Determination of low-aliphatic aldehydes indoors by micellar electrokinetic chromatography using sample dissolution manipulation for signal enhancement

This work describes a novel approach for the analysis of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) and acetone in environmental samples using micellar electrokinetic chromatography (MEKC). The method is based on the reaction of carbonyl compounds with 3-methyl-2-benzothiazoline hydrazone (MBTH) that gives an azine intermediate with maximum absorbance at 216 nm. A systematic evaluation of sample dissolution medium was conducted as a means to enhancing sensitivity. In the best condition, samples were dissolved in 0.030 mol.L-1 tetraborate solution. This condition presented enhancement factors in the range of 35-54 for the aldehydes under investigation, computed as the improvement of the concentration limits of detection (LODs) with reference to the sample dissolved in pure water. The running buffer was 0.020 mol.L-1 tetraborate, pH 9.3, containing 0.050 mol-L-1 sodium dodecyly sulfate (SIDS). The overall methodology presented several advantages over established methods for aldehydes. Worthy mentioning that MBTH is available in high purity degree, dispensing laborious reagent purification procedures. A few method validation parameters were determined revealing good migration time repeatability (< 2.5% coefficient of variation, CV) and area repeatability (< 4% CV), excellent linearity (20-120 mug/L, r > 0.995) and adequate sensitivity for environmental applications. The LODs with respect to each single aldehyde were in the range of 0.54-4.0 mug.L-1 and 11 mug.L-1 for acetone. The methodology was applied to the determination of aldehydes indoors. Samples were collected in an impinger flask containing 0.05% MBTH solution, at a flow rate of 0.80 L.min(-1), during 2.5 h, at different times during the day. The most abundant carbonyls in the samples were acetone, followed by formaldehyde and acetaldehyde, with estimate peak concentrations of 452, 5.2 and 2.2 ppbv, respectively.

Evaluation of sample treatment for the simultaneous flow injection hydride generation and determination of As, Bi, Sb and Se by GRAS

A new method was developed for the simultaneous determination of As, Bi, Sb, and Se by flow injection hydride generation graphite furnace atomic absorption spectrometry. An alternative two-step sample treatment procedure was used. The sample was heated (80degreesC) for 10 min in 6 M HCl to reduce Se(VI) to Se(IV), followed by the addition of 1% (m/v) thiourea solution to reduce arsenic and antimony from the pentavalent to the trivalent states.With this procedure, all analytes were converted to their most favorable and sensitive oxidation states to generate the corresponding hydrides. The pre-treated sample solution was then processed in the flow system for in situ trapping and atomization in a graphite tube coated with iridium. The impermanent modifier remained stable up to 300 firings and new coating out significant were possible wit changes in the analytical performance.The accuracy was checked for As, Bi, Sb, and Se determination in water standard reference materials NIST 1640 and 1643d and the results were in agreement with the certified values at a 95% confidence level. Good recoveries (94-104%.) of spiked mineral waters and synthetic As(V), Sb(Ill), mixtures of As(Ill), Sb(V), Se(VI), and Se(IV) were also found. Calculated characteristic masses were 32 mug As, 79 mug Bi, 35 mug Sb, and 130 pg Se, and the corresponding limits of detection were 0.06, 0.16, 0.19, and 0.59 mug L-1, respectively. The repeatability for a typical solution containing 5 mug L-1 As, Bi, Sb, and Se was in the 1-3% range.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Monitoring the covariance matrix with the VMAX chart

In this article, we propose a new statistic to control the covariance matrix of bivariate processes. This new statistic is based on the sample vat-lances of the two quality characteristics, shortly VMAX statistic. The points plotted on the chart correspond to the maximum of the values of these two variances. The reasons to consider the VMAX statistic instead of the generalized variance vertical bar S vertical bar are faster detection of process changes and better diagnostic feature, that is, with the VMAX statistic It is easier to identify the out-of-control variable.

The Variable Sample Size (X)over-bar Chart with Estimated Parameters

The VSS X chart, dedicated to the detection of small to moderate mean shifts in the process, has been investigated by several researchers under the assumption of known process parameters. In practice, the process parameters are rarely known and are usually estimated from an in-control Phase I data set. In this paper, we evaluate the (run length) performances of the VSS chart when the process parameters are estimated, we compare them in the case where the process parameters are assumed known and we propose specific optimal control chart parameters taking the number of Phase I samples into account.

A single statistic for monitoring the covariance matrix of bivariate processes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

X̄ charts with variable sample size

The usual practice in using a control chart to monitor a process is to take samples of size n from the process every h hours. This article considers the properties of the X̄ chart when the size of each sample depends on what is observed in the preceding sample. The idea is that the sample should be large if the sample point of the preceding sample is close to but not actually outside the control limits and small if the sample point is close to the target. The properties of the variable sample size (VSS) X̄ chart are obtained using Markov chains. The VSS X̄ chart is substantially quicker than the traditional X̄ chart in detecting moderate shifts in the process.

