ALBERT

Description: We describe the large-scale meteorological conditions that affected atmospheric chemistry over Mexico during March 2006 when several field campaigns were conducted in the region. In-situ and remote-sensing instrumentation was deployed to obtain measurements of wind, temperature, and humidity profiles in the boundary layer and free atmosphere at four primary sampling sites in central Mexico. Several models were run operationally during the field campaign to provide forecasts of the local, regional, and synoptic meteorology as well as the predicted location of the Mexico City pollutant plume for aircraft flight planning purposes. Field campaign measurements and large-scale analyses are used to define three regimes that characterize the overall meteorological conditions: the first regime prior to 14 March, the second regime between 14 and 23 March, and the third regime after 23 March. Mostly sunny and dry conditions with periods of cirrus and marine stratus along the coast occurred during the first regime. The beginning of the second regime was characterized by a sharp increase in humidity over the central plateau and the development of late afternoon convection associated with the passage of a weak cold surge on 14 March. Over the next several days, the atmosphere over the central plateau became drier so that deep convection gradually diminished. The third regime began with the passage of a strong cold surge that lead to humidity, afternoon convection, and precipitation over the central plateau that was higher than during the second regime. The frequency and intensity of fires, as determined by satellite measurements, also diminished significantly after the third cold surge. The synoptic-scale flow patterns that govern the transport of pollutants in the region are described and compared to previous March periods to put the transport into a climatological context. The complex terrain surrounding Mexico City produces local and regional circulations that govern short-range transport; however, the mean synoptic conditions modulate the thermally-driven circulations and on several days the near-surface flow is coupled to the ambient winds aloft.

Description: Surface pollutant concentrations in México City show a distinct pattern of weekly variations similar to that observed in many other cities of the world. Measurements of the concentrations of carbon monoxide (CO), nitrogen oxides (NOx=NO+NO2), particulate matter smaller than 10 μm (PM10), and ozone (O3) collected hourly over 22 years (1986–2007) at 32 urban monitoring locations were analyzed. Morning concentrations of CO, NOx, and PM10 are lower on Saturdays and even more so on Sundays, compared to workdays (Monday–Friday), while afternoon O3 concentrations change minimally and are occasionally even higher. This weekend effect is empirical evidence that photochemical O3 production is NOx-inhibited, and to the extent that emissions of CO are correlated with reactive volatile organic compounds (VOCs), it is VOC-limited, at least in the urban areas for which the monitoring stations are representative. The VOC-limitation has increased in the past decade, due to decreases in the concentrations of CO (and presumably VOCs) and consequent decreases in the CO/NOx and VOC/NOx ratios. Enhancements of photolysis frequencies resulting from smaller weekend aerosol burdens are not negligible, but fall short of being an alternate explanation for the observed weekend effect. The strength of the weekend effect indicates that local radical termination occurs primarily via formation of nitric acid and other NOx-related compounds, some of which (e.g. peroxy acyl nitrates) can contribute to the regional NOx budget. While VOC emission reductions would be most effective in reducing local O3 production, NOx emission reduction may be more important for controlling regional oxidants.

Description: The NO-NO2 system was analyzed in different chemical regimes/air masses based on observations of reactive nitrogen species and peroxy radicals made during the intensive field campaign MIRAGE-Mex (4 to 29 March 2006). In general, NO2/NO ratios, which can be used as an indicator to test current understanding of tropospheric chemistry mechanism, are near photostationary state. The air masses were categorized into 5 groups: boundary layer (labeled as "BL"), free troposphere (continental, "FTCO" and marine, "FTMA"), biomass burning ("BB"), and Tula industrial complex ("TIC"). The time- and air mass-dependent NO2/NO ratios ranged from 2.35 (TIC) to 5.18 (BB), while the NOx/NOy ratios varied from 0.17 (FTCO) to 0.54 (BL). The ozone production efficiency for the 5 air mass categories ranged from 5.0 (TIC) to 10.2 (BL), indicating photochemically young and reactive air masses.

