SSCI-VIDE+ATARI:CARE+BNO:BDAInternational audienc

Highly oxygenated compounds assigned to be oxidation products of α‐pinene have recently been observed in substantial concentrations in ambient aerosols. Here, we confirm the unknown α‐pinene tracer compound with molecular weight (MW) 204 as the C8‐tricarboxylic acid 3‐methyl‐1,2,3‐butanetricarboxylic acid. Its gas and liquid chromatographic behaviors and its mass spectral characteristics in electron ionization and negative ion electrospray ionization perfectly agree with those of a synthesized reference compound. The formation of this compound is explained by further reaction of cis‐pinonic acid involving participation of the OH radical. This study illustrates that complex, multi‐generation chemistry holds for the photooxidation of α‐pinene in the presence of NOx.

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[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

Detailed organic analysis of fine (PM2.5) rural aerosol collected during summer at K-puszta, Hungary from a mixed deciduous/coniferous forest site shows the presence of polar oxygenated compounds that are also formed in laboratory irradiated alpha-pinene/NOx/air mixtures. In the present work, two major photooxidation products of alpha-pinene were characterized as the hydroxydicarboxylic acids, 3-hydroxyglutaric acid, and 2-hydroxy-4-isopropyladipic acid, based on chemical, chromatographic, and mass spectral data. Different types of volatile derivatives, including trimethylsilyl ester/ether, methyl ester trimethylsilyl ether, and ethyl ester trimethylsilyl ether derivatives were measured by gas chromatography/mass spectrometry (GC/MS), and their electron ionization (El) spectra were interpreted in detail. The proposed structures of the hydroxydicarboxylic acids were confirmed or supported with reference compounds. 2-Hydroxy-4-isopropyladipic acid formally corresponds to a further reaction product of pinic acid involving addition of a molecule of water and opening of the dimethylcyclobutane ring; this proposal is supported by a laboratory irradiation experiment with alpha-pinene/NOJ0 air. In addition, we report the presence of a structurally related minor alpha-pinene photooxidation product, which was tentatively identified as the C7 homolog of 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid. The detection of 2-hydroxy-4-isopropyladipic acid in ambient aerosol provides an explanation for the relatively low atmospheric concentrations of pinic acid found during daytime in forest environments.