RESUMO
Using highly precise and accurate Monte Carlo simulations of 20,000,000 replications and 102 independent simulation experiments with extremely low simulation errors and total uncertainties, we evaluated the performance of four single outlier discordancy tests (Grubbs test N2, Dixon test N8, skewness test N14, and kurtosis test N15) for normal samples of sizes 5 to 20. Statistical contaminations of a single observation resulting from parameters called δ from ±0.1 up to ±20 for modeling the slippage of central tendency or ε from ±1.1 up to ±200 for slippage of dispersion, as well as no contamination (δ = 0 and ε = ±1), were simulated. Because of the use of precise and accurate random and normally distributed simulated data, very large replications, and a large number of independent experiments, this paper presents a novel approach for precise and accurate estimations of power functions of four popular discordancy tests and, therefore, should not be considered as a simple simulation exercise unrelated to probability and statistics. From both criteria of the Power of Test proposed by Hayes and Kinsella and the Test Performance Criterion of Barnett and Lewis, Dixon test N8 performs less well than the other three tests. The overall performance of these four tests could be summarized as N2â N15 > N14 > N8.
Assuntos
Método de Monte Carlo , Simulação por Computador , Modelos EstatísticosRESUMO
Serious limitations of the existing water classification schemes prompted us to propose a new statistically coherent water nomenclature system. An extensive database of ionic charge-balanced concentrations of 8 elements (4 cations Ca, Mg, Na, and K; and 4 anions SO4, Cl, HCO3, and CO3), in 46,292 multivariate outlier-free simulated samples, was used for training the multidimensional classification system. The initial assignment for 16 classes was achieved from the greater molar concentration concept of each cation and anion, called the Greater molar conc model. Seven hybrid log-ratios (hlr) from 8 elemental concentrations were used for linear discriminant analysis (LDA) and canonical analysis to propose 16 multidimensional discriminant functions from the 7 hlr model. The LDA and canonical analysis were also performed on the initial molar concentrations of 7 elements, without any log-transformation, which was designated as the 7 M conc model. The robustness of these three classification systems (7 hlr, 7 M conc, and Greater molar conc) was tested against analytical uncertainty propagation and mineral-water interaction effects. The 7 hlr model, due to its higher robustness, was considered as the best option for the nomenclature of the 16 types of water. From the probability concept, it was possible to identify hybrid water types, along with the basic or primary types of water. Our water classification scheme (7 hlr model under the "basic+hybrid" option) can classify as many as 256 different classes of water. Due to the clearly high complexity of the proposed classification scheme, we developed a new online computer program WaterMClaSys_LDA (Water Molar Classification System from Linear Discriminant Analysis) available at our web portal http://tlaloc.ier.unam.mx, for use by anyone after registration and log-in. The usefulness of the new classification scheme is illustrated by applications to groundwater, lake water, and geothermal water samples from South India, Mongolia, and western Turkey, respectively.
