Reinvestigation of the oxidation of organic contaminants by Fe(VI): Kinetics and effects of water matrix constituents.

Since previous studies mostly ignored the contributions of Fe(IV) and Fe(V) during the determination of reaction rate constants of ferrate (Fe(VI)) with trace organic contaminants (TrOCs), the intrinsic oxidation ability of Fe(VI) was overestimated. For the first time, this study systemically evaluated the reactivity of Fe(VI) towards four kinds of TrOCs by blocking Fe(IV)/Fe(V) over the TrOCs degradation, and evaluated the effects of coexisting water matrix constituents. Results revealed that Fe(VI) exhibited superior reactivity towards phenolic compounds. Different from other tested TrOCs, phenolic compounds were mainly degraded by Fe(VI) rather than Fe(IV)/Fe(V). Taking bisphenol A (BPA) as the target TrOC, we found that the coexisting constituents can not only affect the reactivity of different ferrate species (i.e., Fe(IV), Fe(V), and Fe(VI)), but also alter the concentrations of ferrates. HPO42- inhibited the reaction between Fe(VI) and H2O2, while Ca2+, Mg2+, and NH4+ promoted the generation of Fe(IV)/Fe(V) from Fe(VI). Besides, humic acid could increase the contribution of Fe(IV)/Fe(V) to the oxidation of BPA. These findings were validated in real water samples. Taken together, this study provides a new perspective regarding the intrinsic oxidation reactivity of Fe(VI), thereby urging reconsideration of the proper strategies for utilization of high-valent Fe species in practices.

The effect of micro-mechanical signatures of constituent phases in modern dental restorative materials on their macro-mechanical property: A statistical nanoindentation approach.

This study utilized a statistical nanoindentation analysis technique (SNT) to measure the amount of organic and inorganic constituents of twenty different brands of dental resin-based composites (RBCs) and tested whether their macro-property such as flexural modulus could be approximated by the proportions of constituents' micromechanical signatures using various rules of mixtures. The probability density function (PDF) of constitutive moduli per RBC brand were measured for three groups, comprised of different indent arrays and inter-indent spacings. SNT was then applied to deconvolute each PDF, from which the effective filler (µF) and matrix (µM) moduli and filler (VF) and matrix (VM) volume fractions per RBC brand were computed. VF and VM values obtained via SNT were strongly correlated with VF and VM obtained via Thermogravimetric Analysis and Archimedes method. The "observed" flexural modulus (EcFS) measured under macro-experiment were well associated with "predicted" effective modulus (EcEff) measured under nano-experiment, thereby establishing that global modulus was strongly affected by the constituents' micromechanics. However, the "predicted" EcEff were proportionally higher than the "observed" EcFS. VF was a confounder to EcFS and EcEff, whereby the influence of VF on both modular ratios (EcFS/µM and EcEff/µM) was best modeled by an exponential regression.

Direct large-volume injection analysis of polycyclic aromatic hydrocarbons in water / Análisis de inyección directa en gran volumen de hidrocarburos aromáticos policíclicos en agua / Análise de injeção direta de grande volume de hidrocarbonos aromáticos policíclicos em água

Abstract Due to the health risks for both humans and living beings caused by polycyclic aromatic hydrocarbons (PAHs), the monitoring of these compounds in environmental matrices is mandatory. This work proposes an analytical method for analyzing anthracene (AN) and benzo[a]pyrene (BaP), two of the most representative PAHs, at ultra-trace concentrations in water, employing direct injection of large volumes of samples coupled with reversed-phase high-performance liquid chromatography. For this purpose, principal component analysis was used to examine the behavior of AN and BaP within the chromatographic system. Results showed that AN and BaP chromatographic behavior can be described by three models representing their identification, the quantification of AN and that of BaP, respectively. The factors affecting the obtained models, such as the injection volume, column temperature, flow rate, strength of the mobile phase, and the excitation and emission wavelengths, were examined and optimized by means of design of experiments. Finally, the analytical method was validated, obtaining promising limits of detection and quantification. The developed analytical method was demonstrated to be useful for a sensitive analysis of the target analytes in relatively clean natural water matrices.

Resumen Los hidrocarburos aromáticos policíclicos (HAPs) causan problemas en la salud de los seres humanos y seres vivos, por lo que se requiere un monitoreo de estos compuestos en matrices ambientales. Este trabajo propone un método analítico para analizar el antraceno (AN) y el benzopireno (BAP), los hidrocarburos más representativos en concentraciones de ultra trazas en el agua, empleando inyección directa en grandes volúmenes en muestras acopladas a la fase inversa con cromatografía líquida de alto rendimiento. Por tal razón, se utilizó el análisis de componentes principales para examinar el comportamiento de AN y BAP en el sistema cromatográfico. Los resultados mostraron que el comportamiento cromatográfico de AN y BAP podría describirse por medio de tres modelos que representan su identificación, la cuantificación de AN y de BAP, respectivamente. Se examinaron los factores que afectan a los modelos obtenidos, como el volumen de inyección, la temperatura de la columna, la tasa de flujo, la fuerza de la fase móvil, y las longitudes de las ondas de excitación y emisión, y se optimizaron mediante el diseño de experimentos. Finalmente, se validó el método analítico, obteniendo límites de detección y cuantificación. Se demostró que el método analítico desarrollado fue útil para el análisis sensible de los analitos en matrices de agua natural relativamente limpia.

Resumo Devido aos riscos para a saúde tanto para humanos como para os seres vivos em geral causados pelos hidrocarbonos aromáticos policíclicos (HAPs), o monitoramento de estes compostos em matrizes ambientais é prioritário. Este trabalho propõem um método analítico para analisar antraceno (AN) e benzo[a]pireno (BaP), dois dos hidrocarbonos mais representativos, em concentrações de ultra traços em água, empregando injeções diretas de grandes volumes de amostra acoplada a cromatografia líquida de alta eficiência em fase reversa. Usando Análises por Componentes Principais e desenho experimental, foram avaliados os efeitos de diversos fatores que afetam o sistema cromatográfico, tais como o volume de injeção, a temperatura da coluna, fluxo, forca da fase móvel e comprimentos de onda de excitação e emissão. Os resultados demonstraram que o comportamento cromatográfico de AN e BaP pode ser descrito por meio de três que representam sua identificação, quantificação de AN e de BaP, respectivamente. Os resultados mostraram que o comportamento cromatográfico de NA e BAP poderia ser descrito por meio de três modelos que representam sua identificação, a quantificação de NA e de BAP, respectivamente. Examinaram-se os fatores que afetam aos modelos obtidos, como o volume de injeção, a temperatura da coluna, a taxa de fluxo, a forca da fase móvel, e as longitudes das ondas de excitação e emissão, e se otimizaram mediante o desenho experimental. Finalmente, se validou o m todo analítico, obtendo os limites de detecção e quantificação. O método analítico desenvolvido demonstrou ser útil para uma análise sensível para os compostos de interesse em matrizes de água natural relativamente limpas.