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.     

Modeling Inorganic Aerosols and Their Response to Changes in Precursor Concentration in Mexico City

Abstract

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM_2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM_2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

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.     

Tethered balloon-based soundings of ozone,aerosols, and solar radiation near Mexico City during MIRAGE-MEX

A tethered balloon sampling system was used to measure vertical profiles of ozone, particles, and solar radiation in the atmospheric boundary layer on the northern edge of Mexico City, in March 2006 as part of the Megacity Impact on Regional and Global Environment-Mexico experiment. Several commercial sensors, designed for surface applications, were deployed on a tethered balloon platform.Profiles indicate that for these 3 scalars the boundary layer (surface up to 700 m) was well mixed in the period 10:00–16:00 LST. Good agreement was observed for median surface and balloon ozone and particle number concentrations. For most profiles, the surface deposition of ozone was not significant compared to median profile concentrations. Particle number concentration (0.3, 0.5, 1.0 and 5.0 μm) also showed little variation with attitude. Radiatprofiles showed a monotonic increase in diffuse radiation from the maximum altitude of profiles to the surface. Consequently, it was inferred that surface measurements of these likely were representative of lower boundary layer values during this time period.     

Study of radioactive contamination in silts and aerosols at Aldama City,Mexico, due to the operation of a yellow-cake processing plant

The city of Aldama, Chihuahua, Mexico is located 30 km NNE of Chihuahua city. Three high-volume collectors with PM₁₀ heads were placed in specific locations in Aldama during the year 2011 to measure radioisotope concentrations in the air. The city area of 16 km² was divided into 64 squares of 500 × 500 m. At the vertices of the grid, silt samples were taken between January and June 2011, before the rains began. The concentrations of natural, cosmogenic, and anthropogenic radioactive isotopes were calculated in both filters and silts samples. The isotopes selected for the measurement were ²³⁸U, ²³²Th, ⁷Be, ¹³⁷Cs, and ⁴⁰K. Measurements of PM₁₀ and silts were performed during 2011, coinciding with the accident at Fukushima, Japan, on March 11. For this reason, we could see the ¹³⁷Cs in PM₁₀ increase between April and July; with the arrival of the rains, the ¹³⁷Cs concentration began to decrease in the air. The concentration of PM₁₀ measured by the equipment located at the Mexican Uranium plant (URAMEX, initials in Spanish) that was processing radioactive ores exceeded the standard values in February and March, when the air velocity increases. At City Hall, the concentration of PM₁₀ surpassed the value of the standard between May and July. This increased concentration is likely due to increased automobile traffic because City Hall is located in the city center. At a private home, the concentration of PM₁₀ surpassed the standard on several days during the year because the home is located on the outskirts of the city, where most of the streets are not paved. Due to the high concentrations of PM₁₀, especially at the collection point located at the private home, it is necessary to start taking steps to mitigate their spread before they cause health problems in the younger population and in older adults.

Implications: The radioisotope content found in the PM₁₀ confirms that the decision to place the Mexican Uranium plant (URAMEX, initials in Spanish) processing radioactive ores near the town of Aldama was not well thought out. Because the monitoring work was carried out in 2011 and coincided with the Fukushima accident, an increased concentration of ¹³⁷Cs could be detected in the PM₁₀. We made recommendations to the municipal authorities of the city to mitigate the concentration of particles in the air.     

Absolute principal component analysis of atmospheric aerosols in Mexico city

A receptor model is presented based on absolute principal component analysis (APCA) of elemental concentrations in atmospheric aerosols from Mexico City during the Summer of 1995. Elemental contents on samples collected with a Stacking Filter Unit of the Davis design was carried out using Particle Induced X-ray Emission (PIXE). The sampling device allowed the separation of particles with mean aerodynamic diameters ranging from 2.5 μm to 15 μm (coarse fraction) and smaller than 2.5 μm (fine fraction). Sampling was divided into morning, afternoon and night periods, with higher concentrations being found during the morning. Seasonal variation is observed when comparisons with other studies are carried out. The application of APCA allowed identification of four sources for each fraction, with a soil-derived dust predominance in the coarse one. The influence of meteorological parameters is studied using cluster analysis, showing that during the morning there is a transport of pollutants from the west towards the sampling site, while the night transport corresponds to soil-derived dust from the north.     

Mice exposure to tannery effluents changes their olfactory capacity,and their response to predators and to the inhibitory avoidance test

Environmental Science and Pollution Research - The current study has assessed whether the oral and/or dermal exposure of C57Bl/6 J mice to tannery effluent (a complex pollutant consisting of...     

Estimating middle-, neighborhood-, and urban-scale contributions to elemental carbon in Mexico City with a rapid response aethalometer.

