroscopy in Tandem with Chemometrics

NASA Astrophysics Data System (ADS)

Suhandy, D.; Yulia, M.; Ogawa, Y.; Kondo, N.

2018-05-01

In the present research, an evaluation of using near infrared (NIR) spectroscopy in tandem with full spectrum partial least squares (FS-PLS) regression for quantification of degree of adulteration in civet coffee was conducted. A number of 126 ground roasted coffee samples with degree of adulteration 0-51% were prepared. Spectral data were acquired using a NIR spectrometer equipped with an integrating sphere for diffuse reflectance measurement in the range of 1300-2500 nm. The samples were divided into two groups calibration sample set (84 samples) and prediction sample set (42 samples). The calibration model was developed on original spectra using FS-PLS regression with full-cross validation method. The calibration model exhibited the determination coefficient R2=0.96 for calibration and R2=0.92 for validation. The prediction resulted in low root mean square error of prediction (RMSEP) (4.67%) and high ratio prediction to deviation (RPD) (3.75). In conclusion, the degree of adulteration in civet coffee have been quantified successfully by using NIR spectroscopy and FS-PLS regression in a non-destructive, economical, precise, and highly sensitive method, which uses very simple sample preparation.

Calibration Designs for Non-Monolithic Wind Tunnel Force Balances

NASA Technical Reports Server (NTRS)

Johnson, Thomas H.; Parker, Peter A.; Landman, Drew

2010-01-01

This research paper investigates current experimental designs and regression models for calibrating internal wind tunnel force balances of non-monolithic design. Such calibration methods are necessary for this class of balance because it has an electrical response that is dependent upon the sign of the applied forces and moments. This dependency gives rise to discontinuities in the response surfaces that are not easily modeled using traditional response surface methodologies. An analysis of current recommended calibration models is shown to lead to correlated response model terms. Alternative modeling methods are explored which feature orthogonal or near-orthogonal terms.

Evaluation of in-line Raman data for end-point determination of a coating process: Comparison of Science-Based Calibration, PLS-regression and univariate data analysis.

PubMed

Barimani, Shirin; Kleinebudde, Peter

2017-10-01

A multivariate analysis method, Science-Based Calibration (SBC), was used for the first time for endpoint determination of a tablet coating process using Raman data. Two types of tablet cores, placebo and caffeine cores, received a coating suspension comprising a polyvinyl alcohol-polyethylene glycol graft-copolymer and titanium dioxide to a maximum coating thickness of 80µm. Raman spectroscopy was used as in-line PAT tool. The spectra were acquired every minute and correlated to the amount of applied aqueous coating suspension. SBC was compared to another well-known multivariate analysis method, Partial Least Squares-regression (PLS) and a simpler approach, Univariate Data Analysis (UVDA). All developed calibration models had coefficient of determination values (R 2 ) higher than 0.99. The coating endpoints could be predicted with root mean square errors (RMSEP) less than 3.1% of the applied coating suspensions. Compared to PLS and UVDA, SBC proved to be an alternative multivariate calibration method with high predictive power. Copyright © 2017 Elsevier B.V. All rights reserved.

A graphical method to evaluate spectral preprocessing in multivariate regression calibrations: example with Savitzky-Golay filters and partial least squares regression

USDA-ARS?s Scientific Manuscript database

In multivariate regression analysis of spectroscopy data, spectral preprocessing is often performed to reduce unwanted background information (offsets, sloped baselines) or accentuate absorption features in intrinsically overlapping bands. These procedures, also known as pretreatments, are commonly ...

Robust best linear estimator for Cox regression with instrumental variables in whole cohort and surrogates with additive measurement error in calibration sample

PubMed Central

Wang, Ching-Yun; Song, Xiao

2017-01-01

SUMMARY Biomedical researchers are often interested in estimating the effect of an environmental exposure in relation to a chronic disease endpoint. However, the exposure variable of interest may be measured with errors. In a subset of the whole cohort, a surrogate variable is available for the true unobserved exposure variable. The surrogate variable satisfies an additive measurement error model, but it may not have repeated measurements. The subset in which the surrogate variables are available is called a calibration sample. In addition to the surrogate variables that are available among the subjects in the calibration sample, we consider the situation when there is an instrumental variable available for all study subjects. An instrumental variable is correlated with the unobserved true exposure variable, and hence can be useful in the estimation of the regression coefficients. In this paper, we propose a nonparametric method for Cox regression using the observed data from the whole cohort. The nonparametric estimator is the best linear combination of a nonparametric correction estimator from the calibration sample and the difference of the naive estimators from the calibration sample and the whole cohort. The asymptotic distribution is derived, and the finite sample performance of the proposed estimator is examined via intensive simulation studies. The methods are applied to the Nutritional Biomarkers Study of the Women’s Health Initiative. PMID:27546625

Bayesian calibration for forensic age estimation.

PubMed

Ferrante, Luigi; Skrami, Edlira; Gesuita, Rosaria; Cameriere, Roberto

2015-05-10

Forensic medicine is increasingly called upon to assess the age of individuals. Forensic age estimation is mostly required in relation to illegal immigration and identification of bodies or skeletal remains. A variety of age estimation methods are based on dental samples and use of regression models, where the age of an individual is predicted by morphological tooth changes that take place over time. From the medico-legal point of view, regression models, with age as the dependent random variable entail that age tends to be overestimated in the young and underestimated in the old. To overcome this bias, we describe a new full Bayesian calibration method (asymmetric Laplace Bayesian calibration) for forensic age estimation that uses asymmetric Laplace distribution as the probability model. The method was compared with three existing approaches (two Bayesian and a classical method) using simulated data. Although its accuracy was comparable with that of the other methods, the asymmetric Laplace Bayesian calibration appears to be significantly more reliable and robust in case of misspecification of the probability model. The proposed method was also applied to a real dataset of values of the pulp chamber of the right lower premolar measured on x-ray scans of individuals of known age. Copyright © 2015 John Wiley & Sons, Ltd.

Linear regression in astronomy. II

NASA Technical Reports Server (NTRS)

Feigelson, Eric D.; Babu, Gutti J.

1992-01-01

A wide variety of least-squares linear regression procedures used in observational astronomy, particularly investigations of the cosmic distance scale, are presented and discussed. The classes of linear models considered are (1) unweighted regression lines, with bootstrap and jackknife resampling; (2) regression solutions when measurement error, in one or both variables, dominates the scatter; (3) methods to apply a calibration line to new data; (4) truncated regression models, which apply to flux-limited data sets; and (5) censored regression models, which apply when nondetections are present. For the calibration problem we develop two new procedures: a formula for the intercept offset between two parallel data sets, which propagates slope errors from one regression to the other; and a generalization of the Working-Hotelling confidence bands to nonstandard least-squares lines. They can provide improved error analysis for Faber-Jackson, Tully-Fisher, and similar cosmic distance scale relations.

Calibrating random forests for probability estimation.

PubMed

Dankowski, Theresa; Ziegler, Andreas

2016-09-30

Probabilities can be consistently estimated using random forests. It is, however, unclear how random forests should be updated to make predictions for other centers or at different time points. In this work, we present two approaches for updating random forests for probability estimation. The first method has been proposed by Elkan and may be used for updating any machine learning approach yielding consistent probabilities, so-called probability machines. The second approach is a new strategy specifically developed for random forests. Using the terminal nodes, which represent conditional probabilities, the random forest is first translated to logistic regression models. These are, in turn, used for re-calibration. The two updating strategies were compared in a simulation study and are illustrated with data from the German Stroke Study Collaboration. In most simulation scenarios, both methods led to similar improvements. In the simulation scenario in which the stricter assumptions of Elkan's method were not met, the logistic regression-based re-calibration approach for random forests outperformed Elkan's method. It also performed better on the stroke data than Elkan's method. The strength of Elkan's method is its general applicability to any probability machine. However, if the strict assumptions underlying this approach are not met, the logistic regression-based approach is preferable for updating random forests for probability estimation. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd. © 2016 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd.

Prediction models for clustered data: comparison of a random intercept and standard regression model.

PubMed

Bouwmeester, Walter; Twisk, Jos W R; Kappen, Teus H; van Klei, Wilton A; Moons, Karel G M; Vergouwe, Yvonne

2013-02-15

When study data are clustered, standard regression analysis is considered inappropriate and analytical techniques for clustered data need to be used. For prediction research in which the interest of predictor effects is on the patient level, random effect regression models are probably preferred over standard regression analysis. It is well known that the random effect parameter estimates and the standard logistic regression parameter estimates are different. Here, we compared random effect and standard logistic regression models for their ability to provide accurate predictions. Using an empirical study on 1642 surgical patients at risk of postoperative nausea and vomiting, who were treated by one of 19 anesthesiologists (clusters), we developed prognostic models either with standard or random intercept logistic regression. External validity of these models was assessed in new patients from other anesthesiologists. We supported our results with simulation studies using intra-class correlation coefficients (ICC) of 5%, 15%, or 30%. Standard performance measures and measures adapted for the clustered data structure were estimated. The model developed with random effect analysis showed better discrimination than the standard approach, if the cluster effects were used for risk prediction (standard c-index of 0.69 versus 0.66). In the external validation set, both models showed similar discrimination (standard c-index 0.68 versus 0.67). The simulation study confirmed these results. For datasets with a high ICC (≥15%), model calibration was only adequate in external subjects, if the used performance measure assumed the same data structure as the model development method: standard calibration measures showed good calibration for the standard developed model, calibration measures adapting the clustered data structure showed good calibration for the prediction model with random intercept. The models with random intercept discriminate better than the standard model only if the cluster effect is used for predictions. The prediction model with random intercept had good calibration within clusters.

A Comparison of Two Balance Calibration Model Building Methods

NASA Technical Reports Server (NTRS)

DeLoach, Richard; Ulbrich, Norbert

2007-01-01

Simulated strain-gage balance calibration data is used to compare the accuracy of two balance calibration model building methods for different noise environments and calibration experiment designs. The first building method obtains a math model for the analysis of balance calibration data after applying a candidate math model search algorithm to the calibration data set. The second building method uses stepwise regression analysis in order to construct a model for the analysis. Four balance calibration data sets were simulated in order to compare the accuracy of the two math model building methods. The simulated data sets were prepared using the traditional One Factor At a Time (OFAT) technique and the Modern Design of Experiments (MDOE) approach. Random and systematic errors were introduced in the simulated calibration data sets in order to study their influence on the math model building methods. Residuals of the fitted calibration responses and other statistical metrics were compared in order to evaluate the calibration models developed with different combinations of noise environment, experiment design, and model building method. Overall, predicted math models and residuals of both math model building methods show very good agreement. Significant differences in model quality were attributable to noise environment, experiment design, and their interaction. Generally, the addition of systematic error significantly degraded the quality of calibration models developed from OFAT data by either method, but MDOE experiment designs were more robust with respect to the introduction of a systematic component of the unexplained variance.

Evaluation of Automated Model Calibration Techniques for Residential Building Energy Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robertson, J.; Polly, B.; Collis, J.

2013-09-01

This simulation study adapts and applies the general framework described in BESTEST-EX (Judkoff et al 2010) for self-testing residential building energy model calibration methods. BEopt/DOE-2.2 is used to evaluate four mathematical calibration methods in the context of monthly, daily, and hourly synthetic utility data for a 1960's-era existing home in a cooling-dominated climate. The home's model inputs are assigned probability distributions representing uncertainty ranges, random selections are made from the uncertainty ranges to define 'explicit' input values, and synthetic utility billing data are generated using the explicit input values. The four calibration methods evaluated in this study are: an ASHRAEmore » 1051-RP-based approach (Reddy and Maor 2006), a simplified simulated annealing optimization approach, a regression metamodeling optimization approach, and a simple output ratio calibration approach. The calibration methods are evaluated for monthly, daily, and hourly cases; various retrofit measures are applied to the calibrated models and the methods are evaluated based on the accuracy of predicted savings, computational cost, repeatability, automation, and ease of implementation.« less

Evaluation of Automated Model Calibration Techniques for Residential Building Energy Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

and Ben Polly, Joseph Robertson; Polly, Ben; Collis, Jon

2013-09-01

This simulation study adapts and applies the general framework described in BESTEST-EX (Judkoff et al 2010) for self-testing residential building energy model calibration methods. BEopt/DOE-2.2 is used to evaluate four mathematical calibration methods in the context of monthly, daily, and hourly synthetic utility data for a 1960's-era existing home in a cooling-dominated climate. The home's model inputs are assigned probability distributions representing uncertainty ranges, random selections are made from the uncertainty ranges to define "explicit" input values, and synthetic utility billing data are generated using the explicit input values. The four calibration methods evaluated in this study are: an ASHRAEmore » 1051-RP-based approach (Reddy and Maor 2006), a simplified simulated annealing optimization approach, a regression metamodeling optimization approach, and a simple output ratio calibration approach. The calibration methods are evaluated for monthly, daily, and hourly cases; various retrofit measures are applied to the calibrated models and the methods are evaluated based on the accuracy of predicted savings, computational cost, repeatability, automation, and ease of implementation.« less

Stellar Color Regression: A Spectroscopy-based Method for Color Calibration to a Few Millimagnitude Accuracy and the Recalibration of Stripe 82

NASA Astrophysics Data System (ADS)

Yuan, Haibo; Liu, Xiaowei; Xiang, Maosheng; Huang, Yang; Zhang, Huihua; Chen, Bingqiu

2015-02-01

In this paper we propose a spectroscopy-based stellar color regression (SCR) method to perform accurate color calibration for modern imaging surveys, taking advantage of millions of stellar spectra now available. The method is straightforward, insensitive to systematic errors in the spectroscopically determined stellar atmospheric parameters, applicable to regions that are effectively covered by spectroscopic surveys, and capable of delivering an accuracy of a few millimagnitudes for color calibration. As an illustration, we have applied the method to the Sloan Digital Sky Survey (SDSS) Stripe 82 data. With a total number of 23,759 spectroscopically targeted stars, we have mapped out the small but strongly correlated color zero-point errors present in the photometric catalog of Stripe 82, and we improve the color calibration by a factor of two to three. Our study also reveals some small but significant magnitude dependence errors in the z band for some charge-coupled devices (CCDs). Such errors are likely to be present in all the SDSS photometric data. Our results are compared with those from a completely independent test based on the intrinsic colors of red galaxies presented by Ivezić et al. The comparison, as well as other tests, shows that the SCR method has achieved a color calibration internally consistent at a level of about 5 mmag in u - g, 3 mmag in g - r, and 2 mmag in r - i and i - z. Given the power of the SCR method, we discuss briefly the potential benefits by applying the method to existing, ongoing, and upcoming imaging surveys.

Estimation of the quantification uncertainty from flow injection and liquid chromatography transient signals in inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Laborda, Francisco; Medrano, Jesús; Castillo, Juan R.

2004-06-01

The quality of the quantitative results obtained from transient signals in high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS) and flow injection-inductively coupled plasma mass spectrometry (FI-ICPMS) was investigated under multielement conditions. Quantification methods were based on multiple-point calibration by simple and weighted linear regression, and double-point calibration (measurement of the baseline and one standard). An uncertainty model, which includes the main sources of uncertainty from FI-ICPMS and HPLC-ICPMS (signal measurement, sample flow rate and injection volume), was developed to estimate peak area uncertainties and statistical weights used in weighted linear regression. The behaviour of the ICPMS instrument was characterized in order to be considered in the model, concluding that the instrument works as a concentration detector when it is used to monitorize transient signals from flow injection or chromatographic separations. Proper quantification by the three calibration methods was achieved when compared to reference materials, although the double-point calibration allowed to obtain results of the same quality as the multiple-point calibration, shortening the calibration time. Relative expanded uncertainties ranged from 10-20% for concentrations around the LOQ to 5% for concentrations higher than 100 times the LOQ.

Application of factor analysis of infrared spectra for quantitative determination of beta-tricalcium phosphate in calcium hydroxylapatite.

PubMed

Arsenyev, P A; Trezvov, V V; Saratovskaya, N V

1997-01-01

This work represents a method, which allows to determine phase composition of calcium hydroxylapatite basing on its infrared spectrum. The method uses factor analysis of the spectral data of calibration set of samples to determine minimal number of factors required to reproduce the spectra within experimental error. Multiple linear regression is applied to establish correlation between factor scores of calibration standards and their properties. The regression equations can be used to predict the property value of unknown sample. The regression model was built for determination of beta-tricalcium phosphate content in hydroxylapatite. Statistical estimation of quality of the model was carried out. Application of the factor analysis on spectral data allows to increase accuracy of beta-tricalcium phosphate determination and expand the range of determination towards its less concentration. Reproducibility of results is retained.

Robust best linear estimator for Cox regression with instrumental variables in whole cohort and surrogates with additive measurement error in calibration sample.

PubMed

Wang, Ching-Yun; Song, Xiao

2016-11-01

Biomedical researchers are often interested in estimating the effect of an environmental exposure in relation to a chronic disease endpoint. However, the exposure variable of interest may be measured with errors. In a subset of the whole cohort, a surrogate variable is available for the true unobserved exposure variable. The surrogate variable satisfies an additive measurement error model, but it may not have repeated measurements. The subset in which the surrogate variables are available is called a calibration sample. In addition to the surrogate variables that are available among the subjects in the calibration sample, we consider the situation when there is an instrumental variable available for all study subjects. An instrumental variable is correlated with the unobserved true exposure variable, and hence can be useful in the estimation of the regression coefficients. In this paper, we propose a nonparametric method for Cox regression using the observed data from the whole cohort. The nonparametric estimator is the best linear combination of a nonparametric correction estimator from the calibration sample and the difference of the naive estimators from the calibration sample and the whole cohort. The asymptotic distribution is derived, and the finite sample performance of the proposed estimator is examined via intensive simulation studies. The methods are applied to the Nutritional Biomarkers Study of the Women's Health Initiative. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrologic calibration of paired watersheds using a MOSUM approach

DOE PAGES

Ssegane, H.; Amatya, D. M.; Muwamba, A.; ...

2015-01-09

Paired watershed studies have historically been used to quantify hydrologic effects of land use and management practices by concurrently monitoring two neighboring watersheds (a control and a treatment) during the calibration (pre-treatment) and post-treatment periods. This study characterizes seasonal water table and flow response to rainfall during the calibration period and tests a change detection technique of moving sums of recursive residuals (MOSUM) to select calibration periods for each control-treatment watershed pair when the regression coefficients for daily water table elevation (WTE) were most stable to reduce regression model uncertainty. The control and treatment watersheds included 1–3 year intensively managedmore » loblolly pine ( Pinus taeda L.) with natural understory, same age loblolly pine intercropped with switchgrass ( Panicum virgatum), 14–15 year thinned loblolly pine with natural understory (control), and switchgrass only. Although monitoring during the calibration period spanned 2009 to 2012, silvicultural operational practices that occurred during this period such as harvesting of existing stand and site preparation for pine and switchgrass establishment may have acted as external factors, potentially shifting hydrologic calibration relationships between control and treatment watersheds. Results indicated that MOSUM was able to detect significant changes in regression parameters for WTE due to silvicultural operations. This approach also minimized uncertainty of calibration relationships which could otherwise mask marginal treatment effects. All calibration relationships developed using this MOSUM method were quantifiable, strong, and consistent with Nash–Sutcliffe Efficiency (NSE) greater than 0.97 for WTE and NSE greater than 0.92 for daily flow, indicating its applicability for choosing calibration periods of paired watershed studies.« less

A Calibration to Predict the Concentrations of Impurities in Plutonium Oxide by Prompt Gamma Analysis Revision 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narlesky, Joshua Edward; Kelly, Elizabeth J.

2015-09-10

This report documents the new PG calibration regression equation. These calibration equations incorporate new data that have become available since revision 1 of “A Calibration to Predict the Concentrations of Impurities in Plutonium Oxide by Prompt Gamma Analysis” was issued [3] The calibration equations are based on a weighted least squares (WLS) approach for the regression. The WLS method gives each data point its proper amount of influence over the parameter estimates. This gives two big advantages, more precise parameter estimates and better and more defensible estimates of uncertainties. The WLS approach makes sense both statistically and experimentally because themore » variances increase with concentration, and there are physical reasons that the higher measurements are less reliable and should be less influential. The new magnesium calibration includes a correction for sodium and separate calibration equation for items with and without chlorine. These additional calibration equations allow for better predictions and smaller uncertainties for sodium in materials with and without chlorine. Chlorine and sodium have separate equations for RICH materials. Again, these equations give better predictions and smaller uncertainties chlorine and sodium for RICH materials.« less

Method validation using weighted linear regression models for quantification of UV filters in water samples.

PubMed

da Silva, Claudia Pereira; Emídio, Elissandro Soares; de Marchi, Mary Rosa Rodrigues

2015-01-01

This paper describes the validation of a method consisting of solid-phase extraction followed by gas chromatography-tandem mass spectrometry for the analysis of the ultraviolet (UV) filters benzophenone-3, ethylhexyl salicylate, ethylhexyl methoxycinnamate and octocrylene. The method validation criteria included evaluation of selectivity, analytical curve, trueness, precision, limits of detection and limits of quantification. The non-weighted linear regression model has traditionally been used for calibration, but it is not necessarily the optimal model in all cases. Because the assumption of homoscedasticity was not met for the analytical data in this work, a weighted least squares linear regression was used for the calibration method. The evaluated analytical parameters were satisfactory for the analytes and showed recoveries at four fortification levels between 62% and 107%, with relative standard deviations less than 14%. The detection limits ranged from 7.6 to 24.1 ng L(-1). The proposed method was used to determine the amount of UV filters in water samples from water treatment plants in Araraquara and Jau in São Paulo, Brazil. Copyright © 2014 Elsevier B.V. All rights reserved.

A method for addressing differences in concentrations of fipronil and three degradates obtained by two different laboratory methods

USGS Publications Warehouse

Crawford, Charles G.; Martin, Jeffrey D.

2017-07-21

In October 2012, the U.S. Geological Survey (USGS) began measuring the concentration of the pesticide fipronil and three of its degradates (desulfinylfipronil, fipronil sulfide, and fipronil sulfone) by a new laboratory method using direct aqueous-injection liquid chromatography tandem mass spectrometry (DAI LC–MS/MS). This method replaced the previous method—in use since 2002—that used gas chromatography/mass spectrometry (GC/MS). The performance of the two methods is not comparable for fipronil and the three degradates. Concentrations of these four chemical compounds determined by the DAI LC–MS/MS method are substantially lower than the GC/MS method. A method was developed to correct for the difference in concentrations obtained by the two laboratory methods based on a methods comparison field study done in 2012. Environmental and field matrix spike samples to be analyzed by both methods from 48 stream sites from across the United States were sampled approximately three times each for this study. These data were used to develop a relation between the two laboratory methods for each compound using regression analysis. The relations were used to calibrate data obtained by the older method to the new method in order to remove any biases attributable to differences in the methods. The coefficients of the equations obtained from the regressions were used to calibrate over 16,600 observations of fipronil, as well as the three degradates determined by the GC/MS method retrieved from the USGS National Water Information System. The calibrated values were then compared to over 7,800 observations of fipronil and to the three degradates determined by the DAI LC–MS/MS method also retrieved from the National Water Information System. The original and calibrated values from the GC/MS method, along with measures of uncertainty in the calibrated values and the original values from the DAI LC–MS/MS method, are provided in an accompanying data release.

Fresh Biomass Estimation in Heterogeneous Grassland Using Hyperspectral Measurements and Multivariate Statistical Analysis

NASA Astrophysics Data System (ADS)

Darvishzadeh, R.; Skidmore, A. K.; Mirzaie, M.; Atzberger, C.; Schlerf, M.

2014-12-01

Accurate estimation of grassland biomass at their peak productivity can provide crucial information regarding the functioning and productivity of the rangelands. Hyperspectral remote sensing has proved to be valuable for estimation of vegetation biophysical parameters such as biomass using different statistical techniques. However, in statistical analysis of hyperspectral data, multicollinearity is a common problem due to large amount of correlated hyper-spectral reflectance measurements. The aim of this study was to examine the prospect of above ground biomass estimation in a heterogeneous Mediterranean rangeland employing multivariate calibration methods. Canopy spectral measurements were made in the field using a GER 3700 spectroradiometer, along with concomitant in situ measurements of above ground biomass for 170 sample plots. Multivariate calibrations including partial least squares regression (PLSR), principal component regression (PCR), and Least-Squared Support Vector Machine (LS-SVM) were used to estimate the above ground biomass. The prediction accuracy of the multivariate calibration methods were assessed using cross validated R2 and RMSE. The best model performance was obtained using LS_SVM and then PLSR both calibrated with first derivative reflectance dataset with R2cv = 0.88 & 0.86 and RMSEcv= 1.15 & 1.07 respectively. The weakest prediction accuracy was appeared when PCR were used (R2cv = 0.31 and RMSEcv= 2.48). The obtained results highlight the importance of multivariate calibration methods for biomass estimation when hyperspectral data are used.

Sensitivity analysis, calibration, and testing of a distributed hydrological model using error‐based weighting and one objective function

USGS Publications Warehouse

Foglia, L.; Hill, Mary C.; Mehl, Steffen W.; Burlando, P.

2009-01-01

We evaluate the utility of three interrelated means of using data to calibrate the fully distributed rainfall‐runoff model TOPKAPI as applied to the Maggia Valley drainage area in Switzerland. The use of error‐based weighting of observation and prior information data, local sensitivity analysis, and single‐objective function nonlinear regression provides quantitative evaluation of sensitivity of the 35 model parameters to the data, identification of data types most important to the calibration, and identification of correlations among parameters that contribute to nonuniqueness. Sensitivity analysis required only 71 model runs, and regression required about 50 model runs. The approach presented appears to be ideal for evaluation of models with long run times or as a preliminary step to more computationally demanding methods. The statistics used include composite scaled sensitivities, parameter correlation coefficients, leverage, Cook's D, and DFBETAS. Tests suggest predictive ability of the calibrated model typical of hydrologic models.

Effects of Serum Creatinine Calibration on Estimated Renal Function in African Americans: the Jackson Heart Study

PubMed Central

Wang, Wei; Young, Bessie A.; Fülöp, Tibor; de Boer, Ian H.; Boulware, L. Ebony; Katz, Ronit; Correa, Adolfo; Griswold, Michael E.

2015-01-01

Background The calibration to Isotope Dilution Mass Spectroscopy (IDMS) traceable creatinine is essential for valid use of the new Chronic Kidney Disease Epidemiology Collaboration (CKD-EPI) equation to estimate the glomerular filtration rate (GFR). Methods For 5,210 participants in the Jackson Heart Study (JHS), serum creatinine was measured with a multipoint enzymatic spectrophotometric assay at the baseline visit (2000–2004) and re-measured using the Roche enzymatic method, traceable to IDMS in a subset of 206 subjects. The 200 eligible samples (6 were excluded, 1 for failure of the re-measurement and 5 for outliers) were divided into three disjoint sets - training, validation, and test - to select a calibration model, estimate true errors, and assess performance of the final calibration equation. The calibration equation was applied to serum creatinine measurements of 5,210 participants to estimate GFR and the prevalence of CKD. Results The selected Deming regression model provided a slope of 0.968 (95% Confidence Interval (CI), 0.904 to 1.053) and intercept of −0.0248 (95% CI, −0.0862 to 0.0366) with R squared 0.9527. Calibrated serum creatinine showed high agreement with actual measurements when applying to the unused test set (concordance correlation coefficient 0.934, 95% CI, 0.894 to 0.960). The baseline prevalence of CKD in the JHS (2000–2004) was 6.30% using calibrated values, compared with 8.29% using non-calibrated serum creatinine with the CKD-EPI equation (P < 0.001). Conclusions A Deming regression model was chosen to optimally calibrate baseline serum creatinine measurements in the JHS and the calibrated values provide a lower CKD prevalence estimate. PMID:25806862

STELLAR COLOR REGRESSION: A SPECTROSCOPY-BASED METHOD FOR COLOR CALIBRATION TO A FEW MILLIMAGNITUDE ACCURACY AND THE RECALIBRATION OF STRIPE 82

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Haibo; Liu, Xiaowei; Xiang, Maosheng

In this paper we propose a spectroscopy-based stellar color regression (SCR) method to perform accurate color calibration for modern imaging surveys, taking advantage of millions of stellar spectra now available. The method is straightforward, insensitive to systematic errors in the spectroscopically determined stellar atmospheric parameters, applicable to regions that are effectively covered by spectroscopic surveys, and capable of delivering an accuracy of a few millimagnitudes for color calibration. As an illustration, we have applied the method to the Sloan Digital Sky Survey (SDSS) Stripe 82 data. With a total number of 23,759 spectroscopically targeted stars, we have mapped out the smallmore » but strongly correlated color zero-point errors present in the photometric catalog of Stripe 82, and we improve the color calibration by a factor of two to three. Our study also reveals some small but significant magnitude dependence errors in the z band for some charge-coupled devices (CCDs). Such errors are likely to be present in all the SDSS photometric data. Our results are compared with those from a completely independent test based on the intrinsic colors of red galaxies presented by Ivezić et al. The comparison, as well as other tests, shows that the SCR method has achieved a color calibration internally consistent at a level of about 5 mmag in u – g, 3 mmag in g – r, and 2 mmag in r – i and i – z. Given the power of the SCR method, we discuss briefly the potential benefits by applying the method to existing, ongoing, and upcoming imaging surveys.« less

[Hyperspectral Estimation of Apple Tree Canopy LAI Based on SVM and RF Regression].

PubMed

Han, Zhao-ying; Zhu, Xi-cun; Fang, Xian-yi; Wang, Zhuo-yuan; Wang, Ling; Zhao, Geng-Xing; Jiang, Yuan-mao

2016-03-01

Leaf area index (LAI) is the dynamic index of crop population size. Hyperspectral technology can be used to estimate apple canopy LAI rapidly and nondestructively. It can be provide a reference for monitoring the tree growing and yield estimation. The Red Fuji apple trees of full bearing fruit are the researching objects. Ninety apple trees canopies spectral reflectance and LAI values were measured by the ASD Fieldspec3 spectrometer and LAI-2200 in thirty orchards in constant two years in Qixia research area of Shandong Province. The optimal vegetation indices were selected by the method of correlation analysis of the original spectral reflectance and vegetation indices. The models of predicting the LAI were built with the multivariate regression analysis method of support vector machine (SVM) and random forest (RF). The new vegetation indices, GNDVI527, ND-VI676, RVI682, FD-NVI656 and GRVI517 and the previous two main vegetation indices, NDVI670 and NDVI705, are in accordance with LAI. In the RF regression model, the calibration set decision coefficient C-R2 of 0.920 and validation set decision coefficient V-R2 of 0.889 are higher than the SVM regression model by 0.045 and 0.033 respectively. The root mean square error of calibration set C-RMSE of 0.249, the root mean square error validation set V-RMSE of 0.236 are lower than that of the SVM regression model by 0.054 and 0.058 respectively. Relative analysis of calibrating error C-RPD and relative analysis of validation set V-RPD reached 3.363 and 2.520, 0.598 and 0.262, respectively, which were higher than the SVM regression model. The measured and predicted the scatterplot trend line slope of the calibration set and validation set C-S and V-S are close to 1. The estimation result of RF regression model is better than that of the SVM. RF regression model can be used to estimate the LAI of red Fuji apple trees in full fruit period.

Calibration of limited-area ensemble precipitation forecasts for hydrological predictions

NASA Astrophysics Data System (ADS)

Diomede, Tommaso; Marsigli, Chiara; Montani, Andrea; Nerozzi, Fabrizio; Paccagnella, Tiziana

2015-04-01

The main objective of this study is to investigate the impact of calibration for limited-area ensemble precipitation forecasts, to be used for driving discharge predictions up to 5 days in advance. A reforecast dataset, which spans 30 years, based on the Consortium for Small Scale Modeling Limited-Area Ensemble Prediction System (COSMO-LEPS) was used for testing the calibration strategy. Three calibration techniques were applied: quantile-to-quantile mapping, linear regression, and analogs. The performance of these methodologies was evaluated in terms of statistical scores for the precipitation forecasts operationally provided by COSMO-LEPS in the years 2003-2007 over Germany, Switzerland, and the Emilia-Romagna region (northern Italy). The analog-based method seemed to be preferred because of its capability of correct position errors and spread deficiencies. A suitable spatial domain for the analog search can help to handle model spatial errors as systematic errors. However, the performance of the analog-based method may degrade in cases where a limited training dataset is available. A sensitivity test on the length of the training dataset over which to perform the analog search has been performed. The quantile-to-quantile mapping and linear regression methods were less effective, mainly because the forecast-analysis relation was not so strong for the available training dataset. A comparison between the calibration based on the deterministic reforecast and the calibration based on the full operational ensemble used as training dataset has been considered, with the aim to evaluate whether reforecasts are really worthy for calibration, given that their computational cost is remarkable. The verification of the calibration process was then performed by coupling ensemble precipitation forecasts with a distributed rainfall-runoff model. This test was carried out for a medium-sized catchment located in Emilia-Romagna, showing a beneficial impact of the analog-based method on the reduction of missed events for discharge predictions.

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

USGS Publications Warehouse

Anderson, Ryan; Clegg, Samuel M.; Frydenvang, Jens; Wiens, Roger C.; McLennan, Scott M.; Morris, Richard V.; Ehlmann, Bethany L.; Dyar, M. Darby

2017-01-01

Accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the Laser-Induced Breakdown Spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response of an element’s emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “sub-model” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. The sub-model method, using partial least squares regression (PLS), is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.

An efficient surrogate-based simulation-optimization method for calibrating a regional MODFLOW model

NASA Astrophysics Data System (ADS)

Chen, Mingjie; Izady, Azizallah; Abdalla, Osman A.

2017-01-01

Simulation-optimization method entails a large number of model simulations, which is computationally intensive or even prohibitive if the model simulation is extremely time-consuming. Statistical models have been examined as a surrogate of the high-fidelity physical model during simulation-optimization process to tackle this problem. Among them, Multivariate Adaptive Regression Splines (MARS), a non-parametric adaptive regression method, is superior in overcoming problems of high-dimensions and discontinuities of the data. Furthermore, the stability and accuracy of MARS model can be improved by bootstrap aggregating methods, namely, bagging. In this paper, Bagging MARS (BMARS) method is integrated to a surrogate-based simulation-optimization framework to calibrate a three-dimensional MODFLOW model, which is developed to simulate the groundwater flow in an arid hardrock-alluvium region in northwestern Oman. The physical MODFLOW model is surrogated by the statistical model developed using BMARS algorithm. The surrogate model, which is fitted and validated using training dataset generated by the physical model, can approximate solutions rapidly. An efficient Sobol' method is employed to calculate global sensitivities of head outputs to input parameters, which are used to analyze their importance for the model outputs spatiotemporally. Only sensitive parameters are included in the calibration process to further improve the computational efficiency. Normalized root mean square error (NRMSE) between measured and simulated heads at observation wells is used as the objective function to be minimized during optimization. The reasonable history match between the simulated and observed heads demonstrated feasibility of this high-efficient calibration framework.

Wind Tunnel Strain-Gage Balance Calibration Data Analysis Using a Weighted Least Squares Approach

NASA Technical Reports Server (NTRS)

Ulbrich, N.; Volden, T.

2017-01-01

A new approach is presented that uses a weighted least squares fit to analyze wind tunnel strain-gage balance calibration data. The weighted least squares fit is specifically designed to increase the influence of single-component loadings during the regression analysis. The weighted least squares fit also reduces the impact of calibration load schedule asymmetries on the predicted primary sensitivities of the balance gages. A weighting factor between zero and one is assigned to each calibration data point that depends on a simple count of its intentionally loaded load components or gages. The greater the number of a data point's intentionally loaded load components or gages is, the smaller its weighting factor becomes. The proposed approach is applicable to both the Iterative and Non-Iterative Methods that are used for the analysis of strain-gage balance calibration data in the aerospace testing community. The Iterative Method uses a reasonable estimate of the tare corrected load set as input for the determination of the weighting factors. The Non-Iterative Method, on the other hand, uses gage output differences relative to the natural zeros as input for the determination of the weighting factors. Machine calibration data of a six-component force balance is used to illustrate benefits of the proposed weighted least squares fit. In addition, a detailed derivation of the PRESS residuals associated with a weighted least squares fit is given in the appendices of the paper as this information could not be found in the literature. These PRESS residuals may be needed to evaluate the predictive capabilities of the final regression models that result from a weighted least squares fit of the balance calibration data.

Analyses of Field Test Data at the Atucha-1 Spent Fuel Pools

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sitaraman, S.

A field test was conducted at the Atucha-1 spent nuclear fuel pools to validate a software package for gross defect detection that is used in conjunction with the inspection tool, Spent Fuel Neutron Counter (SFNC). A set of measurements was taken with the SFNC and the software predictions were compared with these data and analyzed. The data spanned a wide range of cooling times and a set of burnup levels leading to count rates from the several hundreds to around twenty per second. The current calibration in the software using linear fitting required the use of multiple calibration factors tomore » cover the entire range of count rates recorded. The solution to this was to use power regression data fitting to normalize the predicted response and derive one calibration factor that can be applied to the entire set of data. The resulting comparisons between the predicted and measured responses were generally good and provided a quantitative method of detecting missing fuel in virtually all situations. Since the current version of the software uses the linear calibration method, it would need to be updated with the new power regression method to make it more user-friendly for real time verification and fieldable for the range of responses that will be encountered.« less

Wind tunnel test of Teledyne Geotech model 1564B cup anemometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, M.J.; Addis, R.P.

1991-04-04

The Department of Energy (DOE) Environment, Safety and Health Compliance Assessment (Tiger Team) of the Savannah River Site (SRS) questioned the method by which wind speed sensors (cup anemometers) are calibrated by the Environmental Technology Section (ETS). The Tiger Team member was concerned that calibration data was generated by running the wind tunnel to only 26 miles per hour (mph) when speeds exceeding 50 mph are readily obtainable. A wind tunnel experiment was conducted and confirmed the validity of the practice. Wind speeds common to SRS (6 mph) were predicted more accurately by 0--25 mph regression equations than 0--50 mphmore » regression equations. Higher wind speeds were slightly overpredicted by the 0--25 mph regression equations when compared to 0--50 mph regression equations. However, the greater benefit of more accurate lower wind speed predictions accuracy outweight the benefit of slightly better high (extreme) wind speed predictions. Therefore, it is concluded that 0--25 mph regression equations should continue to be utilized by ETS at SRS. During the Department of Energy Tiger Team audit, concerns were raised about the calibration of SRS cup anemometers. Wind speed is measured by ETS with Teledyne Geotech model 1564B cup anemometers, which are calibrated in the ETS wind tunnel. Linear regression lines are fitted to data points of tunnel speed versus anemometer output voltages up to 25 mph. The regression coefficients are then implemented into the data acquisition computer software when an instrument is installed in the field. The concern raised was that since the wind tunnel at SRS is able to generate a maximum wind speed higher than 25 mph, errors may be introduced in not using the full range of the wind tunnel.« less

Wind tunnel test of Teledyne Geotech model 1564B cup anemometer

NASA Astrophysics Data System (ADS)

Parker, M. J.; Addis, R. P.

1991-04-01

The Department of Energy (DOE) Environment, Safety, and Health Compliance Assessment (Tiger Team) of the Savannah River Site (SRS) questioned the method by which wind speed sensors (cup anemometers) are calibrated by the Environmental Technology Section (ETS). The Tiger Team member was concerned that calibration data was generated by running the wind tunnel to only 26 miles per hour (mph) when speeds exceeding 50 mph are readily obtainable. A wind tunnel experiment was conducted and confirmed the validity of the practice. Wind speeds common to SRS (6 mph) were predicted more accurately by 0-25 mph regression equations than 0-50 mph regression equations. Higher wind speeds were slightly overpredicted by the 0-25 mph regression equations when compared to 0-50 mph regression equations. However, the greater benefit of more accurate lower wind speed predictions accuracy outweigh the benefit of slightly better high (extreme) wind speed predictions. Therefore, it is concluded that 0-25 mph regression equations should continue to be utilized by ETS at SRS. During the Department of Energy Tiger Team audit, concerns were raised about the calibration of SRS cup anemometers. Wind speed is measured by ETS with Teledyne Geotech model 1564B cup anemometers, which are calibrated in the ETS wind tunnel. Linear regression lines are fitted to data points of tunnel speed versus anemometer output voltages up to 25 mph. The regression coefficients are then implemented into the data acquisition computer software when an instrument is installed in the field. The concern raised was that since the wind tunnel at SRS is able to generate a maximum wind speed higher than 25 mph, errors may be introduced in not using the full range of the wind tunnel.

Survival analysis with error-prone time-varying covariates: a risk set calibration approach

PubMed Central

Liao, Xiaomei; Zucker, David M.; Li, Yi; Spiegelman, Donna

2010-01-01

Summary Occupational, environmental, and nutritional epidemiologists are often interested in estimating the prospective effect of time-varying exposure variables such as cumulative exposure or cumulative updated average exposure, in relation to chronic disease endpoints such as cancer incidence and mortality. From exposure validation studies, it is apparent that many of the variables of interest are measured with moderate to substantial error. Although the ordinary regression calibration approach is approximately valid and efficient for measurement error correction of relative risk estimates from the Cox model with time-independent point exposures when the disease is rare, it is not adaptable for use with time-varying exposures. By re-calibrating the measurement error model within each risk set, a risk set regression calibration method is proposed for this setting. An algorithm for a bias-corrected point estimate of the relative risk using an RRC approach is presented, followed by the derivation of an estimate of its variance, resulting in a sandwich estimator. Emphasis is on methods applicable to the main study/external validation study design, which arises in important applications. Simulation studies under several assumptions about the error model were carried out, which demonstrated the validity and efficiency of the method in finite samples. The method was applied to a study of diet and cancer from Harvard’s Health Professionals Follow-up Study (HPFS). PMID:20486928

Photometric calibration of the COMBO-17 survey with the Softassign Procrustes Matching method

NASA Astrophysics Data System (ADS)

Sheikhbahaee, Z.; Nakajima, R.; Erben, T.; Schneider, P.; Hildebrandt, H.; Becker, A. C.

2017-11-01

Accurate photometric calibration of optical data is crucial for photometric redshift estimation. We present the Softassign Procrustes Matching (SPM) method to improve the colour calibration upon the commonly used Stellar Locus Regression (SLR) method for the COMBO-17 survey. Our colour calibration approach can be categorised as a point-set matching method, which is frequently used in medical imaging and pattern recognition. We attain a photometric redshift precision Δz/(1 + zs) of better than 2 per cent. Our method is based on aligning the stellar locus of the uncalibrated stars to that of a spectroscopic sample of the Sloan Digital Sky Survey standard stars. We achieve our goal by finding a correspondence matrix between the two point-sets and applying the matrix to estimate the appropriate translations in multidimensional colour space. The SPM method is able to find the translation between two point-sets, despite the existence of noise and incompleteness of the common structures in the sets, as long as there is a distinct structure in at least one of the colour-colour pairs. We demonstrate the precision of our colour calibration method with a mock catalogue. The SPM colour calibration code is publicly available at https://neuronphysics@bitbucket.org/neuronphysics/spm.git.

Calibration of volume and component biomass equations for Douglas-fir and lodgepole pine in Western Oregon forests

Treesearch

Krishna P. Poudel; Temesgen Hailemariam

2016-01-01

Using data from destructively sampled Douglas-fir and lodgepole pine trees, we evaluated the performance of regional volume and component biomass equations in terms of bias and RMSE. The volume and component biomass equations were calibrated using three different adjustment methods that used: (a) a correction factor based on ordinary least square regression through...

Reduction of interferences in graphite furnace atomic absorption spectrometry by multiple linear regression modelling

NASA Astrophysics Data System (ADS)

Grotti, Marco; Abelmoschi, Maria Luisa; Soggia, Francesco; Tiberiade, Christian; Frache, Roberto

2000-12-01

The multivariate effects of Na, K, Mg and Ca as nitrates on the electrothermal atomisation of manganese, cadmium and iron were studied by multiple linear regression modelling. Since the models proved to efficiently predict the effects of the considered matrix elements in a wide range of concentrations, they were applied to correct the interferences occurring in the determination of trace elements in seawater after pre-concentration of the analytes. In order to obtain a statistically significant number of samples, a large volume of the certified seawater reference materials CASS-3 and NASS-3 was treated with Chelex-100 resin; then, the chelating resin was separated from the solution, divided into several sub-samples, each of them was eluted with nitric acid and analysed by electrothermal atomic absorption spectrometry (for trace element determinations) and inductively coupled plasma optical emission spectrometry (for matrix element determinations). To minimise any other systematic error besides that due to matrix effects, accuracy of the pre-concentration step and contamination levels of the procedure were checked by inductively coupled plasma mass spectrometric measurements. Analytical results obtained by applying the multiple linear regression models were compared with those obtained with other calibration methods, such as external calibration using acid-based standards, external calibration using matrix-matched standards and the analyte addition technique. Empirical models proved to efficiently reduce interferences occurring in the analysis of real samples, allowing an improvement of accuracy better than for other calibration methods.

Inverse models: A necessary next step in ground-water modeling

USGS Publications Warehouse

Poeter, E.P.; Hill, M.C.

1997-01-01

Inverse models using, for example, nonlinear least-squares regression, provide capabilities that help modelers take full advantage of the insight available from ground-water models. However, lack of information about the requirements and benefits of inverse models is an obstacle to their widespread use. This paper presents a simple ground-water flow problem to illustrate the requirements and benefits of the nonlinear least-squares repression method of inverse modeling and discusses how these attributes apply to field problems. The benefits of inverse modeling include: (1) expedited determination of best fit parameter values; (2) quantification of the (a) quality of calibration, (b) data shortcomings and needs, and (c) confidence limits on parameter estimates and predictions; and (3) identification of issues that are easily overlooked during nonautomated calibration.Inverse models using, for example, nonlinear least-squares regression, provide capabilities that help modelers take full advantage of the insight available from ground-water models. However, lack of information about the requirements and benefits of inverse models is an obstacle to their widespread use. This paper presents a simple ground-water flow problem to illustrate the requirements and benefits of the nonlinear least-squares regression method of inverse modeling and discusses how these attributes apply to field problems. The benefits of inverse modeling include: (1) expedited determination of best fit parameter values; (2) quantification of the (a) quality of calibration, (b) data shortcomings and needs, and (c) confidence limits on parameter estimates and predictions; and (3) identification of issues that are easily overlooked during nonautomated calibration.

Predicting ecological flow regime at ungaged sites: A comparison of methods

USGS Publications Warehouse

Murphy, Jennifer C.; Knight, Rodney R.; Wolfe, William J.; Gain, W. Scott

2012-01-01

Nineteen ecologically relevant streamflow characteristics were estimated using published rainfall–runoff and regional regression models for six sites with observed daily streamflow records in Kentucky. The regional regression model produced median estimates closer to the observed median for all but two characteristics. The variability of predictions from both models was generally less than the observed variability. The variability of the predictions from the rainfall–runoff model was greater than that from the regional regression model for all but three characteristics. Eight characteristics predicted by the rainfall–runoff model display positive or negative bias across all six sites; biases are not as pronounced for the regional regression model. Results suggest that a rainfall–runoff model calibrated on a single characteristic is less likely to perform well as a predictor of a range of other characteristics (flow regime) when compared with a regional regression model calibrated individually on multiple characteristics used to represent the flow regime. Poor model performance may misrepresent hydrologic conditions, potentially distorting the perceived risk of ecological degradation. Without prior selection of streamflow characteristics, targeted calibration, and error quantification, the widespread application of general hydrologic models to ecological flow studies is problematic. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.

Membrane Introduction Mass Spectrometry Combined with an Orthogonal Partial-Least Squares Calibration Model for Mixture Analysis.

PubMed

Li, Min; Zhang, Lu; Yao, Xiaolong; Jiang, Xingyu

2017-01-01

The emerging membrane introduction mass spectrometry technique has been successfully used to detect benzene, toluene, ethyl benzene and xylene (BTEX), while overlapped spectra have unfortunately hindered its further application to the analysis of mixtures. Multivariate calibration, an efficient method to analyze mixtures, has been widely applied. In this paper, we compared univariate and multivariate analyses for quantification of the individual components of mixture samples. The results showed that the univariate analysis creates poor models with regression coefficients of 0.912, 0.867, 0.440 and 0.351 for BTEX, respectively. For multivariate analysis, a comparison to the partial-least squares (PLS) model shows that the orthogonal partial-least squares (OPLS) regression exhibits an optimal performance with regression coefficients of 0.995, 0.999, 0.980 and 0.976, favorable calibration parameters (RMSEC and RMSECV) and a favorable validation parameter (RMSEP). Furthermore, the OPLS exhibits a good recovery of 73.86 - 122.20% and relative standard deviation (RSD) of the repeatability of 1.14 - 4.87%. Thus, MIMS coupled with the OPLS regression provides an optimal approach for a quantitative BTEX mixture analysis in monitoring and predicting water pollution.

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Ryan B.; Clegg, Samuel M.; Frydenvang, Jens

We report that accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the Laser-Induced Breakdown Spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response ofmore » an element’s emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “submodel” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. Lastly, the sub-model method, using partial least squares regression (PLS), is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.« less

Improved accuracy in quantitative laser-induced breakdown spectroscopy using sub-models

DOE PAGES

Anderson, Ryan B.; Clegg, Samuel M.; Frydenvang, Jens; ...

2016-12-15

We report that accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the Laser-Induced Breakdown Spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response ofmore » an element’s emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “submodel” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. Lastly, the sub-model method, using partial least squares regression (PLS), is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.« less

Determination of thiamine HCl and pyridoxine HCl in pharmaceutical preparations using UV-visible spectrophotometry and genetic algorithm based multivariate calibration methods.

PubMed

Ozdemir, Durmus; Dinc, Erdal

2004-07-01

Simultaneous determination of binary mixtures pyridoxine hydrochloride and thiamine hydrochloride in a vitamin combination using UV-visible spectrophotometry and classical least squares (CLS) and three newly developed genetic algorithm (GA) based multivariate calibration methods was demonstrated. The three genetic multivariate calibration methods are Genetic Classical Least Squares (GCLS), Genetic Inverse Least Squares (GILS) and Genetic Regression (GR). The sample data set contains the UV-visible spectra of 30 synthetic mixtures (8 to 40 microg/ml) of these vitamins and 10 tablets containing 250 mg from each vitamin. The spectra cover the range from 200 to 330 nm in 0.1 nm intervals. Several calibration models were built with the four methods for the two components. Overall, the standard error of calibration (SEC) and the standard error of prediction (SEP) for the synthetic data were in the range of <0.01 and 0.43 microg/ml for all the four methods. The SEP values for the tablets were in the range of 2.91 and 11.51 mg/tablets. A comparison of genetic algorithm selected wavelengths for each component using GR method was also included.

Linear regression analysis of survival data with missing censoring indicators.

PubMed

Wang, Qihua; Dinse, Gregg E

2011-04-01

Linear regression analysis has been studied extensively in a random censorship setting, but typically all of the censoring indicators are assumed to be observed. In this paper, we develop synthetic data methods for estimating regression parameters in a linear model when some censoring indicators are missing. We define estimators based on regression calibration, imputation, and inverse probability weighting techniques, and we prove all three estimators are asymptotically normal. The finite-sample performance of each estimator is evaluated via simulation. We illustrate our methods by assessing the effects of sex and age on the time to non-ambulatory progression for patients in a brain cancer clinical trial.

Application of nonlinear-regression methods to a ground-water flow model of the Albuquerque Basin, New Mexico

USGS Publications Warehouse

Tiedeman, C.R.; Kernodle, J.M.; McAda, D.P.

1998-01-01

This report documents the application of nonlinear-regression methods to a numerical model of ground-water flow in the Albuquerque Basin, New Mexico. In the Albuquerque Basin, ground water is the primary source for most water uses. Ground-water withdrawal has steadily increased since the 1940's, resulting in large declines in water levels in the Albuquerque area. A ground-water flow model was developed in 1994 and revised and updated in 1995 for the purpose of managing basin ground- water resources. In the work presented here, nonlinear-regression methods were applied to a modified version of the previous flow model. Goals of this work were to use regression methods to calibrate the model with each of six different configurations of the basin subsurface and to assess and compare optimal parameter estimates, model fit, and model error among the resulting calibrations. The Albuquerque Basin is one in a series of north trending structural basins within the Rio Grande Rift, a region of Cenozoic crustal extension. Mountains, uplifts, and fault zones bound the basin, and rock units within the basin include pre-Santa Fe Group deposits, Tertiary Santa Fe Group basin fill, and post-Santa Fe Group volcanics and sediments. The Santa Fe Group is greater than 14,000 feet (ft) thick in the central part of the basin. During deposition of the Santa Fe Group, crustal extension resulted in development of north trending normal faults with vertical displacements of as much as 30,000 ft. Ground-water flow in the Albuquerque Basin occurs primarily in the Santa Fe Group and post-Santa Fe Group deposits. Water flows between the ground-water system and surface-water bodies in the inner valley of the basin, where the Rio Grande, a network of interconnected canals and drains, and Cochiti Reservoir are located. Recharge to the ground-water flow system occurs as infiltration of precipitation along mountain fronts and infiltration of stream water along tributaries to the Rio Grande; subsurface flow from adjacent regions; irrigation and septic field seepage; and leakage through the Rio Grande, canal, and Cochiti Reservoir beds. Ground water is discharged from the basin by withdrawal; evapotranspiration; subsurface flow; and flow to the Rio Grande, canals, and drains. The transient, three-dimensional numerical model of ground-water flow to which nonlinear-regression methods were applied simulates flow in the Albuquerque Basin from 1900 to March 1995. Six different basin subsurface configurations are considered in the model. These configurations are designed to test the effects of (1) varying the simulated basin thickness, (2) including a hypothesized hydrogeologic unit with large hydraulic conductivity in the western part of the basin (the west basin high-K zone), and (3) substantially lowering the simulated hydraulic conductivity of a fault in the western part of the basin (the low-K fault zone). The model with each of the subsurface configurations was calibrated using a nonlinear least- squares regression technique. The calibration data set includes 802 hydraulic-head measurements that provide broad spatial and temporal coverage of basin conditions, and one measurement of net flow from the Rio Grande and drains to the ground-water system in the Albuquerque area. Data are weighted on the basis of estimates of the standard deviations of measurement errors. The 10 to 12 parameters to which the calibration data as a whole are generally most sensitive were estimated by nonlinear regression, whereas the remaining model parameter values were specified. Results of model calibration indicate that the optimal parameter estimates as a whole are most reasonable in calibrations of the model with with configurations 3 (which contains 1,600-ft-thick basin deposits and the west basin high-K zone), 4 (which contains 5,000-ft-thick basin de

Calibration transfer of a Raman spectroscopic quantification method for the assessment of liquid detergent compositions from at-line laboratory to in-line industrial scale.

PubMed

Brouckaert, D; Uyttersprot, J-S; Broeckx, W; De Beer, T

2018-03-01

Calibration transfer or standardisation aims at creating a uniform spectral response on different spectroscopic instruments or under varying conditions, without requiring a full recalibration for each situation. In the current study, this strategy is applied to construct at-line multivariate calibration models and consequently employ them in-line in a continuous industrial production line, using the same spectrometer. Firstly, quantitative multivariate models are constructed at-line at laboratory scale for predicting the concentration of two main ingredients in hard surface cleaners. By regressing the Raman spectra of a set of small-scale calibration samples against their reference concentration values, partial least squares (PLS) models are developed to quantify the surfactant levels in the liquid detergent compositions under investigation. After evaluating the models performance with a set of independent validation samples, a univariate slope/bias correction is applied in view of transporting these at-line calibration models to an in-line manufacturing set-up. This standardisation technique allows a fast and easy transfer of the PLS regression models, by simply correcting the model predictions on the in-line set-up, without adjusting anything to the original multivariate calibration models. An extensive statistical analysis is performed in order to assess the predictive quality of the transferred regression models. Before and after transfer, the R 2 and RMSEP of both models is compared for evaluating if their magnitude is similar. T-tests are then performed to investigate whether the slope and intercept of the transferred regression line are not statistically different from 1 and 0, respectively. Furthermore, it is inspected whether no significant bias can be noted. F-tests are executed as well, for assessing the linearity of the transfer regression line and for investigating the statistical coincidence of the transfer and validation regression line. Finally, a paired t-test is performed to compare the original at-line model to the slope/bias corrected in-line model, using interval hypotheses. It is shown that the calibration models of Surfactant 1 and Surfactant 2 yield satisfactory in-line predictions after slope/bias correction. While Surfactant 1 passes seven out of eight statistical tests, the recommended validation parameters are 100% successful for Surfactant 2. It is hence concluded that the proposed strategy for transferring at-line calibration models to an in-line industrial environment via a univariate slope/bias correction of the predicted values offers a successful standardisation approach. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantifying prognosis with risk predictions.

PubMed

Pace, Nathan L; Eberhart, Leopold H J; Kranke, Peter R

2012-01-01

Prognosis is a forecast, based on present observations in a patient, of their probable outcome from disease, surgery and so on. Research methods for the development of risk probabilities may not be familiar to some anaesthesiologists. We briefly describe methods for identifying risk factors and risk scores. A probability prediction rule assigns a risk probability to a patient for the occurrence of a specific event. Probability reflects the continuum between absolute certainty (Pi = 1) and certified impossibility (Pi = 0). Biomarkers and clinical covariates that modify risk are known as risk factors. The Pi as modified by risk factors can be estimated by identifying the risk factors and their weighting; these are usually obtained by stepwise logistic regression. The accuracy of probabilistic predictors can be separated into the concepts of 'overall performance', 'discrimination' and 'calibration'. Overall performance is the mathematical distance between predictions and outcomes. Discrimination is the ability of the predictor to rank order observations with different outcomes. Calibration is the correctness of prediction probabilities on an absolute scale. Statistical methods include the Brier score, coefficient of determination (Nagelkerke R2), C-statistic and regression calibration. External validation is the comparison of the actual outcomes to the predicted outcomes in a new and independent patient sample. External validation uses the statistical methods of overall performance, discrimination and calibration and is uniformly recommended before acceptance of the prediction model. Evidence from randomised controlled clinical trials should be obtained to show the effectiveness of risk scores for altering patient management and patient outcomes.

Identification method of laser gyro error model under changing physical field

NASA Astrophysics Data System (ADS)

Wang, Qingqing; Niu, Zhenzhong

2018-04-01

In this paper, the influence mechanism of temperature, temperature changing rate and temperature gradient on the inertial devices is studied. The two-order model of zero bias and the three-order model of the calibration factor of lster gyro under temperature variation are deduced. The calibration scheme of temperature error is designed, and the experiment is carried out. Two methods of stepwise regression analysis and BP neural network are used to identify the parameters of the temperature error model, and the effectiveness of the two methods is proved by the temperature error compensation.

Guidelines 13 and 14—Prediction uncertainty

USGS Publications Warehouse

Hill, Mary C.; Tiedeman, Claire

2005-01-01

An advantage of using optimization for model development and calibration is that optimization provides methods for evaluating and quantifying prediction uncertainty. Both deterministic and statistical methods can be used. Guideline 13 discusses using regression and post-audits, which we classify as deterministic methods. Guideline 14 discusses inferential statistics and Monte Carlo methods, which we classify as statistical methods.

Analysis of Sting Balance Calibration Data Using Optimized Regression Models

NASA Technical Reports Server (NTRS)

Ulbrich, N.; Bader, Jon B.

2010-01-01

Calibration data of a wind tunnel sting balance was processed using a candidate math model search algorithm that recommends an optimized regression model for the data analysis. During the calibration the normal force and the moment at the balance moment center were selected as independent calibration variables. The sting balance itself had two moment gages. Therefore, after analyzing the connection between calibration loads and gage outputs, it was decided to choose the difference and the sum of the gage outputs as the two responses that best describe the behavior of the balance. The math model search algorithm was applied to these two responses. An optimized regression model was obtained for each response. Classical strain gage balance load transformations and the equations of the deflection of a cantilever beam under load are used to show that the search algorithm s two optimized regression models are supported by a theoretical analysis of the relationship between the applied calibration loads and the measured gage outputs. The analysis of the sting balance calibration data set is a rare example of a situation when terms of a regression model of a balance can directly be derived from first principles of physics. In addition, it is interesting to note that the search algorithm recommended the correct regression model term combinations using only a set of statistical quality metrics that were applied to the experimental data during the algorithm s term selection process.

Salting-out assisted liquid-liquid extraction and partial least squares regression to assay low molecular weight polycyclic aromatic hydrocarbons leached from soils and sediments

NASA Astrophysics Data System (ADS)

Bressan, Lucas P.; do Nascimento, Paulo Cícero; Schmidt, Marcella E. P.; Faccin, Henrique; de Machado, Leandro Carvalho; Bohrer, Denise

2017-02-01

A novel method was developed to determine low molecular weight polycyclic aromatic hydrocarbons in aqueous leachates from soils and sediments using a salting-out assisted liquid-liquid extraction, synchronous fluorescence spectrometry and a multivariate calibration technique. Several experimental parameters were controlled and the optimum conditions were: sodium carbonate as the salting-out agent at concentration of 2 mol L- 1, 3 mL of acetonitrile as extraction solvent, 6 mL of aqueous leachate, vortexing for 5 min and centrifuging at 4000 rpm for 5 min. The partial least squares calibration was optimized to the lowest values of root mean squared error and five latent variables were chosen for each of the targeted compounds. The regression coefficients for the true versus predicted concentrations were higher than 0.99. Figures of merit for the multivariate method were calculated, namely sensitivity, multivariate detection limit and multivariate quantification limit. The selectivity was also evaluated and other polycyclic aromatic hydrocarbons did not interfere in the analysis. Likewise, high performance liquid chromatography was used as a comparative methodology, and the regression analysis between the methods showed no statistical difference (t-test). The proposed methodology was applied to soils and sediments of a Brazilian river and the recoveries ranged from 74.3% to 105.8%. Overall, the proposed methodology was suitable for the targeted compounds, showing that the extraction method can be applied to spectrofluorometric analysis and that the multivariate calibration is also suitable for these compounds in leachates from real samples.

A consensus least squares support vector regression (LS-SVR) for analysis of near-infrared spectra of plant samples.

PubMed

Li, Yankun; Shao, Xueguang; Cai, Wensheng

2007-04-15

Consensus modeling of combining the results of multiple independent models to produce a single prediction avoids the instability of single model. Based on the principle of consensus modeling, a consensus least squares support vector regression (LS-SVR) method for calibrating the near-infrared (NIR) spectra was proposed. In the proposed approach, NIR spectra of plant samples were firstly preprocessed using discrete wavelet transform (DWT) for filtering the spectral background and noise, then, consensus LS-SVR technique was used for building the calibration model. With an optimization of the parameters involved in the modeling, a satisfied model was achieved for predicting the content of reducing sugar in plant samples. The predicted results show that consensus LS-SVR model is more robust and reliable than the conventional partial least squares (PLS) and LS-SVR methods.

Calibration Adjustment of the Mid-infrared Analyzer for an Accurate Determination of the Macronutrient Composition of Human Milk.

PubMed

Billard, Hélène; Simon, Laure; Desnots, Emmanuelle; Sochard, Agnès; Boscher, Cécile; Riaublanc, Alain; Alexandre-Gouabau, Marie-Cécile; Boquien, Clair-Yves

2016-08-01

Human milk composition analysis seems essential to adapt human milk fortification for preterm neonates. The Miris human milk analyzer (HMA), based on mid-infrared methodology, is convenient for a unique determination of macronutrients. However, HMA measurements are not totally comparable with reference methods (RMs). The primary aim of this study was to compare HMA results with results from biochemical RMs for a large range of protein, fat, and carbohydrate contents and to establish a calibration adjustment. Human milk was fractionated in protein, fat, and skim milk by covering large ranges of protein (0-3 g/100 mL), fat (0-8 g/100 mL), and carbohydrate (5-8 g/100 mL). For each macronutrient, a calibration curve was plotted by linear regression using measurements obtained using HMA and RMs. For fat, 53 measurements were performed, and the linear regression equation was HMA = 0.79RM + 0.28 (R(2) = 0.92). For true protein (29 measurements), the linear regression equation was HMA = 0.9RM + 0.23 (R(2) = 0.98). For carbohydrate (15 measurements), the linear regression equation was HMA = 0.59RM + 1.86 (R(2) = 0.95). A homogenization step with a disruptor coupled to a sonication step was necessary to obtain better accuracy of the measurements. Good repeatability (coefficient of variation < 7%) and reproducibility (coefficient of variation < 17%) were obtained after calibration adjustment. New calibration curves were developed for the Miris HMA, allowing accurate measurements in large ranges of macronutrient content. This is necessary for reliable use of this device in individualizing nutrition for preterm newborns. © The Author(s) 2015.

The Prediction Properties of Inverse and Reverse Regression for the Simple Linear Calibration Problem

NASA Technical Reports Server (NTRS)

Parker, Peter A.; Geoffrey, Vining G.; Wilson, Sara R.; Szarka, John L., III; Johnson, Nels G.

2010-01-01

The calibration of measurement systems is a fundamental but under-studied problem within industrial statistics. The origins of this problem go back to basic chemical analysis based on NIST standards. In today's world these issues extend to mechanical, electrical, and materials engineering. Often, these new scenarios do not provide "gold standards" such as the standard weights provided by NIST. This paper considers the classic "forward regression followed by inverse regression" approach. In this approach the initial experiment treats the "standards" as the regressor and the observed values as the response to calibrate the instrument. The analyst then must invert the resulting regression model in order to use the instrument to make actual measurements in practice. This paper compares this classical approach to "reverse regression," which treats the standards as the response and the observed measurements as the regressor in the calibration experiment. Such an approach is intuitively appealing because it avoids the need for the inverse regression. However, it also violates some of the basic regression assumptions.

Acidity measurement of iron ore powders using laser-induced breakdown spectroscopy with partial least squares regression.

PubMed

Hao, Z Q; Li, C M; Shen, M; Yang, X Y; Li, K H; Guo, L B; Li, X Y; Lu, Y F; Zeng, X Y

2015-03-23

Laser-induced breakdown spectroscopy (LIBS) with partial least squares regression (PLSR) has been applied to measuring the acidity of iron ore, which can be defined by the concentrations of oxides: CaO, MgO, Al₂O₃, and SiO₂. With the conventional internal standard calibration, it is difficult to establish the calibration curves of CaO, MgO, Al₂O₃, and SiO₂ in iron ore due to the serious matrix effects. PLSR is effective to address this problem due to its excellent performance in compensating the matrix effects. In this work, fifty samples were used to construct the PLSR calibration models for the above-mentioned oxides. These calibration models were validated by the 10-fold cross-validation method with the minimum root-mean-square errors (RMSE). Another ten samples were used as a test set. The acidities were calculated according to the estimated concentrations of CaO, MgO, Al₂O₃, and SiO₂ using the PLSR models. The average relative error (ARE) and RMSE of the acidity achieved 3.65% and 0.0048, respectively, for the test samples.

Multivariate calibration on NIR data: development of a model for the rapid evaluation of ethanol content in bakery products.

PubMed

Bello, Alessandra; Bianchi, Federica; Careri, Maria; Giannetto, Marco; Mori, Giovanni; Musci, Marilena

2007-11-05

A new NIR method based on multivariate calibration for determination of ethanol in industrially packed wholemeal bread was developed and validated. GC-FID was used as reference method for the determination of actual ethanol concentration of different samples of wholemeal bread with proper content of added ethanol, ranging from 0 to 3.5% (w/w). Stepwise discriminant analysis was carried out on the NIR dataset, in order to reduce the number of original variables by selecting those that were able to discriminate between the samples of different ethanol concentrations. With the so selected variables a multivariate calibration model was then obtained by multiple linear regression. The prediction power of the linear model was optimized by a new "leave one out" method, so that the number of original variables resulted further reduced.

Spreadsheet for designing valid least-squares calibrations: A tutorial.

PubMed

Bettencourt da Silva, Ricardo J N

2016-02-01

Instrumental methods of analysis are used to define the price of goods, the compliance of products with a regulation, or the outcome of fundamental or applied research. These methods can only play their role properly if reported information is objective and their quality is fit for the intended use. If measurement results are reported with an adequately small measurement uncertainty both of these goals are achieved. The evaluation of the measurement uncertainty can be performed by the bottom-up approach, that involves a detailed description of the measurement process, or using a pragmatic top-down approach that quantify major uncertainty components from global performance data. The bottom-up approach is not so frequently used due to the need to master the quantification of individual components responsible for random and systematic effects that affect measurement results. This work presents a tutorial that can be easily used by non-experts in the accurate evaluation of the measurement uncertainty of instrumental methods of analysis calibrated using least-squares regressions. The tutorial includes the definition of the calibration interval, the assessments of instrumental response homoscedasticity, the definition of calibrators preparation procedure required for least-squares regression model application, the assessment of instrumental response linearity and the evaluation of measurement uncertainty. The developed measurement model is only applicable in calibration ranges where signal precision is constant. A MS-Excel file is made available to allow the easy application of the tutorial. This tool can be useful for cases where top-down approaches cannot produce results with adequately low measurement uncertainty. An example of the application of this tool to the determination of nitrate in water by ion chromatography is presented. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of boiling point of petrochemicals by gas chromatography-mass spectrometry and multivariate regression analysis of structural activity relationship.

PubMed

Fakayode, Sayo O; Mitchell, Breanna S; Pollard, David A

2014-08-01

Accurate understanding of analyte boiling points (BP) is of critical importance in gas chromatographic (GC) separation and crude oil refinery operation in petrochemical industries. This study reported the first combined use of GC separation and partial-least-square (PLS1) multivariate regression analysis of petrochemical structural activity relationship (SAR) for accurate BP determination of two commercially available (D3710 and MA VHP) calibration gas mix samples. The results of the BP determination using PLS1 multivariate regression were further compared with the results of traditional simulated distillation method of BP determination. The developed PLS1 regression was able to correctly predict analytes BP in D3710 and MA VHP calibration gas mix samples, with a root-mean-square-%-relative-error (RMS%RE) of 6.4%, and 10.8% respectively. In contrast, the overall RMS%RE of 32.9% and 40.4%, respectively obtained for BP determination in D3710 and MA VHP using a traditional simulated distillation method were approximately four times larger than the corresponding RMS%RE of BP prediction using MRA, demonstrating the better predictive ability of MRA. The reported method is rapid, robust, and promising, and can be potentially used routinely for fast analysis, pattern recognition, and analyte BP determination in petrochemical industries. Copyright © 2014 Elsevier B.V. All rights reserved.

Improved CRDS δ13C Stability Through New Calibration Application For CO2 and CH4

NASA Astrophysics Data System (ADS)

Arata, C.; Rella, C.

2014-12-01

Stable carbon isotope ratio measurements of CO2 and CH4 provide valuable insight into global and regional sources and sinks of the two most important greenhouse gasses. Methodologies based on Cavity Ring-Down Spectroscopy (CRDS) have been developed capable of delivering δ13C measurements with a precision greater than 0.12 permil for CO2 and 0.4 permil for CH4 (1 hour window, 5 minute average). Here we present a method to further improve this measurement's stability. We have developed a two point calibration method which corrects for δ13C drift due to a dependance on carbon species concentration. This method calibrates for both carbon species concentration as well as δ13C. We go on to show that this added stability is especially valuable when using carbon isotope data in linear regression models such as Keeling plots, where even small amounts of error can be magnified to give inconclusive results. This method is demonstrated in both laboratory and ambient atmospheric conditions, and we demonstrate how to select the calibration frequency.

Color calibration of an RGB camera mounted in front of a microscope with strong color distortion.

PubMed

Charrière, Renée; Hébert, Mathieu; Trémeau, Alain; Destouches, Nathalie

2013-07-20

This paper aims at showing that performing color calibration of an RGB camera can be achieved even in the case where the optical system before the camera introduces strong color distortion. In the present case, the optical system is a microscope containing a halogen lamp, with a nonuniform irradiance on the viewed surface. The calibration method proposed in this work is based on an existing method, but it is preceded by a three-step preprocessing of the RGB images aiming at extracting relevant color information from the strongly distorted images, taking especially into account the nonuniform irradiance map and the perturbing texture due to the surface topology of the standard color calibration charts when observed at micrometric scale. The proposed color calibration process consists first in computing the average color of the color-chart patches viewed under the microscope; then computing white balance, gamma correction, and saturation enhancement; and finally applying a third-order polynomial regression color calibration transform. Despite the nonusual conditions for color calibration, fairly good performance is achieved from a 48 patch Lambertian color chart, since an average CIE-94 color difference on the color-chart colors lower than 2.5 units is obtained.

Rapid prediction of total petroleum hydrocarbons concentration in contaminated soil using vis-NIR spectroscopy and regression techniques.

PubMed

Douglas, R K; Nawar, S; Alamar, M C; Mouazen, A M; Coulon, F

2018-03-01

Visible and near infrared spectrometry (vis-NIRS) coupled with data mining techniques can offer fast and cost-effective quantitative measurement of total petroleum hydrocarbons (TPH) in contaminated soils. Literature showed however significant differences in the performance on the vis-NIRS between linear and non-linear calibration methods. This study compared the performance of linear partial least squares regression (PLSR) with a nonlinear random forest (RF) regression for the calibration of vis-NIRS when analysing TPH in soils. 88 soil samples (3 uncontaminated and 85 contaminated) collected from three sites located in the Niger Delta were scanned using an analytical spectral device (ASD) spectrophotometer (350-2500nm) in diffuse reflectance mode. Sequential ultrasonic solvent extraction-gas chromatography (SUSE-GC) was used as reference quantification method for TPH which equal to the sum of aliphatic and aromatic fractions ranging between C 10 and C 35 . Prior to model development, spectra were subjected to pre-processing including noise cut, maximum normalization, first derivative and smoothing. Then 65 samples were selected as calibration set and the remaining 20 samples as validation set. Both vis-NIR spectrometry and gas chromatography profiles of the 85 soil samples were subjected to RF and PLSR with leave-one-out cross-validation (LOOCV) for the calibration models. Results showed that RF calibration model with a coefficient of determination (R 2 ) of 0.85, a root means square error of prediction (RMSEP) 68.43mgkg -1 , and a residual prediction deviation (RPD) of 2.61 outperformed PLSR (R 2 =0.63, RMSEP=107.54mgkg -1 and RDP=2.55) in cross-validation. These results indicate that RF modelling approach is accounting for the nonlinearity of the soil spectral responses hence, providing significantly higher prediction accuracy compared to the linear PLSR. It is recommended to adopt the vis-NIRS coupled with RF modelling approach as a portable and cost effective method for the rapid quantification of TPH in soils. Copyright © 2017 Elsevier B.V. All rights reserved.

Calibrating the Decline Rate - Peak Luminosity Relation for Type Ia Supernovae

NASA Astrophysics Data System (ADS)

Rust, Bert W.; Pruzhinskaya, Maria V.; Thijsse, Barend J.

2015-08-01

The correlation between peak luminosity and rate of decline in luminosity for Type I supernovae was first studied by B. W. Rust [Ph.D. thesis, Univ. of Illinois (1974) ORNL-4953] and Yu. P. Pskovskii [Sov. Astron., 21 (1977) 675] in the 1970s. Their work was little-noted until Phillips rediscovered the correlation in 1993 [ApJ, 413 (1993) L105] and attempted to derive a calibration relation using a difference quotient approximation Δm15(B) to the decline rate after peak luminosity Mmax(B). Numerical differentiation of data containing measuring errors is a notoriously unstable calculation, but Δm15(B) remains the parameter of choice for most calibration methods developed since 1993. To succeed, it should be computed from good functional fits to the lightcurves, but most workers never exhibit their fits. In the few instances where they have, the fits are not very good. Some of the 9 supernovae in the Phillips study required extinction corrections in their estimates of the Mmax(B), and so were not appropriate for establishing a calibration relation. Although the relative uncertainties in his Δm15(B) estimates were comparable to those in his Mmax(B) estimates, he nevertheless used simple linear regression of the latter on the former, rather than major-axis regression (total least squares) which would have been more appropriate.Here we determine some new calibration relations using a sample of nearby "pure" supernovae suggested by M. V. Pruzhinskaya [Astron. Lett., 37 (2011) 663]. Their parent galaxies are all in the NED collection, with good distance estimates obtained by several different methods. We fit each lightcurve with an optimal regression spline obtained by B. J. Thijsse's spline2 [Comp. in Sci. & Eng., 10 (2008) 49]. The fits, which explain more that 99% of the variance in each case, are better than anything heretofore obtained by stretching "template" lightcurves or fitting combinations of standard lightcurves. We use the fits to compute estimates of Δm15(B) and some other calibration parameters suggested by Pskovskii [Sov. Astron., 28 (1984) 858] and compare their utility for cosmological testing.

Using ridge regression in systematic pointing error corrections

NASA Technical Reports Server (NTRS)

Guiar, C. N.

1988-01-01

A pointing error model is used in the antenna calibration process. Data from spacecraft or radio star observations are used to determine the parameters in the model. However, the regression variables are not truly independent, displaying a condition known as multicollinearity. Ridge regression, a biased estimation technique, is used to combat the multicollinearity problem. Two data sets pertaining to Voyager 1 spacecraft tracking (days 105 and 106 of 1987) were analyzed using both linear least squares and ridge regression methods. The advantages and limitations of employing the technique are presented. The problem is not yet fully resolved.

Spectral multivariate calibration without laboratory prepared or determined reference analyte values.

