[1] Size-segregated marine aerosols were collected at Mace Head Atmospheric Research Station (Ireland) during spring and autumn 2002 corresponding with the phytoplankton bloom periods in the North Atlantic. Strict control of the sampling, air mass back trajectory analysis, and analysis of pollutant tracers allowed the selection of a set of samples representative of clean marine conditions. A comprehensive chemical characterization of both (1) water-soluble and water-insoluble organic fraction and (2) water-soluble inorganic ions was performed. The selected samples illustrated a consistent picture in terms of chemical composition. The supermicron mode predominantly comprises sea-salt aerosol with a mass concentration of 10.16 ± 0.80 mg m À3 , the remainder being non-sea-salt (nss) sulphate, 0.03 ± 0.01 mg m À3 , and nitrate, 0.13 ± 0.04 mg m À3 . By comparison, the mass of sea salt, nss sulphate, and nitrate in the submicron mode is found to be 0.39 ± 0.08 mg m À3 , 0.26 ± 0.04 mg m À3 , and 0.02 ± 0.01 mg m À3 , respectively. Water-soluble organic carbon (WSOC) is observed in the submicron mode with a mass concentration of 0.25 ± 0.04 mg m À3 , comparable to that of nss sulphate, and in the supermicron mode with a mass concentration of 0.17 ± 0.04 mg m À3 . The WSOC to total carbon (TC) ratio is found to be 0.20 ± 0.12 for the submicron fraction and 0.29 ± 0.08 for the supermicron fraction, while the black carbon (BC) to TC ratio is, on average, 0.032 ± 0.001 for both aerosol modes. The remaining carbon, water-insoluble organic carbon, contributes 0.66 ± 0.11 mg m À3 and 0.26 ± 0.06 mg m À3 to the submicron and supermicron modes, respectively and, thus, represents the dominant submicron aerosol species. Furthermore, the WSOC chemical composition comprises mainly aliphatic and only partially oxidized species and humiclike substances, resulting in appreciable surface-active properties. The observed organic matter chemical features (size-dependent concentration, hydrophobic nature of a substantial fraction of the organic matter, and low oxidized and surface-active WSOC species) are consistent with the hypothesis of a primary marine source; bubble-bursting processes, occurring at the surface of the North Atlantic Ocean during phytoplankton blooms, effectively transfer organic matter into marine aerosol particles, particularly enriching the fine-aerosol fraction.

[1] The aerosol characterization experiment performed within the Large-Scale BiosphereAtmosphere Experiment in Amazonia-Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) field experiment carried out in Rondônia, Brazil, in the period from September to November 2002 provides a unique data set of size-resolved chemical composition of boundary layer aerosol over the Amazon Basin from the intense biomassburning period to the onset of the wet season. Three main periods were clearly distinguished on the basis of the PM 10 concentration trend during the experiment: (1) dry period, with average PM 10 well above 50 mg m À3 ; (2) transition period, during which the 24-hour-averaged PM 10 never exceeded 40 mg m À3 and never dropped below 10 mg m À3 ; (3) and wet period, characterized by 48-hour-averaged concentrations of PM 10 below 12 mg m À3 and sometimes as low as 2 mg m À3 . The trend of PM 10 reflects that of CO concentration and can be directly linked to the decreasing intensity of the biomass-burning activities from September through November, because of the progressive onset of the wet season. Two prominent aerosol modes, in the submicron and supermicron size ranges, were detected throughout the experiment. Dry period size distributions are dominated by the fine mode, while the fine and coarse modes show almost the same concentrations during the wet period. The supermicron fraction of the aerosol is composed mainly of primary particles of crustal or biological origin, whereas submicron particles are produced in high concentrations only during the biomass-burning periods and are mainly composed of organic material, mostly water-soluble, and $10% of soluble inorganic salts, with sulphate as the major anion. Size-resolved average aerosol chemical compositions are reported for the dry, transition, and wet periods. However, significant variations in the aerosol composition and concentrations were observed within each period, which can be classified into two categories: (1) diurnal oscillations, caused by the diurnal cycle of the boundary layer and the different combustion phase active during day (flaming) or night (smouldering); and (2) day-to-day variations, due to alternating phases of relatively wet and dry conditions. In a second part of the study, three subperiods representative of the JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 112, D01201, doi:10

Abstract. The chemical composition of carbonaceous aerosols collected during the LBA-SMOCC field experiment, conducted in Rondônia, Brazil, in 2002 during the transition from the dry to the wet season, was investigated by a suite of state-of-the-art analytical techniques. The period of most intense biomass burning was characterized by high concentrations of submicron particles rich in carbonaceous material and water-soluble organic compounds (WSOC). At the onset of the rainy period, submicron total carbon (TC) concentrations decreased by about 20 times. In contrast, the concentration of supermicron TC was fairly constant throughout the experiment, pointing to a constant emission of coarse particles from the natural background. About 6-8% of TC (9-11% of WSOC) was speciated at the molecular level by GC-MS and liquid chromatography. Polyhydroxylated compounds, aliphatic and aromatic acids were the main classes of compounds accounted for by individual compound analysis. Functional group analysis by proton NMR and chromatographic separation on ion-exchange columns allowed characterization of ca. 50-90% of WSOC into broad chemical classes (neutral species/light acids/humic-like substances). In spite of the significant change in the chemical composition of tracer compounds from the dry to the wet period, the functional groups and the general chemical classes of WSOC changed only to a small extent. Model compounds representing size-resolved WSOC chemical composition forCorrespondence to: S. Decesari (s.decesari@isac.cnr.it) the different periods of the campaign are then proposed in this paper, based on the chemical characterization by both individual compound analysis and functional group analysis deployed during the LBA-SMOCC experiment. Model compounds reproduce quantitatively the average chemical structure of WSOC and can be used as best-guess surrogates in microphysical models involving organic aerosol particles over tropical areas affected by biomass burning.

Abstract. The chemical composition of carbonaceous aerosols collected during the LBA-SMOCC field experiment, conducted in Rondônia, Brazil, in 2002 during the transition from the dry to the wet season, was investigated by a suite of advanced analytical techniques. The period of most intense biomass burning was characterized by high concentrations of submicron particles rich in carbonaceous material and water-soluble organic compounds (WSOC). At the onset of the rainy period, submicron total carbon (TC) concentrations had decreased by about 20 times. In contrast, the concentration of supermicron TC was fairly constant throughout the experiment, pointing to a constant emission of coarse particles from the natural background. About 6–8% of TC (9–11% of WSOC) was speciated at the molecular level by GC-MS and liquid chromatography. Poly-hydroxylated compounds, aliphatic and aromatic acids were the main classes of compounds accounted for by individual compound analysis. Functional group analysis by proton NMR and chromatographic separation on ion-exchange columns allowed characterization of ca. 50–90% of WSOC into broad chemical classes (neutral species/light acids/humic-like substances). In spite of the significant change in the chemical composition of tracer compounds from the dry to the wet period, the functional groups and the general chemical classes of WSOC changed only to a lesser extent. Model compounds representing size-resolved WSOC chemical composition for the different periods of the campaign are then proposed in this paper, based on the chemical characterization by both individual compound analysis and functional group analysis deployed during the LBA-SMOCC experiment. Model compounds reproduce quantitatively the average chemical structure of WSOC and can be used as best-guess surrogates in microphysical models involving organic aerosol particles over tropical areas affected by biomass burning.