RESUMO
The OH-initiated degradation of 2-amino-2-methyl-1-propanol [CH3C(NH2)(CH3)CH2OH, AMP] was investigated in a large atmospheric simulation chamber, employing time-resolved online high-resolution proton-transfer reaction-time-of-flight mass spectrometry (PTR-ToF-MS) and chemical analysis of aerosol online PTR-ToF-MS (CHARON-PTR-ToF-MS) instrumentation, and by theoretical calculations based on M06-2X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The quantum chemistry calculations reproduce the experimental rate coefficient of the AMP + OH reaction, aligning k(T) = 5.2 × 10-12 × exp (505/T) cm3 molecule-1 s-1 to the experimental value kexp,300K = 2.8 × 10-11 cm3 molecule-1 s-1. The theoretical calculations predict that the AMP + OH reaction proceeds via hydrogen abstraction from the -CH3 groups (5-10%), -CH2- group, (>70%) and -NH2 group (5-20%), whereas hydrogen abstraction from the -OH group can be disregarded under atmospheric conditions. A detailed mechanism for atmospheric AMP degradation was obtained as part of the theoretical study. The photo-oxidation experiments show 2-amino-2-methylpropanal [CH3C(NH2)(CH3)CHO] as the major gas-phase product and propan-2-imine [(CH3)2CâNH], 2-iminopropanol [(CH3)(CH2OH)CâNH], acetamide [CH3C(O)NH2], formaldehyde (CH2O), and nitramine 2-methyl-2-(nitroamino)-1-propanol [AMPNO2, CH3C(CH3)(NHNO2)CH2OH] as minor primary products; there is no experimental evidence of nitrosamine formation. The branching in the initial H abstraction by OH radicals was derived in analyses of the temporal gas-phase product profiles to be BCH3/BCH2/BNH2 = 6:70:24. Secondary photo-oxidation products and products resulting from particle and surface processing of the primary gas-phase products were also observed and quantified. All the photo-oxidation experiments were accompanied by extensive particle formation that was initiated by the reaction of AMP with nitric acid and that mainly consisted of this salt. Minor amounts of the gas-phase photo-oxidation products, including AMPNO2, were detected in the particles by CHARON-PTR-ToF-MS and GC×GC-NCD. Volatility measurements of laboratory-generated AMP nitrate nanoparticles gave ΔvapH = 80 ± 16 kJ mol-1 and an estimated vapor pressure of (1.3 ± 0.3) × 10-5 Pa at 298 K. The atmospheric chemistry of AMP is evaluated and a validated chemistry model for implementation in dispersion models is presented.
RESUMO
The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH3)3CNH2, was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NO x), generates tert-butylnitramine, (CH3)3CNHNO2, and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH3)3CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH3)3CNâNOH, with OH radicals, which yield nitrous oxide (N2O) and the (CH3)3C radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10-6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10-12 cm3 molecule-1 s-1 at 305 ± 2 K and 1015 ± 1 hPa.
RESUMO
The application of fuels from renewable sources ("alternative fuels") in aviation is important for the reduction of anthropogenic carbon dioxide emissions, but may also attribute to reduced release of particles from jet engines. The present experiment describes ground-based measurements in the framework of the ECLIF (Emission and Climate Impact of Alternative Fuels) campaign using an Airbus A320 (V2527-A5 engines) burning six fuels of chemically different composition. Two reference Jet A-1 with slightly different chemical parameters were applied and further used in combination with a Fischer-Tropsch synthetic paraffinic kerosene (FT-SPK) to prepare three semi synthetic jet fuels (SSJF) of different aromatic content. In addition, one commercially available fully synthetic jet fuel (FSJF) featured the lowest aromatic content of the fuel selection. Neither the release of nitrogen oxide or carbon monoxide was significantly affected by the different fuel composition. The measured particle emission indices showed a reduction up to 50% (number) and 70% (mass) for two alternative jet fuels (FSJF, SSJF2) at low power settings in comparison to the reference fuels. The reduction is less pronounced at higher operating conditions but the release of particle number and particle mass is still significantly lower for the alternative fuels than for both reference fuels. The observed correlation between emitted particle mass and fuel aromatics is not strict. Here, the H/C ratio is a better indicator for soot emission.
Assuntos
Aviação , Emissões de Veículos , Dióxido de Carbono , Monóxido de Carbono , FuligemRESUMO
We report on a new method for analyzing atmospheric submicrometer particulate organic matter which combines direct particle sampling and volatilization with online chemical ionization mass spectrometric analysis. Technically, the method relies on the combined use of a CHARON ("Chemical Analysis of Aerosol Online") particle inlet and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). Laboratory studies on target analytes showed that the ionization conditions in the PTR-ToF-MS lead to extensive fragmentation of levoglucosan and cis-pinonic acid, while protonated oleic acid and 5α-cholestane molecules remain intact. Potential problems and biases in quantitative and qualitative analyses are discussed. Side-by-side atmospheric comparison measurements of total particulate organic mass and levoglucosan with an aerosol mass spectrometer (AMS) were in good agreement. Complex and clearly distinct organic mass spectra were obtained from atmospheric measurements in three European cities (Lyon, Valencia, Innsbruck). Data visualization in reduced-parameter frameworks (e.g., oxidation state of carbon vs carbon number) revealed that the CHARON-PTR-ToF-MS technique adds significant analytical capabilities for characterizing particulate organic carbon in the Earth's atmosphere. Positive matrix factorization (PMF) was used for apportioning sources of atmospheric particles in late fall in Innsbruck. The m/z signatures of known source marker compounds (levoglucosan and resin acids, polycyclic aromatic hydrocarbons, nicotine) in the mass spectra were used to assign PMF factors to biomass burning, traffic, and smoking emission sources.