The local and regional atmospheric oxidants at Athens (Greece)

In the present study, the investigation of the levels of the local and regional oxidants concentration at Athens, Greece, is attempted by analyzing the observations obtained at an urban and a rural station, during 2001–2011 and 2007–2011, respectively. A progressive increase of the daytime and nighttime average of [NO₂]/[O_x] versus [NO_x] is observed showing a larger proportion of O_x in the form of NO₂ when the level of NO_x increases. Similar results are observed when studying the variation of mean values of [NO₂]/[NO_x] versus [NO_x]. The results obtained when compared with those that have earlier detected elsewhere, revealed similarities and discrepancies that are discussed in detail. The parameterized curves that are presented for the first time in this paper may be used by the air quality planners to track the trends in other cities also, and to understand what is or was driving them.     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Particulate Air Pollution in Mexico City: A Collaborative Research Project

ABSTRACT

PM₁₀, PM₂₅, precursor gas, and upper-air meteorological measurements were taken in Mexico City, Mexico, from February 23 to March 22, 1997, to understand concentrations and chemical compositions of the city's particulate matter (PM). Average 24-hr PM₁₀ concentrations over the period of study at the core sites in the city were 75 H g/m³. The 24-hr standard of 150 μ g/m³ was exceeded for seven samples taken during the study period; the maximum 24-hr concentration measured was 542 μ g/m³. Nearly half of the PM₁₀ was composed of fugitive dust from roadways, construction, and bare land. About 50% of the PM₁₀ consisted of PM_2.5, with higher percentages during the morning hours. Organic and black carbon constituted up to half of the PM_2.5. PM concentrations were highest during the early morning and after sunset, when the mixed layers were shallow. Meteorological measurements taken during the field campaign show that on most days air was transported out of the Mexico City basin during the afternoon with little day-to-day carryover.     

The impact of megacity pollution on local climate and implications for the regional environment: Mexico City

We present calculations to estimate potential changes to the local climate and photochemistry caused by pollutants (gases and particles) produced in Mexico City, and the implications for the regional scale when pollutants are exported to surrounding regions. Measured aerosol optical properties are used in a 2-stream delta-Eddington radiative transfer model (Slingo and Schrecker, 1982. Quarterly Journal of the Royal Meteorological Society 108, 407–426) to estimate net radiative fluxes and heating rates, while photolysis rates for nitrogen dioxide and ozone are estimated from a much more detailed model (Madronich, 1987. Journal of Geophysical Research 92, 9740–9752). The presence of highly absorbing aerosols in Mexico City leads to a 17.6% reduction in solar radiative flux at the surface when an optical depth of 0.55 is considered. Photolysis rates for nitrogen dioxide and ozone are reduced between 18 and 21% at the surface, while an increase of between 15 and 17% is predicted above the boundary layer, for local noon calculations.The non-uniform vertical structure of aerosol concentrations observed (Pérez Vidal and Raga, 1998. Atmosfera 11, 95–108) plays a significant role in determining localized regions of heating, i.e. stabilization at the top of the boundary layer that results in a temperature increase of 0.4K h⁻¹ at that level. The presence of a 200 m-deep aerosol layer at the top of the boundary layer results in vertical profiles of the photolysis rates that are significantly different from the case where the aerosols are uniformly distributed in the mixed layer. At the bottom of the aerosol layer (about 1 km above the surface), the rates are about 28% lower than when there is a uniform aerosol distribution in the boundary layer. Finally, there is also an enhancement of photolysis rates at the top of the boundary layer that may lead to increased ozone production compared to the non-aerosol case.     

Measurement and modeling of O3 variability in Shanghai,China: Application of the WRF-Chem model

Since 2005, Shanghai Meteorological Bureau (SMB) has established an observational network for measuring VOC, NO_x, O₃ and aerosols in the Shanghai region. In this study, a rapid O₃ changes from Aug/02/2007 to Aug/11/2007 was observed in the region. During this 10 day period, the noontime O₃ maximum decreased from 100 to 130 ppbv to about 20–30 ppbv. In order to analyze the processes in controlling this rapid change of O₃ during this short period, a newly developed regional chemical/dynamical model (WRF-Chem) is applied to study O₃ variability in the Shanghai region. The model performances are evaluated by comparing the model calculation to the measurement. The result shows that the calculated magnitudes and diurnal variations of O₃ are close to the measured results in city sites, but are underestimated at a rural petroleum industrial site, suggesting that the emissions from petroleum factories around this rural site are significantly underestimated and need to be improved. The calculated rapid changes of O₃ concentrations, O₃ precursors, and aerosols are consistent with the measured results, suggesting that the model is suitable to study the causes of this rapid O₃ change. The model analysis indicates that weather conditions play important roles in controlling the surface O₃ in the Shanghai region. During summer, there is a persistent sub-tropical high pressure system (SUBH) in southeast of Shanghai over Pacific Ocean. During the earlier time of the period (Aug/02–Aug/05), the SUBH system was weak, resulting in weak surface winds. With the calm winds, a noticeable noontime sea-breeze produced an inflow from ocean to land, generating a cycling pattern of wind directions. As a result, the high O₃ concentrations were trapped in the Shanghai region, with a maximum concentration of 100–130 ppbv. By contrast, during the later time of the period (Aug/06–Aug/11), the SUBH was enhanced, resulting in strong surface winds. The high O₃ concentrations formed in the city were rapidly transported to the downwind region of the city, resulting in low O₃ concentrations in the Shanghai region. This study illustrates that the WRF-Chem model is a useful tool for studying the high variability of O₃ concentrations in Shanghai, which has important implication for the prediction of high O₃ concentration events in the city.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Decline of sacred fir (Abies religiosa) in a forest park south of Mexico City