A successive moving average subtraction method is developed and applied to black carbon measured over 5-min intervals at a downtown location near many small emitters and at a suburban residential site within the urban plume but distant from specific emitters. Short-duration pulses assumed to originate from nearby sources are subtracted from the concentrations at each site and are summed to estimate middle-scale (approximately 0.1-1 km) contributions. The difference of the remaining baselines at the urban and suburban monitors is interpreted as the contribution to the downtown monitor from source emissions mixed over a neighborhood scale (1-5 km). The baseline at the suburban site is interpreted as the contribution of the mixture of black carbon sources for the entire city. When applied to a 24-day period from February and March 1997 in Mexico City, the analysis showed that 65% of the 24-hr black carbon was part of the urban mixture, 23% originated in the neighborhood surrounding the monitor, and only 12% was contributed from nearby sources. These analyses indicate that a fixed-site monitor can reasonably represent exposures in its surrounding neighborhood even when many local sources, such as exhaust from diesel buses and trucks, affect the monitor.     

Formaldehyde levels in air and wet precipitation at Mexico City, Mexico

Formaldehyde concentrations in ambient air and in rain water were measured at the University of Mexico, Mexico City. Air samples were taken twice a day, from 9:00 to 13:00 h and from 13:00 to 16:00 h local time from July to December 1985. Rain water was collected on daily bases from July to October, i.e. during the rainy season. The ambient air mean value was 24.4 x 10(-3) ppmv for morning hours, while the afternoon mean value was 18.5 x 10(-3) ppmv. The formaldehyde concentration in wet precipitation ranged from 0.10 to 0.80 mg liter(-1) (3.3 to 26.6 micromoles liter(-1)) 0.41 mg liter(-1) (13.7 microoles liter(-1)). A comparison of the results of this study with some measurements made at remote maritime sites, rural and urban areas, indicated that the formaldehyde levels in the atmosphere and rain water of Mexico City are among the highest reported in the literature, including the data reported by Grosjean (1982) for Los Angeles, California, during severe photochemical pollution conditions.     

PM composition and source reconciliation in Mexico City

PM_2.5 and PM₁₀ were collected during 24-h sampling intervals from March 1st to 31st, 2006 during the MILAGRO campaign carried out in Mexico City's northern region, in order to determine their chemical composition, oxidative activity and the estimation of the source contributions during the sampling period by means of the chemical mass balance (CMB) receptor model. PM_2.5 concentrations ranged from 32 to 70 μg m⁻³ while that of PM10 did so from 51 to 132 μg m⁻³. The most abundant chemical species for both PM fractions were: OC, EC, SO₄²⁻, NO₃⁻, NH₄⁺, Si, Fe and Ca. The majority of the PM mass was comprised of carbon, up to about 52% and 30% of the PM2.5 and PM10, respectively. PM2.5 constituted more than 50% of PM10. The redox activity, assessed by the dithiothreitol (DTT) assay, was greater for PM_2.5 than for PM₁₀, and did not display significant differences during the sampling period. The PM_2.5 source reconciliation showed that in average, vehicle exhaust emissions were its most important source in an urban site with a 42% contribution, followed by re-suspended dust with 26%, secondary inorganic aerosols with 11%, and industrial emissions and food cooking with 10% each. These results had a good agreement with the Emission Inventory. In average, the greater mass concentration occurred during O₃S that corresponds to a wind shift initially with transport to the South but moving back to the North. Taken together these results show that PM chemical composition, oxidative potential, and source contribution is influenced by the meteorological conditions.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Projected ozone trends and changes in the ozone-precursor relationship in the South Coast Air Basin in response to varying reductions of precursor emissions

This study examined the effects of varying future reductions in emissions of oxides of nitrogen (NO_x) and volatile organic compounds (VOC) on the location and magnitude of peak ozone levels within California’s South Coast Air Basin (SoCAB or Basin). As ozone formation is currently VOC-limited in the Basin, model simulations with 2030 baseline emissions (?61% for NO_x and ?32% for VOC from 2008) predict 10–20% higher peak ozone levels (i.e., NO_x disbenefit) in the western and central SoCAB compared with the 2008 base simulation. With additional NO_x reductions of 50% beyond the 2030 baseline emissions (?81% from 2008), the predicted ozone levels are reduced by about 15% in the eastern SoCAB but remain comparable to 2008 levels in the western and central Basin. The Basin maximum ozone site shifts westward to more populated areas of the Basin and will result potentially in greater population-weighted exposure to ozone with even a relatively small shortfall in the required NO_x reductions unless accompanied by additional VOC reductions beyond 2030 baseline levels. Once committed to a NO_x-focused control strategy, NO_x reductions exceeding 90% from 2008 levels will be necessary to attain the ozone National Ambient Air Quality Standards (NAAQS). The findings from this study and other recent work that the current VOC emission estimates are underestimated by about 50% suggest that greater future VOC reductions will be necessary to reach the projected 2030 baseline emissions. Increasing the base year VOC emissions by a factor of 1.5 result in higher 2008 baseline ozone predictions, lower relative response factors, and about 20% lower projected design values. If correct, these findings have important implications for the total and optimum mix of VOC and NO_x emission reductions that will be required to attain the ozone NAAQS in the SoCAB.

