15 research outputs found

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    Heterogeneous Interaction of H2O2 with Arizona Test Dust

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    International audienceThe heterogeneous interaction of H2O2 with solid films of Arizona Test Dust (ATD) was investigated under dark conditions and in presence of UV light using a low pressure flow tube reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of gaseous H2O2 ([H2O2]0 = (0.18 – 5.1) × 1012 molecules cm–3), irradiance intensity (JNO2 = 0.002 – 0.012 s–1), relative humidity (RH = 0.002 – 69%), and temperature (T = 268 – 320 K). The initial uptake coefficient was found to be independent of the concentration of H2O2 and UV irradiation intensity and to decrease with increasing RH and temperature according to the following expressions: Îł0 = 4.8 × 10–4/(1+ RH0.66) at T = 275 K and Îł0 = 3.2 × 10–4/(1 + 2.5 × 1010exp(−7360/T)) at RH = 0.35% (calculated using BET surface area, estimated conservative uncertainty of 30%). By contrast, the steady state uptake coefficient was found to be independent of temperature, to increase upon UV irradiation of the surface, and to be inversely (ÎłSS ∌ [H2O2]−0.6) dependent on the concentration of H2O2. The RH independent steady state uptake coefficient was measured under dark and UV irradiation conditions: ÎłSS(dark) = (0.95 ± 0.30) × 10–5 and ÎłSS(UV) = (1.85 ± 0.55) × 10–5, for RH = (2 – 69)% and [H2O2]0 ≅ 1.0 × 1012 molecules cm–3. The present experimental data support current considerations that uptake of H2O2 on mineral aerosol is potentially an important atmospheric process

    Mineral Oxides Change the Atmospheric Reactivity of Soot: NO<sub>2</sub> Uptake under Dark and UV Irradiation Conditions

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    The heterogeneous reactions between trace gases and aerosol surfaces have been widely studied over the past decades, revealing the crucial role of these reactions in atmospheric chemistry. However, existing knowledge on the reactivity of mixed aerosols is limited, even though they have been observed in field measurements. In the current study, the heterogeneous interaction of NO<sub>2</sub> with solid surfaces of Al<sub>2</sub>O<sub>3</sub> covered with kerosene soot was investigated under dark conditions and in the presence of UV light. Experiments were performed at 293 K using a low-pressure flow-tube reactor coupled with a quadrupole mass spectrometer. The steady-state uptake coefficient, Îł<sub>ss</sub>, and the distribution of the gas-phase products were determined as functions of the Al<sub>2</sub>O<sub>3</sub> mass; soot mass; NO<sub>2</sub> concentration, varied in the range of (0.2–10) × 10<sup>12</sup> molecules cm<sup>–3</sup>; photon flux; and relative humidity, ranging from 0.0032% to 32%. On Al<sub>2</sub>O<sub>3</sub>/soot surfaces, the reaction rate was substantially increased, and the formation of HONO was favored compared with that on individual pure soot and pure Al<sub>2</sub>O<sub>3</sub> surfaces. Uptake of NO<sub>2</sub> was enhanced in the presence of H<sub>2</sub>O under both dark and UV irradiation conditions, and the following empirical expressions were obtained: Îł<sub>ss,BET,dark</sub> = (7.3 ± 0.9) × 10<sup>–7</sup> + (3.2 ± 0.5) × 10<sup>–8</sup> × RH and Îł<sub>ss,BET,UV</sub> = (1.4 ± 0.2) × 10<sup>–6</sup> + (4.0 ± 0.9) × 10<sup>–8</sup> × RH. Specific experiments, with solid sample preheating and doping with polycyclic aromatic hydrocarbons (PAHs), showed that UV-absorbing organic compounds significantly affect the chemical reactivity of the mixed mineral/soot surfaces. A mechanistic scheme is proposed, in which Al<sub>2</sub>O<sub>3</sub> can either collect electrons, initiating a sequence of redox reactions, or prevent the charge-recombination process, extending the lifetime of the excited state and enhancing the reactivity of the organics. Finally, the atmospheric implications of the observed results are briefly discussed

    Gender and pension individualisation: the case of Greece

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    Within pension reforms in Europe, one of the policy trends with significant gender implications is a gradual emphasis on individual pension rights based on labour market participation and the recognition of periods of care, and a decrease in the importance of derived pension rights for women’s pension income. The paper analyses six pension reforms in Greece between 1982-2002 to illustrate a gradual shift towards greater pension individualisation for women. It argues that unless this shift is coordinated with employment and family policies that allow both women and men to build adequate individual pension rights, greater pension individualisation could have adverse consequences for those with weak links to the labour market

    A review of coarse mineral dust in the Earth system

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    Mineral dust particles suspended in the atmosphere span more than three orders of magnitude in diameter, from <0.1 ”m to more than 100 ”m. This wide size range makes dust a unique aerosol species with the ability to interact with many aspects of the Earth system, including radiation, clouds, hydrology, atmospheric chemistry, and biogeochemistry. This review focuses on coarse and super-coarse dust aerosols, which we respectively define as dust particles with a diameter of 2.5–10 ”m and 10–62.5 ”m. We review several lines of observational evidence indicating that coarse and super-coarse dust particles are transported farther than previously expected and that the abundance of these particles is substantially underestimated in current global models. We synthesize previous studies that used observations, theories, and model simulations to highlight the impacts of coarse and super-coarse dust aerosols on the Earth system, including their effects on dust-radiation interactions, dust-cloud interactions, atmospheric chemistry, and biogeochemistry. Specifically, coarse and super-coarse dust aerosols produce a net positive direct radiative effect (warming) at the top of the atmosphere and can modify temperature and water vapor profiles, influencing the distribution of clouds and precipitation. In addition, coarse and super-coarse dust aerosols contribute a substantial fraction of ice-nucleating particles, especially at temperatures above –23 °C. They also contribute a substantial fraction to the available reactive surfaces for atmospheric processing and the dust deposition flux that impacts land and ocean biogeochemistry by supplying important nutrients such as iron and phosphorus. Furthermore, we examine several limitations in the representation of coarse and super-coarse dust aerosols in current model simulations and remote-sensing retrievals. Because these limitations substantially contribute to the uncertainties in simulating the abundance and impacts of coarse and super-coarse dust aerosols, we offer some recommendations to facilitate future studies. Overall, we conclude that an accurate representation of coarse and super-coarse properties is critical in understanding the impacts of dust aerosols on the Earth system
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