Decline of sacred fir (Abies religiosa) trees in the high elevation forest park, Desierto de los Leones, located south of Mexico City, is described. Trees located in the windward zone (exposed to air masses from Mexico City) were the most severely affected, especially trees at the distal ends of ravines. Examination of tree growth rings indicated decreases in ring widths for the past 30 years. Polluted air from Mexico City may be an important causal factor in fir decline. Drought, due to excessive removal of soil water, insects, mites and pathogens, and poor forest management are possible contributing and interactive factors in fir decline.     

Satellite observations of Mexico City pollution outflow from the Tropospheric Emissions Spectrometer (TES)

Concurrent tropospheric O₃ and CO vertical profiles from the Tropospheric Emission Spectrometer (TES) during the MILAGRO/INTEX-B aircraft campaigns over the Mexico City Metropolitan Area (MCMA) and its surrounding regions were used to examine Mexico City pollution outflow on a regional scale. The pollution outflow from the MCMA occurred predominantly at 600–800 hPa as evident in O₃, CO, and NO_x enhancements in the in situ aircraft observations. TES O₃ and CO are sensitive to the MCMA pollution outflow due to their relatively high sensitivities at 600–800 hPa. We examined O₃, CO, and their correlation at 600–800 hPa from TES retrievals, aircraft measurements, and GEOS-Chem model results. TES captures much of the spatial and day-to-day variability of O₃ seen in the in situ data. TES CO, however, shows much less spatial and day-to-day variability compared with the in situ observations. The ΔO₃/ΔCO slope is significantly higher in the TES data (0.43) than the in situ data (0.28) due partly to the lack of variability in TES CO. Extraordinarily high ΔO₃/ΔCO slope (0.81) from TES observations at 618 hPa over the Eastern U.S. was previously reported by Zhang et al. [Zhang, L., Jacob, D.J., Bowman, K.W., et al., 2006. Ozone–CO correlations determined by the TES satellite instrument in continental outflow regions. Geophys. Res. Lett. 33, L18804. 10.1029/2006GL026399.]. Thus the application of TES CO–O₃ correlation to map continental pollution outflow needs further examination.     

Preliminary study of the determination of ambient carbonyls in Xalapa City,Veracruz, Mexico

A preliminary study of ambient carbonyls was performed in Xalapa City to measure carbonyls in the atmosphere of this City, because it has an explosive increase in population and traffic density, but few industries. The city is located at the eastern flanks of the Sierra Madre Oriental, between 1350 and 1550 m above sea level. Acetone was the most abundant carbonyl in June, followed by formaldehyde and acetaldehyde, whereas acetaldehyde was the most abundant one in November. Higher concentrations were observed in autumn than in spring, probably due to stagnation conditions in autumn and heavy rains from late spring to early autumn. The very high concentrations of acetaldehyde found in November could have been caused by an accidental leak or spill from a truck, since no stationary sources were identified and acetaldehyde concentrations steeply rose and constantly decreased after few days. Moreover, a highly transited highway traverses Xalapa. The most important ozone and carbon monoxide concentrations were below the Mexican Air Quality Standards; 216 μg m⁻³ (0.11 ppm) for 1 h average and 12.6 mg m⁻³ (11 ppm) for 8 h moving average, respectively. The low concentrations of the main carbonyls, compared with the values reported for other urban areas, and of carbon monoxide, seem to indicate that air quality is still satisfactory in Xalapa City.     

