Effects of various meteorological conditions and spatial emission resolutions on the ozone concentration & ROG/NO_x limitation in the Milan area (I)

International audienceThe three-dimensional photochemical model UAM-V is used to investigate the effects of various meteorological conditions and of the coarseness of emission inventories on the ozone concentration and ROG/NOx limitation of the ozone production in the Po Basin in the northern part of Italy. As a base case, the high ozone episode with up to 200 ppb on 13 May 1998 was modelled and previously thoroughly evaluated with measurements gained during a large field experiment. The performed variations in meteorology are applied to mixing height, air temperature, specific humidity and wind speed. Three coarser emission inventories are obtained by resampling from 3×3 km2 up to 54×54 km2 emission grids. The model results show that changes in meteorological input files have the largest effect on peak ozone. In the modelled ozone plume a slope of 10.1 ppb ozone/°C and in Milan of 2.8 ppb ozone/°C were found. The net ozone formation in northern Italy is more strongly temperature than humidity dependent, while the humidity is very important for the ROG/NOx limitation of the ozone production. For each of the meteorological variations (e.g. doubling the mixing height), the modelled ozone plume remains ROG limited for this case. A strong change towards NOx sensitivity in the ROG limited areas is only found if much coarser emission inventories were applied. Increasing ROG limited areas with increasing wind speed are found, because the ROG limited ozone chemistry induced by point sources is spread over a larger area. Simulations without point sources tend to increase the NOx limited areas

Effects of various meteorological conditions and spatial emissionresolutions on the ozone concentration and ROG/NO_x limitationin the Milan area (I)

The three-dimensional photochemical model UAM-V is used to investigate the effects of various meteorological conditions and of the coarseness of emission inventories on the ozone concentration and ROG/NO_x limitation of the ozone production in the Po Basin in the northern part of Italy. As a base case, the high ozone episode with up to 200ppb on 13 May 1998 was modelled and previously thoroughly evaluated with measurements gained during a large field experiment. Systematic variations in meteorology are applied to mixing height, air temperature, specific humidity and wind speed. Three coarser emission inventories are obtained by resampling from 3x3km² up to 54x54km² emission grids. The model results show that changes in meteorological input files strongly influence ozone in this area. For instance, temperature changes peak ozone by 10.1ppb/&degC and the ozone concentrations in Milan by 2.8ppb/&degC. The net ozone formation in northern Italy is more strongly temperature than humidity dependent, while the humidity is very important for the ROG/NO_x limitation of the ozone production. For all meteorological changes (e.g. doubling the mixing height), the modelled peak ozone remains ROG limited. A strong change towards NO_x sensitivity in the ROG limited areas is only found if much coarser emission inventories were applied. Increasing ROG limited areas with increasing wind speed are found, because the ROG limited ozone chemistry induced by point sources is spread over a larger area. Simulations without point sources tend to increase the NO_x limited areas

Volatile Organic Compounds in the Po Basin. Part A: Anthropogenic VOCs

Measurements of volatile organic compounds (VOCs) were performed in the Po Basin, northern Italy in early summer 1998 within the PIPAPO project as well as in summer 2002 and autumn 2003 within the FORMAT project. During the three campaigns, trace gases and meteorological parameters were measured at a semi-rural station, around 35 km north of the city center of Milan. Low toluene and benzene concentrations and lower toluene to benzene ratios on weekends, on Sundays, and in August enabled the identification of a ‘weekend' and a ‘vacation' effect when anthropogenic emissions were lower due to less traffic and reduced industrial activities, respectively. Recurrent nighttime cyclohexane peaks suggested a periodical short-term release of cyclohexane close to the semi-rural sampling site. A multivariate receptor model analysis resulted in the distinction of different characteristic concentration profiles attributed to natural gas, biogenic impact, vehicle exhaust, industrial activities, and a single cyclohexane sourc

The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide

Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ<sup>13</sup>C and δ<sup>18</sup>O) for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NO<sub>x</sub>-concentration, aerosol light absorption at different wavelengths). We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ<sup>18</sup>O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ<sup>18</sup>O-variations of CO with an amplitude of up to 8‰. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air) resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NO<sub>x</sub>-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NO<sub>x</sub> emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ<sup>18</sup>O-values of CO was found (<i>r</i>=0.67, <i>p</i><0.001). While different proxies for wood combustion all have their uncertainties, our results indicate that the oxygen isotope ratio of CO (but not the carbon isotope ratio) is an independent sensitive tool for source attribution studies

Volatile Organic Compounds in the Po Basin. Part B: Biogenic VOCs

Measurements of volatile organic compounds (VOCs) were performed in the Po Basin, northern Italy in early summer 1998, summer 2002, and autumn 2003. During the three campaigns, trace gases and meteorological parameters were measured at a semi-rural station, around 35 km north of the city center of Milan. Bimodal diurnal cycles of isoprene with highest concentrations in the morning and evening were found and could be explained by the interaction of emissions, chemical reactions, and vertical mixing. The diurnal cycle could be qualitatively reproduced by a three-dimensional Eulerian model. The nighttime decay of isoprene could be attributed mostly to reactions with NO3, while the decay of the isoprene oxidation products could not be explained with the considered chemical reactions. Methanol reached very high mixing ratios, up to 150 ppb. High concentrations with considerable variability occurred during nights with high relative humidities and low wind speeds. The origin of these nighttime methanol concentrations is most likely local and biogenic but the specific source could not be identifie

Flux measurements of biogenic VOCs during ECHO 2003

International audienceWithin the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany using the eddy covariance (EC) technique. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. As a consequence, a considerable fraction of the measurements did not qualify for flux calculations by EC and had to be discarded. The validated results show light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average emissions (normalised to 30°C and 1000 µmoles m?2 s?1 PAR) of 1.5 and 0.39 µg m?2 s?1, respectively. Emissions of methanol reached on average 0.087 µg m?2 s?1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also found, being two orders of magnitude lower than those of isoprene. The observed fluxes are consistent with upscalings from leaf-level emission measurements of representative tree species in this forest and, in the case of MVK and MACR, can plausibly be explained by chemical production through oxidation of isoprene within the canopy. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement

Formation of highly oxygenated organic molecules from aromatic compounds

Anthropogenic volatile organic compounds (AV-OCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O:C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AV-OCs may contribute substantially to new particle formation events that have been detected in urban areas.Peer reviewe