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Pierlot, Christel,Barbillat, Jacques,Nardello-Rataj, Veronique,Mathieu, Didier,Sergent, Michelle,Marko, Jean,Aubry, Jean-Marie Korean Society of Photoscience 2009 Photochemical & photobiological sciences Vol.8 No.7
A near-IR chemiluminescence spectrometer designed to study chemical sources of singlet oxygen ($^1O_2$, $^1{\Delta}_g$), was built by coupling a reactor compartment to a nitrogen-cooled Ge diode through a bundle of optical fibres. This device was used to optimise the generation of $^1O_2$ from the hydrogen peroxide.lanthanum(III) catalytic system. The reaction kinetics were studied with a $2^33^3$//12 screening experimental design comprising twelve experiments. The influence of six factors was examined: the nature of the lanthanum salt (hydroxide, oxide or nitrate) and its concentration (0.05 or 0.1 mol $L^{-1}$), the pH value (5, 7 or 9), the concentration of $H_2O_2$ (0.5, 1 or 2 mol $L^{-1}$), the temperature (20 or $30^{\circ}C$) and the concentration of EDTA (0 or 5 mmol $L^{-1}$). Two responses were measured: the rate of $H_2O_2$ disproportionation and the intensity of the luminescence of $^1O_2$ at 1270 nm. The essential factor is the nature of the lanthanum salt since $La(NO_3)_3$ induces the disproportionation of $H_2O_2$ about $60{\tims}$ faster than $La_2O_3$ or $La(OH)_3$. Other influencing factors are the pH value, the concentration of $H_2O_2$, the temperature and the concentration of the lanthanum salt whereas the concentration of EDTA has no effect on the reaction. The catalytic activity of $La(NO_3)_3$ was then investigated in further detail by studying the influence of two factors (pH and $[H_2O_2]$) thanks to a Doehlert design.
Sobanska, Sophie,Hwang, HeeJin,Choë,l, Marie,Jung, Hae-Jin,Eom, Hyo-Jin,Kim, HyeKyeong,Barbillat, Jacques,Ro, Chul-Un American ChemicalSociety 2012 ANALYTICAL CHEMISTRY - Vol.84 No.7
<P>In this work, quantitative electron probe X-ray microanalysis (EPMA) and Raman microspectrometry (RMS) were applied in combination for the first time to characterize the complex internal structure and physicochemical properties of the same ensemble of Asian dust particles. The analytical methodology to obtain the chemical composition, mixing state, and spatial distribution of chemical species within single particles through the combined use of the two techniques is described. Asian dust aerosol particles collected in Incheon, Korea, during a moderate dust storm event were examined to assess the applicability of the methodology to resolve internal mixtures within single particles. Among 92 individual analyzed particles, EPMA and RMS identified 53% of the particles to be internally mixed with two or more chemical species. Information on the spatial distribution of chemical compounds within internally mixed individual particles can be useful for deciphering the particle aging mechanisms and sources. This study demonstrates that the characterization of individual particles, including chemical speciation and mixing state analysis, can be performed more in detail using EPMA and RMS in combination than with the two single-particle techniques alone.</P>