A pesticide emission model (PEM) Part I: model development

The application of pesticides to cultivated soil and crops is a major source of pesticides that are found in the atmosphere and which are transported and deposited to land and water surfaces over distances that range from local to global scales. In this first part of a two-part paper, a pesticide emission model (PEM) is proposed for estimating the exchange with the atmosphere of pesticides applied to soils and crops. The basis of PEM is a one-dimensional numerical solution of the dynamic equations describing the advection and diffusion of heat, moisture and pesticide within the soil column and exchange with the atmosphere through heat transfer, evapotranspiration and volatilization. The soil model is coupled with an atmospheric surface layer and a simple canopy model that includes: the interception of sprayed pesticide by the crop foliage; the partitioning of pesticide within a wet or dry canopy; and, the volatilization of pesticide to the atmosphere or the wash-off to the soil by precipitation. The finite-element technique used for solving the model equations is mass conservative and multi-year periods of simulation are possible while maintaining a proper mass balance of pesticide in the soil. The model is solved using 1200 s time-steps and 49 variably spaced levels in the soil to a depth of 2 m, with the highest vertical resolution (0.002 m spacing) near the soil surface. Similarity theory is used to parameterize the fluxes of heat, moisture and pesticide through the atmospheric surface layer with hourly meteorology being provided by either climate station observations or a meteorological model. In the second part to this paper, the results of an evaluation of PEM are reported.     

A pesticide emission model (PEM) Part II: model evaluation

In the first part of the paper, the development of a numerical pesticide emission model (PEM) is described for predicting the volatilization of pesticides applied to agricultural soils and crops through soil incorporation, surface spraying, or in the furrow at the time of planting. In this paper the results of three steps toward the evaluation of PEM are reported. The evaluation involves: (i) verifying the numerical algorithms and computer code through comparison of PEM simulations with an available analytical solution of the advection/diffusion equation for semi-volatile solutes in soil; (ii) comparing hourly heat, moisture and emission fluxes of trifluralin and triallate modeled by PEM with fluxes measured using the relaxed eddy-accumulation technique; and (iii) comparison of the PEM predictions of persistence half-life for 29 pesticides with the ranges of persistence found in the literature. The overall conclusion from this limited evaluation study is that PEM is a useful model for estimating the volatilization rates of pesticides from agricultural soils and crops. The lack of reliable estimates of chemical and photochemical degradation rates of pesticide on foliage, however, introduces large uncertainties in the estimates from any model of the volatilization of pesticide that impacts the canopy.     

Chemical composition of fugitive dust emitters in Mexico City

The gravimetric and chemical composition of fugitive dust emitters of Mexico City were analyzed to determine the particulate matter source profiles. Samples of geological material, unpaved and paved roads, agricultural soil, dried lake, asphalt, cement plants, landfill, gravel, and tezontle soil, were collected directly from the ground using a broom and a dustpan. These were dried, sieved and taken through a laboratory resuspension chamber to emulate the natural wind-blown processes of bulk soils and also to provide a uniform deposit on Teflon membrane and quartz fiber filters for further gravimetric and chemical analyses of PM_2.5 and PM₁₀ size fractions. Chemical analyses of the filters included X-ray fluorescence for elemental composition, ion chromatography for water soluble anions, atomic absorption for water soluble metals, automated colorimetric analysis for ammonium and thermal/optical reflectance analysis for carbon species. The data show that most fugitive emitters are composed of 20–30% PM_2.5, which is relatively less than the reported contribution by fossil fuels and biomass (40–60%).     

Fuel reformulation in the Metropolitan Area of Mexico City

Two models frequently used to simulate the dispersion of pollutants in the atmosphere have been compared. This is necessary because only a well-tested and well-calibrated simulation model can be a good representation of the reality of the dispersion of pollutants. The models evaluated (HYSPLIT_4 with its four variants and MEDIA) were run using as input parameters the same meteorological dataset (for 23-26 October 1994) from the French model ARPEGE. The following statistical criteria were compared: the space and time evolution of the pollutant cloud; the variation of statistical parameters in time and space; and the differences between the simulated and measured values of concentration in time for six different stations. The results emphasise the characteristics of the two models and their abilities in the framework of the air quality monitoring.     

Long-term efficiency of catalytic converters operating in Mexico City

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones. The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NOx emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure FTP-75. Our results suggest that the replacement of old catalytic converters with new ones will have little effect on decreasing polluting emissions because these vehicles were in very bad mechanical condition. Results of catalytic activity as a function of mileage indicated inefficient catalyst performance for the fleets tested. All pollutant conversions were below 90% efficiency, and they deteriorated by an average of 30% after the vehicles were run for 100,000 km.     

Long-Term Efficiency of Catalytic Converters Operating in Mexico City

ABSTRACT

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones.