PubMed

Ottaway, Josh; Farrell, Jeremy A; Kalivas, John H

2013-02-05

An essential part to calibration is establishing the analyte calibration reference samples. These samples must characterize the sample matrix and measurement conditions (chemical, physical, instrumental, and environmental) of any sample to be predicted. Calibration usually requires measuring spectra for numerous reference samples in addition to determining the corresponding analyte reference values. Both tasks are typically time-consuming and costly. This paper reports on a method named pure component Tikhonov regularization (PCTR) that does not require laboratory prepared or determined reference values. Instead, an analyte pure component spectrum is used in conjunction with nonanalyte spectra for calibration. Nonanalyte spectra can be from different sources including pure component interference samples, blanks, and constant analyte samples. The approach is also applicable to calibration maintenance when the analyte pure component spectrum is measured in one set of conditions and nonanalyte spectra are measured in new conditions. The PCTR method balances the trade-offs between calibration model shrinkage and the degree of orthogonality to the nonanalyte content (model direction) in order to obtain accurate predictions. Using visible and near-infrared (NIR) spectral data sets, the PCTR results are comparable to those obtained using ridge regression (RR) with reference calibration sets. The flexibility of PCTR also allows including reference samples if such samples are available.

Calibration for the shear strain of 3-component borehole strainmeters in eastern Taiwan through Earth and ocean tidal waveform modeling

NASA Astrophysics Data System (ADS)

Canitano, Alexandre; Hsu, Ya-Ju; Lee, Hsin-Ming; Linde, Alan T.; Sacks, Selwyn

2018-03-01

We propose an approach for calibrating the horizontal tidal shear components [(differential extension (γ _1) and engineering shear (γ _2)] of two Sacks-Evertson (in Pap Meteorol Geophys 22:195-208, 1971) SES-3 borehole strainmeters installed in the Longitudinal Valley in eastern Taiwan. The method is based on the waveform reconstruction of the Earth and ocean tidal shear signals through linear regressions on strain gauge signals, with variable sensor azimuth. This method allows us to derive the orientation of the sensor without any initial constraints and to calibrate the shear strain components γ _1 and γ _2 against M_2 tidal constituent. The results illustrate the potential of tensor strainmeters for recording horizontal tidal shear strain.

Sensitive analytical method for simultaneous analysis of some vasoconstrictors with highly overlapped analytical signals

NASA Astrophysics Data System (ADS)

Nikolić, G. S.; Žerajić, S.; Cakić, M.

2011-10-01

Multivariate calibration method is a powerful mathematical tool that can be applied in analytical chemistry when the analytical signals are highly overlapped. The method with regression by partial least squares is proposed for the simultaneous spectrophotometric determination of adrenergic vasoconstrictors in decongestive solution containing two active components: phenyleprine hydrochloride and trimazoline hydrochloride. These sympathomimetic agents are that frequently associated in pharmaceutical formulations against the common cold. The proposed method, which is, simple and rapid, offers the advantages of sensitivity and wide range of determinations without the need for extraction of the vasoconstrictors. In order to minimize the optimal factors necessary to obtain the calibration matrix by multivariate calibration, different parameters were evaluated. The adequate selection of the spectral regions proved to be important on the number of factors. In order to simultaneously quantify both hydrochlorides among excipients, the spectral region between 250 and 290 nm was selected. A recovery for the vasoconstrictor was 98-101%. The developed method was applied to assay of two decongestive pharmaceutical preparations.

Calibration of groundwater vulnerability mapping using the generalized reduced gradient method.

PubMed

Elçi, Alper

2017-12-01

Groundwater vulnerability assessment studies are essential in water resources management. Overlay-and-index methods such as DRASTIC are widely used for mapping of groundwater vulnerability, however, these methods mainly suffer from a subjective selection of model parameters. The objective of this study is to introduce a calibration procedure that results in a more accurate assessment of groundwater vulnerability. The improvement of the assessment is formulated as a parameter optimization problem using an objective function that is based on the correlation between actual groundwater contamination and vulnerability index values. The non-linear optimization problem is solved with the generalized-reduced-gradient (GRG) method, which is numerical algorithm based optimization method. To demonstrate the applicability of the procedure, a vulnerability map for the Tahtali stream basin is calibrated using nitrate concentration data. The calibration procedure is easy to implement and aims the maximization of correlation between observed pollutant concentrations and groundwater vulnerability index values. The influence of each vulnerability parameter in the calculation of the vulnerability index is assessed by performing a single-parameter sensitivity analysis. Results of the sensitivity analysis show that all factors are effective on the final vulnerability index. Calibration of the vulnerability map improves the correlation between index values and measured nitrate concentrations by 19%. The regression coefficient increases from 0.280 to 0.485. It is evident that the spatial distribution and the proportions of vulnerability class areas are significantly altered with the calibration process. Although the applicability of the calibration method is demonstrated on the DRASTIC model, the applicability of the approach is not specific to a certain model and can also be easily applied to other overlay-and-index methods. Copyright © 2017 Elsevier B.V. All rights reserved.

Calibration of groundwater vulnerability mapping using the generalized reduced gradient method

NASA Astrophysics Data System (ADS)

Elçi, Alper

2017-12-01

Groundwater vulnerability assessment studies are essential in water resources management. Overlay-and-index methods such as DRASTIC are widely used for mapping of groundwater vulnerability, however, these methods mainly suffer from a subjective selection of model parameters. The objective of this study is to introduce a calibration procedure that results in a more accurate assessment of groundwater vulnerability. The improvement of the assessment is formulated as a parameter optimization problem using an objective function that is based on the correlation between actual groundwater contamination and vulnerability index values. The non-linear optimization problem is solved with the generalized-reduced-gradient (GRG) method, which is numerical algorithm based optimization method. To demonstrate the applicability of the procedure, a vulnerability map for the Tahtali stream basin is calibrated using nitrate concentration data. The calibration procedure is easy to implement and aims the maximization of correlation between observed pollutant concentrations and groundwater vulnerability index values. The influence of each vulnerability parameter in the calculation of the vulnerability index is assessed by performing a single-parameter sensitivity analysis. Results of the sensitivity analysis show that all factors are effective on the final vulnerability index. Calibration of the vulnerability map improves the correlation between index values and measured nitrate concentrations by 19%. The regression coefficient increases from 0.280 to 0.485. It is evident that the spatial distribution and the proportions of vulnerability class areas are significantly altered with the calibration process. Although the applicability of the calibration method is demonstrated on the DRASTIC model, the applicability of the approach is not specific to a certain model and can also be easily applied to other overlay-and-index methods.

Calibration methods influence quantitative material decomposition in photon-counting spectral CT

NASA Astrophysics Data System (ADS)

Curtis, Tyler E.; Roeder, Ryan K.

2017-03-01

Photon-counting detectors and nanoparticle contrast agents can potentially enable molecular imaging and material decomposition in computed tomography (CT). Material decomposition has been investigated using both simulated and acquired data sets. However, the effect of calibration methods on material decomposition has not been systematically investigated. Therefore, the objective of this study was to investigate the influence of the range and number of contrast agent concentrations within a modular calibration phantom on quantitative material decomposition. A commerciallyavailable photon-counting spectral micro-CT (MARS Bioimaging) was used to acquire images with five energy bins selected to normalize photon counts and leverage the contrast agent k-edge. Material basis matrix values were determined using multiple linear regression models and material decomposition was performed using a maximum a posteriori estimator. The accuracy of quantitative material decomposition was evaluated by the root mean squared error (RMSE), specificity, sensitivity, and area under the curve (AUC). An increased maximum concentration (range) in the calibration significantly improved RMSE, specificity and AUC. The effects of an increased number of concentrations in the calibration were not statistically significant for the conditions in this study. The overall results demonstrated that the accuracy of quantitative material decomposition in spectral CT is significantly influenced by calibration methods, which must therefore be carefully considered for the intended diagnostic imaging application.

Effects of serum creatinine calibration on estimated renal function in african americans: the Jackson heart study.

PubMed

Wang, Wei; Young, Bessie A; Fülöp, Tibor; de Boer, Ian H; Boulware, L Ebony; Katz, Ronit; Correa, Adolfo; Griswold, Michael E

2015-05-01

The calibration to isotope dilution mass spectrometry-traceable creatinine is essential for valid use of the new Chronic Kidney Disease Epidemiology Collaboration equation to estimate the glomerular filtration rate. For 5,210 participants in the Jackson Heart Study (JHS), serum creatinine was measured with a multipoint enzymatic spectrophotometric assay at the baseline visit (2000-2004) and remeasured using the Roche enzymatic method, traceable to isotope dilution mass spectrometry in a subset of 206 subjects. The 200 eligible samples (6 were excluded, 1 for failure of the remeasurement and 5 for outliers) were divided into 3 disjoint sets-training, validation and test-to select a calibration model, estimate true errors and assess performance of the final calibration equation. The calibration equation was applied to serum creatinine measurements of 5,210 participants to estimate glomerular filtration rate and the prevalence of chronic kidney disease (CKD). The selected Deming regression model provided a slope of 0.968 (95% confidence interval [CI], 0.904-1.053) and intercept of -0.0248 (95% CI, -0.0862 to 0.0366) with R value of 0.9527. Calibrated serum creatinine showed high agreement with actual measurements when applying to the unused test set (concordance correlation coefficient 0.934, 95% CI, 0.894-0.960). The baseline prevalence of CKD in the JHS (2000-2004) was 6.30% using calibrated values compared with 8.29% using noncalibrated serum creatinine with the Chronic Kidney Disease Epidemiology Collaboration equation (P < 0.001). A Deming regression model was chosen to optimally calibrate baseline serum creatinine measurements in the JHS, and the calibrated values provide a lower CKD prevalence estimate.

Influence of Primary Gage Sensitivities on the Convergence of Balance Load Iterations

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert Manfred

2012-01-01

The connection between the convergence of wind tunnel balance load iterations and the existence of the primary gage sensitivities of a balance is discussed. First, basic elements of two load iteration equations that the iterative method uses in combination with results of a calibration data analysis for the prediction of balance loads are reviewed. Then, the connection between the primary gage sensitivities, the load format, the gage output format, and the convergence characteristics of the load iteration equation choices is investigated. A new criterion is also introduced that may be used to objectively determine if the primary gage sensitivity of a balance gage exists. Then, it is shown that both load iteration equations will converge as long as a suitable regression model is used for the analysis of the balance calibration data, the combined influence of non linear terms of the regression model is very small, and the primary gage sensitivities of all balance gages exist. The last requirement is fulfilled, e.g., if force balance calibration data is analyzed in force balance format. Finally, it is demonstrated that only one of the two load iteration equation choices, i.e., the iteration equation used by the primary load iteration method, converges if one or more primary gage sensitivities are missing. This situation may occur, e.g., if force balance calibration data is analyzed in direct read format using the original gage outputs. Data from the calibration of a six component force balance is used to illustrate the connection between the convergence of the load iteration equation choices and the existence of the primary gage sensitivities.

Stepwise Regression Analysis of MDOE Balance Calibration Data Acquired at DNW

NASA Technical Reports Server (NTRS)

DeLoach, RIchard; Philipsen, Iwan

2007-01-01

This paper reports a comparison of two experiment design methods applied in the calibration of a strain-gage balance. One features a 734-point test matrix in which loads are varied systematically according to a method commonly applied in aerospace research and known in the literature of experiment design as One Factor At a Time (OFAT) testing. Two variations of an alternative experiment design were also executed on the same balance, each with different features of an MDOE experiment design. The Modern Design of Experiments (MDOE) is an integrated process of experiment design, execution, and analysis applied at NASA's Langley Research Center to achieve significant reductions in cycle time, direct operating cost, and experimental uncertainty in aerospace research generally and in balance calibration experiments specifically. Personnel in the Instrumentation and Controls Department of the German Dutch Wind Tunnels (DNW) have applied MDOE methods to evaluate them in the calibration of a balance using an automated calibration machine. The data have been sent to Langley Research Center for analysis and comparison. This paper reports key findings from this analysis. The chief result is that a 100-point calibration exploiting MDOE principles delivered quality comparable to a 700+ point OFAT calibration with significantly reduced cycle time and attendant savings in direct and indirect costs. While the DNW test matrices implemented key MDOE principles and produced excellent results, additional MDOE concepts implemented in balance calibrations at Langley Research Center are also identified and described.

Nondestructive evaluation of soluble solid content in strawberry by near infrared spectroscopy

NASA Astrophysics Data System (ADS)

Guo, Zhiming; Huang, Wenqian; Chen, Liping; Wang, Xiu; Peng, Yankun

This paper indicates the feasibility to use near infrared (NIR) spectroscopy combined with synergy interval partial least squares (siPLS) algorithms as a rapid nondestructive method to estimate the soluble solid content (SSC) in strawberry. Spectral preprocessing methods were optimized selected by cross-validation in the model calibration. Partial least squares (PLS) algorithm was conducted on the calibration of regression model. The performance of the final model was back-evaluated according to root mean square error of calibration (RMSEC) and correlation coefficient (R2 c) in calibration set, and tested by mean square error of prediction (RMSEP) and correlation coefficient (R2 p) in prediction set. The optimal siPLS model was obtained with after first derivation spectra preprocessing. The measurement results of best model were achieved as follow: RMSEC = 0.2259, R2 c = 0.9590 in the calibration set; and RMSEP = 0.2892, R2 p = 0.9390 in the prediction set. This work demonstrated that NIR spectroscopy and siPLS with efficient spectral preprocessing is a useful tool for nondestructively evaluation SSC in strawberry.

Parameter estimation procedure for complex non-linear systems: calibration of ASM No. 1 for N-removal in a full-scale oxidation ditch.

PubMed

Abusam, A; Keesman, K J; van Straten, G; Spanjers, H; Meinema, K

2001-01-01

When applied to large simulation models, the process of parameter estimation is also called calibration. Calibration of complex non-linear systems, such as activated sludge plants, is often not an easy task. On the one hand, manual calibration of such complex systems is usually time-consuming, and its results are often not reproducible. On the other hand, conventional automatic calibration methods are not always straightforward and often hampered by local minima problems. In this paper a new straightforward and automatic procedure, which is based on the response surface method (RSM) for selecting the best identifiable parameters, is proposed. In RSM, the process response (output) is related to the levels of the input variables in terms of a first- or second-order regression model. Usually, RSM is used to relate measured process output quantities to process conditions. However, in this paper RSM is used for selecting the dominant parameters, by evaluating parameters sensitivity in a predefined region. Good results obtained in calibration of ASM No. 1 for N-removal in a full-scale oxidation ditch proved that the proposed procedure is successful and reliable.

Food adulteration analysis without laboratory prepared or determined reference food adulterant values.

PubMed

Kalivas, John H; Georgiou, Constantinos A; Moira, Marianna; Tsafaras, Ilias; Petrakis, Eleftherios A; Mousdis, George A

2014-04-01

Quantitative analysis of food adulterants is an important health and economic issue that needs to be fast and simple. Spectroscopy has significantly reduced analysis time. However, still needed are preparations of analyte calibration samples matrix matched to prediction samples which can be laborious and costly. Reported in this paper is the application of a newly developed pure component Tikhonov regularization (PCTR) process that does not require laboratory prepared or reference analysis methods, and hence, is a greener calibration method. The PCTR method requires an analyte pure component spectrum and non-analyte spectra. As a food analysis example, synchronous fluorescence spectra of extra virgin olive oil samples adulterated with sunflower oil is used. Results are shown to be better than those obtained using ridge regression with reference calibration samples. The flexibility of PCTR allows including reference samples and is generic for use with other instrumental methods and food products. Copyright © 2013 Elsevier Ltd. All rights reserved.

Covariate Measurement Error Correction Methods in Mediation Analysis with Failure Time Data

PubMed Central

Zhao, Shanshan

2014-01-01

Summary Mediation analysis is important for understanding the mechanisms whereby one variable causes changes in another. Measurement error could obscure the ability of the potential mediator to explain such changes. This paper focuses on developing correction methods for measurement error in the mediator with failure time outcomes. We consider a broad definition of measurement error, including technical error and error associated with temporal variation. The underlying model with the ‘true’ mediator is assumed to be of the Cox proportional hazards model form. The induced hazard ratio for the observed mediator no longer has a simple form independent of the baseline hazard function, due to the conditioning event. We propose a mean-variance regression calibration approach and a follow-up time regression calibration approach, to approximate the partial likelihood for the induced hazard function. Both methods demonstrate value in assessing mediation effects in simulation studies. These methods are generalized to multiple biomarkers and to both case-cohort and nested case-control sampling design. We apply these correction methods to the Women's Health Initiative hormone therapy trials to understand the mediation effect of several serum sex hormone measures on the relationship between postmenopausal hormone therapy and breast cancer risk. PMID:25139469

Covariate measurement error correction methods in mediation analysis with failure time data.

PubMed

Zhao, Shanshan; Prentice, Ross L

2014-12-01

Mediation analysis is important for understanding the mechanisms whereby one variable causes changes in another. Measurement error could obscure the ability of the potential mediator to explain such changes. This article focuses on developing correction methods for measurement error in the mediator with failure time outcomes. We consider a broad definition of measurement error, including technical error, and error associated with temporal variation. The underlying model with the "true" mediator is assumed to be of the Cox proportional hazards model form. The induced hazard ratio for the observed mediator no longer has a simple form independent of the baseline hazard function, due to the conditioning event. We propose a mean-variance regression calibration approach and a follow-up time regression calibration approach, to approximate the partial likelihood for the induced hazard function. Both methods demonstrate value in assessing mediation effects in simulation studies. These methods are generalized to multiple biomarkers and to both case-cohort and nested case-control sampling designs. We apply these correction methods to the Women's Health Initiative hormone therapy trials to understand the mediation effect of several serum sex hormone measures on the relationship between postmenopausal hormone therapy and breast cancer risk. © 2014, The International Biometric Society.

[Gaussian process regression and its application in near-infrared spectroscopy analysis].

PubMed

Feng, Ai-Ming; Fang, Li-Min; Lin, Min

2011-06-01

Gaussian process (GP) is applied in the present paper as a chemometric method to explore the complicated relationship between the near infrared (NIR) spectra and ingredients. After the outliers were detected by Monte Carlo cross validation (MCCV) method and removed from dataset, different preprocessing methods, such as multiplicative scatter correction (MSC), smoothing and derivate, were tried for the best performance of the models. Furthermore, uninformative variable elimination (UVE) was introduced as a variable selection technique and the characteristic wavelengths obtained were further employed as input for modeling. A public dataset with 80 NIR spectra of corn was introduced as an example for evaluating the new algorithm. The optimal models for oil, starch and protein were obtained by the GP regression method. The performance of the final models were evaluated according to the root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV), root mean square error of prediction (RMSEP) and correlation coefficient (r). The models give good calibration ability with r values above 0.99 and the prediction ability is also satisfactory with r values higher than 0.96. The overall results demonstrate that GP algorithm is an effective chemometric method and is promising for the NIR analysis.

Multiple calibrator measurements improve accuracy and stability estimates of automated assays.

PubMed

Akbas, Neval; Budd, Jeffrey R; Klee, George G

2016-01-01

The effects of combining multiple calibrations on assay accuracy (bias) and measurement of calibration stability were investigated for total triiodothyronine (TT3), vitamin B12 and luteinizing hormone (LH) using Beckman Coulter's Access 2 analyzer. Three calibration procedures (CC1, CC2 and CC3) combined 12, 34 and 56 calibrator measurements over 1, 2, and 3 days. Bias was calculated between target values and average measured value over 3 consecutive days after calibration. Using regression analysis of calibrator measurements versus measurement date, calibration stability was determined as the maximum number of days before a calibrator measurement exceeded 5% tolerance limits. Competitive assays (TT3, vitamin B12) had positive time regression slopes, while sandwich assay (LH) had a negative slope. Bias values for TT3 were -2.49%, 1.49%, and -0.50% using CC1, CC2 and CC3 respectively, with calibrator stability of 32, 20, and 30 days. Bias values for vitamin B12 were 2.44%, 0.91%, and -0.50%, with calibrator stability of 4, 9, and 12 days. Bias values for LH were 2.26%, 1.44% and -0.29% with calibrator stability of >43, 39 and 36 days. Measured stability was more consistent across calibration procedures using percent change rather than difference from target: 26 days for TT3, 12 days for B12 and 31 days for LH. Averaging over multiple calibrations produced smaller bias, consistent with improved accuracy. Time regression slopes in percent change were unaffected by number of calibration measurements but calibrator stability measured from the target value was highly affected by the calibrator value at time zero.

Rivaroxaban Levels in Patients' Plasmas are Comparable by Using Two Different Anti Xa Assay/Coagulometer Systems Calibrated with Two Different Calibrators.

PubMed

Martinuzzo, Marta E; Duboscq, Cristina; Lopez, Marina S; Barrera, Luis H; Vinuales, Estela S; Ceresetto, Jose; Forastiero, Ricardo R; Oyhamburu, Jose

2018-06-01

Rivaroxaban oral anticoagulant does not need laboratory monitoring, but in some situations plasma level measurement is useful. The objective of this paper was to verify analytical performance and compare two rivaroxaban calibrated anti Xa assays/coagulometer systems with specific or other branch calibrators. In 59 samples drawn at trough or peak from patients taking rivaroxaban, plasma levels were measured by HemosIL Liquid anti Xa in ACLTOP 300/500, and STA liquid Anti Xa in TCoag Destiny Plus. HemosIL and STA rivaroxaban calibrators and controls were used. CLSI guideline procedures EP15A3 for precision and trueness, EP6 for linearity, and EP9 for methods comparison were used. Coefficient of variation within run and total precision (CVR and CVWL respectively) of plasmatic rivaroxaban were < 4.2 and < 4.85% and BIAS < 7.4 and < 6.5%, for HemosIL-ACL TOP and STA-Destiny systems, respectively. Linearity verification 8 - 525 ng/mL a Deming regression for methods comparison presented R 0.963, 0.968 and 0.982, with a mean CV 13.3% when using different systems and calibrations. The analytical performance of plasma rivaroxaban was acceptable in both systems, and results from reagent/coagulometer systems are comparable even when calibrating with different branch material.

Online shaft encoder geometry compensation for arbitrary shaft speed profiles using Bayesian regression

NASA Astrophysics Data System (ADS)

Diamond, D. H.; Heyns, P. S.; Oberholster, A. J.

2016-12-01

The measurement of instantaneous angular speed is being increasingly investigated for its use in a wide range of condition monitoring and prognostic applications. Central to many measurement techniques are incremental shaft encoders recording the arrival times of shaft angular increments. The conventional approach to processing these signals assumes that the angular increments are equidistant. This assumption is generally incorrect when working with toothed wheels and especially zebra tape encoders and has been shown to introduce errors in the estimated shaft speed. There are some proposed methods in the literature that aim to compensate for this geometric irregularity. Some of the methods require the shaft speed to be perfectly constant for calibration, something rarely achieved in practice. Other methods assume the shaft speed to be nearly constant with minor deviations. Therefore existing methods cannot calibrate the entire shaft encoder geometry for arbitrary shaft speeds. The present article presents a method to calculate the shaft encoder geometry for arbitrary shaft speed profiles. The method uses Bayesian linear regression to calculate the encoder increment distances. The method is derived and then tested against simulated and laboratory experiments. The results indicate that the proposed method is capable of accurately determining the shaft encoder geometry for any shaft speed profile.

Application of principal component regression and artificial neural network in FT-NIR soluble solids content determination of intact pear fruit

NASA Astrophysics Data System (ADS)

Ying, Yibin; Liu, Yande; Fu, Xiaping; Lu, Huishan

2005-11-01

The artificial neural networks (ANNs) have been used successfully in applications such as pattern recognition, image processing, automation and control. However, majority of today's applications of ANNs is back-propagate feed-forward ANN (BP-ANN). In this paper, back-propagation artificial neural networks (BP-ANN) were applied for modeling soluble solid content (SSC) of intact pear from their Fourier transform near infrared (FT-NIR) spectra. One hundred and sixty-four pear samples were used to build the calibration models and evaluate the models predictive ability. The results are compared to the classical calibration approaches, i.e. principal component regression (PCR), partial least squares (PLS) and non-linear PLS (NPLS). The effects of the optimal methods of training parameters on the prediction model were also investigated. BP-ANN combine with principle component regression (PCR) resulted always better than the classical PCR, PLS and Weight-PLS methods, from the point of view of the predictive ability. Based on the results, it can be concluded that FT-NIR spectroscopy and BP-ANN models can be properly employed for rapid and nondestructive determination of fruit internal quality.

Quantification of endocrine disruptors and pesticides in water by gas chromatography-tandem mass spectrometry. Method validation using weighted linear regression schemes.

PubMed

Mansilha, C; Melo, A; Rebelo, H; Ferreira, I M P L V O; Pinho, O; Domingues, V; Pinho, C; Gameiro, P

2010-10-22

A multi-residue methodology based on a solid phase extraction followed by gas chromatography-tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC-MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness. Copyright © 2010 Elsevier B.V. All rights reserved.

Use of empirical likelihood to calibrate auxiliary information in partly linear monotone regression models.

PubMed

Chen, Baojiang; Qin, Jing

2014-05-10

In statistical analysis, a regression model is needed if one is interested in finding the relationship between a response variable and covariates. When the response depends on the covariate, then it may also depend on the function of this covariate. If one has no knowledge of this functional form but expect for monotonic increasing or decreasing, then the isotonic regression model is preferable. Estimation of parameters for isotonic regression models is based on the pool-adjacent-violators algorithm (PAVA), where the monotonicity constraints are built in. With missing data, people often employ the augmented estimating method to improve estimation efficiency by incorporating auxiliary information through a working regression model. However, under the framework of the isotonic regression model, the PAVA does not work as the monotonicity constraints are violated. In this paper, we develop an empirical likelihood-based method for isotonic regression model to incorporate the auxiliary information. Because the monotonicity constraints still hold, the PAVA can be used for parameter estimation. Simulation studies demonstrate that the proposed method can yield more efficient estimates, and in some situations, the efficiency improvement is substantial. We apply this method to a dementia study. Copyright © 2013 John Wiley & Sons, Ltd.

Application of Fluorescence Spectrometry With Multivariate Calibration to the Enantiomeric Recognition of Fluoxetine in Pharmaceutical Preparations.

PubMed

Poláček, Roman; Májek, Pavel; Hroboňová, Katarína; Sádecká, Jana

2016-04-01

Fluoxetine is the most prescribed antidepressant chiral drug worldwide. Its enantiomers have a different duration of serotonin inhibition. A novel simple and rapid method for determination of the enantiomeric composition of fluoxetine in pharmaceutical pills is presented. Specifically, emission, excitation, and synchronous fluorescence techniques were employed to obtain the spectral data, which with multivariate calibration methods, namely, principal component regression (PCR) and partial least square (PLS), were investigated. The chiral recognition of fluoxetine enantiomers in the presence of β-cyclodextrin was based on diastereomeric complexes. The results of the multivariate calibration modeling indicated good prediction abilities. The obtained results for tablets were compared with those from chiral HPLC and no significant differences are shown by Fisher's (F) test and Student's t-test. The smallest residuals between reference or nominal values and predicted values were achieved by multivariate calibration of synchronous fluorescence spectral data. This conclusion is supported by calculated values of the figure of merit.

Improved CRDS δ13C Stability Through New Calibration Application For CO2 And CH4

NASA Astrophysics Data System (ADS)

Rella, Chris; Arata, Caleb; Saad, Nabil; Leggett, Graham; Miles, Natasha; Richardson, Scott; Davis, Ken

2015-04-01

Stable carbon isotope ratio measurements of CO2 and CH4 provide valuable insight into global and regional sources and sinks of the two most important greenhouse gases. Methodologies based on Cavity Ring-Down Spectroscopy (CRDS) have been developed and are capable of delivering δ13C measurements with a precision better than 0.12 permil for CO2 and 0.4 permil for CH4 (1 hour window, 5 minute average). Here we present a method to further improve this measurement stability. We have developed a two-point calibration method which corrects for δ13C drift due to a dependence on carbon species concentration. This method calibrates for both carbon species concentration as well as δ13C. In addition, we further demonstrate that this added stability is especially valuable when using carbon isotope data in linear regression models such as Keeling plots, where even small amounts of error can be magnified to give inconclusive results. Furthermore, we show how this method is used to validate multiple instruments simultaneously and can be used to create the standard samples needed for field calibrations.

A Robust Bayesian Random Effects Model for Nonlinear Calibration Problems

PubMed Central

Fong, Y.; Wakefield, J.; De Rosa, S.; Frahm, N.

2013-01-01

Summary In the context of a bioassay or an immunoassay, calibration means fitting a curve, usually nonlinear, through the observations collected on a set of samples containing known concentrations of a target substance, and then using the fitted curve and observations collected on samples of interest to predict the concentrations of the target substance in these samples. Recent technological advances have greatly improved our ability to quantify minute amounts of substance from a tiny volume of biological sample. This has in turn led to a need to improve statistical methods for calibration. In this paper, we focus on developing calibration methods robust to dependent outliers. We introduce a novel normal mixture model with dependent error terms to model the experimental noise. In addition, we propose a re-parameterization of the five parameter logistic nonlinear regression model that allows us to better incorporate prior information. We examine the performance of our methods with simulation studies and show that they lead to a substantial increase in performance measured in terms of mean squared error of estimation and a measure of the average prediction accuracy. A real data example from the HIV Vaccine Trials Network Laboratory is used to illustrate the methods. PMID:22551415

Use of Two-Part Regression Calibration Model to Correct for Measurement Error in Episodically Consumed Foods in a Single-Replicate Study Design: EPIC Case Study

PubMed Central

Agogo, George O.; van der Voet, Hilko; Veer, Pieter van’t; Ferrari, Pietro; Leenders, Max; Muller, David C.; Sánchez-Cantalejo, Emilio; Bamia, Christina; Braaten, Tonje; Knüppel, Sven; Johansson, Ingegerd; van Eeuwijk, Fred A.; Boshuizen, Hendriek

2014-01-01

In epidemiologic studies, measurement error in dietary variables often attenuates association between dietary intake and disease occurrence. To adjust for the attenuation caused by error in dietary intake, regression calibration is commonly used. To apply regression calibration, unbiased reference measurements are required. Short-term reference measurements for foods that are not consumed daily contain excess zeroes that pose challenges in the calibration model. We adapted two-part regression calibration model, initially developed for multiple replicates of reference measurements per individual to a single-replicate setting. We showed how to handle excess zero reference measurements by two-step modeling approach, how to explore heteroscedasticity in the consumed amount with variance-mean graph, how to explore nonlinearity with the generalized additive modeling (GAM) and the empirical logit approaches, and how to select covariates in the calibration model. The performance of two-part calibration model was compared with the one-part counterpart. We used vegetable intake and mortality data from European Prospective Investigation on Cancer and Nutrition (EPIC) study. In the EPIC, reference measurements were taken with 24-hour recalls. For each of the three vegetable subgroups assessed separately, correcting for error with an appropriately specified two-part calibration model resulted in about three fold increase in the strength of association with all-cause mortality, as measured by the log hazard ratio. Further found is that the standard way of including covariates in the calibration model can lead to over fitting the two-part calibration model. Moreover, the extent of adjusting for error is influenced by the number and forms of covariates in the calibration model. For episodically consumed foods, we advise researchers to pay special attention to response distribution, nonlinearity, and covariate inclusion in specifying the calibration model. PMID:25402487

Determination of polyphenolic compounds of red wines by UV-VIS-NIR spectroscopy and chemometrics tools.

PubMed

Martelo-Vidal, M J; Vázquez, M

2014-09-01

Spectral analysis is a quick and non-destructive method to analyse wine. In this work, trans-resveratrol, oenin, malvin, catechin, epicatechin, quercetin and syringic acid were determined in commercial red wines from DO Rías Baixas and DO Ribeira Sacra (Spain) by UV-VIS-NIR spectroscopy. Calibration models were developed using principal component regression (PCR) or partial least squares (PLS) regression. HPLC was used as reference method. The results showed that reliable PLS models were obtained to quantify all polyphenols for Rías Baixas wines. For Ribeira Sacra, feasible models were obtained to determine quercetin, epicatechin, oenin and syringic acid. PCR calibration models showed worst reliable of prediction than PLS models. For red wines from mencía grapes, feasible models were obtained for catechin and oenin, regardless the geographical origin. The results obtained demonstrate that UV-VIS-NIR spectroscopy can be used to determine individual polyphenolic compounds in red wines. Copyright © 2014 Elsevier Ltd. All rights reserved.

Comparative study between derivative spectrophotometry and multivariate calibration as analytical tools applied for the simultaneous quantitation of Amlodipine, Valsartan and Hydrochlorothiazide

NASA Astrophysics Data System (ADS)

Darwish, Hany W.; Hassan, Said A.; Salem, Maissa Y.; El-Zeany, Badr A.

2013-09-01

Four simple, accurate and specific methods were developed and validated for the simultaneous estimation of Amlodipine (AML), Valsartan (VAL) and Hydrochlorothiazide (HCT) in commercial tablets. The derivative spectrophotometric methods include Derivative Ratio Zero Crossing (DRZC) and Double Divisor Ratio Spectra-Derivative Spectrophotometry (DDRS-DS) methods, while the multivariate calibrations used are Principal Component Regression (PCR) and Partial Least Squares (PLSs). The proposed methods were applied successfully in the determination of the drugs in laboratory-prepared mixtures and in commercial pharmaceutical preparations. The validity of the proposed methods was assessed using the standard addition technique. The linearity of the proposed methods is investigated in the range of 2-32, 4-44 and 2-20 μg/mL for AML, VAL and HCT, respectively.

Spatio-thermal depth correction of RGB-D sensors based on Gaussian processes in real-time

NASA Astrophysics Data System (ADS)

Heindl, Christoph; Pönitz, Thomas; Stübl, Gernot; Pichler, Andreas; Scharinger, Josef

2018-04-01

Commodity RGB-D sensors capture color images along with dense pixel-wise depth information in real-time. Typical RGB-D sensors are provided with a factory calibration and exhibit erratic depth readings due to coarse calibration values, ageing and thermal influence effects. This limits their applicability in computer vision and robotics. We propose a novel method to accurately calibrate depth considering spatial and thermal influences jointly. Our work is based on Gaussian Process Regression in a four dimensional Cartesian and thermal domain. We propose to leverage modern GPUs for dense depth map correction in real-time. For reproducibility we make our dataset and source code publicly available.

Radiometric Cross-Calibration of the HJ-1B IRS in the Thermal Infrared Spectral Band

NASA Astrophysics Data System (ADS)

Sun, K.

2012-12-01

The natural calamities occur continually, environment pollution and destruction in a severe position on the earth presently, which restricts societal and economic development. The satellite remote sensing technology has an important effect on improving surveillance ability of environment pollution and natural calamities. The radiometric calibration is precondition of quantitative remote sensing; which accuracy decides quality of the retrieval parameters. Since the China Environment Satellite (HJ-1A/B) has been launched successfully on September 6th, 2008, it has made an important role in the economic development of China. The satellite has four infrared bands; and one of it is thermal infrared. With application fields of quantitative remote sensing in china, finding appropriate calibration method becomes more and more important. Many kinds of independent methods can be used to do the absolute radiometric calibration. In this paper, according to the characteristic of thermal infrared channel of HJ-1B thermal infrared multi-spectral camera, the thermal infrared spectral band of HJ-1B IRS was calibrated using cross-calibration methods based on MODIS data. Firstly, the corresponding bands of the two sensors were obtained. Secondly, the MONDTRAN was run to analyze the influences of different spectral response, satellite view zenith angle, atmosphere condition and temperature on the match factor. In the end, their band match factor was calculated in different temperature, considering the dissimilar band response of the match bands. Seven images of Lake Qinghai in different time were chosen as the calibration data. On the basis of radiance of MODIS and match factor, the IRS radiance was calculated. And then the calibration coefficients were obtained by linearly regressing the radiance and the DN value. We compared the result of this cross-calibration with that of the onboard blackbody calibration, which consistency was good.The maximum difference of brightness temperature between HJ-1B IRS band4 and MODIS band 31 is less than 1 K. Therefore cross-calibration is a rapid and financial way to get calibration coefficients of HJ-1B, however, the matched factor calculation method need further research in order to further improve cross-calibration precision.

Quantitative laser-induced breakdown spectroscopy data using peak area step-wise regression analysis: an alternative method for interpretation of Mars science laboratory results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clegg, Samuel M; Barefield, James E; Wiens, Roger C

2008-01-01

The ChemCam instrument on the Mars Science Laboratory (MSL) will include a laser-induced breakdown spectrometer (LIBS) to quantify major and minor elemental compositions. The traditional analytical chemistry approach to calibration curves for these data regresses a single diagnostic peak area against concentration for each element. This approach contrasts with a new multivariate method in which elemental concentrations are predicted by step-wise multiple regression analysis based on areas of a specific set of diagnostic peaks for each element. The method is tested on LIBS data from igneous and metamorphosed rocks. Between 4 and 13 partial regression coefficients are needed to describemore » each elemental abundance accurately (i.e., with a regression line of R{sup 2} > 0.9995 for the relationship between predicted and measured elemental concentration) for all major and minor elements studied. Validation plots suggest that the method is limited at present by the small data set, and will work best for prediction of concentration when a wide variety of compositions and rock types has been analyzed.« less

Quantitative methods for compensation of matrix effects and self-absorption in Laser Induced Breakdown Spectroscopy signals of solids

NASA Astrophysics Data System (ADS)

Takahashi, Tomoko; Thornton, Blair

2017-12-01

This paper reviews methods to compensate for matrix effects and self-absorption during quantitative analysis of compositions of solids measured using Laser Induced Breakdown Spectroscopy (LIBS) and their applications to in-situ analysis. Methods to reduce matrix and self-absorption effects on calibration curves are first introduced. The conditions where calibration curves are applicable to quantification of compositions of solid samples and their limitations are discussed. While calibration-free LIBS (CF-LIBS), which corrects matrix effects theoretically based on the Boltzmann distribution law and Saha equation, has been applied in a number of studies, requirements need to be satisfied for the calculation of chemical compositions to be valid. Also, peaks of all elements contained in the target need to be detected, which is a bottleneck for in-situ analysis of unknown materials. Multivariate analysis techniques are gaining momentum in LIBS analysis. Among the available techniques, principal component regression (PCR) analysis and partial least squares (PLS) regression analysis, which can extract related information to compositions from all spectral data, are widely established methods and have been applied to various fields including in-situ applications in air and for planetary explorations. Artificial neural networks (ANNs), where non-linear effects can be modelled, have also been investigated as a quantitative method and their applications are introduced. The ability to make quantitative estimates based on LIBS signals is seen as a key element for the technique to gain wider acceptance as an analytical method, especially in in-situ applications. In order to accelerate this process, it is recommended that the accuracy should be described using common figures of merit which express the overall normalised accuracy, such as the normalised root mean square errors (NRMSEs), when comparing the accuracy obtained from different setups and analytical methods.

Noncontact analysis of the fiber weight per unit area in prepreg by near-infrared spectroscopy.

PubMed

Jiang, B; Huang, Y D

2008-05-26

The fiber weight per unit area in prepreg is an important factor to ensure the quality of the composite products. Near-infrared spectroscopy (NIRS) technology together with a noncontact reflectance sources has been applied for quality analysis of the fiber weight per unit area. The range of the unit area fiber weight was 13.39-14.14mgcm(-2). The regression method was employed by partial least squares (PLS) and principal components regression (PCR). The calibration model was developed by 55 samples to determine the fiber weight per unit area in prepreg. The determination coefficient (R(2)), root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) were 0.82, 0.092, 0.099, respectively. The predicted values of the fiber weight per unit area in prepreg measured by NIRS technology were comparable to the values obtained by the reference method. For this technology, the noncontact reflectance sources focused directly on the sample with neither previous treatment nor manipulation. The results of the paired t-test revealed that there was no significant difference between the NIR method and the reference method. Besides, the prepreg could be analyzed one time within 20s without sample destruction.

Radiometric and spectral calibrations of the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) using principle component analysis

NASA Astrophysics Data System (ADS)

Tian, Jialin; Smith, William L.; Gazarik, Michael J.

2008-10-01

The ultimate remote sensing benefits of the high resolution Infrared radiance spectrometers will be realized with their geostationary satellite implementation in the form of imaging spectrometers. This will enable dynamic features of the atmosphere's thermodynamic fields and pollutant and greenhouse gas constituents to be observed for revolutionary improvements in weather forecasts and more accurate air quality and climate predictions. As an important step toward realizing this application objective, the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) Engineering Demonstration Unit (EDU) was successfully developed under the NASA New Millennium Program, 2000-2006. The GIFTS-EDU instrument employs three focal plane arrays (FPAs), which gather measurements across the long-wave IR (LWIR), short/mid-wave IR (SMWIR), and visible spectral bands. The raw GIFTS interferogram measurements are radiometrically and spectrally calibrated to produce radiance spectra, which are further processed to obtain atmospheric profiles via retrieval algorithms. The radiometric calibration is achieved using internal blackbody calibration references at ambient (260 K) and hot (286 K) temperatures. The absolute radiometric performance of the instrument is affected by several factors including the FPA off-axis effect, detector/readout electronics induced nonlinearity distortions, and fore-optics offsets. The GIFTS-EDU, being the very first imaging spectrometer to use ultra-high speed electronics to readout its large area format focal plane array detectors, operating at wavelengths as large as 15 microns, possessed non-linearity's not easily removable in the initial calibration process. In this paper, we introduce a refined calibration technique that utilizes Principle Component (PC) analysis to compensate for instrument distortions and artifacts remaining after the initial radiometric calibration process, thus, further enhance the absolute calibration accuracy. This method is applied to data collected during an atmospheric measurement experiment with the GIFTS, together with simultaneous observations by the accurately calibrated AERI (Atmospheric Emitted Radiance Interferometer), both simultaneously zenith viewing the sky through the same external scene mirror at ten-minute intervals throughout a cloudless day at Logan Utah on September 13, 2006. The PC vectors of the calibrated radiance spectra are defined from the AERI observations and regression matrices relating the initial GIFTS radiance PC scores to the AERI radiance PC scores are calculated using the least squares inverse method. A new set of accurately calibrated GIFTS radiances are produced using the first four PC scores in the regression model. Temperature and moisture profiles retrieved from the PC-calibrated GIFTS radiances are verified against radiosonde measurements collected throughout the GIFTS sky measurement period.

Detection of Bi-Directionality in Strain-Gage Balance Calibration Data

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert

2012-01-01

An indicator variable was developed for both visualization and detection of bi-directionality in wind tunnel strain-gage balance calibration data. First, the calculation of the indicator variable is explained in detail. Then, a criterion is discussed that may be used to decide which gage outputs of a balance have bi- directional behavior. The result of this analysis could be used, for example, to justify the selection of certain absolute value or other even function terms in the regression model of gage outputs whenever the Iterative Method is chosen for the balance calibration data analysis. Calibration data of NASA s MK40 Task balance is analyzed to illustrate both the calculation of the indicator variable and the application of the proposed criterion. Finally, bi directionality characteristics of typical multi piece, hybrid, single piece, and semispan balances are determined and discussed.

Alternative Internal Standard Calibration of an Indirect Enzymatic Analytical Method for 2-MCPD Fatty Acid Esters.

PubMed

Koyama, Kazuo; Miyazaki, Kinuko; Abe, Kousuke; Egawa, Yoshitsugu; Fukazawa, Toru; Kitta, Tadashi; Miyashita, Takashi; Nezu, Toru; Nohara, Hidenori; Sano, Takashi; Takahashi, Yukinari; Taniguchi, Hideji; Yada, Hiroshi; Yamazaki, Kumiko; Watanabe, Yomi

2017-06-01

An indirect enzymatic analysis method for the quantification of fatty acid esters of 2-/3-monochloro-1,2-propanediol (2/3-MCPD) and glycidol was developed, using the deuterated internal standard of each free-form component. A statistical method for calibration and quantification of 2-MCPD-d 5 , which is difficult to obtain, is substituted by 3-MCPD-d 5 used for calculation of 3-MCPD. Using data from a previous collaborative study, the current method for the determination of 2-MCPD content using 2-MCPD-d 5 was compared to three alternative new methods using 3-MCPD-d 5 . The regression analysis showed that the alternative methods were unbiased compared to the current method. The relative standard deviation (RSD R ) among the testing laboratories was ≤ 15% and the Horwitz ratio was ≤ 1.0, a satisfactory value.

Reliable probabilities through statistical post-processing of ensemble predictions

NASA Astrophysics Data System (ADS)

Van Schaeybroeck, Bert; Vannitsem, Stéphane

2013-04-01

We develop post-processing or calibration approaches based on linear regression that make ensemble forecasts more reliable. We enforce climatological reliability in the sense that the total variability of the prediction is equal to the variability of the observations. Second, we impose ensemble reliability such that the spread around the ensemble mean of the observation coincides with the one of the ensemble members. In general the attractors of the model and reality are inhomogeneous. Therefore ensemble spread displays a variability not taken into account in standard post-processing methods. We overcome this by weighting the ensemble by a variable error. The approaches are tested in the context of the Lorenz 96 model (Lorenz 1996). The forecasts become more reliable at short lead times as reflected by a flatter rank histogram. Our best method turns out to be superior to well-established methods like EVMOS (Van Schaeybroeck and Vannitsem, 2011) and Nonhomogeneous Gaussian Regression (Gneiting et al., 2005). References [1] Gneiting, T., Raftery, A. E., Westveld, A., Goldman, T., 2005: Calibrated probabilistic forecasting using ensemble model output statistics and minimum CRPS estimation. Mon. Weather Rev. 133, 1098-1118. [2] Lorenz, E. N., 1996: Predictability - a problem partly solved. Proceedings, Seminar on Predictability ECMWF. 1, 1-18. [3] Van Schaeybroeck, B., and S. Vannitsem, 2011: Post-processing through linear regression, Nonlin. Processes Geophys., 18, 147.

Energy Calibration of a Silicon-Strip Detector for Photon-Counting Spectral CT by Direct Usage of the X-ray Tube Spectrum

NASA Astrophysics Data System (ADS)

Liu, Xuejin; Chen, Han; Bornefalk, Hans; Danielsson, Mats; Karlsson, Staffan; Persson, Mats; Xu, Cheng; Huber, Ben

2015-02-01

The variation among energy thresholds in a multibin detector for photon-counting spectral CT can lead to ring artefacts in the reconstructed images. Calibration of the energy thresholds can be used to achieve homogeneous threshold settings or to develop compensation methods to reduce the artefacts. We have developed an energy-calibration method for the different comparator thresholds employed in a photon-counting silicon-strip detector. In our case, this corresponds to specifying the linear relation between the threshold positions in units of mV and the actual deposited photon energies in units of keV. This relation is determined by gain and offset values that differ for different detector channels due to variations in the manufacturing process. Typically, the calibration is accomplished by correlating the peak positions of obtained pulse-height spectra to known photon energies, e.g. with the aid of mono-energetic x rays from synchrotron radiation, radioactive isotopes or fluorescence materials. Instead of mono-energetic x rays, the calibration method presented in this paper makes use of a broad x-ray spectrum provided by commercial x-ray tubes. Gain and offset as the calibration parameters are obtained by a regression analysis that adjusts a simulated spectrum of deposited energies to a measured pulse-height spectrum. Besides the basic photon interactions such as Rayleigh scattering, Compton scattering and photo-electric absorption, the simulation takes into account the effect of pulse pileup, charge sharing and the electronic noise of the detector channels. We verify the method for different detector channels with the aid of a table-top setup, where we find the uncertainty of the keV-value of a calibrated threshold to be between 0.1 and 0.2 keV.

System calibration method for Fourier ptychographic microscopy

NASA Astrophysics Data System (ADS)

Pan, An; Zhang, Yan; Zhao, Tianyu; Wang, Zhaojun; Dan, Dan; Lei, Ming; Yao, Baoli

2017-09-01

Fourier ptychographic microscopy (FPM) is a recently proposed computational imaging technique with both high-resolution and wide field of view. In current FPM imaging platforms, systematic error sources come from aberrations, light-emitting diode (LED) intensity fluctuation, parameter imperfections, and noise, all of which may severely corrupt the reconstruction results with similar artifacts. Therefore, it would be unlikely to distinguish the dominating error from these degraded reconstructions without any preknowledge. In addition, systematic error is generally a mixture of various error sources in the real situation, and it cannot be separated due to their mutual restriction and conversion. To this end, we report a system calibration procedure, termed SC-FPM, to calibrate the mixed systematic errors simultaneously from an overall perspective, based on the simulated annealing algorithm, the LED intensity correction method, the nonlinear regression process, and the adaptive step-size strategy, which involves the evaluation of an error metric at each iteration step, followed by the re-estimation of accurate parameters. The performance achieved both in simulations and experiments demonstrates that the proposed method outperforms other state-of-the-art algorithms. The reported system calibration scheme improves the robustness of FPM, relaxes the experiment conditions, and does not require any preknowledge, which makes the FPM more pragmatic.

Prediction of valid acidity in intact apples with Fourier transform near infrared spectroscopy.

PubMed

Liu, Yan-De; Ying, Yi-Bin; Fu, Xia-Ping

2005-03-01

To develop nondestructive acidity prediction for intact Fuji apples, the potential of Fourier transform near infrared (FT-NIR) method with fiber optics in interactance mode was investigated. Interactance in the 800 nm to 2619 nm region was measured for intact apples, harvested from early to late maturity stages. Spectral data were analyzed by two multivariate calibration techniques including partial least squares (PLS) and principal component regression (PCR) methods. A total of 120 Fuji apples were tested and 80 of them were used to form a calibration data set. The influences of different data preprocessing and spectra treatments were also quantified. Calibration models based on smoothing spectra were slightly worse than that based on derivative spectra, and the best result was obtained when the segment length was 5 nm and the gap size was 10 points. Depending on data preprocessing and PLS method, the best prediction model yielded correlation coefficient of determination (r2) of 0.759, low root mean square error of prediction (RMSEP) of 0.0677, low root mean square error of calibration (RMSEC) of 0.0562. The results indicated the feasibility of FT-NIR spectral analysis for predicting apple valid acidity in a nondestructive way.

Prediction of valid acidity in intact apples with Fourier transform near infrared spectroscopy*

PubMed Central

Liu, Yan-de; Ying, Yi-bin; Fu, Xia-ping

2005-01-01

To develop nondestructive acidity prediction for intact Fuji apples, the potential of Fourier transform near infrared (FT-NIR) method with fiber optics in interactance mode was investigated. Interactance in the 800 nm to 2619 nm region was measured for intact apples, harvested from early to late maturity stages. Spectral data were analyzed by two multivariate calibration techniques including partial least squares (PLS) and principal component regression (PCR) methods. A total of 120 Fuji apples were tested and 80 of them were used to form a calibration data set. The influences of different data preprocessing and spectra treatments were also quantified. Calibration models based on smoothing spectra were slightly worse than that based on derivative spectra, and the best result was obtained when the segment length was 5 nm and the gap size was 10 points. Depending on data preprocessing and PLS method, the best prediction model yielded correlation coefficient of determination (r 2) of 0.759, low root mean square error of prediction (RMSEP) of 0.0677, low root mean square error of calibration (RMSEC) of 0.0562. The results indicated the feasibility of FT-NIR spectral analysis for predicting apple valid acidity in a nondestructive way. PMID:15682498

Standardization of gamma-glutamyltransferase assays by intermethod calibration. Effect on determining common reference limits.

PubMed

Steinmetz, Josiane; Schiele, Françoise; Gueguen, René; Férard, Georges; Henny, Joseph

2007-01-01

The improvement of the consistency of gamma-glutamyltransferase (GGT) activity results among different assays after calibration with a common material was estimated. We evaluated if this harmonization could lead to reference limits common to different routine methods. Seven laboratories measured GGT activity using their own routine analytical system both according to the manufacturer's recommendation and after calibration with a multi-enzyme calibrator [value assigned by the International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) reference procedure]. All samples were re-measured using the IFCC reference procedure. Two groups of subjects were selected in each laboratory: a group of healthy men aged 18-25 years without long-term medication and with alcohol consumption less than 44 g/day and a group of subjects with elevated GGT activity. The day-to-day coefficients of variation were less than 2.9% in each laboratory. The means obtained in the group of healthy subjects without common calibration (range of the means 16-23 U/L) were significantly different from those obtained by the IFCC procedure in five laboratories. After calibration, the means remained significantly different from the IFCC procedure results in only one laboratory. For three calibrated methods, the slope values of linear regression vs. the IFCC procedure were not different from the value 1. The results obtained with these three methods for healthy subjects (n=117) were gathered and reference limits were calculated. These were 11-49 U/L (2.5th-97.5th percentiles). The calibration also improved the consistency of elevated results when compared to the IFCC procedure. The common calibration improved the level of consistency between different routine methods. It permitted to define common reference limits which are quite similar to those proposed by the IFCC. This approach should lead to a real benefit in terms of prevention, screening, diagnosis, therapeutic monitoring and for epidemiological studies.

Comparison of two-concentration with multi-concentration linear regressions: Retrospective data analysis of multiple regulated LC-MS bioanalytical projects.

PubMed

Musuku, Adrien; Tan, Aimin; Awaiye, Kayode; Trabelsi, Fethi

2013-09-01

Linear calibration is usually performed using eight to ten calibration concentration levels in regulated LC-MS bioanalysis because a minimum of six are specified in regulatory guidelines. However, we have previously reported that two-concentration linear calibration is as reliable as or even better than using multiple concentrations. The purpose of this research is to compare two-concentration with multiple-concentration linear calibration through retrospective data analysis of multiple bioanalytical projects that were conducted in an independent regulated bioanalytical laboratory. A total of 12 bioanalytical projects were randomly selected: two validations and two studies for each of the three most commonly used types of sample extraction methods (protein precipitation, liquid-liquid extraction, solid-phase extraction). When the existing data were retrospectively linearly regressed using only the lowest and the highest concentration levels, no extra batch failure/QC rejection was observed and the differences in accuracy and precision between the original multi-concentration regression and the new two-concentration linear regression are negligible. Specifically, the differences in overall mean apparent bias (square root of mean individual bias squares) are within the ranges of -0.3% to 0.7% and 0.1-0.7% for the validations and studies, respectively. The differences in mean QC concentrations are within the ranges of -0.6% to 1.8% and -0.8% to 2.5% for the validations and studies, respectively. The differences in %CV are within the ranges of -0.7% to 0.9% and -0.3% to 0.6% for the validations and studies, respectively. The average differences in study sample concentrations are within the range of -0.8% to 2.3%. With two-concentration linear regression, an average of 13% of time and cost could have been saved for each batch together with 53% of saving in the lead-in for each project (the preparation of working standard solutions, spiking, and aliquoting). Furthermore, examples are given as how to evaluate the linearity over the entire concentration range when only two concentration levels are used for linear regression. To conclude, two-concentration linear regression is accurate and robust enough for routine use in regulated LC-MS bioanalysis and it significantly saves time and cost as well. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparative study between derivative spectrophotometry and multivariate calibration as analytical tools applied for the simultaneous quantitation of Amlodipine, Valsartan and Hydrochlorothiazide.

PubMed

Darwish, Hany W; Hassan, Said A; Salem, Maissa Y; El-Zeany, Badr A

2013-09-01

Four simple, accurate and specific methods were developed and validated for the simultaneous estimation of Amlodipine (AML), Valsartan (VAL) and Hydrochlorothiazide (HCT) in commercial tablets. The derivative spectrophotometric methods include Derivative Ratio Zero Crossing (DRZC) and Double Divisor Ratio Spectra-Derivative Spectrophotometry (DDRS-DS) methods, while the multivariate calibrations used are Principal Component Regression (PCR) and Partial Least Squares (PLSs). The proposed methods were applied successfully in the determination of the drugs in laboratory-prepared mixtures and in commercial pharmaceutical preparations. The validity of the proposed methods was assessed using the standard addition technique. The linearity of the proposed methods is investigated in the range of 2-32, 4-44 and 2-20 μg/mL for AML, VAL and HCT, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

A Novel Method for Constructing a WIFI Positioning System with Efficient Manpower

PubMed Central

Du, Yuanfeng; Yang, Dongkai; Xiu, Chundi

2015-01-01

With the rapid development of WIFI technology, WIFI-based indoor positioning technology has been widely studied for location-based services. To solve the problems related to the signal strength database adopted in the widely used fingerprint positioning technology, we first introduce a new system framework in this paper, which includes a modified AP firmware and some cheap self-made WIFI sensor anchors. The periodically scanned reports regarding the neighboring APs and sensor anchors are sent to the positioning server and serve as the calibration points. Besides the calculation of correlations between the target points and the neighboring calibration points, we take full advantage of the important but easily overlooked feature that the signal attenuation model varies in different regions in the regression algorithm to get more accurate results. Thus, a novel method called RSSI Geography Weighted Regression (RGWR) is proposed to solve the fingerprint database construction problem. The average error of all the calibration points’ self-localization results will help to make the final decision of whether the database is the latest or has to be updated automatically. The effects of anchors on system performance are further researched to conclude that the anchors should be deployed at the locations that stand for the features of RSSI distributions. The proposed system is convenient for the establishment of practical positioning system and extensive experiments have been performed to validate that the proposed method is robust and manpower efficient. PMID:25868078

A novel method for constructing a WIFI positioning system with efficient manpower.

PubMed

Du, Yuanfeng; Yang, Dongkai; Xiu, Chundi

2015-04-10

With the rapid development of WIFI technology, WIFI-based indoor positioning technology has been widely studied for location-based services. To solve the problems related to the signal strength database adopted in the widely used fingerprint positioning technology, we first introduce a new system framework in this paper, which includes a modified AP firmware and some cheap self-made WIFI sensor anchors. The periodically scanned reports regarding the neighboring APs and sensor anchors are sent to the positioning server and serve as the calibration points. Besides the calculation of correlations between the target points and the neighboring calibration points, we take full advantage of the important but easily overlooked feature that the signal attenuation model varies in different regions in the regression algorithm to get more accurate results. Thus, a novel method called RSSI Geography Weighted Regression (RGWR) is proposed to solve the fingerprint database construction problem. The average error of all the calibration points' self-localization results will help to make the final decision of whether the database is the latest or has to be updated automatically. The effects of anchors on system performance are further researched to conclude that the anchors should be deployed at the locations that stand for the features of RSSI distributions. The proposed system is convenient for the establishment of practical positioning system and extensive experiments have been performed to validate that the proposed method is robust and manpower efficient.

Simultaneous spectrophotometric determination of valsartan and hydrochlorothiazide by H-point standard addition method and partial least squares regression.

PubMed

Lakshmi, Karunanidhi Santhana; Lakshmi, Sivasubramanian

2011-03-01

Simultaneous determination of valsartan and hydrochlorothiazide by the H-point standard additions method (HPSAM) and partial least squares (PLS) calibration is described. Absorbances at a pair of wavelengths, 216 and 228 nm, were monitored with the addition of standard solutions of valsartan. Results of applying HPSAM showed that valsartan and hydrochlorothiazide can be determined simultaneously at concentration ratios varying from 20:1 to 1:15 in a mixed sample. The proposed PLS method does not require chemical separation and spectral graphical procedures for quantitative resolution of mixtures containing the titled compounds. The calibration model was based on absorption spectra in the 200-350 nm range for 25 different mixtures of valsartan and hydrochlorothiazide. Calibration matrices contained 0.5-3 μg mL-1 of both valsartan and hydrochlorothiazide. The standard error of prediction (SEP) for valsartan and hydrochlorothiazide was 0.020 and 0.038 μg mL-1, respectively. Both proposed methods were successfully applied to the determination of valsartan and hydrochlorothiazide in several synthetic and real matrix samples.

Firefly algorithm versus genetic algorithm as powerful variable selection tools and their effect on different multivariate calibration models in spectroscopy: A comparative study

NASA Astrophysics Data System (ADS)

Attia, Khalid A. M.; Nassar, Mohammed W. I.; El-Zeiny, Mohamed B.; Serag, Ahmed

2017-01-01

For the first time, a new variable selection method based on swarm intelligence namely firefly algorithm is coupled with three different multivariate calibration models namely, concentration residual augmented classical least squares, artificial neural network and support vector regression in UV spectral data. A comparative study between the firefly algorithm and the well-known genetic algorithm was developed. The discussion revealed the superiority of using this new powerful algorithm over the well-known genetic algorithm. Moreover, different statistical tests were performed and no significant differences were found between all the models regarding their predictabilities. This ensures that simpler and faster models were obtained without any deterioration of the quality of the calibration.

Parameter estimation for groundwater models under uncertain irrigation data

USGS Publications Warehouse

Demissie, Yonas; Valocchi, Albert J.; Cai, Ximing; Brozovic, Nicholas; Senay, Gabriel; Gebremichael, Mekonnen

2015-01-01

The success of modeling groundwater is strongly influenced by the accuracy of the model parameters that are used to characterize the subsurface system. However, the presence of uncertainty and possibly bias in groundwater model source/sink terms may lead to biased estimates of model parameters and model predictions when the standard regression-based inverse modeling techniques are used. This study first quantifies the levels of bias in groundwater model parameters and predictions due to the presence of errors in irrigation data. Then, a new inverse modeling technique called input uncertainty weighted least-squares (IUWLS) is presented for unbiased estimation of the parameters when pumping and other source/sink data are uncertain. The approach uses the concept of generalized least-squares method with the weight of the objective function depending on the level of pumping uncertainty and iteratively adjusted during the parameter optimization process. We have conducted both analytical and numerical experiments, using irrigation pumping data from the Republican River Basin in Nebraska, to evaluate the performance of ordinary least-squares (OLS) and IUWLS calibration methods under different levels of uncertainty of irrigation data and calibration conditions. The result from the OLS method shows the presence of statistically significant (p < 0.05) bias in estimated parameters and model predictions that persist despite calibrating the models to different calibration data and sample sizes. However, by directly accounting for the irrigation pumping uncertainties during the calibration procedures, the proposed IUWLS is able to minimize the bias effectively without adding significant computational burden to the calibration processes.

Effective Data-Driven Calibration for a Galvanometric Laser Scanning System Using Binocular Stereo Vision.

PubMed

Tu, Junchao; Zhang, Liyan

2018-01-12

A new solution to the problem of galvanometric laser scanning (GLS) system calibration is presented. Under the machine learning framework, we build a single-hidden layer feedforward neural network (SLFN）to represent the GLS system, which takes the digital control signal at the drives of the GLS system as input and the space vector of the corresponding outgoing laser beam as output. The training data set is obtained with the aid of a moving mechanism and a binocular stereo system. The parameters of the SLFN are efficiently solved in a closed form by using extreme learning machine (ELM). By quantitatively analyzing the regression precision with respective to the number of hidden neurons in the SLFN, we demonstrate that the proper number of hidden neurons can be safely chosen from a broad interval to guarantee good generalization performance. Compared to the traditional model-driven calibration, the proposed calibration method does not need a complex modeling process and is more accurate and stable. As the output of the network is the space vectors of the outgoing laser beams, it costs much less training time and can provide a uniform solution to both laser projection and 3D-reconstruction, in contrast with the existing data-driven calibration method which only works for the laser triangulation problem. Calibration experiment, projection experiment and 3D reconstruction experiment are respectively conducted to test the proposed method, and good results are obtained.

Determination of volatile compounds in wine by gas chromatography-flame ionization detection: comparison between the U.S. Environmental Protection Agency 3sigma approach and Hubaux-Vos calculation of detection limits using ordinary and bivariate least squares.

PubMed

Caruso, Rosario; Scordino, Monica; Traulo, Pasqualino; Gagliano, Giacomo

2012-01-01

A capillary GC-flame ionization detection (FID) method to determine volatile compounds (ethyl acetate, 1,1-diethoxyethane, methyl alcohol, 1-propanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-butanol, and 2-butanol) in wine was investigated in terms of calculation of detection limits and calibration method. The main objectives were: (1) calculation of regression coefficient parameters by ordinary least-squares (OLS) and bivariate least-squares (BLS) regression models, taking into account errors in both axes; (2) estimation of linear dynamic range (LDR) according to International Conference on Harmonization recommendations; (3) performance evaluation of a method by using three different internal standards (ISs) such as acetonitrile, acetone, and 1-pentanol; (4) evaluation of LODs according to the U.S. Environmental Protection Agency (EPA) 3sigma approach and the Hubaux-Vos (H-V) method; (5) application of H-V theory to a gas chromatographic analytical method and to a food matrix; and (6) accuracy assessment of the method relative to methyl alcohol content through a Unione Italiana Vini (UIV) interlaboratory proficiency test. Calibration curves calculated via BLS and OLS show similar slopes, while intercepts are closer to zero in the first case, independent of the chosen IS. The studied ISs show a substantially equivalent behavior, even though the IS closer to the analyte retention time seems to be more appropriate in terms of LDR and LOD. Results indicate an underestimation of LODs using the EPA 3sigma approach instead of the more realistic H-V method, both with OLS and BLS regression models. Methanol contents compared with UIV average values indicate recovery between 90 and 110%.

Procedures for adjusting regional regression models of urban-runoff quality using local data

USGS Publications Warehouse

Hoos, A.B.; Sisolak, J.K.

1993-01-01

Statistical operations termed model-adjustment procedures (MAP?s) can be used to incorporate local data into existing regression models to improve the prediction of urban-runoff quality. Each MAP is a form of regression analysis in which the local data base is used as a calibration data set. Regression coefficients are determined from the local data base, and the resulting `adjusted? regression models can then be used to predict storm-runoff quality at unmonitored sites. The response variable in the regression analyses is the observed load or mean concentration of a constituent in storm runoff for a single storm. The set of explanatory variables used in the regression analyses is different for each MAP, but always includes the predicted value of load or mean concentration from a regional regression model. The four MAP?s examined in this study were: single-factor regression against the regional model prediction, P, (termed MAP-lF-P), regression against P,, (termed MAP-R-P), regression against P, and additional local variables (termed MAP-R-P+nV), and a weighted combination of P, and a local-regression prediction (termed MAP-W). The procedures were tested by means of split-sample analysis, using data from three cities included in the Nationwide Urban Runoff Program: Denver, Colorado; Bellevue, Washington; and Knoxville, Tennessee. The MAP that provided the greatest predictive accuracy for the verification data set differed among the three test data bases and among model types (MAP-W for Denver and Knoxville, MAP-lF-P and MAP-R-P for Bellevue load models, and MAP-R-P+nV for Bellevue concentration models) and, in many cases, was not clearly indicated by the values of standard error of estimate for the calibration data set. A scheme to guide MAP selection, based on exploratory data analysis of the calibration data set, is presented and tested. The MAP?s were tested for sensitivity to the size of a calibration data set. As expected, predictive accuracy of all MAP?s for the verification data set decreased as the calibration data-set size decreased, but predictive accuracy was not as sensitive for the MAP?s as it was for the local regression models.

Influence of Individual Differences on the Calculation Method for FBG-Type Blood Pressure Sensors

PubMed Central

Koyama, Shouhei; Ishizawa, Hiroaki; Fujimoto, Keisaku; Chino, Shun; Kobayashi, Yuka

2016-01-01

In this paper, we propose a blood pressure calculation and associated measurement method that by using a fiber Bragg grating (FBG) sensor. There are several points at which the pulse can be measured on the surface of the human body, and when a FBG sensor located at any of these points, the pulse wave signal can be measured. The measured waveform is similar to the acceleration pulse wave. The pulse wave signal changes depending on several factors, including whether or not the individual is healthy and/or elderly. The measured pulse wave signal can be used to calculate the blood pressure using a calibration curve, which is constructed by a partial least squares (PLS) regression analysis using a reference blood pressure and the pulse wave signal. In this paper, we focus on the influence of individual differences from calculated blood pressure based on each calibration curve. In our study, the calculated blood pressure from both the individual and overall calibration curves were compared, and our results show that the calculated blood pressure based on the overall calibration curve had a lower measurement accuracy than that based on an individual calibration curve. We also found that the influence of the individual differences on the calculated blood pressure when using the FBG sensor method were very low. Therefore, the FBG sensor method that we developed for measuring the blood pressure was found to be suitable for use by many people. PMID:28036015

Influence of Individual Differences on the Calculation Method for FBG-Type Blood Pressure Sensors.

PubMed

Koyama, Shouhei; Ishizawa, Hiroaki; Fujimoto, Keisaku; Chino, Shun; Kobayashi, Yuka

2016-12-28

In this paper, we propose a blood pressure calculation and associated measurement method that by using a fiber Bragg grating (FBG) sensor. There are several points at which the pulse can be measured on the surface of the human body, and when a FBG sensor located at any of these points, the pulse wave signal can be measured. The measured waveform is similar to the acceleration pulse wave. The pulse wave signal changes depending on several factors, including whether or not the individual is healthy and/or elderly. The measured pulse wave signal can be used to calculate the blood pressure using a calibration curve, which is constructed by a partial least squares (PLS) regression analysis using a reference blood pressure and the pulse wave signal. In this paper, we focus on the influence of individual differences from calculated blood pressure based on each calibration curve. In our study, the calculated blood pressure from both the individual and overall calibration curves were compared, and our results show that the calculated blood pressure based on the overall calibration curve had a lower measurement accuracy than that based on an individual calibration curve. We also found that the influence of the individual differences on the calculated blood pressure when using the FBG sensor method were very low. Therefore, the FBG sensor method that we developed for measuring the blood pressure was found to be suitable for use by many people.

Quality evaluation of frozen guava and yellow passion fruit pulps by NIR spectroscopy and chemometrics.

PubMed

Alamar, Priscila D; Caramês, Elem T S; Poppi, Ronei J; Pallone, Juliana A L

2016-07-01

The present study investigated the application of near infrared spectroscopy as a green, quick, and efficient alternative to analytical methods currently used to evaluate the quality (moisture, total sugars, acidity, soluble solids, pH and ascorbic acid) of frozen guava and passion fruit pulps. Fifty samples were analyzed by near infrared spectroscopy (NIR) and reference methods. Partial least square regression (PLSR) was used to develop calibration models to relate the NIR spectra and the reference values. Reference methods indicated adulteration by water addition in 58% of guava pulp samples and 44% of yellow passion fruit pulp samples. The PLS models produced lower values of root mean squares error of calibration (RMSEC), root mean squares error of prediction (RMSEP), and coefficient of determination above 0.7. Moisture and total sugars presented the best calibration models (RMSEP of 0.240 and 0.269, respectively, for guava pulp; RMSEP of 0.401 and 0.413, respectively, for passion fruit pulp) which enables the application of these models to determine adulteration in guava and yellow passion fruit pulp by water or sugar addition. The models constructed for calibration of quality parameters of frozen fruit pulps in this study indicate that NIR spectroscopy coupled with the multivariate calibration technique could be applied to determine the quality of guava and yellow passion fruit pulp. Copyright © 2016 Elsevier Ltd. All rights reserved.

Validation of a light-scattering PM2.5 sensor monitor based on the long-term gravimetric measurements in field tests

PubMed Central

Shi, Jingjin; Chen, Fei’er; Cai, Yunfei; Fan, Shichen; Cai, Jing; Chen, Renjie; Kan, Haidong; Lu, Yihan

2017-01-01

Background Portable direct-reading instruments by light-scattering method are increasingly used in airborne fine particulate matter (PM2.5) monitoring. However, there are limited calibration studies on such instruments by applying the gravimetric method as reference method in field tests. Methods An 8-month sampling was performed and 96 pairs of PM2.5 data by both the gravimetric method and the simultaneous light-scattering real-time monitoring (QT-50) were obtained from July, 2015 to February, 2016 in Shanghai. Temperature and relative humidity (RH) were recorded. Mann-Whitney U nonparametric test and Spearman correlation were used to investigate the differences between the two measurements. Multiple linear regression (MLR) model was applied to set up the calibration model for the light-scattering device. Results The average PM2.5 concentration (median) was 48.1μg/m3 (min-max 10.4–95.8μg/m3) by the gravimetric method and 58.1μg/m3 (19.2–315.9μg/m3) by the light-scattering method, respectively. By time trend analyses, they were significantly correlated with each other (Spearman correlation coefficient 0.889, P<0.01). By MLR, the calibration model for the light-scattering instrument was Y(calibrated) = 57.45 + 0.47 × X(the QT – 50 measurements) – 0.53 × RH – 0.41 × Temp with both RH and temperature adjusted. The 10-fold cross-validation R2 and the root mean squared error of the calibration model were 0.79 and 11.43 μg/m3, respectively. Conclusion Light-scattering measurements of PM2.5 by QT-50 instrument overestimated the concentration levels and were affected by temperature and RH. The calibration model for QT-50 instrument was firstly set up against the gravimetric method with temperature and RH adjusted. PMID:29121101

Wavelet analysis techniques applied to removing varying spectroscopic background in calibration model for pear sugar content

NASA Astrophysics Data System (ADS)

Liu, Yande; Ying, Yibin; Lu, Huishan; Fu, Xiaping

2005-11-01

A new method is proposed to eliminate the varying background and noise simultaneously for multivariate calibration of Fourier transform near infrared (FT-NIR) spectral signals. An ideal spectrum signal prototype was constructed based on the FT-NIR spectrum of fruit sugar content measurement. The performances of wavelet based threshold de-noising approaches via different combinations of wavelet base functions were compared. Three families of wavelet base function (Daubechies, Symlets and Coiflets) were applied to estimate the performance of those wavelet bases and threshold selection rules by a series of experiments. The experimental results show that the best de-noising performance is reached via the combinations of Daubechies 4 or Symlet 4 wavelet base function. Based on the optimization parameter, wavelet regression models for sugar content of pear were also developed and result in a smaller prediction error than a traditional Partial Least Squares Regression (PLSR) mode.

Comparative study of some robust statistical methods: weighted, parametric, and nonparametric linear regression of HPLC convoluted peak responses using internal standard method in drug bioavailability studies.

PubMed

Korany, Mohamed A; Maher, Hadir M; Galal, Shereen M; Ragab, Marwa A A

2013-05-01

This manuscript discusses the application and the comparison between three statistical regression methods for handling data: parametric, nonparametric, and weighted regression (WR). These data were obtained from different chemometric methods applied to the high-performance liquid chromatography response data using the internal standard method. This was performed on a model drug Acyclovir which was analyzed in human plasma with the use of ganciclovir as internal standard. In vivo study was also performed. Derivative treatment of chromatographic response ratio data was followed by convolution of the resulting derivative curves using 8-points sin x i polynomials (discrete Fourier functions). This work studies and also compares the application of WR method and Theil's method, a nonparametric regression (NPR) method with the least squares parametric regression (LSPR) method, which is considered the de facto standard method used for regression. When the assumption of homoscedasticity is not met for analytical data, a simple and effective way to counteract the great influence of the high concentrations on the fitted regression line is to use WR method. WR was found to be superior to the method of LSPR as the former assumes that the y-direction error in the calibration curve will increase as x increases. Theil's NPR method was also found to be superior to the method of LSPR as the former assumes that errors could occur in both x- and y-directions and that might not be normally distributed. Most of the results showed a significant improvement in the precision and accuracy on applying WR and NPR methods relative to LSPR.

Chemical Contaminant and Decontaminant Test Methodology Source Document. Second Edition

DTIC Science & Technology

2012-07-01

performance as described in “A Statistical Overview on Univariate Calibration, Inverse Regression, and Detection Limits: Application to Gas Chromatography...Overview on Univariate Calibration, Inverse Regression, and Detection Limits: Application to Gas Chromatography/Mass Spectrometry Technique. Mass... APPLICATIONS INTERNATIONAL CORPORATION Gunpowder, MD 21010-0068 July 2012 Approved for public release; distribution is unlimited

Near Infrared Spectrometry of Clinically Significant Fatty Acids Using Multicomponent Regression

NASA Astrophysics Data System (ADS)

Kalinin, A. V.; Krasheninnikov, V. N.; Sviridov, A. P.; Titov, V. N.

2016-11-01

We have developed methods for determining the content of clinically important fatty acids (FAs), primarily saturated palmitic acid, monounsaturated oleic acid, and the sum of polyenoic fatty acids (eicosapentaenoic + docosahexaenoic), in oily media (food products and supplements, fish oils) using different types of near infrared (NIR) spectrometers: Fourier-transform, linear photodiode array, and Raman. Based on a calibration method (regression) by means of projections to latent structures, using standard samples of oil and fat mixtures, we have confirmed the feasibility of reliable and selective quantitative analysis of the above-indicated fatty acids. As a result of comparing the calibration models for Fourier-transform spectrometers in different parts of the NIR range (based on different overtones and combinations of fatty acid absorption), we have provided a basis for selection of the spectral range for a portable linear InGaAs-photodiode array spectrometer. In testing the calibrations of a linear InGaAs-photodiode array spectrometer which is a prototype for a portable instrument, for palmitic and oleic acids and also the sum of the polyenoic fatty acids we have achieved a multiple correlation coefficient of 0.89, 0.85, and 0.96 and a standard error of 0.53%, 1.43%, and 0.39% respectively. We have confirmed the feasibility of using Raman spectra to determine the content of the above-indicated fatty acids in media where water is present.

Bayesian correction for covariate measurement error: A frequentist evaluation and comparison with regression calibration.

PubMed

Bartlett, Jonathan W; Keogh, Ruth H

2018-06-01

Bayesian approaches for handling covariate measurement error are well established and yet arguably are still relatively little used by researchers. For some this is likely due to unfamiliarity or disagreement with the Bayesian inferential paradigm. For others a contributory factor is the inability of standard statistical packages to perform such Bayesian analyses. In this paper, we first give an overview of the Bayesian approach to handling covariate measurement error, and contrast it with regression calibration, arguably the most commonly adopted approach. We then argue why the Bayesian approach has a number of statistical advantages compared to regression calibration and demonstrate that implementing the Bayesian approach is usually quite feasible for the analyst. Next, we describe the closely related maximum likelihood and multiple imputation approaches and explain why we believe the Bayesian approach to generally be preferable. We then empirically compare the frequentist properties of regression calibration and the Bayesian approach through simulation studies. The flexibility of the Bayesian approach to handle both measurement error and missing data is then illustrated through an analysis of data from the Third National Health and Nutrition Examination Survey.

Calibration Model for Apnea-Hypopnea Indices: Impact of Alternative Criteria for Hypopneas

PubMed Central

Ho, Vu; Crainiceanu, Ciprian M.; Punjabi, Naresh M.; Redline, Susan; Gottlieb, Daniel J.