RESUMO
The weighted least-squares (WLS) regression method was successfully applied to establish calibration curves with variable amounts of lanthanides ranging from 0.002 to 0.430 microg. These curves were employed for the analysis of 13 lanthanides (La-Nd, Sm-Tb, and Ho-Lu) in 12 international geochemical reference materials (IGRM). The separation of the lanthanide group was achieved in approximately 15 min. Dysprosium could not be determined in IGRM because of its co-elution with Yttrium. A linear gradient program of alpha-HIBA eluent with a concentration ranging from 0.05 to 0.5 M (0.1 M OS, pH 3.8 with NH(4)OH, and a flow-rate of 1.0 ml/min) was employed. The detection was performed with a UV-vis system at 658 nm using a post-column reagent of Arsenazo III (0.5 ml/min). With this set of RP-HPLC conditions together with the use of both the ordinary least-squares (OLS) and the WLS regressions, we report the results of the measurements along with the total propagated uncertainties in individual concentration values. The uncertainties were obtained by combining standard errors in both regression parameters (slope and intercept) with those related to the chromatographic peak areas. The straight-line slopes and intercepts calculated by the WLS method provided not only considerably smaller errors than the conventional OLS method but also a much better estimation of the limits of detection. The concentrations calculated were compared with the "most probable" concentration values of these reference materials reported in the literature. Statistically significant agreement was consistently observed between the HPLC data and the literature values. The total uncertainties in estimated concentration values for the WLS were consistently smaller than the respective errors for the OLS.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Elementos da Série dos Lantanídeos/análise , Algoritmos , Calibragem , Elementos da Série dos Lantanídeos/isolamento & purificação , Elementos da Série dos Lantanídeos/normas , Análise dos Mínimos Quadrados , Padrões de Referência , Análise de Regressão , Reprodutibilidade dos TestesRESUMO
The determination of silica concentrations in geothermal brines is widely recognized as a difficult analytical task due to its complex chemical polymerization kinetics that occurs during sample collection and chemical analysis. Capillary electrophoresis (CE) has been evaluated as a new reliable analytical method to measure silica (as silicates) in geothermal brines. Synthetic and geothermal brine samples were used to evaluate CE methodology. A capillary electrophoresis instrument, Quanta 4000 (Waters-Millipore) coupled with a Waters 820 workstation was used to carry out the experimental work. The separation of silicates was completed in approximately 5.5 min using a conventional fused-silica capillary (75 microm i.d. x 375 microm o.d. x 60 cm total length). A hydrostatic injection (10 cm for 20 s at 25 degrees C) was employed for introducing the samples. The carrier electrolyte consisted of 10 mM sodium chromate, 3 mM tetradecyltrimethyl-ammonium hydroxide (TTAOH), 2 mM sodium carbonate, and 1 mM sodium hydroxide, adjusted to a pH 11.0 +/- 0.1. Silicates were determined using an indirect UV detection at a wavelength of 254 nm with a mercury lamp and with a negative power supply (-15 kV). A good reproducibility in the migration times (%R.S.D. approximately 1.6%) based on six non-consecutive injections of synthetic brine solutions was obtained. A linear response between silica concentration and corrected peak area was observed. Ordinary (OLR) and weighted (WLR) linear regression models were used for calculating silica concentrations in all samples using the corresponding fitted calibration curves. The analytical results of CE were finally compared with the most probable values of synthetic reference standards of silica using the Student's t-test. No significant differences were found between them at P = 0.01. Similarly, the atomic absorption spectrometry (AAS) results were also compared with the most probable concentrations of the same reference standards, finding significant differences at P = 0.01.
Assuntos
Eletroforese Capilar/métodos , Sais/química , Dióxido de Silício/análise , Calibragem , Padrões de Referência , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Espectrofotometria Atômica , Espectrofotometria UltravioletaRESUMO