The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NO_x emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure     

Some aspects of boundary layer evolution in Mexico City

Measurements of chemical species and meteorological parameters were made at a site located 440 m above the mean basin level of Mexico City, over a two-week period in November during Project Azteca. Data from three of the stations of Mexico City's air quality monitoring network (Red Automática de Monitoreo Ambiental, RAMA) were also used to estimate the dilution in concentration experienced by pollutants as they are transported upslope during the course of the day. Both carbon monoxide and sulfur dioxide show a dilution of up to 50%, while ozone is usually more concentrated at the elevated site. These comparisons clearly highlight the intrinsic differences between primary and secondary gases, which are supported also by time–space, cross correlation analysis. The thermal mesoscale wind circulation dominates concentrations of pollutants at the research site: upslope during the day and downslope during the night. The data present clear evidence that downslope flows during the night contribute to ozone concentration at basin sites.     

Variation of Different Pollutants in the Atmosphere of Mexico City

The first regional warning system was developed by the New York-New Jersey Cooperative Committee on Air Pollution and was put into operation in 1964. In 1967, new criteria were adopted based on recommendations of a workshop sponsored by City College of New York at the request of State agencies. With the passage of time, it has been recognized that the criteria necessary to call an alert required updating and strengthening. In recognition of this, the Commission sponsored a workshop of government officials to evaluate the criteria and levels of the sulfur dioxide, carbon monoxide, and particulate parameters used in the system and to consider the addition of other parameters.     

Fine Particle Receptor Modeling in the Atmosphere of Mexico City

Abstract

Source apportionment analyses were carried out by means of receptor modeling techniques to determine the contribution of major fine particulate matter (PM_2.5) sources found at six sites in Mexico City. Thirty-six source profiles were determined within Mexico City to establish the fingerprints of particulate matter sources. Additionally, the profiles under the same source category were averaged using cluster analysis and the fingerprints of 10 sources were included. Before application of the chemical mass balance (CMB), several tests were carried out to determine the best combination of source profiles and species used for the fitting. CMB results showed significant spatial variations in source contributions among the six sites that are influenced by local soil types and land use. On average, 24-hr PM_2.5 concentrations were dominated by mobile source emissions (45%), followed by secondary inorganic aerosols (16%) and geological material (17%). Industrial emissions representing oil combustion and incineration contributed less than 5%, and their contribution was higher at the industrial areas of Tlalnepantla (11%) and Xalostoc (8%). Other sources such as cooking, biomass burning, and oil fuel combustion were identified at lower levels. A second receptor model (principal component analysis, [PCA]) was subsequently applied to three of the monitoring sites for comparison purposes. Although differences were obtained between source contributions, results evidence the advantages of the combined use of different receptor modeling techniques for source apportionment, given the complementary nature of their results. Further research is needed in this direction to reach a better agreement between the estimated source contributions to the particulate matter mass.     

The influence of aerosols on photochemical smog in Mexico City

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J_NO2) for the key reaction NO₂+hν→NO+O (λ<430 nm). The calculated values are in good agreement with previously published measurements of J_NO2at two sites in Mexico City: Palacio de Minerı́a (19°25′59″N, 99°07′58″W, 2233 masl), and IMP (19°28′48″N, 99°11′07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03′N, 99°14′W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J_NO2 by 10–30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.     

Developing intake fraction estimates with limited data: Comparison of methods in Mexico City

In order to estimate the health benefits of reducing mobile source emissions, analysts typically use detailed atmospheric models to estimate the change in population exposure that results from a given change in emissions. However, this may not be feasible in settings where data are limited or policy decisions are needed in the short term. Intake fraction (iF), defined as the fraction of emissions of a pollutant or its precursor that is inhaled by the population, is a metric that can be used to compare exposure assessment methods in a health benefits analysis context. To clarify the utility of rapid-assessment methods, we calculate particulate matter iFs for the Mexico City Metropolitan Area using five methods, some more resource intensive than others. First, we create two simple box models to describe dispersion of primary fine particulate matter (PM_2.5) in the Mexico City basin. Second, we extrapolate iFs for primary PM_2.5, ammonium sulfate, and ammonium nitrate from US values using a regression model. Third, we calculate iFs by assuming a linear relationship between emissions and population-weighted concentrations of primary PM_2.5, ammonium nitrate, and ammonium sulfate (a particle composition method). Finally, we estimate PM iFs from detailed atmospheric dispersion and chemistry models run for only a short period of time. Intake fractions vary by up to a factor of five, from 23 to 120 per million for primary PM_2.5. Estimates of 60, 7, and 0.7 per million for primary PM, secondary ammonium sulfate, and secondary ammonium nitrate, respectively, represent credible central estimates, with an approximate factor of two uncertainty surrounding each estimate. Our results emphasize that multiple rapid-assessment methods can provide meaningful estimates of iFs in resource-limited environments, and that formal uncertainty analysis, with special attention to model biases and uncertainty, would be important for health benefits analyses.