2015-01-01

Study Objective: To characterize the association among apnea-hypopnea indices (AHIs) determined using three common metrics for defining hypopnea, and to develop a model to calibrate between these AHIs. Design: Cross-sectional analysis of Sleep Heart Health Study Data. Setting: Community-based. Participants: There were 6,441 men and women age 40 y or older. Measurement and Results: Three separate AHIs have been calculated, using all apneas (defined as a decrease in airflow greater than 90% from baseline for ≥ 10 sec) plus hypopneas (defined as a decrease in airflow or chest wall or abdominal excursion greater than 30% from baseline, but not meeting apnea definitions) associated with either: (1) a 4% or greater fall in oxyhemoglobin saturation—AHI4; (2) a 3% or greater fall in oxyhemoglobin saturation—AHI3; or (3) a 3% or greater fall in oxyhemoglobin saturation or an event-related arousal—AHI3a. Median values were 5.4, 9.7, and 13.4 for AHI4, AHI3, and AHI3a, respectively (P < 0.0001). Penalized spline regression models were used to compare AHI values across the three metrics and to calculate prediction intervals. Comparison of regression models demonstrates divergence in AHI scores among the three methods at low AHI values and gradual convergence at higher levels of AHI. Conclusions: The three methods of scoring hypopneas yielded significantly different estimates of the apnea-hypopnea index (AHI), although the relative difference is reduced in severe disease. The regression models presented will enable clinicians and researchers to more appropriately compare AHI values obtained using differing metrics for hypopnea. Citation: Ho V, Crainiceanu CM, Punjabi NM, Redline S, Gottlieb DJ. Calibration model for apnea-hypopnea indices: impact of alternative criteria for hypopneas. SLEEP 2015;38(12):1887–1892. PMID:26564122

Simultaneous chemometric determination of pyridoxine hydrochloride and isoniazid in tablets by multivariate regression methods.

PubMed

Dinç, Erdal; Ustündağ, Ozgür; Baleanu, Dumitru

2010-08-01

The sole use of pyridoxine hydrochloride during treatment of tuberculosis gives rise to pyridoxine deficiency. Therefore, a combination of pyridoxine hydrochloride and isoniazid is used in pharmaceutical dosage form in tuberculosis treatment to reduce this side effect. In this study, two chemometric methods, partial least squares (PLS) and principal component regression (PCR), were applied to the simultaneous determination of pyridoxine (PYR) and isoniazid (ISO) in their tablets. A concentration training set comprising binary mixtures of PYR and ISO consisting of 20 different combinations were randomly prepared in 0.1 M HCl. Both multivariate calibration models were constructed using the relationships between the concentration data set (concentration data matrix) and absorbance data matrix in the spectral region 200-330 nm. The accuracy and the precision of the proposed chemometric methods were validated by analyzing synthetic mixtures containing the investigated drugs. The recovery results obtained by applying PCR and PLS calibrations to the artificial mixtures were found between 100.0 and 100.7%. Satisfactory results obtained by applying the PLS and PCR methods to both artificial and commercial samples were obtained. The results obtained in this manuscript strongly encourage us to use them for the quality control and the routine analysis of the marketing tablets containing PYR and ISO drugs. Copyright © 2010 John Wiley & Sons, Ltd.

Retention modelling of polychlorinated biphenyls in comprehensive two-dimensional gas chromatography.

PubMed

D'Archivio, Angelo Antonio; Incani, Angela; Ruggieri, Fabrizio

2011-01-01

In this paper, we use a quantitative structure-retention relationship (QSRR) method to predict the retention times of polychlorinated biphenyls (PCBs) in comprehensive two-dimensional gas chromatography (GC×GC). We analyse the GC×GC retention data taken from the literature by comparing predictive capability of different regression methods. The various models are generated using 70 out of 209 PCB congeners in the calibration stage, while their predictive performance is evaluated on the remaining 139 compounds. The two-dimensional chromatogram is initially estimated by separately modelling retention times of PCBs in the first and in the second column ((1) t (R) and (2) t (R), respectively). In particular, multilinear regression (MLR) combined with genetic algorithm (GA) variable selection is performed to extract two small subsets of predictors for (1) t (R) and (2) t (R) from a large set of theoretical molecular descriptors provided by the popular software Dragon, which after removal of highly correlated or almost constant variables consists of 237 structure-related quantities. Based on GA-MLR analysis, a four-dimensional and a five-dimensional relationship modelling (1) t (R) and (2) t (R), respectively, are identified. Single-response partial least square (PLS-1) regression is alternatively applied to independently model (1) t (R) and (2) t (R) without the need for preliminary GA variable selection. Further, we explore the possibility of predicting the two-dimensional chromatogram of PCBs in a single calibration procedure by using a two-response PLS (PLS-2) model or a feed-forward artificial neural network (ANN) with two output neurons. In the first case, regression is carried out on the full set of 237 descriptors, while the variables previously selected by GA-MLR are initially considered as ANN inputs and subjected to a sensitivity analysis to remove the redundant ones. Results show PLS-1 regression exhibits a noticeably better descriptive and predictive performance than the other investigated approaches. The observed values of determination coefficients for (1) t (R) and (2) t (R) in calibration (0.9999 and 0.9993, respectively) and prediction (0.9987 and 0.9793, respectively) provided by PLS-1 demonstrate that GC×GC behaviour of PCBs is properly modelled. In particular, the predicted two-dimensional GC×GC chromatogram of 139 PCBs not involved in the calibration stage closely resembles the experimental one. Based on the above lines of evidence, the proposed approach ensures accurate simulation of the whole GC×GC chromatogram of PCBs using experimental determination of only 1/3 retention data of representative congeners.

Quick method (FT-NIR) for the determination of oil and major fatty acids content in whole achenes of milk thistle (Silybum marianum (L.) Gaertn.).

PubMed

Koláčková, Pavla; Růžičková, Gabriela; Gregor, Tomáš; Šišperová, Eliška

2015-08-30

Calibration models for the Fourier transform-near infrared (FT-NIR) instrument were developed for quick and non-destructive determination of oil and fatty acids in whole achenes of milk thistle. Samples with a range of oil and fatty acid levels were collected and their transmittance spectra were obtained by the FT-NIR instrument. Based on these spectra and data gained by the means of the reference method - Soxhlet extraction and gas chromatography (GC) - calibration models were created by means of partial least square (PLS) regression analysis. Precision and accuracy of the calibration models was verified via the cross-validation of validation samples whose spectra were not part of the calibration model and also according to the root mean square error of prediction (RMSEP), root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV) and the validation coefficient of determination (R(2) ). R(2) for whole seeds were 0.96, 0.96, 0.83 and 0.67 and the RMSEP values were 0.76, 1.68, 1.24, 0.54 for oil, linoleic (C18:2), oleic (C18:1) and palmitic (C16:0) acids, respectively. The calibration models are appropriate for the non-destructive determination of oil and fatty acids levels in whole seeds of milk thistle. © 2014 Society of Chemical Industry.

Measurement of tidal volume using respiratory ultrasonic plethysmography in anaesthetized, mechanically ventilated horses.

PubMed

Russold, Elena; Ambrisko, Tamas D; Schramel, Johannes P; Auer, Ulrike; Van Den Hoven, Rene; Moens, Yves P

2013-01-01

To compare tidal volume estimations obtained from Respiratory Ultrasonic Plethysmography (RUP) with simultaneous spirometric measurements in anaesthetized, mechanically ventilated horses. Prospective randomized experimental study. Five experimental horses. Five horses were anaesthetized twice (1 week apart) in random order in lateral and in dorsal recumbency. Nine ventilation modes (treatments) were scheduled in random order (each lasting 4 minutes) applying combinations of different tidal volumes (8, 10, 12 mL kg(-1)) and positive end-expiratory pressures (PEEP) (0, 10, 20 cm H(2)O). Baseline ventilation mode (tidal volume=15 mL kg(-1), PEEP=0 cm H(2)O) was applied for 4 minutes between all treatments. Spirometry and RUP data were downloaded to personal computers. Linear regression analyses (RUP versus spirometric tidal volume) were performed using different subsets of data. Additonally RUP was calibrated against spirometry using a regression equation for all RUP signal values (thoracic, abdominal and combined) with all data collectively and also by an individually determined best regression equation (highest R(2)) for each experiment (horse versus recumbency) separately. Agreement between methods was assessed with Bland-Altman analyses. The highest correlation of RUP and spirometric tidal volume (R(2)=0.81) was found with the combined RUP signal in horses in lateral recumbency and ventilated without PEEP. The bias ±2 SD was 0±2.66 L when RUP was calibrated for collective data, but decreased to 0±0.87 L when RUP was calibrated with individual data. A possible use of RUP for tidal volume measurement during IPPV needs individual calibration to obtain limits of agreement within ±20%. © 2012 The Authors. Veterinary Anaesthesia and Analgesia. © 2012 Association of Veterinary Anaesthetists and the American College of Veterinary Anesthesiologists.

Validation of a light-scattering PM2.5 sensor monitor based on the long-term gravimetric measurements in field tests.

PubMed

Shi, Jingjin; Chen, Fei'er; Cai, Yunfei; Fan, Shichen; Cai, Jing; Chen, Renjie; Kan, Haidong; Lu, Yihan; Zhao, Zhuohui

2017-01-01

Portable direct-reading instruments by light-scattering method are increasingly used in airborne fine particulate matter (PM2.5) monitoring. However, there are limited calibration studies on such instruments by applying the gravimetric method as reference method in field tests. An 8-month sampling was performed and 96 pairs of PM2.5 data by both the gravimetric method and the simultaneous light-scattering real-time monitoring (QT-50) were obtained from July, 2015 to February, 2016 in Shanghai. Temperature and relative humidity (RH) were recorded. Mann-Whitney U nonparametric test and Spearman correlation were used to investigate the differences between the two measurements. Multiple linear regression (MLR) model was applied to set up the calibration model for the light-scattering device. The average PM2.5 concentration (median) was 48.1μg/m3 (min-max 10.4-95.8μg/m3) by the gravimetric method and 58.1μg/m3 (19.2-315.9μg/m3) by the light-scattering method, respectively. By time trend analyses, they were significantly correlated with each other (Spearman correlation coefficient 0.889, P<0.01). By MLR, the calibration model for the light-scattering instrument was Y(calibrated) = 57.45 + 0.47 × X(the QT - 50 measurements) - 0.53 × RH - 0.41 × Temp with both RH and temperature adjusted. The 10-fold cross-validation R2 and the root mean squared error of the calibration model were 0.79 and 11.43 μg/m3, respectively. Light-scattering measurements of PM2.5 by QT-50 instrument overestimated the concentration levels and were affected by temperature and RH. The calibration model for QT-50 instrument was firstly set up against the gravimetric method with temperature and RH adjusted.

The feasibility of using explicit method for linear correction of the particle size variation using NIR Spectroscopy combined with PLS2regression method

NASA Astrophysics Data System (ADS)

Yulia, M.; Suhandy, D.

2018-03-01

NIR spectra obtained from spectral data acquisition system contains both chemical information of samples as well as physical information of the samples, such as particle size and bulk density. Several methods have been established for developing calibration models that can compensate for sample physical information variations. One common approach is to include physical information variation in the calibration model both explicitly and implicitly. The objective of this study was to evaluate the feasibility of using explicit method to compensate the influence of different particle size of coffee powder in NIR calibration model performance. A number of 220 coffee powder samples with two different types of coffee (civet and non-civet) and two different particle sizes (212 and 500 µm) were prepared. Spectral data was acquired using NIR spectrometer equipped with an integrating sphere for diffuse reflectance measurement. A discrimination method based on PLS-DA was conducted and the influence of different particle size on the performance of PLS-DA was investigated. In explicit method, we add directly the particle size as predicted variable results in an X block containing only the NIR spectra and a Y block containing the particle size and type of coffee. The explicit inclusion of the particle size into the calibration model is expected to improve the accuracy of type of coffee determination. The result shows that using explicit method the quality of the developed calibration model for type of coffee determination is a little bit superior with coefficient of determination (R2) = 0.99 and root mean square error of cross-validation (RMSECV) = 0.041. The performance of the PLS2 calibration model for type of coffee determination with particle size compensation was quite good and able to predict the type of coffee in two different particle sizes with relatively high R2 pred values. The prediction also resulted in low bias and RMSEP values.

An interlaboratory comparison study on the measurement of elements in PM10

NASA Astrophysics Data System (ADS)

Yatkin, Sinan; Belis, Claudio A.; Gerboles, Michel; Calzolai, Giulia; Lucarelli, Franco; Cavalli, Fabrizia; Trzepla, Krystyna

2016-01-01

An inter-laboratory comparison study was conducted to measure elemental loadings on PM10 samples, collected in Ispra, a regional background/rural site in Italy, using three different XRF (X-ray Fluorescence) methods, namely Epsilon 5 by linear calibration, Quant'X by the standardless analysis, and PIXE (Particle Induced X-ray Emission) with linear calibration. A subset of samples was also analyzed by ICP-MS (Inductively Coupled Plasma-Mass Spectrometry). Several metrics including method detection limits (MDLs), precision, bias from a NIST standard reference material (SRM 2783) quoted values, relative absolute difference, orthogonal regression and the ratio of the absolute difference between the methods to claimed uncertainty were used to compare the laboratories. The MDLs were found to be comparable for many elements. Precision estimates were less than 10% for the majority of the elements. Absolute biases from SRM 2783 remained less than 20% for the majority of certified elements. The regression results of PM10 samples showed that the three XRF laboratories measured very similar mass loadings for S, K, Ti, Mn, Fe, Cu, Br, Sr and Pb with slopes within 20% of unity. The ICP-MS results confirmed the agreement and discrepancies between XRF laboratories for Al, K, Ca, Ti, V, Cu, Sr and Pb. The ICP-MS results are inconsistent with the XRF laboratories for Fe and Zn. The absolute differences between the XRF laboratories generally remained within their claimed uncertainties, showing a pattern generally consistent with the orthogonal regression results.

Using DMSP/OLS nighttime imagery to estimate carbon dioxide emission

NASA Astrophysics Data System (ADS)

Desheng, B.; Letu, H.; Bao, Y.; Naizhuo, Z.; Hara, M.; Nishio, F.

2012-12-01

This study highlighted a method for estimating CO2 emission from electric power plants using the Defense Meteorological Satellite Program's Operational Linescan System (DMSP/OLS) stable light image product for 1999. CO2 emissions from power plants account for a high percentage of CO2 emissions from fossil fuel consumptions. Thermal power plants generate the electricity by burning fossil fuels, so they emit CO2 directly. In many Asian countries such as China, Japan, India, and South Korea, the amounts of electric power generated by thermal power accounts over 58% in the total amount of electric power in 1999. So far, figures of the CO2 emission were obtained mainly by traditional statistical methods. Moreover, the statistical data were summarized as administrative regions, so it is difficult to examine the spatial distribution of non-administrative division. In some countries the reliability of such CO2 emission data is relatively low. However, satellite remote sensing can observe the earth surface without limitation of administrative regions. Thus, it is important to estimate CO2 using satellite remote sensing. In this study, we estimated the CO2 emission by fossil fuel consumption from electric power plant using stable light image of the DMSP/OLS satellite data for 1999 after correction for saturation effect in Japan. Digital number (DN) values of the stable light images in center areas of cities are saturated due to the large nighttime light intensities and characteristics of the OLS satellite sensors. To more accurately estimate the CO2 emission using the stable light images, a saturation correction method was developed by using the DMSP radiance calibration image, which does not include any saturation pixels. A regression equation was developed by the relationship between DN values of non-saturated pixels in the stable light image and those in the radiance calibration image. And, regression equation was used to adjust the DNs of the radiance calibration image. Then, saturated DNs of the stable light image was corrected using adjusted radiance calibration image. After that, regression analysis was performed with cumulative DNs of the corrected stable light image, electric power consumption, electric power generation and CO2 emission by fossil fuel consumption from electric power plant each other. Results indicated that there are good relationships (R2>90%) between DNs of the corrected stable light image and other parameters. Based on the above results, we estimated the CO2 emission from electric power plant using corrected stable light image. Keywords: DMSP/OLS, stable light, saturation light correction method, regression analysis Acknowledgment: The research was financially supported by the Sasakawa Scientific Research Grant from the Japan Science Society.

Firefly algorithm versus genetic algorithm as powerful variable selection tools and their effect on different multivariate calibration models in spectroscopy: A comparative study.

PubMed

Attia, Khalid A M; Nassar, Mohammed W I; El-Zeiny, Mohamed B; Serag, Ahmed

2017-01-05

For the first time, a new variable selection method based on swarm intelligence namely firefly algorithm is coupled with three different multivariate calibration models namely, concentration residual augmented classical least squares, artificial neural network and support vector regression in UV spectral data. A comparative study between the firefly algorithm and the well-known genetic algorithm was developed. The discussion revealed the superiority of using this new powerful algorithm over the well-known genetic algorithm. Moreover, different statistical tests were performed and no significant differences were found between all the models regarding their predictabilities. This ensures that simpler and faster models were obtained without any deterioration of the quality of the calibration. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and Optimization of a Chemometric-Assisted Spectrophotometric Determination of Telmisartan and Hydrochlorothiazide in Pharmaceutical Dosage Form

PubMed Central

Lakshmi, KS; Lakshmi, S

2010-01-01

Two chemometric methods were developed for the simultaneous determination of telmisartan and hydrochlorothiazide. The chemometric methods applied were principal component regression (PCR) and partial least square (PLS-1). These approaches were successfully applied to quantify the two drugs in the mixture using the information included in the UV absorption spectra of appropriate solutions in the range of 200-350 nm with the intervals Δλ = 1 nm. The calibration of PCR and PLS-1 models was evaluated by internal validation (prediction of compounds in its own designed training set of calibration) and by external validation over laboratory prepared mixtures and pharmaceutical preparations. The PCR and PLS-1 methods require neither any separation step, nor any prior graphical treatment of the overlapping spectra of the two drugs in a mixture. The results of PCR and PLS-1 methods were compared with each other and a good agreement was found. PMID:21331198

Design and optimization of a chemometric-assisted spectrophotometric determination of telmisartan and hydrochlorothiazide in pharmaceutical dosage form.

PubMed

Lakshmi, Ks; Lakshmi, S

2010-01-01

Two chemometric methods were developed for the simultaneous determination of telmisartan and hydrochlorothiazide. The chemometric methods applied were principal component regression (PCR) and partial least square (PLS-1). These approaches were successfully applied to quantify the two drugs in the mixture using the information included in the UV absorption spectra of appropriate solutions in the range of 200-350 nm with the intervals Δλ = 1 nm. The calibration of PCR and PLS-1 models was evaluated by internal validation (prediction of compounds in its own designed training set of calibration) and by external validation over laboratory prepared mixtures and pharmaceutical preparations. The PCR and PLS-1 methods require neither any separation step, nor any prior graphical treatment of the overlapping spectra of the two drugs in a mixture. The results of PCR and PLS-1 methods were compared with each other and a good agreement was found.

Study of continuous blood pressure estimation based on pulse transit time, heart rate and photoplethysmography-derived hemodynamic covariates.

PubMed

Feng, Jingjie; Huang, Zhongyi; Zhou, Congcong; Ye, Xuesong

2018-06-01

It is widely recognized that pulse transit time (PTT) can track blood pressure (BP) over short periods of time, and hemodynamic covariates such as heart rate, stiffness index may also contribute to BP monitoring. In this paper, we derived a proportional relationship between BP and PPT -2 and proposed an improved method adopting hemodynamic covariates in addition to PTT for continuous BP estimation. We divided 28 subjects from the Multi-parameter Intelligent Monitoring for Intensive Care database into two groups (with/without cardiovascular diseases) and utilized a machine learning strategy based on regularized linear regression (RLR) to construct BP models with different covariates for corresponding groups. RLR was performed for individuals as the initial calibration, while recursive least square algorithm was employed for the re-calibration. The results showed that errors of BP estimation by our method stayed within the Association of Advancement of Medical Instrumentation limits (- 0.98 ± 6.00 mmHg @ SBP, 0.02 ± 4.98 mmHg @ DBP) when the calibration interval extended to 1200-beat cardiac cycles. In comparison with other two representative studies, Chen's method kept accurate (0.32 ± 6.74 mmHg @ SBP, 0.94 ± 5.37 mmHg @ DBP) using a 400-beat calibration interval, while Poon's failed (- 1.97 ± 10.59 mmHg @ SBP, 0.70 ± 4.10 mmHg @ DBP) when using a 200-beat calibration interval. With additional hemodynamic covariates utilized, our method improved the accuracy of PTT-based BP estimation, decreased the calibration frequency and had the potential for better continuous BP estimation.

Impact of Uncertainties in Exposure Assessment on Thyroid Cancer Risk among Persons in Belarus Exposed as Children or Adolescents Due to the Chernobyl Accident.

PubMed

Little, Mark P; Kwon, Deukwoo; Zablotska, Lydia B; Brenner, Alina V; Cahoon, Elizabeth K; Rozhko, Alexander V; Polyanskaya, Olga N; Minenko, Victor F; Golovanov, Ivan; Bouville, André; Drozdovitch, Vladimir

2015-01-01

The excess incidence of thyroid cancer in Ukraine and Belarus observed a few years after the Chernobyl accident is considered to be largely the result of 131I released from the reactor. Although the Belarus thyroid cancer prevalence data has been previously analyzed, no account was taken of dose measurement error. We examined dose-response patterns in a thyroid screening prevalence cohort of 11,732 persons aged under 18 at the time of the accident, diagnosed during 1996-2004, who had direct thyroid 131I activity measurement, and were resident in the most radio-actively contaminated regions of Belarus. Three methods of dose-error correction (regression calibration, Monte Carlo maximum likelihood, Bayesian Markov Chain Monte Carlo) were applied. There was a statistically significant (p<0.001) increasing dose-response for prevalent thyroid cancer, irrespective of regression-adjustment method used. Without adjustment for dose errors the excess odds ratio was 1.51 Gy- (95% CI 0.53, 3.86), which was reduced by 13% when regression-calibration adjustment was used, 1.31 Gy- (95% CI 0.47, 3.31). A Monte Carlo maximum likelihood method yielded an excess odds ratio of 1.48 Gy- (95% CI 0.53, 3.87), about 2% lower than the unadjusted analysis. The Bayesian method yielded a maximum posterior excess odds ratio of 1.16 Gy- (95% BCI 0.20, 4.32), 23% lower than the unadjusted analysis. There were borderline significant (p = 0.053-0.078) indications of downward curvature in the dose response, depending on the adjustment methods used. There were also borderline significant (p = 0.102) modifying effects of gender on the radiation dose trend, but no significant modifying effects of age at time of accident, or age at screening as modifiers of dose response (p>0.2). In summary, the relatively small contribution of unshared classical dose error in the current study results in comparatively modest effects on the regression parameters.

On state-of-charge determination for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Zhe; Huang, Jun; Liaw, Bor Yann; Zhang, Jianbo

2017-04-01

Accurate estimation of state-of-charge (SOC) of a battery through its life remains challenging in battery research. Although improved precisions continue to be reported at times, almost all are based on regression methods empirically, while the accuracy is often not properly addressed. Here, a comprehensive review is set to address such issues, from fundamental principles that are supposed to define SOC to methodologies to estimate SOC for practical use. It covers topics from calibration, regression (including modeling methods) to validation in terms of precision and accuracy. At the end, we intend to answer the following questions: 1) can SOC estimation be self-adaptive without bias? 2) Why Ah-counting is a necessity in almost all battery-model-assisted regression methods? 3) How to establish a consistent framework of coupling in multi-physics battery models? 4) To assess the accuracy in SOC estimation, statistical methods should be employed to analyze factors that contribute to the uncertainty. We hope, through this proper discussion of the principles, accurate SOC estimation can be widely achieved.

System calibration method for Fourier ptychographic microscopy.

PubMed

Pan, An; Zhang, Yan; Zhao, Tianyu; Wang, Zhaojun; Dan, Dan; Lei, Ming; Yao, Baoli

2017-09-01

Fourier ptychographic microscopy (FPM) is a recently proposed computational imaging technique with both high-resolution and wide field of view. In current FPM imaging platforms, systematic error sources come from aberrations, light-emitting diode (LED) intensity fluctuation, parameter imperfections, and noise, all of which may severely corrupt the reconstruction results with similar artifacts. Therefore, it would be unlikely to distinguish the dominating error from these degraded reconstructions without any preknowledge. In addition, systematic error is generally a mixture of various error sources in the real situation, and it cannot be separated due to their mutual restriction and conversion. To this end, we report a system calibration procedure, termed SC-FPM, to calibrate the mixed systematic errors simultaneously from an overall perspective, based on the simulated annealing algorithm, the LED intensity correction method, the nonlinear regression process, and the adaptive step-size strategy, which involves the evaluation of an error metric at each iteration step, followed by the re-estimation of accurate parameters. The performance achieved both in simulations and experiments demonstrates that the proposed method outperforms other state-of-the-art algorithms. The reported system calibration scheme improves the robustness of FPM, relaxes the experiment conditions, and does not require any preknowledge, which makes the FPM more pragmatic. (2017) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Calibration Experiments for a Computer Vision Oyster Volume Estimation System

ERIC Educational Resources Information Center

Chang, G. Andy; Kerns, G. Jay; Lee, D. J.; Stanek, Gary L.

2009-01-01

Calibration is a technique that is commonly used in science and engineering research that requires calibrating measurement tools for obtaining more accurate measurements. It is an important technique in various industries. In many situations, calibration is an application of linear regression, and is a good topic to be included when explaining and…

Digital Correlation Microwave Polarimetry: Analysis and Demonstration

NASA Technical Reports Server (NTRS)

Piepmeier, J. R.; Gasiewski, A. J.; Krebs, Carolyn A. (Technical Monitor)

2000-01-01

The design, analysis, and demonstration of a digital-correlation microwave polarimeter for use in earth remote sensing is presented. We begin with an analysis of three-level digital correlation and develop the correlator transfer function and radiometric sensitivity. A fifth-order polynomial regression is derived for inverting the digital correlation coefficient into the analog statistic. In addition, the effects of quantizer threshold asymmetry and hysteresis are discussed. A two-look unpolarized calibration scheme is developed for identifying correlation offsets. The developed theory and calibration method are verified using a 10.7 GHz and a 37.0 GHz polarimeter. The polarimeters are based upon 1-GS/s three-level digital correlators and measure the first three Stokes parameters. Through experiment, the radiometric sensitivity is shown to approach the theoretical as derived earlier in the paper and the two-look unpolarized calibration method is successfully compared with results using a polarimetric scheme. Finally, sample data from an aircraft experiment demonstrates that the polarimeter is highly-useful for ocean wind-vector measurement.

Scaling field data to calibrate and validate moderate spatial resolution remote sensing models

USGS Publications Warehouse

Baccini, A.; Friedl, M.A.; Woodcock, C.E.; Zhu, Z.

2007-01-01

Validation and calibration are essential components of nearly all remote sensing-based studies. In both cases, ground measurements are collected and then related to the remote sensing observations or model results. In many situations, and particularly in studies that use moderate resolution remote sensing, a mismatch exists between the sensor's field of view and the scale at which in situ measurements are collected. The use of in situ measurements for model calibration and validation, therefore, requires a robust and defensible method to spatially aggregate ground measurements to the scale at which the remotely sensed data are acquired. This paper examines this challenge and specifically considers two different approaches for aggregating field measurements to match the spatial resolution of moderate spatial resolution remote sensing data: (a) landscape stratification; and (b) averaging of fine spatial resolution maps. The results show that an empirically estimated stratification based on a regression tree method provides a statistically defensible and operational basis for performing this type of procedure. 

Stability indicating high performance thin-layer chromatographic method for simultaneous estimation of pantoprazole sodium and itopride hydrochloride in combined dosage form

PubMed Central

Bageshwar, Deepak; Khanvilkar, Vineeta; Kadam, Vilasrao

2011-01-01

A specific, precise and stability indicating high-performance thin-layer chromatographic method for simultaneous estimation of pantoprazole sodium and itopride hydrochloride in pharmaceutical formulations was developed and validated. The method employed TLC aluminium plates precoated with silica gel 60F254 as the stationary phase. The solvent system consisted of methanol:water:ammonium acetate; 4.0:1.0:0.5 (v/v/v). This system was found to give compact and dense spots for both itopride hydrochloride (Rf value of 0.55±0.02) and pantoprazole sodium (Rf value of 0.85±0.04). Densitometric analysis of both drugs was carried out in the reflectance–absorbance mode at 289 nm. The linear regression analysis data for the calibration plots showed a good linear relationship with R2=0.9988±0.0012 in the concentration range of 100–400 ng for pantoprazole sodium. Also, the linear regression analysis data for the calibration plots showed a good linear relationship with R2=0.9990±0.0008 in the concentration range of 200–1200 ng for itopride hydrochloride. The method was validated for specificity, precision, robustness and recovery. Statistical analysis proves that the method is repeatable and selective for the estimation of both the said drugs. As the method could effectively separate the drug from its degradation products, it can be employed as a stability indicating method. PMID:29403710

Stability indicating high performance thin-layer chromatographic method for simultaneous estimation of pantoprazole sodium and itopride hydrochloride in combined dosage form.

PubMed

Bageshwar, Deepak; Khanvilkar, Vineeta; Kadam, Vilasrao

2011-11-01

A specific, precise and stability indicating high-performance thin-layer chromatographic method for simultaneous estimation of pantoprazole sodium and itopride hydrochloride in pharmaceutical formulations was developed and validated. The method employed TLC aluminium plates precoated with silica gel 60F 254 as the stationary phase. The solvent system consisted of methanol:water:ammonium acetate; 4.0:1.0:0.5 (v/v/v). This system was found to give compact and dense spots for both itopride hydrochloride ( R f value of 0.55±0.02) and pantoprazole sodium ( R f value of 0.85±0.04). Densitometric analysis of both drugs was carried out in the reflectance-absorbance mode at 289 nm. The linear regression analysis data for the calibration plots showed a good linear relationship with R 2 =0.9988±0.0012 in the concentration range of 100-400 ng for pantoprazole sodium. Also, the linear regression analysis data for the calibration plots showed a good linear relationship with R 2 =0.9990±0.0008 in the concentration range of 200-1200 ng for itopride hydrochloride. The method was validated for specificity, precision, robustness and recovery. Statistical analysis proves that the method is repeatable and selective for the estimation of both the said drugs. As the method could effectively separate the drug from its degradation products, it can be employed as a stability indicating method.

A crystal plasticity model for slip in hexagonal close packed metals based on discrete dislocation simulations

NASA Astrophysics Data System (ADS)

Messner, Mark C.; Rhee, Moono; Arsenlis, Athanasios; Barton, Nathan R.

2017-06-01

This work develops a method for calibrating a crystal plasticity model to the results of discrete dislocation (DD) simulations. The crystal model explicitly represents junction formation and annihilation mechanisms and applies these mechanisms to describe hardening in hexagonal close packed metals. The model treats these dislocation mechanisms separately from elastic interactions among populations of dislocations, which the model represents through a conventional strength-interaction matrix. This split between elastic interactions and junction formation mechanisms more accurately reproduces the DD data and results in a multi-scale model that better represents the lower scale physics. The fitting procedure employs concepts of machine learning—feature selection by regularized regression and cross-validation—to develop a robust, physically accurate crystal model. The work also presents a method for ensuring the final, calibrated crystal model respects the physical symmetries of the crystal system. Calibrating the crystal model requires fitting two linear operators: one describing elastic dislocation interactions and another describing junction formation and annihilation dislocation reactions. The structure of these operators in the final, calibrated model reflect the crystal symmetry and slip system geometry of the DD simulations.

Predicting ambient aerosol Thermal Optical Reflectance (TOR) measurements from infrared spectra: organic carbon

NASA Astrophysics Data System (ADS)

Dillner, A. M.; Takahama, S.

2014-11-01

Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, the organic carbon concentration is measured using thermal methods such as Thermal-Optical Reflectance (TOR) from quartz fiber filters. Here, methods are presented whereby Fourier Transform Infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters are used to accurately predict TOR OC. Transmittance FT-IR analysis is rapid, inexpensive, and non-destructive to the PTFE filters. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites sampled during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to artifact-corrected TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date which leads to precise and accurate OC predictions by FT-IR as indicated by high coefficient of determination (R2; 0.96), low bias (0.02 μg m-3, all μg m-3 values based on the nominal IMPROVE sample volume of 32.8 m-3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. FT-IR spectra are also divided into calibration and test sets by OC mass and by OM / OC which reflects the organic composition of the particulate matter and is obtained from organic functional group composition; this division also leads to precise and accurate OC predictions. Low OC concentrations have higher bias and normalized error due to TOR analytical errors and artifact correction errors, not due to the range of OC mass of the samples in the calibration set. However, samples with low OC mass can be used to predict samples with high OC mass indicating that the calibration is linear. Using samples in the calibration set that have a different OM / OC or ammonium / OC distributions than the test set leads to only a modest increase in bias and normalized error in the predicted samples. We conclude that FT-IR analysis with partial least squares regression is a robust method for accurately predicting TOR OC in IMPROVE network samples; providing complementary information to the organic functional group composition and organic aerosol mass estimated previously from the same set of sample spectra (Ruthenburg et al., 2014).

Development and implementation of a regression model for predicting recreational water quality in the Cuyahoga River, Cuyahoga Valley National Park, Ohio 2009-11

USGS Publications Warehouse

Brady, Amie M.G.; Plona, Meg B.

2012-01-01

The Cuyahoga River within Cuyahoga Valley National Park (CVNP) is at times impaired for recreational use due to elevated concentrations of Escherichia coli (E. coli), a fecal-indicator bacterium. During the recreational seasons of mid-May through September during 2009–11, samples were collected 4 days per week and analyzed for E. coli concentrations at two sites within CVNP. Other water-quality and environ-mental data, including turbidity, rainfall, and streamflow, were measured and (or) tabulated for analysis. Regression models developed to predict recreational water quality in the river were implemented during the recreational seasons of 2009–11 for one site within CVNP–Jaite. For the 2009 and 2010 seasons, the regression models were better at predicting exceedances of Ohio's single-sample standard for primary-contact recreation compared to the traditional method of using the previous day's E. coli concentration. During 2009, the regression model was based on data collected during 2005 through 2008, excluding available 2004 data. The resulting model for 2009 did not perform as well as expected (based on the calibration data set) and tended to overestimate concentrations (correct responses at 69 percent). During 2010, the regression model was based on data collected during 2004 through 2009, including all of the available data. The 2010 model performed well, correctly predicting 89 percent of the samples above or below the single-sample standard, even though the predictions tended to be lower than actual sample concentrations. During 2011, the regression model was based on data collected during 2004 through 2010 and tended to overestimate concentrations. The 2011 model did not perform as well as the traditional method or as expected, based on the calibration dataset (correct responses at 56 percent). At a second site—Lock 29, approximately 5 river miles upstream from Jaite, a regression model based on data collected at the site during the recreational seasons of 2008–10 also did not perform as well as the traditional method or as well as expected (correct responses at 60 percent). Above normal precipitation in the region and a delayed start to the 2011 sampling season (sampling began mid-June) may have affected how well the 2011 models performed. With these new data, however, updated regression models may be better able to predict recreational water quality conditions due to the increased amount of diverse water quality conditions included in the calibration data. Daily recreational water-quality predictions for Jaite were made available on the Ohio Nowcast Web site at www.ohionowcast.info. Other public outreach included signage at trailheads in the park, articles in the park's quarterly-published schedule of events and volunteer newsletters. A U.S. Geological Survey Fact Sheet was also published to bring attention to water-quality issues in the park.

Beyond discrimination: A comparison of calibration methods and clinical usefulness of predictive models of readmission risk.

PubMed

Walsh, Colin G; Sharman, Kavya; Hripcsak, George

2017-12-01

Prior to implementing predictive models in novel settings, analyses of calibration and clinical usefulness remain as important as discrimination, but they are not frequently discussed. Calibration is a model's reflection of actual outcome prevalence in its predictions. Clinical usefulness refers to the utilities, costs, and harms of using a predictive model in practice. A decision analytic approach to calibrating and selecting an optimal intervention threshold may help maximize the impact of readmission risk and other preventive interventions. To select a pragmatic means of calibrating predictive models that requires a minimum amount of validation data and that performs well in practice. To evaluate the impact of miscalibration on utility and cost via clinical usefulness analyses. Observational, retrospective cohort study with electronic health record data from 120,000 inpatient admissions at an urban, academic center in Manhattan. The primary outcome was thirty-day readmission for three causes: all-cause, congestive heart failure, and chronic coronary atherosclerotic disease. Predictive modeling was performed via L1-regularized logistic regression. Calibration methods were compared including Platt Scaling, Logistic Calibration, and Prevalence Adjustment. Performance of predictive modeling and calibration was assessed via discrimination (c-statistic), calibration (Spiegelhalter Z-statistic, Root Mean Square Error [RMSE] of binned predictions, Sanders and Murphy Resolutions of the Brier Score, Calibration Slope and Intercept), and clinical usefulness (utility terms represented as costs). The amount of validation data necessary to apply each calibration algorithm was also assessed. C-statistics by diagnosis ranged from 0.7 for all-cause readmission to 0.86 (0.78-0.93) for congestive heart failure. Logistic Calibration and Platt Scaling performed best and this difference required analyzing multiple metrics of calibration simultaneously, in particular Calibration Slopes and Intercepts. Clinical usefulness analyses provided optimal risk thresholds, which varied by reason for readmission, outcome prevalence, and calibration algorithm. Utility analyses also suggested maximum tolerable intervention costs, e.g., $1720 for all-cause readmissions based on a published cost of readmission of $11,862. Choice of calibration method depends on availability of validation data and on performance. Improperly calibrated models may contribute to higher costs of intervention as measured via clinical usefulness. Decision-makers must understand underlying utilities or costs inherent in the use-case at hand to assess usefulness and will obtain the optimal risk threshold to trigger intervention with intervention cost limits as a result. Copyright © 2017 Elsevier Inc. All rights reserved.

Five-Hole Flow Angle Probe Calibration for the NASA Glenn Icing Research Tunnel

NASA Technical Reports Server (NTRS)

Gonsalez, Jose C.; Arrington, E. Allen

1999-01-01

A spring 1997 test section calibration program is scheduled for the NASA Glenn Research Center Icing Research Tunnel following the installation of new water injecting spray bars. A set of new five-hole flow angle pressure probes was fabricated to properly calibrate the test section for total pressure, static pressure, and flow angle. The probes have nine pressure ports: five total pressure ports on a hemispherical head and four static pressure ports located 14.7 diameters downstream of the head. The probes were calibrated in the NASA Glenn 3.5-in.-diameter free-jet calibration facility. After completing calibration data acquisition for two probes, two data prediction models were evaluated. Prediction errors from a linear discrete model proved to be no worse than those from a full third-order multiple regression model. The linear discrete model only required calibration data acquisition according to an abridged test matrix, thus saving considerable time and financial resources over the multiple regression model that required calibration data acquisition according to a more extensive test matrix. Uncertainties in calibration coefficients and predicted values of flow angle, total pressure, static pressure. Mach number. and velocity were examined. These uncertainties consider the instrumentation that will be available in the Icing Research Tunnel for future test section calibration testing.

Calibration of the dietary data obtained from the Brazilian center of the Natural History of HPV Infection in Men study: the HIM Study.

PubMed

Teixeira, Juliana Araujo; Baggio, Maria Luiza; Fisberg, Regina Mara; Marchioni, Dirce Maria Lobo

2010-12-01

The objective of this study was to estimate the regressions calibration for the dietary data that were measured using the quantitative food frequency questionnaire (QFFQ) in the Natural History of HPV Infection in Men: the HIM Study in Brazil. A sample of 98 individuals from the HIM study answered one QFFQ and three 24-hour recalls (24HR) at interviews. The calibration was performed using linear regression analysis in which the 24HR was the dependent variable and the QFFQ was the independent variable. Age, body mass index, physical activity, income and schooling were used as adjustment variables in the models. The geometric means between the 24HR and the calibration-corrected QFFQ were statistically equal. The dispersion graphs between the instruments demonstrate increased correlation after making the correction, although there is greater dispersion of the points with worse explanatory power of the models. Identification of the regressions calibration for the dietary data of the HIM study will make it possible to estimate the effect of the diet on HPV infection, corrected for the measurement error of the QFFQ.

Analysis of Sting Balance Calibration Data Using Optimized Regression Models

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert; Bader, Jon B.

2009-01-01

Calibration data of a wind tunnel sting balance was processed using a search algorithm that identifies an optimized regression model for the data analysis. The selected sting balance had two moment gages that were mounted forward and aft of the balance moment center. The difference and the sum of the two gage outputs were fitted in the least squares sense using the normal force and the pitching moment at the balance moment center as independent variables. The regression model search algorithm predicted that the difference of the gage outputs should be modeled using the intercept and the normal force. The sum of the two gage outputs, on the other hand, should be modeled using the intercept, the pitching moment, and the square of the pitching moment. Equations of the deflection of a cantilever beam are used to show that the search algorithm s two recommended math models can also be obtained after performing a rigorous theoretical analysis of the deflection of the sting balance under load. The analysis of the sting balance calibration data set is a rare example of a situation when regression models of balance calibration data can directly be derived from first principles of physics and engineering. In addition, it is interesting to see that the search algorithm recommended the same regression models for the data analysis using only a set of statistical quality metrics.

TSS concentration in sewers estimated from turbidity measurements by means of linear regression accounting for uncertainties in both variables.

PubMed

Bertrand-Krajewski, J L

2004-01-01

In order to replace traditional sampling and analysis techniques, turbidimeters can be used to estimate TSS concentration in sewers, by means of sensor and site specific empirical equations established by linear regression of on-site turbidity Tvalues with TSS concentrations C measured in corresponding samples. As the ordinary least-squares method is not able to account for measurement uncertainties in both T and C variables, an appropriate regression method is used to solve this difficulty and to evaluate correctly the uncertainty in TSS concentrations estimated from measured turbidity. The regression method is described, including detailed calculations of variances and covariance in the regression parameters. An example of application is given for a calibrated turbidimeter used in a combined sewer system, with data collected during three dry weather days. In order to show how the established regression could be used, an independent 24 hours long dry weather turbidity data series recorded at 2 min time interval is used, transformed into estimated TSS concentrations, and compared to TSS concentrations measured in samples. The comparison appears as satisfactory and suggests that turbidity measurements could replace traditional samples. Further developments, including wet weather periods and other types of sensors, are suggested.

Using multiple calibration sets to improve the quantitative accuracy of partial least squares (PLS) regression on open-path fourier transform infrared (OP/FT-IR) spectra of ammonia over wide concentration ranges

USDA-ARS?s Scientific Manuscript database

A technique of using multiple calibration sets in partial least squares regression (PLS) was proposed to improve the quantitative determination of ammonia from open-path Fourier transform infrared spectra. The spectra were measured near animal farms, and the path-integrated concentration of ammonia...

Feasibility of using near infrared spectroscopy to detect and quantify an adulterant in high quality sandalwood oil.

PubMed

Kuriakose, Saji; Joe, I Hubert

2013-11-01

Determination of the authenticity of essential oils has become more significant, in recent years, following some illegal adulteration and contamination scandals. The present investigative study focuses on the application of near infrared spectroscopy to detect sample authenticity and quantify economic adulteration of sandalwood oils. Several data pre-treatments are investigated for calibration and prediction using partial least square regression (PLSR). The quantitative data analysis is done using a new spectral approach - full spectrum or sequential spectrum. The optimum number of PLS components is obtained according to the lowest root mean square error of calibration (RMSEC=0.00009% v/v). The lowest root mean square error of prediction (RMSEP=0.00016% v/v) in the test set and the highest coefficient of determination (R(2)=0.99989) are used as the evaluation tools for the best model. A nonlinear method, locally weighted regression (LWR), is added to extract nonlinear information and to compare with the linear PLSR model. Copyright © 2013 Elsevier B.V. All rights reserved.

Feasibility of using near infrared spectroscopy to detect and quantify an adulterant in high quality sandalwood oil

NASA Astrophysics Data System (ADS)

Kuriakose, Saji; Joe, I. Hubert

2013-11-01

Determination of the authenticity of essential oils has become more significant, in recent years, following some illegal adulteration and contamination scandals. The present investigative study focuses on the application of near infrared spectroscopy to detect sample authenticity and quantify economic adulteration of sandalwood oils. Several data pre-treatments are investigated for calibration and prediction using partial least square regression (PLSR). The quantitative data analysis is done using a new spectral approach - full spectrum or sequential spectrum. The optimum number of PLS components is obtained according to the lowest root mean square error of calibration (RMSEC = 0.00009% v/v). The lowest root mean square error of prediction (RMSEP = 0.00016% v/v) in the test set and the highest coefficient of determination (R2 = 0.99989) are used as the evaluation tools for the best model. A nonlinear method, locally weighted regression (LWR), is added to extract nonlinear information and to compare with the linear PLSR model.

Calibration strategies for the direct determination of Ca, K, and Mg in commercial samples of powdered milk and solid dietary supplements using laser-induced breakdown spectroscopy (LIBS).

PubMed

Dos Santos Augusto, Amanda; Barsanelli, Paulo Lopes; Pereira, Fabiola Manhas Verbi; Pereira-Filho, Edenir Rodrigues

2017-04-01

This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered milk and solid dietary supplements. The following two calibration strategies were applied: (i) use of the samples to calculate calibration models (milk) and (ii) use of sample mixtures (supplements) to obtain a calibration curve. In both cases, reference values obtained from inductively coupled plasma optical emission spectroscopy (ICP OES) after acid digestion were used. The emission line selection from LIBS spectra was accomplished by analysing the regression coefficients of partial least squares (PLS) regression models, and wavelengths of 534.947, 766.490 and 285.213nm were chosen for Ca, K and Mg, respectively. In the case of the determination of Ca in supplements, it was necessary to perform a dilution (10-fold) of the standards and samples to minimize matrix interference. The average accuracy for powdered milk ranged from 60% to 168% for Ca, 77% to 152% for K and 76% to 131% for Mg. In the case of dietary supplements, standard error of prediction (SEP) varied from 295 (Mg) to 3782mgkg -1 (Ca). The proposed method presented an analytical frequency of around 60 samples per hour and the step of sample manipulation was drastically reduced, with no generation of toxic chemical residues. Copyright © 2017 Elsevier Ltd. All rights reserved.

Estimation Methods for Non-Homogeneous Regression - Minimum CRPS vs Maximum Likelihood

NASA Astrophysics Data System (ADS)

Gebetsberger, Manuel; Messner, Jakob W.; Mayr, Georg J.; Zeileis, Achim

2017-04-01

Non-homogeneous regression models are widely used to statistically post-process numerical weather prediction models. Such regression models correct for errors in mean and variance and are capable to forecast a full probability distribution. In order to estimate the corresponding regression coefficients, CRPS minimization is performed in many meteorological post-processing studies since the last decade. In contrast to maximum likelihood estimation, CRPS minimization is claimed to yield more calibrated forecasts. Theoretically, both scoring rules used as an optimization score should be able to locate a similar and unknown optimum. Discrepancies might result from a wrong distributional assumption of the observed quantity. To address this theoretical concept, this study compares maximum likelihood and minimum CRPS estimation for different distributional assumptions. First, a synthetic case study shows that, for an appropriate distributional assumption, both estimation methods yield to similar regression coefficients. The log-likelihood estimator is slightly more efficient. A real world case study for surface temperature forecasts at different sites in Europe confirms these results but shows that surface temperature does not always follow the classical assumption of a Gaussian distribution. KEYWORDS: ensemble post-processing, maximum likelihood estimation, CRPS minimization, probabilistic temperature forecasting, distributional regression models

Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry

NASA Astrophysics Data System (ADS)

Braga, Jez Willian Batista; Trevizan, Lilian Cristina; Nunes, Lidiane Cristina; Rufini, Iolanda Aparecida; Santos, Dário, Jr.; Krug, Francisco José

2010-01-01

The application of laser induced breakdown spectrometry (LIBS) aiming the direct analysis of plant materials is a great challenge that still needs efforts for its development and validation. In this way, a series of experimental approaches has been carried out in order to show that LIBS can be used as an alternative method to wet acid digestions based methods for analysis of agricultural and environmental samples. The large amount of information provided by LIBS spectra for these complex samples increases the difficulties for selecting the most appropriated wavelengths for each analyte. Some applications have suggested that improvements in both accuracy and precision can be achieved by the application of multivariate calibration in LIBS data when compared to the univariate regression developed with line emission intensities. In the present work, the performance of univariate and multivariate calibration, based on partial least squares regression (PLSR), was compared for analysis of pellets of plant materials made from an appropriate mixture of cryogenically ground samples with cellulose as the binding agent. The development of a specific PLSR model for each analyte and the selection of spectral regions containing only lines of the analyte of interest were the best conditions for the analysis. In this particular application, these models showed a similar performance, but PLSR seemed to be more robust due to a lower occurrence of outliers in comparison to the univariate method. Data suggests that efforts dealing with sample presentation and fitness of standards for LIBS analysis must be done in order to fulfill the boundary conditions for matrix independent development and validation.

Globally efficient non-parametric inference of average treatment effects by empirical balancing calibration weighting

PubMed Central

Chan, Kwun Chuen Gary; Yam, Sheung Chi Phillip; Zhang, Zheng

2015-01-01

Summary The estimation of average treatment effects based on observational data is extremely important in practice and has been studied by generations of statisticians under different frameworks. Existing globally efficient estimators require non-parametric estimation of a propensity score function, an outcome regression function or both, but their performance can be poor in practical sample sizes. Without explicitly estimating either functions, we consider a wide class calibration weights constructed to attain an exact three-way balance of the moments of observed covariates among the treated, the control, and the combined group. The wide class includes exponential tilting, empirical likelihood and generalized regression as important special cases, and extends survey calibration estimators to different statistical problems and with important distinctions. Global semiparametric efficiency for the estimation of average treatment effects is established for this general class of calibration estimators. The results show that efficiency can be achieved by solely balancing the covariate distributions without resorting to direct estimation of propensity score or outcome regression function. We also propose a consistent estimator for the efficient asymptotic variance, which does not involve additional functional estimation of either the propensity score or the outcome regression functions. The proposed variance estimator outperforms existing estimators that require a direct approximation of the efficient influence function. PMID:27346982

Globally efficient non-parametric inference of average treatment effects by empirical balancing calibration weighting.

PubMed

Chan, Kwun Chuen Gary; Yam, Sheung Chi Phillip; Zhang, Zheng

2016-06-01

The estimation of average treatment effects based on observational data is extremely important in practice and has been studied by generations of statisticians under different frameworks. Existing globally efficient estimators require non-parametric estimation of a propensity score function, an outcome regression function or both, but their performance can be poor in practical sample sizes. Without explicitly estimating either functions, we consider a wide class calibration weights constructed to attain an exact three-way balance of the moments of observed covariates among the treated, the control, and the combined group. The wide class includes exponential tilting, empirical likelihood and generalized regression as important special cases, and extends survey calibration estimators to different statistical problems and with important distinctions. Global semiparametric efficiency for the estimation of average treatment effects is established for this general class of calibration estimators. The results show that efficiency can be achieved by solely balancing the covariate distributions without resorting to direct estimation of propensity score or outcome regression function. We also propose a consistent estimator for the efficient asymptotic variance, which does not involve additional functional estimation of either the propensity score or the outcome regression functions. The proposed variance estimator outperforms existing estimators that require a direct approximation of the efficient influence function.

Least median of squares and iteratively re-weighted least squares as robust linear regression methods for fluorimetric determination of α-lipoic acid in capsules in ideal and non-ideal cases of linearity.

PubMed

Korany, Mohamed A; Gazy, Azza A; Khamis, Essam F; Ragab, Marwa A A; Kamal, Miranda F

2018-06-01

This study outlines two robust regression approaches, namely least median of squares (LMS) and iteratively re-weighted least squares (IRLS) to investigate their application in instrument analysis of nutraceuticals (that is, fluorescence quenching of merbromin reagent upon lipoic acid addition). These robust regression methods were used to calculate calibration data from the fluorescence quenching reaction (∆F and F-ratio) under ideal or non-ideal linearity conditions. For each condition, data were treated using three regression fittings: Ordinary Least Squares (OLS), LMS and IRLS. Assessment of linearity, limits of detection (LOD) and quantitation (LOQ), accuracy and precision were carefully studied for each condition. LMS and IRLS regression line fittings showed significant improvement in correlation coefficients and all regression parameters for both methods and both conditions. In the ideal linearity condition, the intercept and slope changed insignificantly, but a dramatic change was observed for the non-ideal condition and linearity intercept. Under both linearity conditions, LOD and LOQ values after the robust regression line fitting of data were lower than those obtained before data treatment. The results obtained after statistical treatment indicated that the linearity ranges for drug determination could be expanded to lower limits of quantitation by enhancing the regression equation parameters after data treatment. Analysis results for lipoic acid in capsules, using both fluorimetric methods, treated by parametric OLS and after treatment by robust LMS and IRLS were compared for both linearity conditions. Copyright © 2018 John Wiley & Sons, Ltd.

Adulteration of diesel/biodiesel blends by vegetable oil as determined by Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy.

PubMed

Oliveira, Flavia C C; Brandão, Christian R R; Ramalho, Hugo F; da Costa, Leonardo A F; Suarez, Paulo A Z; Rubim, Joel C

2007-03-28

In this work it has been shown that the routine ASTM methods (ASTM 4052, ASTM D 445, ASTM D 4737, ASTM D 93, and ASTM D 86) recommended by the ANP (the Brazilian National Agency for Petroleum, Natural Gas and Biofuels) to determine the quality of diesel/biodiesel blends are not suitable to prevent the adulteration of B2 or B5 blends with vegetable oils. Considering the previous and actual problems with fuel adulterations in Brazil, we have investigated the application of vibrational spectroscopy (Fourier transform (FT) near infrared spectrometry and FT-Raman) to identify adulterations of B2 and B5 blends with vegetable oils. Partial least square regression (PLS), principal component regression (PCR), and artificial neural network (ANN) calibration models were designed and their relative performances were evaluated by external validation using the F-test. The PCR, PLS, and ANN calibration models based on the Fourier transform (FT) near infrared spectrometry and FT-Raman spectroscopy were designed using 120 samples. Other 62 samples were used in the validation and external validation, for a total of 182 samples. The results have shown that among the designed calibration models, the ANN/FT-Raman presented the best accuracy (0.028%, w/w) for samples used in the external validation.

Detection of heavy metal Cd in polluted fresh leafy vegetables by laser-induced breakdown spectroscopy.

PubMed

Yao, Mingyin; Yang, Hui; Huang, Lin; Chen, Tianbing; Rao, Gangfu; Liu, Muhua

2017-05-10

In seeking a novel method with the ability of green analysis in monitoring toxic heavy metals residue in fresh leafy vegetables, laser-induced breakdown spectroscopy (LIBS) was applied to prove its capability in performing this work. The spectra of fresh vegetable samples polluted in the lab were collected by optimized LIBS experimental setup, and the reference concentrations of cadmium (Cd) from samples were obtained by conventional atomic absorption spectroscopy after wet digestion. The direct calibration employing intensity of single Cd line and Cd concentration exposed the weakness of this calibration method. Furthermore, the accuracy of linear calibration can be improved a little by triple Cd lines as characteristic variables, especially after the spectra were pretreated. However, it is not enough in predicting Cd in samples. Therefore, partial least-squares regression (PLSR) was utilized to enhance the robustness of quantitative analysis. The results of the PLSR model showed that the prediction accuracy of the Cd target can meet the requirement of determination in food safety. This investigation presented that LIBS is a promising and emerging method in analyzing toxic compositions in agricultural products, especially combined with suitable chemometrics.

A fast and direct spectrophotometric method for the simultaneous determination of methyl paraben and hydroquinone in cosmetic products using successive projections algorithm.

PubMed

Esteki, M; Nouroozi, S; Shahsavari, Z

2016-02-01

To develop a simple and efficient spectrophotometric technique combined with chemometrics for the simultaneous determination of methyl paraben (MP) and hydroquinone (HQ) in cosmetic products, and specifically, to: (i) evaluate the potential use of successive projections algorithm (SPA) to derivative spectrophotometric data in order to provide sufficient accuracy and model robustness and (ii) determine MP and HQ concentration in cosmetics without tedious pre-treatments such as derivatization or extraction techniques which are time-consuming and require hazardous solvents. The absorption spectra were measured in the wavelength range of 200-350 nm. Prior to performing chemometric models, the original and first-derivative absorption spectra of binary mixtures were used as calibration matrices. Variable selected by successive projections algorithm was used to obtain multiple linear regression (MLR) models based on a small subset of wavelengths. The number of wavelengths and the starting vector were optimized, and the comparison of the root mean square error of calibration (RMSEC) and cross-validation (RMSECV) was applied to select effective wavelengths with the least collinearity and redundancy. Principal component regression (PCR) and partial least squares (PLS) were also developed for comparison. The concentrations of the calibration matrix ranged from 0.1 to 20 μg mL(-1) for MP, and from 0.1 to 25 μg mL(-1) for HQ. The constructed models were tested on an external validation data set and finally cosmetic samples. The results indicated that successive projections algorithm-multiple linear regression (SPA-MLR), applied on the first-derivative spectra, achieved the optimal performance for two compounds when compared with the full-spectrum PCR and PLS. The root mean square error of prediction (RMSEP) was 0.083, 0.314 for MP and HQ, respectively. To verify the accuracy of the proposed method, a recovery study on real cosmetic samples was carried out with satisfactory results (84-112%). The proposed method, which is an environmentally friendly approach, using minimum amount of solvent, is a simple, fast and low-cost analysis method that can provide high accuracy and robust models. The suggested method does not need any complex extraction procedure which is time-consuming and requires hazardous solvents. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Analysis of Multivariate Experimental Data Using A Simplified Regression Model Search Algorithm

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert M.

2013-01-01

A new regression model search algorithm was developed that may be applied to both general multivariate experimental data sets and wind tunnel strain-gage balance calibration data. The algorithm is a simplified version of a more complex algorithm that was originally developed for the NASA Ames Balance Calibration Laboratory. The new algorithm performs regression model term reduction to prevent overfitting of data. It has the advantage that it needs only about one tenth of the original algorithm's CPU time for the completion of a regression model search. In addition, extensive testing showed that the prediction accuracy of math models obtained from the simplified algorithm is similar to the prediction accuracy of math models obtained from the original algorithm. The simplified algorithm, however, cannot guarantee that search constraints related to a set of statistical quality requirements are always satisfied in the optimized regression model. Therefore, the simplified algorithm is not intended to replace the original algorithm. Instead, it may be used to generate an alternate optimized regression model of experimental data whenever the application of the original search algorithm fails or requires too much CPU time. Data from a machine calibration of NASA's MK40 force balance is used to illustrate the application of the new search algorithm.

Quantitative Analysis of Single and Mix Food Antiseptics Basing on SERS Spectra with PLSR Method

NASA Astrophysics Data System (ADS)

Hou, Mengjing; Huang, Yu; Ma, Lingwei; Zhang, Zhengjun

2016-06-01

Usage and dosage of food antiseptics are very concerned due to their decisive influence in food safety. Surface-enhanced Raman scattering (SERS) effect was employed in this research to realize trace potassium sorbate (PS) and sodium benzoate (SB) detection. HfO2 ultrathin film-coated Ag NR array was fabricated as SERS substrate. Protected by HfO2 film, the SERS substrate possesses good acid resistance, which enables it to be applicable in acidic environment where PS and SB work. Regression relationship between SERS spectra of 0.3~10 mg/L PS solution and their concentration was calibrated by partial least squares regression (PLSR) method, and the concentration prediction performance was quite satisfactory. Furthermore, mixture solution of PS and SB was also quantitatively analyzed by PLSR method. Spectrum data of characteristic peak sections corresponding to PS and SB was used to establish the regression models of these two solutes, respectively, and their concentrations were determined accurately despite their characteristic peak sections overlapping. It is possible that the unique modeling process of PLSR method prevented the overlapped Raman signal from reducing the model accuracy.

Strategic development of a multivariate calibration model for the uniformity testing of tablets by transmission NIR analysis.

PubMed

Sasakura, D; Nakayama, K; Sakamoto, T; Chikuma, T

2015-05-01

The use of transmission near infrared spectroscopy (TNIRS) is of particular interest in the pharmaceutical industry. This is because TNIRS does not require sample preparation and can analyze several tens of tablet samples in an hour. It has the capability to measure all relevant information from a tablet, while still on the production line. However, TNIRS has a narrow spectrum range and overtone vibrations often overlap. To perform content uniformity testing in tablets by TNIRS, various properties in the tableting process need to be analyzed by a multivariate prediction model, such as a Partial Least Square Regression modeling. One issue is that typical approaches require several hundred reference samples to act as the basis of the method rather than a strategically designed method. This means that many batches are needed to prepare the reference samples; this requires time and is not cost effective. Our group investigated the concentration dependence of the calibration model with a strategic design. Consequently, we developed a more effective approach to the TNIRS calibration model than the existing methodology.

Rapid quantification of multi-components in alcohol precipitation liquid of Codonopsis Radix using near infrared spectroscopy (NIRS).

PubMed

Luo, Yu; Li, Wen-Long; Huang, Wen-Hua; Liu, Xue-Hua; Song, Yan-Gang; Qu, Hai-Bin

2017-05-01

A near infrared spectroscopy (NIRS) approach was established for quality control of the alcohol precipitation liquid in the manufacture of Codonopsis Radix. By applying NIRS with multivariate analysis, it was possible to build variation into the calibration sample set, and the Plackett-Burman design, Box-Behnken design, and a concentrating-diluting method were used to obtain the sample set covered with sufficient fluctuation of process parameters and extended concentration information. NIR data were calibrated to predict the four quality indicators using partial least squares regression (PLSR). In the four calibration models, the root mean squares errors of prediction (RMSEPs) were 1.22 μg/ml, 10.5 μg/ml, 1.43 μg/ml, and 0.433% for lobetyolin, total flavonoids, pigments, and total solid contents, respectively. The results indicated that multi-components quantification of the alcohol precipitation liquid of Codonopsis Radix could be achieved with an NIRS-based method, which offers a useful tool for real-time release testing (RTRT) of intermediates in the manufacture of Codonopsis Radix.

[Determination of fat, protein and DM in raw milk by portable short-wave near infrared spectrometer].

PubMed

Li, Xiao-yun; Wang, Jia-hua; Huang, Ya-wei; Han, Dong-hai

2011-03-01

Near infrared diffuse reflectance spectroscopy calibrations of fat, protein and DM in raw milk were studied with partial least-squares (PLS) regression using portable short-wave near infrared spectrometer. The results indicated that good calibrations of fat and DM were found, the correlation coefficients were all 0.98, the RMSEC were 0.187 and 0.217, RMSEP were 0.187 and 0.296, the RPDs were 5.02 and 3.20 respectively; the calibration of protein needed to be improved but can be used for practice, the correlation coefficient was 0.95, RMSEC was 0.105, RMSEP was 0.120, and RPD was 2.60. Furthermore, the measuring accuracy was improved by analyzing the correction relation of fat and DM in raw milk This study will probably provide a new on-site method for nondestructive and rapid measurement of milk.

Studies in Software Cost Model Behavior: Do We Really Understand Cost Model Performance?

NASA Technical Reports Server (NTRS)

Lum, Karen; Hihn, Jairus; Menzies, Tim

2006-01-01

While there exists extensive literature on software cost estimation techniques, industry practice continues to rely upon standard regression-based algorithms. These software effort models are typically calibrated or tuned to local conditions using local data. This paper cautions that current approaches to model calibration often produce sub-optimal models because of the large variance problem inherent in cost data and by including far more effort multipliers than the data supports. Building optimal models requires that a wider range of models be considered while correctly calibrating these models requires rejection rules that prune variables and records and use multiple criteria for evaluating model performance. The main contribution of this paper is to document a standard method that integrates formal model identification, estimation, and validation. It also documents what we call the large variance problem that is a leading cause of cost model brittleness or instability.

Updating a synchronous fluorescence spectroscopic virgin olive oil adulteration calibration to a new geographical region.

PubMed

Kunz, Matthew Ross; Ottaway, Joshua; Kalivas, John H; Georgiou, Constantinos A; Mousdis, George A

2011-02-23

Detecting and quantifying extra virgin olive adulteration is of great importance to the olive oil industry. Many spectroscopic methods in conjunction with multivariate analysis have been used to solve these issues. However, successes to date are limited as calibration models are built to a specific set of geographical regions, growing seasons, cultivars, and oil extraction methods (the composite primary condition). Samples from new geographical regions, growing seasons, etc. (secondary conditions) are not always correctly predicted by the primary model due to different olive oil and/or adulterant compositions stemming from secondary conditions not matching the primary conditions. Three Tikhonov regularization (TR) variants are used in this paper to allow adulterant (sunflower oil) concentration predictions in samples from geographical regions not part of the original primary calibration domain. Of the three TR variants, ridge regression with an additional 2-norm penalty provides the smallest validation sample prediction errors. Although the paper reports on using TR for model updating to predict adulterant oil concentration, the methods should also be applicable to updating models distinguishing adulterated samples from pure extra virgin olive oil. Additionally, the approaches are general and can be used with other spectroscopic methods and adulterants as well as with other agriculture products.

Partial Least Squares Regression Calibration of an Ultraviolet-Visible Spectrophotometer for Measurements of Chemical Oxygen Demand in Dye Wastewater

NASA Astrophysics Data System (ADS)

Mai, W.; Zhang, J.-F.; Zhao, X.-M.; Li, Z.; Xu, Z.-W.

2017-11-01

Wastewater from the dye industry is typically analyzed using a standard method for measurement of chemical oxygen demand (COD) or by a single-wavelength spectroscopic method. To overcome the disadvantages of these methods, ultraviolet-visible (UV-Vis) spectroscopy was combined with principal component regression (PCR) and partial least squares regression (PLSR) in this study. Unlike the standard method, this method does not require digestion of the samples for preparation. Experiments showed that the PLSR model offered high prediction performance for COD, with a mean relative error of about 5% for two dyes. This error is similar to that obtained with the standard method. In this study, the precision of the PLSR model decreased with the number of dye compounds present. It is likely that multiple models will be required in reality, and the complexity of a COD monitoring system would be greatly reduced if the PLSR model is used because it can include several dyes. UV-Vis spectroscopy with PLSR successfully enhanced the performance of COD prediction for dye wastewater and showed good potential for application in on-line water quality monitoring.

AN ASSESSMENT OF SUNSPOT NUMBER DATA COMPOSITES OVER 1845–2014

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lockwood, M.; Owens, M. J.; Barnard, L.

2016-06-10

New sunspot data composites, some of which are radically different in the character of their long-term variation, are evaluated over the interval 1845–2014. The method commonly used to calibrate historic sunspot data, relative to modern-day data, is “daisy-chaining,” whereby calibration is passed from one data subset to the neighboring one, usually using regressions of the data subsets for the intervals of their overlap. Recent studies have illustrated serious pitfalls in these regressions, and the resulting errors can be compounded by their repeated use as the data sequence is extended back in time. Hence, the recent composite data series by Usoskinmore » et al., R {sub UEA}, is a very important advance because it avoids regressions, daisy-chaining, and other common, but invalid, assumptions: this is achieved by comparing the statistics of “active-day” fractions to those for a single reference data set. We study six sunspot data series, including R {sub UEA} and the new “backbone” data series ( R {sub BB}, recently generated by Svalgaard and Schatten by employing both regression and daisy-chaining). We show that all six can be used with a continuity model to reproduce the main features of the open solar flux variation for 1845–2014, as reconstructed from geomagnetic activity data. However, some differences can be identified that are consistent with tests using a basket of other proxies for solar magnetic fields. Using data from a variety of sunspot observers, we illustrate problems with the method employed in generating R {sub BB} that cause it to increasingly overestimate sunspot numbers going back in time, and we recommend using R {sub UEA} because it employs more robust procedures that avoid such problems.« less

Ensuring the consistancy of Flow Direction Curve reconstructions: the 'quantile solidarity' approach

NASA Astrophysics Data System (ADS)

Poncelet, Carine; Andreassian, Vazken; Oudin, Ludovic

2015-04-01

Flow Duration Curves (FDCs) are a hydrologic tool describing the distribution of streamflows at a catchment outlet. FDCs are usually used for calibration of hydrological models, managing water quality and classifying catchments, among others. For gauged catchments, empirical FDCs can be computed from streamflow records. For ungauged catchments, on the other hand, FDCs cannot be obtained from streamflow records and must therefore be obtained in another manner, for example through reconstructions. Regression-based reconstructions are methods relying on the evaluation of quantiles separately from catchments' attributes (climatic or physical features).The advantage of this category of methods is that it is informative about the processes and it is non-parametric. However, the large number of parameters required can cause unwanted artifacts, typically reconstructions that do not always produce increasing quantiles. In this paper we propose a new approach named Quantile Solidarity (QS), which is applied under strict proxy-basin test conditions (Klemes, 1986) to a set of 600 French catchments. Half of the catchments are considered as gauged and used to calibrate the regression and compute residuals of the regression. The QS approach consists in a three-step regionalization scheme, which first links quantile values to physical descriptors, then reduces the number of regression parameters and finally exploits the spatial correlation of the residuals. The innovation is the utilisation of the parameters continuity across the quantiles to dramatically reduce the number of parameters. The second half of catchment is used as an independent validation set over which we show that the QS approach ensures strictly growing FDC reconstructions in ungauged conditions. Reference: V. KLEMEŠ (1986) Operational testing of hydrological simulation models, Hydrological Sciences Journal, 31:1, 13-24

Nondestructive prediction of the drug content of an aspirin suppository by near-infrared spectroscopy.

PubMed

Otsuka, Eri; Abe, Hiroyuki; Aburada, Masaki; Otsuka, Makoto

2010-07-01

A suppository dosage form has a rapid effect on therapeutics, because it dissolves in the rectum, is absorbed in the bloodstream, and passes the hepatic metabolism. However, the dosage form is unstable, because a suppository is made in a semisolid form, and so it is not easy to mix the bulk drug powder in the base. This article describes a nondestructive method of determining the drug content of suppositories using near-infrared spectrometry (NIR) combined with chemometrics. Suppositories (aspirin content: 1.8, 2.7, 4.5, 7.3, and 9.1%, w/w) were produced by mixing an aspirin bulk powder with hard fat at 50 degrees C and pouring the melt mixture into a plastic mold (2.25 mL). NIR spectra of 12 calibration and 12 validation sample sets were recorded 5 times. A total of 60 spectral data were used as a calibration set to establish a calibration model to predict drug content with a partial least-squares (PLS) regression analysis. NIR data of the suppository samples were divided into two wave number ranges, 4000-12500 cm(-1) (LR), and 5900-6300 cm(-1) (SR). Calibration models for the aspirin content of the suppositories were calculated based on LR and SR ranges of second-derivative NIR spectra using PLS. The models for LR and SR consisted of five and one principal components (PC), respectively. The plots of predicted values against actual values gave a straight line with regression coefficient constants of 0.9531 and 0.9749, respectively. The mean bias and mean accuracy of the calibration models were calculated based on the SR of variation data sets, and were lower than those of LR, respectively. Limiting the wave number of spectral data sets is useful to help understand the calibration model because of noise cancellation and to measure objective functions.

Ethnic Variability in Body Size, Proportions and Composition in Children Aged 5 to 11 Years: Is Ethnic-Specific Calibration of Bioelectrical Impedance Required?

PubMed Central

Lee, Simon; Bountziouka, Vassiliki; Lum, Sooky; Stocks, Janet; Bonner, Rachel; Naik, Mitesh; Fothergill, Helen; Wells, Jonathan C. K.

2014-01-01

Background Bioelectrical Impedance Analysis (BIA) has the potential to be used widely as a method of assessing body fatness and composition, both in clinical and community settings. BIA provides bioelectrical properties, such as whole-body impedance which ideally needs to be calibrated against a gold-standard method in order to provide accurate estimates of fat-free mass. UK studies in older children and adolescents have shown that, when used in multi-ethnic populations, calibration equations need to include ethnic-specific terms, but whether this holds true for younger children remains to be elucidated. The aims of this study were to examine ethnic differences in body size, proportions and composition in children aged 5 to 11 years, and to establish the extent to which such differences could influence BIA calibration. Methods In a multi-ethnic population of 2171 London primary school-children (47% boys; 34% White, 29% Black African/Caribbean, 25% South Asian, 12% Other) detailed anthropometric measurements were performed and ethnic differences in body size and proportion were assessed. Ethnic differences in fat-free mass, derived by deuterium dilution, were further evaluated in a subsample of the population (n = 698). Multiple linear regression models were used to calibrate BIA against deuterium dilution. Results In children <11 years of age, Black African/Caribbean children were significantly taller, heavier and had larger body size than children of other ethnicities. They also had larger waist and limb girths and relatively longer legs. Despite these differences, ethnic-specific terms did not contribute significantly to the BIA calibration equation (Fat-free mass = 1.12+0.71*(height2/impedance)+0.18*weight). Conclusion Although clear ethnic differences in body size, proportions and composition were evident in this population of young children aged 5 to 11 years, an ethnic-specific BIA calibration equation was not required. PMID:25478928

Exploring the calibration of a wind forecast ensemble for energy applications

NASA Astrophysics Data System (ADS)

Heppelmann, Tobias; Ben Bouallegue, Zied; Theis, Susanne

2015-04-01

In the German research project EWeLiNE, Deutscher Wetterdienst (DWD) and Fraunhofer Institute for Wind Energy and Energy System Technology (IWES) are collaborating with three German Transmission System Operators (TSO) in order to provide the TSOs with improved probabilistic power forecasts. Probabilistic power forecasts are derived from probabilistic weather forecasts, themselves derived from ensemble prediction systems (EPS). Since the considered raw ensemble wind forecasts suffer from underdispersiveness and bias, calibration methods are developed for the correction of the model bias and the ensemble spread bias. The overall aim is to improve the ensemble forecasts such that the uncertainty of the possible weather deployment is depicted by the ensemble spread from the first forecast hours. Additionally, the ensemble members after calibration should remain physically consistent scenarios. We focus on probabilistic hourly wind forecasts with horizon of 21 h delivered by the convection permitting high-resolution ensemble system COSMO-DE-EPS which has become operational in 2012 at DWD. The ensemble consists of 20 ensemble members driven by four different global models. The model area includes whole Germany and parts of Central Europe with a horizontal resolution of 2.8 km and a vertical resolution of 50 model levels. For verification we use wind mast measurements around 100 m height that corresponds to the hub height of wind energy plants that belong to wind farms within the model area. Calibration of the ensemble forecasts can be performed by different statistical methods applied to the raw ensemble output. Here, we explore local bivariate Ensemble Model Output Statistics at individual sites and quantile regression with different predictors. Applying different methods, we already show an improvement of ensemble wind forecasts from COSMO-DE-EPS for energy applications. In addition, an ensemble copula coupling approach transfers the time-dependencies of the raw ensemble to the calibrated ensemble. The calibrated wind forecasts are evaluated first with univariate probabilistic scores and additionally with diagnostics of wind ramps in order to assess the time-consistency of the calibrated ensemble members.

Extreme wind-wave modeling and analysis in the south Atlantic ocean

NASA Astrophysics Data System (ADS)

Campos, R. M.; Alves, J. H. G. M.; Guedes Soares, C.; Guimaraes, L. G.; Parente, C. E.

2018-04-01

A set of wave hindcasts is constructed using two different types of wind calibration, followed by an additional test retuning the input source term Sin in the wave model. The goal is to improve the simulation in extreme wave events in the South Atlantic Ocean without compromising average conditions. Wind fields are based on Climate Forecast System Reanalysis (CFSR/NCEP). The first wind calibration applies a simple linear regression model, with coefficients obtained from the comparison of CFSR against buoy data. The second is a method where deficiencies of the CFSR associated with severe sea state events are remedied, whereby "defective" winds are replaced with satellite data within cyclones. A total of six wind datasets forced WAVEWATCH-III and additional three tests with modified Sin in WAVEWATCH III lead to a total of nine wave hindcasts that are evaluated against satellite and buoy data for ambient and extreme conditions. The target variable considered is the significant wave height (Hs). The increase of sea-state severity shows a progressive increase of the hindcast underestimation which could be calculated as a function of percentiles. The wind calibration using a linear regression function shows similar results to the adjustments to Sin term (increase of βmax parameter) in WAVEWATCH-III - it effectively reduces the average bias of Hs but cannot avoid the increase of errors with percentiles. The use of blended scatterometer winds within cyclones could reduce the increasing wave hindcast errors mainly above the 93rd percentile and leads to a better representation of Hs at the peak of the storms. The combination of linear regression calibration of non-cyclonic winds with scatterometer winds within the cyclones generated a wave hindcast with small errors from calm to extreme conditions. This approach led to a reduction of the percentage error of Hs from 14% to less than 8% for extreme waves, while also improving the RMSE.

Comparison of three chemometrics methods for near-infrared spectra of glucose in the whole blood

NASA Astrophysics Data System (ADS)

Zhang, Hongyan; Ding, Dong; Li, Xin; Chen, Yu; Tang, Yuguo

2005-01-01

Principal Component Regression (PCR), Partial Least Square (PLS) and Artificial Neural Networks (ANN) methods are used in the analysis for the near infrared (NIR) spectra of glucose in the whole blood. The calibration model is built up in the spectrum band where there are the glucose has much more spectral absorption than the water, fat, and protein with these methods and the correlation coefficients of the model are showed in this paper. Comparing these results, a suitable method to analyze the glucose NIR spectrum in the whole blood is found.

Revision and proposed modification for a total maximum daily load model for Upper Klamath Lake, Oregon

USGS Publications Warehouse

Wherry, Susan A.; Wood, Tamara M.; Anderson, Chauncey W.