Description: The present study investigates effects of wildfire emissions on air quality in Europe during an intense fire season that occurred in summer 2003. A meso-scale chemistry transport model CHIMERE is used, together with ground based and satellite aerosol optical measurements, to assess the dispersion of fire emissions and to quantify the associated radiative effects. The model has been improved to take into account a MODIS-derived daily smoke emission inventory as well as the injection altitude of smoke particles. The simulated aerosol optical properties are put into a radiative transfer model to estimate (off-line) the effects of smoke particles on photolysis rates and atmospheric radiative forcing. We have found that the simulated wildfires generated comparable amounts of primary aerosol pollutants (130 kTons of PM2.5, fine particles) to anthropogenic sources during August 2003, and caused significant changes in aerosol optical properties not only close to the fire source regions, but also over a large part of Europe as a result of the long-range transport of the smoke. Including these emissions into the model significantly improved its performance in simulating observed aerosol concentrations and optical properties. Quantitative comparison with MODIS and POLDER data during the major fire event (3–8 August 2003) showed the ability of the model to reproduce high aerosol optical thickness (AOT) over Northern Europe caused by the advection of the smoke plume from the Portugal source region. Although there was a fairly good spatial agreement with satellite data (correlation coefficients ranging from 0.4 to 0.9), the temporal variability of AOT data at specific AERONET locations was not well captured by the model. Statistical analyses of model-simulated AOT data at AERONET ground stations showed a significant decrease in the model biases suggesting that wildfire emissions are responsible for a 30% enhancement in mean AOT values during the heat-wave episode. The implications for air quality over a large part of Europe are significant during this episode. First, directly, the modeled wildfire emissions caused an increase in average PM2.5 ground concentrations from 20 to 200%. The largest enhancement in PM2.5 concentrations stayed, however, confined within a 200 km area around the fire source locations and reached up to 40 μg/m³. Second, indirectly, the presence of elevated smoke layers over Europe significantly altered atmospheric radiative properties: the model results imply a 10 to 30% decrease in photolysis rates and an increase in atmospheric radiative forcing of 10–35 W m−2 during the period of strong fire influence throughout a large part of Europe. These results suggest that sporadic wildfire events may have significant effects on regional photochemistry and atmospheric stability, and need to be considered in current chemistry-transport models.

Description: We describe the large-scale meteorological conditions that affected atmospheric chemistry over Mexico during March 2006 when several field campaigns were conducted in the region. In-situ and remote-sensing instrumentation was deployed to obtain measurements of wind, temperature, and humidity profiles in the boundary layer and free atmosphere at four primary sampling sites in central Mexico. Several models were run operationally during the field campaign to provide forecasts of the local, regional, and synoptic meteorology as well as the predicted location of the Mexico City pollutant plume for aircraft flight planning purposes. Field campaign measurements and large-scale analyses are used to define three regimes that characterize the overall meteorological conditions: the first regime prior to 14 March, the second regime between 14 and 23 March, and the third regime after 23 March. Mostly sunny and dry conditions with periods of cirrus and marine stratus along the coast occurred during the first regime. The beginning of the second regime was characterized by a sharp increase in humidity over the central plateau and the development of late afternoon convection associated with the passage of a weak cold surge on 14 March. Over the next several days, the atmosphere over the central plateau became drier so that deep convection gradually diminished. The third regime began with the passage of a strong cold surge that lead to humidity, afternoon convection, and precipitation over the central plateau that was higher than during the second regime. The frequency and intensity of fires, as determined by satellite measurements, also diminished significantly after the third cold surge. The synoptic-scale flow patterns that govern the transport of pollutants in the region are described and compared to previous March periods to put the transport into a climatological context. The complex terrain surrounding Mexico City produces local and regional circulations that govern short-range transport; however, the mean synoptic conditions modulate the thermally-driven circulations and on several days the near-surface flow is coupled to the ambient winds aloft.

