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Abstract. This study presents measurements of acetonitrile, benzene, toluene, methanol and acetone made using the proton-transfer-reaction mass spectrometry (PTR-MS) technique at the Finokalia ground station in Crete during the Mediterranean INtensive Oxidant Study (MINOS) in JulyAugust 2001. Three periods during the campaign with broadly consistent back trajectories are examined in detail. In the first, air was advected from Eastern Europe without significant biomass burning influence (mean acetonitrile mixing ratio 154 pmol/mol). In the second period, the sampled air masses originated in Western Europe, and were advected approximately east-south-east, before turning southwest over the Black Sea and north-western Turkey. The third well-defined period included air masses advected from Eastern Europe passing east and south of/over the Sea of Azov, and showed significant influence by biomass burning (mean acetonitrile mixing ratio 436 pmol/mol), confirmed by satellite pictures. The mean toluene:benzene ratios observed in the three campaign periods described were 0.35, 0.37 and 0.22, respectively; the use of this quantity to determine air mass age is discussed. Methanol and acetone were generally well-correlated both with each other and with carbon monoxide throughout the campaign. Comparison of the acetone and methanol measurements with the MATCH-MPIC model showed that the model underestimated both species by a factor of 4, on average. The correlations between acetone, methanol and CO implied that the relatively high levels of methanol observed during MINOS were largely due to direct biogenic emissions, and also that biogenic sources of acetone were highly significant during MINOS (∼35%). This in turn suggests that the model deficit in both species may be due, at least in part, to missing biogenic emissions.

Abstract. An intensive field measurement campaign was performed in July/August 2002 at the Global Atmospheric Watch station Izaña on Tenerife to study the interaction of mineral dust aerosol and tropospheric chemistry (MINATROC). A dense Saharan dust plume, with aerosol masses exceeding 500 µg m-3, persisted for three days. During this dust event strongly reduced mixing ratios of ROx (HO2, CH3O2 and higher organic peroxy radicals), H2O2, NOx (NO and NO2) and O3 were observed. A chemistry boxmodel, constrained by the measurements, has been used to study gas phase and heterogeneous chemistry. It appeared to be difficult to reproduce the observed HCHO mixing ratios with the model, possibly related to the representation of precursor gas concentrations or the absence of dry deposition. The model calculations indicate that the reduced H2O2 mixing ratios in the dust plume can be explained by including the heterogeneous removal reaction of HO2 with an uptake coefficient of 0.2, or by assuming heterogeneous removal of H2O2 with an accommodation coefficient of 5x10-4. However, these heterogeneous reactions cannot explain the low ROx mixing ratios observed during the dust event. Whereas a mean daytime net ozone production rate (NOP) of 1.06 ppbv/hr occurred throughout the campaign, the reduced ROx and NOx mixing ratios in the Saharan dust plume contributed to a reduced NOP of 0.14-0.33 ppbv/hr, which likely explains the relatively low ozone mixing ratios observed during this event.

Abstract. Airborne measurements of acetone, methanol, PAN, acetonitrile (by Proton Transfer Reaction Mass Spectrometry), and CO (by Tunable Diode Laser Absorption Spectroscopy) have been performed during the Mediterranean Intensive Oxidants Study (MINOS August 2001). We have identified ten biomass burning plumes from strongly elevated acetonitrile mixing ratios. The characteristic biomass burning signatures obtained from these plumes reveal secondary production of acetone and methanol, while CO photochemically declines in the plumes. Mean excess mixing ratios -normalized to CO -of 1.8%, 0.20%, 3.8%, and 0.65% for acetone, acetonitrile, methanol, and PAN, respectively, were found. By scaling to an assumed global annual source of 663-807 Tg CO, biomass burning emissions of 25-31 and 29-35 Tg/yr for acetone and methanol are estimated, respectively. Our measurements suggest that the present biomass burning contributions of acetone and methanol are significantly underestimated due to the neglect of secondary formation within the plume. Median acetonitrile mixing ratios throughout the troposphere were around 150 pmol/mol, in accord with current biomass burning inventories and an atmospheric lifetime of ∼6 months.

[1] An observationally constrained box model has been used to investigate the chemistry of the marine boundary layer at the Mace Head Atmospheric Research Station, a remote site on the west coast of Ireland. The model aims to simulate concentrations of the hydroxyl (OH) and hydroperoxy (HO 2 ) radicals measured by an in situ fluorescence assay by gas expansion instrument, and the sum of peroxy radicals , respectively, between 1100 and 1500 hours: the level of agreement is better for all three sets of radicals in the cleanest air mass. Possible reasons for the observed discrepancies are discussed. In addition, a rate of production analysis is used to identify key OH and HO 2 reactions in the three air masses. The rate of OH production from HO 2 with NO exceeds that from ozone photolysis by factors of 2-6 in the polluted air masses studied. In cleaner air from the northern polar region, primary production from ozone photolysis exceeds that from HO 2 + NO by a factor of 2.5. HO 2 and CH 3 O 2 dominate the peroxy radical composition in all air masses, but peroxy radicals derived from the oxidation of nonmethane hydrocarbons are more important in polluted air masses.