2015-01-01

Using the extended 1991–2010 external phosphorus loading dataset, the lake TMDL model was recalibrated following the same procedures outlined in the Phase 1 review. The version of the model selected for further development incorporated an updated sediment initial condition, a numerical solution method for the chlorophyll a model, changes to light and phosphorus factors limiting algal growth, and a new pH-model regression, which removed Julian day dependence in order to avoid discontinuities in pH at year boundaries. This updated lake TMDL model was recalibrated using the extended dataset in order to compare calibration parameters to those obtained from a calibration with the original 7.5-year dataset. The resulting algal settling velocity calibrated from the extended dataset was more than twice the value calibrated with the original dataset, and, because the calibrated values of algal settling velocity and recycle rate are related (more rapid settling required more rapid recycling), the recycling rate also was larger than that determined with the original dataset. These changes in calibration parameters highlight the uncertainty in critical rates in the Upper Klamath Lake TMDL model and argue for their direct measurement in future data collection to increase confidence in the model predictions.

Learning an Eddy Viscosity Model Using Shrinkage and Bayesian Calibration: A Jet-in-Crossflow Case Study

DOE PAGES

Ray, Jaideep; Lefantzi, Sophia; Arunajatesan, Srinivasan; ...

2017-09-07

In this paper, we demonstrate a statistical procedure for learning a high-order eddy viscosity model (EVM) from experimental data and using it to improve the predictive skill of a Reynolds-averaged Navier–Stokes (RANS) simulator. The method is tested in a three-dimensional (3D), transonic jet-in-crossflow (JIC) configuration. The process starts with a cubic eddy viscosity model (CEVM) developed for incompressible flows. It is fitted to limited experimental JIC data using shrinkage regression. The shrinkage process removes all the terms from the model, except an intercept, a linear term, and a quadratic one involving the square of the vorticity. The shrunk eddy viscositymore » model is implemented in an RANS simulator and calibrated, using vorticity measurements, to infer three parameters. The calibration is Bayesian and is solved using a Markov chain Monte Carlo (MCMC) method. A 3D probability density distribution for the inferred parameters is constructed, thus quantifying the uncertainty in the estimate. The phenomenal cost of using a 3D flow simulator inside an MCMC loop is mitigated by using surrogate models (“curve-fits”). A support vector machine classifier (SVMC) is used to impose our prior belief regarding parameter values, specifically to exclude nonphysical parameter combinations. The calibrated model is compared, in terms of its predictive skill, to simulations using uncalibrated linear and CEVMs. Finally, we find that the calibrated model, with one quadratic term, is more accurate than the uncalibrated simulator. The model is also checked at a flow condition at which the model was not calibrated.« less

Learning an Eddy Viscosity Model Using Shrinkage and Bayesian Calibration: A Jet-in-Crossflow Case Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ray, Jaideep; Lefantzi, Sophia; Arunajatesan, Srinivasan

In this paper, we demonstrate a statistical procedure for learning a high-order eddy viscosity model (EVM) from experimental data and using it to improve the predictive skill of a Reynolds-averaged Navier–Stokes (RANS) simulator. The method is tested in a three-dimensional (3D), transonic jet-in-crossflow (JIC) configuration. The process starts with a cubic eddy viscosity model (CEVM) developed for incompressible flows. It is fitted to limited experimental JIC data using shrinkage regression. The shrinkage process removes all the terms from the model, except an intercept, a linear term, and a quadratic one involving the square of the vorticity. The shrunk eddy viscositymore » model is implemented in an RANS simulator and calibrated, using vorticity measurements, to infer three parameters. The calibration is Bayesian and is solved using a Markov chain Monte Carlo (MCMC) method. A 3D probability density distribution for the inferred parameters is constructed, thus quantifying the uncertainty in the estimate. The phenomenal cost of using a 3D flow simulator inside an MCMC loop is mitigated by using surrogate models (“curve-fits”). A support vector machine classifier (SVMC) is used to impose our prior belief regarding parameter values, specifically to exclude nonphysical parameter combinations. The calibrated model is compared, in terms of its predictive skill, to simulations using uncalibrated linear and CEVMs. Finally, we find that the calibrated model, with one quadratic term, is more accurate than the uncalibrated simulator. The model is also checked at a flow condition at which the model was not calibrated.« less

Development of a near-infrared spectroscopy method (NIRS) for fast analysis of total, indolic, aliphatic and individual glucosinolates in new bred open pollinating genotypes of broccoli (Brassica oleracea convar. botrytis var. italica).

PubMed

Sahamishirazi, Samira; Zikeli, Sabine; Fleck, Michael; Claupein, Wilhelm; Graeff-Hoenninger, Simone

2017-10-01

This study describes the development of near-infrared spectroscopy (NIRS) calibration to determine individual and total glucosinolates (GSLs) content of 12 new-bred open-pollinating genotypes of broccoli (Brassica oleracea convar. botrytis var. italica). Six individual GSLs were identified using high-performance-liquid chromatography (HPLC). The NIRS calibration was established based on modified partial least squares regression with reference values of HPLC. The calibration was analyzed using coefficient of determination in prediction (R 2 ) and ratio of preference of determination (RPD). Large variation occurred in the calibrations, R 2 and RPD due to the variability of the samples. Derived calibrations for total-GSLs, aliphatic-GSLs, glucoraphanin and 4-methoxyglucobrassicin were quantitative with a high accuracy (RPD=1.36, 1.65, 1.63, 1.11) while, for indole-GSLs, glucosinigrin, glucoiberin, glucobrassicin and 1-methoxyglucobrassicin were more qualitative (RPD=0.95, 0.62, 0.67, 0.81, 0.56). Overall, the results indicated NIRS has a good potential to determine different GSLs in a large sample pool of broccoli quantitatively and qualitatively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ratio manipulating spectrophotometry versus chemometry as stability indicating methods for cefquinome sulfate determination

NASA Astrophysics Data System (ADS)

Yehia, Ali M.; Arafa, Reham M.; Abbas, Samah S.; Amer, Sawsan M.

2016-01-01

Spectral resolution of cefquinome sulfate (CFQ) in the presence of its degradation products was studied. Three selective, accurate and rapid spectrophotometric methods were performed for the determination of CFQ in the presence of either its hydrolytic, oxidative or photo-degradation products. The proposed ratio difference, derivative ratio and mean centering are ratio manipulating spectrophotometric methods that were satisfactorily applied for selective determination of CFQ within linear range of 5.0-40.0 μg mL- 1. Concentration Residuals Augmented Classical Least Squares was applied and evaluated for the determination of the cited drug in the presence of its all degradation products. Traditional Partial Least Squares regression was also applied and benchmarked against the proposed advanced multivariate calibration. Experimentally designed 25 synthetic mixtures of three factors at five levels were used to calibrate and validate the multivariate models. Advanced chemometrics succeeded in quantitative and qualitative analyses of CFQ along with its hydrolytic, oxidative and photo-degradation products. The proposed methods were applied successfully for different pharmaceutical formulations analyses. These developed methods were simple and cost-effective compared with the manufacturer's RP-HPLC method.

A simplified approach to the pooled analysis of calibration of clinical prediction rules for systematic reviews of validation studies

PubMed Central

Dimitrov, Borislav D; Motterlini, Nicola; Fahey, Tom

2015-01-01

Objective Estimating calibration performance of clinical prediction rules (CPRs) in systematic reviews of validation studies is not possible when predicted values are neither published nor accessible or sufficient or no individual participant or patient data are available. Our aims were to describe a simplified approach for outcomes prediction and calibration assessment and evaluate its functionality and validity. Study design and methods: Methodological study of systematic reviews of validation studies of CPRs: a) ABCD2 rule for prediction of 7 day stroke; and b) CRB-65 rule for prediction of 30 day mortality. Predicted outcomes in a sample validation study were computed by CPR distribution patterns (“derivation model”). As confirmation, a logistic regression model (with derivation study coefficients) was applied to CPR-based dummy variables in the validation study. Meta-analysis of validation studies provided pooled estimates of “predicted:observed” risk ratios (RRs), 95% confidence intervals (CIs), and indexes of heterogeneity (I2) on forest plots (fixed and random effects models), with and without adjustment of intercepts. The above approach was also applied to the CRB-65 rule. Results Our simplified method, applied to ABCD2 rule in three risk strata (low, 0–3; intermediate, 4–5; high, 6–7 points), indicated that predictions are identical to those computed by univariate, CPR-based logistic regression model. Discrimination was good (c-statistics =0.61–0.82), however, calibration in some studies was low. In such cases with miscalibration, the under-prediction (RRs =0.73–0.91, 95% CIs 0.41–1.48) could be further corrected by intercept adjustment to account for incidence differences. An improvement of both heterogeneities and P-values (Hosmer-Lemeshow goodness-of-fit test) was observed. Better calibration and improved pooled RRs (0.90–1.06), with narrower 95% CIs (0.57–1.41) were achieved. Conclusion Our results have an immediate clinical implication in situations when predicted outcomes in CPR validation studies are lacking or deficient by describing how such predictions can be obtained by everyone using the derivation study alone, without any need for highly specialized knowledge or sophisticated statistics. PMID:25931829

Simulation-extrapolation method to address errors in atomic bomb survivor dosimetry on solid cancer and leukaemia mortality risk estimates, 1950-2003.

PubMed

Allodji, Rodrigue S; Schwartz, Boris; Diallo, Ibrahima; Agbovon, Césaire; Laurier, Dominique; de Vathaire, Florent

2015-08-01

Analyses of the Life Span Study (LSS) of Japanese atomic bombing survivors have routinely incorporated corrections for additive classical measurement errors using regression calibration. Recently, several studies reported that the efficiency of the simulation-extrapolation method (SIMEX) is slightly more accurate than the simple regression calibration method (RCAL). In the present paper, the SIMEX and RCAL methods have been used to address errors in atomic bomb survivor dosimetry on solid cancer and leukaemia mortality risk estimates. For instance, it is shown that using the SIMEX method, the ERR/Gy is increased by an amount of about 29 % for all solid cancer deaths using a linear model compared to the RCAL method, and the corrected EAR 10(-4) person-years at 1 Gy (the linear terms) is decreased by about 8 %, while the corrected quadratic term (EAR 10(-4) person-years/Gy(2)) is increased by about 65 % for leukaemia deaths based on a linear-quadratic model. The results with SIMEX method are slightly higher than published values. The observed differences were probably due to the fact that with the RCAL method the dosimetric data were partially corrected, while all doses were considered with the SIMEX method. Therefore, one should be careful when comparing the estimated risks and it may be useful to use several correction techniques in order to obtain a range of corrected estimates, rather than to rely on a single technique. This work will enable to improve the risk estimates derived from LSS data, and help to make more reliable the development of radiation protection standards.

Noninvasive and fast measurement of blood glucose in vivo by near infrared (NIR) spectroscopy

NASA Astrophysics Data System (ADS)

Jintao, Xue; Liming, Ye; Yufei, Liu; Chunyan, Li; Han, Chen

2017-05-01

This research was to develop a method for noninvasive and fast blood glucose assay in vivo. Near-infrared (NIR) spectroscopy, a more promising technique compared to other methods, was investigated in rats with diabetes and normal rats. Calibration models are generated by two different multivariate strategies: partial least squares (PLS) as linear regression method and artificial neural networks (ANN) as non-linear regression method. The PLS model was optimized individually by considering spectral range, spectral pretreatment methods and number of model factors, while the ANN model was studied individually by selecting spectral pretreatment methods, parameters of network topology, number of hidden neurons, and times of epoch. The results of the validation showed the two models were robust, accurate and repeatable. Compared to the ANN model, the performance of the PLS model was much better, with lower root mean square error of validation (RMSEP) of 0.419 and higher correlation coefficients (R) of 96.22%.

Variable selection in near-infrared spectroscopy: benchmarking of feature selection methods on biodiesel data.

PubMed

Balabin, Roman M; Smirnov, Sergey V

2011-04-29

During the past several years, near-infrared (near-IR/NIR) spectroscopy has increasingly been adopted as an analytical tool in various fields from petroleum to biomedical sectors. The NIR spectrum (above 4000 cm(-1)) of a sample is typically measured by modern instruments at a few hundred of wavelengths. Recently, considerable effort has been directed towards developing procedures to identify variables (wavelengths) that contribute useful information. Variable selection (VS) or feature selection, also called frequency selection or wavelength selection, is a critical step in data analysis for vibrational spectroscopy (infrared, Raman, or NIRS). In this paper, we compare the performance of 16 different feature selection methods for the prediction of properties of biodiesel fuel, including density, viscosity, methanol content, and water concentration. The feature selection algorithms tested include stepwise multiple linear regression (MLR-step), interval partial least squares regression (iPLS), backward iPLS (BiPLS), forward iPLS (FiPLS), moving window partial least squares regression (MWPLS), (modified) changeable size moving window partial least squares (CSMWPLS/MCSMWPLSR), searching combination moving window partial least squares (SCMWPLS), successive projections algorithm (SPA), uninformative variable elimination (UVE, including UVE-SPA), simulated annealing (SA), back-propagation artificial neural networks (BP-ANN), Kohonen artificial neural network (K-ANN), and genetic algorithms (GAs, including GA-iPLS). Two linear techniques for calibration model building, namely multiple linear regression (MLR) and partial least squares regression/projection to latent structures (PLS/PLSR), are used for the evaluation of biofuel properties. A comparison with a non-linear calibration model, artificial neural networks (ANN-MLP), is also provided. Discussion of gasoline, ethanol-gasoline (bioethanol), and diesel fuel data is presented. The results of other spectroscopic techniques application, such as Raman, ultraviolet-visible (UV-vis), or nuclear magnetic resonance (NMR) spectroscopies, can be greatly improved by an appropriate feature selection choice. Copyright © 2011 Elsevier B.V. All rights reserved.

Performance of the score systems Acute Physiology and Chronic Health Evaluation II and III at an interdisciplinary intensive care unit, after customization

PubMed Central

Markgraf, Rainer; Deutschinoff, Gerd; Pientka, Ludger; Scholten, Theo; Lorenz, Cristoph

2001-01-01

Background: Mortality predictions calculated using scoring scales are often not accurate in populations other than those in which the scales were developed because of differences in case-mix. The present study investigates the effect of first-level customization, using a logistic regression technique, on discrimination and calibration of the Acute Physiology and Chronic Health Evaluation (APACHE) II and III scales. Method: Probabilities of hospital death for patients were estimated by applying APACHE II and III and comparing these with observed outcomes. Using the split sample technique, a customized model to predict outcome was developed by logistic regression. The overall goodness-of-fit of the original and the customized models was assessed. Results: Of 3383 consecutive intensive care unit (ICU) admissions over 3 years, 2795 patients could be analyzed, and were split randomly into development and validation samples. The discriminative powers of APACHE II and III were unchanged by customization (areas under the receiver operating characteristic [ROC] curve 0.82 and 0.85, respectively). Hosmer-Lemeshow goodness-of-fit tests showed good calibration for APACHE II, but insufficient calibration for APACHE III. Customization improved calibration for both models, with a good fit for APACHE III as well. However, fit was different for various subgroups. Conclusions: The overall goodness-of-fit of APACHE III mortality prediction was improved significantly by customization, but uniformity of fit in different subgroups was not achieved. Therefore, application of the customized model provides no advantage, because differences in case-mix still limit comparisons of quality of care. PMID:11178223

Calibration and validation of wearable monitors.

PubMed

Bassett, David R; Rowlands, Alex; Trost, Stewart G

2012-01-01

Wearable monitors are increasingly being used to objectively monitor physical activity in research studies within the field of exercise science. Calibration and validation of these devices are vital to obtaining accurate data. This article is aimed primarily at the physical activity measurement specialist, although the end user who is conducting studies with these devices also may benefit from knowing about this topic. Initially, wearable physical activity monitors should undergo unit calibration to ensure interinstrument reliability. The next step is to simultaneously collect both raw signal data (e.g., acceleration) from the wearable monitors and rates of energy expenditure, so that algorithms can be developed to convert the direct signals into energy expenditure. This process should use multiple wearable monitors and a large and diverse subject group and should include a wide range of physical activities commonly performed in daily life (from sedentary to vigorous). New methods of calibration now use "pattern recognition" approaches to train the algorithms on various activities, and they provide estimates of energy expenditure that are much better than those previously available with the single-regression approach. Once a method of predicting energy expenditure has been established, the next step is to examine its predictive accuracy by cross-validating it in other populations. In this article, we attempt to summarize the best practices for calibration and validation of wearable physical activity monitors. Finally, we conclude with some ideas for future research ideas that will move the field of physical activity measurement forward.

Hyperspectral imaging for predicting the allicin and soluble solid content of garlic with variable selection algorithms and chemometric models.

PubMed

Rahman, Anisur; Faqeerzada, Mohammad A; Cho, Byoung-Kwan

2018-03-14

Allicin and soluble solid content (SSC) in garlic is the responsible for its pungent flavor and odor. However, current conventional methods such as the use of high-pressure liquid chromatography and a refractometer have critical drawbacks in that they are time-consuming, labor-intensive and destructive procedures. The present study aimed to predict allicin and SSC in garlic using hyperspectral imaging in combination with variable selection algorithms and calibration models. Hyperspectral images of 100 garlic cloves were acquired that covered two spectral ranges, from which the mean spectra of each clove were extracted. The calibration models included partial least squares (PLS) and least squares-support vector machine (LS-SVM) regression, as well as different spectral pre-processing techniques, from which the highest performing spectral preprocessing technique and spectral range were selected. Then, variable selection methods, such as regression coefficients, variable importance in projection (VIP) and the successive projections algorithm (SPA), were evaluated for the selection of effective wavelengths (EWs). Furthermore, PLS and LS-SVM regression methods were applied to quantitatively predict the quality attributes of garlic using the selected EWs. Of the established models, the SPA-LS-SVM model obtained an Rpred2 of 0.90 and standard error of prediction (SEP) of 1.01% for SSC prediction, whereas the VIP-LS-SVM model produced the best result with an Rpred2 of 0.83 and SEP of 0.19 mg g -1 for allicin prediction in the range 1000-1700 nm. Furthermore, chemical images of garlic were developed using the best predictive model to facilitate visualization of the spatial distributions of allicin and SSC. The present study clearly demonstrates that hyperspectral imaging combined with an appropriate chemometrics method can potentially be employed as a fast, non-invasive method to predict the allicin and SSC in garlic. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Can multi-slice or navigator-gated R2* MRI replace single-slice breath-hold acquisition for hepatic iron quantification?

PubMed

Loeffler, Ralf B; McCarville, M Beth; Wagstaff, Anne W; Smeltzer, Matthew P; Krafft, Axel J; Song, Ruitian; Hankins, Jane S; Hillenbrand, Claudia M

2017-01-01

Liver R2* values calculated from multi-gradient echo (mGRE) magnetic resonance images (MRI) are strongly correlated with hepatic iron concentration (HIC) as shown in several independently derived biopsy calibration studies. These calibrations were established for axial single-slice breath-hold imaging at the location of the portal vein. Scanning in multi-slice mode makes the exam more efficient, since whole-liver coverage can be achieved with two breath-holds and the optimal slice can be selected afterward. Navigator echoes remove the need for breath-holds and allow use in sedated patients. To evaluate if the existing biopsy calibrations can be applied to multi-slice and navigator-controlled mGRE imaging in children with hepatic iron overload, by testing if there is a bias-free correlation between single-slice R2* and multi-slice or multi-slice navigator controlled R2*. This study included MRI data from 71 patients with transfusional iron overload, who received an MRI exam to estimate HIC using gradient echo sequences. Patient scans contained 2 or 3 of the following imaging methods used for analysis: single-slice images (n = 71), multi-slice images (n = 69) and navigator-controlled images (n = 17). Small and large blood corrected region of interests were selected on axial images of the liver to obtain R2* values for all data sets. Bland-Altman and linear regression analysis were used to compare R2* values from single-slice images to those of multi-slice images and navigator-controlled images. Bland-Altman analysis showed that all imaging method comparisons were strongly associated with each other and had high correlation coefficients (0.98 ≤ r ≤ 1.00) with P-values ≤0.0001. Linear regression yielded slopes that were close to 1. We found that navigator-gated or breath-held multi-slice R2* MRI for HIC determination measures R2* values comparable to the biopsy-validated single-slice, single breath-hold scan. We conclude that these three R2* methods can be interchangeably used in existing R2*-HIC calibrations.

Predicting ambient aerosol thermal-optical reflectance (TOR) measurements from infrared spectra: organic carbon

NASA Astrophysics Data System (ADS)

Dillner, A. M.; Takahama, S.

2015-03-01

Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, organic carbon is measured from a quartz fiber filter that has been exposed to a volume of ambient air and analyzed using thermal methods such as thermal-optical reflectance (TOR). Here, methods are presented that show the feasibility of using Fourier transform infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters to accurately predict TOR OC. This work marks an initial step in proposing a method that can reduce the operating costs of large air quality monitoring networks with an inexpensive, non-destructive analysis technique using routinely collected PTFE filter samples which, in addition to OC concentrations, can concurrently provide information regarding the composition of organic aerosol. This feasibility study suggests that the minimum detection limit and errors (or uncertainty) of FT-IR predictions are on par with TOR OC such that evaluation of long-term trends and epidemiological studies would not be significantly impacted. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least-squares regression is used to calibrate sample FT-IR absorbance spectra to TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date. The calibration produces precise and accurate TOR OC predictions of the test set samples by FT-IR as indicated by high coefficient of variation (R2; 0.96), low bias (0.02 μg m-3, the nominal IMPROVE sample volume is 32.8 m3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision to collocated TOR measurements. FT-IR spectra are also divided into calibration and test sets by OC mass and by OM / OC ratio, which reflects the organic composition of the particulate matter and is obtained from organic functional group composition; these divisions also leads to precise and accurate OC predictions. Low OC concentrations have higher bias and normalized error due to TOR analytical errors and artifact-correction errors, not due to the range of OC mass of the samples in the calibration set. However, samples with low OC mass can be used to predict samples with high OC mass, indicating that the calibration is linear. Using samples in the calibration set that have different OM / OC or ammonium / OC distributions than the test set leads to only a modest increase in bias and normalized error in the predicted samples. We conclude that FT-IR analysis with partial least-squares regression is a robust method for accurately predicting TOR OC in IMPROVE network samples - providing complementary information to the organic functional group composition and organic aerosol mass estimated previously from the same set of sample spectra (Ruthenburg et al., 2014).

Does Nonlinear Modeling Play a Role in Plasmid Bioprocess Monitoring Using Fourier Transform Infrared Spectra?

PubMed

Lopes, Marta B; Calado, Cecília R C; Figueiredo, Mário A T; Bioucas-Dias, José M

2017-06-01

The monitoring of biopharmaceutical products using Fourier transform infrared (FT-IR) spectroscopy relies on calibration techniques involving the acquisition of spectra of bioprocess samples along the process. The most commonly used method for that purpose is partial least squares (PLS) regression, under the assumption that a linear model is valid. Despite being successful in the presence of small nonlinearities, linear methods may fail in the presence of strong nonlinearities. This paper studies the potential usefulness of nonlinear regression methods for predicting, from in situ near-infrared (NIR) and mid-infrared (MIR) spectra acquired in high-throughput mode, biomass and plasmid concentrations in Escherichia coli DH5-α cultures producing the plasmid model pVAX-LacZ. The linear methods PLS and ridge regression (RR) are compared with their kernel (nonlinear) versions, kPLS and kRR, as well as with the (also nonlinear) relevance vector machine (RVM) and Gaussian process regression (GPR). For the systems studied, RR provided better predictive performances compared to the remaining methods. Moreover, the results point to further investigation based on larger data sets whenever differences in predictive accuracy between a linear method and its kernelized version could not be found. The use of nonlinear methods, however, shall be judged regarding the additional computational cost required to tune their additional parameters, especially when the less computationally demanding linear methods herein studied are able to successfully monitor the variables under study.

Exploration of attenuated total reflectance mid-infrared spectroscopy and multivariate calibration to measure immunoglobulin G in human sera.

PubMed

Hou, Siyuan; Riley, Christopher B; Mitchell, Cynthia A; Shaw, R Anthony; Bryanton, Janet; Bigsby, Kathryn; McClure, J Trenton

2015-09-01

Immunoglobulin G (IgG) is crucial for the protection of the host from invasive pathogens. Due to its importance for human health, tools that enable the monitoring of IgG levels are highly desired. Consequently there is a need for methods to determine the IgG concentration that are simple, rapid, and inexpensive. This work explored the potential of attenuated total reflectance (ATR) infrared spectroscopy as a method to determine IgG concentrations in human serum samples. Venous blood samples were collected from adults and children, and from the umbilical cord of newborns. The serum was harvested and tested using ATR infrared spectroscopy. Partial least squares (PLS) regression provided the basis to develop the new analytical methods. Three PLS calibrations were determined: one for the combined set of the venous and umbilical cord serum samples, the second for only the umbilical cord samples, and the third for only the venous samples. The number of PLS factors was chosen by critical evaluation of Monte Carlo-based cross validation results. The predictive performance for each PLS calibration was evaluated using the Pearson correlation coefficient, scatter plot and Bland-Altman plot, and percent deviations for independent prediction sets. The repeatability was evaluated by standard deviation and relative standard deviation. The results showed that ATR infrared spectroscopy is potentially a simple, quick, and inexpensive method to measure IgG concentrations in human serum samples. The results also showed that it is possible to build a united calibration curve for the umbilical cord and the venous samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Terahertz thickness measurements for real industrial applications: from automotive paints to aerospace industry (Conference Presentation)

NASA Astrophysics Data System (ADS)

Krimi, Soufiene; Beigang, René

2017-02-01

In this contribution, we present a highly accurate approach for real-time thickness measurements of multilayered coatings using terahertz time domain spectroscopy in reflection geometry. The proposed approach combines the benefits of a model-based material parameters extraction method to calibrate the specimen under test, a generalized modeling method to simulate the terahertz radiation behavior within arbitrary thin films, and the robustness of a powerful evolutionary optimization algorithm to increase the sensitivity and the precision of the minimum thickness measurement limit. Furthermore, a novel self-calibration model is introduced, which takes into consideration the real industrial challenges such as the effect of wet-on-wet spray in the car painting process and the influence of the spraying conditions and the sintering process on ceramic thermal barrier coatings (TBCs) in aircraft industry. In addition, the developed approach enables for some applications the simultaneous determination of the complex refractive index and the coating thickness. Hence, a pre-calibration of the specimen under test is not required for such cases. Due to the high robustness of the self-calibration method and the genetic optimization algorithms, the approach has been successfully applied to resolve individual layer thicknesses within multi-layered coated samples down to less than 10 µm. The regression method can be applied in time-domain, frequency-domain or in both the time and frequency-domain simultaneously. The data evaluation uses general-purpose computing on graphics processing units and thanks to the developed highly parallelized algorithm lasts less than 300 ms. Thus, industrial requirements for fast thickness measurements with an "every-second-cycle" can be fulfilled.

Simultaneous determination of Nifuroxazide and Drotaverine hydrochloride in pharmaceutical preparations by bivariate and multivariate spectral analysis

NASA Astrophysics Data System (ADS)

Metwally, Fadia H.

2008-02-01

The quantitative predictive abilities of the new and simple bivariate spectrophotometric method are compared with the results obtained by the use of multivariate calibration methods [the classical least squares (CLS), principle component regression (PCR) and partial least squares (PLS)], using the information contained in the absorption spectra of the appropriate solutions. Mixtures of the two drugs Nifuroxazide (NIF) and Drotaverine hydrochloride (DRO) were resolved by application of the bivariate method. The different chemometric approaches were applied also with previous optimization of the calibration matrix, as they are useful in simultaneous inclusion of many spectral wavelengths. The results found by application of the bivariate, CLS, PCR and PLS methods for the simultaneous determinations of mixtures of both components containing 2-12 μg ml -1 of NIF and 2-8 μg ml -1 of DRO are reported. Both approaches were satisfactorily applied to the simultaneous determination of NIF and DRO in pure form and in pharmaceutical formulation. The results were in accordance with those given by the EVA Pharma reference spectrophotometric method.

Detection and quantification of adulteration in sandalwood oil through near infrared spectroscopy.

PubMed

Kuriakose, Saji; Thankappan, Xavier; Joe, Hubert; Venkataraman, Venkateswaran

2010-10-01

The confirmation of authenticity of essential oils and the detection of adulteration are problems of increasing importance in the perfumes, pharmaceutical, flavor and fragrance industries. This is especially true for 'value added' products like sandalwood oil. A methodical study is conducted here to demonstrate the potential use of Near Infrared (NIR) spectroscopy along with multivariate calibration models like principal component regression (PCR) and partial least square regression (PLSR) as rapid analytical techniques for the qualitative and quantitative determination of adulterants in sandalwood oil. After suitable pre-processing of the NIR raw spectral data, the models are built-up by cross-validation. The lowest Root Mean Square Error of Cross-Validation and Calibration (RMSECV and RMSEC % v/v) are used as a decision supporting system to fix the optimal number of factors. The coefficient of determination (R(2)) and the Root Mean Square Error of Prediction (RMSEP % v/v) in the prediction sets are used as the evaluation parameters (R(2) = 0.9999 and RMSEP = 0.01355). The overall result leads to the conclusion that NIR spectroscopy with chemometric techniques could be successfully used as a rapid, simple, instant and non-destructive method for the detection of adulterants, even 1% of the low-grade oils, in the high quality form of sandalwood oil.

Constrained Maximum Likelihood Estimation for Model Calibration Using Summary-level Information from External Big Data Sources

PubMed Central

Chatterjee, Nilanjan; Chen, Yi-Hau; Maas, Paige; Carroll, Raymond J.

2016-01-01

Information from various public and private data sources of extremely large sample sizes are now increasingly available for research purposes. Statistical methods are needed for utilizing information from such big data sources while analyzing data from individual studies that may collect more detailed information required for addressing specific hypotheses of interest. In this article, we consider the problem of building regression models based on individual-level data from an “internal” study while utilizing summary-level information, such as information on parameters for reduced models, from an “external” big data source. We identify a set of very general constraints that link internal and external models. These constraints are used to develop a framework for semiparametric maximum likelihood inference that allows the distribution of covariates to be estimated using either the internal sample or an external reference sample. We develop extensions for handling complex stratified sampling designs, such as case-control sampling, for the internal study. Asymptotic theory and variance estimators are developed for each case. We use simulation studies and a real data application to assess the performance of the proposed methods in contrast to the generalized regression (GR) calibration methodology that is popular in the sample survey literature. PMID:27570323

Statistical Characterization of Environmental Error Sources Affecting Electronically Scanned Pressure Transducers

NASA Technical Reports Server (NTRS)

Green, Del L.; Walker, Eric L.; Everhart, Joel L.

2006-01-01

Minimization of uncertainty is essential to extend the usable range of the 15-psid Electronically Scanned Pressure [ESP) transducer measurements to the low free-stream static pressures found in hypersonic wind tunnels. Statistical characterization of environmental error sources inducing much of this uncertainty requires a well defined and controlled calibration method. Employing such a controlled calibration system, several studies were conducted that provide quantitative information detailing the required controls needed to minimize environmental and human induced error sources. Results of temperature, environmental pressure, over-pressurization, and set point randomization studies for the 15-psid transducers are presented along with a comparison of two regression methods using data acquired with both 0.36-psid and 15-psid transducers. Together these results provide insight into procedural and environmental controls required for long term high-accuracy pressure measurements near 0.01 psia in the hypersonic testing environment using 15-psid ESP transducers.

Statistical Characterization of Environmental Error Sources Affecting Electronically Scanned Pressure Transducers

NASA Technical Reports Server (NTRS)

Green, Del L.; Walker, Eric L.; Everhart, Joel L.

2006-01-01

Minimization of uncertainty is essential to extend the usable range of the 15-psid Electronically Scanned Pressure (ESP) transducer measurements to the low free-stream static pressures found in hypersonic wind tunnels. Statistical characterization of environmental error sources inducing much of this uncertainty requires a well defined and controlled calibration method. Employing such a controlled calibration system, several studies were conducted that provide quantitative information detailing the required controls needed to minimize environmental and human induced error sources. Results of temperature, environmental pressure, over-pressurization, and set point randomization studies for the 15-psid transducers are presented along with a comparison of two regression methods using data acquired with both 0.36-psid and 15-psid transducers. Together these results provide insight into procedural and environmental controls required for long term high-accuracy pressure measurements near 0.01 psia in the hypersonic testing environment using 15-psid ESP transducers.

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics.

PubMed

Ni, Yongnian; Wang, Lin; Kokot, Serge

2011-01-01

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D - first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.

Rapid analysis of pharmaceutical drugs using LIBS coupled with multivariate analysis.

PubMed

Tiwari, P K; Awasthi, S; Kumar, R; Anand, R K; Rai, P K; Rai, A K

2018-02-01

Type 2 diabetes drug tablets containing voglibose having dose strengths of 0.2 and 0.3 mg of various brands have been examined, using laser-induced breakdown spectroscopy (LIBS) technique. The statistical methods such as the principal component analysis (PCA) and the partial least square regression analysis (PLSR) have been employed on LIBS spectral data for classifying and developing the calibration models of drug samples. We have developed the ratio-based calibration model applying PLSR in which relative spectral intensity ratios H/C, H/N and O/N are used. Further, the developed model has been employed to predict the relative concentration of element in unknown drug samples. The experiment has been performed in air and argon atmosphere, respectively, and the obtained results have been compared. The present model provides rapid spectroscopic method for drug analysis with high statistical significance for online control and measurement process in a wide variety of pharmaceutical industrial applications.

Simultaneous estimation of ramipril, acetylsalicylic acid and atorvastatin calcium by chemometrics assisted UV-spectrophotometric method in capsules.

PubMed

Sankar, A S Kamatchi; Vetrichelvan, Thangarasu; Venkappaya, Devashya

2011-09-01

In the present work, three different spectrophotometric methods for simultaneous estimation of ramipril, aspirin and atorvastatin calcium in raw materials and in formulations are described. Overlapped data was quantitatively resolved by using chemometric methods, viz. inverse least squares (ILS), principal component regression (PCR) and partial least squares (PLS). Calibrations were constructed using the absorption data matrix corresponding to the concentration data matrix. The linearity range was found to be 1-5, 10-50 and 2-10 μg mL-1 for ramipril, aspirin and atorvastatin calcium, respectively. The absorbance matrix was obtained by measuring the zero-order absorbance in the wavelength range between 210 and 320 nm. A training set design of the concentration data corresponding to the ramipril, aspirin and atorvastatin calcium mixtures was organized statistically to maximize the information content from the spectra and to minimize the error of multivariate calibrations. By applying the respective algorithms for PLS 1, PCR and ILS to the measured spectra of the calibration set, a suitable model was obtained. This model was selected on the basis of RMSECV and RMSEP values. The same was applied to the prediction set and capsule formulation. Mean recoveries of the commercial formulation set together with the figures of merit (calibration sensitivity, selectivity, limit of detection, limit of quantification and analytical sensitivity) were estimated. Validity of the proposed approaches was successfully assessed for analyses of drugs in the various prepared physical mixtures and formulations.

Analysis of Multivariate Experimental Data Using A Simplified Regression Model Search Algorithm

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert Manfred

2013-01-01

A new regression model search algorithm was developed in 2011 that may be used to analyze both general multivariate experimental data sets and wind tunnel strain-gage balance calibration data. The new algorithm is a simplified version of a more complex search algorithm that was originally developed at the NASA Ames Balance Calibration Laboratory. The new algorithm has the advantage that it needs only about one tenth of the original algorithm's CPU time for the completion of a search. In addition, extensive testing showed that the prediction accuracy of math models obtained from the simplified algorithm is similar to the prediction accuracy of math models obtained from the original algorithm. The simplified algorithm, however, cannot guarantee that search constraints related to a set of statistical quality requirements are always satisfied in the optimized regression models. Therefore, the simplified search algorithm is not intended to replace the original search algorithm. Instead, it may be used to generate an alternate optimized regression model of experimental data whenever the application of the original search algorithm either fails or requires too much CPU time. Data from a machine calibration of NASA's MK40 force balance is used to illustrate the application of the new regression model search algorithm.

Process analytical technology in continuous manufacturing of a commercial pharmaceutical product.

PubMed

Vargas, Jenny M; Nielsen, Sarah; Cárdenas, Vanessa; Gonzalez, Anthony; Aymat, Efrain Y; Almodovar, Elvin; Classe, Gustavo; Colón, Yleana; Sanchez, Eric; Romañach, Rodolfo J

2018-03-01

The implementation of process analytical technology and continuous manufacturing at an FDA approved commercial manufacturing site is described. In this direct compaction process the blends produced were monitored with a Near Infrared (NIR) spectroscopic calibration model developed with partial least squares (PLS) regression. The authors understand that this is the first study where the continuous manufacturing (CM) equipment was used as a gravimetric reference method for the calibration model. A principal component analysis (PCA) model was also developed to identify the powder blend, and determine whether it was similar to the calibration blends. An air diagnostic test was developed to assure that powder was present within the interface when the NIR spectra were obtained. The air diagnostic test as well the PCA and PLS calibration model were integrated into an industrial software platform that collects the real time NIR spectra and applies the calibration models. The PCA test successfully detected an equipment malfunction. Variographic analysis was also performed to estimate the sampling analytical errors that affect the results from the NIR spectroscopic method during commercial production. The system was used to monitor and control a 28 h continuous manufacturing run, where the average drug concentration determined by the NIR method was 101.17% of label claim with a standard deviation of 2.17%, based on 12,633 spectra collected. The average drug concentration for the tablets produced from these blends was 100.86% of label claim with a standard deviation of 0.4%, for 500 tablets analyzed by Fourier Transform Near Infrared (FT-NIR) transmission spectroscopy. The excellent agreement between the mean drug concentration values in the blends and tablets produced provides further evidence of the suitability of the validation strategy that was followed. Copyright © 2018 Elsevier B.V. All rights reserved.

Determination of alcohol and extract concentration in beer samples using a combined method of near-infrared (NIR) spectroscopy and refractometry.

PubMed

Castritius, Stefan; Kron, Alexander; Schäfer, Thomas; Rädle, Matthias; Harms, Diedrich

2010-12-22

A new approach of combination of near-infrared (NIR) spectroscopy and refractometry was developed in this work to determine the concentration of alcohol and real extract in various beer samples. A partial least-squares (PLS) regression, as multivariate calibration method, was used to evaluate the correlation between the data of spectroscopy/refractometry and alcohol/extract concentration. This multivariate combination of spectroscopy and refractometry enhanced the precision in the determination of alcohol, compared to single spectroscopy measurements, due to the effect of high extract concentration on the spectral data, especially of nonalcoholic beer samples. For NIR calibration, two mathematical pretreatments (first-order derivation and linear baseline correction) were applied to eliminate light scattering effects. A sample grouping of the refractometry data was also applied to increase the accuracy of the determined concentration. The root mean squared errors of validation (RMSEV) of the validation process concerning alcohol and extract concentration were 0.23 Mas% (method A), 0.12 Mas% (method B), and 0.19 Mas% (method C) and 0.11 Mas% (method A), 0.11 Mas% (method B), and 0.11 Mas% (method C), respectively.

Spectrometric Estimation of Total Nitrogen Concentration in Douglas-Fir Foliage

NASA Technical Reports Server (NTRS)

Johnson, Lee F.; Billow, Christine R.; Peterson, David L. (Technical Monitor)

1995-01-01

Spectral measurements of fresh and dehydrated Douglas-fir foliage, from trees cultivated under three fertilization treatments, were acquired with a laboratory spectrophotometer. The slope (first-derivative) of the fresh- and dry-leaf absorbance spectra at locations near known protein absorption features was strongly correlated with total nitrogen (TN) concentration of the foliage samples. Particularly strong correlation was observed between the first-derivative spectra in the 2150-2170 nm region and TN, reaching a local maximum in the fresh-leaf spectra of -0.84 at 2 160 nm. Stepwise regression was used to generate calibration equations relating first derivative spectra from fresh, dry/intact, and dry/ground samples to TN concentration. Standard errors of calibration were 1.52 mg g-1 (fresh), 1.33 (dry/intact), and 1.20 (dry/ground), with goodness-of-fit 0.94 and greater. Cross-validation was performed with the fresh-leaf dataset to examine the predictive capability of the regression method; standard errors of prediction ranged from 1.47 - 2.37 mg g(exp -1) across seven different validation sets, prediction goodness of fit ranged from .85-.94, and wavelength selection was fairly insensitive to the membership of the calibration set. All regressions in this study tended to select wavelengths in the 2100-2350 nm region, with the primary selection in the 2142-2172 nm region. The study provides positive evidence concerning the feasibility of assessing TN status of fresh-leaf samples by spectrometric means. We assert that the ability to extract biochemical information from fresh-leaf spectra is a necessary but insufficient condition regarding the use of remote sensing for canopy-level biochemical estimation.

Improved intact soil-core carbon determination applying regression shrinkage and variable selection techniques to complete spectrum laser-induced breakdown spectroscopy (LIBS).

PubMed

Bricklemyer, Ross S; Brown, David J; Turk, Philip J; Clegg, Sam M

2013-10-01

Laser-induced breakdown spectroscopy (LIBS) provides a potential method for rapid, in situ soil C measurement. In previous research on the application of LIBS to intact soil cores, we hypothesized that ultraviolet (UV) spectrum LIBS (200-300 nm) might not provide sufficient elemental information to reliably discriminate between soil organic C (SOC) and inorganic C (IC). In this study, using a custom complete spectrum (245-925 nm) core-scanning LIBS instrument, we analyzed 60 intact soil cores from six wheat fields. Predictive multi-response partial least squares (PLS2) models using full and reduced spectrum LIBS were compared for directly determining soil total C (TC), IC, and SOC. Two regression shrinkage and variable selection approaches, the least absolute shrinkage and selection operator (LASSO) and sparse multivariate regression with covariance estimation (MRCE), were tested for soil C predictions and the identification of wavelengths important for soil C prediction. Using complete spectrum LIBS for PLS2 modeling reduced the calibration standard error of prediction (SEP) 15 and 19% for TC and IC, respectively, compared to UV spectrum LIBS. The LASSO and MRCE approaches provided significantly improved calibration accuracy and reduced SEP 32-55% over UV spectrum PLS2 models. We conclude that (1) complete spectrum LIBS is superior to UV spectrum LIBS for predicting soil C for intact soil cores without pretreatment; (2) LASSO and MRCE approaches provide improved calibration prediction accuracy over PLS2 but require additional testing with increased soil and target analyte diversity; and (3) measurement errors associated with analyzing intact cores (e.g., sample density and surface roughness) require further study and quantification.

Prediction of brain tissue temperature using near-infrared spectroscopy.

PubMed

Holper, Lisa; Mitra, Subhabrata; Bale, Gemma; Robertson, Nicola; Tachtsidis, Ilias

2017-04-01

Broadband near-infrared spectroscopy (NIRS) can provide an endogenous indicator of tissue temperature based on the temperature dependence of the water absorption spectrum. We describe a first evaluation of the calibration and prediction of brain tissue temperature obtained during hypothermia in newborn piglets (animal dataset) and rewarming in newborn infants (human dataset) based on measured body (rectal) temperature. The calibration using partial least squares regression proved to be a reliable method to predict brain tissue temperature with respect to core body temperature in the wavelength interval of 720 to 880 nm with a strong mean predictive power of [Formula: see text] (animal dataset) and [Formula: see text] (human dataset). In addition, we applied regression receiver operating characteristic curves for the first time to evaluate the temperature prediction, which provided an overall mean error bias between NIRS predicted brain temperature and body temperature of [Formula: see text] (animal dataset) and [Formula: see text] (human dataset). We discuss main methodological aspects, particularly the well-known aspect of over- versus underestimation between brain and body temperature, which is relevant for potential clinical applications.

Experimental Investigations of Non-Stationary Properties In Radiometer Receivers Using Measurements of Multiple Calibration References

NASA Technical Reports Server (NTRS)

Racette, Paul; Lang, Roger; Zhang, Zhao-Nan; Zacharias, David; Krebs, Carolyn A. (Technical Monitor)

2002-01-01

Radiometers must be periodically calibrated because the receiver response fluctuates. Many techniques exist to correct for the time varying response of a radiometer receiver. An analytical technique has been developed that uses generalized least squares regression (LSR) to predict the performance of a wide variety of calibration algorithms. The total measurement uncertainty including the uncertainty of the calibration can be computed using LSR. The uncertainties of the calibration samples used in the regression are based upon treating the receiver fluctuations as non-stationary processes. Signals originating from the different sources of emission are treated as simultaneously existing random processes. Thus, the radiometer output is a series of samples obtained from these random processes. The samples are treated as random variables but because the underlying processes are non-stationary the statistics of the samples are treated as non-stationary. The statistics of the calibration samples depend upon the time for which the samples are to be applied. The statistics of the random variables are equated to the mean statistics of the non-stationary processes over the interval defined by the time of calibration sample and when it is applied. This analysis opens the opportunity for experimental investigation into the underlying properties of receiver non stationarity through the use of multiple calibration references. In this presentation we will discuss the application of LSR to the analysis of various calibration algorithms, requirements for experimental verification of the theory, and preliminary results from analyzing experiment measurements.

Online low-field NMR spectroscopy for process control of an industrial lithiation reaction-automated data analysis.

PubMed

Kern, Simon; Meyer, Klas; Guhl, Svetlana; Gräßer, Patrick; Paul, Andrea; King, Rudibert; Maiwald, Michael

2018-05-01

Monitoring specific chemical properties is the key to chemical process control. Today, mainly optical online methods are applied, which require time- and cost-intensive calibration effort. NMR spectroscopy, with its advantage being a direct comparison method without need for calibration, has a high potential for enabling closed-loop process control while exhibiting short set-up times. Compact NMR instruments make NMR spectroscopy accessible in industrial and rough environments for process monitoring and advanced process control strategies. We present a fully automated data analysis approach which is completely based on physically motivated spectral models as first principles information (indirect hard modeling-IHM) and applied it to a given pharmaceutical lithiation reaction in the framework of the European Union's Horizon 2020 project CONSENS. Online low-field NMR (LF NMR) data was analyzed by IHM with low calibration effort, compared to a multivariate PLS-R (partial least squares regression) approach, and both validated using online high-field NMR (HF NMR) spectroscopy. Graphical abstract NMR sensor module for monitoring of the aromatic coupling of 1-fluoro-2-nitrobenzene (FNB) with aniline to 2-nitrodiphenylamine (NDPA) using lithium-bis(trimethylsilyl) amide (Li-HMDS) in continuous operation. Online 43.5 MHz low-field NMR (LF) was compared to 500 MHz high-field NMR spectroscopy (HF) as reference method.

Prediction of the air-water partition coefficient for perfluoro-2-methyl-3-pentanone using high-level Gaussian-4 composite theoretical methods.

PubMed

Rayne, Sierra; Forest, Kaya

2014-09-19

The air-water partition coefficient (Kaw) of perfluoro-2-methyl-3-pentanone (PFMP) was estimated using the G4MP2/G4 levels of theory and the SMD solvation model. A suite of 31 fluorinated compounds was employed to calibrate the theoretical method. Excellent agreement between experimental and directly calculated Kaw values was obtained for the calibration compounds. The PCM solvation model was found to yield unsatisfactory Kaw estimates for fluorinated compounds at both levels of theory. The HENRYWIN Kaw estimation program also exhibited poor Kaw prediction performance on the training set. Based on the resulting regression equation for the calibration compounds, the G4MP2-SMD method constrained the estimated Kaw of PFMP to the range 5-8 × 10(-6) M atm(-1). The magnitude of this Kaw range indicates almost all PFMP released into the atmosphere or near the land-atmosphere interface will reside in the gas phase, with only minor quantities dissolved in the aqueous phase as the parent compound and/or its hydrate/hydrate conjugate base. Following discharge into aqueous systems not at equilibrium with the atmosphere, significant quantities of PFMP will be present as the dissolved parent compound and/or its hydrate/hydrate conjugate base.

A partial least square regression method to quantitatively retrieve soil salinity using hyper-spectral reflectance data

NASA Astrophysics Data System (ADS)

Qu, Yonghua; Jiao, Siong; Lin, Xudong

2008-10-01

Hetao Irrigation District located in Inner Mongolia, is one of the three largest irrigated area in China. In the irrigational agriculture region, for the reasons that many efforts have been put on irrigation rather than on drainage, as a result much sedimentary salt that usually is solved in water has been deposited in surface soil. So there has arisen a problem in such irrigation district that soil salinity has become a chief fact which causes land degrading. Remote sensing technology is an efficiency way to map the salinity in regional scale. In the principle of remote sensing, soil spectrum is one of the most important indications which can be used to reflect the status of soil salinity. In the past decades, many efforts have been made to reveal the spectrum characteristics of the salinized soil, such as the traditional statistic regression method. But it also has been found that when the hyper-spectral reflectance data are considered, the traditional regression method can't be treat the large dimension data, because the hyper-spectral data usually have too higher spectral band number. In this paper, a partial least squares regression (PLSR) model was established based on the statistical analysis on the soil salinity and the reflectance of hyper-spectral. Dataset were collect through the field soil samples were collected in the region of Hetao irrigation from the end of July to the beginning of August. The independent validation using data which are not included in the calibration model reveals that the proposed model can predicate the main soil components such as the content of total ions(S%), PH with higher determination coefficients(R2) of 0.728 and 0.715 respectively. And the rate of prediction to deviation(RPD) of the above predicted value are larger than 1.6, which indicates that the calibrated PLSR model can be used as a tool to retrieve soil salinity with accurate results. When the PLSR model's regression coefficients were aggregated according to the wavelength of visual (blue, green, red) and near infrared bands of LandSat Thematic Mapper(TM) sensor, some significant response values were observed, which indicates that the proposed method in this paper can be used to analysis the remotely sensed data from the space-boarded platform.

On-line monitoring the extract process of Fu-fang Shuanghua oral solution using near infrared spectroscopy and different PLS algorithms

NASA Astrophysics Data System (ADS)

Kang, Qian; Ru, Qingguo; Liu, Yan; Xu, Lingyan; Liu, Jia; Wang, Yifei; Zhang, Yewen; Li, Hui; Zhang, Qing; Wu, Qing

2016-01-01

An on-line near infrared (NIR) spectroscopy monitoring method with an appropriate multivariate calibration method was developed for the extraction process of Fu-fang Shuanghua oral solution (FSOS). On-line NIR spectra were collected through two fiber optic probes, which were designed to transmit NIR radiation by a 2 mm flange. Partial least squares (PLS), interval PLS (iPLS) and synergy interval PLS (siPLS) algorithms were used comparatively for building the calibration regression models. During the extraction process, the feasibility of NIR spectroscopy was employed to determine the concentrations of chlorogenic acid (CA) content, total phenolic acids contents (TPC), total flavonoids contents (TFC) and soluble solid contents (SSC). High performance liquid chromatography (HPLC), ultraviolet spectrophotometric method (UV) and loss on drying methods were employed as reference methods. Experiment results showed that the performance of siPLS model is the best compared with PLS and iPLS. The calibration models for AC, TPC, TFC and SSC had high values of determination coefficients of (R2) (0.9948, 0.9992, 0.9950 and 0.9832) and low root mean square error of cross validation (RMSECV) (0.0113, 0.0341, 0.1787 and 1.2158), which indicate a good correlation between reference values and NIR predicted values. The overall results show that the on line detection method could be feasible in real application and would be of great value for monitoring the mixed decoction process of FSOS and other Chinese patent medicines.

An augmented classical least squares method for quantitative Raman spectral analysis against component information loss.

PubMed

Zhou, Yan; Cao, Hui

2013-01-01

We propose an augmented classical least squares (ACLS) calibration method for quantitative Raman spectral analysis against component information loss. The Raman spectral signals with low analyte concentration correlations were selected and used as the substitutes for unknown quantitative component information during the CLS calibration procedure. The number of selected signals was determined by using the leave-one-out root-mean-square error of cross-validation (RMSECV) curve. An ACLS model was built based on the augmented concentration matrix and the reference spectral signal matrix. The proposed method was compared with partial least squares (PLS) and principal component regression (PCR) using one example: a data set recorded from an experiment of analyte concentration determination using Raman spectroscopy. A 2-fold cross-validation with Venetian blinds strategy was exploited to evaluate the predictive power of the proposed method. The one-way variance analysis (ANOVA) was used to access the predictive power difference between the proposed method and existing methods. Results indicated that the proposed method is effective at increasing the robust predictive power of traditional CLS model against component information loss and its predictive power is comparable to that of PLS or PCR.

Bayesian regression models outperform partial least squares methods for predicting milk components and technological properties using infrared spectral data

PubMed Central

Ferragina, A.; de los Campos, G.; Vazquez, A. I.; Cecchinato, A.; Bittante, G.

2017-01-01

The aim of this study was to assess the performance of Bayesian models commonly used for genomic selection to predict “difficult-to-predict” dairy traits, such as milk fatty acid (FA) expressed as percentage of total fatty acids, and technological properties, such as fresh cheese yield and protein recovery, using Fourier-transform infrared (FTIR) spectral data. Our main hypothesis was that Bayesian models that can estimate shrinkage and perform variable selection may improve our ability to predict FA traits and technological traits above and beyond what can be achieved using the current calibration models (e.g., partial least squares, PLS). To this end, we assessed a series of Bayesian methods and compared their prediction performance with that of PLS. The comparison between models was done using the same sets of data (i.e., same samples, same variability, same spectral treatment) for each trait. Data consisted of 1,264 individual milk samples collected from Brown Swiss cows for which gas chromatographic FA composition, milk coagulation properties, and cheese-yield traits were available. For each sample, 2 spectra in the infrared region from 5,011 to 925 cm−1 were available and averaged before data analysis. Three Bayesian models: Bayesian ridge regression (Bayes RR), Bayes A, and Bayes B, and 2 reference models: PLS and modified PLS (MPLS) procedures, were used to calibrate equations for each of the traits. The Bayesian models used were implemented in the R package BGLR (http://cran.r-project.org/web/packages/BGLR/index.html), whereas the PLS and MPLS were those implemented in the WinISI II software (Infrasoft International LLC, State College, PA). Prediction accuracy was estimated for each trait and model using 25 replicates of a training-testing validation procedure. Compared with PLS, which is currently the most widely used calibration method, MPLS and the 3 Bayesian methods showed significantly greater prediction accuracy. Accuracy increased in moving from calibration to external validation methods, and in moving from PLS and MPLS to Bayesian methods, particularly Bayes A and Bayes B. The maximum R2 value of validation was obtained with Bayes B and Bayes A. For the FA, C10:0 (% of each FA on total FA basis) had the highest R2 (0.75, achieved with Bayes A and Bayes B), and among the technological traits, fresh cheese yield R2 of 0.82 (achieved with Bayes B). These 2 methods have proven to be useful instruments in shrinking and selecting very informative wavelengths and inferring the structure and functions of the analyzed traits. We conclude that Bayesian models are powerful tools for deriving calibration equations, and, importantly, these equations can be easily developed using existing open-source software. As part of our study, we provide scripts based on the open source R software BGLR, which can be used to train customized prediction equations for other traits or populations. PMID:26387015

Evaluation of Regression Models of Balance Calibration Data Using an Empirical Criterion

NASA Technical Reports Server (NTRS)

Ulbrich, Norbert; Volden, Thomas R.

2012-01-01

An empirical criterion for assessing the significance of individual terms of regression models of wind tunnel strain gage balance outputs is evaluated. The criterion is based on the percent contribution of a regression model term. It considers a term to be significant if its percent contribution exceeds the empirical threshold of 0.05%. The criterion has the advantage that it can easily be computed using the regression coefficients of the gage outputs and the load capacities of the balance. First, a definition of the empirical criterion is provided. Then, it is compared with an alternate statistical criterion that is widely used in regression analysis. Finally, calibration data sets from a variety of balances are used to illustrate the connection between the empirical and the statistical criterion. A review of these results indicated that the empirical criterion seems to be suitable for a crude assessment of the significance of a regression model term as the boundary between a significant and an insignificant term cannot be defined very well. Therefore, regression model term reduction should only be performed by using the more universally applicable statistical criterion.

Streamflow and Nutrient Fluxes of the Mississippi-Atchafalaya River Basin and Subbasins for the Period of Record Through 2005

USGS Publications Warehouse

Aulenbach, Brent T.; Buxton, Herbert T.; Battaglin, William A.; Coupe, Richard H.

2007-01-01

U.S. Geological Survey has monitored streamflow and water quality systematically in the Mississippi-Atchafalaya River Basin (MARB) for more than five decades. This report provides streamflow and estimates of nutrient delivery (flux) to the Gulf of Mexico from both the Atchafalaya River and the main stem of the Mississippi River. This report provides streamflow and nutrient flux estimates for nine major subbasins of the Mississippi River. This report also provides streamflow and flux estimates for 21 selected subbasins of various sizes, hydrology, land use, and geographic location within the Basin. The information is provided at each station for the period for which sufficient water-quality data are available to make statistically based flux estimates (starting as early as water year1 1960 and going through water year 2005). Nutrient fluxes are estimated using the adjusted maximum likelihood estimate, a type of regression-model method; nutrient fluxes to the Gulf of Mexico also are estimated using the composite method. Regression models were calibrated using a 5-year moving calibration period; the model was used to estimate the last year of the calibration period. Nutrient flux estimates are provided for six water-quality constituents: dissolved nitrite plus nitrate, total organic nitrogen plus ammonia nitrogen (total Kjeldahl nitrogen), dissolved ammonia, total phosphorous, dissolved orthophosphate, and dissolved silica. Additionally, the contribution of streamflow and net nutrient flux for five large subbasins comprising the MARB were determined from streamflow and nutrient fluxes from seven of the aforementioned major subbasins. These five large subbasins are: 1. Lower Mississippi, 2. Upper Mississippi, 3. Ohio/Tennessee, 4. Missouri, and 5. Arkansas/Red.

A Case Study on a Combination NDVI Forecasting Model Based on the Entropy Weight Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Shengzhi; Ming, Bo; Huang, Qiang

It is critically meaningful to accurately predict NDVI (Normalized Difference Vegetation Index), which helps guide regional ecological remediation and environmental managements. In this study, a combination forecasting model (CFM) was proposed to improve the performance of NDVI predictions in the Yellow River Basin (YRB) based on three individual forecasting models, i.e., the Multiple Linear Regression (MLR), Artificial Neural Network (ANN), and Support Vector Machine (SVM) models. The entropy weight method was employed to determine the weight coefficient for each individual model depending on its predictive performance. Results showed that: (1) ANN exhibits the highest fitting capability among the four orecastingmore » models in the calibration period, whilst its generalization ability becomes weak in the validation period; MLR has a poor performance in both calibration and validation periods; the predicted results of CFM in the calibration period have the highest stability; (2) CFM generally outperforms all individual models in the validation period, and can improve the reliability and stability of predicted results through combining the strengths while reducing the weaknesses of individual models; (3) the performances of all forecasting models are better in dense vegetation areas than in sparse vegetation areas.« less

A study on the use of near-infrared spectroscopy for the rapid quantification of major compounds in Tanreqing injection

NASA Astrophysics Data System (ADS)

Li, Wenlong; Cheng, Zhiwei; Wang, Yuefei; Qu, Haibin

2013-01-01

In this paper we describe the strategy used in the development and validation of a near infrared spectroscopy method for the rapid determination of baicalin, chlorogenic acid, ursodeoxycholic acid (UDCA), chenodeoxycholic acid (CDCA), and the total solid contents (TSCs) in the Tanreqing injection. To increase the representativeness of calibration sample set, a concentrating-diluting method was adopted to artificially prepare samples. Partial least square regression (PLSR) was used to establish calibration models, with which the five quality indicators can be determined with satisfied accuracy and repeatability. In addition, the slope/bias (S/B) method was used for the models transfer between two different types of NIR instruments from the same manufacturer, which is contributing to enlarge the application range of the established models. With the presented method, a great deal of time, effort and money can be saved when large amounts of Tanreqing injection samples need to be analyzed in a relatively short period of time, which is of great significance to the traditional Chinese medicine (TCM) industries.

Development and Validation of a Prototype Vacuum Sensing Unit for the DD2011 Chairside Amalgam Separators

DTIC Science & Technology

2015-10-30

pressure values onto the SD card. The addition of free and open-source Arduino libraries allowed for the seamless integration of the shield into the...alert the user when replacing the separator is necessary. Methods: A sensor was built to measure and record differential pressure values within the...from the transducers during simulated blockages were transformed into pressure values using linear regression equations from the calibration data

Prospective Analyses of Hormone Levels, Alcohol Intake, and Body Fat Distribution in Relation to Breast Cancer Risk

DTIC Science & Technology

1998-07-01

for reproducibility and validity (40,41). More extensive dietary questionnaires were included in the 1984, 1986, and 1990 follow-up; over 80 nutritional ...DJH, RB, FES); Departments of Epidemiology (SEH, WCW, JEM, GAC, DJH, DS) Environmental Health (FES), Nutrition (WCW), and Biostatistics (DS), Harvard...McDermott A, Rosner BA. Regression calibration methods for correcting measurement-error bias in nutritional epidemiology. Am J Clin Nutr 1997; 65

Real Time Monitoring of Dissolved Organic Carbon Concentration and Disinfection By-Product Formation Potential in a Surface Water Treatment Plant with Simulaneous UV-VIS Absorbance and Fluorescence Excitation-Emission Mapping

NASA Astrophysics Data System (ADS)

Gilmore, A. M.

2015-12-01

This study describes a method based on simultaneous absorbance and fluorescence excitation-emission mapping for rapidly and accurately monitoring dissolved organic carbon concentration and disinfection by-product formation potential for surface water sourced drinking water treatment. The method enables real-time monitoring of the Dissolved Organic Carbon (DOC), absorbance at 254 nm (UVA), the Specific UV Absorbance (SUVA) as well as the Simulated Distribution System Trihalomethane (THM) Formation Potential (SDS-THMFP) for the source and treated water among other component parameters. The method primarily involves Parallel Factor Analysis (PARAFAC) decomposition of the high and lower molecular weight humic and fulvic organic component concentrations. The DOC calibration method involves calculating a single slope factor (with the intercept fixed at 0 mg/l) by linear regression for the UVA divided by the ratio of the high and low molecular weight component concentrations. This method thus corrects for the changes in the molecular weight component composition as a function of the source water composition and coagulation treatment effects. The SDS-THMFP calibration involves a multiple linear regression of the DOC, organic component ratio, chlorine residual, pH and alkalinity. Both the DOC and SDS-THMFP correlations over a period of 18 months exhibited adjusted correlation coefficients with r2 > 0.969. The parameters can be reported as a function of compliance rules associated with required % removals of DOC (as a function of alkalinity) and predicted maximum contaminant levels (MCL) of THMs. The single instrument method, which is compatible with continuous flow monitoring or grab sampling, provides a rapid (2-3 minute) and precise indicator of drinking water disinfectant treatability without the need for separate UV photometric and DOC meter measurements or independent THM determinations.

Reliable prediction intervals with regression neural networks.

PubMed

Papadopoulos, Harris; Haralambous, Haris

2011-10-01

This paper proposes an extension to conventional regression neural networks (NNs) for replacing the point predictions they produce with prediction intervals that satisfy a required level of confidence. Our approach follows a novel machine learning framework, called Conformal Prediction (CP), for assigning reliable confidence measures to predictions without assuming anything more than that the data are independent and identically distributed (i.i.d.). We evaluate the proposed method on four benchmark datasets and on the problem of predicting Total Electron Content (TEC), which is an important parameter in trans-ionospheric links; for the latter we use a dataset of more than 60000 TEC measurements collected over a period of 11 years. Our experimental results show that the prediction intervals produced by our method are both well calibrated and tight enough to be useful in practice. Copyright © 2011 Elsevier Ltd. All rights reserved.

Connections between survey calibration estimators and semiparametric models for incomplete data

PubMed Central

Lumley, Thomas; Shaw, Pamela A.; Dai, James Y.

2012-01-01

Survey calibration (or generalized raking) estimators are a standard approach to the use of auxiliary information in survey sampling, improving on the simple Horvitz–Thompson estimator. In this paper we relate the survey calibration estimators to the semiparametric incomplete-data estimators of Robins and coworkers, and to adjustment for baseline variables in a randomized trial. The development based on calibration estimators explains the ‘estimated weights’ paradox and provides useful heuristics for constructing practical estimators. We present some examples of using calibration to gain precision without making additional modelling assumptions in a variety of regression models. PMID:23833390

Calibration and Data Processing in Gas Chromatography Combustion Isotope Ratio Mass Spectrometry

PubMed Central

Zhang, Ying; Tobias, Herbert J.; Sacks, Gavin L.; Brenna, J. Thomas

2013-01-01

Compound-specific isotope analysis (CSIA) by gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) is a powerful technique for the sourcing of substances, such as determination of the geographic or chemical origin of drugs and food adulteration, and it is especially invaluable as a confirmatory tool for detection of the use of synthetic steroids in competitive sport. We review here principles and practices for data processing and calibration of GCC-IRMS data with consideration to anti-doping analyses, with a focus on carbon isotopic analysis (13C/12C). After a brief review of peak definition, the isotopologue signal reduction methods of summation, curve-fitting, and linear regression are described and reviewed. Principles for isotopic calibration are considered in the context of the Δ13C = δ13CM – δ13CE difference measurements required for establishing adverse analytical findings for metabolites relative to endogenous reference compounds. Considerations for the anti-doping analyst are reviewed. PMID:22362612

Calibrators measurement system for headlamp tester of motor vehicle base on machine vision

NASA Astrophysics Data System (ADS)

Pan, Yue; Zhang, Fan; Xu, Xi-ping; Zheng, Zhe

2014-09-01

With the development of photoelectric detection technology, machine vision has a wider use in the field of industry. The paper mainly introduces auto lamps tester calibrator measuring system, of which CCD image sampling system is the core. Also, it shows the measuring principle of optical axial angle and light intensity, and proves the linear relationship between calibrator's facula illumination and image plane illumination. The paper provides an important specification of CCD imaging system. Image processing by MATLAB can get flare's geometric midpoint and average gray level. By fitting the statistics via the method of the least square, we can get regression equation of illumination and gray level. It analyzes the error of experimental result of measurement system, and gives the standard uncertainty of synthesis and the resource of optical axial angle. Optical axial angle's average measuring accuracy is controlled within 40''. The whole testing process uses digital means instead of artificial factors, which has higher accuracy, more repeatability and better mentality than any other measuring systems.

Quantitative monitoring of sucrose, reducing sugar and total sugar dynamics for phenotyping of water-deficit stress tolerance in rice through spectroscopy and chemometrics

NASA Astrophysics Data System (ADS)

Das, Bappa; Sahoo, Rabi N.; Pargal, Sourabh; Krishna, Gopal; Verma, Rakesh; Chinnusamy, Viswanathan; Sehgal, Vinay K.; Gupta, Vinod K.; Dash, Sushanta K.; Swain, Padmini

2018-03-01

In the present investigation, the changes in sucrose, reducing and total sugar content due to water-deficit stress in rice leaves were modeled using visible, near infrared (VNIR) and shortwave infrared (SWIR) spectroscopy. The objectives of the study were to identify the best vegetation indices and suitable multivariate technique based on precise analysis of hyperspectral data (350 to 2500 nm) and sucrose, reducing sugar and total sugar content measured at different stress levels from 16 different rice genotypes. Spectral data analysis was done to identify suitable spectral indices and models for sucrose estimation. Novel spectral indices in near infrared (NIR) range viz. ratio spectral index (RSI) and normalised difference spectral indices (NDSI) sensitive to sucrose, reducing sugar and total sugar content were identified which were subsequently calibrated and validated. The RSI and NDSI models had R2 values of 0.65, 0.71 and 0.67; RPD values of 1.68, 1.95 and 1.66 for sucrose, reducing sugar and total sugar, respectively for validation dataset. Different multivariate spectral models such as artificial neural network (ANN), multivariate adaptive regression splines (MARS), multiple linear regression (MLR), partial least square regression (PLSR), random forest regression (RFR) and support vector machine regression (SVMR) were also evaluated. The best performing multivariate models for sucrose, reducing sugars and total sugars were found to be, MARS, ANN and MARS, respectively with respect to RPD values of 2.08, 2.44, and 1.93. Results indicated that VNIR and SWIR spectroscopy combined with multivariate calibration can be used as a reliable alternative to conventional methods for measurement of sucrose, reducing sugars and total sugars of rice under water-deficit stress as this technique is fast, economic, and noninvasive.

A Consistent EPIC Visible Channel Calibration Using VIIRS and MODIS as a Reference.

NASA Astrophysics Data System (ADS)

Haney, C.; Doelling, D. R.; Minnis, P.; Bhatt, R.; Scarino, B. R.; Gopalan, A.

2017-12-01

The Earth Polychromatic Imaging Camera (EPIC) aboard the Deep Space Climate Observatory (DSCOVR) satellite constantly images the sunlit disk of Earth from the Lagrange-1 (L1) point in 10 spectral channels spanning the UV, VIS, and NIR spectrums. Recently, the DSCOVR EPIC team has publicly released version 2 dataset, which has implemented improved navigation, stray-light correction, and flat-fielding of the CCD array. The EPIC 2-year data record must be well-calibrated for consistent cloud, aerosol, trace gas, land use and other retrievals. Because EPIC lacks onboard calibrators, the observations made by EPIC channels must be calibrated vicariously using the coincident measurements from radiometrically stable instruments that have onboard calibration systems. MODIS and VIIRS are best-suited instruments for this task as they contain similar spectral bands that are well-calibrated onboard using solar diffusers and lunar tracking. We have previously calibrated the EPIC version 1 dataset by using EPIC and VIIRS angularly matched radiance pairs over both all-sky ocean and deep convective clouds (DCC). We noted that the EPIC image required navigations adjustments, and that the EPIC stray-light correction provided an offset term closer to zero based on the linear regression of the EPIC and VIIRS ray-matched radiance pairs. We will evaluate the EPIC version 2 navigation and stray-light improvements using the same techniques. In addition, we will monitor the EPIC channel calibration over the two years for any temporal degradation or anomalous behavior. These two calibration methods will be further validated using desert and DCC invariant Earth targets. The radiometric characterization of the selected invariant targets is performed using multiple years of MODIS and VIIRS measurements. Results of these studies will be shown at the conference.

A Consistent EPIC Visible Channel Calibration using VIIRS and MODIS as a Reference

NASA Technical Reports Server (NTRS)

Haney, C. O.; Doelling, D. R.; Minnis, P.; Bhatt, R.; Scarino, B. R.; Gopalan, A.

2017-01-01

The Earth Polychromatic Imaging Camera (EPIC) aboard the Deep Space Climate Observatory (DSCOVR) satellite constantly images the sunlit disk of Earth from the Lagrange-1 (L1) point in 10 spectral channels spanning the UV, VIS, and NIR spectrums. Recently, the DSCOVR EPIC team has publicly released version 2 dataset, which has implemented improved navigation, stray-light correction, and flat-fielding of the CCD array. The EPIC 2-year data record must be well-calibrated for consistent cloud, aerosol, trace gas, land use and other retrievals. Because EPIC lacks onboard calibrators, the observations made by EPIC channels must be calibrated vicariously using the coincident measurements from radiometrically stable instruments that have onboard calibration systems. MODIS and VIIRS are best-suited instruments for this task as they contain similar spectral bands that are well-calibrated onboard using solar diffusers and lunar tracking. We have previously calibrated the EPIC version 1 dataset by using EPIC and VIIRS angularly matched radiance pairs over both all-sky ocean and deep convective clouds (DCC). We noted that the EPIC image required navigations adjustments, and that the EPIC stray-light correction provided an offset term closer to zero based on the linear regression of the EPIC and VIIRS ray-matched radiance pairs. We will evaluate the EPIC version 2 navigation and stray-light improvements using the same techniques. In addition, we will monitor the EPIC channel calibration over the two years for any temporal degradation or anomalous behavior. These two calibration methods will be further validated using desert and DCC invariant Earth targets. The radiometric characterization of the selected invariant targets is performed using multiple years of MODIS and VIIRS measurements. Results of these studies will be shown at the conference.

Robust Ultraviolet-Visible (UV-Vis) Partial Least-Squares (PLS) Models for Tannin Quantification in Red Wine.

PubMed

Aleixandre-Tudo, José Luis; Nieuwoudt, Helené; Aleixandre, José Luis; Du Toit, Wessel J

2015-02-04

The validation of ultraviolet-visible (UV-vis) spectroscopy combined with partial least-squares (PLS) regression to quantify red wine tannins is reported. The methylcellulose precipitable (MCP) tannin assay and the bovine serum albumin (BSA) tannin assay were used as reference methods. To take the high variability of wine tannins into account when the calibration models were built, a diverse data set was collected from samples of South African red wines that consisted of 18 different cultivars, from regions spanning the wine grape-growing areas of South Africa with their various sites, climates, and soils, ranging in vintage from 2000 to 2012. A total of 240 wine samples were analyzed, and these were divided into a calibration set (n = 120) and a validation set (n = 120) to evaluate the predictive ability of the models. To test the robustness of the PLS calibration models, the predictive ability of the classifying variables cultivar, vintage year, and experimental versus commercial wines was also tested. In general, the statistics obtained when BSA was used as a reference method were slightly better than those obtained with MCP. Despite this, the MCP tannin assay should also be considered as a valid reference method for developing PLS calibrations. The best calibration statistics for the prediction of new samples were coefficient of correlation (R 2 val) = 0.89, root mean standard error of prediction (RMSEP) = 0.16, and residual predictive deviation (RPD) = 3.49 for MCP and R 2 val = 0.93, RMSEP = 0.08, and RPD = 4.07 for BSA, when only the UV region (260-310 nm) was selected, which also led to a faster analysis time. In addition, a difference in the results obtained when the predictive ability of the classifying variables vintage, cultivar, or commercial versus experimental wines was studied suggests that tannin composition is highly affected by many factors. This study also discusses the correlations in tannin values between the methylcellulose and protein precipitation methods.

External validation of a Cox prognostic model: principles and methods

PubMed Central

2013-01-01

Background A prognostic model should not enter clinical practice unless it has been demonstrated that it performs a useful role. External validation denotes evaluation of model performance in a sample independent of that used to develop the model. Unlike for logistic regression models, external validation of Cox models is sparsely treated in the literature. Successful validation of a model means achieving satisfactory discrimination and calibration (prediction accuracy) in the validation sample. Validating Cox models is not straightforward because event probabilities are estimated relative to an unspecified baseline function. Methods We describe statistical approaches to external validation of a published Cox model according to the level of published information, specifically (1) the prognostic index only, (2) the prognostic index together with Kaplan-Meier curves for risk groups, and (3) the first two plus the baseline survival curve (the estimated survival function at the mean prognostic index across the sample). The most challenging task, requiring level 3 information, is assessing calibration, for which we suggest a method of approximating the baseline survival function. Results We apply the methods to two comparable datasets in primary breast cancer, treating one as derivation and the other as validation sample. Results are presented for discrimination and calibration. We demonstrate plots of survival probabilities that can assist model evaluation. Conclusions Our validation methods are applicable to a wide range of prognostic studies and provide researchers with a toolkit for external validation of a published Cox model. PMID:23496923

Ratio manipulating spectrophotometry versus chemometry as stability indicating methods for cefquinome sulfate determination.

PubMed

Yehia, Ali M; Arafa, Reham M; Abbas, Samah S; Amer, Sawsan M

2016-01-15

Spectral resolution of cefquinome sulfate (CFQ) in the presence of its degradation products was studied. Three selective, accurate and rapid spectrophotometric methods were performed for the determination of CFQ in the presence of either its hydrolytic, oxidative or photo-degradation products. The proposed ratio difference, derivative ratio and mean centering are ratio manipulating spectrophotometric methods that were satisfactorily applied for selective determination of CFQ within linear range of 5.0-40.0 μg mL(-1). Concentration Residuals Augmented Classical Least Squares was applied and evaluated for the determination of the cited drug in the presence of its all degradation products. Traditional Partial Least Squares regression was also applied and benchmarked against the proposed advanced multivariate calibration. Experimentally designed 25 synthetic mixtures of three factors at five levels were used to calibrate and validate the multivariate models. Advanced chemometrics succeeded in quantitative and qualitative analyses of CFQ along with its hydrolytic, oxidative and photo-degradation products. The proposed methods were applied successfully for different pharmaceutical formulations analyses. These developed methods were simple and cost-effective compared with the manufacturer's RP-HPLC method. Copyright © 2015 Elsevier B.V. All rights reserved.

The creation and evaluation of a model to simulate the probability of conception in seasonal-calving pasture-based dairy heifers.

PubMed

Fenlon, Caroline; O'Grady, Luke; Butler, Stephen; Doherty, Michael L; Dunnion, John

2017-01-01

Herd fertility in pasture-based dairy farms is a key driver of farm economics. Models for predicting nulliparous reproductive outcomes are rare, but age, genetics, weight, and BCS have been identified as factors influencing heifer conception. The aim of this study was to create a simulation model of heifer conception to service with thorough evaluation. Artificial Insemination service records from two research herds and ten commercial herds were provided to build and evaluate the models. All were managed as spring-calving pasture-based systems. The factors studied were related to age, genetics, and time of service. The data were split into training and testing sets and bootstrapping was used to train the models. Logistic regression (with and without random effects) and generalised additive modelling were selected as the model-building techniques. Two types of evaluation were used to test the predictive ability of the models: discrimination and calibration. Discrimination, which includes sensitivity, specificity, accuracy and ROC analysis, measures a model's ability to distinguish between positive and negative outcomes. Calibration measures the accuracy of the predicted probabilities with the Hosmer-Lemeshow goodness-of-fit, calibration plot and calibration error. After data cleaning and the removal of services with missing values, 1396 services remained to train the models and 597 were left for testing. Age, breed, genetic predicted transmitting ability for calving interval, month and year were significant in the multivariate models. The regression models also included an interaction between age and month. Year within herd was a random effect in the mixed regression model. Overall prediction accuracy was between 77.1% and 78.9%. All three models had very high sensitivity, but low specificity. The two regression models were very well-calibrated. The mean absolute calibration errors were all below 4%. Because the models were not adept at identifying unsuccessful services, they are not suggested for use in predicting the outcome of individual heifer services. Instead, they are useful for the comparison of services with different covariate values or as sub-models in whole-farm simulations. The mixed regression model was identified as the best model for prediction, as the random effects can be ignored and the other variables can be easily obtained or simulated.

