Heteroscedastic controlled calibration model applied to analytical chemistry

In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so-called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright (C) 2010 John Wiley & Sons, Ltd.

Development and calibration of a portable radon sampling system for groundwater (222)Rn activity concentration measurements

The assembling of a system for field sampling and activity concentration measurement of radon dissolved in groundwater is described. Special attention is given in presenting the calibration procedure to obtain the radon activity concentration in groundwater from the raw counting rate registered in a portable scintillation detector and in establishing the precision of the activity concentration measurements. A field procedure was established and the system tested during one year of monthly observations of (222)Rn activity concentration in groundwater drawn from two wells drilled on metamorphic rocks exposed at Eastern Sao Paulo State, Brazil. The observed mean (222)Rn activity concentrations are 374 Bq/dm(3) in one well and about 1275 Bq/dm(3) in the other one. In both wells the (222)Rn activity concentrations showed a seasonal variation similar to variations previously reported in the literature for the same region. (C) 2009 Elsevier Ltd. All rights reserved.

Hypotheses testing for structural calibration model

The main objective of this paper is to discuss maximum likelihood inference for the comparative structural calibration model (Barnett, in Biometrics 25:129-142, 1969), which is frequently used in the problem of assessing the relative calibrations and relative accuracies of a set of p instruments, each designed to measure the same characteristic on a common group of n experimental units. We consider asymptotic tests to answer the outlined questions. The methodology is applied to a real data set and a small simulation study is presented.

Chemostratigraphy of the Tamengo Formation (Corumba Group, Brazil) A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumba Group cropping out in the southern Paraguay Belt in Brazil is one of the most complete Ediacaran sedimentary archives of palaeogeographic climatic biogeochemical and biotic evolution in southwestern Gondwana The unit hosts a rich fossil record including acritarchs vendotaenids (Vendo taenia Eoholynia) soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina Titanotheca) The Tamengo Formation made up mainly of limestones and marls provides a rich bio- and chemostratigraphic record Several outcrops formerly assigned to the Cuiaba Group are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria High-resolution carbon isotopic analyses are reported for the Tamengo Formation showing (from base to top) (1) a positive delta(13)C excursion to +4 parts per thousand PDB above post-glacial negative values (2) a negative excursion to -3 5 parts per thousand associated with a marked regression and subsequent transgression (3) a positive excursion to +5 5 parts per thousand and (4) a plateau characterized by delta(13)C around +3 parts per thousand A U-Pb SHRIMP zircon age of an ash bed Interbedded in the upper part of the delta(13)C positive plateau yielded 543 +/- 3 Ma which is considered as the depositional age (Babinski et al 2008a) The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide including the Nama Group (Namibia) the Dengying Formation (South China) and the Nafun and Ara groups (Oman) This plateau is constrained between 542 and 551 Ma thus consistent with the age of the upper Tamengo Formation The negative excursion of the lower Tamengo Formation may be correlated to the Shuram-Wonoka negative anomaly although delta(13)C values do not fall beyond -3 5 parts per thousand in the Brazilian sections Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall but a tectonic interpretation cannot be completely ruled out Published by Elsevier B V

Improved maximum likelihood estimators in a heteroskedastic errors-in-variables model

This paper develops a bias correction scheme for a multivariate heteroskedastic errors-in-variables model. The applicability of this model is justified in areas such as astrophysics, epidemiology and analytical chemistry, where the variables are subject to measurement errors and the variances vary with the observations. We conduct Monte Carlo simulations to investigate the performance of the corrected estimators. The numerical results show that the bias correction scheme yields nearly unbiased estimates. We also give an application to a real data set.

A Bayesian Semiparametric Approach for Solving the Discrete Calibration Problem

In this article, we introduce a semi-parametric Bayesian approach based on Dirichlet process priors for the discrete calibration problem in binomial regression models. An interesting topic is the dosimetry problem related to the dose-response model. A hierarchical formulation is provided so that a Markov chain Monte Carlo approach is developed. The methodology is applied to simulated and real data.

On the skew-normal calibration model

In this article, we present the EM-algorithm for performing maximum likelihood estimation of an asymmetric linear calibration model with the assumption of skew-normally distributed error. A simulation study is conducted for evaluating the performance of the calibration estimator with interpolation and extrapolation situations. As one application in a real data set, we fitted the model studied in a dimensional measurement method used for calculating the testicular volume through a caliper and its calibration by using ultrasonography as the standard method. By applying this methodology, we do not need to transform the variables to have symmetrical errors. Another interesting aspect of the approach is that the developed transformation to make the information matrix nonsingular, when the skewness parameter is near zero, leaves the parameter of interest unchanged. Model fitting is implemented and the best choice between the usual calibration model and the model proposed in this article was evaluated by developing the Akaike information criterion, Schwarz`s Bayesian information criterion and Hannan-Quinn criterion.

Skew-normal linear calibration: a Bayesian perspective

In this paper, we present a Bayesian approach for estimation in the skew-normal calibration model, as well as the conditional posterior distributions which are useful for implementing the Gibbs sampler. Data transformation is thus avoided by using the methodology proposed. Model fitting is implemented by proposing the asymmetric deviance information criterion, ADIC, a modification of the ordinary DIC. We also report an application of the model studied by using a real data set, related to the relationship between the resistance and the elasticity of a sample of concrete beams. Copyright (C) 2008 John Wiley & Sons, Ltd.

A matrix formula for the skewness of maximum likelihood estimators

We give a general matrix formula for computing the second-order skewness of maximum likelihood estimators. The formula was firstly presented in a tensorial version by Bowman and Shenton (1998). Our matrix formulation has numerical advantages, since it requires only simple operations on matrices and vectors. We apply the second-order skewness formula to a normal model with a generalized parametrization and to an ARMA model. (c) 2010 Elsevier B.V. All rights reserved.

Bias-corrected estimators for dispersion models with dispersion covariates

In this paper we discuss bias-corrected estimators for the regression and the dispersion parameters in an extended class of dispersion models (Jorgensen, 1997b). This class extends the regular dispersion models by letting the dispersion parameter vary throughout the observations, and contains the dispersion models as particular case. General formulae for the O(n(-1)) bias are obtained explicitly in dispersion models with dispersion covariates, which generalize previous results obtained by Botter and Cordeiro (1998), Cordeiro and McCullagh (1991), Cordeiro and Vasconcellos (1999), and Paula (1992). The practical use of the formulae is that we can derive closed-form expressions for the O(n(-1)) biases of the maximum likelihood estimators of the regression and dispersion parameters when the information matrix has a closed-form. Various expressions for the O(n(-1)) biases are given for special models. The formulae have advantages for numerical purposes because they require only a supplementary weighted linear regression. We also compare these bias-corrected estimators with two different estimators which are also bias-free to order O(n(-1)) that are based on bootstrap methods. These estimators are compared by simulation. (C) 2011 Elsevier B.V. All rights reserved.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.