Description: The objective of this work was to develop and assess an automatic procedure to generate reduced chemical schemes for the atmospheric photooxidation of volatile organic carbon (VOC) compounds. The procedure is based on (i) the development of a tool for writing the fully explicit schemes for VOC oxidation (see companion paper Aumont et al., 2005), (ii) the application of several commonly used reduction methods to the fully explicit scheme, and (iii) the assessment of resulting errors based on direct comparison between the reduced and full schemes. The reference scheme included seventy emitted VOCs chosen to be representative of both anthropogenic and biogenic emissions, and their atmospheric degradation chemistry required more than two million reactions among 350000 species. Three methods were applied to reduce the size of the reference chemical scheme: (i) use of operators, based on the redundancy of the reaction sequences involved in the VOC oxidation, (ii) grouping of primary species having similar reactivities into surrogate species and (iii) grouping of some secondary products into surrogate species. The number of species in the final reduced scheme is 147, this being small enough for practical inclusion in current three-dimensional models. Comparisons between the fully explicit and reduced schemes, carried out with a box model for several typical tropospheric conditions, showed that the reduced chemical scheme accurately predicts ozone concentrations and some other aspects of oxidant chemistry for both polluted and clean tropospheric conditions.

Description: Organic compounds emitted in the atmosphere are oxidized in complex reaction sequences that produce a myriad of intermediates. Although the cumulative importance of these organic intermediates is widely acknowledged, there is still a critical lack of information concerning the detailed composition of the highly functionalized secondary organics in the gas and condensed phases. The evaluation of their impacts on pollution episodes, climate, and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various phases down to the ultimate oxidation products, CO and CO2. However, a fully detailed representation of the atmospheric transformations of organic compounds involves a very large number of intermediate species, far in excess of the number that can be reasonably written manually. This paper describes (1) the development of a data processing tool to generate the explicit gas-phase oxidation schemes of acyclic hydrocarbons and their oxidation products under tropospheric conditions and (2) the protocol used to select the reaction products and the rate constants. Results are presented using the fully explicit oxidation schemes generated for two test species: n-heptane and isoprene. Comparisons with well-established mechanisms were performed to evaluate these generated schemes. Some preliminary results describing the gradual change of organic carbon during the oxidation of a given parent compound are presented.

Description: Surface measurements of direct and diffuse voltages at UV wavelengths were made at the T1 site during the MILAGRO (Megacity Initiative: Local and Global Research Observations) field campaign in March 2006, using a multifilter rotating shadowband radiometer (UV-MFRSR). We used the MFRSR data, together with measurements from a co-located CIMEL Sun photometer at the site operating as part of the AERONET network, to deduce aerosol single scattering albedo (ω) at 368 and 332 nm for four cloud-free days during the study. Our retrievals suggest that T1 aerosols with aerosol extinction optical depth τ368〉0.1 that are influenced by Mexico City emissions, blowing dust, and biomass burning, are characterized by low ω368=0.73–0.85 and ω332=0.70–0.86, with small or no spectral variation of ω between 368 and 332 nm. Our findings are consistent with other published estimates of ω for Mexico City aerosols, including those that suggest that the absorption attributable to these aerosols is enhanced at UV wavelengths relative to visible wavelengths. We also demonstrate, via sensitivity tests, the importance of accurate τ and surface albedo measurements in ω retrievals at UV wavelengths.

Description: The NO-NO2 system was analyzed in different chemical regimes/air masses based on observations of reactive nitrogen species and peroxy radicals made during the intensive field campaign MIRAGE-Mex (4 to 29 March 2006). The air masses were categorized into 5 groups based on combinations of macroscopic observations, geographical location, meteorological parameters, models, and observations of trace gases: boundary layer (labeled as "BL"), biomass burning ("BB"), free troposphere (continental, "FTCO" and marine, "FTMA"), and Tula industrial complex ("TIC"). In general, NO2/NO ratios in different air masses are near photostationary state. Analysis of this ratio can be useful for testing current understanding of tropospheric chemistry. The ozone production efficiency (OPE) for the 5 air mass categories ranged from 4.5 (TIC) to 8.5 (FTMA), consistent with photochemical aging of air masses exiting the Mexico City Metropolitan Area.