Robust colour calibration of an imaging system using a colour space transform and advanced regression modelling.

PubMed

Jackman, Patrick; Sun, Da-Wen; Elmasry, Gamal

2012-08-01

A new algorithm for the conversion of device dependent RGB colour data into device independent L*a*b* colour data without introducing noticeable error has been developed. By combining a linear colour space transform and advanced multiple regression methodologies it was possible to predict L*a*b* colour data with less than 2.2 colour units of error (CIE 1976). By transforming the red, green and blue colour components into new variables that better reflect the structure of the L*a*b* colour space, a low colour calibration error was immediately achieved (ΔE(CAL) = 14.1). Application of a range of regression models on the data further reduced the colour calibration error substantially (multilinear regression ΔE(CAL) = 5.4; response surface ΔE(CAL) = 2.9; PLSR ΔE(CAL) = 2.6; LASSO regression ΔE(CAL) = 2.1). Only the PLSR models deteriorated substantially under cross validation. The algorithm is adaptable and can be easily recalibrated to any working computer vision system. The algorithm was tested on a typical working laboratory computer vision system and delivered only a very marginal loss of colour information ΔE(CAL) = 2.35. Colour features derived on this system were able to safely discriminate between three classes of ham with 100% correct classification whereas colour features measured on a conventional colourimeter were not. Copyright © 2012 Elsevier Ltd. All rights reserved.

New reconstruction of the sunspot group numbers since 1739 using direct calibration and "backbone" methods

NASA Astrophysics Data System (ADS)

Chatzistergos, Theodosios; Usoskin, Ilya G.; Kovaltsov, Gennady A.; Krivova, Natalie A.; Solanki, Sami K.

2017-06-01

Context. The group sunspot number (GSN) series constitute the longest instrumental astronomical database providing information on solar activity. This database is a compilation of observations by many individual observers, and their inter-calibration has usually been performed using linear rescaling. There are multiple published series that show different long-term trends for solar activity. Aims: We aim at producing a GSN series, with a non-linear non-parametric calibration. The only underlying assumptions are that the differences between the various series are due to different acuity thresholds of the observers, and that the threshold of each observer remains constant throughout the observing period. Methods: We used a daisy chain process with backbone (BB) observers and calibrated all overlapping observers to them. We performed the calibration of each individual observer with a probability distribution function (PDF) matrix constructed considering all daily values for the overlapping period with the BB. The calibration of the BBs was carried out in a similar manner. The final series was constructed by merging different BB series. We modelled the propagation of errors straightforwardly with Monte Carlo simulations. A potential bias due to the selection of BBs was investigated and the effect was shown to lie within the 1σ interval of the produced series. The exact selection of the reference period was shown to have a rather small effect on our calibration as well. Results: The final series extends back to 1739 and includes data from 314 observers. This series suggests moderate activity during the 18th and 19th century, which is significantly lower than the high level of solar activity predicted by other recent reconstructions applying linear regressions. Conclusions: The new series provides a robust reconstruction, based on modern and non-parametric methods, of sunspot group numbers since 1739, and it confirms the existence of the modern grand maximum of solar activity in the second half of the 20th century. Values of the group sunspot number series are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/602/A69

Predicting ambient aerosol thermal-optical reflectance measurements from infrared spectra: elemental carbon

NASA Astrophysics Data System (ADS)

Dillner, A. M.; Takahama, S.

2015-10-01

Elemental carbon (EC) is an important constituent of atmospheric particulate matter because it absorbs solar radiation influencing climate and visibility and it adversely affects human health. The EC measured by thermal methods such as thermal-optical reflectance (TOR) is operationally defined as the carbon that volatilizes from quartz filter samples at elevated temperatures in the presence of oxygen. Here, methods are presented to accurately predict TOR EC using Fourier transform infrared (FT-IR) absorbance spectra from atmospheric particulate matter collected on polytetrafluoroethylene (PTFE or Teflon) filters. This method is similar to the procedure developed for OC in prior work (Dillner and Takahama, 2015). Transmittance FT-IR analysis is rapid, inexpensive and nondestructive to the PTFE filter samples which are routinely collected for mass and elemental analysis in monitoring networks. FT-IR absorbance spectra are obtained from 794 filter samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to collocated TOR EC measurements. The FT-IR spectra are divided into calibration and test sets. Two calibrations are developed: one developed from uniform distribution of samples across the EC mass range (Uniform EC) and one developed from a uniform distribution of Low EC mass samples (EC < 2.4 μg, Low Uniform EC). A hybrid approach which applies the Low EC calibration to Low EC samples and the Uniform EC calibration to all other samples is used to produce predictions for Low EC samples that have mean error on par with parallel TOR EC samples in the same mass range and an estimate of the minimum detection limit (MDL) that is on par with TOR EC MDL. For all samples, this hybrid approach leads to precise and accurate TOR EC predictions by FT-IR as indicated by high coefficient of determination (R2; 0.96), no bias (0.00 μg m-3, a concentration value based on the nominal IMPROVE sample volume of 32.8 m3), low error (0.03 μg m-3) and reasonable normalized error (21 %). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. Only the normalized error is higher for the FT-IR EC measurements than for collocated TOR. FT-IR spectra are also divided into calibration and test sets by the ratios OC/EC and ammonium/EC to determine the impact of OC and ammonium on EC prediction. We conclude that FT-IR analysis with partial least squares regression is a robust method for accurately predicting TOR EC in IMPROVE network samples, providing complementary information to TOR OC predictions (Dillner and Takahama, 2015) and the organic functional group composition and organic matter estimated previously from the same set of sample spectra (Ruthenburg et al., 2014).

Predicting ambient aerosol Thermal Optical Reflectance (TOR) measurements from infrared spectra: elemental carbon

NASA Astrophysics Data System (ADS)

Dillner, A. M.; Takahama, S.

2015-06-01

Elemental carbon (EC) is an important constituent of atmospheric particulate matter because it absorbs solar radiation influencing climate and visibility and it adversely affects human health. The EC measured by thermal methods such as Thermal-Optical Reflectance (TOR) is operationally defined as the carbon that volatilizes from quartz filter samples at elevated temperatures in the presence of oxygen. Here, methods are presented to accurately predict TOR EC using Fourier Transform Infrared (FT-IR) absorbance spectra from atmospheric particulate matter collected on polytetrafluoroethylene (PTFE or Teflon) filters. This method is similar to the procedure tested and developed for OC in prior work (Dillner and Takahama, 2015). Transmittance FT-IR analysis is rapid, inexpensive, and non-destructive to the PTFE filter samples which are routinely collected for mass and elemental analysis in monitoring networks. FT-IR absorbance spectra are obtained from 794 filter samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to collocated TOR EC measurements. The FTIR spectra are divided into calibration and test sets. Two calibrations are developed, one which is developed from uniform distribution of samples across the EC mass range (Uniform EC) and one developed from a~uniform distribution of low EC mass samples (EC < 2.4 μg, Low Uniform EC). A hybrid approach which applies the low EC calibration to low EC samples and the Uniform EC calibration to all other samples is used to produces predictions for low EC samples that have mean error on par with parallel TOR EC samples in the same mass range and an estimate of the minimum detection limit (MDL) that is on par with TOR EC MDL. For all samples, this hybrid approach leads to precise and accurate TOR EC predictions by FT-IR as indicated by high coefficient of variation (R2; 0.96), no bias (0.00 μg m-3, concentration value based on the nominal IMPROVE sample volume of 32.8 m-3), low error (0.03 μg m-3) and reasonable normalized error (21 %). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. Only the normalized error is higher for the FT-IR EC measurements than for collocated TOR. FT-IR spectra are also divided into calibration and test sets by the ratios OC/EC and ammonium/EC to determine the impact of OC and ammonium on EC prediction. We conclude that FT-IR analysis with partial least squares regression is a robust method for accurately predicting TOR EC in IMPROVE network samples; providing complementary information to TOR OC predictions (Dillner and Takahama, 2015) and the organic functional group composition and organic matter (OM) estimated previously from the same set of sample spectra (Ruthenburg et al., 2014).

Evaluation of ISCCP multisatellite radiance calibration for geostationary imager visible channels using the moon

USGS Publications Warehouse

Stone, Thomas C.; William B. Rossow,; Joseph Ferrier,; Laura M. Hinkelman,

2013-01-01

Since 1983, the International Satellite Cloud Climatology Project (ISCCP) has collected Earth radiance data from the succession of geostationary and polar-orbiting meteorological satellites operated by weather agencies worldwide. Meeting the ISCCP goals of global coverage and decade-length time scales requires consistent and stable calibration of the participating satellites. For the geostationary imager visible channels, ISCCP calibration provides regular periodic updates from regressions of radiances measured from coincident and collocated observations taken by Advanced Very High Resolution Radiometer instruments. As an independent check of the temporal stability and intersatellite consistency of ISCCP calibrations, we have applied lunar calibration techniques to geostationary imager visible channels using images of the Moon found in the ISCCP data archive. Lunar calibration enables using the reflected light from the Moon as a stable and consistent radiometric reference. Although the technique has general applicability, limitations of the archived image data have restricted the current study to Geostationary Operational Environmental Satellite and Geostationary Meteorological Satellite series. The results of this lunar analysis confirm that ISCCP calibration exhibits negligible temporal trends in sensor response but have revealed apparent relative biases between the satellites at various levels. However, these biases amount to differences of only a few percent in measured absolute reflectances. Since the lunar analysis examines only the lower end of the radiance range, the results suggest that the ISCCP calibration regression approach does not precisely determine the intercept or the zero-radiance response level. We discuss the impact of these findings on the development of consistent calibration for multisatellite global data sets.

Influenza detection and prediction algorithms: comparative accuracy trial in Östergötland county, Sweden, 2008-2012.

PubMed

Spreco, A; Eriksson, O; Dahlström, Ö; Timpka, T

2017-07-01

Methods for the detection of influenza epidemics and prediction of their progress have seldom been comparatively evaluated using prospective designs. This study aimed to perform a prospective comparative trial of algorithms for the detection and prediction of increased local influenza activity. Data on clinical influenza diagnoses recorded by physicians and syndromic data from a telenursing service were used. Five detection and three prediction algorithms previously evaluated in public health settings were calibrated and then evaluated over 3 years. When applied on diagnostic data, only detection using the Serfling regression method and prediction using the non-adaptive log-linear regression method showed acceptable performances during winter influenza seasons. For the syndromic data, none of the detection algorithms displayed a satisfactory performance, while non-adaptive log-linear regression was the best performing prediction method. We conclude that evidence was found for that available algorithms for influenza detection and prediction display satisfactory performance when applied on local diagnostic data during winter influenza seasons. When applied on local syndromic data, the evaluated algorithms did not display consistent performance. Further evaluations and research on combination of methods of these types in public health information infrastructures for 'nowcasting' (integrated detection and prediction) of influenza activity are warranted.

Variability of creatinine measurements in clinical laboratories: results from the CRIC study.

PubMed

Joffe, Marshall; Hsu, Chi-yuan; Feldman, Harold I; Weir, Matthew; Landis, J R; Hamm, L Lee

2010-01-01

Estimating equations using serum creatinine (SCr) are often used to assess glomerular filtration rate (GFR). Such creatinine (Cr)-based formulae may produce biased estimates of GFR when using Cr measurements that have not been calibrated to reference laboratories. In this paper, we sought to examine the degree of this variation in Cr assays in several laboratories associated with academic medical centers affiliated with the Chronic Renal Insufficiency Cohort (CRIC) Study; to consider how best to correct for this variation, and to quantify the impact of such corrections on eligibility for participation in CRIC. Variability of Cr is of particular concern in the conduct of CRIC, a large multicenter study of subjects with chronic renal disease, because eligibility for the study depends on Cr-based assessment of GFR. A library of 5 large volume plasma specimens from apheresis patients was assembled, representing levels of plasma Cr from 0.8 to 2.4 mg/dl. Samples from this library were used for measurement of Cr at each of the 14 CRIC laboratories repetitively over time. We used graphical displays and linear regression methods to examine the variability in Cr, and used linear regression to develop calibration equations. We also examined the impact of the various calibration equations on the proportion of subjects screened as potential participants who were actually eligible for the study. There was substantial variability in Cr assays across laboratories and over time. We developed calibration equations for each laboratory; these equations varied substantially among laboratories and somewhat over time in some laboratories. The laboratory site contributed the most to variability (51% of the variance unexplained by the specimen) and variation with time accounted for another 15%. In some laboratories, calibration equations resulted in differences in eligibility for CRIC of as much as 20%. The substantial variability in SCr assays across laboratories necessitates calibration of SCr measures to a common standard. Failing to do so may substantially affect study eligibility and clinical interpretations when they are determined by Cr-based estimates of GFR. 2010 S. Karger AG, Basel.

4SM: A Novel Self-Calibrated Algebraic Ratio Method for Satellite-Derived Bathymetry and Water Column Correction

PubMed Central

Morel, Yann G.; Favoretto, Fabio

2017-01-01

All empirical water column correction methods have consistently been reported to require existing depth sounding data for the purpose of calibrating a simple depth retrieval model; they yield poor results over very bright or very dark bottoms. In contrast, we set out to (i) use only the relative radiance data in the image along with published data, and several new assumptions; (ii) in order to specify and operate the simplified radiative transfer equation (RTE); (iii) for the purpose of retrieving both the satellite derived bathymetry (SDB) and the water column corrected spectral reflectance over shallow seabeds. Sea truth regressions show that SDB depths retrieved by the method only need tide correction. Therefore it shall be demonstrated that, under such new assumptions, there is no need for (i) formal atmospheric correction; (ii) conversion of relative radiance into calibrated reflectance; or (iii) existing depth sounding data, to specify the simplified RTE and produce both SDB and spectral water column corrected radiance ready for bottom typing. Moreover, the use of the panchromatic band for that purpose is introduced. Altogether, we named this process the Self-Calibrated Supervised Spectral Shallow-sea Modeler (4SM). This approach requires a trained practitioner, though, to produce its results within hours of downloading the raw image. The ideal raw image should be a “near-nadir” view, exhibit homogeneous atmosphere and water column, include some coverage of optically deep waters and bare land, and lend itself to quality removal of haze, atmospheric adjacency effect, and sun/sky glint. PMID:28754028

4SM: A Novel Self-Calibrated Algebraic Ratio Method for Satellite-Derived Bathymetry and Water Column Correction.

PubMed

Morel, Yann G; Favoretto, Fabio

2017-07-21

All empirical water column correction methods have consistently been reported to require existing depth sounding data for the purpose of calibrating a simple depth retrieval model; they yield poor results over very bright or very dark bottoms. In contrast, we set out to (i) use only the relative radiance data in the image along with published data, and several new assumptions; (ii) in order to specify and operate the simplified radiative transfer equation (RTE); (iii) for the purpose of retrieving both the satellite derived bathymetry (SDB) and the water column corrected spectral reflectance over shallow seabeds. Sea truth regressions show that SDB depths retrieved by the method only need tide correction. Therefore it shall be demonstrated that, under such new assumptions, there is no need for (i) formal atmospheric correction; (ii) conversion of relative radiance into calibrated reflectance; or (iii) existing depth sounding data, to specify the simplified RTE and produce both SDB and spectral water column corrected radiance ready for bottom typing. Moreover, the use of the panchromatic band for that purpose is introduced. Altogether, we named this process the Self-Calibrated Supervised Spectral Shallow-sea Modeler (4SM). This approach requires a trained practitioner, though, to produce its results within hours of downloading the raw image. The ideal raw image should be a "near-nadir" view, exhibit homogeneous atmosphere and water column, include some coverage of optically deep waters and bare land, and lend itself to quality removal of haze, atmospheric adjacency effect, and sun/sky glint.

A panning DLT procedure for three-dimensional videography.

PubMed

Yu, B; Koh, T J; Hay, J G

1993-06-01

The direct linear transformation (DLT) method [Abdel-Aziz and Karara, APS Symposium on Photogrammetry. American Society of Photogrammetry, Falls Church, VA (1971)] is widely used in biomechanics to obtain three-dimensional space coordinates from film and video records. This method has some major shortcomings when used to analyze events which take place over large areas. To overcome these shortcomings, a three-dimensional data collection method based on the DLT method, and making use of panning cameras, was developed. Several small single control volumes were combined to construct a large total control volume. For each single control volume, a regression equation (calibration equation) is developed to express each of the 11 DLT parameters as a function of camera orientation, so that the DLT parameters can then be estimated from arbitrary camera orientations. Once the DLT parameters are known for at least two cameras, and the associated two-dimensional film or video coordinates of the event are obtained, the desired three-dimensional space coordinates can be computed. In a laboratory test, five single control volumes (in a total control volume of 24.40 x 2.44 x 2.44 m3) were used to test the effect of the position of the single control volume on the accuracy of the computed three dimensional space coordinates. Linear and quadratic calibration equations were used to test the effect of the order of the equation on the accuracy of the computed three dimensional space coordinates. For four of the five single control volumes tested, the mean resultant errors associated with the use of the linear calibration equation were significantly larger than those associated with the use of the quadratic calibration equation. The position of the single control volume had no significant effect on the mean resultant errors in computed three dimensional coordinates when the quadratic calibration equation was used. Under the same data collection conditions, the mean resultant errors in the computed three dimensional coordinates associated with the panning and stationary DLT methods were 17 and 22 mm, respectively. The major advantages of the panning DLT method lie in the large image sizes obtained and in the ease with which the data can be collected. The method also has potential for use in a wide variety of contexts. The major shortcoming of the method is the large amount of digitizing necessary to calibrate the total control volume. Adaptations of the method to reduce the amount of digitizing required are being explored.

Prediction of erodibility in Oxisols using iron oxides, soil color and diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Arantes Camargo, Livia; Marques, José, Jr.

2015-04-01

The prediction of erodibility using indirect methods such as diffuse reflectance spectroscopy could facilitate the characterization of the spatial variability in large areas and optimize implementation of conservation practices. The aim of this study was to evaluate the prediction of interrill erodibility (Ki) and rill erodibility (Kr) by means of iron oxides content and soil color using multiple linear regression and diffuse reflectance spectroscopy (DRS) using regression analysis by least squares partial (PLSR). The soils were collected from three geomorphic surfaces and analyzed for chemical, physical and mineralogical properties, plus scanned in the spectral range from the visible and infrared. Maps of spatial distribution of Ki and Kr were built with the values calculated by the calibrated models that obtained the best accuracy using geostatistics. Interrill-rill erodibility presented negative correlation with iron extracted by dithionite-citrate-bicarbonate, hematite, and chroma, confirming the influence of iron oxides in soil structural stability. Hematite and hue were the attributes that most contributed in calibration models by multiple linear regression for the prediction of Ki (R2 = 0.55) and Kr (R2 = 0.53). The diffuse reflectance spectroscopy via PLSR allowed to predict Interrill-rill erodibility with high accuracy (R2adj = 0.76, 0.81 respectively and RPD> 2.0) in the range of the visible spectrum (380-800 nm) and the characterization of the spatial variability of these attributes by geostatistics.

Application of near-infrared spectroscopy for the rapid quality assessment of Radix Paeoniae Rubra

NASA Astrophysics Data System (ADS)

Zhan, Hao; Fang, Jing; Tang, Liying; Yang, Hongjun; Li, Hua; Wang, Zhuju; Yang, Bin; Wu, Hongwei; Fu, Meihong

2017-08-01

Near-infrared (NIR) spectroscopy with multivariate analysis was used to quantify gallic acid, catechin, albiflorin, and paeoniflorin in Radix Paeoniae Rubra, and the feasibility to classify the samples originating from different areas was investigated. A new high-performance liquid chromatography method was developed and validated to analyze gallic acid, catechin, albiflorin, and paeoniflorin in Radix Paeoniae Rubra as the reference. Partial least squares (PLS), principal component regression (PCR), and stepwise multivariate linear regression (SMLR) were performed to calibrate the regression model. Different data pretreatments such as derivatives (1st and 2nd), multiplicative scatter correction, standard normal variate, Savitzky-Golay filter, and Norris derivative filter were applied to remove the systematic errors. The performance of the model was evaluated according to the root mean square of calibration (RMSEC), root mean square error of prediction (RMSEP), root mean square error of cross-validation (RMSECV), and correlation coefficient (r). The results show that compared to PCR and SMLR, PLS had a lower RMSEC, RMSECV, and RMSEP and higher r for all the four analytes. PLS coupled with proper pretreatments showed good performance in both the fitting and predicting results. Furthermore, the original areas of Radix Paeoniae Rubra samples were partly distinguished by principal component analysis. This study shows that NIR with PLS is a reliable, inexpensive, and rapid tool for the quality assessment of Radix Paeoniae Rubra.

Ethnic variability in body size, proportions and composition in children aged 5 to 11 years: is ethnic-specific calibration of bioelectrical impedance required?

PubMed

Lee, Simon; Bountziouka, Vassiliki; Lum, Sooky; Stocks, Janet; Bonner, Rachel; Naik, Mitesh; Fothergill, Helen; Wells, Jonathan C K

2014-01-01

Bioelectrical Impedance Analysis (BIA) has the potential to be used widely as a method of assessing body fatness and composition, both in clinical and community settings. BIA provides bioelectrical properties, such as whole-body impedance which ideally needs to be calibrated against a gold-standard method in order to provide accurate estimates of fat-free mass. UK studies in older children and adolescents have shown that, when used in multi-ethnic populations, calibration equations need to include ethnic-specific terms, but whether this holds true for younger children remains to be elucidated. The aims of this study were to examine ethnic differences in body size, proportions and composition in children aged 5 to 11 years, and to establish the extent to which such differences could influence BIA calibration. In a multi-ethnic population of 2171 London primary school-children (47% boys; 34% White, 29% Black African/Caribbean, 25% South Asian, 12% Other) detailed anthropometric measurements were performed and ethnic differences in body size and proportion were assessed. Ethnic differences in fat-free mass, derived by deuterium dilution, were further evaluated in a subsample of the population (n = 698). Multiple linear regression models were used to calibrate BIA against deuterium dilution. In children < 11 years of age, Black African/Caribbean children were significantly taller, heavier and had larger body size than children of other ethnicities. They also had larger waist and limb girths and relatively longer legs. Despite these differences, ethnic-specific terms did not contribute significantly to the BIA calibration equation (Fat-free mass = 1.12+0.71*(height2/impedance)+0.18*weight). Although clear ethnic differences in body size, proportions and composition were evident in this population of young children aged 5 to 11 years, an ethnic-specific BIA calibration equation was not required.

Calibration of the maximum carboxylation velocity (Vcmax) using data mining techniques and ecophysiological data from the Brazilian semiarid region, for use in Dynamic Global Vegetation Models.

PubMed

Rezende, L F C; Arenque-Musa, B C; Moura, M S B; Aidar, S T; Von Randow, C; Menezes, R S C; Ometto, J P B H

2016-06-01

The semiarid region of northeastern Brazil, the Caatinga, is extremely important due to its biodiversity and endemism. Measurements of plant physiology are crucial to the calibration of Dynamic Global Vegetation Models (DGVMs) that are currently used to simulate the responses of vegetation in face of global changes. In a field work realized in an area of preserved Caatinga forest located in Petrolina, Pernambuco, measurements of carbon assimilation (in response to light and CO2) were performed on 11 individuals of Poincianella microphylla, a native species that is abundant in this region. These data were used to calibrate the maximum carboxylation velocity (Vcmax) used in the INLAND model. The calibration techniques used were Multiple Linear Regression (MLR), and data mining techniques as the Classification And Regression Tree (CART) and K-MEANS. The results were compared to the UNCALIBRATED model. It was found that simulated Gross Primary Productivity (GPP) reached 72% of observed GPP when using the calibrated Vcmax values, whereas the UNCALIBRATED approach accounted for 42% of observed GPP. Thus, this work shows the benefits of calibrating DGVMs using field ecophysiological measurements, especially in areas where field data is scarce or non-existent, such as in the Caatinga.

Water content determination of superdisintegrants by means of ATR-FTIR spectroscopy.

PubMed

Szakonyi, G; Zelkó, R

2012-04-07

Water contents of superdisintegrant pharmaceutical excipients were determined by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy using simple linear regression. Water contents of the investigated three common superdisintegrants (crospovidone, croscarmellose sodium, sodium starch glycolate) varied over a wide range (0-24%, w/w). In the case of crospovidone three different samples from two manufacturers were examined in order to study the effects of different grades on the calibration curves. Water content determinations were based on strong absorption of water between 3700 and 2800 cm⁻¹, other spectral changes associated with the different compaction of samples on the ATR crystal using the same pressure were followed by the infrared region between 1510 and 1050 cm⁻¹. The calibration curves were constructed using the ratio of absorbance intensities in the two investigated regions. Using appropriate baseline correction the linearity of the calibration curves was maintained over the entire investigated water content regions and the effect of particle size on the calibration was not significant in the case of crospovidones from the same manufacturer. The described method enables the water content determination of powdered hygroscopic materials containing homogeneously distributed water. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of Flavonoids in Wine by High Performance Liquid Chromatography

NASA Astrophysics Data System (ADS)

da Queija, Celeste; Queirós, M. A.; Rodrigues, Ligia M.

2001-02-01

The experiment presented is an application of HPLC to the analysis of flavonoids in wines, designed for students of instrumental methods. It is done in two successive 4-hour laboratory sessions. While the hydrolysis of the wines is in progress, the students prepare the calibration curves with standard solutions of flavonoids and calculate the regression lines and correlation coefficients. During the second session they analyze the hydrolyzed wine samples and calculate the concentrations of the flavonoids using the calibration curves obtained earlier. This laboratory work is very attractive to students because they deal with a common daily product whose components are reported to have preventive and therapeutic effects. Furthermore, students can execute preparative work and apply a more elaborate technique that is nowadays an indispensable tool in instrumental analysis.

Comparative study between univariate spectrophotometry and multivariate calibration as analytical tools for quantitation of Benazepril alone and in combination with Amlodipine.

PubMed

Farouk, M; Elaziz, Omar Abd; Tawakkol, Shereen M; Hemdan, A; Shehata, Mostafa A

2014-04-05

Four simple, accurate, reproducible, and selective methods have been developed and subsequently validated for the determination of Benazepril (BENZ) alone and in combination with Amlodipine (AML) in pharmaceutical dosage form. The first method is pH induced difference spectrophotometry, where BENZ can be measured in presence of AML as it showed maximum absorption at 237nm and 241nm in 0.1N HCl and 0.1N NaOH, respectively, while AML has no wavelength shift in both solvents. The second method is the new Extended Ratio Subtraction Method (EXRSM) coupled to Ratio Subtraction Method (RSM) for determination of both drugs in commercial dosage form. The third and fourth methods are multivariate calibration which include Principal Component Regression (PCR) and Partial Least Squares (PLSs). A detailed validation of the methods was performed following the ICH guidelines and the standard curves were found to be linear in the range of 2-30μg/mL for BENZ in difference and extended ratio subtraction spectrophotometric method, and 5-30 for AML in EXRSM method, with well accepted mean correlation coefficient for each analyte. The intra-day and inter-day precision and accuracy results were well within the acceptable limits. Copyright © 2013 Elsevier B.V. All rights reserved.

A simple method for HPLC retention time prediction: linear calibration using two reference substances.

PubMed

Sun, Lei; Jin, Hong-Yu; Tian, Run-Tao; Wang, Ming-Juan; Liu, Li-Na; Ye, Liu-Ping; Zuo, Tian-Tian; Ma, Shuang-Cheng

2017-01-01

Analysis of related substances in pharmaceutical chemicals and multi-components in traditional Chinese medicines needs bulk of reference substances to identify the chromatographic peaks accurately. But the reference substances are costly. Thus, the relative retention (RR) method has been widely adopted in pharmacopoeias and literatures for characterizing HPLC behaviors of those reference substances unavailable. The problem is it is difficult to reproduce the RR on different columns due to the error between measured retention time (t R ) and predicted t R in some cases. Therefore, it is useful to develop an alternative and simple method for prediction of t R accurately. In the present study, based on the thermodynamic theory of HPLC, a method named linear calibration using two reference substances (LCTRS) was proposed. The method includes three steps, procedure of two points prediction, procedure of validation by multiple points regression and sequential matching. The t R of compounds on a HPLC column can be calculated by standard retention time and linear relationship. The method was validated in two medicines on 30 columns. It was demonstrated that, LCTRS method is simple, but more accurate and more robust on different HPLC columns than RR method. Hence quality standards using LCTRS method are easy to reproduce in different laboratories with lower cost of reference substances.

Determination of the spectral values of the real part of the relative refractive index of human blood erythrocytes from the measured directional scattering coefficients

NASA Astrophysics Data System (ADS)

Kugeiko, M. M.; Lisenko, S. A.

2008-07-01

An easily automated method for determining the real part of the refractive index of human blood erythrocytes in the range 0.3 1.2 μm is proposed. The method is operationally and metrologically reliable and is based on the measurement of the coefficients of light scattering from forward and backward hemisphere by two pairs of angles and on the use of multiple regression equations. An engineering solution for constructing a measurement system according to this method is proposed, which makes it possible to maximally reduce the calibration errors and effects of destabilizing factors.

Validation of an assay for quantification of free normetanephrine, metanephrine and methoxytyramine in plasma by high performance liquid chromatography with coulometric detection: Comparison of peak-area vs. peak-height measurements.

PubMed

Nieć, Dawid; Kunicki, Paweł K

2015-10-01

Measurements of plasma concentrations of free normetanephrine (NMN), metanephrine (MN) and methoxytyramine (MTY) constitute the most diagnostically accurate screening test for pheochromocytomas and paragangliomas. The aim of this article is to present the results from a validation of an analytical method utilizing high performance liquid chromatography with coulometric detection (HPLC-CD) for quantifying plasma free NMN, MN and MTY. Additionally, peak integration by height and area and the use of one calibration curve for all batches or individual calibration curve for each batch of samples was explored as to determine the optimal approach with regard to accuracy and precision. The method was validated using charcoal stripped plasma spiked with solutions of NMN, MN, MTY and internal standard (4-hydroxy-3-methoxybenzylamine) with the exception of selectivity which was evaluated by analysis of real plasma samples. Calibration curve performance, accuracy, precision and recovery were determined following both peak-area and peak-height measurements and the obtained results were compared. The most accurate and precise method of calibration was evaluated by analyzing quality control samples at three concentration levels in 30 analytical runs. The detector response was linear over the entire tested concentration range from 10 to 2000pg/mL with R(2)≥0.9988. The LLOQ was 10pg/mL for each analyte of interest. To improve accuracy for measurements at low concentrations, a weighted (1/amount) linear regression model was employed, which resulted in inaccuracies of -2.48 to 9.78% and 0.22 to 7.81% following peak-area and peak-height integration, respectively. The imprecisions ranged from 1.07 to 15.45% and from 0.70 to 11.65% for peak-area and peak-height measurements, respectively. The optimal approach to calibration was the one utilizing an individual calibration curve for each batch of samples and peak-height measurements. It was characterized by inaccuracies ranging from -3.39 to +3.27% and imprecisions from 2.17 to 13.57%. The established HPLC-CD method enables accurate and precise measurements of plasma free NMN, MN and MTY with reasonable selectivity. Preparing calibration curve based on peak-height measurements for each batch of samples yields optimal accuracy and precision. Copyright © 2015. Published by Elsevier B.V.

Effective groundwater model calibration: With analysis of data, sensitivities, predictions, and uncertainty

USGS Publications Warehouse

Hill, Mary C.; Tiedeman, Claire

2007-01-01

Methods and guidelines for developing and using mathematical modelsTurn to Effective Groundwater Model Calibration for a set of methods and guidelines that can help produce more accurate and transparent mathematical models. The models can represent groundwater flow and transport and other natural and engineered systems. Use this book and its extensive exercises to learn methods to fully exploit the data on hand, maximize the model's potential, and troubleshoot any problems that arise. Use the methods to perform:Sensitivity analysis to evaluate the information content of dataData assessment to identify (a) existing measurements that dominate model development and predictions and (b) potential measurements likely to improve the reliability of predictionsCalibration to develop models that are consistent with the data in an optimal mannerUncertainty evaluation to quantify and communicate errors in simulated results that are often used to make important societal decisionsMost of the methods are based on linear and nonlinear regression theory.Fourteen guidelines show the reader how to use the methods advantageously in practical situations.Exercises focus on a groundwater flow system and management problem, enabling readers to apply all the methods presented in the text. The exercises can be completed using the material provided in the book, or as hands-on computer exercises using instructions and files available on the text's accompanying Web site.Throughout the book, the authors stress the need for valid statistical concepts and easily understood presentation methods required to achieve well-tested, transparent models. Most of the examples and all of the exercises focus on simulating groundwater systems; other examples come from surface-water hydrology and geophysics.The methods and guidelines in the text are broadly applicable and can be used by students, researchers, and engineers to simulate many kinds systems.

Integration of logistic regression, Markov chain and cellular automata models to simulate urban expansion

NASA Astrophysics Data System (ADS)

Jokar Arsanjani, Jamal; Helbich, Marco; Kainz, Wolfgang; Darvishi Boloorani, Ali

2013-04-01

This research analyses the suburban expansion in the metropolitan area of Tehran, Iran. A hybrid model consisting of logistic regression model, Markov chain (MC), and cellular automata (CA) was designed to improve the performance of the standard logistic regression model. Environmental and socio-economic variables dealing with urban sprawl were operationalised to create a probability surface of spatiotemporal states of built-up land use for the years 2006, 2016, and 2026. For validation, the model was evaluated by means of relative operating characteristic values for different sets of variables. The approach was calibrated for 2006 by cross comparing of actual and simulated land use maps. The achieved outcomes represent a match of 89% between simulated and actual maps of 2006, which was satisfactory to approve the calibration process. Thereafter, the calibrated hybrid approach was implemented for forthcoming years. Finally, future land use maps for 2016 and 2026 were predicted by means of this hybrid approach. The simulated maps illustrate a new wave of suburban development in the vicinity of Tehran at the western border of the metropolis during the next decades.

Forecasting financial asset processes: stochastic dynamics via learning neural networks.

PubMed

Giebel, S; Rainer, M

2010-01-01

Models for financial asset dynamics usually take into account their inherent unpredictable nature by including a suitable stochastic component into their process. Unknown (forward) values of financial assets (at a given time in the future) are usually estimated as expectations of the stochastic asset under a suitable risk-neutral measure. This estimation requires the stochastic model to be calibrated to some history of sufficient length in the past. Apart from inherent limitations, due to the stochastic nature of the process, the predictive power is also limited by the simplifying assumptions of the common calibration methods, such as maximum likelihood estimation and regression methods, performed often without weights on the historic time series, or with static weights only. Here we propose a novel method of "intelligent" calibration, using learning neural networks in order to dynamically adapt the parameters of the stochastic model. Hence we have a stochastic process with time dependent parameters, the dynamics of the parameters being themselves learned continuously by a neural network. The back propagation in training the previous weights is limited to a certain memory length (in the examples we consider 10 previous business days), which is similar to the maximal time lag of autoregressive processes. We demonstrate the learning efficiency of the new algorithm by tracking the next-day forecasts for the EURTRY and EUR-HUF exchange rates each.

Estimating current and future streamflow characteristics at ungaged sites, central and eastern Montana, with application to evaluating effects of climate change on fish populations

USGS Publications Warehouse

Sando, Roy; Chase, Katherine J.

2017-03-23

A common statistical procedure for estimating streamflow statistics at ungaged locations is to develop a relational model between streamflow and drainage basin characteristics at gaged locations using least squares regression analysis; however, least squares regression methods are parametric and make constraining assumptions about the data distribution. The random forest regression method provides an alternative nonparametric method for estimating streamflow characteristics at ungaged sites and requires that the data meet fewer statistical conditions than least squares regression methods.Random forest regression analysis was used to develop predictive models for 89 streamflow characteristics using Precipitation-Runoff Modeling System simulated streamflow data and drainage basin characteristics at 179 sites in central and eastern Montana. The predictive models were developed from streamflow data simulated for current (baseline, water years 1982–99) conditions and three future periods (water years 2021–38, 2046–63, and 2071–88) under three different climate-change scenarios. These predictive models were then used to predict streamflow characteristics for baseline conditions and three future periods at 1,707 fish sampling sites in central and eastern Montana. The average root mean square error for all predictive models was about 50 percent. When streamflow predictions at 23 fish sampling sites were compared to nearby locations with simulated data, the mean relative percent difference was about 43 percent. When predictions were compared to streamflow data recorded at 21 U.S. Geological Survey streamflow-gaging stations outside of the calibration basins, the average mean absolute percent error was about 73 percent.

Calibration of self-report tools for physical activity research: the Physical Activity Questionnaire (PAQ)

PubMed Central

2014-01-01

Background The utility of self-report measures of physical activity (PA) in youth can be greatly enhanced by calibrating self-report output against objectively measured PA data. This study demonstrates the potential of calibrating self-report output against objectively measured physical activity (PA) in youth by using a commonly used self-report tool called the Physical Activity Questionnaire (PAQ). Methods A total of 148 participants (grades 4 through 12) from 9 schools (during the 2009–2010 school year) wore an Actigraph accelerometer for 7 days and then completed the PAQ. Multiple linear regression modeling was used on 70% of the available sample to develop a calibration equation and this was cross validated on an independent sample of participants (30% of sample). Results A calibration model with age, gender, and PAQ scores explained 40% of the variance in values for the percentage of time in moderate-to-vigorous PA (%MVPA) measured from the accelerometers (%MVPA = 14.56 - (sex*0.98) - (0.84*age) + (1.01*PAQ)). When tested on an independent, hold-out sample, the model estimated %MVPA values that were highly correlated with the recorded accelerometer values (r = .63) and there was no significant difference between the estimated and recorded activity values (mean diff. = 25.3 ± 18.1 min; p = .17). Conclusions These results suggest that the calibrated PAQ may be a valid alternative tool to activity monitoring instruments for estimating %MVPA in groups of youth. PMID:24886625

Tests of Sunspot Number Sequences: 3. Effects of Regression Procedures on the Calibration of Historic Sunspot Data

NASA Astrophysics Data System (ADS)

Lockwood, M.; Owens, M. J.; Barnard, L.; Usoskin, I. G.

2016-11-01

We use sunspot-group observations from the Royal Greenwich Observatory (RGO) to investigate the effects of intercalibrating data from observers with different visual acuities. The tests are made by counting the number of groups [RB] above a variable cut-off threshold of observed total whole spot area (uncorrected for foreshortening) to simulate what a lower-acuity observer would have seen. The synthesised annual means of RB are then re-scaled to the full observed RGO group number [RA] using a variety of regression techniques. It is found that a very high correlation between RA and RB (r_{AB} > 0.98) does not prevent large errors in the intercalibration (for example sunspot-maximum values can be over 30 % too large even for such levels of r_{AB}). In generating the backbone sunspot number [R_{BB}], Svalgaard and Schatten ( Solar Phys., 2016) force regression fits to pass through the scatter-plot origin, which generates unreliable fits (the residuals do not form a normal distribution) and causes sunspot-cycle amplitudes to be exaggerated in the intercalibrated data. It is demonstrated that the use of Quantile-Quantile ("Q-Q") plots to test for a normal distribution is a useful indicator of erroneous and misleading regression fits. Ordinary least-squares linear fits, not forced to pass through the origin, are sometimes reliable (although the optimum method used is shown to be different when matching peak and average sunspot-group numbers). However, other fits are only reliable if non-linear regression is used. From these results it is entirely possible that the inflation of solar-cycle amplitudes in the backbone group sunspot number as one goes back in time, relative to related solar-terrestrial parameters, is entirely caused by the use of inappropriate and non-robust regression techniques to calibrate the sunspot data.

The Use of Partial Least Square Regression and Spectral Data in UV-Visible Region for Quantification of Adulteration in Indonesian Palm Civet Coffee

PubMed Central

Yulia, Meinilwita

2017-01-01

Asian palm civet coffee or kopi luwak (Indonesian words for coffee and palm civet) is well known as the world's priciest and rarest coffee. To protect the authenticity of luwak coffee and protect consumer from luwak coffee adulteration, it is very important to develop a robust and simple method for determining the adulteration of luwak coffee. In this research, the use of UV-Visible spectra combined with PLSR was evaluated to establish rapid and simple methods for quantification of adulteration in luwak-arabica coffee blend. Several preprocessing methods were tested and the results show that most of the preprocessing spectra were effective in improving the quality of calibration models with the best PLS calibration model selected for Savitzky-Golay smoothing spectra which had the lowest RMSECV (0.039) and highest RPDcal value (4.64). Using this PLS model, a prediction for quantification of luwak content was calculated and resulted in satisfactory prediction performance with high both RPDp and RER values. PMID:28913348

Tablet potency of Tianeptine in coated tablets by near infrared spectroscopy: model optimisation, calibration transfer and confidence intervals.

PubMed

Boiret, Mathieu; Meunier, Loïc; Ginot, Yves-Michel

2011-02-20

A near infrared (NIR) method was developed for determination of tablet potency of active pharmaceutical ingredient (API) in a complex coated tablet matrix. The calibration set contained samples from laboratory and production scale batches. The reference values were obtained by high performance liquid chromatography (HPLC) and partial least squares (PLS) regression was used to establish a model. The model was challenged by calculating tablet potency of two external test sets. Root mean square errors of prediction were respectively equal to 2.0% and 2.7%. To use this model with a second spectrometer from the production field, a calibration transfer method called piecewise direct standardisation (PDS) was used. After the transfer, the root mean square error of prediction of the first test set was 2.4% compared to 4.0% without transferring the spectra. A statistical technique using bootstrap of PLS residuals was used to estimate confidence intervals of tablet potency calculations. This method requires an optimised PLS model, selection of the bootstrap number and determination of the risk. In the case of a chemical analysis, the tablet potency value will be included within the confidence interval calculated by the bootstrap method. An easy to use graphical interface was developed to easily determine if the predictions, surrounded by minimum and maximum values, are within the specifications defined by the regulatory organisation. Copyright © 2010 Elsevier B.V. All rights reserved.

Calibration and use of plate meter regressions for pasture mass estimation in an Appalachian silvopasture

USDA-ARS?s Scientific Manuscript database

A standardized plate meter for measuring pasture mass was calibrated at the Agroforestry Research and Demonstration Site in Blacksburg, VA, using six ungrazed plots of established tall fescue (Festuca arundinaceae) overseeded with orchardgrass (Dactylis glomerata). Each plot was interplanted with b...

Determination of elemental composition of shale rocks by laser induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Sanghapi, Hervé K.; Jain, Jinesh; Bol'shakov, Alexander; Lopano, Christina; McIntyre, Dustin; Russo, Richard

2016-08-01

In this study laser induced breakdown spectroscopy (LIBS) is used for elemental characterization of outcrop samples from the Marcellus Shale. Powdered samples were pressed to form pellets and used for LIBS analysis. Partial least squares regression (PLS-R) and univariate calibration curves were used for quantification of analytes. The matrix effect is substantially reduced using the partial least squares calibration method. Predicted results with LIBS are compared to ICP-OES results for Si, Al, Ti, Mg, and Ca. As for C, its results are compared to those obtained by a carbon analyzer. Relative errors of the LIBS measurements are in the range of 1.7 to 12.6%. The limits of detection (LODs) obtained for Si, Al, Ti, Mg and Ca are 60.9, 33.0, 15.6, 4.2 and 0.03 ppm, respectively. An LOD of 0.4 wt.% was obtained for carbon. This study shows that the LIBS method can provide a rapid analysis of shale samples and can potentially benefit depleted gas shale carbon storage research.

Classical and Bayesian Seismic Yield Estimation: The 1998 Indian and Pakistani Tests

NASA Astrophysics Data System (ADS)

Shumway, R. H.

2001-10-01

- The nuclear tests in May, 1998, in India and Pakistan have stimulated a renewed interest in yield estimation, based on limited data from uncalibrated test sites. We study here the problem of estimating yields using classical and Bayesian methods developed by Shumway (1992), utilizing calibration data from the Semipalatinsk test site and measured magnitudes for the 1998 Indian and Pakistani tests given by Murphy (1998). Calibration is done using multivariate classical or Bayesian linear regression, depending on the availability of measured magnitude-yield data and prior information. Confidence intervals for the classical approach are derived applying an extension of Fieller's method suggested by Brown (1982). In the case where prior information is available, the posterior predictive magnitude densities are inverted to give posterior intervals for yield. Intervals obtained using the joint distribution of magnitudes are comparable to the single-magnitude estimates produced by Murphy (1998) and reinforce the conclusion that the announced yields of the Indian and Pakistani tests were too high.

Classical and Bayesian Seismic Yield Estimation: The 1998 Indian and Pakistani Tests

NASA Astrophysics Data System (ADS)

Shumway, R. H.

The nuclear tests in May, 1998, in India and Pakistan have stimulated a renewed interest in yield estimation, based on limited data from uncalibrated test sites. We study here the problem of estimating yields using classical and Bayesian methods developed by Shumway (1992), utilizing calibration data from the Semipalatinsk test site and measured magnitudes for the 1998 Indian and Pakistani tests given by Murphy (1998). Calibration is done using multivariate classical or Bayesian linear regression, depending on the availability of measured magnitude-yield data and prior information. Confidence intervals for the classical approach are derived applying an extension of Fieller's method suggested by Brown (1982). In the case where prior information is available, the posterior predictive magnitude densities are inverted to give posterior intervals for yield. Intervals obtained using the joint distribution of magnitudes are comparable to the single-magnitude estimates produced by Murphy (1998) and reinforce the conclusion that the announced yields of the Indian and Pakistani tests were too high.

Estimation of water quality by UV/Vis spectrometry in the framework of treated wastewater reuse.

PubMed

Carré, Erwan; Pérot, Jean; Jauzein, Vincent; Lin, Liming; Lopez-Ferber, Miguel

2017-07-01

The aim of this study is to investigate the potential of ultraviolet/visible (UV/Vis) spectrometry as a complementary method for routine monitoring of reclaimed water production. Robustness of the models and compliance of their sensitivity with current quality limits are investigated. The following indicators are studied: total suspended solids (TSS), turbidity, chemical oxygen demand (COD) and nitrate. Partial least squares regression (PLSR) is used to find linear correlations between absorbances and indicators of interest. Artificial samples are made by simulating a sludge leak on the wastewater treatment plant and added to the original dataset, then divided into calibration and prediction datasets. The models are built on the calibration set, and then tested on the prediction set. The best models are developed with: PLSR for COD (R pred 2 = 0.80), TSS (R pred 2 = 0.86) and turbidity (R pred 2 = 0.96), and with a simple linear regression from absorbance at 208 nm (R pred 2 = 0.95) for nitrate concentration. The input of artificial data significantly enhances the robustness of the models. The sensitivity of the UV/Vis spectrometry monitoring system developed is compatible with quality requirements of reclaimed water production processes.

[Prediction of total nitrogen and alkali hydrolysable nitrogen content in loess using hyperspectral data based on correlation analysis and partial least squares regression].

PubMed

Liu, Xiu-ying; Wang, Li; Chang, Qing-rui; Wang, Xiao-xing; Shang, Yan

2015-07-01

Wuqi County of Shaanxi Province, where the vegetation recovering measures have been carried out for years, was taken as the study area. A total of 100 loess samples from 24 different profiles were collected. Total nitrogen (TN) and alkali hydrolysable nitrogen (AHN) contents of the soil samples were analyzed, and the soil samples were scanned in the visible/near-infrared (VNIR) region of 350-2500 nm in the laboratory. The calibration models were developed between TN and AHN contents and VNIR values based on correlation analysis (CA) and partial least squares regression (PLS). Independent samples validated the calibration models. The results indicated that the optimum model for predicting TN of loess was established by using first derivative of reflectance. The best model for predicting AHN of loess was established by using normal derivative spectra. The optimum TN model could effectively predict TN in loess from 0 to 40 cm, but the optimum AHN model could only roughly predict AHN at the same depth. This study provided a good method for rapidly predicting TN of loess where vegetation recovering measures have been adopted, but prediction of AHN needs to be further studied.

Prediction of brain tissue temperature using near-infrared spectroscopy

PubMed Central

Holper, Lisa; Mitra, Subhabrata; Bale, Gemma; Robertson, Nicola; Tachtsidis, Ilias

2017-01-01

Abstract. Broadband near-infrared spectroscopy (NIRS) can provide an endogenous indicator of tissue temperature based on the temperature dependence of the water absorption spectrum. We describe a first evaluation of the calibration and prediction of brain tissue temperature obtained during hypothermia in newborn piglets (animal dataset) and rewarming in newborn infants (human dataset) based on measured body (rectal) temperature. The calibration using partial least squares regression proved to be a reliable method to predict brain tissue temperature with respect to core body temperature in the wavelength interval of 720 to 880 nm with a strong mean predictive power of R2=0.713±0.157 (animal dataset) and R2=0.798±0.087 (human dataset). In addition, we applied regression receiver operating characteristic curves for the first time to evaluate the temperature prediction, which provided an overall mean error bias between NIRS predicted brain temperature and body temperature of 0.436±0.283°C (animal dataset) and 0.162±0.149°C (human dataset). We discuss main methodological aspects, particularly the well-known aspect of over- versus underestimation between brain and body temperature, which is relevant for potential clinical applications. PMID:28630878

Intrinsic Raman spectroscopy for quantitative biological spectroscopy Part II

PubMed Central

Bechtel, Kate L.; Shih, Wei-Chuan; Feld, Michael S.

2009-01-01

We demonstrate the effectiveness of intrinsic Raman spectroscopy (IRS) at reducing errors caused by absorption and scattering. Physical tissue models, solutions of varying absorption and scattering coefficients with known concentrations of Raman scatterers, are studied. We show significant improvement in prediction error by implementing IRS to predict concentrations of Raman scatterers using both ordinary least squares regression (OLS) and partial least squares regression (PLS). In particular, we show that IRS provides a robust calibration model that does not increase in error when applied to samples with optical properties outside the range of calibration. PMID:18711512

Bayesian regression models outperform partial least squares methods for predicting milk components and technological properties using infrared spectral data.

PubMed

Ferragina, A; de los Campos, G; Vazquez, A I; Cecchinato, A; Bittante, G

2015-11-01

The aim of this study was to assess the performance of Bayesian models commonly used for genomic selection to predict "difficult-to-predict" dairy traits, such as milk fatty acid (FA) expressed as percentage of total fatty acids, and technological properties, such as fresh cheese yield and protein recovery, using Fourier-transform infrared (FTIR) spectral data. Our main hypothesis was that Bayesian models that can estimate shrinkage and perform variable selection may improve our ability to predict FA traits and technological traits above and beyond what can be achieved using the current calibration models (e.g., partial least squares, PLS). To this end, we assessed a series of Bayesian methods and compared their prediction performance with that of PLS. The comparison between models was done using the same sets of data (i.e., same samples, same variability, same spectral treatment) for each trait. Data consisted of 1,264 individual milk samples collected from Brown Swiss cows for which gas chromatographic FA composition, milk coagulation properties, and cheese-yield traits were available. For each sample, 2 spectra in the infrared region from 5,011 to 925 cm(-1) were available and averaged before data analysis. Three Bayesian models: Bayesian ridge regression (Bayes RR), Bayes A, and Bayes B, and 2 reference models: PLS and modified PLS (MPLS) procedures, were used to calibrate equations for each of the traits. The Bayesian models used were implemented in the R package BGLR (http://cran.r-project.org/web/packages/BGLR/index.html), whereas the PLS and MPLS were those implemented in the WinISI II software (Infrasoft International LLC, State College, PA). Prediction accuracy was estimated for each trait and model using 25 replicates of a training-testing validation procedure. Compared with PLS, which is currently the most widely used calibration method, MPLS and the 3 Bayesian methods showed significantly greater prediction accuracy. Accuracy increased in moving from calibration to external validation methods, and in moving from PLS and MPLS to Bayesian methods, particularly Bayes A and Bayes B. The maximum R(2) value of validation was obtained with Bayes B and Bayes A. For the FA, C10:0 (% of each FA on total FA basis) had the highest R(2) (0.75, achieved with Bayes A and Bayes B), and among the technological traits, fresh cheese yield R(2) of 0.82 (achieved with Bayes B). These 2 methods have proven to be useful instruments in shrinking and selecting very informative wavelengths and inferring the structure and functions of the analyzed traits. We conclude that Bayesian models are powerful tools for deriving calibration equations, and, importantly, these equations can be easily developed using existing open-source software. As part of our study, we provide scripts based on the open source R software BGLR, which can be used to train customized prediction equations for other traits or populations. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Improvement of near infrared spectroscopic (NIRS) analysis of caffeine in roasted Arabica coffee by variable selection method of stability competitive adaptive reweighted sampling (SCARS).

PubMed

Zhang, Xuan; Li, Wei; Yin, Bin; Chen, Weizhong; Kelly, Declan P; Wang, Xiaoxin; Zheng, Kaiyi; Du, Yiping

2013-10-01

Coffee is the most heavily consumed beverage in the world after water, for which quality is a key consideration in commercial trade. Therefore, caffeine content which has a significant effect on the final quality of the coffee products requires to be determined fast and reliably by new analytical techniques. The main purpose of this work was to establish a powerful and practical analytical method based on near infrared spectroscopy (NIRS) and chemometrics for quantitative determination of caffeine content in roasted Arabica coffees. Ground coffee samples within a wide range of roasted levels were analyzed by NIR, meanwhile, in which the caffeine contents were quantitative determined by the most commonly used HPLC-UV method as the reference values. Then calibration models based on chemometric analyses of the NIR spectral data and reference concentrations of coffee samples were developed. Partial least squares (PLS) regression was used to construct the models. Furthermore, diverse spectra pretreatment and variable selection techniques were applied in order to obtain robust and reliable reduced-spectrum regression models. Comparing the respective quality of the different models constructed, the application of second derivative pretreatment and stability competitive adaptive reweighted sampling (SCARS) variable selection provided a notably improved regression model, with root mean square error of cross validation (RMSECV) of 0.375 mg/g and correlation coefficient (R) of 0.918 at PLS factor of 7. An independent test set was used to assess the model, with the root mean square error of prediction (RMSEP) of 0.378 mg/g, mean relative error of 1.976% and mean relative standard deviation (RSD) of 1.707%. Thus, the results provided by the high-quality calibration model revealed the feasibility of NIR spectroscopy for at-line application to predict the caffeine content of unknown roasted coffee samples, thanks to the short analysis time of a few seconds and non-destructive advantages of NIRS. Copyright © 2013 Elsevier B.V. All rights reserved.

Improvement of near infrared spectroscopic (NIRS) analysis of caffeine in roasted Arabica coffee by variable selection method of stability competitive adaptive reweighted sampling (SCARS)

NASA Astrophysics Data System (ADS)

Zhang, Xuan; Li, Wei; Yin, Bin; Chen, Weizhong; Kelly, Declan P.; Wang, Xiaoxin; Zheng, Kaiyi; Du, Yiping

2013-10-01

Coffee is the most heavily consumed beverage in the world after water, for which quality is a key consideration in commercial trade. Therefore, caffeine content which has a significant effect on the final quality of the coffee products requires to be determined fast and reliably by new analytical techniques. The main purpose of this work was to establish a powerful and practical analytical method based on near infrared spectroscopy (NIRS) and chemometrics for quantitative determination of caffeine content in roasted Arabica coffees. Ground coffee samples within a wide range of roasted levels were analyzed by NIR, meanwhile, in which the caffeine contents were quantitative determined by the most commonly used HPLC-UV method as the reference values. Then calibration models based on chemometric analyses of the NIR spectral data and reference concentrations of coffee samples were developed. Partial least squares (PLS) regression was used to construct the models. Furthermore, diverse spectra pretreatment and variable selection techniques were applied in order to obtain robust and reliable reduced-spectrum regression models. Comparing the respective quality of the different models constructed, the application of second derivative pretreatment and stability competitive adaptive reweighted sampling (SCARS) variable selection provided a notably improved regression model, with root mean square error of cross validation (RMSECV) of 0.375 mg/g and correlation coefficient (R) of 0.918 at PLS factor of 7. An independent test set was used to assess the model, with the root mean square error of prediction (RMSEP) of 0.378 mg/g, mean relative error of 1.976% and mean relative standard deviation (RSD) of 1.707%. Thus, the results provided by the high-quality calibration model revealed the feasibility of NIR spectroscopy for at-line application to predict the caffeine content of unknown roasted coffee samples, thanks to the short analysis time of a few seconds and non-destructive advantages of NIRS.

Study on rapid valid acidity evaluation of apple by fiber optic diffuse reflectance technique

NASA Astrophysics Data System (ADS)

Liu, Yande; Ying, Yibin; Fu, Xiaping; Jiang, Xuesong

2004-03-01

Some issues related to nondestructive evaluation of valid acidity in intact apples by means of Fourier transform near infrared (FTNIR) (800-2631nm) method were addressed. A relationship was established between the diffuse reflectance spectra recorded with a bifurcated optic fiber and the valid acidity. The data were analyzed by multivariate calibration analysis such as partial least squares (PLS) analysis and principal component regression (PCR) technique. A total of 120 Fuji apples were tested and 80 of them were used to form a calibration data set. The influence of data preprocessing and different spectra treatments were also investigated. Models based on smoothing spectra were slightly worse than models based on derivative spectra and the best result was obtained when the segment length was 5 and the gap size was 10. Depending on data preprocessing and multivariate calibration technique, the best prediction model had a correlation efficient (0.871), a low RMSEP (0.0677), a low RMSEC (0.056) and a small difference between RMSEP and RMSEC by PLS analysis. The results point out the feasibility of FTNIR spectral analysis to predict the fruit valid acidity non-destructively. The ratio of data standard deviation to the root mean square error of prediction (SDR) is better to be less than 3 in calibration models, however, the results cannot meet the demand of actual application. Therefore, further study is required for better calibration and prediction.

Rapid measurement of methyl cellulose precipitable tannins using ultraviolet spectroscopy with chemometrics: application to red wine and inter-laboratory calibration transfer.

PubMed

Dambergs, Robert G; Mercurio, Meagan D; Kassara, Stella; Cozzolino, Daniel; Smith, Paul A

2012-06-01

Information relating to tannin concentration in grapes and wine is not currently available simply and rapidly enough to inform decision-making by grape growers, winemakers, and wine researchers. Spectroscopy and chemometrics have been implemented for the analysis of critical grape and wine parameters and offer a possible solution for rapid tannin analysis. We report here the development and validation of an ultraviolet (UV) spectral calibration for the prediction of tannin concentration in red wines. Such spectral calibrations reduce the time and resource requirements involved in measuring tannins. A diverse calibration set (n = 204) was prepared with samples of Australian wines of five varieties (Cabernet Sauvignon, Shiraz, Merlot, Pinot Noir, and Durif), from regions spanning the wine grape growing areas of Australia, with varying climate and soils, and with vintages ranging from 1991 to 2007. The relationship between tannin measured by the methyl cellulose precipitation (MCP) reference method at 280 nm and tannin predicted with a multiple linear regression (MLR) calibration, using ultraviolet (UV) absorbance at 250, 270, 280, 290, and 315 nm, was strong (r(2)val = 0.92; SECV = 0.20 g/L). An independent validation set (n = 85) was predicted using the MLR algorithm developed with the calibration set and gave confidence in the ability to predict new samples, independent of the samples used to prepare the calibration (r(2)val = 0.94; SEP = 0.18 g/L). The MLR algorithm could also predict tannin in fermenting wines (r(2)val = 0.76; SEP = 0.18 g/L), but worked best from the second day of ferment on. This study also explored instrument-to-instrument transfer of a spectral calibration for MCP tannin. After slope and bias adjustments of the calibration, efficient calibration transfer to other laboratories was clearly demonstrated, with all instruments in the study effectively giving identical results on a transfer set.

Radiometric modeling and calibration of the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) ground based measurement experiment

NASA Astrophysics Data System (ADS)

Tian, Jialin; Smith, William L.; Gazarik, Michael J.

2008-12-01

The ultimate remote sensing benefits of the high resolution Infrared radiance spectrometers will be realized with their geostationary satellite implementation in the form of imaging spectrometers. This will enable dynamic features of the atmosphere's thermodynamic fields and pollutant and greenhouse gas constituents to be observed for revolutionary improvements in weather forecasts and more accurate air quality and climate predictions. As an important step toward realizing this application objective, the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) Engineering Demonstration Unit (EDU) was successfully developed under the NASA New Millennium Program, 2000-2006. The GIFTS-EDU instrument employs three focal plane arrays (FPAs), which gather measurements across the long-wave IR (LWIR), short/mid-wave IR (SMWIR), and visible spectral bands. The GIFTS calibration is achieved using internal blackbody calibration references at ambient (260 K) and hot (286 K) temperatures. In this paper, we introduce a refined calibration technique that utilizes Principle Component (PC) analysis to compensate for instrument distortions and artifacts, therefore, enhancing the absolute calibration accuracy. This method is applied to data collected during the GIFTS Ground Based Measurement (GBM) experiment, together with simultaneous observations by the accurately calibrated AERI (Atmospheric Emitted Radiance Interferometer), both simultaneously zenith viewing the sky through the same external scene mirror at ten-minute intervals throughout a cloudless day at Logan Utah on September 13, 2006. The accurately calibrated GIFTS radiances are produced using the first four PC scores in the GIFTS-AERI regression model. Temperature and moisture profiles retrieved from the PC-calibrated GIFTS radiances are verified against radiosonde measurements collected throughout the GIFTS sky measurement period. Using the GIFTS GBM calibration model, we compute the calibrated radiances from data collected during the moon tracking and viewing experiment events. From which, we derive the lunar surface temperature and emissivity associated with the moon viewing measurements.

Radiometric Modeling and Calibration of the Geostationary Imaging Fourier Transform Spectrometer (GIFTS)Ground Based Measurement Experiment

NASA Technical Reports Server (NTRS)

Tian, Jialin; Smith, William L.; Gazarik, Michael J.

2008-01-01

The ultimate remote sensing benefits of the high resolution Infrared radiance spectrometers will be realized with their geostationary satellite implementation in the form of imaging spectrometers. This will enable dynamic features of the atmosphere s thermodynamic fields and pollutant and greenhouse gas constituents to be observed for revolutionary improvements in weather forecasts and more accurate air quality and climate predictions. As an important step toward realizing this application objective, the Geostationary Imaging Fourier Transform Spectrometer (GIFTS) Engineering Demonstration Unit (EDU) was successfully developed under the NASA New Millennium Program, 2000-2006. The GIFTS-EDU instrument employs three focal plane arrays (FPAs), which gather measurements across the long-wave IR (LWIR), short/mid-wave IR (SMWIR), and visible spectral bands. The GIFTS calibration is achieved using internal blackbody calibration references at ambient (260 K) and hot (286 K) temperatures. In this paper, we introduce a refined calibration technique that utilizes Principle Component (PC) analysis to compensate for instrument distortions and artifacts, therefore, enhancing the absolute calibration accuracy. This method is applied to data collected during the GIFTS Ground Based Measurement (GBM) experiment, together with simultaneous observations by the accurately calibrated AERI (Atmospheric Emitted Radiance Interferometer), both simultaneously zenith viewing the sky through the same external scene mirror at ten-minute intervals throughout a cloudless day at Logan Utah on September 13, 2006. The accurately calibrated GIFTS radiances are produced using the first four PC scores in the GIFTS-AERI regression model. Temperature and moisture profiles retrieved from the PC-calibrated GIFTS radiances are verified against radiosonde measurements collected throughout the GIFTS sky measurement period. Using the GIFTS GBM calibration model, we compute the calibrated radiances from data collected during the moon tracking and viewing experiment events. From which, we derive the lunar surface temperature and emissivity associated with the moon viewing measurements.

Comparison of Benchtop Fourier-Transform (FT) and Portable Grating Scanning Spectrometers for Determination of Total Soluble Solid Contents in Single Grape Berry (Vitis vinifera L.) and Calibration Transfer.

PubMed

Xiao, Hui; Sun, Ke; Sun, Ye; Wei, Kangli; Tu, Kang; Pan, Leiqing

2017-11-22

Near-infrared (NIR) spectroscopy was applied for the determination of total soluble solid contents (SSC) of single Ruby Seedless grape berries using both benchtop Fourier transform (VECTOR 22/N) and portable grating scanning (SupNIR-1500) spectrometers in this study. The results showed that the best SSC prediction was obtained by VECTOR 22/N in the range of 12,000 to 4000 cm -1 (833-2500 nm) for Ruby Seedless with determination coefficient of prediction (R p ²) of 0.918, root mean squares error of prediction (RMSEP) of 0.758% based on least squares support vector machine (LS-SVM). Calibration transfer was conducted on the same spectral range of two instruments (1000-1800 nm) based on the LS-SVM model. By conducting Kennard-Stone (KS) to divide sample sets, selecting the optimal number of standardization samples and applying Passing-Bablok regression to choose the optimal instrument as the master instrument, a modified calibration transfer method between two spectrometers was developed. When 45 samples were selected for the standardization set, the linear interpolation-piecewise direct standardization (linear interpolation-PDS) performed well for calibration transfer with R p ² of 0.857 and RMSEP of 1.099% in the spectral region of 1000-1800 nm. And it was proved that re-calculating the standardization samples into master model could improve the performance of calibration transfer in this study. This work indicated that NIR could be used as a rapid and non-destructive method for SSC prediction, and provided a feasibility to solve the transfer difficulty between totally different NIR spectrometers.

Assessment of parametric uncertainty for groundwater reactive transport modeling,

USGS Publications Warehouse

Shi, Xiaoqing; Ye, Ming; Curtis, Gary P.; Miller, Geoffery L.; Meyer, Philip D.; Kohler, Matthias; Yabusaki, Steve; Wu, Jichun

2014-01-01

The validity of using Gaussian assumptions for model residuals in uncertainty quantification of a groundwater reactive transport model was evaluated in this study. Least squares regression methods explicitly assume Gaussian residuals, and the assumption leads to Gaussian likelihood functions, model parameters, and model predictions. While the Bayesian methods do not explicitly require the Gaussian assumption, Gaussian residuals are widely used. This paper shows that the residuals of the reactive transport model are non-Gaussian, heteroscedastic, and correlated in time; characterizing them requires using a generalized likelihood function such as the formal generalized likelihood function developed by Schoups and Vrugt (2010). For the surface complexation model considered in this study for simulating uranium reactive transport in groundwater, parametric uncertainty is quantified using the least squares regression methods and Bayesian methods with both Gaussian and formal generalized likelihood functions. While the least squares methods and Bayesian methods with Gaussian likelihood function produce similar Gaussian parameter distributions, the parameter distributions of Bayesian uncertainty quantification using the formal generalized likelihood function are non-Gaussian. In addition, predictive performance of formal generalized likelihood function is superior to that of least squares regression and Bayesian methods with Gaussian likelihood function. The Bayesian uncertainty quantification is conducted using the differential evolution adaptive metropolis (DREAM(zs)) algorithm; as a Markov chain Monte Carlo (MCMC) method, it is a robust tool for quantifying uncertainty in groundwater reactive transport models. For the surface complexation model, the regression-based local sensitivity analysis and Morris- and DREAM(ZS)-based global sensitivity analysis yield almost identical ranking of parameter importance. The uncertainty analysis may help select appropriate likelihood functions, improve model calibration, and reduce predictive uncertainty in other groundwater reactive transport and environmental modeling.

Development of the Chemical Exposure Monitor with Indoor Positioning (CEMWIP) for Workplace VOC Surveys

PubMed Central

Brown, KK; Shaw, PB; Mead, KR; Kovein, RJ; Voorhees, RT; Brandes, AR

2016-01-01

The purpose of this project was to research and develop a direct-reading exposure assessment method that combined a real-time location system with a wireless direct-reading personal chemical sensor. The personal chemical sensor was a photoionization device for detecting volatile organic compounds. The combined system was calibrated and tested against the same four standard gas concentrations and calibrated at one standard location and tested at four locations that included the standard locations. Data were wirelessly collected from the chemical sensor every 1.4 seconds, for volatile organic compounds concentration, location, temperature, humidity, and time. Regression analysis of the photo-ionization device voltage response against calibration gases showed the chemical sensor had a limit of detection of 0.2 ppm. The real-time location system was accurate to 13 cm ± 6 cm (standard deviation) in an open area and to 57 cm ± 31 cm in a closed room where the radio frequency has to penetrate drywall-finished walls. The streaming data were collected and graphically displayed as a three-dimensional hazard map for assessment of peak exposure with location. A real-time personal exposure assessment device with indoor positioning was practical and provided new knowledge on direct reading exposure assessment methods. PMID:26786234

Development of the chemical exposure monitor with indoor positioning (CEMWIP) for workplace VOC surveys.

PubMed

Brown, K K; Shaw, P B; Mead, K R; Kovein, R J; Voorhees, R T; Brandes, A R

2016-01-01

The purpose of this article was to research and develop a direct-reading exposure assessment method that combined a real-time location system with a wireless direct-reading personal chemical sensor. The personal chemical sensor was a photoionization device for detecting volatile organic compounds. The combined system was calibrated and tested against the same four standard gas concentrations and calibrated at one standard location and tested at four locations that included the standard locations. Data were wirelessly collected from the chemical sensor every 1.4 sec, for volatile organic compounds concentration, location, temperature, humidity, and time. Regression analysis of the photo-ionization device voltage response against calibration gases showed the chemical sensor had a limit of detection of 0.2 ppm. The real-time location system was accurate to 13 cm ± 6 cm (standard deviation) in an open area and to 57 cm ± 31 cm in a closed room where the radio frequency has to penetrate drywall-finished walls. The streaming data were collected and graphically displayed as a three-dimensional hazard map for assessment of peak exposure with location. A real-time personal exposure assessment device with indoor positioning was practical and provided new knowledge on direct reading exposure assessment methods.

In-line monitoring of extraction process of scutellarein from Erigeron breviscapus (vant.) Hand-Mazz based on qualitative and quantitative uses of near-infrared spectroscopy.

PubMed

Wu, Yongjiang; Jin, Ye; Ding, Haiying; Luan, Lianjun; Chen, Yong; Liu, Xuesong

2011-09-01

The application of near-infrared (NIR) spectroscopy for in-line monitoring of extraction process of scutellarein from Erigeron breviscapus (vant.) Hand-Mazz was investigated. For NIR measurements, two fiber optic probes designed to transmit NIR radiation through a 2 mm pathlength flow cell were utilized to collect spectra in real-time. High performance liquid chromatography (HPLC) was used as a reference method to determine scutellarein in extract solution. Partial least squares regression (PLSR) calibration model of Savitzky-Golay smoothing NIR spectra in the 5450-10,000 cm(-1) region gave satisfactory predictive results for scutellarein. The results showed that the correlation coefficients of calibration and cross validation were 0.9967 and 0.9811, respectively, and the root mean square error of calibration and cross validation were 0.044 and 0.105, respectively. Furthermore, both the moving block standard deviation (MBSD) method and conformity test were used to identify the end point of extraction process, providing real-time data and instant feedback about the extraction course. The results obtained in this study indicated that the NIR spectroscopy technique provides an efficient and environmentally friendly approach for fast determination of scutellarein and end point control of extraction process. Copyright © 2011 Elsevier B.V. All rights reserved.

Measuring coronary calcium on CT images adjusted for attenuation differences.

PubMed

Nelson, Jennifer Clark; Kronmal, Richard A; Carr, J Jeffrey; McNitt-Gray, Michael F; Wong, Nathan D; Loria, Catherine M; Goldin, Jonathan G; Williams, O Dale; Detrano, Robert

2005-05-01

To quantify scanner and participant variability in attenuation values for computed tomographic (CT) images assessed for coronary calcium and define a method for standardizing attenuation values and calibrating calcium measurements. Institutional review board approval and participant informed consent were obtained at all study sites. An image attenuation adjustment method involving the use of available calibration phantom data to define standard attenuation values was developed. The method was applied to images from two population-based multicenter studies: the Coronary Artery Risk Development in Young Adults study (3041 participants) and the Multi-Ethnic Study of Atherosclerosis (6814 participants). To quantify the variability in attenuation, analysis of variance techniques were used to compare the CT numbers of standardized torso phantom regions across study sites, and multivariate linear regression models of participant-specific calibration phantom attenuation values that included participant age, race, sex, body mass index (BMI), smoking status, and site as covariates were developed. To assess the effect of the calibration method on calcium measurements, Pearson correlation coefficients between unadjusted and attenuation-adjusted calcium measurements were computed. Multivariate models were used to examine the effect of sex, race, BMI, smoking status, unadjusted score, and site on Agatston score adjustments. Mean attenuation values (CT numbers) of a standard calibration phantom scanned beneath participants varied significantly according to scanner and participant BMI (P < .001 for both). Values were lowest for Siemens multi-detector row CT scanners (110.0 HU), followed by GE-Imatron electron-beam (116.0 HU) and GE LightSpeed multi-detector row scanners (121.5 HU). Values were also lower for morbidly obese (BMI, > or =40.0 kg/m(2)) participants (108.9 HU), followed by obese (BMI, 30.0-39.9 kg/m(2)) (114.8 HU), overweight (BMI, 25.0-29.9 kg/m(2)) (118.5 HU), and normal-weight or underweight (BMI, <25.0 kg/m(2)) (120.1 HU) participants. Agatston score calibration adjustments ranged from -650 to 1071 (mean, -8 +/- 50 [standard deviation]) and increased with Agatston score (P < .001). The direction and magnitude of adjustment varied significantly according to scanner and BMI (P < .001 for both) and were consistent with phantom attenuation results in that calibration resulted in score decreases for images with higher phantom attenuation values. Image attenuation values vary by scanner and participant body size, producing calcium score differences that are not due to true calcium burden disparities. Use of calibration phantoms to adjust attenuation values and calibrate calcium measurements in research studies and clinical practice may improve the comparability of such measurements between persons scanned with different scanners and within persons over time.

Assessing and adjusting for differences between HIV prevalence estimates derived from national population-based surveys and antenatal care surveillance, with applications for Spectrum 2013

PubMed Central

Marsh, Kimberly; Mahy, Mary; Salomon, Joshua A.; Hogan, Daniel R.

2014-01-01

Objective(s): To assess differences between HIV prevalence estimates derived from national population surveys and antenatal care (ANC) surveillance sites and to improve the calibration of ANC-derived estimates in Spectrum 2013 to more appropriately account for differences between these data. Design: Retrospective analysis of national population survey and ANC surveillance data from 25 countries with generalized epidemics in sub-Saharan Africa and 8 countries with concentrated epidemics. Methods: Adult national population survey and ANC surveillance HIV prevalence estimates were compared for all available national population survey data points for the years 1999–2012. For sub-Saharan Africa, a mixed-effects linear regression model determined whether the relationship between national population and ANC estimates was constant across surveys. A new calibration method was developed to incorporate national population survey data directly into the likelihood for HIV prevalence in countries with generalized epidemics. Results were used to develop default rules for adjusting ANC data for countries with no national population surveys. Results: ANC surveillance data typically overestimate population prevalence, although a wide variation, particularly in rural areas, is observed across countries and survey years. The new calibration method yields similar point estimates to previous approaches, but leads to an average 44% increase in the width of 95% uncertainty intervals. Conclusion: Important biases remain in ANC surveillance data for HIV prevalence. The new approach to model-fitting in Spectrum 2013 more appropriately accounts for this bias when producing national estimates in countries with generalized epidemics. In countries with concentrated epidemics, local sex ratios should be used to calibrate ANC surveillance estimates. PMID:25203158

Risk prediction models for major adverse cardiac event (MACE) following percutaneous coronary intervention (PCI): A review

NASA Astrophysics Data System (ADS)

Manan, Norhafizah A.; Abidin, Basir

2015-02-01

Five percent of patients who went through Percutaneous Coronary Intervention (PCI) experienced Major Adverse Cardiac Events (MACE) after PCI procedure. Risk prediction of MACE following a PCI procedure therefore is helpful. This work describes a review of such prediction models currently in use. Literature search was done on PubMed and SCOPUS database. Thirty literatures were found but only 4 studies were chosen based on the data used, design, and outcome of the study. Particular emphasis was given and commented on the study design, population, sample size, modeling method, predictors, outcomes, discrimination and calibration of the model. All the models had acceptable discrimination ability (C-statistics >0.7) and good calibration (Hosmer-Lameshow P-value >0.05). Most common model used was multivariate logistic regression and most popular predictor was age.

Comparison between light scattering and gravimetric samplers for PM10 mass concentration in poultry and pig houses

NASA Astrophysics Data System (ADS)

Cambra-López, María; Winkel, Albert; Mosquera, Julio; Ogink, Nico W. M.; Aarnink, André J. A.

2015-06-01

The objective of this study was to compare co-located real-time light scattering devices and equivalent gravimetric samplers in poultry and pig houses for PM10 mass concentration, and to develop animal-specific calibration factors for light scattering samplers. These results will contribute to evaluate the comparability of different sampling instruments for PM10 concentrations. Paired DustTrak light scattering device (DustTrak aerosol monitor, TSI, U.S.) and PM10 gravimetric cyclone sampler were used for measuring PM10 mass concentrations during 24 h periods (from noon to noon) inside animal houses. Sampling was conducted in 32 animal houses in the Netherlands, including broilers, broiler breeders, layers in floor and in aviary system, turkeys, piglets, growing-finishing pigs in traditional and low emission housing with dry and liquid feed, and sows in individual and group housing. A total of 119 pairs of 24 h measurements (55 for poultry and 64 for pigs) were recorded and analyzed using linear regression analysis. Deviations between samplers were calculated and discussed. In poultry, cyclone sampler and DustTrak data fitted well to a linear regression, with a regression coefficient equal to 0.41, an intercept of 0.16 mg m-3 and a correlation coefficient of 0.91 (excluding turkeys). Results in turkeys showed a regression coefficient equal to 1.1 (P = 0.49), an intercept of 0.06 mg m-3 (P < 0.0001) and a correlation coefficient of 0.98. In pigs, we found a regression coefficient equal to 0.61, an intercept of 0.05 mg m-3 and a correlation coefficient of 0.84. Measured PM10 concentrations using DustTraks were clearly underestimated (approx. by a factor 2) in both poultry and pig housing systems compared with cyclone pre-separators. Absolute, relative, and random deviations increased with concentration. DustTrak light scattering devices should be self-calibrated to investigate PM10 mass concentrations accurately in animal houses. We recommend linear regression equations as animal-specific calibration factors for DustTraks instead of manufacturer calibration factors, especially in heavily dusty environments such as animal houses.

