Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy.

The functional group compositions of atmospheric aerosol water-soluble organic compoundswere obtained employing proton nuclear magnetic resonance (1H NMR) spectroscopy in a series of recent experiments in several areas of the world characterized by different aerosol sources and pollution levels. Here, we discuss the possibility of using 1H NMR functional group distributions to identifythe sources of aerosol in the different areas. Despite the limited variability of functional group compositions of atmospheric aerosol samples, characteristic 1H NMR fingerprints were derived for three major aerosol sources: biomass burning, secondary formation from anthropogenic and biogenic VOCs, and emission from the ocean. The functional group patterns obtained in areas characterized by one of the above dominant source processes were then compared to identify the dominant sources for samples coming from mixed sources. This analysis shows that H NMR spectroscopy can profitably be used as a valuable tool for aerosol source identification. In addition, compared to other existing methodologies, it is able to relate the source fingerprints to integral chemical properties of the organic mixtures, which determine their reactivity and their physicochemical properties and ultimately the fate of the organic particles in the atmosphere.

Biogenically driven organic contribution to marine aerosol.

Marine aerosol contributes significantly to the global aerosol load and consequently has an important impact on both the Earth's albedo and climate. So far, much of the focus on marine aerosol has centred on the production of aerosol from sea-salt and non-sea-salt sulphates. Recent field experiments, however, have shown that known aerosol production processes for inorganic species cannot account for the entire aerosol mass that occurs in submicrometre sizes. Several experimental studies have pointed to the presence of significant concentrations of organic matter in marine aerosol. There is some information available about the composition of organic matter, but the contribution of organic matter to marine aerosol, as a function of aerosol size, as well as its characterization as hydrophilic or hydrophobic, has been lacking. Here we measure the physical and chemical characteristics of submicrometre marine aerosol over the North Atlantic Ocean during plankton blooms progressing from spring through to autumn. We find that during bloom periods, the organic fraction dominates and contributes 63% to the submicrometre aerosol mass (about 45% is water-insoluble and about 18% water-soluble). In winter, when biological activity is at its lowest, the organic fraction decreases to 15%. Our model simulations indicate that organic matter can enhance the cloud droplet concentration by 15% to more than 100% and is therefore an important component of the aerosol-cloud-climate feedback system involving marine biota.

FTIR kinetic, product, and modeling study of the OH-initiated oxidation of 1-butanol in air.

A kinetic and product study was performed on the reaction of OH radicals with 1-butanol in a 480 L indoor photoreactor and also in the EUPHORE outdoor smog chamber in Valencia, Spain. Long path in situ FTIR spectroscopy and gas chromatography with photoionization detection were used to analyze reactants and products. Using a kinetic relative rate technique, a rate coefficient of k(OH + 1-butanol) = (8.28 +/- 0.85) x 10(-12) cm3 s(-1) was measured in 740 Torr synthetic air at 298 +/- 2 K. The reaction products observed and their fractional molar yields were (in percent) butanal (51.8 +/- 7.1), propanal (23.4 +/- 3.5), ethanal (12.7 +/- 2.2), and formaldehyde (43.4 +/- 2.4). In addition, the results support the probable formation of 4-hydroxy-2-butanone. Propanal, ethanal, and formaldehyde could also be formed in secondary reactions of some of the primary aldehydic products. However, under the conditions employed in the experiments, the contribution from secondary reactions is very minor. On the basis of the product studies, a detailed atmospheric degradation mechanism was constructed and tested against experimental data by chemical box model calculations. Measured and simulated concentration-time profiles for selected reactants were in excellent agreement.