X̄ chart with variable sample size and sampling intervals

Recent theoretical studies have shown that the X̄ chart with variable sampling intervals (VSI) and the X̄ chart with variable sample size (VSS) are quicker than the traditional X̄ chart in detecting shifts in the process. This article considers the X̄ chart with variable sample size and sampling intervals (VSSI). It is assumed that the amount of time the process remains in control has exponential distribution. The properties of the VSSI X̄ chart are obtained using Markov chains. The VSSI X̄ chart is even quicker than the VSI or VSS X̄ charts in detecting moderate shifts in the process.

Joint X̄ and R Charts with Variable Sample Sizes and Sampling Intervals

Recent studies have shown that the X̄ chart with variable sampling intervals (VSI) and/or with variable sample sizes (VSS) detects process shifts faster than the traditional X̄ chart. This article extends these studies for processes that are monitored by both the X̄ and R charts. A Markov chain model is used to determine the properties of the joint X and R charts with variable sample sizes and sampling intervals (VSSI). The VSSI scheme improves the joint X̄ and R control chart performance in terms of the speed with which shifts in the process mean and/or variance are detected.

Estimation of variances of the effects of incomplete diallels using a matrix approach

A matrix approach is described for assessing the variance of effects in incomplete diallels designs. The method is illustrated by reference to simulated complete and incomplete diallels using different combinations of constraints, average degree of dominance and, for the incomplete diallel, number of hybrids. Our results showed that caution should be taken in working with incomplete diallels under conditions of overdominance because there were changes in the rank of the genotypes when the excluded hybrid had parents with a low frequency of the favorable allele (i.e. the allele which increases expression of a character). The expression described in this paper is a rapid and safe approach to estimate variances and covariances of the effects of contrasts of incomplete diallels. Copyright by the Brazilian Society of Genetics.

Simultaneous effects of total solids content, milk base, heat treatment temperature and sample temperature on the rheological properties of plain stirred yogurt

Response surface methodology was used to establish a relationship between total solids content, milk base, heat treatment temperature, and sample temperature, and consistency index, flow behaviour index, and apparent viscosity of plain stirred yogurts. Statistical treatments resulted in developments of mathematical models. All samples presented shear thinning fluid behaviour. The increase of the content of total solids (9.3-22.7 %) and milk base heat treatment temperature (81.6-98.4°C) resulted in a significant increase in consistency index and a decrease in flow behaviour index. Increase in the sample temperature (1.6-18.4°C) caused a decrease in consistency index and increase in flow behaviour index. Apparent viscosity was directly related to the content of total solids. Rheological properties of yogurt were highly dependent on the content of total solids in milk.

Comparative studies of the sample decomposition of green and roasted coffee for determination of nutrients and data exploratory analysis

The contents of some nutrients in 35 Brazilian green and roasted coffee samples were determined by flame atomic absorption spectrometry (Ca, Mg, Fe, Cu, Mn, and Zn), flame atomic emission photometry (Na and K) and Kjeldahl (N) after preparing the samples by wet digestion procedures using i) a digester heating block and ii) a conventional microwave oven system with pressure and temperature control. The accuracy of the procedures was checked using three standard reference materials (National Institute of Standards and Technology, SRM 1573a Tomato Leaves, SRM 1547 Peach Leaves, SRM 1570a Trace Elements in Spinach). Analysis of data after application of t-test showed that results obtained by microwave-assisted digestion were more accurate than those obtained by block digester at 95% confidence level. Additionally to better accuracy, other favorable characteristics found were lower analytical blanks, lower reagent consumption, and shorter digestion time. Exploratory analysis of results using Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) showed that Na, K, Ca, Cu, Mg, and Fe were the principal elements to discriminate between green and roasted coffee samples. ©2007 Sociedade Brasileira de Química.

Slurry sample injection for determination of ferrite nanocolloids chemical composition by ICP spectrometry

This work proposes a new method to determine the chemical composition of magnetic ferrite nanoparticles by the slurry injection technique using the inductively coupled plasma optical emission spectroscopy. In this way, experimental conditions such as aerosol gas flow rate and colloidal stability were optimized in order to use aqueous calibration curves in the slurry nebulization and to determine the chemical composition of a series of sols containing chemically synthesized size-tailored NiFe 2O 4 nanograms. Then, the results of direct sampling and those of conventional aqueous introduction analysis are compared, showing the efficiency of the proposed method.

Childhood trauma in substance use disorder and depression: An analysis by gender among a Brazilian clinical sample

Objective: In this study, we compared the frequency and intensity of childhood traumas in alcohol- or other drug-dependent patients, in patients with depression, and in a control group without psychiatric diagnoses. Methods: The study had a retrospective design of a clinical sample of men and women from the groups listed above. They were evaluated by the same standardized instrument: the Childhood Trauma Questionnaire.. Results: A higher frequency and intensity of emotional, physical, and sexual abuse were found in alcohol- and other drug-dependent patients than in patients with depression, who, in turn, presented significantly higher proportions than the control group. In all of the cases, the frequency was higher among women than men. Conclusion: Because of the high frequency and intensity of childhood traumas among alcohol- or other drug-dependent patients and depressed patients, the assessment of problems due to childhood traumas among these patients is essential to a better understanding of the etiology of those disorders and to their treatment. © 2010 Elsevier Ltd. All rights reserved.