A comparison of two adaptive multivariate analysis methods (PLSR and ANN) for winter wheat yield forecasting using Landsat-8 OLI images

NASA Astrophysics Data System (ADS)

Chen, Pengfei; Jing, Qi

2017-02-01

An assumption that the non-linear method is more reasonable than the linear method when canopy reflectance is used to establish the yield prediction model was proposed and tested in this study. For this purpose, partial least squares regression (PLSR) and artificial neural networks (ANN), represented linear and non-linear analysis method, were applied and compared for wheat yield prediction. Multi-period Landsat-8 OLI images were collected at two different wheat growth stages, and a field campaign was conducted to obtain grain yields at selected sampling sites in 2014. The field data were divided into a calibration database and a testing database. Using calibration data, a cross-validation concept was introduced for the PLSR and ANN model construction to prevent over-fitting. All models were tested using the test data. The ANN yield-prediction model produced R2, RMSE and RMSE% values of 0.61, 979 kg ha-1, and 10.38%, respectively, in the testing phase, performing better than the PLSR yield-prediction model, which produced R2, RMSE, and RMSE% values of 0.39, 1211 kg ha-1, and 12.84%, respectively. Non-linear method was suggested as a better method for yield prediction.

40 CFR 91.321 - NDIR analyzer calibration.

Code of Federal Regulations, 2014 CFR

2014-07-01

... of full-scale concentration. A minimum of six evenly spaced points covering at least 80 percent of..., a linear calibration may be used. To determine if this criterion is met: (1) Perform a linear least-square regression on the data generated. Use an equation of the form y=mx, where x is the actual chart...

40 CFR 91.321 - NDIR analyzer calibration.

Code of Federal Regulations, 2012 CFR

2012-07-01

... of full-scale concentration. A minimum of six evenly spaced points covering at least 80 percent of..., a linear calibration may be used. To determine if this criterion is met: (1) Perform a linear least-square regression on the data generated. Use an equation of the form y=mx, where x is the actual chart...

40 CFR 91.321 - NDIR analyzer calibration.

Code of Federal Regulations, 2011 CFR

2011-07-01

... of full-scale concentration. A minimum of six evenly spaced points covering at least 80 percent of..., a linear calibration may be used. To determine if this criterion is met: (1) Perform a linear least-square regression on the data generated. Use an equation of the form y=mx, where x is the actual chart...

40 CFR 91.321 - NDIR analyzer calibration.

Code of Federal Regulations, 2013 CFR

2013-07-01

... of full-scale concentration. A minimum of six evenly spaced points covering at least 80 percent of..., a linear calibration may be used. To determine if this criterion is met: (1) Perform a linear least-square regression on the data generated. Use an equation of the form y=mx, where x is the actual chart...

Relationship of physiography and snow area to stream discharge. [Kings River Watershed, California

NASA Technical Reports Server (NTRS)

Mccuen, R. H. (Principal Investigator)

1979-01-01

The author has identified the following significant results. A comparison of snowmelt runoff models shows that the accuracy of the Tangborn model and regression models is greater if the test data falls within the range of calibration than if the test data lies outside the range of calibration data. The regression models are significantly more accurate for forecasts of 60 days or more than for shorter prediction periods. The Tangborn model is more accurate for forecasts of 90 days or more than for shorter prediction periods. The Martinec model is more accurate for forecasts of one or two days than for periods of 3,5,10, or 15 days. Accuracy of the long-term models seems to be independent of forecast data. The sufficiency of the calibration data base is a function not only of the number of years of record but also of the accuracy with which the calibration years represent the total population of data years. Twelve years appears to be a sufficient length of record for each of the models considered, as long as the twelve years are representative of the population.

A machine learning calibration model using random forests to improve sensor performance for lower-cost air quality monitoring

NASA Astrophysics Data System (ADS)

Zimmerman, Naomi; Presto, Albert A.; Kumar, Sriniwasa P. N.; Gu, Jason; Hauryliuk, Aliaksei; Robinson, Ellis S.; Robinson, Allen L.; Subramanian, R.

2018-01-01

Low-cost sensing strategies hold the promise of denser air quality monitoring networks, which could significantly improve our understanding of personal air pollution exposure. Additionally, low-cost air quality sensors could be deployed to areas where limited monitoring exists. However, low-cost sensors are frequently sensitive to environmental conditions and pollutant cross-sensitivities, which have historically been poorly addressed by laboratory calibrations, limiting their utility for monitoring. In this study, we investigated different calibration models for the Real-time Affordable Multi-Pollutant (RAMP) sensor package, which measures CO, NO2, O3, and CO2. We explored three methods: (1) laboratory univariate linear regression, (2) empirical multiple linear regression, and (3) machine-learning-based calibration models using random forests (RF). Calibration models were developed for 16-19 RAMP monitors (varied by pollutant) using training and testing windows spanning August 2016 through February 2017 in Pittsburgh, PA, US. The random forest models matched (CO) or significantly outperformed (NO2, CO2, O3) the other calibration models, and their accuracy and precision were robust over time for testing windows of up to 16 weeks. Following calibration, average mean absolute error on the testing data set from the random forest models was 38 ppb for CO (14 % relative error), 10 ppm for CO2 (2 % relative error), 3.5 ppb for NO2 (29 % relative error), and 3.4 ppb for O3 (15 % relative error), and Pearson r versus the reference monitors exceeded 0.8 for most units. Model performance is explored in detail, including a quantification of model variable importance, accuracy across different concentration ranges, and performance in a range of monitoring contexts including the National Ambient Air Quality Standards (NAAQS) and the US EPA Air Sensors Guidebook recommendations of minimum data quality for personal exposure measurement. A key strength of the RF approach is that it accounts for pollutant cross-sensitivities. This highlights the importance of developing multipollutant sensor packages (as opposed to single-pollutant monitors); we determined this is especially critical for NO2 and CO2. The evaluation reveals that only the RF-calibrated sensors meet the US EPA Air Sensors Guidebook recommendations of minimum data quality for personal exposure measurement. We also demonstrate that the RF-model-calibrated sensors could detect differences in NO2 concentrations between a near-road site and a suburban site less than 1.5 km away. From this study, we conclude that combining RF models with carefully controlled state-of-the-art multipollutant sensor packages as in the RAMP monitors appears to be a very promising approach to address the poor performance that has plagued low-cost air quality sensors.

A Simple and Specific Stability- Indicating RP-HPLC Method for Routine Assay of Adefovir Dipivoxil in Bulk and Tablet Dosage Form.

PubMed

Darsazan, Bahar; Shafaati, Alireza; Mortazavi, Seyed Alireza; Zarghi, Afshin

2017-01-01

A simple and reliable stability-indicating RP-HPLC method was developed and validated for analysis of adefovir dipivoxil (ADV).The chromatographic separation was performed on a C 18 column using a mixture of acetonitrile-citrate buffer (10 mM at pH 5.2) 36:64 (%v/v) as mobile phase, at a flow rate of 1.5 mL/min. Detection was carried out at 260 nm and a sharp peak was obtained for ADV at a retention time of 5.8 ± 0.01 min. No interferences were observed from its stress degradation products. The method was validated according to the international guidelines. Linear regression analysis of data for the calibration plot showed a linear relationship between peak area and concentration over the range of 0.5-16 μg/mL; the regression coefficient was 0.9999and the linear regression equation was y = 24844x-2941.3. The detection (LOD) and quantification (LOQ) limits were 0.12 and 0.35 μg/mL, respectively. The results proved the method was fast (analysis time less than 7 min), precise, reproducible, and accurate for analysis of ADV over a wide range of concentration. The proposed specific method was used for routine quantification of ADV in pharmaceutical bulk and a tablet dosage form.

Calibration sets selection strategy for the construction of robust PLS models for prediction of biodiesel/diesel blends physico-chemical properties using NIR spectroscopy

NASA Astrophysics Data System (ADS)

Palou, Anna; Miró, Aira; Blanco, Marcelo; Larraz, Rafael; Gómez, José Francisco; Martínez, Teresa; González, Josep Maria; Alcalà, Manel

2017-06-01

Even when the feasibility of using near infrared (NIR) spectroscopy combined with partial least squares (PLS) regression for prediction of physico-chemical properties of biodiesel/diesel blends has been widely demonstrated, inclusion in the calibration sets of the whole variability of diesel samples from diverse production origins still remains as an important challenge when constructing the models. This work presents a useful strategy for the systematic selection of calibration sets of samples of biodiesel/diesel blends from diverse origins, based on a binary code, principal components analysis (PCA) and the Kennard-Stones algorithm. Results show that using this methodology the models can keep their robustness over time. PLS calculations have been done using a specialized chemometric software as well as the software of the NIR instrument installed in plant, and both produced RMSEP under reproducibility values of the reference methods. The models have been proved for on-line simultaneous determination of seven properties: density, cetane index, fatty acid methyl esters (FAME) content, cloud point, boiling point at 95% of recovery, flash point and sulphur.

Dynamic calibration of a wheelchair dynamometer.

PubMed

DiGiovine, C P; Cooper, R A; Boninger, M L

2001-01-01

The inertia and resistance of a wheelchair dynamometer must be determined in order to compare the results of one study to another, independent of the type of device used. The purpose of this study was to describe and implement a dynamic calibration test for characterizing the electro-mechanical properties of a dynamometer. The inertia, the viscous friction, the kinetic friction, the motor back-electromotive force constant, and the motor constant were calculated using three different methods. The methodology based on a dynamic calibration test along with a nonlinear regression analysis produced the best results. The coefficient of determination comparing the dynamometer model output to the measured angular velocity and torque was 0.999 for a ramp input and 0.989 for a sinusoidal input. The inertia and resistance were determined for the rollers and the wheelchair wheels. The calculation of the electro-mechanical parameters allows for the complete description of the propulsive torque produced by an individual, given only the angular velocity and acceleration. The measurement of the electro-mechanical properties of the dynamometer as well as the wheelchair/human system provides the information necessary to simulate real-world conditions.

Multivariate methods on the excitation emission matrix fluorescence spectroscopic data of diesel-kerosene mixtures: a comparative study.

PubMed

Divya, O; Mishra, Ashok K

2007-05-29

Quantitative determination of kerosene fraction present in diesel has been carried out based on excitation emission matrix fluorescence (EEMF) along with parallel factor analysis (PARAFAC) and N-way partial least squares regression (N-PLS). EEMF is a simple, sensitive and nondestructive method suitable for the analysis of multifluorophoric mixtures. Calibration models consisting of varying compositions of diesel and kerosene were constructed and their validation was carried out using leave-one-out cross validation method. The accuracy of the model was evaluated through the root mean square error of prediction (RMSEP) for the PARAFAC, N-PLS and unfold PLS methods. N-PLS was found to be a better method compared to PARAFAC and unfold PLS method because of its low RMSEP values.

Predicting heavy metal concentrations in soils and plants using field spectrophotometry

NASA Astrophysics Data System (ADS)

Muradyan, V.; Tepanosyan, G.; Asmaryan, Sh.; Sahakyan, L.; Saghatelyan, A.; Warner, T. A.

2017-09-01

Aim of this study is to predict heavy metal (HM) concentrations in soils and plants using field remote sensing methods. The studied sites were an industrial town of Kajaran and city of Yerevan. The research also included sampling of soils and leaves of two tree species exposed to different pollution levels and determination of contents of HM in lab conditions. The obtained spectral values were then collated with contents of HM in Kajaran soils and the tree leaves sampled in Yerevan, and statistical analysis was done. Consequently, Zn and Pb have a negative correlation coefficient (p <0.01) in a 2498 nm spectral range for soils. Pb has a significantly higher correlation at red edge for plants. A regression models and artificial neural network (ANN) for HM prediction were developed. Good results were obtained for the best stress sensitive spectral band ANN (R2 0.9, RPD 2.0), Simple Linear Regression (SLR) and Partial Least Squares Regression (PLSR) (R2 0.7, RPD 1.4) models. Multiple Linear Regression (MLR) model was not applicable to predict Pb and Zn concentrations in soils in this research. Almost all full spectrum PLS models provide good calibration and validation results (RPD>1.4). Full spectrum ANN models are characterized by excellent calibration R2, rRMSE and RPD (0.9; 0.1 and >2.5 respectively). For prediction of Pb and Ni contents in plants SLR and PLS models were used. The latter provide almost the same results. Our findings indicate that it is possible to make coarse direct estimation of HM content in soils and plants using rapid and economic reflectance spectroscopy.

Calibration of BK Virus Nucleic Acid Amplification Testing to the 1st WHO International Standard for BK Virus

PubMed Central

Tan, Susanna K.; Milligan, Stephen; Sahoo, Malaya K.; Taylor, Nathaniel

2017-01-01

ABSTRACT Significant interassay variability in the quantification of BK virus (BKV) DNA precludes establishing broadly applicable thresholds for the management of BKV infection in transplantation. The 1st WHO International Standard for BKV (primary standard) was introduced in 2016 as a common calibrator for improving the harmonization of BKV nucleic acid amplification testing (NAAT) and enabling comparisons of biological measurements worldwide. Here, we evaluated the Altona RealStar BKV assay (Altona) and calibrated the results to the international unit (IU) using the Exact Diagnostics BKV verification panel, a secondary standard traceable to the primary standard. The primary and secondary standards on Altona had nearly identical linear regression equations (primary standard, Y = 1.05X − 0.28, R2 = 0.99; secondary standard, Y = 1.04X − 0.26, R2 = 0.99) and conversion factors (primary standard, 1.11 IU/copy; secondary standard, 1.09 IU/copy). A comparison of Altona with a laboratory-developed BKV NAAT assay in IU/ml versus copies/ml using Passing-Bablok regression revealed similar regression lines, no proportional bias, and improvement in the systematic bias (95% confidence interval of intercepts: copies/ml, −0.52 to −1.01; IU/ml, 0.07 to −0.36). Additionally, Bland-Altman analyses revealed a clinically significant reduction of bias when results were reported in IU/ml (IU/ml, −0.10 log10; copies/ml, −0.70 log10). These results indicate that the use of a common calibrator improved the agreement between the two assays. As clinical laboratories worldwide use calibrators traceable to the primary standard to harmonize BKV NAAT results, we anticipate improved interassay comparisons with a potential for establishing broadly applicable quantitative BKV DNA load cutoffs for clinical practice. PMID:28053213

Psychrometric measurement of soil water potential: Stability of calibration and test of pressure-plate samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, T.L.; Gee, G.W.; Heller, P.R.

1990-08-01

A commercially available thermocouple psychrometer sample changer (Decagon SC-10A) was used to measure the water potential of field soils ranging in texture from sand to silty clay loam over a range of {minus}0.5 to {minus}20.0 MPa. The standard error of prediction based on regression statistics was generally between 0.04 and 0.14 MPa at {minus}5 MPa. Replacing the measuring junction of the unit changed the calibration slightly; however, it did not significantly alter measurement accuracy. Calibration curves measured throughout a year of testing are consistent and indicate no systematic drift in calibration. Most measurement uncertainty is produced by shifts in themore » intercept in the calibration equation rather than the slope. Both the variability in intercept and the regression error seem to be random. Measurements taken with the SC-10A show that water potential in both sand and silt loam samples removed from 1.5-MPa pressure plates was often 0.5 to 1.0 MPa greater than the 1.5-MPa applied pressure. Limited data from 0.5-MPa pressure plates show close agreement between SC-10A measurements and pressure applied to these more permeable plates.« less

Parts-Per-Billion Mass Measurement Accuracy Achieved through the Combination of Multiple Linear Regression and Automatic Gain Control in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

PubMed Central

Williams, D. Keith; Muddiman, David C.

2008-01-01

Fourier transform ion cyclotron resonance mass spectrometry has the ability to achieve unprecedented mass measurement accuracy (MMA); MMA is one of the most significant attributes of mass spectrometric measurements as it affords extraordinary molecular specificity. However, due to space-charge effects, the achievable MMA significantly depends on the total number of ions trapped in the ICR cell for a particular measurement. Even through the use of automatic gain control (AGC), the total ion population is not constant between spectra. Multiple linear regression calibration in conjunction with AGC is utilized in these experiments to formally account for the differences in total ion population in the ICR cell between the external calibration spectra and experimental spectra. This ability allows for the extension of dynamic range of the instrument while allowing mean MMA values to remain less than 1 ppm. In addition, multiple linear regression calibration is used to account for both differences in total ion population in the ICR cell as well as relative ion abundance of a given species, which also affords mean MMA values at the parts-per-billion level. PMID:17539605

Strategies for minimizing sample size for use in airborne LiDAR-based forest inventory

USGS Publications Warehouse

Junttila, Virpi; Finley, Andrew O.; Bradford, John B.; Kauranne, Tuomo

2013-01-01

Recently airborne Light Detection And Ranging (LiDAR) has emerged as a highly accurate remote sensing modality to be used in operational scale forest inventories. Inventories conducted with the help of LiDAR are most often model-based, i.e. they use variables derived from LiDAR point clouds as the predictive variables that are to be calibrated using field plots. The measurement of the necessary field plots is a time-consuming and statistically sensitive process. Because of this, current practice often presumes hundreds of plots to be collected. But since these plots are only used to calibrate regression models, it should be possible to minimize the number of plots needed by carefully selecting the plots to be measured. In the current study, we compare several systematic and random methods for calibration plot selection, with the specific aim that they be used in LiDAR based regression models for forest parameters, especially above-ground biomass. The primary criteria compared are based on both spatial representativity as well as on their coverage of the variability of the forest features measured. In the former case, it is important also to take into account spatial auto-correlation between the plots. The results indicate that choosing the plots in a way that ensures ample coverage of both spatial and feature space variability improves the performance of the corresponding models, and that adequate coverage of the variability in the feature space is the most important condition that should be met by the set of plots collected.

Discordant prostate specific antigen test results despite WHO assay standardization.

PubMed

Boegemann, Martin; Arsov, Christian; Hadaschik, Boris; Herkommer, Kathleen; Imkamp, Florian; Nofer, Jerzy-Roch; Gerß, Joachim; Albers, Peter; Semjonow, Axel

2018-05-01

Total PSA (tPSA) and free PSA (fPSA) are the most commonly used biomarkers for early detection of prostate cancer. Despite standardization efforts, many available PSA assays may still produce discordant results. In the present study, we compared four PSA assays calibrated to the WHO standards 96/670 and 96/668 for tPSA and fPSA, respectively. Within the scope of the Prostate Cancer Early Detection Study Based on a ''Baseline'' PSA Value in Young Men (PROBASE), we tested tPSA and fPSA in serum samples from 50 patients in the four different PROBASE sites using four WHO-calibrated assays from Roche (Elecsys, Cobas), Beckman-Coulter (Access-II) and Siemens (ADVIA Centaur). The comparison was performed using the Passing-Bablok regression method. Compared to Access, the median tPSA levels for Centaur, Elecsys, and Cobas were +3%, +11%-20%, and +17%-23%, respectively, while for median fPSA levels the differences for Centaur, Elecsys, and Cobas were +49%, +29%-31%, and +22%, respectively. Despite all investigated assays being WHO-calibrated, the Elecsys and Cobas tPSA assays produced considerably higher results than the Access and Centaur assays. Differences in fPSA-recovery between all investigated assays were even more pronounced. When applying the tPSA cutoff of 3.1 μg/L recommended for WHO-calibrated assays, the use of higher calibrated assays may lead to unnecessary prostate biopsies. Conversely, if the historical threshold of 4 μg/L is applied when using WHO-calibrated assays, it could lead to falsely omitted prostate biopsies.

Determination of polarimetric parameters of honey by near-infrared transflectance spectroscopy.

PubMed

García-Alvarez, M; Ceresuela, S; Huidobro, J F; Hermida, M; Rodríguez-Otero, J L

2002-01-30

NIR transflectance spectroscopy was used to determine polarimetric parameters (direct polarization, polarization after inversion, specific rotation in dry matter, and polarization due to nonmonosaccharides) and sucrose in honey. In total, 156 honey samples were collected during 1992 (45 samples), 1995 (56 samples), and 1996 (55 samples). Samples were analyzed by NIR spectroscopy and polarimetric methods. Calibration (118 samples) and validation (38 samples) sets were made up; honeys from the three years were included in both sets. Calibrations were performed by modified partial least-squares regression and scatter correction by standard normal variation and detrend methods. For direct polarization, polarization after inversion, specific rotation in dry matter, and polarization due to nonmonosaccharides, good statistics (bias, SEV, and R(2)) were obtained for the validation set, and no statistically (p = 0.05) significant differences were found between instrumental and polarimetric methods for these parameters. Statistical data for sucrose were not as good as those of the other parameters. Therefore, NIR spectroscopy is not an effective method for quantitative analysis of sucrose in these honey samples. However, NIR spectroscopy may be an acceptable method for semiquantitative evaluation of sucrose for honeys, such as those in our study, containing up to 3% of sucrose. Further work is necessary to validate the uncertainty at higher levels.

[Application of near infrared reflectance spectroscopy to predict meat chemical compositions: a review].

PubMed

Tao, Lin-Li; Yang, Xiu-Juan; Deng, Jun-Ming; Zhang, Xi

2013-11-01

In contrast to conventional methods for the determination of meat chemical composition, near infrared reflectance spectroscopy enables rapid, simple, secure and simultaneous assessment of numerous meat properties. The present review focuses on the use of near infrared reflectance spectroscopy to predict meat chemical compositions. The potential of near infrared reflectance spectroscopy to predict crude protein, intramuscular fat, fatty acid, moisture, ash, myoglobin and collagen of beef, pork, chicken and lamb is reviewed. This paper discusses existing questions and reasons in the current research. According to the published results, although published results vary considerably, they suggest that near-infrared reflectance spectroscopy shows a great potential to replace the expensive and time-consuming chemical analysis of meat composition. In particular, under commercial conditions where simultaneous measurements of different chemical components are required, near infrared reflectance spectroscopy is expected to be the method of choice. The majority of studies selected feature-related wavelengths using principal components regression, developed the calibration model using partial least squares and modified partial least squares, and estimated the prediction accuracy by means of cross-validation using the same sample set previously used for the calibration. Meat fatty acid composition predicted by near-infrared spectroscopy and non-destructive prediction and visualization of chemical composition in meat using near-infrared hyperspectral imaging and multivariate regression are the hot studying field now. On the other hand, near infrared reflectance spectroscopy shows great difference for predicting different attributes of meat quality which are closely related to the selection of calibration sample set, preprocessing of near-infrared spectroscopy and modeling approach. Sample preparation also has an important effect on the reliability of NIR prediction; in particular, lack of homogeneity of the meat samples influenced the accuracy of estimation of chemical components. In general the predicting results of intramuscular fat, fatty acid and moisture are best, the predicting results of crude protein and myoglobin are better, while the predicting results of ash and collagen are less accurate.

Moisture Influence Reducing Method for Heavy Metals Detection in Plant Materials Using Laser-Induced Breakdown Spectroscopy: A Case Study for Chromium Content Detection in Rice Leaves.

PubMed

Peng, Jiyu; He, Yong; Ye, Lanhan; Shen, Tingting; Liu, Fei; Kong, Wenwen; Liu, Xiaodan; Zhao, Yun

2017-07-18

Fast detection of heavy metals in plant materials is crucial for environmental remediation and ensuring food safety. However, most plant materials contain high moisture content, the influence of which cannot be simply ignored. Hence, we proposed moisture influence reducing method for fast detection of heavy metals using laser-induced breakdown spectroscopy (LIBS). First, we investigated the effect of moisture content on signal intensity, stability, and plasma parameters (temperature and electron density) and determined the main influential factors (experimental parameters F and the change of analyte concentration) on the variations of signal. For chromium content detection, the rice leaves were performed with a quick drying procedure, and two strategies were further used to reduce the effect of moisture content and shot-to-shot fluctuation. An exponential model based on the intensity of background was used to correct the actual element concentration in analyte. Also, the ratio of signal-to-background for univariable calibration and partial least squared regression (PLSR) for multivariable calibration were used to compensate the prediction deviations. The PLSR calibration model obtained the best result, with the correlation coefficient of 0.9669 and root-mean-square error of 4.75 mg/kg in the prediction set. The preliminary results indicated that the proposed method allowed for the detection of heavy metals in plant materials using LIBS, and it could be possibly used for element mapping in future work.

A calibration method for fringe reflection technique based on the analytical phase-slope description

NASA Astrophysics Data System (ADS)

Wu, Yuxiang; Yue, Huimin; Pan, Zhipeng; Liu, Yong

2018-05-01

The fringe reflection technique (FRT) has been one of the most popular methods to measure the shape of specular surface these years. The existing system calibration methods of FRT usually contain two parts, which are camera calibration and geometric calibration. In geometric calibration, the liquid crystal display (LCD) screen position calibration is one of the most difficult steps among all the calibration procedures, and its accuracy is affected by the factors such as the imaging aberration, the plane mirror flatness, and LCD screen pixel size accuracy. In this paper, based on the deduction of FRT analytical phase-slope description, we present a novel calibration method with no requirement to calibrate the position of LCD screen. On the other hand, the system can be arbitrarily arranged, and the imaging system can either be telecentric or non-telecentric. In our experiment of measuring the 5000mm radius sphere mirror, the proposed calibration method achieves 2.5 times smaller measurement error than the geometric calibration method. In the wafer surface measuring experiment, the measurement result with the proposed calibration method is closer to the interferometer result than the geometric calibration method.

Nighttime lidar water vapor mixing ratio profiling over Warsaw - impact of the relative humidity profile on cloud formation

NASA Astrophysics Data System (ADS)

Costa Surós, Montserrat; Stachlewska, Iwona S.

2016-04-01

A long-term study, assessing ground-based remote Raman lidar versus in-situ radiosounding has been conducted with the aim of improving the knowledge on the water content vertical profile through the atmosphere, and thus the conditions for cloud formation processes. Water vapor mixing ratio (WVMR) and relative humidity (RH) profiles were retrieved from ADR Lidar (PollyXT-type, EARLINET site in Warsaw). So far, more than 100 nighttime profiles averaged over 1h around midnight from July 2013 to December 2015 have been investigated. Data were evaluated with molecular extinctions calculated using two approximations: the US62 standard atmosphere and the radiosounding launched in Legionowo (12374). The calibration factor CH2O for lidar retrievals was obtained for each profile using the regression method and the profile method to determine the best calibration factor approximation to be used in the final WVMR and RH calculation. Thus, statistically representative results for comparisons between lidar WVMR median profiles obtained by calibrating using radiosounding profiles and using atmospheric synthetic profiles, all of them with the best calibration factor, will be presented. Finally, in order to constrain the conditions of cloud formation in function of the RH profile, the COS14 algorithm, capable of deriving cloud bases and tops by applying thresholds to the RH profiles, was applied to find the cloud vertical structure (CVS). The algorithm was former applied to radiosounding profiles at SGP-ARM site and tested against the CVS obtained from the Active Remote Sensing of Clouds (ARSCL) data. Similarly, it was applied for lidar measurements at the Warsaw measurement site.

Multicomponent kinetic spectrophotometric determination of pefloxacin and norfloxacin in pharmaceutical preparations and human plasma samples with the aid of chemometrics

NASA Astrophysics Data System (ADS)

Ni, Yongnian; Wang, Yong; Kokot, Serge

2008-10-01

A spectrophotometric method for the simultaneous determination of the important pharmaceuticals, pefloxacin and its structurally similar metabolite, norfloxacin, is described for the first time. The analysis is based on the monitoring of a kinetic spectrophotometric reaction of the two analytes with potassium permanganate as the oxidant. The measurement of the reaction process followed the absorbance decrease of potassium permanganate at 526 nm, and the accompanying increase of the product, potassium manganate, at 608 nm. It was essential to use multivariate calibrations to overcome severe spectral overlaps and similarities in reaction kinetics. Calibration curves for the individual analytes showed linear relationships over the concentration ranges of 1.0-11.5 mg L -1 at 526 and 608 nm for pefloxacin, and 0.15-1.8 mg L -1 at 526 and 608 nm for norfloxacin. Various multivariate calibration models were applied, at the two analytical wavelengths, for the simultaneous prediction of the two analytes including classical least squares (CLS), principal component regression (PCR), partial least squares (PLS), radial basis function-artificial neural network (RBF-ANN) and principal component-radial basis function-artificial neural network (PC-RBF-ANN). PLS and PC-RBF-ANN calibrations with the data collected at 526 nm, were the preferred methods—%RPE T ˜ 5, and LODs for pefloxacin and norfloxacin of 0.36 and 0.06 mg L -1, respectively. Then, the proposed method was applied successfully for the simultaneous determination of pefloxacin and norfloxacin present in pharmaceutical and human plasma samples. The results compared well with those from the alternative analysis by HPLC.

Prediction of Ba, Mn and Zn for tropical soils using iron oxides and magnetic susceptibility

NASA Astrophysics Data System (ADS)

Marques Júnior, José; Arantes Camargo, Livia; Reynaldo Ferracciú Alleoni, Luís; Tadeu Pereira, Gener; De Bortoli Teixeira, Daniel; Santos Rabelo de Souza Bahia, Angelica

2017-04-01

Agricultural activity is an important source of potentially toxic elements (PTEs) in soil worldwide but particularly in heavily farmed areas. Spatial distribution characterization of PTE contents in farming areas is crucial to assess further environmental impacts caused by soil contamination. Designing prediction models become quite useful to characterize the spatial variability of continuous variables, as it allows prediction of soil attributes that might be difficult to attain in a large number of samples through conventional methods. This study aimed to evaluate, in three geomorphic surfaces of Oxisols, the capacity for predicting PTEs (Ba, Mn, Zn) and their spatial variability using iron oxides and magnetic susceptibility (MS). Soil samples were collected from three geomorphic surfaces and analyzed for chemical, physical, mineralogical properties, as well as magnetic susceptibility (MS). PTE prediction models were calibrated by multiple linear regression (MLR). MLR calibration accuracy was evaluated using the coefficient of determination (R2). PTE spatial distribution maps were built using the values calculated by the calibrated models that reached the best accuracy by means of geostatistics. The high correlations between the attributes clay, MS, hematite (Hm), iron oxides extracted by sodium dithionite-citrate-bicarbonate (Fed), and iron oxides extracted using acid ammonium oxalate (Feo) with the elements Ba, Mn, and Zn enabled them to be selected as predictors for PTEs. Stepwise multiple linear regression showed that MS and Fed were the best PTE predictors individually, as they promoted no significant increase in R2 when two or more attributes were considered together. The MS-calibrated models for Ba, Mn, and Zn prediction exhibited R2 values of 0.88, 0.66, and 0.55, respectively. These are promising results since MS is a fast, cheap, and non-destructive tool, allowing the prediction of a large number of samples, which in turn enables detailed mapping of large areas. MS predicted values enabled the characterization and the understanding of spatial variability of the studied PTEs.

Statistical Post-Processing of Wind Speed Forecasts to Estimate Relative Economic Value

NASA Astrophysics Data System (ADS)

Courtney, Jennifer; Lynch, Peter; Sweeney, Conor

2013-04-01

The objective of this research is to get the best possible wind speed forecasts for the wind energy industry by using an optimal combination of well-established forecasting and post-processing methods. We start with the ECMWF 51 member ensemble prediction system (EPS) which is underdispersive and hence uncalibrated. We aim to produce wind speed forecasts that are more accurate and calibrated than the EPS. The 51 members of the EPS are clustered to 8 weighted representative members (RMs), chosen to minimize the within-cluster spread, while maximizing the inter-cluster spread. The forecasts are then downscaled using two limited area models, WRF and COSMO, at two resolutions, 14km and 3km. This process creates four distinguishable ensembles which are used as input to statistical post-processes requiring multi-model forecasts. Two such processes are presented here. The first, Bayesian Model Averaging, has been proven to provide more calibrated and accurate wind speed forecasts than the ECMWF EPS using this multi-model input data. The second, heteroscedastic censored regression is indicating positive results also. We compare the two post-processing methods, applied to a year of hindcast wind speed data around Ireland, using an array of deterministic and probabilistic verification techniques, such as MAE, CRPS, probability transform integrals and verification rank histograms, to show which method provides the most accurate and calibrated forecasts. However, the value of a forecast to an end-user cannot be fully quantified by just the accuracy and calibration measurements mentioned, as the relationship between skill and value is complex. Capturing the full potential of the forecast benefits also requires detailed knowledge of the end-users' weather sensitive decision-making processes and most importantly the economic impact it will have on their income. Finally, we present the continuous relative economic value of both post-processing methods to identify which is more beneficial to the wind energy industry of Ireland.

Coping with matrix effects in headspace solid phase microextraction gas chromatography using multivariate calibration strategies.

PubMed

Ferreira, Vicente; Herrero, Paula; Zapata, Julián; Escudero, Ana

2015-08-14

SPME is extremely sensitive to experimental parameters affecting liquid-gas and gas-solid distribution coefficients. Our aims were to measure the weights of these factors and to design a multivariate strategy based on the addition of a pool of internal standards, to minimize matrix effects. Synthetic but real-like wines containing selected analytes and variable amounts of ethanol, non-volatile constituents and major volatile compounds were prepared following a factorial design. The ANOVA study revealed that even using a strong matrix dilution, matrix effects are important and additive with non-significant interaction effects and that it is the presence of major volatile constituents the most dominant factor. A single internal standard provided a robust calibration for 15 out of 47 analytes. Then, two different multivariate calibration strategies based on Partial Least Square Regression were run in order to build calibration functions based on 13 different internal standards able to cope with matrix effects. The first one is based in the calculation of Multivariate Internal Standards (MIS), linear combinations of the normalized signals of the 13 internal standards, which provide the expected area of a given unit of analyte present in each sample. The second strategy is a direct calibration relating concentration to the 13 relative areas measured in each sample for each analyte. Overall, 47 different compounds can be reliably quantified in a single fully automated method with overall uncertainties better than 15%. Copyright © 2015 Elsevier B.V. All rights reserved.

Conversion of calibration curves for accurate estimation of molecular weight averages and distributions of polyether polyols by conventional size exclusion chromatography.

PubMed

Xu, Xiuqing; Yang, Xiuhan; Martin, Steven J; Mes, Edwin; Chen, Junlan; Meunier, David M

2018-08-17

Accurate measurement of molecular weight averages (M¯ n, M¯ w, M¯ z ) and molecular weight distributions (MWD) of polyether polyols by conventional SEC (size exclusion chromatography) is not as straightforward as it would appear. Conventional calibration with polystyrene (PS) standards can only provide PS apparent molecular weights which do not provide accurate estimates of polyol molecular weights. Using polyethylene oxide/polyethylene glycol (PEO/PEG) for molecular weight calibration could improve the accuracy, but the retention behavior of PEO/PEG is not stable in THF-based (tetrahydrofuran) SEC systems. In this work, two approaches for calibration curve conversion with narrow PS and polyol molecular weight standards were developed. Equations to convert PS-apparent molecular weight to polyol-apparent molecular weight were developed using both a rigorous mathematical analysis and graphical plot regression method. The conversion equations obtained by the two approaches were in good agreement. Factors influencing the conversion equation were investigated. It was concluded that the separation conditions such as column batch and operating temperature did not have significant impact on the conversion coefficients and a universal conversion equation could be obtained. With this conversion equation, more accurate estimates of molecular weight averages and MWDs for polyether polyols can be achieved from conventional PS-THF SEC calibration. Moreover, no additional experimentation is required to convert historical PS equivalent data to reasonably accurate molecular weight results. Copyright © 2018. Published by Elsevier B.V.

Spectral Reconstruction Based on Svm for Cross Calibration

NASA Astrophysics Data System (ADS)

Gao, H.; Ma, Y.; Liu, W.; He, H.

2017-05-01

Chinese HY-1C/1D satellites will use a 5nm/10nm-resolutional visible-near infrared(VNIR) hyperspectral sensor with the solar calibrator to cross-calibrate with other sensors. The hyperspectral radiance data are composed of average radiance in the sensor's passbands and bear a spectral smoothing effect, a transform from the hyperspectral radiance data to the 1-nm-resolution apparent spectral radiance by spectral reconstruction need to be implemented. In order to solve the problem of noise cumulation and deterioration after several times of iteration by the iterative algorithm, a novel regression method based on SVM is proposed, which can approach arbitrary complex non-linear relationship closely and provide with better generalization capability by learning. In the opinion of system, the relationship between the apparent radiance and equivalent radiance is nonlinear mapping introduced by spectral response function(SRF), SVM transform the low-dimensional non-linear question into high-dimensional linear question though kernel function, obtaining global optimal solution by virtue of quadratic form. The experiment is performed using 6S-simulated spectrums considering the SRF and SNR of the hyperspectral sensor, measured reflectance spectrums of water body and different atmosphere conditions. The contrastive result shows: firstly, the proposed method is with more reconstructed accuracy especially to the high-frequency signal; secondly, while the spectral resolution of the hyperspectral sensor reduces, the proposed method performs better than the iterative method; finally, the root mean square relative error(RMSRE) which is used to evaluate the difference of the reconstructed spectrum and the real spectrum over the whole spectral range is calculated, it decreses by one time at least by proposed method.

Simultaneous Quantification of Apolipoprotein A-I and Apolipoprotein B by Liquid-Chromatography–Multiple-Reaction–Monitoring Mass Spectrometry

PubMed Central

Agger, Sean A.; Marney, Luke C.; Hoofnagle, Andrew N.

2011-01-01

BACKGROUND If liquid-chromatography–multiple-reaction–monitoring mass spectrometry (LC-MRM/MS) could be used in the large-scale preclinical verification of putative biomarkers, it would obviate the need for the development of expensive immunoassays. In addition, the translation of novel biomarkers to clinical use would be accelerated if the assays used in preclinical studies were the same as those used in the clinical laboratory. To validate this approach, we developed a multiplexed assay for the quantification of 2 clinically well-known biomarkers in human plasma, apolipoprotein A-I and apolipoprotein B (apoA-I and apoB). METHODS We used PeptideAtlas to identify candidate peptides. Human samples were denatured with urea or trifluoroethanol, reduced and alkylated, and digested with trypsin. We compared reversed-phase chromatographic separation of peptides with normal flow and microflow, and we normalized endogenous peptide peak areas to internal standard peptides. We evaluated different methods of calibration and compared the final method with a nephelometric immunoassay. RESULTS We developed a final method using trifluoroethanol denaturation, 21-h digestion, normal flow chromatography-electrospray ionization, and calibration with a single normal human plasma sample. For samples injected in duplicate, the method had intraassay CVs <6% and interassay CVs <12% for both proteins, and compared well with immunoassay (n = 47; Deming regression, LC-MRM/MS = 1.17 × immunoassay – 36.6; Sx|y = 10.3 for apoA-I and LC-MRM/MS = 1.21 × immunoassay + 7.0; Sx|y = 7.9 for apoB). CONCLUSIONS Multiplexed quantification of proteins in human plasma/serum by LC-MRM/MS is possible and compares well with clinically useful immunoassays. The potential application of single-point calibration to large clinical studies could simplify efforts to reduce day-to-day digestion variability. PMID:20923952

Simultaneous determination of rifampicin, isoniazid and pyrazinamide in tablet preparations by multivariate spectrophotometric calibration.

PubMed

Goicoechea, H C; Olivieri, A C

1999-08-01

The use of multivariate spectrophotometric calibration is presented for the simultaneous determination of the active components of tablets used in the treatment of pulmonary tuberculosis. The resolution of ternary mixtures of rifampicin, isoniazid and pyrazinamide has been accomplished by using partial least squares (PLS-1) regression analysis. Although the components show an important degree of spectral overlap, they have been simultaneously determined with high accuracy and precision, rapidly and with no need of nonaqueous solvents for dissolving the samples. No interference has been observed from the tablet excipients. A comparison is presented with the related multivariate method of classical least squares (CLS) analysis, which is shown to yield less reliable results due to the severe spectral overlap among the studied compounds. This is highlighted in the case of isoniazid, due to the small absorbances measured for this component.

Selecting the optimum number of partial least squares components for the calibration of attenuated total reflectance-mid-infrared spectra of undesigned kerosene samples.

PubMed

Gómez-Carracedo, M P; Andrade, J M; Rutledge, D N; Faber, N M

2007-03-07

Selecting the correct dimensionality is critical for obtaining partial least squares (PLS) regression models with good predictive ability. Although calibration and validation sets are best established using experimental designs, industrial laboratories cannot afford such an approach. Typically, samples are collected in an (formally) undesigned way, spread over time and their measurements are included in routine measurement processes. This makes it hard to evaluate PLS model dimensionality. In this paper, classical criteria (leave-one-out cross-validation and adjusted Wold's criterion) are compared to recently proposed alternatives (smoothed PLS-PoLiSh and a randomization test) to seek out the optimum dimensionality of PLS models. Kerosene (jet fuel) samples were measured by attenuated total reflectance-mid-IR spectrometry and their spectra where used to predict eight important properties determined using reference methods that are time-consuming and prone to analytical errors. The alternative methods were shown to give reliable dimensionality predictions when compared to external validation. By contrast, the simpler methods seemed to be largely affected by the largest changes in the modeling capabilities of the first components.

Nomogram Prediction of Overall Survival After Curative Irradiation for Uterine Cervical Cancer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seo, YoungSeok; Yoo, Seong Yul; Kim, Mi-Sook

Purpose: The purpose of this study was to develop a nomogram capable of predicting the probability of 5-year survival after radical radiotherapy (RT) without chemotherapy for uterine cervical cancer. Methods and Materials: We retrospectively analyzed 549 patients that underwent radical RT for uterine cervical cancer between March 1994 and April 2002 at our institution. Multivariate analysis using Cox proportional hazards regression was performed and this Cox model was used as the basis for the devised nomogram. The model was internally validated for discrimination and calibration by bootstrap resampling. Results: By multivariate regression analysis, the model showed that age, hemoglobin levelmore » before RT, Federation Internationale de Gynecologie Obstetrique (FIGO) stage, maximal tumor diameter, lymph node status, and RT dose at Point A significantly predicted overall survival. The survival prediction model demonstrated good calibration and discrimination. The bootstrap-corrected concordance index was 0.67. The predictive ability of the nomogram proved to be superior to FIGO stage (p = 0.01). Conclusions: The devised nomogram offers a significantly better level of discrimination than the FIGO staging system. In particular, it improves predictions of survival probability and could be useful for counseling patients, choosing treatment modalities and schedules, and designing clinical trials. However, before this nomogram is used clinically, it should be externally validated.« less

Estimation of soil pH at Mount Beigu Wetland based on visible and near infrared reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Hu, Yongguang; Li, Pingping; Mao, Hanping; Chen, Bin; Wang, Xi

2006-12-01

pH of the wetland soil is one of the most important indicators for aquatic vegetation and water bodies. Mount Beigu Wetland, just near the Yangtse River, is under ecological recovery. Visible and near infrared reflectance spectroscopy was adopted to estimate soil pH of the wetland. The spectroradiometer, FieldSpec 3 (ASD) with a full spectral range (350-2500 nm), was used to acquire the reflectance spectra of wetland soil, and soil pH was measured with the pH meter of IQ150 (Spectrum) and InPro 3030 (Mettler Toledo). 146 soil samples were taken with soil sampler (Eijkelkamp) according to different position and depth, which covered the wider range of pH value from 7.1 to 8.39. 133 samples were used to establish the calibration model with the method of partial least square regression and principal component analysis regression. 13 soil samples were used to validate the model. The results show that the model is not good, but the mean error and root mean standard error of prediction are less (1.846% and 0.186 respectively). Spectral reflectancebased estimation of soil pH of the wetland is applicable and the calibration model needs to be improved.

Application of nonlinear least-squares regression to ground-water flow modeling, west-central Florida

USGS Publications Warehouse

Yobbi, D.K.

2000-01-01

A nonlinear least-squares regression technique for estimation of ground-water flow model parameters was applied to an existing model of the regional aquifer system underlying west-central Florida. The regression technique minimizes the differences between measured and simulated water levels. Regression statistics, including parameter sensitivities and correlations, were calculated for reported parameter values in the existing model. Optimal parameter values for selected hydrologic variables of interest are estimated by nonlinear regression. Optimal estimates of parameter values are about 140 times greater than and about 0.01 times less than reported values. Independently estimating all parameters by nonlinear regression was impossible, given the existing zonation structure and number of observations, because of parameter insensitivity and correlation. Although the model yields parameter values similar to those estimated by other methods and reproduces the measured water levels reasonably accurately, a simpler parameter structure should be considered. Some possible ways of improving model calibration are to: (1) modify the defined parameter-zonation structure by omitting and/or combining parameters to be estimated; (2) carefully eliminate observation data based on evidence that they are likely to be biased; (3) collect additional water-level data; (4) assign values to insensitive parameters, and (5) estimate the most sensitive parameters first, then, using the optimized values for these parameters, estimate the entire data set.

Fast Detection of Copper Content in Rice by Laser-Induced Breakdown Spectroscopy with Uni- and Multivariate Analysis.

PubMed

Liu, Fei; Ye, Lanhan; Peng, Jiyu; Song, Kunlin; Shen, Tingting; Zhang, Chu; He, Yong

2018-02-27

Fast detection of heavy metals is very important for ensuring the quality and safety of crops. Laser-induced breakdown spectroscopy (LIBS), coupled with uni- and multivariate analysis, was applied for quantitative analysis of copper in three kinds of rice (Jiangsu rice, regular rice, and Simiao rice). For univariate analysis, three pre-processing methods were applied to reduce fluctuations, including background normalization, the internal standard method, and the standard normal variate (SNV). Linear regression models showed a strong correlation between spectral intensity and Cu content, with an R 2 more than 0.97. The limit of detection (LOD) was around 5 ppm, lower than the tolerance limit of copper in foods. For multivariate analysis, partial least squares regression (PLSR) showed its advantage in extracting effective information for prediction, and its sensitivity reached 1.95 ppm, while support vector machine regression (SVMR) performed better in both calibration and prediction sets, where R c 2 and R p 2 reached 0.9979 and 0.9879, respectively. This study showed that LIBS could be considered as a constructive tool for the quantification of copper contamination in rice.

Fast Detection of Copper Content in Rice by Laser-Induced Breakdown Spectroscopy with Uni- and Multivariate Analysis

PubMed Central

Ye, Lanhan; Song, Kunlin; Shen, Tingting

2018-01-01

Fast detection of heavy metals is very important for ensuring the quality and safety of crops. Laser-induced breakdown spectroscopy (LIBS), coupled with uni- and multivariate analysis, was applied for quantitative analysis of copper in three kinds of rice (Jiangsu rice, regular rice, and Simiao rice). For univariate analysis, three pre-processing methods were applied to reduce fluctuations, including background normalization, the internal standard method, and the standard normal variate (SNV). Linear regression models showed a strong correlation between spectral intensity and Cu content, with an R2 more than 0.97. The limit of detection (LOD) was around 5 ppm, lower than the tolerance limit of copper in foods. For multivariate analysis, partial least squares regression (PLSR) showed its advantage in extracting effective information for prediction, and its sensitivity reached 1.95 ppm, while support vector machine regression (SVMR) performed better in both calibration and prediction sets, where Rc2 and Rp2 reached 0.9979 and 0.9879, respectively. This study showed that LIBS could be considered as a constructive tool for the quantification of copper contamination in rice. PMID:29495445

Methods for estimating tributary streamflow in the Chattahoochee River basin between Buford Dam and Franklin, Georgia

USGS Publications Warehouse

Stamey, Timothy C.

1998-01-01

Simple and reliable methods for estimating hourly streamflow are needed for the calibration and verification of a Chattahoochee River basin model between Buford Dam and Franklin, Ga. The river basin model is being developed by Georgia Department of Natural Resources, Environmental Protection Division, as part of their Chattahoochee River Modeling Project. Concurrent streamflow data collected at 19 continuous-record, and 31 partial-record streamflow stations, were used in ordinary least-squares linear regression analyses to define estimating equations, and in verifying drainage-area prorations. The resulting regression or drainage-area ratio estimating equations were used to compute hourly streamflow at the partial-record stations. The coefficients of determination (r-squared values) for the regression estimating equations ranged from 0.90 to 0.99. Observed and estimated hourly and daily streamflow data were computed for May 1, 1995, through October 31, 1995. Comparisons of observed and estimated daily streamflow data for 12 continuous-record tributary stations, that had available streamflow data for all or part of the period from May 1, 1995, to October 31, 1995, indicate that the mean error of estimate for the daily streamflow was about 25 percent.

Strain-gage bridge calibration and flight loads measurements on a low-aspect-ratio thin wing

NASA Technical Reports Server (NTRS)

Peele, E. L.; Eckstrom, C. V.

1975-01-01

Strain-gage bridges were used to make in-flight measurements of bending moment, shear, and torque loads on a low-aspect-ratio, thin, swept wing having a full depth honeycomb sandwich type structure. Standard regression analysis techniques were employed in the calibration of the strain bridges. Comparison of the measured loads with theoretical loads are included.

Calibration method for a large-scale structured light measurement system.

PubMed

Wang, Peng; Wang, Jianmei; Xu, Jing; Guan, Yong; Zhang, Guanglie; Chen, Ken

2017-05-10

The structured light method is an effective non-contact measurement approach. The calibration greatly affects the measurement precision of structured light systems. To construct a large-scale structured light system with high accuracy, a large-scale and precise calibration gauge is always required, which leads to an increased cost. To this end, in this paper, a calibration method with a planar mirror is proposed to reduce the calibration gauge size and cost. An out-of-focus camera calibration method is also proposed to overcome the defocusing problem caused by the shortened distance during the calibration procedure. The experimental results verify the accuracy of the proposed calibration method.

Near-infrared diffuse reflection systems for chlorophyll content of tomato leaves measurement

NASA Astrophysics Data System (ADS)

Jiang, Huanyu; Ying, Yibin; Lu, Huishan

2006-10-01

In this study, two measuring systems for chlorophyll content of tomato leaves were developed based on near-infrared spectral techniques. The systems mainly consists of a FT-IR spectrum analyzer, optic fiber diffuses reflection accessories and data card. Diffuse reflectance of intact tomato leaves was measured by an optics fiber optic fiber diffuses reflection accessory and a smart diffuses reflection accessory. Calibration models were developed from spectral and constituent measurements. 90 samples served as the calibration sets and 30 samples served as the validation sets. Partial least squares (PLS) and principal component regression (PCR) technique were used to develop the prediction models by different data preprocessing. The best model for chlorophyll content had a high correlation efficient of 0.9348 and a low standard error of prediction RMSEP of 4.79 when we select full range (12500-4000 cm -1), MSC path length correction method by the log(1/R). The results of this study suggest that FT-NIR method can be feasible to detect chlorophyll content of tomato leaves rapidly and nondestructively.

Quantitative Determination of Fluorine Content in Blends of Polylactide (PLA)–Talc Using Near Infrared Spectroscopy

PubMed Central

Tamburini, Elena; Tagliati, Chiara; Bonato, Tiziano; Costa, Stefania; Scapoli, Chiara; Pedrini, Paola

2016-01-01

Near-infrared spectroscopy (NIRS) has been widely used for quantitative and/or qualitative determination of a wide range of matrices. The objective of this study was to develop a NIRS method for the quantitative determination of fluorine content in polylactide (PLA)-talc blends. A blending profile was obtained by mixing different amounts of PLA granules and talc powder. The calibration model was built correlating wet chemical data (alkali digestion method) and NIR spectra. Using FT (Fourier Transform)-NIR technique, a Partial Least Squares (PLS) regression model was set-up, in a concentration interval of 0 ppm of pure PLA to 800 ppm of pure talc. Fluorine content prediction (R2cal = 0.9498; standard error of calibration, SEC = 34.77; standard error of cross-validation, SECV = 46.94) was then externally validated by means of a further 15 independent samples (R2EX.V = 0.8955; root mean standard error of prediction, RMSEP = 61.08). A positive relationship between an inorganic component as fluorine and NIR signal has been evidenced, and used to obtain quantitative analytical information from the spectra. PMID:27490548

Online EEG artifact removal for BCI applications by adaptive spatial filtering.

PubMed

Guarnieri, Roberto; Marino, Marco; Barban, Federico; Ganzetti, Marco; Mantini, Dante

2018-06-28

The performance of brain computer interfaces (BCIs) based on electroencephalography (EEG) data strongly depends on the effective attenuation of artifacts that are mixed in the recordings. To address this problem, we have developed a novel online EEG artifact removal method for BCI applications, which combines blind source separation (BSS) and regression (REG) analysis. The BSS-REG method relies on the availability of a calibration dataset of limited duration for the initialization of a spatial filter using BSS. Online artifact removal is implemented by dynamically adjusting the spatial filter in the actual experiment, based on a linear regression technique. Our results showed that the BSS-REG method is capable of attenuating different kinds of artifacts, including ocular and muscular, while preserving true neural activity. Thanks to its low computational requirements, BSS-REG can be applied to low-density as well as high-density EEG data. We argue that BSS-REG may enable the development of novel BCI applications requiring high-density recordings, such as source-based neurofeedback and closed-loop neuromodulation. © 2018 IOP Publishing Ltd.

[Quantitative structure-gas chromatographic retention relationship of polycyclic aromatic sulfur heterocycles using molecular electronegativity-distance vector].

PubMed

Li, Zhenghua; Cheng, Fansheng; Xia, Zhining

2011-01-01

The chemical structures of 114 polycyclic aromatic sulfur heterocycles (PASHs) have been studied by molecular electronegativity-distance vector (MEDV). The linear relationships between gas chromatographic retention index and the MEDV have been established by a multiple linear regression (MLR) model. The results of variable selection by stepwise multiple regression (SMR) and the powerful predictive abilities of the optimization model appraised by leave-one-out cross-validation showed that the optimization model with the correlation coefficient (R) of 0.994 7 and the cross-validated correlation coefficient (Rcv) of 0.994 0 possessed the best statistical quality. Furthermore, when the 114 PASHs compounds were divided into calibration and test sets in the ratio of 2:1, the statistical analysis showed our models possesses almost equal statistical quality, the very similar regression coefficients and the good robustness. The quantitative structure-retention relationship (QSRR) model established may provide a convenient and powerful method for predicting the gas chromatographic retention of PASHs.

Short wavelength Raman spectroscopy applied to the discrimination and characterization of three cultivars of extra virgin olive oils in different maturation stages.

PubMed

Gouvinhas, Irene; Machado, Nelson; Carvalho, Teresa; de Almeida, José M M M; Barros, Ana I R N A

2015-01-01

Extra virgin olive oils produced from three cultivars on different maturation stages were characterized using Raman spectroscopy. Chemometric methods (principal component analysis, discriminant analysis, principal component regression and partial least squares regression) applied to Raman spectral data were utilized to evaluate and quantify the statistical differences between cultivars and their ripening process. The models for predicting the peroxide value and free acidity of olive oils showed good calibration and prediction values and presented high coefficients of determination (>0.933). Both the R(2), and the correlation equations between the measured chemical parameters, and the values predicted by each approach are presented; these comprehend both PCR and PLS, used to assess SNV normalized Raman data, as well as first and second derivative of the spectra. This study demonstrates that a combination of Raman spectroscopy with multivariate analysis methods can be useful to predict rapidly olive oil chemical characteristics during the maturation process. Copyright © 2014 Elsevier B.V. All rights reserved.

Methods for Adjusting U.S. Geological Survey Rural Regression Peak Discharges in an Urban Setting

USGS Publications Warehouse

Moglen, Glenn E.; Shivers, Dorianne E.

2006-01-01

A study was conducted of 78 U.S. Geological Survey gaged streams that have been subjected to varying degrees of urbanization over the last three decades. Flood-frequency analysis coupled with nonlinear regression techniques were used to generate a set of equations for converting peak discharge estimates determined from rural regression equations to a set of peak discharge estimates that represent known urbanization. Specifically, urban regression equations for the 2-, 5-, 10-, 25-, 50-, 100-, and 500-year return periods were calibrated as a function of the corresponding rural peak discharge and the percentage of impervious area in a watershed. The results of this study indicate that two sets of equations, one set based on imperviousness and one set based on population density, performed well. Both sets of equations are dependent on rural peak discharges, a measure of development (average percentage of imperviousness or average population density), and a measure of homogeneity of development within a watershed. Average imperviousness was readily determined by using geographic information system methods and commonly available land-cover data. Similarly, average population density was easily determined from census data. Thus, a key advantage to the equations developed in this study is that they do not require field measurements of watershed characteristics as did the U.S. Geological Survey urban equations developed in an earlier investigation. During this study, the U.S. Geological Survey PeakFQ program was used as an integral tool in the calibration of all equations. The scarcity of historical land-use data, however, made exclusive use of flow records necessary for the 30-year period from 1970 to 2000. Such relatively short-duration streamflow time series required a nonstandard treatment of the historical data function of the PeakFQ program in comparison to published guidelines. Thus, the approach used during this investigation does not fully comply with the guidelines set forth in U.S. Geological Survey Bulletin 17B, and modifications may be needed before it can be applied in practice.

Calibration power of the Braden scale in predicting pressure ulcer development.

PubMed

Chen, Hong-Lin; Cao, Ying-Juan; Wang, Jing; Huai, Bao-Sha

2016-11-02

Calibration is the degree of correspondence between the estimated probability produced by a model and the actual observed probability. The aim of this study was to investigate the calibration power of the Braden scale in predicting pressure ulcer development (PU). A retrospective analysis was performed among consecutive patients in 2013. The patients were separated into training a group and a validation group. The predicted incidence was calculated using a logistic regression model in the training group and the Hosmer-Lemeshow test was used for assessing the goodness of fit. In the validation cohort, the observed and the predicted incidence were compared by the Chi-square (χ 2 ) goodness of fit test for calibration power. We included 2585 patients in the study, of these 78 patients (3.0%) developed a PU. Between the training and validation groups the patient characteristics were non-significant (p>0.05). In the training group, the logistic regression model for predicting pressure ulcer was Logit(P) = -0.433*Braden score+2.616. The Hosmer-Lemeshow test showed no goodness fit (χ 2 =13.472; p=0.019). In the validation group, the predicted pressure ulcer incidence also did not fit well with the observed incidence (χ 2 =42.154, p=0.000 by Braden scores; and χ 2 =17.223, p=0.001 by Braden scale risk classification). The Braden scale has low calibration power in predicting PU formation.

A practical approach for linearity assessment of calibration curves under the International Union of Pure and Applied Chemistry (IUPAC) guidelines for an in-house validation of method of analysis.

PubMed

Sanagi, M Marsin; Nasir, Zalilah; Ling, Susie Lu; Hermawan, Dadan; Ibrahim, Wan Aini Wan; Naim, Ahmedy Abu

2010-01-01

Linearity assessment as required in method validation has always been subject to different interpretations and definitions by various guidelines and protocols. However, there are very limited applicable implementation procedures that can be followed by a laboratory chemist in assessing linearity. Thus, this work proposes a simple method for linearity assessment in method validation by a regression analysis that covers experimental design, estimation of the parameters, outlier treatment, and evaluation of the assumptions according to the International Union of Pure and Applied Chemistry guidelines. The suitability of this procedure was demonstrated by its application to an in-house validation for the determination of plasticizers in plastic food packaging by GC.

Estimating peak discharges, flood volumes, and hydrograph shapes of small ungaged urban streams in Ohio

USGS Publications Warehouse

Sherwood, J.M.

1986-01-01

Methods are presented for estimating peak discharges, flood volumes and hydrograph shapes of small (less than 5 sq mi) urban streams in Ohio. Examples of how to use the various regression equations and estimating techniques also are presented. Multiple-regression equations were developed for estimating peak discharges having recurrence intervals of 2, 5, 10, 25, 50, and 100 years. The significant independent variables affecting peak discharge are drainage area, main-channel slope, average basin-elevation index, and basin-development factor. Standard errors of regression and prediction for the peak discharge equations range from +/-37% to +/-41%. An equation also was developed to estimate the flood volume of a given peak discharge. Peak discharge, drainage area, main-channel slope, and basin-development factor were found to be the significant independent variables affecting flood volumes for given peak discharges. The standard error of regression for the volume equation is +/-52%. A technique is described for estimating the shape of a runoff hydrograph by applying a specific peak discharge and the estimated lagtime to a dimensionless hydrograph. An equation for estimating the lagtime of a basin was developed. Two variables--main-channel length divided by the square root of the main-channel slope and basin-development factor--have a significant effect on basin lagtime. The standard error of regression for the lagtime equation is +/-48%. The data base for the study was established by collecting rainfall-runoff data at 30 basins distributed throughout several metropolitan areas of Ohio. Five to eight years of data were collected at a 5-min record interval. The USGS rainfall-runoff model A634 was calibrated for each site. The calibrated models were used in conjunction with long-term rainfall records to generate a long-term streamflow record for each site. Each annual peak-discharge record was fitted to a Log-Pearson Type III frequency curve. Multiple-regression techniques were then used to analyze the peak discharge data as a function of the basin characteristics of the 30 sites. (Author 's abstract)

Identification of spectral regions for the quantification of red wine tannins with fourier transform mid-infrared spectroscopy.

PubMed

Jensen, Jacob S; Egebo, Max; Meyer, Anne S

2008-05-28

Accomplishment of fast tannin measurements is receiving increased interest as tannins are important for the mouthfeel and color properties of red wines. Fourier transform mid-infrared spectroscopy allows fast measurement of different wine components, but quantification of tannins is difficult due to interferences from spectral responses of other wine components. Four different variable selection tools were investigated for the identification of the most important spectral regions which would allow quantification of tannins from the spectra using partial least-squares regression. The study included the development of a new variable selection tool, iterative backward elimination of changeable size intervals PLS. The spectral regions identified by the different variable selection methods were not identical, but all included two regions (1485-1425 and 1060-995 cm(-1)), which therefore were concluded to be particularly important for tannin quantification. The spectral regions identified from the variable selection methods were used to develop calibration models. All four variable selection methods identified regions that allowed an improved quantitative prediction of tannins (RMSEP = 69-79 mg of CE/L; r = 0.93-0.94) as compared to a calibration model developed using all variables (RMSEP = 115 mg of CE/L; r = 0.87). Only minor differences in the performance of the variable selection methods were observed.

A projector calibration method for monocular structured light system based on digital image correlation

NASA Astrophysics Data System (ADS)

Feng, Zhixin

2018-02-01

Projector calibration is crucial for a camera-projector three-dimensional (3-D) structured light measurement system, which has one camera and one projector. In this paper, a novel projector calibration method is proposed based on digital image correlation. In the method, the projector is viewed as an inverse camera, and a plane calibration board with feature points is used to calibrate the projector. During the calibration processing, a random speckle pattern is projected onto the calibration board with different orientations to establish the correspondences between projector images and camera images. Thereby, dataset for projector calibration are generated. Then the projector can be calibrated using a well-established camera calibration algorithm. The experiment results confirm that the proposed method is accurate and reliable for projector calibration.

Criteria for the use of regression analysis for remote sensing of sediment and pollutants

NASA Technical Reports Server (NTRS)

Whitlock, C. H.; Kuo, C. Y.; Lecroy, S. R. (Principal Investigator)

1982-01-01

Data analysis procedures for quantification of water quality parameters that are already identified and are known to exist within the water body are considered. The liner multiple-regression technique was examined as a procedure for defining and calibrating data analysis algorithms for such instruments as spectrometers and multispectral scanners.

Thermal sensation and climate: a comparison of UTCI and PET thresholds in different climates

NASA Astrophysics Data System (ADS)

Pantavou, Katerina; Lykoudis, Spyridon; Nikolopoulou, Marialena; Tsiros, Ioannis X.

2018-06-01

The influence of physiological acclimatization and psychological adaptation on thermal perception is well documented and has revealed the importance of thermal experience and expectation in the evaluation of environmental stimuli. Seasonal patterns of thermal perception have been studied, and calibrated thermal indices' scales have been proposed to obtain meaningful interpretations of thermal sensation indices in different climate regions. The current work attempts to quantify the contribution of climate to the long-term thermal adaptation by examining the relationship between climate normal annual air temperature (1971-2000) and such climate-calibrated thermal indices' assessment scales. The thermal sensation ranges of two thermal indices, the Universal Thermal Climate Index (UTCI) and the Physiological Equivalent Temperature Index (PET), were calibrated for three warm temperate climate contexts (Cfa, Cfb, Csa), against the subjective evaluation of the thermal environment indicated by interviewees during field surveys conducted at seven European cities: Athens (GR), Thessaloniki (GR), Milan (IT), Fribourg (CH), Kassel (DE), Cambridge (UK), and Sheffield (UK), under the same research protocol. Then, calibrated scales for other climate contexts were added from the literature, and the relationship between the respective scales' thresholds and climate normal annual air temperature was examined. To maintain the maximum possible comparability, three methods were applied for the calibration, namely linear, ordinal, and probit regression. The results indicated that the calibrated UTCI and PET thresholds increase with the climate normal annual air temperature of the survey city. To investigate further climates, we also included in the analysis results of previous studies presenting only thresholds for neutral thermal sensation. The average increase of the respective thresholds in the case of neutral thermal sensation was about 0.6 °C for each 1 °C increase of the normal annual air temperature for both indices, statistically significant only for PET though.

Application of near-infrared spectroscopy for estimation of non-structural carbohydrates in foliar samples of Eucalyptus globulus Labilladière.

PubMed

Quentin, A G; Rodemann, T; Doutreleau, M-F; Moreau, M; Davies, N W; Millard, Peter

2017-01-31

Near-infrared reflectance spectroscopy (NIRS) is frequently used for the assessment of key nutrients of forage or crops but remains underused in ecological and physiological studies, especially to quantify non-structural carbohydrates. The aim of this study was to develop calibration models to assess the content in soluble sugars (fructose, glucose, sucrose) and starch in foliar material of Eucalyptus globulus. A partial least squares (PLS) regression was used on the sample spectral data and was compared to the contents measured using standard wet chemistry methods. The calibration models were validated using a completely independent set of samples. We used key indicators such as the ratio of prediction to deviation (RPD) and the range error ratio to give an assessment of the performance of the calibration models. Accurate calibration models were obtained for fructose and sucrose content (R2 > 0.85, root mean square error of prediction (RMSEP) of 0.95%–1.26% in the validation models), followed by sucrose and total soluble sugar content (R2 ~ 0.70 and RMSEP > 2.3%). In comparison to the others, calibration of the starch model performed very poorly with RPD = 1.70. This study establishes the ability of the NIRS calibration model to infer soluble sugar content in foliar samples of E. globulus in a rapid and cost-effective way. We suggest a complete redevelopment of the starch analysis using more specific quantification such as an HPLC-based technique to reach higher performance in the starch model. Overall, NIRS could serve as a high-throughput phenotyping tool to study plant response to stress factors.

Parameterizing sorption isotherms using a hybrid global-local fitting procedure.

PubMed

Matott, L Shawn; Singh, Anshuman; Rabideau, Alan J

2017-05-01

Predictive modeling of the transport and remediation of groundwater contaminants requires an accurate description of the sorption process, which is usually provided by fitting an isotherm model to site-specific laboratory data. Commonly used calibration procedures, listed in order of increasing sophistication, include: trial-and-error, linearization, non-linear regression, global search, and hybrid global-local search. Given the considerable variability in fitting procedures applied in published isotherm studies, we investigated the importance of algorithm selection through a series of numerical experiments involving 13 previously published sorption datasets. These datasets, considered representative of state-of-the-art for isotherm experiments, had been previously analyzed using trial-and-error, linearization, or non-linear regression methods. The isotherm expressions were re-fit using a 3-stage hybrid global-local search procedure (i.e. global search using particle swarm optimization followed by Powell's derivative free local search method and Gauss-Marquardt-Levenberg non-linear regression). The re-fitted expressions were then compared to previously published fits in terms of the optimized weighted sum of squared residuals (WSSR) fitness function, the final estimated parameters, and the influence on contaminant transport predictions - where easily computed concentration-dependent contaminant retardation factors served as a surrogate measure of likely transport behavior. Results suggest that many of the previously published calibrated isotherm parameter sets were local minima. In some cases, the updated hybrid global-local search yielded order-of-magnitude reductions in the fitness function. In particular, of the candidate isotherms, the Polanyi-type models were most likely to benefit from the use of the hybrid fitting procedure. In some cases, improvements in fitness function were associated with slight (<10%) changes in parameter values, but in other cases significant (>50%) changes in parameter values were noted. Despite these differences, the influence of isotherm misspecification on contaminant transport predictions was quite variable and difficult to predict from inspection of the isotherms. Copyright © 2017 Elsevier B.V. All rights reserved.

Accounting for inter-annual and seasonal variability in regionalization of hydrologic response in the Great Lakes basin

NASA Astrophysics Data System (ADS)

Kult, J. M.; Fry, L. M.; Gronewold, A. D.

2012-12-01

Methods for predicting streamflow in areas with limited or nonexistent measures of hydrologic response typically invoke the concept of regionalization, whereby knowledge pertaining to gauged catchments is transferred to ungauged catchments. In this study, we identify watershed physical characteristics acting as primary drivers of hydrologic response throughout the US portion of the Great Lakes basin. Relationships between watershed physical characteristics and hydrologic response are generated from 166 catchments spanning a variety of climate, soil, land cover, and land form regimes through regression tree analysis, leading to a grouping of watersheds exhibiting similar hydrologic response characteristics. These groupings are then used to predict response in ungauged watersheds in an uncertainty framework. Results from this method are assessed alongside one historical regionalization approach which, while simple, has served as a cornerstone of Great Lakes regional hydrologic research for several decades. Our approach expands upon previous research by considering multiple temporal characterizations of hydrologic response. Due to the substantial inter-annual and seasonal variability in hydrologic response observed over the Great Lakes basin, results from the regression tree analysis differ considerably depending on the level of temporal aggregation used to define the response. Specifically, higher levels of temporal aggregation for the response metric (for example, indices derived from long-term means of climate and streamflow observations) lead to improved watershed groupings with lower within-group variance. However, this perceived improvement in model skill occurs at the cost of understated uncertainty when applying the regression to time series simulations or as a basis for model calibration. In such cases, our results indicate that predictions based on long-term characterizations of hydrologic response can produce misleading conclusions when applied at shorter time steps. This study suggests that measures of hydrologic response quantified at these shorter time steps may provide a more robust basis for making predictions in applications of water resource management, model calibration and simulations, and human health and safety.

Calcic amphibole thermobarometry in metamorphic and igneous rocks: New calibrations based on plagioclase/amphibole Al-Si partitioning and amphibole/liquid Mg partitioning

NASA Astrophysics Data System (ADS)

Molina, J. F.; Moreno, J. A.; Castro, A.; Rodríguez, C.; Fershtater, G. B.

2015-09-01

Dependencies of plagioclase/amphibole Al-Si partitioning, DAl/Siplg/amp, and amphibole/liquid Mg partitioning, DMgamp/liq, on temperature, pressure and phase compositions are investigated employing robust regression methods based on MM-estimators. A database with 92 amphibole-plagioclase pairs - temperature range: 650-1050 °C; amphibole compositional limits: > 0.02 apfu (23O) Ti and > 0.05 apfu Al - and 148 amphibole-glass pairs - temperature range: 800-1100 °C; amphibole compositional limit: CaM4/(CaM4 + NaM4) > 0.75 - compiled from experiments in the literature was used for the calculations (amphibole normalization scheme: 13-CNK method).

Indirect spectrophotometric determination of arbutin, whitening agent through oxidation by periodate and complexation with ferric chloride

NASA Astrophysics Data System (ADS)

Barsoom, B. N.; Abdelsamad, A. M. E.; Adib, N. M.

2006-07-01

A simple and accurate spectrophotometric method for the determination of arbutin (glycosylated hydroquinone) is described. It is based on the oxidation of arbutin by periodate in presence of iodate. Excess periodate causes liberation of iodine at pH 8.0. The unreacted periodate is determined by measurement of the liberated iodine spectrophotometrically in the wavelength range (300-500 nm). A calibration curve was constructed for more accurate results and the correlation coefficient of linear regression analysis was -0.9778. The precision of this method was better than 6.17% R.S.D. ( n = 3). Regression analysis of Bear-Lambert plot shows good correlation in the concentration range 25-125 ug/ml. The identification limit was determined to be 25 ug/ml a detailed study of the reaction conditions was carried out, including effect of changing pH, time, temperature and volume of periodate. Analyzing pure and authentic samples containing arbutin tested the validity of the proposed method which has an average percent recovery of 100.86%. An alternative method is also proposed which involves a complexation reaction between arbutin and ferric chloride solution. The produced complex which is yellowish-green in color was determined spectophotometrically.

Non-contact thrust stand calibration method for repetitively pulsed electric thrusters.

PubMed

Wong, Andrea R; Toftul, Alexandra; Polzin, Kurt A; Pearson, J Boise

2012-02-01

A thrust stand calibration technique for use in testing repetitively pulsed electric thrusters for in-space propulsion has been developed and tested using a modified hanging pendulum thrust stand. In the implementation of this technique, current pulses are applied to a solenoid to produce a pulsed magnetic field that acts against a permanent magnet mounted to the thrust stand pendulum arm. The force on the magnet is applied in this non-contact manner, with the entire pulsed force transferred to the pendulum arm through a piezoelectric force transducer to provide a time-accurate force measurement. Modeling of the pendulum arm dynamics reveals that after an initial transient in thrust stand motion the quasi-steady average deflection of the thrust stand arm away from the unforced or "zero" position can be related to the average applied force through a simple linear Hooke's law relationship. Modeling demonstrates that this technique is universally applicable except when the pulsing period is increased to the point where it approaches the period of natural thrust stand motion. Calibration data were obtained using a modified hanging pendulum thrust stand previously used for steady-state thrust measurements. Data were obtained for varying impulse bit at constant pulse frequency and for varying pulse frequency. The two data sets exhibit excellent quantitative agreement with each other. The overall error on the linear regression fit used to determine the calibration coefficient was roughly 1%.

Using a gradient boosting model to improve the performance of low-cost aerosol monitors in a dense, heterogeneous urban environment

NASA Astrophysics Data System (ADS)

Johnson, Nicholas E.; Bonczak, Bartosz; Kontokosta, Constantine E.

2018-07-01

The increased availability and improved quality of new sensing technologies have catalyzed a growing body of research to evaluate and leverage these tools in order to quantify and describe urban environments. Air quality, in particular, has received greater attention because of the well-established links to serious respiratory illnesses and the unprecedented levels of air pollution in developed and developing countries and cities around the world. Though numerous laboratory and field evaluation studies have begun to explore the use and potential of low-cost air quality monitoring devices, the performance and stability of these tools has not been adequately evaluated in complex urban environments, and further research is needed. In this study, we present the design of a low-cost air quality monitoring platform based on the Shinyei PPD42 aerosol monitor and examine the suitability of the sensor for deployment in a dense heterogeneous urban environment. We assess the sensor's performance during a field calibration campaign from February 7th to March 25th 2017 with a reference instrument in New York City, and present a novel calibration approach using a machine learning method that incorporates publicly available meteorological data in order to improve overall sensor performance. We find that while the PPD42 performs well in relation to the reference instrument using linear regression (R2 = 0.36-0.51), a gradient boosting regression tree model can significantly improve device calibration (R2 = 0.68-0.76). We discuss the sensor's performance and reliability when deployed in a dense, heterogeneous urban environment during a period of significant variation in weather conditions, and important considerations when using machine learning techniques to improve the performance of low-cost air quality monitors.

Calibration in dogs of a subcutaneous miniaturized glucose sensor using a glucose meter for blood glucose determination.

PubMed

Poitout, V; Moatti-Sirat, D; Reach, G

1992-01-01

The feasibility of calibrating a glucose sensor by using a wearable glucose meter for blood glucose determination and moderate variations of blood glucose concentration was assessed. Six miniaturized glucose sensors were implanted in the subcutaneous tissue of conscious dogs, and the parameters used for the in vivo calibration of the sensor (sensitivity coefficient and extrapolated current in the absence of glucose) were determined from values of blood glucose and sensor response obtained during glucose infusion. (1) Venous plasma glucose level and venous total blood glucose level were measured simultaneously on the same sample, using a Beckman analyser and a Glucometer II, respectively. The regression between plasma glucose (x) and whole blood glucose (y) was y = 1.12x-0.08 mM (n = 114 values, r = 0.96, p = 0.0001). The error grid analysis indicated that the use of a Glucometer II for blood glucose determination was appropriate in dogs. (2) The in vivo sensitivity coefficients were 0.57 +/- 0.11 nA mM-1 when determined from plasma glucose, and 0.51 +/- 0.07 nA mM-1 when determined from whole blood glucose (t = 1.53, p = 0.18, n.s.). The background currents were 0.88 +/- 0.57 nA when determined from plasma glucose, and 0.63 +/- 0.77 nA when determined from whole blood glucose (t = 0.82, p = 0.45, n.s.). (3) The regression equation of the estimation of the subcutaneous glucose level obtained from the two methods was y = 1.04x + 0.56 mM (n = 171 values, r = 0.98, p = 0.0001).(ABSTRACT TRUNCATED AT 250 WORDS)

Support vector machine regression (SVR/LS-SVM)--an alternative to neural networks (ANN) for analytical chemistry? Comparison of nonlinear methods on near infrared (NIR) spectroscopy data.