Implications: Results of this study indicate that ozone levels in the western and central SoCAB would remain the same or increase with even a relatively small shortfall in the projected NO_x reductions under planned NO_x-focused controls. This possibility, therefore, warrants a rigorous analysis of the costs and effects of varying reductions of VOC and NO_x on the formation and combined health impacts of ozone and secondary particles. Given the nonlinearity of ozone formation, such analyses should include the implications of gradually increasing global background ozone concentrations and the Basin’s topography and meteorology on the practical limits of alternative emission control strategies.     

Size-differentiated composition of inorganic atmospheric aerosols of both marine and polluted continental origin

Atmospheric aerosols were sampled with a high volume impactor/diffusion battery system and the collected fractions analysed for their major water-soluble inorganic constituents. Sulphate, nitrate and chloride showed bimodal distributions; sulphate and nitrate were mainly associated with NH₄⁺, having approximately log-normal distributions with modes at 1.0 μm. In unpolluted maritime air, chlorides appeared as salts of sodium and magnesium with average modes at c. 5 μm, whilst in polluted air masses significant concentrations of ammonium chloride sub-μm aerosols were detected. Sodium nitrate and sodium sulphate aerosols having average modes of c. 3.5 μm were observed in mixed maritime/polluted air masses. The dimensions of these particles indicate formation from absorption of H₂SO₄ and HNO₃ at the surface of marine NaCl particles. The concentration of H⁺ was very low, but the possibility of its neutralization by atmospheric ammonia during sampling was ruled out by parallel air sampling using an ‘ammonia denuder’.     

Combustion aerosols: factors governing their size and composition and implications to human health

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 microns (PM2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-temperature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Long-term trends of primary and secondary pollutant concentrations in Switzerland and their response to emission controls and economic changes

A detrending technique is developed for short-term and yearly variations in order to identify long-term trends in primary and secondary pollutants. In this approach, seasonal and weekly variations are removed by using a mean year; the residual meteorological short-term variation is removed by using a multiple linear regression model. This methodology is employed to detrend ozone (O₃), NO_x, VOC and CO concentrations in Switzerland. We show that primary pollutants (NO_x,VOC and CO) at urban and sub-urban stations show a downward trend over the last decade which correlates well with the reductions in the estimated Swiss emissions. In spite of these large decreases achieved in precursor emissions, summer peak ozone concentrations do not show any statistically significant trend over the last decade. Application of this method to ozone concentrations measured at the Jungfraujoch (3580 m a.s.l.) also shows no trend over the last 10 years. Detrended summer ozone correlates well with European Union gross national product and industrial production growth rates. These results suggest that if substantial reductions in summer peak ozone in Switzerland are desired, emissions reduction strategies must be part of control program involving a much larger region.     

ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site

An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ～33% of the PM_1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional groups than the urban source.     

An Air Pollution Modeling Study Using Three Surface Coverings Near the New International Airport of Mexico City

Abstract

The dry lakebed of what once was the lake of Texcoco is the location selected for the New International Airport of Mexico City. This project will generate an important urban development near the airport with regional implications on air quality. Using a prognostic air quality model, the consequences of photochemical air pollution in the metropolitan area of Mexico City resulting from three possible coverings for the areas of the lakebed that are not occupied by the runway and terminal building are investigated. These coverings are desert, grassland, and water and occupy an area of 63 km². This study is based on a representative high pollution episode. In addition to reducing the emission of primary natural particles, the water covering generates a land-water breeze capable of maintaining enough ventilation to reduce pollutant concentrations over a localized region of the metropolitan area and may enhance the wind speed on the coasts of the proposed lake.     

Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

An Air Quality Modeling Study Comparing Two Possible Sites for the New International Airport for Mexico City

Abstract

Using an air quality model, two future urban scenarios induced by the construction of the new international airport for Mexico City are compared at a regional level. The air quality model couples the meteorology model MM5 and state-of-the-art photochemistry. The air quality comparison is made using metrics for the criterion gases selected for the study. From the two urban scenarios compared, the option for Tizayuca is moderately better than the option for Texcoco, because relative reductions in O₃ and other photochemical pollutants are achieved over highly populated areas. Regardless of the site, the air quality for the central region of Mexico in the future will deteriorate. In the region of central Mexico, SO₂ and NO₂ will become important pollutants.