A reversed-phase liquid chromatography method was used for determining lanthanides in synthetic standards. The separation of lanthanide group was achieved in less than 15 min using a linear gradient program of alpha-hydroxyisobutyricacid eluent from 0.05 to 0.5 M (pH 3.8) with a UV-Vis detection system at 658 nm. A post-column reagent of Arsenazo III was employed for improving the sensitivity and selectivity of the method as well as for lowering the limits of detection (LODs). Linear calibration curves for all lanthanides were constructed using an ordinary least-squares (OLS) regression as well as a weighted least-squares (WLS) regression model for taking into account the heteroscedastic errors. The WLS model was successfully used for a better estimation of the sensitivities and the LODs of the RP-HPLC method than the conventional OLS model. The lanthanide sensitivity obtained from the slope of each calibration curve seems to be better for a lanthanide with an odd-atomic number compared to its neighboring element with an even-atomic number, as if nature is helping us to quantify the concentrations of the less abundant lanthanides. This observation was also confirmed when the LODs computed for all lanthanides were examined. The LODs observed for all lanthanides depicted a clear systematic "zigzag" pattern. This is actually the first time that the lanthanide detection limits determined by a HPLC method are shown to mimic the zigzag patterns for the concentration data in geological and cosmological materials. Such a "zigzag" pattern should be used as a standard criterion for evaluating the quality of detection limit data.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Elementos da Série dos Lantanídeos/análise , Cromatografia Líquida de Alta Pressão/normas , Análise dos Mínimos Quadrados , Controle de Qualidade , Sensibilidade e EspecificidadeRESUMO
Limit of detection (LOD), being a fundamental quality parameter for analytical techniques, has been recently investigated and a systematic behavior has been observed for most odd-even element pairs for many techniques. However, to the best of our knowledge very few LOD data are available in published literature for electron microprobe analysis; these consist of three papers, two being on rare-earth elements and the third covering a large number of elements of atomic number between 21 and 92. These data confirm the systematic behavior of LODs for many odd-even pairs. To initiate to full this gap, we determined LODs for several major rock-forming chemical elements from Na to Fe with atomic numbers between 11 and 26, during the microprobe analysis of common minerals (olivine, plagioclase, pyroxene, amphibole, quartz, and opaques) in volcanic rocks. The odd-even effect of nuclear stability seems to be present in LOD data for most odd-even pairs investigated. Nevertheless, the experimental strategy concerning the reference materials, calibration procedure, and blank measurements, should be substantially modified to better evaluate the systematic behavior of LOD values in microprobe analysis.
RESUMO
Several papers have reported that low level of genistein (<8 microM), the major bioactive component of isoflavones, stimulates the growth of MCF-7 cells. In the present study, we found that genistein-induced growth stimulation of MCF-7 cells is inhibited in the presence of Cu(2+) (5 microM). Genistein induces the release of nitric oxide in MCF-7 cells in a concentration-dependent manner. The release of nitric oxide was inhibited by N(G)-nitro-L-arginine methyl ester, suggesting the possibility of the activation of nitric oxide synthase. The growth of MCF-7 cells also increases in the presence of low levels of sodium nitriprusside (<10 microM), a nitric oxide donor compound, while high levels (>25 microM) are toxic. The sodium nitroprusside-induced growth of MCF-7 cells is drastically suppressed in the presence of Cu(2+) (5 microM). This parallel behavior between Cu(2+)-genistein and Cu(2+)-sodium nitroprusside mixtures suggests that Cu(2+) and/or copper-protein complexes, that may be formed in the media, may be reacting with nitric oxide or nitric oxide-derived reactive species. The products of these reactions may be responsible for the toxic effects of these mixtures. In contrast, the effect of curcumin that inhibits the growth of both estrogen receptor-positive and -negative breast tumor cells appreciably decreased in the presence of Cu(2+). Since copper is known to overwhelmingly bind with proteins, present data suggest that an increase in copper-protein moieties or complexes formed in the serum containing media and their reactions with nitric oxide may be responsible for their toxic effects. Further studies are needed to characterize these reactions.
Assuntos
Neoplasias da Mama/metabolismo , Cobre/farmacologia , Curcumina/farmacologia , Genisteína/farmacologia , Óxido Nítrico/metabolismo , Neoplasias da Mama/patologia , Divisão Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Humanos , Doadores de Óxido Nítrico/farmacologia , Nitroprussiato/farmacologia , Receptores de Estrogênio/metabolismoRESUMO
A representative database for detection limits for all elements from (55)Cs to (73)Ta reveals that these limits are governed by a systematic zigzag pattern, according to which the odd atomic number elements have systematically lower detection limits than the even atomic number neighbour elements. This is true even when the actual detection limits vary by several orders of magnitude. We propose that such a systematic pattern be used as a requisite analytical criterion to evaluate the detection limit data, and any departure from this pattern be looked on with caution to check the analytical technique for any interference or matrix effect problems.