PubMed

Balabin, Roman M; Lomakina, Ekaterina I

2011-04-21

In this study, we make a general comparison of the accuracy and robustness of five multivariate calibration models: partial least squares (PLS) regression or projection to latent structures, polynomial partial least squares (Poly-PLS) regression, artificial neural networks (ANNs), and two novel techniques based on support vector machines (SVMs) for multivariate data analysis: support vector regression (SVR) and least-squares support vector machines (LS-SVMs). The comparison is based on fourteen (14) different datasets: seven sets of gasoline data (density, benzene content, and fractional composition/boiling points), two sets of ethanol gasoline fuel data (density and ethanol content), one set of diesel fuel data (total sulfur content), three sets of petroleum (crude oil) macromolecules data (weight percentages of asphaltenes, resins, and paraffins), and one set of petroleum resins data (resins content). Vibrational (near-infrared, NIR) spectroscopic data are used to predict the properties and quality coefficients of gasoline, biofuel/biodiesel, diesel fuel, and other samples of interest. The four systems presented here range greatly in composition, properties, strength of intermolecular interactions (e.g., van der Waals forces, H-bonds), colloid structure, and phase behavior. Due to the high diversity of chemical systems studied, general conclusions about SVM regression methods can be made. We try to answer the following question: to what extent can SVM-based techniques replace ANN-based approaches in real-world (industrial/scientific) applications? The results show that both SVR and LS-SVM methods are comparable to ANNs in accuracy. Due to the much higher robustness of the former, the SVM-based approaches are recommended for practical (industrial) application. This has been shown to be especially true for complicated, highly nonlinear objects.

Predicting in ungauged basins using a parsimonious rainfall-runoff model

NASA Astrophysics Data System (ADS)

Skaugen, Thomas; Olav Peerebom, Ivar; Nilsson, Anna

2015-04-01

Prediction in ungauged basins is a demanding, but necessary test for hydrological model structures. Ideally, the relationship between model parameters and catchment characteristics (CC) should be hydrologically justifiable. Many studies, however, report on failure to obtain significant correlations between model parameters and CCs. Under the hypothesis that the lack of correlations stems from non-identifiability of model parameters caused by overparameterization, the relatively new parameter parsimonious DDD (Distance Distribution Dynamics) model was tested for predictions in ungauged basins in Norway. In DDD, the capacity of the subsurface water reservoir M is the only parameter to be calibrated whereas the runoff dynamics is completely parameterised from observed characteristics derived from GIS and runoff recession analysis. Water is conveyed through the soils to the river network by waves with celerities determined by the level of saturation in the catchment. The distributions of distances between points in the catchment to the nearest river reach and of the river network give, together with the celerities, distributions of travel times, and, consequently unit hydrographs. DDD has 6 parameters less to calibrate in the runoff module than, for example, the well-known Swedish HBV model. In this study, multiple regression equations relating CCs and model parameters were trained from 84 calibrated catchments located all over Norway and all model parameters showed significant correlations with catchment characteristics. The significant correlation coefficients (with p- value < 0.05) ranged from 0.22-0.55. The suitability of DDD for predictions in ungauged basins was tested for 17 catchments not used to estimate the multiple regression equations. For 10 of the 17 catchments, deviations in Nash-Suthcliffe Efficiency (NSE) criteria between the calibrated and regionalised model were less than 0.1. The median NSE for the regionalised DDD for the 17 catchments, for two different time series was 0.66 and 0.72. Deviations in NSE between calibrated and regionalised models are well explained by the deviations between calibrated and regressed parameters describing spatial snow distribution and snowmelt, respectively. This latter result indicates the topic for further improvements in the model structure of DDD.

Improved Quantitative Analysis of Ion Mobility Spectrometry by Chemometric Multivariate Calibration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fraga, Carlos G.; Kerr, Dayle; Atkinson, David A.

2009-09-01

Traditional peak-area calibration and the multivariate calibration methods of principle component regression (PCR) and partial least squares (PLS), including unfolded PLS (U-PLS) and multi-way PLS (N-PLS), were evaluated for the quantification of 2,4,6-trinitrotoluene (TNT) and cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) in Composition B samples analyzed by temperature step desorption ion mobility spectrometry (TSD-IMS). The true TNT and RDX concentrations of eight Composition B samples were determined by high performance liquid chromatography with UV absorbance detection. Most of the Composition B samples were found to have distinct TNT and RDX concentrations. Applying PCR and PLS on the exact same IMS spectra used for themore » peak-area study improved quantitative accuracy and precision approximately 3 to 5 fold and 2 to 4 fold, respectively. This in turn improved the probability of correctly identifying Composition B samples based upon the estimated RDX and TNT concentrations from 11% with peak area to 44% and 89% with PLS. This improvement increases the potential of obtaining forensic information from IMS analyzers by providing some ability to differentiate or match Composition B samples based on their TNT and RDX concentrations.« less

[Application of near infrared spectroscopy combined with particle swarm optimization based least square support vactor machine to rapid quantitative analysis of Corni Fructus].

PubMed

Liu, Xue-song; Sun, Fen-fang; Jin, Ye; Wu, Yong-jiang; Gu, Zhi-xin; Zhu, Li; Yan, Dong-lan

2015-12-01

A novel method was developed for the rapid determination of multi-indicators in corni fructus by means of near infrared (NIR) spectroscopy. Particle swarm optimization (PSO) based least squares support vector machine was investigated to increase the levels of quality control. The calibration models of moisture, extractum, morroniside and loganin were established using the PSO-LS-SVM algorithm. The performance of PSO-LS-SVM models was compared with partial least squares regression (PLSR) and back propagation artificial neural network (BP-ANN). The calibration and validation results of PSO-LS-SVM were superior to both PLS and BP-ANN. For PSO-LS-SVM models, the correlation coefficients (r) of calibrations were all above 0.942. The optimal prediction results were also achieved by PSO-LS-SVM models with the RMSEP (root mean square error of prediction) and RSEP (relative standard errors of prediction) less than 1.176 and 15.5% respectively. The results suggest that PSO-LS-SVM algorithm has a good model performance and high prediction accuracy. NIR has a potential value for rapid determination of multi-indicators in Corni Fructus.

Synthetic calibration of a Rainfall-Runoff Model

USGS Publications Warehouse

Thompson, David B.; Westphal, Jerome A.; ,

1990-01-01

A method for synthetically calibrating storm-mode parameters for the U.S. Geological Survey's Precipitation-Runoff Modeling System is described. Synthetic calibration is accomplished by adjusting storm-mode parameters to minimize deviations between the pseudo-probability disributions represented by regional regression equations and actual frequency distributions fitted to model-generated peak discharge and runoff volume. Results of modeling storm hydrographs using synthetic and analytic storm-mode parameters are presented. Comparisons are made between model results from both parameter sets and between model results and observed hydrographs. Although mean storm runoff is reproducible to within about 26 percent of the observed mean storm runoff for five or six parameter sets, runoff from individual storms is subject to large disparities. Predicted storm runoff volume ranged from 2 percent to 217 percent of commensurate observed values. Furthermore, simulation of peak discharges was poor. Predicted peak discharges from individual storm events ranged from 2 percent to 229 percent of commensurate observed values. The model was incapable of satisfactorily executing storm-mode simulations for the study watersheds. This result is not considered a particular fault of the model, but instead is indicative of deficiencies in similar conceptual models.

Improved quantification of important beer quality parameters based on nonlinear calibration methods applied to FT-MIR spectra.

PubMed

Cernuda, Carlos; Lughofer, Edwin; Klein, Helmut; Forster, Clemens; Pawliczek, Marcin; Brandstetter, Markus

2017-01-01

During the production process of beer, it is of utmost importance to guarantee a high consistency of the beer quality. For instance, the bitterness is an essential quality parameter which has to be controlled within the specifications at the beginning of the production process in the unfermented beer (wort) as well as in final products such as beer and beer mix beverages. Nowadays, analytical techniques for quality control in beer production are mainly based on manual supervision, i.e., samples are taken from the process and analyzed in the laboratory. This typically requires significant lab technicians efforts for only a small fraction of samples to be analyzed, which leads to significant costs for beer breweries and companies. Fourier transform mid-infrared (FT-MIR) spectroscopy was used in combination with nonlinear multivariate calibration techniques to overcome (i) the time consuming off-line analyses in beer production and (ii) already known limitations of standard linear chemometric methods, like partial least squares (PLS), for important quality parameters Speers et al. (J I Brewing. 2003;109(3):229-235), Zhang et al. (J I Brewing. 2012;118(4):361-367) such as bitterness, citric acid, total acids, free amino nitrogen, final attenuation, or foam stability. The calibration models are established with enhanced nonlinear techniques based (i) on a new piece-wise linear version of PLS by employing fuzzy rules for local partitioning the latent variable space and (ii) on extensions of support vector regression variants (-PLSSVR and ν-PLSSVR), for overcoming high computation times in high-dimensional problems and time-intensive and inappropriate settings of the kernel parameters. Furthermore, we introduce a new model selection scheme based on bagged ensembles in order to improve robustness and thus predictive quality of the final models. The approaches are tested on real-world calibration data sets for wort and beer mix beverages, and successfully compared to linear methods, showing a clear out-performance in most cases and being able to meet the model quality requirements defined by the experts at the beer company. Figure Workflow for calibration of non-Linear model ensembles from FT-MIR spectra in beer production .

Harmonized Reference Ranges for Circulating Testosterone Levels in Men of Four Cohort Studies in the United States and Europe

PubMed Central

Travison, Thomas G.; Vesper, Hubert W.; Orwoll, Eric; Wu, Frederick; Kaufman, Jean Marc; Wang, Ying; Lapauw, Bruno; Fiers, Tom; Matsumoto, Alvin M.

2017-01-01

Background: Reference ranges for testosterone are essential for making a diagnosis of hypogonadism in men. Objective: To establish harmonized reference ranges for total testosterone in men that can be applied across laboratories by cross-calibrating assays to a reference method and standard. Population: The 9054 community-dwelling men in cohort studies in the United States and Europe: Framingham Heart Study; European Male Aging Study; Osteoporotic Fractures in Men Study; and Male Sibling Study of Osteoporosis. Methods: Testosterone concentrations in 100 participants in each of the four cohorts were measured using a reference method at Centers for Disease Control and Prevention (CDC). Generalized additive models and Bland-Altman analyses supported the use of normalizing equations for transformation between cohort-specific and CDC values. Normalizing equations, generated using Passing-Bablok regression, were used to generate harmonized values, which were used to derive standardized, age-specific reference ranges. Results: Harmonization procedure reduced intercohort variation between testosterone measurements in men of similar ages. In healthy nonobese men, 19 to 39 years, harmonized 2.5th, 5th, 50th, 95th, and 97.5th percentile values were 264, 303, 531, 852, and 916 ng/dL, respectively. Age-specific harmonized testosterone concentrations in nonobese men were similar across cohorts and greater than in all men. Conclusion: Harmonized normal range in a healthy nonobese population of European and American men, 19 to 39 years, is 264 to 916 ng/dL. A substantial proportion of intercohort variation in testosterone levels is due to assay differences. These data demonstrate the feasibility of generating harmonized reference ranges for testosterone that can be applied to assays, which have been calibrated to a reference method and calibrator. PMID:28324103

Estimation of soil clay and organic matter using two quantitative methods (PLSR and MARS) based on reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Nawar, Said; Buddenbaum, Henning; Hill, Joachim

2014-05-01

A rapid and inexpensive soil analytical technique is needed for soil quality assessment and accurate mapping. This study investigated a method for improved estimation of soil clay (SC) and organic matter (OM) using reflectance spectroscopy. Seventy soil samples were collected from Sinai peninsula in Egypt to estimate the soil clay and organic matter relative to the soil spectra. Soil samples were scanned with an Analytical Spectral Devices (ASD) spectrometer (350-2500 nm). Three spectral formats were used in the calibration models derived from the spectra and the soil properties: (1) original reflectance spectra (OR), (2) first-derivative spectra smoothened using the Savitzky-Golay technique (FD-SG) and (3) continuum-removed reflectance (CR). Partial least-squares regression (PLSR) models using the CR of the 400-2500 nm spectral region resulted in R2 = 0.76 and 0.57, and RPD = 2.1 and 1.5 for estimating SC and OM, respectively, indicating better performance than that obtained using OR and SG. The multivariate adaptive regression splines (MARS) calibration model with the CR spectra resulted in an improved performance (R2 = 0.89 and 0.83, RPD = 3.1 and 2.4) for estimating SC and OM, respectively. The results show that the MARS models have a great potential for estimating SC and OM compared with PLSR models. The results obtained in this study have potential value in the field of soil spectroscopy because they can be applied directly to the mapping of soil properties using remote sensing imagery in arid environment conditions. Key Words: soil clay, organic matter, PLSR, MARS, reflectance spectroscopy.

Suitability of satellite derived and gridded sea surface temperature data sets for calibrating high-resolution marine proxy records

NASA Astrophysics Data System (ADS)

Ouellette, G., Jr.; DeLong, K. L.

2016-02-01

High-resolution proxy records of sea surface temperature (SST) are increasingly being produced using trace element and isotope variability within the skeletal materials of marine organisms such as corals, mollusks, sclerosponges, and coralline algae. Translating the geochemical variations within these organisms into records of SST requires calibration with SST observations using linear regression methods, preferably with in situ SST records that span several years. However, locations with such records are sparse; therefore, calibration is often accomplished using gridded SST data products such as the Hadley Center's HADSST (5º) and interpolated HADISST (1º) data sets, NOAA's extended reconstructed SST data set (ERSST; 2º), optimum interpolation SST (OISST; 1º), and Kaplan SST data sets (5º). From these data products, the SST used for proxy calibration is obtained for a single grid cell that includes the proxy's study site. The gridded data sets are based on the International Comprehensive Ocean-Atmosphere Data Set (ICOADS) and each uses different methods of interpolation to produce the globally and temporally complete data products except for HadSST, which is not interpolated but quality controlled. This study compares SST for a single site from these gridded data products with a high-resolution satellite-based SST data set from NOAA (Pathfinder; 4 km) with in situ SST data and coral Sr/Ca variability for our study site in Haiti to assess differences between these SST records with a focus on seasonal variability. Our results indicate substantial differences in the seasonal variability captured for the same site among these data sets on the order of 1-3°C. This analysis suggests that of the data products, high-resolution satellite SST best captured seasonal variability at the study site. Unfortunately, satellite SST records are limited to the past few decades. If satellite SST are to be used to calibrate proxy records, collecting modern, living samples is desirable.

Automatic multi-camera calibration for deployable positioning systems

NASA Astrophysics Data System (ADS)

Axelsson, Maria; Karlsson, Mikael; Rudner, Staffan

2012-06-01

Surveillance with automated positioning and tracking of subjects and vehicles in 3D is desired in many defence and security applications. Camera systems with stereo or multiple cameras are often used for 3D positioning. In such systems, accurate camera calibration is needed to obtain a reliable 3D position estimate. There is also a need for automated camera calibration to facilitate fast deployment of semi-mobile multi-camera 3D positioning systems. In this paper we investigate a method for automatic calibration of the extrinsic camera parameters (relative camera pose and orientation) of a multi-camera positioning system. It is based on estimation of the essential matrix between each camera pair using the 5-point method for intrinsically calibrated cameras. The method is compared to a manual calibration method using real HD video data from a field trial with a multicamera positioning system. The method is also evaluated on simulated data from a stereo camera model. The results show that the reprojection error of the automated camera calibration method is close to or smaller than the error for the manual calibration method and that the automated calibration method can replace the manual calibration.

Advanced Mathematical Tools in Metrology III

NASA Astrophysics Data System (ADS)

Ciarlini, P.

The Table of Contents for the book is as follows: * Foreword * Invited Papers * The ISO Guide to the Expression of Uncertainty in Measurement: A Bridge between Statistics and Metrology * Bootstrap Algorithms and Applications * The TTRSs: 13 Oriented Constraints for Dimensioning, Tolerancing & Inspection * Graded Reference Data Sets and Performance Profiles for Testing Software Used in Metrology * Uncertainty in Chemical Measurement * Mathematical Methods for Data Analysis in Medical Applications * High-Dimensional Empirical Linear Prediction * Wavelet Methods in Signal Processing * Software Problems in Calibration Services: A Case Study * Robust Alternatives to Least Squares * Gaining Information from Biomagnetic Measurements * Full Papers * Increase of Information in the Course of Measurement * A Framework for Model Validation and Software Testing in Regression * Certification of Algorithms for Determination of Signal Extreme Values during Measurement * A Method for Evaluating Trends in Ozone-Concentration Data and Its Application to Data from the UK Rural Ozone Monitoring Network * Identification of Signal Components by Stochastic Modelling in Measurements of Evoked Magnetic Fields from Peripheral Nerves * High Precision 3D-Calibration of Cylindrical Standards * Magnetic Dipole Estimations for MCG-Data * Transfer Functions of Discrete Spline Filters * An Approximation Method for the Linearization of Tridimensional Metrology Problems * Regularization Algorithms for Image Reconstruction from Projections * Quality of Experimental Data in Hydrodynamic Research * Stochastic Drift Models for the Determination of Calibration Intervals * Short Communications * Projection Method for Lidar Measurement * Photon Flux Measurements by Regularised Solution of Integral Equations * Correct Solutions of Fit Problems in Different Experimental Situations * An Algorithm for the Nonlinear TLS Problem in Polynomial Fitting * Designing Axially Symmetric Electromechanical Systems of Superconducting Magnetic Levitation in Matlab Environment * Data Flow Evaluation in Metrology * A Generalized Data Model for Integrating Clinical Data and Biosignal Records of Patients * Assessment of Three-Dimensional Structures in Clinical Dentistry * Maximum Entropy and Bayesian Approaches to Parameter Estimation in Mass Metrology * Amplitude and Phase Determination of Sinusoidal Vibration in the Nanometer Range using Quadrature Signals * A Class of Symmetric Compactly Supported Wavelets and Associated Dual Bases * Analysis of Surface Topography by Maximum Entropy Power Spectrum Estimation * Influence of Different Kinds of Errors on Imaging Results in Optical Tomography * Application of the Laser Interferometry for Automatic Calibration of Height Setting Micrometer * Author Index

Quality assessment of gasoline using comprehensive two-dimensional gas chromatography combined with unfolded partial least squares: A reliable approach for the detection of gasoline adulteration.

PubMed

Parastar, Hadi; Mostafapour, Sara; Azimi, Gholamhasan

2016-01-01

Comprehensive two-dimensional gas chromatography and flame ionization detection combined with unfolded-partial least squares is proposed as a simple, fast and reliable method to assess the quality of gasoline and to detect its potential adulterants. The data for the calibration set are first baseline corrected using a two-dimensional asymmetric least squares algorithm. The number of significant partial least squares components to build the model is determined using the minimum value of root-mean square error of leave-one out cross validation, which was 4. In this regard, blends of gasoline with kerosene, white spirit and paint thinner as frequently used adulterants are used to make calibration samples. Appropriate statistical parameters of regression coefficient of 0.996-0.998, root-mean square error of prediction of 0.005-0.010 and relative error of prediction of 1.54-3.82% for the calibration set show the reliability of the developed method. In addition, the developed method is externally validated with three samples in validation set (with a relative error of prediction below 10.0%). Finally, to test the applicability of the proposed strategy for the analysis of real samples, five real gasoline samples collected from gas stations are used for this purpose and the gasoline proportions were in range of 70-85%. Also, the relative standard deviations were below 8.5% for different samples in the prediction set. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Novel Multi-Camera Calibration Method based on Flat Refractive Geometry

NASA Astrophysics Data System (ADS)

Huang, S.; Feng, M. C.; Zheng, T. X.; Li, F.; Wang, J. Q.; Xiao, L. F.

2018-03-01

Multi-camera calibration plays an important role in many field. In the paper, we present a novel multi-camera calibration method based on flat refractive geometry. All cameras can acquire calibration images of transparent glass calibration board (TGCB) at the same time. The application of TGCB leads to refractive phenomenon which can generate calibration error. The theory of flat refractive geometry is employed to eliminate the error. The new method can solve the refractive phenomenon of TGCB. Moreover, the bundle adjustment method is used to minimize the reprojection error and obtain optimized calibration results. Finally, the four-cameras calibration results of real data show that the mean value and standard deviation of the reprojection error of our method are 4.3411e-05 and 0.4553 pixel, respectively. The experimental results show that the proposed method is accurate and reliable.

Robust Online Monitoring for Calibration Assessment of Transmitters and Instrumentation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramuhalli, Pradeep; Coble, Jamie B.; Shumaker, Brent

Robust online monitoring (OLM) technologies are expected to enable the extension or elimination of periodic sensor calibration intervals in operating and new reactors. These advances in OLM technologies will improve the safety and reliability of current and planned nuclear power systems through improved accuracy and increased reliability of sensors used to monitor key parameters. In this article, we discuss an overview of research being performed within the Nuclear Energy Enabling Technologies (NEET)/Advanced Sensors and Instrumentation (ASI) program, for the development of OLM algorithms to use sensor outputs and, in combination with other available information, 1) determine whether one or moremore » sensors are out of calibration or failing and 2) replace a failing sensor with reliable, accurate sensor outputs. Algorithm development is focused on the following OLM functions: • Signal validation • Virtual sensing • Sensor response-time assessment These algorithms incorporate, at their base, a Gaussian Process-based uncertainty quantification (UQ) method. Various plant models (using kernel regression, GP, or hierarchical models) may be used to predict sensor responses under various plant conditions. These predicted responses can then be applied in fault detection (sensor output and response time) and in computing the correct value (virtual sensing) of a failing physical sensor. The methods being evaluated in this work can compute confidence levels along with the predicted sensor responses, and as a result, may have the potential for compensating for sensor drift in real-time (online recalibration). Evaluation was conducted using data from multiple sources (laboratory flow loops and plant data). Ongoing research in this project is focused on further evaluation of the algorithms, optimization for accuracy and computational efficiency, and integration into a suite of tools for robust OLM that are applicable to monitoring sensor calibration state in nuclear power plants.« less

Determination of glucose in a biological matrix by multivariate analysis of multiple band-pass-filtered Fourier transform near-infrared interferograms.

PubMed

Mattu, M J; Small, G W; Arnold, M A

1997-11-15

A multivariate calibration method is described in which Fourier transform near-infrared interferogram data are used to determine clinically relevant levels of glucose in an aqueous matrix of bovine serum albumin (BSA) and triacetin. BSA and triacetin are used to model the protein and triglycerides in blood, respectively, and are present in levels spanning the normal human physiological range. A full factorial experimental design is constructed for the data collection, with glucose at 10 levels, BSA at 4 levels, and triacetin at 4 levels. Gaussian-shaped band-pass digital filters are applied to the interferogram data to extract frequencies associated with an absorption band of interest. Separate filters of various widths are positioned on the glucose band at 4400 cm-1, the BSA band at 4606 cm-1, and the triacetin band at 4446 cm-1. Each filter is applied to the raw interferogram, producing one, two, or three filtered interferograms, depending on the number of filters used. Segments of these filtered interferograms are used together in a partial least-squares regression analysis to build glucose calibration models. The optimal calibration model is realized by use of separate segments of interferograms filtered with three filters centered on the glucose, BSA, and triacetin bands. Over the physiological range of 1-20 mM glucose, this 17-term model exhibits values of R2, standard error of calibration, and standard error of prediction of 98.85%, 0.631 mM, and 0.677 mM, respectively. These results are comparable to those obtained in a conventional analysis of spectral data. The interferogram-based method operates without the use of a separate background measurement and employs only a short section of the interferogram.

Body composition in Nepalese children using isotope dilution: the production of ethnic-specific calibration equations and an exploration of methodological issues.

PubMed

Devakumar, Delan; Grijalva-Eternod, Carlos S; Roberts, Sebastian; Chaube, Shiva Shankar; Saville, Naomi M; Manandhar, Dharma S; Costello, Anthony; Osrin, David; Wells, Jonathan C K

2015-01-01

Background. Body composition is important as a marker of both current and future health. Bioelectrical impedance (BIA) is a simple and accurate method for estimating body composition, but requires population-specific calibration equations. Objectives. (1) To generate population specific calibration equations to predict lean mass (LM) from BIA in Nepalese children aged 7-9 years. (2) To explore methodological changes that may extend the range and improve accuracy. Methods. BIA measurements were obtained from 102 Nepalese children (52 girls) using the Tanita BC-418. Isotope dilution with deuterium oxide was used to measure total body water and to estimate LM. Prediction equations for estimating LM from BIA data were developed using linear regression, and estimates were compared with those obtained from the Tanita system. We assessed the effects of flexing the arms of children to extend the range of coverage towards lower weights. We also estimated potential error if the number of children included in the study was reduced. Findings. Prediction equations were generated, incorporating height, impedance index, weight and sex as predictors (R (2) 93%). The Tanita system tended to under-estimate LM, with a mean error of 2.2%, but extending up to 25.8%. Flexing the arms to 90° increased the lower weight range, but produced a small error that was not significant when applied to children <16 kg (p 0.42). Reducing the number of children increased the error at the tails of the weight distribution. Conclusions. Population-specific isotope calibration of BIA for Nepalese children has high accuracy. Arm position is important and can be used to extend the range of low weight covered. Smaller samples reduce resource requirements, but leads to large errors at the tails of the weight distribution.

Quantification of febuxostat polymorphs using powder X-ray diffraction technique.

PubMed

Qiu, Jing-bo; Li, Gang; Sheng, Yue; Zhu, Mu-rong

2015-03-25

Febuxostat is a pharmaceutical compound with more than 20 polymorphs of which form A is most widely used and usually exists in a mixed polymorphic form with form G. In the present study, a quantification method for polymorphic form A and form G of febuxostat (FEB) has been developed using powder X-ray diffraction (PXRD). Prior to development of a quantification method, pure polymorphic form A and form G are characterized. A continuous scan with a scan rate of 3° min(-1) over an angular range of 3-40° 2θ is applied for the construction of the calibration curve using the characteristic peaks of form A at 12.78° 2θ (I/I0100%) and form G at 11.72° 2θ (I/I0100%). The linear regression analysis data for the calibration plots shows good linear relationship with R(2)=0.9985 with respect to peak area in the concentration range 10-60 wt.%. The method is validated for precision, recovery and ruggedness. The limits of detection and quantitation are 1.5% and 4.6%, respectively. The obtained results prove that the method is repeatable, sensitive and accurate. The proposed developed PXRD method can be applied for the quantitative analysis of mixtures of febuxostat polymorphs (forms A and G). Copyright © 2015 Elsevier B.V. All rights reserved.

Evaluation of chiller modeling approaches and their usability for fault detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreedharan, Priya

Selecting the model is an important and essential step in model based fault detection and diagnosis (FDD). Several factors must be considered in model evaluation, including accuracy, training data requirements, calibration effort, generality, and computational requirements. All modeling approaches fall somewhere between pure first-principles models, and empirical models. The objective of this study was to evaluate different modeling approaches for their applicability to model based FDD of vapor compression air conditioning units, which are commonly known as chillers. Three different models were studied: two are based on first-principles and the third is empirical in nature. The first-principles models are themore » Gordon and Ng Universal Chiller model (2nd generation), and a modified version of the ASHRAE Primary Toolkit model, which are both based on first principles. The DOE-2 chiller model as implemented in CoolTools{trademark} was selected for the empirical category. The models were compared in terms of their ability to reproduce the observed performance of an older chiller operating in a commercial building, and a newer chiller in a laboratory. The DOE-2 and Gordon-Ng models were calibrated by linear regression, while a direct-search method was used to calibrate the Toolkit model. The ''CoolTools'' package contains a library of calibrated DOE-2 curves for a variety of different chillers, and was used to calibrate the building chiller to the DOE-2 model. All three models displayed similar levels of accuracy. Of the first principles models, the Gordon-Ng model has the advantage of being linear in the parameters, which allows more robust parameter estimation methods to be used and facilitates estimation of the uncertainty in the parameter values. The ASHRAE Toolkit Model may have advantages when refrigerant temperature measurements are also available. The DOE-2 model can be expected to have advantages when very limited data are available to calibrate the model, as long as one of the previously identified models in the CoolTools library matches the performance of the chiller in question.« less

Sample classification for improved performance of PLS models applied to the quality control of deep-frying oils of different botanic origins analyzed using ATR-FTIR spectroscopy.

PubMed

Kuligowski, Julia; Carrión, David; Quintás, Guillermo; Garrigues, Salvador; de la Guardia, Miguel

2011-01-01

The selection of an appropriate calibration set is a critical step in multivariate method development. In this work, the effect of using different calibration sets, based on a previous classification of unknown samples, on the partial least squares (PLS) regression model performance has been discussed. As an example, attenuated total reflection (ATR) mid-infrared spectra of deep-fried vegetable oil samples from three botanical origins (olive, sunflower, and corn oil), with increasing polymerized triacylglyceride (PTG) content induced by a deep-frying process were employed. The use of a one-class-classifier partial least squares-discriminant analysis (PLS-DA) and a rooted binary directed acyclic graph tree provided accurate oil classification. Oil samples fried without foodstuff could be classified correctly, independent of their PTG content. However, class separation of oil samples fried with foodstuff, was less evident. The combined use of double-cross model validation with permutation testing was used to validate the obtained PLS-DA classification models, confirming the results. To discuss the usefulness of the selection of an appropriate PLS calibration set, the PTG content was determined by calculating a PLS model based on the previously selected classes. In comparison to a PLS model calculated using a pooled calibration set containing samples from all classes, the root mean square error of prediction could be improved significantly using PLS models based on the selected calibration sets using PLS-DA, ranging between 1.06 and 2.91% (w/w).

A calibration method of infrared LVF based spectroradiometer

NASA Astrophysics Data System (ADS)

Liu, Jiaqing; Han, Shunli; Liu, Lei; Hu, Dexin

2017-10-01

In this paper, a calibration method of LVF-based spectroradiometer is summarize, including spectral calibration and radiometric calibration. The spectral calibration process as follow: first, the relationship between stepping motor's step number and transmission wavelength is derivative by theoretical calculation, including a non-linearity correction of LVF;second, a line-to-line method was used to corrected the theoretical wavelength; Finally, the 3.39 μm and 10.69 μm laser is used for spectral calibration validation, show the sought 0.1% accuracy or better is achieved.A new sub-region multi-point calibration method is used for radiometric calibration to improving accuracy, results show the sought 1% accuracy or better is achieved.

Simultaneous determination of hydroquinone, resorcinol, phenol, m-cresol and p-cresol in untreated air samples using spectrofluorimetry and a custom multiple linear regression-successive projection algorithm.

PubMed

Pistonesi, Marcelo F; Di Nezio, María S; Centurión, María E; Lista, Adriana G; Fragoso, Wallace D; Pontes, Márcio J C; Araújo, Mário C U; Band, Beatriz S Fernández

2010-12-15

In this study, a novel, simple, and efficient spectrofluorimetric method to determine directly and simultaneously five phenolic compounds (hydroquinone, resorcinol, phenol, m-cresol and p-cresol) in air samples is presented. For this purpose, variable selection by the successive projections algorithm (SPA) is used in order to obtain simple multiple linear regression (MLR) models based on a small subset of wavelengths. For comparison, partial least square (PLS) regression is also employed in full-spectrum. The concentrations of the calibration matrix ranged from 0.02 to 0.2 mg L(-1) for hydroquinone, from 0.05 to 0.6 mg L(-1) for resorcinol, and from 0.05 to 0.4 mg L(-1) for phenol, m-cresol and p-cresol; incidentally, such ranges are in accordance with the Argentinean environmental legislation. To verify the accuracy of the proposed method a recovery study on real air samples of smoking environment was carried out with satisfactory results (94-104%). The advantage of the proposed method is that it requires only spectrofluorimetric measurements of samples and chemometric modeling for simultaneous determination of five phenols. With it, air is simply sampled and no pre-treatment sample is needed (i.e., separation steps and derivatization reagents are avoided) that means a great saving of time. Copyright © 2010 Elsevier B.V. All rights reserved.

Limits to lichenometry

NASA Astrophysics Data System (ADS)

Rosenwinkel, Swenja; Korup, Oliver; Landgraf, Angela; Dzhumabaeva, Atyrgul

2015-12-01

Lichenometry is a straightforward and inexpensive method for dating Holocene rock surfaces. The rationale is that the diameter of the largest lichen scales with the age of the originally fresh rock surface that it colonised. The success of the method depends on finding the largest lichen diameters, a suitable lichen-growth model, and a robust calibration curve. Recent critique of the method motivates us to revisit the accuracy and uncertainties of lichenometry. Specifically, we test how well lichenometry is capable of resolving the ages of different lobes of large active rock glaciers in the Kyrgyz Tien Shan. We use a bootstrapped quantile regression to calibrate local growth curves of Xanthoria elegans, Aspicilia tianshanica, and Rhizocarpon geographicum, and report a nonlinear decrease in dating accuracy with increasing lichen diameter. A Bayesian type of an analysis of variance demonstrates that our calibration allows discriminating credibly between rock-glacier lobes of different ages despite the uncertainties tied to sample size and correctly identifying the largest lichen thalli. Our results also show that calibration error grows with lichen size, so that the separability of rock-glacier lobes of different ages decreases, while the tendency to assign coeval ages increases. The abundant young (<200 yr) specimen of fast-growing X. elegans are in contrast with the fewer, slow-growing, but older (200-1500 yr) R. geographicum and A. tianshanica, and record either a regional reactivation of lobes in the past 200 years, or simply a censoring effect of lichen mortality during early phases of colonisation. The high variance of lichen sizes captures the activity of rock-glacier lobes, which is difficult to explain by regional climatic cooling or earthquake triggers alone. Therefore, we caution against inferring palaeoclimatic conditions from the topographic position of rock-glacier lobes. We conclude that lichenometry works better as a tool for establishing a relative, rather than an absolute, chronology of rock-glacier lobes in the northern Tien Shan.

Bayesian Calibration of Thermodynamic Databases and the Role of Kinetics

NASA Astrophysics Data System (ADS)

Wolf, A. S.; Ghiorso, M. S.

2017-12-01

Self-consistent thermodynamic databases of geologically relevant materials (like Berman, 1988; Holland and Powell, 1998, Stixrude & Lithgow-Bertelloni 2011) are crucial for simulating geological processes as well as interpreting rock samples from the field. These databases form the backbone of our understanding of how fluids and rocks interact at extreme planetary conditions. Considerable work is involved in their construction from experimental phase reaction data, as they must self-consistently describe the free energy surfaces (including relative offsets) of potentially hundreds of interacting phases. Standard database calibration methods typically utilize either linear programming or least squares regression. While both produce a viable model, they suffer from strong limitations on the training data (which must be filtered by hand), along with general ignorance of many of the sources of experimental uncertainty. We develop a new method for calibrating high P-T thermodynamic databases for use in geologic applications. The model is designed to handle pure solid endmember and free fluid phases and can be extended to include mixed solid solutions and melt phases. This new calibration effort utilizes Bayesian techniques to obtain optimal parameter values together with a full family of statistically acceptable models, summarized by the posterior. Unlike previous efforts, the Bayesian Logistic Uncertain Reaction (BLUR) model directly accounts for both measurement uncertainties and disequilibrium effects, by employing a kinetic reaction model whose parameters are empirically determined from the experiments themselves. Thus, along with the equilibrium free energy surfaces, we also provide rough estimates of the activation energies, entropies, and volumes for each reaction. As a first application, we demonstrate this new method on the three-phase aluminosilicate system, illustrating how it can produce superior estimates of the phase boundaries by incorporating constraints from all available data, while automatically handling variable data quality due to a combination of measurement errors and kinetic effects.

Accuracy of Bayes and Logistic Regression Subscale Probabilities for Educational and Certification Tests

ERIC Educational Resources Information Center

Rudner, Lawrence

2016-01-01

In the machine learning literature, it is commonly accepted as fact that as calibration sample sizes increase, Naïve Bayes classifiers initially outperform Logistic Regression classifiers in terms of classification accuracy. Applied to subtests from an on-line final examination and from a highly regarded certification examination, this study shows…

Calibrated Peer Review for Interpreting Linear Regression Parameters: Results from a Graduate Course

ERIC Educational Resources Information Center

Enders, Felicity B.; Jenkins, Sarah; Hoverman, Verna

2010-01-01

Biostatistics is traditionally a difficult subject for students to learn. While the mathematical aspects are challenging, it can also be demanding for students to learn the exact language to use to correctly interpret statistical results. In particular, correctly interpreting the parameters from linear regression is both a vital tool and a…

Error-in-variables models in calibration

NASA Astrophysics Data System (ADS)

Lira, I.; Grientschnig, D.

2017-12-01

In many calibration operations, the stimuli applied to the measuring system or instrument under test are derived from measurement standards whose values may be considered to be perfectly known. In that case, it is assumed that calibration uncertainty arises solely from inexact measurement of the responses, from imperfect control of the calibration process and from the possible inaccuracy of the calibration model. However, the premise that the stimuli are completely known is never strictly fulfilled and in some instances it may be grossly inadequate. Then, error-in-variables (EIV) regression models have to be employed. In metrology, these models have been approached mostly from the frequentist perspective. In contrast, not much guidance is available on their Bayesian analysis. In this paper, we first present a brief summary of the conventional statistical techniques that have been developed to deal with EIV models in calibration. We then proceed to discuss the alternative Bayesian framework under some simplifying assumptions. Through a detailed example about the calibration of an instrument for measuring flow rates, we provide advice on how the user of the calibration function should employ the latter framework for inferring the stimulus acting on the calibrated device when, in use, a certain response is measured.

Optics-Only Calibration of a Neural-Net Based Optical NDE Method for Structural Health Monitoring

NASA Technical Reports Server (NTRS)

Decker, Arthur J.

2004-01-01

A calibration process is presented that uses optical measurements alone to calibrate a neural-net based NDE method. The method itself detects small changes in the vibration mode shapes of structures. The optics-only calibration process confirms previous work that the sensitivity to vibration-amplitude changes can be as small as 10 nanometers. A more practical value in an NDE service laboratory is shown to be 50 nanometers. Both model-generated and experimental calibrations are demonstrated using two implementations of the calibration technique. The implementations are based on previously published demonstrations of the NDE method and an alternative calibration procedure that depends on comparing neural-net and point sensor measurements. The optics-only calibration method, unlike the alternative method, does not require modifications of the structure being tested or the creation of calibration objects. The calibration process can be used to test improvements in the NDE process and to develop a vibration-mode-independence of damagedetection sensitivity. The calibration effort was intended to support NASA s objective to promote safety in the operations of ground test facilities or aviation safety, in general, by allowing the detection of the gradual onset of structural changes and damage.

Sensitivity of solar-cell performance to atmospheric variables. 1: Single cell

NASA Technical Reports Server (NTRS)

Klucher, T. M.

1976-01-01

The short circuit current of a typical silicon solar cell under direct solar radiation was measured for a range of turbidity, water vapor content, and air mass to determine the relation of the solar cell calibration value (current-to-intensity ratio) to those atmospheric variables. A previously developed regression equation was modified to describe the relation between calibration value, turbidity, water vapor content, and air mass. Based on the value of the constants obtained by a least squares fit of the data to the equation, it was found that turbidity lowers the value, while increase in water vapor increases the calibration value. Cell calibration values exhibited a change of about 6% over the range of atmospheric conditions experienced.

Support vector regression and artificial neural network models for stability indicating analysis of mebeverine hydrochloride and sulpiride mixtures in pharmaceutical preparation: A comparative study

NASA Astrophysics Data System (ADS)

Naguib, Ibrahim A.; Darwish, Hany W.

2012-02-01

A comparison between support vector regression (SVR) and Artificial Neural Networks (ANNs) multivariate regression methods is established showing the underlying algorithm for each and making a comparison between them to indicate the inherent advantages and limitations. In this paper we compare SVR to ANN with and without variable selection procedure (genetic algorithm (GA)). To project the comparison in a sensible way, the methods are used for the stability indicating quantitative analysis of mixtures of mebeverine hydrochloride and sulpiride in binary mixtures as a case study in presence of their reported impurities and degradation products (summing up to 6 components) in raw materials and pharmaceutical dosage form via handling the UV spectral data. For proper analysis, a 6 factor 5 level experimental design was established resulting in a training set of 25 mixtures containing different ratios of the interfering species. An independent test set consisting of 5 mixtures was used to validate the prediction ability of the suggested models. The proposed methods (linear SVR (without GA) and linear GA-ANN) were successfully applied to the analysis of pharmaceutical tablets containing mebeverine hydrochloride and sulpiride mixtures. The results manifest the problem of nonlinearity and how models like the SVR and ANN can handle it. The methods indicate the ability of the mentioned multivariate calibration models to deconvolute the highly overlapped UV spectra of the 6 components' mixtures, yet using cheap and easy to handle instruments like the UV spectrophotometer.

A nonparametric multiple imputation approach for missing categorical data.

PubMed

Zhou, Muhan; He, Yulei; Yu, Mandi; Hsu, Chiu-Hsieh

2017-06-06

Incomplete categorical variables with more than two categories are common in public health data. However, most of the existing missing-data methods do not use the information from nonresponse (missingness) probabilities. We propose a nearest-neighbour multiple imputation approach to impute a missing at random categorical outcome and to estimate the proportion of each category. The donor set for imputation is formed by measuring distances between each missing value with other non-missing values. The distance function is calculated based on a predictive score, which is derived from two working models: one fits a multinomial logistic regression for predicting the missing categorical outcome (the outcome model) and the other fits a logistic regression for predicting missingness probabilities (the missingness model). A weighting scheme is used to accommodate contributions from two working models when generating the predictive score. A missing value is imputed by randomly selecting one of the non-missing values with the smallest distances. We conduct a simulation to evaluate the performance of the proposed method and compare it with several alternative methods. A real-data application is also presented. The simulation study suggests that the proposed method performs well when missingness probabilities are not extreme under some misspecifications of the working models. However, the calibration estimator, which is also based on two working models, can be highly unstable when missingness probabilities for some observations are extremely high. In this scenario, the proposed method produces more stable and better estimates. In addition, proper weights need to be chosen to balance the contributions from the two working models and achieve optimal results for the proposed method. We conclude that the proposed multiple imputation method is a reasonable approach to dealing with missing categorical outcome data with more than two levels for assessing the distribution of the outcome. In terms of the choices for the working models, we suggest a multinomial logistic regression for predicting the missing outcome and a binary logistic regression for predicting the missingness probability.

Wavelength calibration of dispersive near-infrared spectrometer using relative k-space distribution with low coherence interferometer

NASA Astrophysics Data System (ADS)

Kim, Ji-hyun; Han, Jae-Ho; Jeong, Jichai

2016-05-01

The commonly employed calibration methods for laboratory-made spectrometers have several disadvantages, including poor calibration when the number of characteristic spectral peaks is low. Therefore, we present a wavelength calibration method using relative k-space distribution with low coherence interferometer. The proposed method utilizes an interferogram with a perfect sinusoidal pattern in k-space for calibration. Zero-crossing detection extracts the k-space distribution of a spectrometer from the interferogram in the wavelength domain, and a calibration lamp provides information about absolute wavenumbers. To assign wavenumbers, wavelength-to-k-space conversion is required for the characteristic spectrum of the calibration lamp with the extracted k-space distribution. Then, the wavelength calibration is completed by inverse conversion of the k-space into wavelength domain. The calibration performance of the proposed method was demonstrated with two experimental conditions of four and eight characteristic spectral peaks. The proposed method elicited reliable calibration results in both cases, whereas the conventional method of third-order polynomial curve fitting failed to determine wavelengths in the case of four characteristic peaks. Moreover, for optical coherence tomography imaging, the proposed method could improve axial resolution due to higher suppression of sidelobes in point spread function than the conventional method. We believe that our findings can improve not only wavelength calibration accuracy but also resolution for optical coherence tomography.

Verification of the ISO calibration method for field pyranometers under tropical sky conditions

NASA Astrophysics Data System (ADS)

Janjai, Serm; Tohsing, Korntip; Pattarapanitchai, Somjet; Detkhon, Pasakorn

2017-02-01

Field pyranomters need to be annually calibrated and the International Organization for Standardization (ISO) has defined a standard method (ISO 9847) for calibrating these pyranometers. According to this standard method for outdoor calibration, the field pyranometers have to be compared to a reference pyranometer for the period of 2 to 14 days, depending on sky conditions. In this work, the ISO 9847 standard method was verified under tropical sky conditions. To verify the standard method, calibration of field pyranometers was conducted at a tropical site located in Nakhon Pathom (13.82o N, 100.04o E), Thailand under various sky conditions. The conditions of the sky were monitored by using a sky camera. The calibration results for different time periods used for the calibration under various sky conditions were analyzed. It was found that the calibration periods given by this standard method could be reduced without significant change in the final calibration result. In addition, recommendation and discussion on the use of this standard method in the tropics were also presented.

Direct-on-Filter α-Quartz Estimation in Respirable Coal Mine Dust Using Transmission Fourier Transform Infrared Spectrometry and Partial Least Squares Regression

PubMed Central

Miller, Arthur L.; Weakley, Andrew Todd; Griffiths, Peter R.; Cauda, Emanuele G.; Bayman, Sean

2017-01-01

In order to help reduce silicosis in miners, the National Institute for Occupational Health and Safety (NIOSH) is developing field-portable methods for measuring airborne respirable crystalline silica (RCS), specifically the polymorph α-quartz, in mine dusts. In this study we demonstrate the feasibility of end-of-shift measurement of α-quartz using a direct-on-filter (DoF) method to analyze coal mine dust samples deposited onto polyvinyl chloride filters. The DoF method is potentially amenable for on-site analyses, but deviates from the current regulatory determination of RCS for coal mines by eliminating two sample preparation steps: ashing the sampling filter and redepositing the ash prior to quantification by Fourier transform infrared (FT-IR) spectrometry. In this study, the FT-IR spectra of 66 coal dust samples from active mines were used, and the RCS was quantified by using: (1) an ordinary least squares (OLS) calibration approach that utilizes standard silica material as done in the Mine Safety and Health Administration's P7 method; and (2) a partial least squares (PLS) regression approach. Both were capable of accounting for kaolinite, which can confound the IR analysis of silica. The OLS method utilized analytical standards for silica calibration and kaolin correction, resulting in a good linear correlation with P7 results and minimal bias but with the accuracy limited by the presence of kaolinite. The PLS approach also produced predictions well-correlated to the P7 method, as well as better accuracy in RCS prediction, and no bias due to variable kaolinite mass. Besides decreased sensitivity to mineral or substrate confounders, PLS has the advantage that the analyst is not required to correct for the presence of kaolinite or background interferences related to the substrate, making the method potentially viable for automated RCS prediction in the field. This study demonstrated the efficacy of FT-IR transmission spectrometry for silica determination in coal mine dusts, using both OLS and PLS analyses, when kaolinite was present. PMID:27645724

Direct-on-Filter α-Quartz Estimation in Respirable Coal Mine Dust Using Transmission Fourier Transform Infrared Spectrometry and Partial Least Squares Regression.

PubMed

Miller, Arthur L; Weakley, Andrew Todd; Griffiths, Peter R; Cauda, Emanuele G; Bayman, Sean

2017-05-01

In order to help reduce silicosis in miners, the National Institute for Occupational Health and Safety (NIOSH) is developing field-portable methods for measuring airborne respirable crystalline silica (RCS), specifically the polymorph α-quartz, in mine dusts. In this study we demonstrate the feasibility of end-of-shift measurement of α-quartz using a direct-on-filter (DoF) method to analyze coal mine dust samples deposited onto polyvinyl chloride filters. The DoF method is potentially amenable for on-site analyses, but deviates from the current regulatory determination of RCS for coal mines by eliminating two sample preparation steps: ashing the sampling filter and redepositing the ash prior to quantification by Fourier transform infrared (FT-IR) spectrometry. In this study, the FT-IR spectra of 66 coal dust samples from active mines were used, and the RCS was quantified by using: (1) an ordinary least squares (OLS) calibration approach that utilizes standard silica material as done in the Mine Safety and Health Administration's P7 method; and (2) a partial least squares (PLS) regression approach. Both were capable of accounting for kaolinite, which can confound the IR analysis of silica. The OLS method utilized analytical standards for silica calibration and kaolin correction, resulting in a good linear correlation with P7 results and minimal bias but with the accuracy limited by the presence of kaolinite. The PLS approach also produced predictions well-correlated to the P7 method, as well as better accuracy in RCS prediction, and no bias due to variable kaolinite mass. Besides decreased sensitivity to mineral or substrate confounders, PLS has the advantage that the analyst is not required to correct for the presence of kaolinite or background interferences related to the substrate, making the method potentially viable for automated RCS prediction in the field. This study demonstrated the efficacy of FT-IR transmission spectrometry for silica determination in coal mine dusts, using both OLS and PLS analyses, when kaolinite was present.

Assessment of measurement errors and dynamic calibration methods for three different tipping bucket rain gauges

NASA Astrophysics Data System (ADS)

Shedekar, Vinayak S.; King, Kevin W.; Fausey, Norman R.; Soboyejo, Alfred B. O.; Harmel, R. Daren; Brown, Larry C.

2016-09-01

Three different models of tipping bucket rain gauges (TBRs), viz. HS-TB3 (Hydrological Services Pty Ltd.), ISCO-674 (Isco, Inc.) and TR-525 (Texas Electronics, Inc.), were calibrated in the lab to quantify measurement errors across a range of rainfall intensities (5 mm·h- 1 to 250 mm·h- 1) and three different volumetric settings. Instantaneous and cumulative values of simulated rainfall were recorded at 1, 2, 5, 10 and 20-min intervals. All three TBR models showed a substantial deviation (α = 0.05) in measurements from actual rainfall depths, with increasing underestimation errors at greater rainfall intensities. Simple linear regression equations were developed for each TBR to correct the TBR readings based on measured intensities (R2 > 0.98). Additionally, two dynamic calibration techniques, viz. quadratic model (R2 > 0.7) and T vs. 1/Q model (R2 = > 0.98), were tested and found to be useful in situations when the volumetric settings of TBRs are unknown. The correction models were successfully applied to correct field-collected rainfall data from respective TBR models. The calibration parameters of correction models were found to be highly sensitive to changes in volumetric calibration of TBRs. Overall, the HS-TB3 model (with a better protected tipping bucket mechanism, and consistent measurement errors across a range of rainfall intensities) was found to be the most reliable and consistent for rainfall measurements, followed by the ISCO-674 (with susceptibility to clogging and relatively smaller measurement errors across a range of rainfall intensities) and the TR-525 (with high susceptibility to clogging and frequent changes in volumetric calibration, and highly intensity-dependent measurement errors). The study demonstrated that corrections based on dynamic and volumetric calibration can only help minimize-but not completely eliminate the measurement errors. The findings from this study will be useful for correcting field data from TBRs; and may have major implications to field- and watershed-scale hydrologic studies.

Linking Parameter Estimates Derived from an Item Response Model through Separate Calibrations. Research Report. ETS RR-09-40

ERIC Educational Resources Information Center

Haberman, Shelby J.

2009-01-01

A regression procedure is developed to link simultaneously a very large number of item response theory (IRT) parameter estimates obtained from a large number of test forms, where each form has been separately calibrated and where forms can be linked on a pairwise basis by means of common items. An application is made to forms in which a…

Identification and quantification of ciprofloxacin in urine through excitation-emission fluorescence and three-way PARAFAC calibration.

PubMed

Ortiz, M C; Sarabia, L A; Sánchez, M S; Giménez, D

2009-05-29

Due to the second-order advantage, calibration models based on parallel factor analysis (PARAFAC) decomposition of three-way data are becoming important in routine analysis. This work studies the possibility of fitting PARAFAC models with excitation-emission fluorescence data for the determination of ciprofloxacin in human urine. The finally chosen PARAFAC decomposition is built with calibration samples spiked with ciprofloxacin, and with other series of urine samples that were also spiked. One of the series of samples has also another drug because the patient was taking mesalazine. The mesalazine is a fluorescent substance that interferes with the ciprofloxacin. Finally, the procedure is applied to samples of a patient who was being treated with ciprofloxacin. The trueness has been established by the regression "predicted concentration versus added concentration". The recovery factor is 88.3% for ciprofloxacin in urine, and the mean of the absolute value of the relative errors is 4.2% for 46 test samples. The multivariate sensitivity of the fit calibration model is evaluated by a regression between the loadings of PARAFAC linked to ciprofloxacin versus the true concentration in spiked samples. The multivariate capability of discrimination is near 8 microg L(-1) when the probabilities of false non-compliance and false compliance are fixed at 5%.

Simultaneous kinetic spectrometric determination of three flavonoid antioxidants in fruit with the aid of chemometrics

NASA Astrophysics Data System (ADS)

Sun, Ruiling; Wang, Yong; Ni, Yongnian; Kokot, Serge

2014-03-01

A simple, inexpensive and sensitive kinetic spectrophotometric method was developed for the simultaneous determination of three anti-carcinogenic flavonoids: catechin, quercetin and naringenin, in fruit samples. A yellow chelate product was produced in the presence neocuproine and Cu(I) - a reduction product of the reaction between the flavonoids with Cu(II), and this enabled the quantitative measurements with UV-vis spectrophotometry. The overlapping spectra obtained, were resolved with chemometrics calibration models, and the best performing method was the fast independent component analysis (fast-ICA/PCR (Principal component regression)); the limits of detection were 0.075, 0.057 and 0.063 mg L-1 for catechin, quercetin and naringenin, respectively. The novel method was found to outperform significantly the common HPLC procedure.

Determination of Trace Available Heavy Metals in Soil Using Laser-Induced Breakdown Spectroscopy Assisted with Phase Transformation Method.

PubMed

Yi, Rongxing; Yang, Xinyan; Zhou, Ran; Li, Jiaming; Yu, Huiwu; Hao, Zhongqi; Guo, Lianbo; Li, Xiangyou; Lu, Yongfeng; Zeng, Xiaoyan

2018-05-18

To detect available heavy metals in soil using laser-induced breakdown spectroscopy (LIBS) and improve its poor detection sensitivity, a simple and low cost sample pretreatment method named solid-liquid-solid transformation was proposed. By this method, available heavy metals were extracted from soil through ultrasonic vibration and centrifuging and then deposited on a glass slide. Utilization of this solid-liquid-solid transformation method, available Cd and Pb elements in soil were detected successfully. The results show that the regression coefficients of calibration curves for soil analyses reach to more than 0.98. The limits of detection could reach to 0.067 and 0.94 ppm for available Cd and Pb elements in soil under optimized conditions, respectively, which are much better than those obtained by conventional LIBS.

Research on camera on orbit radial calibration based on black body and infrared calibration stars

NASA Astrophysics Data System (ADS)

Wang, YuDu; Su, XiaoFeng; Zhang, WanYing; Chen, FanSheng

2018-05-01

Affected by launching process and space environment, the response capability of a space camera must be attenuated. So it is necessary for a space camera to have a spaceborne radiant calibration. In this paper, we propose a method of calibration based on accurate Infrared standard stars was proposed for increasing infrared radiation measurement precision. As stars can be considered as a point target, we use them as the radiometric calibration source and establish the Taylor expansion method and the energy extrapolation model based on WISE catalog and 2MASS catalog. Then we update the calibration results from black body. Finally, calibration mechanism is designed and the technology of design is verified by on orbit test. The experimental calibration result shows the irradiance extrapolation error is about 3% and the accuracy of calibration methods is about 10%, the results show that the methods could satisfy requirements of on orbit calibration.

Multi-satellites normalization of the FengYun-2s visible detectors by the MVP method

NASA Astrophysics Data System (ADS)

Li, Yuan; Rong, Zhi-guo; Zhang, Li-jun; Sun, Ling; Xu, Na

2013-08-01

After January 13, 2012, FY-2F had successfully launched, the total number of the in orbit operating FengYun-2 geostationary meteorological satellites reached three. For accurate and efficient application of multi-satellite observation data, the study of the multi-satellites normalization of the visible detector was urgent. The method required to be non-rely on the in orbit calibration. So as to validate the calibration results before and after the launch; calculate day updating surface bidirectional reflectance distribution function (BRDF); at the same time track the long-term decay phenomenon of the detector's linearity and responsivity. By research of the typical BRDF model, the normalization method was designed. Which could effectively solute the interference of surface directional reflectance characteristics, non-rely on visible detector in orbit calibration. That was the Median Vertical Plane (MVP) method. The MVP method was based on the symmetry of principal plane, which were the directional reflective properties of the general surface targets. Two geostationary satellites were taken as the endpoint of a segment, targets on the intersecting line of the segment's MVP and the earth surface could be used as a normalization reference target (NRT). Observation on the NRT by two satellites at the moment the sun passing through the MVP brought the same observation zenith, solar zenith, and opposite relative direction angle. At that time, the linear regression coefficients of the satellite output data were the required normalization coefficients. The normalization coefficients between FY-2D, FY-2E and FY-2F were calculated, and the self-test method of the normalized results was designed and realized. The results showed the differences of the responsivity between satellites could up to 10.1%(FY-2E to FY-2F); the differences of the output reflectance calculated by the broadcast calibration look-up table could up to 21.1%(FY-2D to FY-2F); the differences of the output reflectance from FY-2D and FY-2E calculated by the site experiment results reduced to 2.9%(13.6% when using the broadcast table). The normalized relative error was also calculated by the self-test method, which was less than 0.2%.

Selecting the correct weighting factors for linear and quadratic calibration curves with least-squares regression algorithm in bioanalytical LC-MS/MS assays and impacts of using incorrect weighting factors on curve stability, data quality, and assay performance.

PubMed

Gu, Huidong; Liu, Guowen; Wang, Jian; Aubry, Anne-Françoise; Arnold, Mark E

2014-09-16

A simple procedure for selecting the correct weighting factors for linear and quadratic calibration curves with least-squares regression algorithm in bioanalytical LC-MS/MS assays is reported. The correct weighting factor is determined by the relationship between the standard deviation of instrument responses (σ) and the concentrations (x). The weighting factor of 1, 1/x, or 1/x(2) should be selected if, over the entire concentration range, σ is a constant, σ(2) is proportional to x, or σ is proportional to x, respectively. For the first time, we demonstrated with detailed scientific reasoning, solid historical data, and convincing justification that 1/x(2) should always be used as the weighting factor for all bioanalytical LC-MS/MS assays. The impacts of using incorrect weighting factors on curve stability, data quality, and assay performance were thoroughly investigated. It was found that the most stable curve could be obtained when the correct weighting factor was used, whereas other curves using incorrect weighting factors were unstable. It was also found that there was a very insignificant impact on the concentrations reported with calibration curves using incorrect weighting factors as the concentrations were always reported with the passing curves which actually overlapped with or were very close to the curves using the correct weighting factor. However, the use of incorrect weighting factors did impact the assay performance significantly. Finally, the difference between the weighting factors of 1/x(2) and 1/y(2) was discussed. All of the findings can be generalized and applied into other quantitative analysis techniques using calibration curves with weighted least-squares regression algorithm.

Estimation of inhalation flow profile using audio-based methods to assess inhaler medication adherence.

PubMed

Taylor, Terence E; Lacalle Muls, Helena; Costello, Richard W; Reilly, Richard B

2018-01-01

Asthma and chronic obstructive pulmonary disease (COPD) patients are required to inhale forcefully and deeply to receive medication when using a dry powder inhaler (DPI). There is a clinical need to objectively monitor the inhalation flow profile of DPIs in order to remotely monitor patient inhalation technique. Audio-based methods have been previously employed to accurately estimate flow parameters such as the peak inspiratory flow rate of inhalations, however, these methods required multiple calibration inhalation audio recordings. In this study, an audio-based method is presented that accurately estimates inhalation flow profile using only one calibration inhalation audio recording. Twenty healthy participants were asked to perform 15 inhalations through a placebo Ellipta™ DPI at a range of inspiratory flow rates. Inhalation flow signals were recorded using a pneumotachograph spirometer while inhalation audio signals were recorded simultaneously using the Inhaler Compliance Assessment device attached to the inhaler. The acoustic (amplitude) envelope was estimated from each inhalation audio signal. Using only one recording, linear and power law regression models were employed to determine which model best described the relationship between the inhalation acoustic envelope and flow signal. Each model was then employed to estimate the flow signals of the remaining 14 inhalation audio recordings. This process repeated until each of the 15 recordings were employed to calibrate single models while testing on the remaining 14 recordings. It was observed that power law models generated the highest average flow estimation accuracy across all participants (90.89±0.9% for power law models and 76.63±2.38% for linear models). The method also generated sufficient accuracy in estimating inhalation parameters such as peak inspiratory flow rate and inspiratory capacity within the presence of noise. Estimating inhaler inhalation flow profiles using audio based methods may be clinically beneficial for inhaler technique training and the remote monitoring of patient adherence.

Estimation of inhalation flow profile using audio-based methods to assess inhaler medication adherence

PubMed Central

Lacalle Muls, Helena; Costello, Richard W.; Reilly, Richard B.

2018-01-01

Asthma and chronic obstructive pulmonary disease (COPD) patients are required to inhale forcefully and deeply to receive medication when using a dry powder inhaler (DPI). There is a clinical need to objectively monitor the inhalation flow profile of DPIs in order to remotely monitor patient inhalation technique. Audio-based methods have been previously employed to accurately estimate flow parameters such as the peak inspiratory flow rate of inhalations, however, these methods required multiple calibration inhalation audio recordings. In this study, an audio-based method is presented that accurately estimates inhalation flow profile using only one calibration inhalation audio recording. Twenty healthy participants were asked to perform 15 inhalations through a placebo Ellipta™ DPI at a range of inspiratory flow rates. Inhalation flow signals were recorded using a pneumotachograph spirometer while inhalation audio signals were recorded simultaneously using the Inhaler Compliance Assessment device attached to the inhaler. The acoustic (amplitude) envelope was estimated from each inhalation audio signal. Using only one recording, linear and power law regression models were employed to determine which model best described the relationship between the inhalation acoustic envelope and flow signal. Each model was then employed to estimate the flow signals of the remaining 14 inhalation audio recordings. This process repeated until each of the 15 recordings were employed to calibrate single models while testing on the remaining 14 recordings. It was observed that power law models generated the highest average flow estimation accuracy across all participants (90.89±0.9% for power law models and 76.63±2.38% for linear models). The method also generated sufficient accuracy in estimating inhalation parameters such as peak inspiratory flow rate and inspiratory capacity within the presence of noise. Estimating inhaler inhalation flow profiles using audio based methods may be clinically beneficial for inhaler technique training and the remote monitoring of patient adherence. PMID:29346430

Geometric calibration of Colour and Stereo Surface Imaging System of ESA's Trace Gas Orbiter

NASA Astrophysics Data System (ADS)

Tulyakov, Stepan; Ivanov, Anton; Thomas, Nicolas; Roloff, Victoria; Pommerol, Antoine; Cremonese, Gabriele; Weigel, Thomas; Fleuret, Francois

2018-01-01

There are many geometric calibration methods for "standard" cameras. These methods, however, cannot be used for the calibration of telescopes with large focal lengths and complex off-axis optics. Moreover, specialized calibration methods for the telescopes are scarce in literature. We describe the calibration method that we developed for the Colour and Stereo Surface Imaging System (CaSSIS) telescope, on board of the ExoMars Trace Gas Orbiter (TGO). Although our method is described in the context of CaSSIS, with camera-specific experiments, it is general and can be applied to other telescopes. We further encourage re-use of the proposed method by making our calibration code and data available on-line.

Variable Selection for Regression Models of Percentile Flows

NASA Astrophysics Data System (ADS)

Fouad, G.

2017-12-01

Percentile flows describe the flow magnitude equaled or exceeded for a given percent of time, and are widely used in water resource management. However, these statistics are normally unavailable since most basins are ungauged. Percentile flows of ungauged basins are often predicted using regression models based on readily observable basin characteristics, such as mean elevation. The number of these independent variables is too large to evaluate all possible models. A subset of models is typically evaluated using automatic procedures, like stepwise regression. This ignores a large variety of methods from the field of feature (variable) selection and physical understanding of percentile flows. A study of 918 basins in the United States was conducted to compare an automatic regression procedure to the following variable selection methods: (1) principal component analysis, (2) correlation analysis, (3) random forests, (4) genetic programming, (5) Bayesian networks, and (6) physical understanding. The automatic regression procedure only performed better than principal component analysis. Poor performance of the regression procedure was due to a commonly used filter for multicollinearity, which rejected the strongest models because they had cross-correlated independent variables. Multicollinearity did not decrease model performance in validation because of a representative set of calibration basins. Variable selection methods based strictly on predictive power (numbers 2-5 from above) performed similarly, likely indicating a limit to the predictive power of the variables. Similar performance was also reached using variables selected based on physical understanding, a finding that substantiates recent calls to emphasize physical understanding in modeling for predictions in ungauged basins. The strongest variables highlighted the importance of geology and land cover, whereas widely used topographic variables were the weakest predictors. Variables suffered from a high degree of multicollinearity, possibly illustrating the co-evolution of climatic and physiographic conditions. Given the ineffectiveness of many variables used here, future work should develop new variables that target specific processes associated with percentile flows.

Near infra red spectroscopy as a multivariate process analytical tool for predicting pharmaceutical co-crystal concentration.

PubMed

Wood, Clive; Alwati, Abdolati; Halsey, Sheelagh; Gough, Tim; Brown, Elaine; Kelly, Adrian; Paradkar, Anant

2016-09-10

The use of near infra red spectroscopy to predict the concentration of two pharmaceutical co-crystals; 1:1 ibuprofen-nicotinamide (IBU-NIC) and 1:1 carbamazepine-nicotinamide (CBZ-NIC) has been evaluated. A partial least squares (PLS) regression model was developed for both co-crystal pairs using sets of standard samples to create calibration and validation data sets with which to build and validate the models. Parameters such as the root mean square error of calibration (RMSEC), root mean square error of prediction (RMSEP) and correlation coefficient were used to assess the accuracy and linearity of the models. Accurate PLS regression models were created for both co-crystal pairs which can be used to predict the co-crystal concentration in a powder mixture of the co-crystal and the active pharmaceutical ingredient (API). The IBU-NIC model had smaller errors than the CBZ-NIC model, possibly due to the complex CBZ-NIC spectra which could reflect the different arrangement of hydrogen bonding associated with the co-crystal compared to the IBU-NIC co-crystal. These results suggest that NIR spectroscopy can be used as a PAT tool during a variety of pharmaceutical co-crystal manufacturing methods and the presented data will facilitate future offline and in-line NIR studies involving pharmaceutical co-crystals. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Irradiation dose detection of irradiated milk powder using visible and near-infrared spectroscopy and chemometrics.

PubMed

Kong, W W; Zhang, C; Liu, F; Gong, A P; He, Y

2013-08-01

The objective of this study was to examine the possibility of applying visible and near-infrared spectroscopy to the quantitative detection of irradiation dose of irradiated milk powder. A total of 150 samples were used: 100 for the calibration set and 50 for the validation set. The samples were irradiated at 5 different dose levels in the dose range 0 to 6.0 kGy. Six different pretreatment methods were compared. The prediction results of full spectra given by linear and nonlinear calibration methods suggested that Savitzky-Golay smoothing and first derivative were suitable pretreatment methods in this study. Regression coefficient analysis was applied to select effective wavelengths (EW). Less than 10 EW were selected and they were useful for portable detection instrument or sensor development. Partial least squares, extreme learning machine, and least squares support vector machine were used. The best prediction performance was achieved by the EW-extreme learning machine model with first-derivative spectra, and correlation coefficients=0.97 and root mean square error of prediction=0.844. This study provided a new approach for the fast detection of irradiation dose of milk powder. The results could be helpful for quality detection and safety monitoring of milk powder. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Calibration of mass spectrometric peptide mass fingerprint data without specific external or internal calibrants

PubMed Central

Wolski, Witold E; Lalowski, Maciej; Jungblut, Peter; Reinert, Knut

2005-01-01

Background Peptide Mass Fingerprinting (PMF) is a widely used mass spectrometry (MS) method of analysis of proteins and peptides. It relies on the comparison between experimentally determined and theoretical mass spectra. The PMF process requires calibration, usually performed with external or internal calibrants of known molecular masses. Results We have introduced two novel MS calibration methods. The first method utilises the local similarity of peptide maps generated after separation of complex protein samples by two-dimensional gel electrophoresis. It computes a multiple peak-list alignment of the data set using a modified Minimum Spanning Tree (MST) algorithm. The second method exploits the idea that hundreds of MS samples are measured in parallel on one sample support. It improves the calibration coefficients by applying a two-dimensional Thin Plate Splines (TPS) smoothing algorithm. We studied the novel calibration methods utilising data generated by three different MALDI-TOF-MS instruments. We demonstrate that a PMF data set can be calibrated without resorting to external or relying on widely occurring internal calibrants. The methods developed here were implemented in R and are part of the BioConductor package mscalib available from . Conclusion The MST calibration algorithm is well suited to calibrate MS spectra of protein samples resulting from two-dimensional gel electrophoretic separation. The TPS based calibration algorithm might be used to correct systematic mass measurement errors observed for large MS sample supports. As compared to other methods, our combined MS spectra calibration strategy increases the peptide/protein identification rate by an additional 5 – 15%. PMID:16102175

In-flight calibration/validation of the ENVISAT/MWR

NASA Astrophysics Data System (ADS)

Tran, N.; Obligis, E.; Eymard, L.

2003-04-01

Retrieval algorithms for wet tropospheric correction, integrated vapor and liquid water contents, atmospheric attenuations of backscattering coefficients in Ku and S band, have been developed using a database of geophysical parameters from global analyses from a meteorological model and corresponding simulated brightness temperatures and backscattering cross-sections by a radiative transfer model. Meteorological data correspond to 12 hours predictions from the European Center for Medium range Weather Forecasts (ECMWF) model. Relationships between satellite measurements and geophysical parameters are determined using a statistical method. The quality of the retrieval algorithms depends therefore on the representativity of the database, the accuracy of the radiative transfer model used for the simulations and finally on the quality of the inversion model. The database has been built using the latest version of the ECMWF forecast model, which has been operationally run since November 2000. The 60 levels in the model allow a complete description of the troposphere/stratosphere profiles and the horizontal resolution is now half of a degree. The radiative transfer model is the emissivity model developed at the Université Catholique de Louvain [Lemaire, 1998], coupled to an atmospheric model [Liebe et al, 1993] for gaseous absorption. For the inversion, we have replaced the classical log-linear regression with a neural networks inversion. For Envisat, the backscattering coefficient in Ku band is used in the different algorithms to take into account the surface roughness as it is done with the 18 GHz channel for the TOPEX algorithms or an additional term in wind speed for ERS2 algorithms. The in-flight calibration/validation of the Envisat radiometer has been performed with the tuning of 3 internal parameters (the transmission coefficient of the reflector, the sky horn feed transmission coefficient and the main antenna transmission coefficient). First an adjustment of the ERS2 brightness temperatures to the simulations for the 2000/2001 version of the ECMWF model has been applied. Then, Envisat brightness temperatures have been calibrated on these adjusted ERS2 values. The advantages of this calibration approach are that : i) such a method provides the relative discrepancy with respect to the simulation chain. The results, obtained simultaneously for several radiometers (we repeat the same analyze with TOPEX and JASON radiometers), can be used to detect significant calibration problems, more than 2 3 K). ii) the retrieval algorithms have been developed using the same meteorological model (2000/2001 version of the ECMWF model), and the same radiative transfer model than the calibration process, insuring the consistency between calibration and retrieval processing. Retrieval parameters are then optimized. iii) the calibration of the Envisat brightness temperatures over the 2000/2001 version of the ECMWF model, as well as the recommendation to use the same model as a reference to correct ERS2 brightness temperatures, allow the use of the same retrieval algorithms for the two missions, providing the continuity between the two. iv) by comparison with other calibration methods (such as systematic calibration of an instrument or products by using respectively the ones from previous mission), this method is more satisfactory since improvements in terms of technology, modelisation, retrieval processing are taken into account. For the validation of the brightness temperatures, we use either a direct comparison with measurements provided by other instruments in similar channel, or the monitoring over stable areas (coldest ocean points, stable continental areas). The validation of the wet tropospheric correction can be also provided by comparison with other radiometer products, but the only real validation rely on the comparison between in-situ measurements (performed by radiosonding) and retrieved products in coincidence.

An investigation into force-moment calibration techniques applicable to a magnetic suspension and balance system. M.S. Thesis

NASA Technical Reports Server (NTRS)

Eskins, Jonathan

1988-01-01

The problem of determining the forces and moments acting on a wind tunnel model suspended in a Magnetic Suspension and Balance System is addressed. Two calibration methods were investigated for three types of model cores, i.e., Alnico, Samarium-Cobalt, and a superconducting solenoid. Both methods involve calibrating the currents in the electromagnetic array against known forces and moments. The first is a static calibration method using calibration weights and a system of pulleys. The other method, dynamic calibration, involves oscillating the model and using its inertia to provide calibration forces and moments. Static calibration data, found to produce the most reliable results, is presented for three degrees of freedom at 0, 15, and -10 deg angle of attack. Theoretical calculations are hampered by the inability to represent iron-cored electromagnets. Dynamic calibrations, despite being quicker and easier to perform, are not as accurate as static calibrations. Data for dynamic calibrations at 0 and 15 deg is compared with the relevant static data acquired. Distortion of oscillation traces is cited as a major source of error in dynamic calibrations.

The calibration methods for Multi-Filter Rotating Shadowband Radiometer: a review

NASA Astrophysics Data System (ADS)

Chen, Maosi; Davis, John; Tang, Hongzhao; Ownby, Carolyn; Gao, Wei

2013-09-01

The continuous, over two-decade data record from the Multi-Filter Rotating Shadowband Radiometer (MFRSR) is ideal for climate research which requires timely and accurate information of important atmospheric components such as gases, aerosols, and clouds. Except for parameters derived from MFRSR measurement ratios, which are not impacted by calibration error, most applications require accurate calibration factor(s), angular correction, and spectral response function(s) from calibration. Although a laboratory lamp (or reference) calibration can provide all the information needed to convert the instrument readings to actual radiation, in situ calibration methods are implemented routinely (daily) to fill the gaps between lamp calibrations. In this paper, the basic structure and the data collection and pretreatment of the MFRSR are described. The laboratory lamp calibration and its limitations are summarized. The cloud screening algorithms for MFRSR data are presented. The in situ calibration methods, the standard Langley method and its variants, the ratio-Langley method, the general method, Alexandrov's comprehensive method, and Chen's multi-channel method, are outlined. The reason that all these methods do not fit for all situations is that they assume some properties, such as aerosol optical depth (AOD), total optical depth (TOD), precipitable water vapor (PWV), effective size of aerosol particles, or angstrom coefficient, are invariant over time. These properties are not universal and some of them rarely happen. In practice, daily calibration factors derived from these methods should be smoothed to restrain error.

Simple transfer calibration method for a Cimel Sun-Moon photometer: calculating lunar calibration coefficients from Sun calibration constants.

PubMed

Li, Zhengqiang; Li, Kaitao; Li, Donghui; Yang, Jiuchun; Xu, Hua; Goloub, Philippe; Victori, Stephane

2016-09-20

The Cimel new technologies allow both daytime and nighttime aerosol optical depth (AOD) measurements. Although the daytime AOD calibration protocols are well established, accurate and simple nighttime calibration is still a challenging task. Standard lunar-Langley and intercomparison calibration methods both require specific conditions in terms of atmospheric stability and site condition. Additionally, the lunar irradiance model also has some known limits on its uncertainty. This paper presents a simple calibration method that transfers the direct-Sun calibration constant, V_0,Sun, to the lunar irradiance calibration coefficient, C_Moon. Our approach is a pure calculation method, independent of site limits, e.g., Moon phase. The method is also not affected by the lunar irradiance model limitations, which is the largest error source of traditional calibration methods. Besides, this new transfer calibration approach is easy to use in the field since C_Moon can be obtained directly once V_0,Sun is known. Error analysis suggests that the average uncertainty of C_Moon over the 440-1640 nm bands obtained with the transfer method is 2.4%-2.8%, depending on the V_0,Sun approach (Langley or intercomparison), which is comparable with that of lunar-Langley approach, theoretically. In this paper, the Sun-Moon transfer and the Langley methods are compared based on site measurements in Beijing, and the day-night measurement continuity and performance are analyzed.

Optimized star sensors laboratory calibration method using a regularization neural network.

PubMed

Zhang, Chengfen; Niu, Yanxiong; Zhang, Hao; Lu, Jiazhen

2018-02-10

High-precision ground calibration is essential to ensure the performance of star sensors. However, the complex distortion and multi-error coupling have brought great difficulties to traditional calibration methods, especially for large field of view (FOV) star sensors. Although increasing the complexity of models is an effective way to improve the calibration accuracy, it significantly increases the demand for calibration data. In order to achieve high-precision calibration of star sensors with large FOV, a novel laboratory calibration method based on a regularization neural network is proposed. A multi-layer structure neural network is designed to represent the mapping of the star vector and the corresponding star point coordinate directly. To ensure the generalization performance of the network, regularization strategies are incorporated into the net structure and the training algorithm. Simulation and experiment results demonstrate that the proposed method can achieve high precision with less calibration data and without any other priori information. Compared with traditional methods, the calibration error of the star sensor decreased by about 30%. The proposed method can satisfy the precision requirement for large FOV star sensors.

Features calibration of the dynamic force transducers

NASA Astrophysics Data System (ADS)

Sc., M. Yu Prilepko D.; Lysenko, V. G.

2018-04-01

The article discusses calibration methods of dynamic forces measuring instruments. The relevance of work is dictated by need to valid definition of the dynamic forces transducers metrological characteristics taking into account their intended application. The aim of this work is choice justification of calibration method, which provides the definition dynamic forces transducers metrological characteristics under simulation operating conditions for determining suitability for using in accordance with its purpose. The following tasks are solved: the mathematical model and the main measurements equation of calibration dynamic forces transducers by load weight, the main budget uncertainty components of calibration are defined. The new method of dynamic forces transducers calibration with use the reference converter “force-deformation” based on the calibrated elastic element and measurement of his deformation by a laser interferometer is offered. The mathematical model and the main measurements equation of the offered method is constructed. It is shown that use of calibration method based on measurements by the laser interferometer of calibrated elastic element deformations allows to exclude or to considerably reduce the uncertainty budget components inherent to method of load weight.

Radiometer calibration methods and resulting irradiance differences: Radiometer calibration methods and resulting irradiance differences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habte, Aron; Sengupta, Manajit; Andreas, Afshin

Accurate solar radiation measured by radiometers depends on instrument performance specifications, installation method, calibration procedure, measurement conditions, maintenance practices, location, and environmental conditions. This study addresses the effect of different calibration methodologies and resulting differences provided by radiometric calibration service providers such as the National Renewable Energy Laboratory (NREL) and manufacturers of radiometers. Some of these methods calibrate radiometers indoors and some outdoors. To establish or understand the differences in calibration methodologies, we processed and analyzed field-measured data from radiometers deployed for 10 months at NREL's Solar Radiation Research Laboratory. These different methods of calibration resulted in a difference ofmore » +/-1% to +/-2% in solar irradiance measurements. Analyzing these differences will ultimately assist in determining the uncertainties of the field radiometer data and will help develop a consensus on a standard for calibration. Further advancing procedures for precisely calibrating radiometers to world reference standards that reduce measurement uncertainties will help the accurate prediction of the output of planned solar conversion projects and improve the bankability of financing solar projects.« less

Total 25-Hydroxyvitamin D Determination by an Entry Level Triple Quadrupole Instrument: Comparison between Two Commercial Kits

PubMed Central

Cocci, Andrea; Zuppi, Cecilia; Persichilli, Silvia

2013-01-01

Objective. 25-hydroxyvitamin D2/D3 (25-OHD2/D3) determination is a reliable biomarker for vitamin D status. Liquid chromatography-tandem mass spectrometry was recently proposed as a reference method for vitamin D status evaluation. The aim of this work is to compare two commercial kits (Chromsystems and PerkinElmer) for 25-OHD2/D3 determination by our entry level LC-MS/MS. Design and Methods. Chromsystems kit adds an online trap column to an HPLC column and provides atmospheric pressure chemical ionization, isotopically labeled internal standard, and 4 calibrator points. PerkinElmer kit uses a solvent extraction and protein precipitation method. This kit can be used with or without derivatization with, respectively, electrospray and atmospheric pressure chemical ionization. For each analyte, there are isotopically labeled internal standards and 7 deuterated calibrator points. Results. Performance characteristics are acceptable for both methods. Mean bias between methods calculated on 70 samples was 1.9 ng/mL. Linear regression analysis gave an R 2 of 0.94. 25-OHD2 is detectable only with PerkinElmer kit in derivatized assay option. Conclusion. Both methods are suitable for routine. Chromsystems kit minimizes manual sample preparation, requiring only protein precipitation, but, with our system, 25-OHD2 is not detectable. PerkinElmer kit without derivatization does not guarantee acceptable performance with our LC-MS/MS system, as sample is not purified online. Derivatization provides sufficient sensitivity for 25-OHD2 detection. PMID:23555079

Iodine intake by adult residents of a farming area in Iwate Prefecture, Japan, and the accuracy of estimated iodine intake calculated using the Standard Tables of Food Composition in Japan.

PubMed

Nakatsuka, Haruo; Chiba, Keiko; Watanabe, Takao; Sawatari, Hideyuki; Seki, Takako

2016-11-01

Iodine intake by adults in farming districts in Northeastern Japan was evaluated by two methods: (1) government-approved food composition tables based calculation and (2) instrumental measurement. The correlation between these two values and a regression model for the calibration of calculated values was presented. Iodine intake was calculated, using the values in the Japan Standard Tables of Food Composition (FCT), through the analysis of duplicate samples of complete 24-h food consumption for 90 adult subjects. In cases where the value for iodine content was not available in the FCT, it was assumed to be zero for that food item (calculated values). Iodine content was also measured by ICP-MS (measured values). Calculated and measured values rendered geometric means (GM) of 336 and 279 μg/day, respectively. There was no statistically significant (p > 0.05) difference between calculated and measured values. The correlation coefficient was 0.646 (p < 0.05). With this high correlation coefficient, a simple regression line can be applied to estimate measured value from calculated value. A survey of the literature suggests that the values in this study were similar to values that have been reported to date for Japan, and higher than those for other countries in Asia. Iodine intake of Japanese adults was 336 μg/day (GM, calculated) and 279 μg/day (GM, measured). Both values correlated so well, with a correlation coefficient of 0.646, that a regression model (Y = 130.8 + 1.9479X, where X and Y are measured and calculated values, respectively) could be used to calibrate calculated values.

A multivariate regression model for detection of fumonisins content in maize from near infrared spectra.

PubMed

Giacomo, Della Riccia; Stefania, Del Zotto

2013-12-15

Fumonisins are mycotoxins produced by Fusarium species that commonly live in maize. Whereas fungi damage plants, fumonisins cause disease both to cattle breedings and human beings. Law limits set fumonisins tolerable daily intake with respect to several maize based feed and food. Chemical techniques assure the most reliable and accurate measurements, but they are expensive and time consuming. A method based on Near Infrared spectroscopy and multivariate statistical regression is described as a simpler, cheaper and faster alternative. We apply Partial Least Squares with full cross validation. Two models are described, having high correlation of calibration (0.995, 0.998) and of validation (0.908, 0.909), respectively. Description of observed phenomenon is accurate and overfitting is avoided. Screening of contaminated maize with respect to European legal limit of 4 mg kg(-1) should be assured. Copyright © 2013 Elsevier Ltd. All rights reserved.

Direct Breakthrough Curve Prediction From Statistics of Heterogeneous Conductivity Fields

NASA Astrophysics Data System (ADS)

Hansen, Scott K.; Haslauer, Claus P.; Cirpka, Olaf A.; Vesselinov, Velimir V.

2018-01-01

This paper presents a methodology to predict the shape of solute breakthrough curves in heterogeneous aquifers at early times and/or under high degrees of heterogeneity, both cases in which the classical macrodispersion theory may not be applicable. The methodology relies on the observation that breakthrough curves in heterogeneous media are generally well described by lognormal distributions, and mean breakthrough times can be predicted analytically. The log-variance of solute arrival is thus sufficient to completely specify the breakthrough curves, and this is calibrated as a function of aquifer heterogeneity and dimensionless distance from a source plane by means of Monte Carlo analysis and statistical regression. Using the ensemble of simulated groundwater flow and solute transport realizations employed to calibrate the predictive regression, reliability estimates for the prediction are also developed. Additional theoretical contributions include heuristics for the time until an effective macrodispersion coefficient becomes applicable, and also an expression for its magnitude that applies in highly heterogeneous systems. It is seen that the results here represent a way to derive continuous time random walk transition distributions from physical considerations rather than from empirical field calibration.

Research on the calibration methods of the luminance parameter of radiation luminance meters

NASA Astrophysics Data System (ADS)

Cheng, Weihai; Huang, Biyong; Lin, Fangsheng; Li, Tiecheng; Yin, Dejin; Lai, Lei

2017-10-01

This paper introduces standard diffusion reflection white plate method and integrating sphere standard luminance source method to calibrate the luminance parameter. The paper compares the effects of calibration results by using these two methods through principle analysis and experimental verification. After using two methods to calibrate the same radiation luminance meter, the data obtained verifies the testing results of the two methods are both reliable. The results show that the display value using standard white plate method has fewer errors and better reproducibility. However, standard luminance source method is more convenient and suitable for on-site calibration. Moreover, standard luminance source method has wider range and can test the linear performance of the instruments.

Comparative evaluation of bioactivity of crystalline trypsin for drying by Fourier-transformed infrared spectroscopy.

PubMed

Otsuka, Makoto; Fukui, Yuya; Ozaki, Yukihiro

2009-03-01

The purpose of this study was to evaluate the enzymatic stability of colloidal trypsin powder during heating in a solid-state by using Fourier transform infrared (FT-IR) spectra with chemoinformatics and generalized two-dimensional (2D) correlation spectroscopy. Colloidal crystalline trypsin powders were heated using differential scanning calorimetry. The enzymatic activity of trypsin was assayed by the kinetic degradation method. Spectra of 10 calibration sample sets were recorded three times with a FT-IR spectrometer. The maximum intensity at 1634cm(-1) of FT-IR spectra and enzymatic activity of trypsin decreased as the temperature increased. The FT-IR spectra of trypsin samples were analyzed by a principal component regression analysis (PCR). A plot of the calibration data obtained was made between the actual and predicted trypsin activity based on a two-component model with gamma(2)=0.962. On the other hand, a 2D method was applied to FT-IR spectra of heat-treated trypsin. The result was consistent with that of the chemoinformetrical method. The results for deactivation of colloidal trypsin powder by heat-treatment indicated that nano-structure of crystalline trypsin changed by heating reflecting that the beta-sheet was mainly transformed, since the peak at 1634cm(-1) decreased with dehydration. The FT-IR chemoinformetrical method allows for a solid-state quantitative analysis of the bioactivity of the bulk powder of trypsin during drying.

WE-G-18A-02: Calibration-Free Combined KV/MV Short Scan CBCT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, M; Loo, B; Bazalova, M

Purpose: To combine orthogonal kilo-voltage (kV) and Mega-voltage (MV) projection data for short scan cone-beam CT to reduce imaging time on current radiation treatment systems, using a calibration-free gain correction method. Methods: Combining two orthogonal projection data sets for kV and MV imaging hardware can reduce the scan angle to as small as 110° (90°+fan) such that the total scan time is ∼18 seconds, or within a breath hold. To obtain an accurate reconstruction, the MV projection data is first linearly corrected using linear regression using the redundant data from the start and end of the sinogram, and then themore » combined data is reconstructed using the FDK method. To correct for the different changes of attenuation coefficients in kV/MV between soft tissue and bone, the forward projection of the segmented bone and soft tissue from the first reconstruction in the redundant region are added to the linear regression model. The MV data is corrected again using the additional information from the segmented image, and combined with kV for a second FDK reconstruction. We simulated polychromatic 120 kVp (conventional a-Si EPID with CsI) and 2.5 MVp (prototype high-DQE MV detector) projection data with Poisson noise using the XCAT phantom. The gain correction and combined kV/MV short scan reconstructions were tested with head and thorax cases, and simple contrast-to-noise ratio measurements were made in a low-contrast pattern in the head. Results: The FDK reconstruction using the proposed gain correction method can effectively reduce artifacts caused by the differences of attenuation coefficients in the kV/MV data. The CNRs of the short scans for kV, MV, and kV/MV are 5.0, 2.6 and 3.4 respectively. The proposed gain correction method also works with truncated projections. Conclusion: A novel gain correction and reconstruction method was developed to generate short scan CBCT from orthogonal kV/MV projections. This work is supported by NIH Grant 5R01CA138426-05.« less

Fast Quantitative Analysis Of Museum Objects Using Laser-Induced Breakdown Spectroscopy And Multiple Regression Algorithms

NASA Astrophysics Data System (ADS)

Lorenzetti, G.; Foresta, A.; Palleschi, V.; Legnaioli, S.

2009-09-01

The recent development of mobile instrumentation, specifically devoted to in situ analysis and study of museum objects, allows the acquisition of many LIBS spectra in very short time. However, such large amount of data calls for new analytical approaches which would guarantee a prompt analysis of the results obtained. In this communication, we will present and discuss the advantages of statistical analytical methods, such as Partial Least Squares Multiple Regression algorithms vs. the classical calibration curve approach. PLS algorithms allows to obtain in real time the information on the composition of the objects under study; this feature of the method, compared to the traditional off-line analysis of the data, is extremely useful for the optimization of the measurement times and number of points associated with the analysis. In fact, the real time availability of the compositional information gives the possibility of concentrating the attention on the most `interesting' parts of the object, without over-sampling the zones which would not provide useful information for the scholars or the conservators. Some example on the applications of this method will be presented, including the studies recently performed by the researcher of the Applied Laser Spectroscopy Laboratory on museum bronze objects.

[Influence of sample surface roughness on mathematical model of NIR quantitative analysis of wood density].

PubMed

Huang, An-Min; Fei, Ben-Hua; Jiang, Ze-Hui; Hse, Chung-Yun

2007-09-01

Near infrared spectroscopy is widely used as a quantitative method, and the main multivariate techniques consist of regression methods used to build prediction models, however, the accuracy of analysis results will be affected by many factors. In the present paper, the influence of different sample roughness on the mathematical model of NIR quantitative analysis of wood density was studied. The result of experiments showed that if the roughness of predicted samples was consistent with that of calibrated samples, the result was good, otherwise the error would be much higher. The roughness-mixed model was more flexible and adaptable to different sample roughness. The prediction ability of the roughness-mixed model was much better than that of the single-roughness model.

Evolution of accelerometer methods for physical activity research.

PubMed

Troiano, Richard P; McClain, James J; Brychta, Robert J; Chen, Kong Y

2014-07-01

The technology and application of current accelerometer-based devices in physical activity (PA) research allow the capture and storage or transmission of large volumes of raw acceleration signal data. These rich data not only provide opportunities to improve PA characterisation, but also bring logistical and analytic challenges. We discuss how researchers and developers from multiple disciplines are responding to the analytic challenges and how advances in data storage, transmission and big data computing will minimise logistical challenges. These new approaches also bring the need for several paradigm shifts for PA researchers, including a shift from count-based approaches and regression calibrations for PA energy expenditure (PAEE) estimation to activity characterisation and EE estimation based on features extracted from raw acceleration signals. Furthermore, a collaborative approach towards analytic methods is proposed to facilitate PA research, which requires a shift away from multiple independent calibration studies. Finally, we make the case for a distinction between PA represented by accelerometer-based devices and PA assessed by self-report. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

A near-infrared reflectance spectroscopic method for the direct analysis of several fodder-related chemical components in drumstick (Moringa oleifera Lam.) leaves.

PubMed

Zhang, Junjie; Li, Shuqi; Lin, Mengfei; Yang, Endian; Chen, Xiaoyang

2018-05-01

The drumstick tree has traditionally been used as foodstuff and fodder in several countries. Due to its high nutritional value and good biomass production, interest in this plant has increased in recent years. It has therefore become important to rapidly and accurately evaluate drumstick quality. In this study, we addressed the optimization of Near-infrared spectroscopy (NIRS) to analyze crude protein, crude fat, crude fiber, iron (Fe), and potassium (K) in a variety of drumstick accessions (N = 111) representing different populations, cultivation programs, and climates. Partial least-squares regression with internal cross-validation was used to evaluate the models and identify possible spectral outliers. The calibration statistics for these fodder-related chemical components suggest that NIRS can predict these parameters in a wide range of drumstick types with high accuracy. The NIRS calibration models developed in this study will be useful in predicting drumstick forage quality for these five quality parameters.

Forecasting Lightning Threat Using WRF Proxy Fields

NASA Technical Reports Server (NTRS)

McCaul, E. W., Jr.

2010-01-01

Objectives: Given that high-resolution WRF forecasts can capture the character of convective outbreaks, we seek to: 1. Create WRF forecasts of LTG threat (1-24 h), based on 2 proxy fields from explicitly simulated convection: - graupel flux near -15 C (captures LTG time variability) - vertically integrated ice (captures LTG threat area). 2. Calibrate each threat to yield accurate quantitative peak flash rate densities. 3. Also evaluate threats for areal coverage, time variability. 4. Blend threats to optimize results. 5. Examine sensitivity to model mesh, microphysics. Methods: 1. Use high-resolution 2-km WRF simulations to prognose convection for a diverse series of selected case studies. 2. Evaluate graupel fluxes; vertically integrated ice (VII). 3. Calibrate WRF LTG proxies using peak total LTG flash rate densities from NALMA; relationships look linear, with regression line passing through origin. 4. Truncate low threat values to make threat areal coverage match NALMA flash extent density obs. 5. Blend proxies to achieve optimal performance 6. Study CAPS 4-km ensembles to evaluate sensitivities.

Physicochemical characterization of Lavandula spp. honey with FT-Raman spectroscopy.

PubMed

Anjos, Ofélia; Santos, António J A; Paixão, Vasco; Estevinho, Letícia M

2018-02-01

This study aimed to evaluate the potential of FT-Raman spectroscopy in the prediction of the chemical composition of Lavandula spp. monofloral honey. Partial Least Squares (PLS) regression models were performed for the quantitative estimation and the results were correlated with those obtained using reference methods. Good calibration models were obtained for electrical conductivity, ash, total acidity, pH, reducing sugars, hydroxymethylfurfural (HMF), proline, diastase index, apparent sucrose, total flavonoids content and total phenol content. On the other hand, the model was less accurate for pH determination. The calibration models had high r 2 (ranging between 92.8% and 99.9%), high residual prediction deviation - RPD (ranging between 4.2 and 26.8) and low root mean square errors. These results confirm the hypothesis that FT-Raman is a useful technique for the quality control and chemical properties' evaluation of Lavandula spp honey. Its application may allow improving the efficiency, speed and cost of the current laboratory analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Limits of detection and decision. Part 3

NASA Astrophysics Data System (ADS)

Voigtman, E.

2008-02-01

It has been shown that the MARLAP (Multi-Agency Radiological Laboratory Analytical Protocols) for estimating the Currie detection limit, which is based on 'critical values of the non-centrality parameter of the non-central t distribution', is intrinsically biased, even if no calibration curve or regression is used. This completed the refutation of the method, begun in Part 2. With the field cleared of obstructions, the true theory underlying Currie's limits of decision, detection and quantification, as they apply in a simple linear chemical measurement system (CMS) having heteroscedastic, Gaussian measurement noise and using weighted least squares (WLS) processing, was then derived. Extensive Monte Carlo simulations were performed, on 900 million independent calibration curves, for linear, "hockey stick" and quadratic noise precision models (NPMs). With errorless NPM parameters, all the simulation results were found to be in excellent agreement with the derived theoretical expressions. Even with as much as 30% noise on all of the relevant NPM parameters, the worst absolute errors in rates of false positives and false negatives, was only 0.3%.

A novel dual-camera calibration method for 3D optical measurement

NASA Astrophysics Data System (ADS)

Gai, Shaoyan; Da, Feipeng; Dai, Xianqiang

2018-05-01

A novel dual-camera calibration method is presented. In the classic methods, the camera parameters are usually calculated and optimized by the reprojection error. However, for a system designed for 3D optical measurement, this error does not denote the result of 3D reconstruction. In the presented method, a planar calibration plate is used. In the beginning, images of calibration plate are snapped from several orientations in the measurement range. The initial parameters of the two cameras are obtained by the images. Then, the rotation and translation matrix that link the frames of two cameras are calculated by using method of Centroid Distance Increment Matrix. The degree of coupling between the parameters is reduced. Then, 3D coordinates of the calibration points are reconstructed by space intersection method. At last, the reconstruction error is calculated. It is minimized to optimize the calibration parameters. This error directly indicates the efficiency of 3D reconstruction, thus it is more suitable for assessing the quality of dual-camera calibration. In the experiments, it can be seen that the proposed method is convenient and accurate. There is no strict requirement on the calibration plate position in the calibration process. The accuracy is improved significantly by the proposed method.

Finding trap stiffness of optical tweezers using digital filters.

PubMed

Almendarez-Rangel, Pedro; Morales-Cruzado, Beatriz; Sarmiento-Gómez, Erick; Pérez-Gutiérrez, Francisco G

2018-02-01

Obtaining trap stiffness and calibration of the position detection system is the basis of a force measurement using optical tweezers. Both calibration quantities can be calculated using several experimental methods available in the literature. In most cases, stiffness determination and detection system calibration are performed separately, often requiring procedures in very different conditions, and thus confidence of calibration methods is not assured due to possible changes in the environment. In this work, a new method to simultaneously obtain both the detection system calibration and trap stiffness is presented. The method is based on the calculation of the power spectral density of positions through digital filters to obtain the harmonic contributions of the position signal. This method has the advantage of calculating both trap stiffness and photodetector calibration factor from the same dataset in situ. It also provides a direct method to avoid unwanted frequencies that could greatly affect calibration procedure, such as electric noise, for example.

Estuarine Sediment Deposition during Wetland Restoration: A GIS and Remote Sensing Modeling Approach

NASA Technical Reports Server (NTRS)

Newcomer, Michelle; Kuss, Amber; Kentron, Tyler; Remar, Alex; Choksi, Vivek; Skiles, J. W.

2011-01-01

Restoration of the industrial salt flats in the San Francisco Bay, California is an ongoing wetland rehabilitation project. Remote sensing maps of suspended sediment concentration, and other GIS predictor variables were used to model sediment deposition within these recently restored ponds. Suspended sediment concentrations were calibrated to reflectance values from Landsat TM 5 and ASTER using three statistical techniques -- linear regression, multivariate regression, and an Artificial Neural Network (ANN), to map suspended sediment concentrations. Multivariate and ANN regressions using ASTER proved to be the most accurate methods, yielding r2 values of 0.88 and 0.87, respectively. Predictor variables such as sediment grain size and tidal frequency were used in the Marsh Sedimentation (MARSED) model for predicting deposition rates for three years. MARSED results for a fully restored pond show a root mean square deviation (RMSD) of 66.8 mm (<1) between modeled and field observations. This model was further applied to a pond breached in November 2010 and indicated that the recently breached pond will reach equilibrium levels after 60 months of tidal inundation.

Improvement of Gaofen-3 Absolute Positioning Accuracy Based on Cross-Calibration

PubMed Central

Deng, Mingjun; Li, Jiansong

2017-01-01

The Chinese Gaofen-3 (GF-3) mission was launched in August 2016, equipped with a full polarimetric synthetic aperture radar (SAR) sensor in the C-band, with a resolution of up to 1 m. The absolute positioning accuracy of GF-3 is of great importance, and in-orbit geometric calibration is a key technology for improving absolute positioning accuracy. Conventional geometric calibration is used to accurately calibrate the geometric calibration parameters of the image (internal delay and azimuth shifts) using high-precision ground control data, which are highly dependent on the control data of the calibration field, but it remains costly and labor-intensive to monitor changes in GF-3’s geometric calibration parameters. Based on the positioning consistency constraint of the conjugate points, this study presents a geometric cross-calibration method for the rapid and accurate calibration of GF-3. The proposed method can accurately calibrate geometric calibration parameters without using corner reflectors and high-precision digital elevation models, thus improving absolute positioning accuracy of the GF-3 image. GF-3 images from multiple regions were collected to verify the absolute positioning accuracy after cross-calibration. The results show that this method can achieve a calibration accuracy as high as that achieved by the conventional field calibration method. PMID:29240675

A study of machine learning regression methods for major elemental analysis of rocks using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Boucher, Thomas F.; Ozanne, Marie V.; Carmosino, Marco L.; Dyar, M. Darby; Mahadevan, Sridhar; Breves, Elly A.; Lepore, Kate H.; Clegg, Samuel M.

2015-05-01

The ChemCam instrument on the Mars Curiosity rover is generating thousands of LIBS spectra and bringing interest in this technique to public attention. The key to interpreting Mars or any other types of LIBS data are calibrations that relate laboratory standards to unknowns examined in other settings and enable predictions of chemical composition. Here, LIBS spectral data are analyzed using linear regression methods including partial least squares (PLS-1 and PLS-2), principal component regression (PCR), least absolute shrinkage and selection operator (lasso), elastic net, and linear support vector regression (SVR-Lin). These were compared against results from nonlinear regression methods including kernel principal component regression (K-PCR), polynomial kernel support vector regression (SVR-Py) and k-nearest neighbor (kNN) regression to discern the most effective models for interpreting chemical abundances from LIBS spectra of geological samples. The results were evaluated for 100 samples analyzed with 50 laser pulses at each of five locations averaged together. Wilcoxon signed-rank tests were employed to evaluate the statistical significance of differences among the nine models using their predicted residual sum of squares (PRESS) to make comparisons. For MgO, SiO2, Fe2O3, CaO, and MnO, the sparse models outperform all the others except for linear SVR, while for Na2O, K2O, TiO2, and P2O5, the sparse methods produce inferior results, likely because their emission lines in this energy range have lower transition probabilities. The strong performance of the sparse methods in this study suggests that use of dimensionality-reduction techniques as a preprocessing step may improve the performance of the linear models. Nonlinear methods tend to overfit the data and predict less accurately, while the linear methods proved to be more generalizable with better predictive performance. These results are attributed to the high dimensionality of the data (6144 channels) relative to the small number of samples studied. The best-performing models were SVR-Lin for SiO2, MgO, Fe2O3, and Na2O, lasso for Al2O3, elastic net for MnO, and PLS-1 for CaO, TiO2, and K2O. Although these differences in model performance between methods were identified, most of the models produce comparable results when p ≤ 0.05 and all techniques except kNN produced statistically-indistinguishable results. It is likely that a combination of models could be used together to yield a lower total error of prediction, depending on the requirements of the user.

Radiometric calibration of the Earth observing system's imaging sensors

NASA Technical Reports Server (NTRS)

Slater, P. N.

1987-01-01

Philosophy, requirements, and methods of calibration of multispectral space sensor systems as applicable to the Earth Observing System (EOS) are discussed. Vicarious methods for calibration of low spatial resolution systems, with respect to the Advanced Very High Resolution Radiometer (AVHRR), are then summarized. Finally, a theoretical introduction is given to a new vicarious method of calibration using the ratio of diffuse-to-global irradiance at the Earth's surfaces as the key input. This may provide an additional independent method for in-flight calibration.

Configurations and calibration methods for passive sampling techniques.

PubMed

Ouyang, Gangfeng; Pawliszyn, Janusz

2007-10-19

Passive sampling technology has developed very quickly in the past 15 years, and is widely used for the monitoring of pollutants in different environments. The design and quantification of passive sampling devices require an appropriate calibration method. Current calibration methods that exist for passive sampling, including equilibrium extraction, linear uptake, and kinetic calibration, are presented in this review. A number of state-of-the-art passive sampling devices that can be used for aqueous and air monitoring are introduced according to their calibration methods.

Application of composite small calibration objects in traffic accident scene photogrammetry.

PubMed

Chen, Qiang; Xu, Hongguo; Tan, Lidong

2015-01-01

In order to address the difficulty of arranging large calibration objects and the low measurement accuracy of small calibration objects in traffic accident scene photogrammetry, a photogrammetric method based on a composite of small calibration objects is proposed. Several small calibration objects are placed around the traffic accident scene, and the coordinate system of the composite calibration object is given based on one of them. By maintaining the relative position and coplanar relationship of the small calibration objects, the local coordinate system of each small calibration object is transformed into the coordinate system of the composite calibration object. The two-dimensional direct linear transformation method is improved based on minimizing the reprojection error of the calibration points of all objects. A rectified image is obtained using the nonlinear optimization method. The increased accuracy of traffic accident scene photogrammetry using a composite small calibration object is demonstrated through the analysis of field experiments and case studies.

Signal inference with unknown response: calibration-uncertainty renormalized estimator.

PubMed

Dorn, Sebastian; Enßlin, Torsten A; Greiner, Maksim; Selig, Marco; Boehm, Vanessa

2015-01-01

The calibration of a measurement device is crucial for every scientific experiment, where a signal has to be inferred from data. We present CURE, the calibration-uncertainty renormalized estimator, to reconstruct a signal and simultaneously the instrument's calibration from the same data without knowing the exact calibration, but its covariance structure. The idea of the CURE method, developed in the framework of information field theory, is to start with an assumed calibration to successively include more and more portions of calibration uncertainty into the signal inference equations and to absorb the resulting corrections into renormalized signal (and calibration) solutions. Thereby, the signal inference and calibration problem turns into a problem of solving a single system of ordinary differential equations and can be identified with common resummation techniques used in field theories. We verify the CURE method by applying it to a simplistic toy example and compare it against existent self-calibration schemes, Wiener filter solutions, and Markov chain Monte Carlo sampling. We conclude that the method is able to keep up in accuracy with the best self-calibration methods and serves as a noniterative alternative to them.

Quantifying and Reducing Curve-Fitting Uncertainty in Isc

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campanelli, Mark; Duck, Benjamin; Emery, Keith

2015-06-14

Current-voltage (I-V) curve measurements of photovoltaic (PV) devices are used to determine performance parameters and to establish traceable calibration chains. Measurement standards specify localized curve fitting methods, e.g., straight-line interpolation/extrapolation of the I-V curve points near short-circuit current, Isc. By considering such fits as statistical linear regressions, uncertainties in the performance parameters are readily quantified. However, the legitimacy of such a computed uncertainty requires that the model be a valid (local) representation of the I-V curve and that the noise be sufficiently well characterized. Using more data points often has the advantage of lowering the uncertainty. However, more data pointsmore » can make the uncertainty in the fit arbitrarily small, and this fit uncertainty misses the dominant residual uncertainty due to so-called model discrepancy. Using objective Bayesian linear regression for straight-line fits for Isc, we investigate an evidence-based method to automatically choose data windows of I-V points with reduced model discrepancy. We also investigate noise effects. Uncertainties, aligned with the Guide to the Expression of Uncertainty in Measurement (GUM), are quantified throughout.« less

A rapid method for detection of fumonisins B1 and B2 in corn meal using Fourier transform near infrared (FT-NIR) spectroscopy implemented with integrating sphere.

PubMed

Gaspardo, B; Del Zotto, S; Torelli, E; Cividino, S R; Firrao, G; Della Riccia, G; Stefanon, B

2012-12-01

Fourier transform near infrared (FT-NIR) spectroscopy is an analytical procedure generally used to detect organic compounds in food. In this work the ability to predict fumonisin B(1)+B(2) contents in corn meal using an FT-NIR spectrophotometer, equipped with an integration sphere, was assessed. A total of 143 corn meal samples were collected in Friuli Venezia Giulia Region (Italy) and used to define a 15 principal components regression model, applying partial least square regression algorithm with full cross validation as internal validation. External validation was performed to 25 unknown samples. Coefficients of correlation, root mean square error and standard error of calibration were 0.964, 0.630 and 0.632, respectively and the external validation confirmed a fair potential of the model in predicting FB(1)+FB(2) concentration. Results suggest that FT-NIR analysis is a suitable method to detect FB(1)+FB(2) in corn meal and to discriminate safe meals from those contaminated. Copyright © 2012 Elsevier Ltd. All rights reserved.

Quantifying and Reducing Curve-Fitting Uncertainty in Isc: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campanelli, Mark; Duck, Benjamin; Emery, Keith

Current-voltage (I-V) curve measurements of photovoltaic (PV) devices are used to determine performance parameters and to establish traceable calibration chains. Measurement standards specify localized curve fitting methods, e.g., straight-line interpolation/extrapolation of the I-V curve points near short-circuit current, Isc. By considering such fits as statistical linear regressions, uncertainties in the performance parameters are readily quantified. However, the legitimacy of such a computed uncertainty requires that the model be a valid (local) representation of the I-V curve and that the noise be sufficiently well characterized. Using more data points often has the advantage of lowering the uncertainty. However, more data pointsmore » can make the uncertainty in the fit arbitrarily small, and this fit uncertainty misses the dominant residual uncertainty due to so-called model discrepancy. Using objective Bayesian linear regression for straight-line fits for Isc, we investigate an evidence-based method to automatically choose data windows of I-V points with reduced model discrepancy. We also investigate noise effects. Uncertainties, aligned with the Guide to the Expression of Uncertainty in Measurement (GUM), are quantified throughout.« less

Structured light system calibration method with optimal fringe angle.

PubMed

Li, Beiwen; Zhang, Song

2014-11-20

For structured light system calibration, one popular approach is to treat the projector as an inverse camera. This is usually performed by projecting horizontal and vertical sequences of patterns to establish one-to-one mapping between camera points and projector points. However, for a well-designed system, either horizontal or vertical fringe images are not sensitive to depth variation and thus yield inaccurate mapping. As a result, the calibration accuracy is jeopardized if a conventional calibration method is used. To address this limitation, this paper proposes a novel calibration method based on optimal fringe angle determination. Experiments demonstrate that our calibration approach can increase the measurement accuracy up to 38% compared to the conventional calibration method with a calibration volume of 300(H)  mm×250(W)  mm×500(D)  mm.

Evaluating the potential for remote bathymetric mapping of a turbid, sand-bed river: 2. Application to hyperspectral image data from the Platte River

USGS Publications Warehouse

Legleiter, C.J.; Kinzel, P.J.; Overstreet, B.T.

2011-01-01

This study examined the possibility of mapping depth from optical image data in turbid, sediment-laden channels. Analysis of hyperspectral images from the Platte River indicated that depth retrieval in these environments is feasible, but might not be highly accurate. Four methods of calibrating image-derived depth estimates were evaluated. The first involved extracting image spectra at survey point locations throughout the reach. These paired observations of depth and reflectance were subjected to optimal band ratio analysis (OBRA) to relate (R2 = 0.596) a spectrally based quantity to flow depth. Two other methods were based on OBRA of data from individual cross sections. A fourth strategy used ground-based reflectance measurements to derive an OBRA relation (R2 = 0.944) that was then applied to the image. Depth retrieval accuracy was assessed by visually inspecting cross sections and calculating various error metrics. Calibration via field spectroscopy resulted in a shallow bias but provided relative accuracies similar to image-based methods. Reach-aggregated OBRA was marginally superior to calibrations based on individual cross sections, and depth retrieval accuracy varied considerably along each reach. Errors were lower and observed versus predicted regression R2 values higher for a relatively simple, deeper site than a shallower, braided reach; errors were 1/3 and 1/2 the mean depth for the two reaches. Bathymetric maps were coherent and hydraulically reasonable, however, and might be more reliable than implied by numerical metrics. As an example application, linear discriminant analysis was used to produce a series of depth threshold maps for characterizing shallow-water habitat for roosting cranes. ?? 2011 by the American Geophysical Union.

Evaluating the potential for remote bathymetric mapping of a turbid, sand-bed river: 2. application to hyperspectral image data from the Platte River

USGS Publications Warehouse

Legleiter, Carl J.; Kinzel, Paul J.; Overstreet, Brandon T.

2011-01-01

This study examined the possibility of mapping depth from optical image data in turbid, sediment-laden channels. Analysis of hyperspectral images from the Platte River indicated that depth retrieval in these environments is feasible, but might not be highly accurate. Four methods of calibrating image-derived depth estimates were evaluated. The first involved extracting image spectra at survey point locations throughout the reach. These paired observations of depth and reflectance were subjected to optimal band ratio analysis (OBRA) to relate (R2 = 0.596) a spectrally based quantity to flow depth. Two other methods were based on OBRA of data from individual cross sections. A fourth strategy used ground-based reflectance measurements to derive an OBRA relation (R2 = 0.944) that was then applied to the image. Depth retrieval accuracy was assessed by visually inspecting cross sections and calculating various error metrics. Calibration via field spectroscopy resulted in a shallow bias but provided relative accuracies similar to image-based methods. Reach-aggregated OBRA was marginally superior to calibrations based on individual cross sections, and depth retrieval accuracy varied considerably along each reach. Errors were lower and observed versus predicted regression R2 values higher for a relatively simple, deeper site than a shallower, braided reach; errors were 1/3 and 1/2 the mean depth for the two reaches. Bathymetric maps were coherent and hydraulically reasonable, however, and might be more reliable than implied by numerical metrics. As an example application, linear discriminant analysis was used to produce a series of depth threshold maps for characterizing shallow-water habitat for roosting cranes.

A rapid field test for the measurement of bovine serum immunoglobulin G using attenuated total reflectance infrared spectroscopy.

PubMed

Elsohaby, Ibrahim; Hou, Siyuan; McClure, J Trenton; Riley, Christopher B; Shaw, R Anthony; Keefe, Gregory P

2015-08-20

Following the recent development of a new approach to quantitative analysis of IgG concentrations in bovine serum using transmission infrared spectroscopy, the potential to measure IgG levels using technology and a device better designed for field use was investigated. A method using attenuated total reflectance infrared (ATR) spectroscopy in combination with partial least squares (PLS) regression was developed to measure bovine serum IgG concentrations. ATR spectroscopy has a distinct ease-of-use advantage that may open the door to routine point-of-care testing. Serum samples were collected from calves and adult cows, tested by a reference RID method, and ATR spectra acquired. The spectra were linked to the RID-IgG concentrations and then randomly split into two sets: calibration and prediction. The calibration set was used to build a calibration model, while the prediction set was used to assess the predictive performance and accuracy of the final model. The procedure was repeated for various spectral data preprocessing approaches. For the prediction set, the Pearson's and concordance correlation coefficients between the IgG measured by RID and predicted by ATR spectroscopy were both 0.93. The Bland Altman plot revealed no obvious systematic bias between the two methods. ATR spectroscopy showed a sensitivity for detection of failure of transfer of passive immunity (FTPI) of 88 %, specificity of 100 % and accuracy of 94 % (with IgG <1000 mg/dL as the FTPI cut-off value). ATR spectroscopy in combination with multivariate data analysis shows potential as an alternative approach for rapid quantification of IgG concentrations in bovine serum and the diagnosis of FTPI in calves.

Simultaneous calibration phantom commission and geometry calibration in cone beam CT

NASA Astrophysics Data System (ADS)

Xu, Yuan; Yang, Shuai; Ma, Jianhui; Li, Bin; Wu, Shuyu; Qi, Hongliang; Zhou, Linghong

2017-09-01

Geometry calibration is a vital step for describing the geometry of a cone beam computed tomography (CBCT) system and is a prerequisite for CBCT reconstruction. In current methods, calibration phantom commission and geometry calibration are divided into two independent tasks. Small errors in ball-bearing (BB) positioning in the phantom-making step will severely degrade the quality of phantom calibration. To solve this problem, we propose an integrated method to simultaneously realize geometry phantom commission and geometry calibration. Instead of assuming the accuracy of the geometry phantom, the integrated method considers BB centers in the phantom as an optimized parameter in the workflow. Specifically, an evaluation phantom and the corresponding evaluation contrast index are used to evaluate geometry artifacts for optimizing the BB coordinates in the geometry phantom. After utilizing particle swarm optimization, the CBCT geometry and BB coordinates in the geometry phantom are calibrated accurately and are then directly used for the next geometry calibration task in other CBCT systems. To evaluate the proposed method, both qualitative and quantitative studies were performed on simulated and realistic CBCT data. The spatial resolution of reconstructed images using dental CBCT can reach up to 15 line pair cm-1. The proposed method is also superior to the Wiesent method in experiments. This paper shows that the proposed method is attractive for simultaneous and accurate geometry phantom commission and geometry calibration.

Simplified method for creating a density-absorbed dose calibration curve for the low dose range from Gafchromic EBT3 film.

PubMed

Gotanda, Tatsuhiro; Katsuda, Toshizo; Gotanda, Rumi; Kuwano, Tadao; Akagawa, Takuya; Tanki, Nobuyoshi; Tabuchi, Akihiko; Shimono, Tetsunori; Kawaji, Yasuyuki

2016-01-01

Radiochromic film dosimeters have a disadvantage in comparison with an ionization chamber in that the dosimetry process is time-consuming for creating a density-absorbed dose calibration curve. The purpose of this study was the development of a simplified method of creating a density-absorbed dose calibration curve from radiochromic film within a short time. This simplified method was performed using Gafchromic EBT3 film with a low energy dependence and step-shaped Al filter. The simplified method was compared with the standard method. The density-absorbed dose calibration curves created using the simplified and standard methods exhibited approximately similar straight lines, and the gradients of the density-absorbed dose calibration curves were -32.336 and -33.746, respectively. The simplified method can obtain calibration curves within a much shorter time compared to the standard method. It is considered that the simplified method for EBT3 film offers a more time-efficient means of determining the density-absorbed dose calibration curve within a low absorbed dose range such as the diagnostic range.

Simplified method for creating a density-absorbed dose calibration curve for the low dose range from Gafchromic EBT3 film

PubMed Central

Gotanda, Tatsuhiro; Katsuda, Toshizo; Gotanda, Rumi; Kuwano, Tadao; Akagawa, Takuya; Tanki, Nobuyoshi; Tabuchi, Akihiko; Shimono, Tetsunori; Kawaji, Yasuyuki

2016-01-01

Radiochromic film dosimeters have a disadvantage in comparison with an ionization chamber in that the dosimetry process is time-consuming for creating a density-absorbed dose calibration curve. The purpose of this study was the development of a simplified method of creating a density-absorbed dose calibration curve from radiochromic film within a short time. This simplified method was performed using Gafchromic EBT3 film with a low energy dependence and step-shaped Al filter. The simplified method was compared with the standard method. The density-absorbed dose calibration curves created using the simplified and standard methods exhibited approximately similar straight lines, and the gradients of the density-absorbed dose calibration curves were −32.336 and −33.746, respectively. The simplified method can obtain calibration curves within a much shorter time compared to the standard method. It is considered that the simplified method for EBT3 film offers a more time-efficient means of determining the density-absorbed dose calibration curve within a low absorbed dose range such as the diagnostic range. PMID:28144120

Rapid estimation of sugar release from winter wheat straw during bioethanol production using FTIR-photoacoustic spectroscopy

DOE PAGES

Bekiaris, Georgios; Lindedam, Jane; Peltre, Clément; ...

2015-06-18

Complexity and high cost are the main limitations for high-throughput screening methods for the estimation of the sugar release from plant materials during bioethanol production. In addition, it is important that we improve our understanding of the mechanisms by which different chemical components are affecting the degradability of plant material. In this study, Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) was combined with advanced chemometrics to develop calibration models predicting the amount of sugars released after pretreatment and enzymatic hydrolysis of wheat straw during bioethanol production, and the spectra were analysed to identify components associated with recalcitrance. A total of 1122more » wheat straw samples from nine different locations in Denmark and one location in the United Kingdom, spanning a large variation in genetic material and environmental conditions during growth, were analysed. The FTIR-PAS spectra of non-pretreated wheat straw were correlated with the measured sugar release, determined by a high-throughput pretreatment and enzymatic hydrolysis (HTPH) assay. A partial least square regression (PLSR) calibration model predicting the glucose and xylose release was developed. The interpretation of the regression coefficients revealed a positive correlation between the released glucose and xylose with easily hydrolysable compounds, such as amorphous cellulose and hemicellulose. Additionally, we observed a negative correlation with crystalline cellulose and lignin, which inhibits cellulose and hemicellulose hydrolysis. FTIR-PAS was used as a reliable method for the rapid estimation of sugar release during bioethanol production. The spectra revealed that lignin inhibited the hydrolysis of polysaccharides into monomers, while the crystallinity of cellulose retarded its hydrolysis into glucose. Amorphous cellulose and xylans were found to contribute significantly to the released amounts of glucose and xylose, respectively.« less

Rapid estimation of sugar release from winter wheat straw during bioethanol production using FTIR-photoacoustic spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bekiaris, Georgios; Lindedam, Jane; Peltre, Clément

Complexity and high cost are the main limitations for high-throughput screening methods for the estimation of the sugar release from plant materials during bioethanol production. In addition, it is important that we improve our understanding of the mechanisms by which different chemical components are affecting the degradability of plant material. In this study, Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) was combined with advanced chemometrics to develop calibration models predicting the amount of sugars released after pretreatment and enzymatic hydrolysis of wheat straw during bioethanol production, and the spectra were analysed to identify components associated with recalcitrance. A total of 1122more » wheat straw samples from nine different locations in Denmark and one location in the United Kingdom, spanning a large variation in genetic material and environmental conditions during growth, were analysed. The FTIR-PAS spectra of non-pretreated wheat straw were correlated with the measured sugar release, determined by a high-throughput pretreatment and enzymatic hydrolysis (HTPH) assay. A partial least square regression (PLSR) calibration model predicting the glucose and xylose release was developed. The interpretation of the regression coefficients revealed a positive correlation between the released glucose and xylose with easily hydrolysable compounds, such as amorphous cellulose and hemicellulose. Additionally, we observed a negative correlation with crystalline cellulose and lignin, which inhibits cellulose and hemicellulose hydrolysis. FTIR-PAS was used as a reliable method for the rapid estimation of sugar release during bioethanol production. The spectra revealed that lignin inhibited the hydrolysis of polysaccharides into monomers, while the crystallinity of cellulose retarded its hydrolysis into glucose. Amorphous cellulose and xylans were found to contribute significantly to the released amounts of glucose and xylose, respectively.« less

Development of a coal quality analyzer for application to power plants based on laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Lei; Gong, Yao; Li, Yufang; Wang, Xin; Fan, Juanjuan; Dong, Lei; Ma, Weiguang; Yin, Wangbao; Jia, Suotang

2015-11-01

It is vitally important for a power plant to determine the coal property rapidly to optimize the combustion process. In this work, a fully software-controlled laser-induced breakdown spectroscopy (LIBS) based coal quality analyzer comprising a LIBS apparatus, a sampling equipment, and a control module, has been designed for possible application to power plants for offering rapid and precise coal quality analysis results. A closed-loop feedback pulsed laser energy stabilization technology is proposed to stabilize the Nd: YAG laser output energy to a preset interval by using the detected laser energy signal so as to enhance the measurement stability and applied in a month-long monitoring experiment. The results show that the laser energy stability has been greatly reduced from ± 5.2% to ± 1.3%. In order to indicate the complex relationship between the concentrations of the analyte of interest and the corresponding plasma spectra, the support vector regression (SVR) is employed as a non-linear regression method. It is shown that this SVR method combined with principal component analysis (PCA) enables a significant improvement in cross-validation accuracy by using the calibration set of coal samples. The root mean square error for prediction of ash content, volatile matter content, and calorific value decreases from 2.74% to 1.82%, 1.69% to 1.22%, and 1.23 MJ/kg to 0.85 MJ/kg, respectively. Meanwhile, the corresponding average relative error of the predicted samples is reduced from 8.3% to 5.48%, 5.83% to 4.42%, and 5.4% to 3.68%, respectively. The enhanced levels of accuracy obtained with the SVR combined with PCA based calibration models open up avenues for prospective prediction in coal properties.

Evaluation of accuracy of linear regression models in predicting urban stormwater discharge characteristics.

PubMed

Madarang, Krish J; Kang, Joo-Hyon

2014-06-01

Stormwater runoff has been identified as a source of pollution for the environment, especially for receiving waters. In order to quantify and manage the impacts of stormwater runoff on the environment, predictive models and mathematical models have been developed. Predictive tools such as regression models have been widely used to predict stormwater discharge characteristics. Storm event characteristics, such as antecedent dry days (ADD), have been related to response variables, such as pollutant loads and concentrations. However it has been a controversial issue among many studies to consider ADD as an important variable in predicting stormwater discharge characteristics. In this study, we examined the accuracy of general linear regression models in predicting discharge characteristics of roadway runoff. A total of 17 storm events were monitored in two highway segments, located in Gwangju, Korea. Data from the monitoring were used to calibrate United States Environmental Protection Agency's Storm Water Management Model (SWMM). The calibrated SWMM was simulated for 55 storm events, and the results of total suspended solid (TSS) discharge loads and event mean concentrations (EMC) were extracted. From these data, linear regression models were developed. R(2) and p-values of the regression of ADD for both TSS loads and EMCs were investigated. Results showed that pollutant loads were better predicted than pollutant EMC in the multiple regression models. Regression may not provide the true effect of site-specific characteristics, due to uncertainty in the data. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Comparative assessment of GIS-based methods and metrics for estimating long-term exposures to air pollution

NASA Astrophysics Data System (ADS)

Gulliver, John; de Hoogh, Kees; Fecht, Daniela; Vienneau, Danielle; Briggs, David

2011-12-01

The development of geographical information system techniques has opened up a wide array of methods for air pollution exposure assessment. The extent to which these provide reliable estimates of air pollution concentrations is nevertheless not clearly established. Nor is it clear which methods or metrics should be preferred in epidemiological studies. This paper compares the performance of ten different methods and metrics in terms of their ability to predict mean annual PM 10 concentrations across 52 monitoring sites in London, UK. Metrics analysed include indicators (distance to nearest road, traffic volume on nearest road, heavy duty vehicle (HDV) volume on nearest road, road density within 150 m, traffic volume within 150 m and HDV volume within 150 m) and four modelling approaches: based on the nearest monitoring site, kriging, dispersion modelling and land use regression (LUR). Measures were computed in a GIS, and resulting metrics calibrated and validated against monitoring data using a form of grouped jack-knife analysis. The results show that PM 10 concentrations across London show little spatial variation. As a consequence, most methods can predict the average without serious bias. Few of the approaches, however, show good correlations with monitored PM 10 concentrations, and most predict no better than a simple classification based on site type. Only land use regression reaches acceptable levels of correlation ( R2 = 0.47), though this can be improved by also including information on site type. This might therefore be taken as a recommended approach in many studies, though care is needed in developing meaningful land use regression models, and like any method they need to be validated against local data before their application as part of epidemiological studies.

Multiple Regression Redshift Calibration for Clusters of Galaxies

NASA Astrophysics Data System (ADS)

Kalinkov, M.; Kuneva, I.; Valtchanov, I.

A new procedure for calibration of distances to ACO (Abell et al.1989) clusters of galaxies has been developed. In the previous version of the Reference Catalog of ACO Clusters of Galaxies (Kalinkov & Kuneva 1992) an attempt has been made to compare various calibration schemes. For the Version 93 we have made some refinements. Many improvements from the early days of the photometric calibration have been made --- from Rowan-Robinson (1972), Corwin (1974), Kalinkov & Kuneva (1975), Mills Hoskins (1977) to more complicated --- Leir & van den Bergh (1977), Postman et al.(1985), Kalinkov Kuneva (1985, 1986, 1990), Scaramella et al.(1991), Zucca et al. (1993). It was shown that it is impossible to use the same calibration relation for northern (A) and southern (ACO) clusters of galaxies. Therefore the calibration have to be made separately for both catalogs. Moreover it is better if one could find relations for the 274 A-clusters, studied by the authors of ACO. We use the luminosity distance for H0=100km/s/Mpc and q0 = 0.5 and we have 1200 clusters with measured redshifts. The first step is to fit log(z) on m10 (magnitude of the tenth rank galaxy) for A-clusters and on m1, m3 and m10 for ACO clusters. The second step is to take into account the K-correction and the Scott effect (Postman et al.1985) with iterative process. To avoid the initial errors of the redshift estimates in A- and ACO catalogs we adopt Hubble's law for the apparent radial distribution of galaxies in clusters. This enable us to calculate a new cluster richness from preliminary redshift estimate. This is the third step. Further continues the study of the correlation matrix between log(z) and prospective predictors --- new richness groups, BM, RS and A types, radio and X-ray fluxes, apparent separations between the first three brightest galaxies, mean population (gal/sq.deg), Multiple linear as well as nonlinear regression estimators are found. Many clusters that deviate by more than 2.5 sigmas are rejected. Each case is examined for observational errors, substructuring, foreground and background. Some of the clusters are doubtful --- most probably they have to be excluded from the catalogs. The multiple regressions allow us to estimate redshift in the range 0.02 to 0.2 with an error of 7 percent.

Two imaging techniques for 3D quantification of pre-cementation space for CAD/CAM crowns.

PubMed

Rungruanganunt, Patchanee; Kelly, J Robert; Adams, Douglas J

2010-12-01

Internal three-dimensional (3D) "fit" of prostheses to prepared teeth is likely more important clinically than "fit" judged only at the level of the margin (i.e. marginal "opening"). This work evaluates two techniques for quantitatively defining 3D "fit", both using pre-cementation space impressions: X-ray microcomputed tomography (micro-CT) and quantitative optical analysis. Both techniques are of interest for comparison of CAD/CAM system capabilities and for documenting "fit" as part of clinical studies. Pre-cementation space impressions were taken of a single zirconia coping on its die using a low viscosity poly(vinyl siloxane) impression material. Calibration specimens of this material were fabricated between the measuring platens of a micrometre. Both calibration curves and pre-cementation space impression data sets were obtained by examination using micro-CT and quantitative optical analysis. Regression analysis was used to compare calibration curves with calibration sets. Micro-CT calibration data showed tighter 95% confidence intervals and was able to measure over a wider thickness range than for the optical technique. Regions of interest (e.g., lingual, cervical) were more easily analysed with optical image analysis and this technique was more suitable for extremely thin impression walls (<10-15μm). Specimen preparation is easier for micro-CT and segmentation parameters appeared to capture dimensions accurately. Both micro-CT and the optical method can be used to quantify the thickness of pre-cementation space impressions. Each has advantages and limitations but either technique has the potential for use as part of clinical studies or CAD/CAM protocol optimization. Copyright © 2010 Elsevier Ltd. All rights reserved.

Exposure measurement error in PM2.5 health effects studies: A pooled analysis of eight personal exposure validation studies

PubMed Central

2014-01-01

Background Exposure measurement error is a concern in long-term PM2.5 health studies using ambient concentrations as exposures. We assessed error magnitude by estimating calibration coefficients as the association between personal PM2.5 exposures from validation studies and typically available surrogate exposures. Methods Daily personal and ambient PM2.5, and when available sulfate, measurements were compiled from nine cities, over 2 to 12 days. True exposure was defined as personal exposure to PM2.5 of ambient origin. Since PM2.5 of ambient origin could only be determined for five cities, personal exposure to total PM2.5 was also considered. Surrogate exposures were estimated as ambient PM2.5 at the nearest monitor or predicted outside subjects’ homes. We estimated calibration coefficients by regressing true on surrogate exposures in random effects models. Results When monthly-averaged personal PM2.5 of ambient origin was used as the true exposure, calibration coefficients equaled 0.31 (95% CI:0.14, 0.47) for nearest monitor and 0.54 (95% CI:0.42, 0.65) for outdoor home predictions. Between-city heterogeneity was not found for outdoor home PM2.5 for either true exposure. Heterogeneity was significant for nearest monitor PM2.5, for both true exposures, but not after adjusting for city-average motor vehicle number for total personal PM2.5. Conclusions Calibration coefficients were <1, consistent with previously reported chronic health risks using nearest monitor exposures being under-estimated when ambient concentrations are the exposure of interest. Calibration coefficients were closer to 1 for outdoor home predictions, likely reflecting less spatial error. Further research is needed to determine how our findings can be incorporated in future health studies. PMID:24410940

Prediction of pH of cola beverage using Vis/NIR spectroscopy and least squares-support vector machine

NASA Astrophysics Data System (ADS)

Liu, Fei; He, Yong

2008-02-01

Visible and near infrared (Vis/NIR) transmission spectroscopy and chemometric methods were utilized to predict the pH values of cola beverages. Five varieties of cola were prepared and 225 samples (45 samples for each variety) were selected for the calibration set, while 75 samples (15 samples for each variety) for the validation set. The smoothing way of Savitzky-Golay and standard normal variate (SNV) followed by first-derivative were used as the pre-processing methods. Partial least squares (PLS) analysis was employed to extract the principal components (PCs) which were used as the inputs of least squares-support vector machine (LS-SVM) model according to their accumulative reliabilities. Then LS-SVM with radial basis function (RBF) kernel function and a two-step grid search technique were applied to build the regression model with a comparison of PLS regression. The correlation coefficient (r), root mean square error of prediction (RMSEP) and bias were 0.961, 0.040 and 0.012 for PLS, while 0.975, 0.031 and 4.697x10 -3 for LS-SVM, respectively. Both methods obtained a satisfying precision. The results indicated that Vis/NIR spectroscopy combined with chemometric methods could be applied as an alternative way for the prediction of pH of cola beverages.

Estimating energy expenditure from heart rate in older adults: a case for calibration.

PubMed

Schrack, Jennifer A; Zipunnikov, Vadim; Goldsmith, Jeff; Bandeen-Roche, Karen; Crainiceanu, Ciprian M; Ferrucci, Luigi

2014-01-01

Accurate measurement of free-living energy expenditure is vital to understanding changes in energy metabolism with aging. The efficacy of heart rate as a surrogate for energy expenditure is rooted in the assumption of a linear function between heart rate and energy expenditure, but its validity and reliability in older adults remains unclear. To assess the validity and reliability of the linear function between heart rate and energy expenditure in older adults using different levels of calibration. Heart rate and energy expenditure were assessed across five levels of exertion in 290 adults participating in the Baltimore Longitudinal Study of Aging. Correlation and random effects regression analyses assessed the linearity of the relationship between heart rate and energy expenditure and cross-validation models assessed predictive performance. Heart rate and energy expenditure were highly correlated (r=0.98) and linear regardless of age or sex. Intra-person variability was low but inter-person variability was high, with substantial heterogeneity of the random intercept (s.d. =0.372) despite similar slopes. Cross-validation models indicated individual calibration data substantially improves accuracy predictions of energy expenditure from heart rate, reducing the potential for considerable measurement bias. Although using five calibration measures provided the greatest reduction in the standard deviation of prediction errors (1.08 kcals/min), substantial improvement was also noted with two (0.75 kcals/min). These findings indicate standard regression equations may be used to make population-level inferences when estimating energy expenditure from heart rate in older adults but caution should be exercised when making inferences at the individual level without proper calibration.

A new systematic calibration method of ring laser gyroscope inertial navigation system

NASA Astrophysics Data System (ADS)

Wei, Guo; Gao, Chunfeng; Wang, Qi; Wang, Qun; Xiong, Zhenyu; Long, Xingwu

2016-10-01

Inertial navigation system has been the core component of both military and civil navigation systems. Before the INS is put into application, it is supposed to be calibrated in the laboratory in order to compensate repeatability error caused by manufacturing. Discrete calibration method cannot fulfill requirements of high-accurate calibration of the mechanically dithered ring laser gyroscope navigation system with shock absorbers. This paper has analyzed theories of error inspiration and separation in detail and presented a new systematic calibration method for ring laser gyroscope inertial navigation system. Error models and equations of calibrated Inertial Measurement Unit are given. Then proper rotation arrangement orders are depicted in order to establish the linear relationships between the change of velocity errors and calibrated parameter errors. Experiments have been set up to compare the systematic errors calculated by filtering calibration result with those obtained by discrete calibration result. The largest position error and velocity error of filtering calibration result are only 0.18 miles and 0.26m/s compared with 2 miles and 1.46m/s of discrete calibration result. These results have validated the new systematic calibration method and proved its importance for optimal design and accuracy improvement of calibration of mechanically dithered ring laser gyroscope inertial navigation system.

Guidelines and Procedures for Computing Time-Series Suspended-Sediment Concentrations and Loads from In-Stream Turbidity-Sensor and Streamflow Data

USGS Publications Warehouse

Rasmussen, Patrick P.; Gray, John R.; Glysson, G. Douglas; Ziegler, Andrew C.

2009-01-01

In-stream continuous turbidity and streamflow data, calibrated with measured suspended-sediment concentration data, can be used to compute a time series of suspended-sediment concentration and load at a stream site. Development of a simple linear (ordinary least squares) regression model for computing suspended-sediment concentrations from instantaneous turbidity data is the first step in the computation process. If the model standard percentage error (MSPE) of the simple linear regression model meets a minimum criterion, this model should be used to compute a time series of suspended-sediment concentrations. Otherwise, a multiple linear regression model using paired instantaneous turbidity and streamflow data is developed and compared to the simple regression model. If the inclusion of the streamflow variable proves to be statistically significant and the uncertainty associated with the multiple regression model results in an improvement over that for the simple linear model, the turbidity-streamflow multiple linear regression model should be used to compute a suspended-sediment concentration time series. The computed concentration time series is subsequently used with its paired streamflow time series to compute suspended-sediment loads by standard U.S. Geological Survey techniques. Once an acceptable regression model is developed, it can be used to compute suspended-sediment concentration beyond the period of record used in model development with proper ongoing collection and analysis of calibration samples. Regression models to compute suspended-sediment concentrations are generally site specific and should never be considered static, but they represent a set period in a continually dynamic system in which additional data will help verify any change in sediment load, type, and source.

Rapid Detection of Volatile Oil in Mentha haplocalyx by Near-Infrared Spectroscopy and Chemometrics.

PubMed

Yan, Hui; Guo, Cheng; Shao, Yang; Ouyang, Zhen

2017-01-01

Near-infrared spectroscopy combined with partial least squares regression (PLSR) and support vector machine (SVM) was applied for the rapid determination of chemical component of volatile oil content in Mentha haplocalyx . The effects of data pre-processing methods on the accuracy of the PLSR calibration models were investigated. The performance of the final model was evaluated according to the correlation coefficient ( R ) and root mean square error of prediction (RMSEP). For PLSR model, the best preprocessing method combination was first-order derivative, standard normal variate transformation (SNV), and mean centering, which had of 0.8805, of 0.8719, RMSEC of 0.091, and RMSEP of 0.097, respectively. The wave number variables linking to volatile oil are from 5500 to 4000 cm-1 by analyzing the loading weights and variable importance in projection (VIP) scores. For SVM model, six LVs (less than seven LVs in PLSR model) were adopted in model, and the result was better than PLSR model. The and were 0.9232 and 0.9202, respectively, with RMSEC and RMSEP of 0.084 and 0.082, respectively, which indicated that the predicted values were accurate and reliable. This work demonstrated that near infrared reflectance spectroscopy with chemometrics could be used to rapidly detect the main content volatile oil in M. haplocalyx . The quality of medicine directly links to clinical efficacy, thus, it is important to control the quality of Mentha haplocalyx . Near-infrared spectroscopy combined with partial least squares regression (PLSR) and support vector machine (SVM) was applied for the rapid determination of chemical component of volatile oil content in Mentha haplocalyx . For SVM model, 6 LVs (less than 7 LVs in PLSR model) were adopted in model, and the result was better than PLSR model. It demonstrated that near infrared reflectance spectroscopy with chemometrics could be used to rapidly detect the main content volatile oil in Mentha haplocalyx . Abbreviations used: 1 st der: First-order derivative; 2 nd der: Second-order derivative; LOO: Leave-one-out; LVs: Latent variables; MC: Mean centering, NIR: Near-infrared; NIRS: Near infrared spectroscopy; PCR: Principal component regression, PLSR: Partial least squares regression; RBF: Radial basis function; RMSEC: Root mean square error of cross validation, RMSEC: Root mean square error of calibration; RMSEP: Root mean square error of prediction; SNV: Standard normal variate transformation; SVM: Support vector machine; VIP: Variable Importance in projection.

A Universal Threshold for the Assessment of Load and Output Residuals of Strain-Gage Balance Data

NASA Technical Reports Server (NTRS)

Ulbrich, N.; Volden, T.

2017-01-01

A new universal residual threshold for the detection of load and gage output residual outliers of wind tunnel strain{gage balance data was developed. The threshold works with both the Iterative and Non{Iterative Methods that are used in the aerospace testing community to analyze and process balance data. It also supports all known load and gage output formats that are traditionally used to describe balance data. The threshold's definition is based on an empirical electrical constant. First, the constant is used to construct a threshold for the assessment of gage output residuals. Then, the related threshold for the assessment of load residuals is obtained by multiplying the empirical electrical constant with the sum of the absolute values of all first partial derivatives of a given load component. The empirical constant equals 2.5 microV/V for the assessment of balance calibration or check load data residuals. A value of 0.5 microV/V is recommended for the evaluation of repeat point residuals because, by design, the calculation of these residuals removes errors that are associated with the regression analysis of the data itself. Data from a calibration of a six-component force balance is used to illustrate the application of the new threshold definitions to real{world balance calibration data.

Calibrating the stress-time curve of a combined finite-discrete element method to a Split Hopkinson Pressure Bar experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osthus, Dave; Godinez, Humberto C.; Rougier, Esteban

We presenmore » t a generic method for automatically calibrating a computer code to an experiment, with uncertainty, for a given “training” set of computer code runs. The calibration technique is general and probabilistic, meaning the calibration uncertainty is represented in the form of a probability distribution. We demonstrate the calibration method by calibrating a combined Finite-Discrete Element Method (FDEM) to a Split Hopkinson Pressure Bar (SHPB) experiment with a granite sample. The probabilistic calibration method combines runs of a FDEM computer simulation for a range of “training” settings and experimental uncertainty to develop a statistical emulator. The process allows for calibration of input parameters and produces output quantities with uncertainty estimates for settings where simulation results are desired. Input calibration and FDEM fitted results are presented. We find that the maximum shear strength σ t max and to a lesser extent maximum tensile strength σ n max govern the behavior of the stress-time curve before and around the peak, while the specific energy in Mode II (shear) E t largely governs the post-peak behavior of the stress-time curve. Good agreement is found between the calibrated FDEM and the SHPB experiment. Interestingly, we find the SHPB experiment to be rather uninformative for calibrating the softening-curve shape parameters (a, b, and c). This work stands as a successful demonstration of how a general probabilistic calibration framework can automatically calibrate FDEM parameters to an experiment.« less

Calibrating the stress-time curve of a combined finite-discrete element method to a Split Hopkinson Pressure Bar experiment

DOE PAGES

Osthus, Dave; Godinez, Humberto C.; Rougier, Esteban; ...

2018-05-01

We presenmore » t a generic method for automatically calibrating a computer code to an experiment, with uncertainty, for a given “training” set of computer code runs. The calibration technique is general and probabilistic, meaning the calibration uncertainty is represented in the form of a probability distribution. We demonstrate the calibration method by calibrating a combined Finite-Discrete Element Method (FDEM) to a Split Hopkinson Pressure Bar (SHPB) experiment with a granite sample. The probabilistic calibration method combines runs of a FDEM computer simulation for a range of “training” settings and experimental uncertainty to develop a statistical emulator. The process allows for calibration of input parameters and produces output quantities with uncertainty estimates for settings where simulation results are desired. Input calibration and FDEM fitted results are presented. We find that the maximum shear strength σ t max and to a lesser extent maximum tensile strength σ n max govern the behavior of the stress-time curve before and around the peak, while the specific energy in Mode II (shear) E t largely governs the post-peak behavior of the stress-time curve. Good agreement is found between the calibrated FDEM and the SHPB experiment. Interestingly, we find the SHPB experiment to be rather uninformative for calibrating the softening-curve shape parameters (a, b, and c). This work stands as a successful demonstration of how a general probabilistic calibration framework can automatically calibrate FDEM parameters to an experiment.« less

Online determination of biophysical parameters of mucous membranes of a human body

NASA Astrophysics Data System (ADS)

Lisenko, S. A.; Kugeiko, M. M.

2013-07-01

We have developed a method for online determination of biophysical parameters of mucous membranes (MMs) of a human body (transport scattering coefficient, scattering anisotropy factor, haemoglobin concentration, degrees of blood oxygenation, average diameter of capillaries with blood) from measurements of spectral and spatial characteristics of diffuse reflection. The method is based on regression relationships between linearly independent components of the measured light signals and the unknown parameters of MMs, obtained by simulation of the radiation transfer in the MM under conditions of its general variability. We have proposed and justified the calibration-free fibre-optic method for determining the concentration of haemoglobin in MMs by measuring the light signals diffusely reflected by the tissue in four spectral regions at two different distances from the illumination spot. We have selected the optimal wavelengths of optical probing for the implementation of the method.

Advanced spectrophotometric chemometric methods for resolving the binary mixture of doxylamine succinate and pyridoxine hydrochloride.

PubMed

Katsarov, Plamen; Gergov, Georgi; Alin, Aylin; Pilicheva, Bissera; Al-Degs, Yahya; Simeonov, Vasil; Kassarova, Margarita

2018-03-01

The prediction power of partial least squares (PLS) and multivariate curve resolution-alternating least squares (MCR-ALS) methods have been studied for simultaneous quantitative analysis of the binary drug combination - doxylamine succinate and pyridoxine hydrochloride. Analysis of first-order UV overlapped spectra was performed using different PLS models - classical PLS1 and PLS2 as well as partial robust M-regression (PRM). These linear models were compared to MCR-ALS with equality and correlation constraints (MCR-ALS-CC). All techniques operated within the full spectral region and extracted maximum information for the drugs analysed. The developed chemometric methods were validated on external sample sets and were applied to the analyses of pharmaceutical formulations. The obtained statistical parameters were satisfactory for calibration and validation sets. All developed methods can be successfully applied for simultaneous spectrophotometric determination of doxylamine and pyridoxine both in laboratory-prepared mixtures and commercial dosage forms.

Shortwave Radiometer Calibration Methods Comparison and Resulting Solar Irradiance Measurement Differences: A User Perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habte, Aron; Sengupta, Manajit; Andreas, Afshin

Banks financing solar energy projects require assurance that these systems will produce the energy predicted. Furthermore, utility planners and grid system operators need to understand the impact of the variable solar resource on solar energy conversion system performance. Accurate solar radiation data sets reduce the expense associated with mitigating performance risk and assist in understanding the impacts of solar resource variability. The accuracy of solar radiation measured by radiometers depends on the instrument performance specification, installation method, calibration procedure, measurement conditions, maintenance practices, location, and environmental conditions. This study addresses the effect of different calibration methods provided by radiometric calibrationmore » service providers, such as NREL and manufacturers of radiometers, on the resulting calibration responsivity. Some of these radiometers are calibrated indoors and some outdoors. To establish or understand the differences in calibration methodology, we processed and analyzed field-measured data from these radiometers. This study investigates calibration responsivities provided by NREL's broadband outdoor radiometer calibration (BORCAL) and a few prominent manufacturers. The BORCAL method provides the outdoor calibration responsivity of pyranometers and pyrheliometers at 45 degree solar zenith angle, and as a function of solar zenith angle determined by clear-sky comparisons with reference irradiance. The BORCAL method also employs a thermal offset correction to the calibration responsivity of single-black thermopile detectors used in pyranometers. Indoor calibrations of radiometers by their manufacturers are performed using a stable artificial light source in a side-by-side comparison between the test radiometer under calibration and a reference radiometer of the same type. In both methods, the reference radiometer calibrations are traceable to the World Radiometric Reference (WRR). These different methods of calibration demonstrated +1% to +2% differences in solar irradiance measurement. Analyzing these differences will ultimately help determine the uncertainty of the field radiometer data and guide the development of a consensus standard for calibration. Further advancing procedures for precisely calibrating radiometers to world reference standards that reduce measurement uncertainty will allow more accurate prediction of solar output and improve the bankability of solar projects.« less

Infrared space observatory photometry of circumstellar dust in Vega-type systems

NASA Technical Reports Server (NTRS)

Fajardo-Acosta, S. B.; Stencel, R. E.; Backman, D. E.; Thakur, N.

1998-01-01

The ISOPHOT (Infrared Space Observatory Photometry) instrument onboard the Infrared Space Observatory (ISO) was used to obtain 3.6-90 micron photometry of Vega-type systems. Photometric data were calibrated with the ISOPHOT fine calibration source 1 (FCS1). Linear regression was used to derive transformations to make comparisons to ground-based and IRAS photometry systems possible. These transformations were applied to the photometry of 14 main-sequence stars. Details of these results are reported on.

Assessment of the first radiances received from the VSSR Atmospheric Sounder (VAS) instrument

NASA Technical Reports Server (NTRS)

Chesters, D.; Uccellini, L. W.; Montgomery, H.; Mostek, A.; Robinson, W.

1981-01-01

The first orderly, calibrated radiances from the VAS-D instrument on the GOES-4 satellite are examined for: image quality, radiometric precision, radiation transfer verification at clear air radiosonde sites, regression retrieval accuracy, and mesoscale analysis features. Postlaunch problems involving calibration and data processing irregularities of scientific or operational significance are included. The radiances provide good visual and relative radiometric data for empirically conditioned retrievals of mesoscale temperature and moisture fields in clear air.

Small Imaging Depth LIDAR and DCNN-Based Localization for Automated Guided Vehicle †

PubMed Central

Ito, Seigo; Hiratsuka, Shigeyoshi; Ohta, Mitsuhiko; Matsubara, Hiroyuki; Ogawa, Masaru

2018-01-01

We present our third prototype sensor and a localization method for Automated Guided Vehicles (AGVs), for which small imaging LIght Detection and Ranging (LIDAR) and fusion-based localization are fundamentally important. Our small imaging LIDAR, named the Single-Photon Avalanche Diode (SPAD) LIDAR, uses a time-of-flight method and SPAD arrays. A SPAD is a highly sensitive photodetector capable of detecting at the single-photon level, and the SPAD LIDAR has two SPAD arrays on the same chip for detection of laser light and environmental light. Therefore, the SPAD LIDAR simultaneously outputs range image data and monocular image data with the same coordinate system and does not require external calibration among outputs. As AGVs travel both indoors and outdoors with vibration, this calibration-less structure is particularly useful for AGV applications. We also introduce a fusion-based localization method, named SPAD DCNN, which uses the SPAD LIDAR and employs a Deep Convolutional Neural Network (DCNN). SPAD DCNN can fuse the outputs of the SPAD LIDAR: range image data, monocular image data and peak intensity image data. The SPAD DCNN has two outputs: the regression result of the position of the SPAD LIDAR and the classification result of the existence of a target to be approached. Our third prototype sensor and the localization method are evaluated in an indoor environment by assuming various AGV trajectories. The results show that the sensor and localization method improve the localization accuracy. PMID:29320434

Small Imaging Depth LIDAR and DCNN-Based Localization for Automated Guided Vehicle.

PubMed

Ito, Seigo; Hiratsuka, Shigeyoshi; Ohta, Mitsuhiko; Matsubara, Hiroyuki; Ogawa, Masaru

2018-01-10

We present our third prototype sensor and a localization method for Automated Guided Vehicles (AGVs), for which small imaging LIght Detection and Ranging (LIDAR) and fusion-based localization are fundamentally important. Our small imaging LIDAR, named the Single-Photon Avalanche Diode (SPAD) LIDAR, uses a time-of-flight method and SPAD arrays. A SPAD is a highly sensitive photodetector capable of detecting at the single-photon level, and the SPAD LIDAR has two SPAD arrays on the same chip for detection of laser light and environmental light. Therefore, the SPAD LIDAR simultaneously outputs range image data and monocular image data with the same coordinate system and does not require external calibration among outputs. As AGVs travel both indoors and outdoors with vibration, this calibration-less structure is particularly useful for AGV applications. We also introduce a fusion-based localization method, named SPAD DCNN, which uses the SPAD LIDAR and employs a Deep Convolutional Neural Network (DCNN). SPAD DCNN can fuse the outputs of the SPAD LIDAR: range image data, monocular image data and peak intensity image data. The SPAD DCNN has two outputs: the regression result of the position of the SPAD LIDAR and the classification result of the existence of a target to be approached. Our third prototype sensor and the localization method are evaluated in an indoor environment by assuming various AGV trajectories. The results show that the sensor and localization method improve the localization accuracy.

Calibration Method to Eliminate Zeroth Order Effect in Lateral Shearing Interferometry

NASA Astrophysics Data System (ADS)

Fang, Chao; Xiang, Yang; Qi, Keqi; Chen, Dawei

2018-04-01

In this paper, a calibration method is proposed which eliminates the zeroth order effect in lateral shearing interferometry. An analytical expression of the calibration error function is deduced, and the relationship between the phase-restoration error and calibration error is established. The analytical results show that the phase-restoration error introduced by the calibration error is proportional to the phase shifting error and zeroth order effect. The calibration method is verified using simulations and experiments. The simulation results show that the phase-restoration error is approximately proportional to the phase shift error and zeroth order effect, when the phase shifting error is less than 2° and the zeroth order effect is less than 0.2. The experimental result shows that compared with the conventional method with 9-frame interferograms, the calibration method with 5-frame interferograms achieves nearly the same restoration accuracy.

Evaluation of the efficiency of continuous wavelet transform as processing and preprocessing algorithm for resolution of overlapped signals in univariate and multivariate regression analyses; an application to ternary and quaternary mixtures

NASA Astrophysics Data System (ADS)

Hegazy, Maha A.; Lotfy, Hayam M.; Mowaka, Shereen; Mohamed, Ekram Hany

2016-07-01

Wavelets have been adapted for a vast number of signal-processing applications due to the amount of information that can be extracted from a signal. In this work, a comparative study on the efficiency of continuous wavelet transform (CWT) as a signal processing tool in univariate regression and a pre-processing tool in multivariate analysis using partial least square (CWT-PLS) was conducted. These were applied to complex spectral signals of ternary and quaternary mixtures. CWT-PLS method succeeded in the simultaneous determination of a quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PAR) and p-aminophenol (PAP, the major impurity of paracetamol). While, the univariate CWT failed to simultaneously determine the quaternary mixture components and was able to determine only PAR and PAP, the ternary mixtures of DRO, CAF, and PAR and CAF, PAR, and PAP. During the calculations of CWT, different wavelet families were tested. The univariate CWT method was validated according to the ICH guidelines. While for the development of the CWT-PLS model a calibration set was prepared by means of an orthogonal experimental design and their absorption spectra were recorded and processed by CWT. The CWT-PLS model was constructed by regression between the wavelet coefficients and concentration matrices and validation was performed by both cross validation and external validation sets. Both methods were successfully applied for determination of the studied drugs in pharmaceutical formulations.

Theoretical foundation, methods, and criteria for calibrating human vibration models using frequency response functions

PubMed Central

Dong, Ren G.; Welcome, Daniel E.; McDowell, Thomas W.; Wu, John Z.

2015-01-01

While simulations of the measured biodynamic responses of the whole human body or body segments to vibration are conventionally interpreted as summaries of biodynamic measurements, and the resulting models are considered quantitative, this study looked at these simulations from a different angle: model calibration. The specific aims of this study are to review and clarify the theoretical basis for model calibration, to help formulate the criteria for calibration validation, and to help appropriately select and apply calibration methods. In addition to established vibration theory, a novel theorem of mechanical vibration is also used to enhance the understanding of the mathematical and physical principles of the calibration. Based on this enhanced understanding, a set of criteria was proposed and used to systematically examine the calibration methods. Besides theoretical analyses, a numerical testing method is also used in the examination. This study identified the basic requirements for each calibration method to obtain a unique calibration solution. This study also confirmed that the solution becomes more robust if more than sufficient calibration references are provided. Practically, however, as more references are used, more inconsistencies can arise among the measured data for representing the biodynamic properties. To help account for the relative reliabilities of the references, a baseline weighting scheme is proposed. The analyses suggest that the best choice of calibration method depends on the modeling purpose, the model structure, and the availability and reliability of representative reference data. PMID:26740726