Laurie A. McNair

Particulate Air Pollution in Mexico City: A Collaborative Research Project

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 citys 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 PM2.5, with higher percentages during the morning hours. Organic and black carbon constituted up to half of the PM2.5. 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.

Motorization of China implies changes in Pacific air chemistry and primary production

The Peoples Republic of China, the worlds most populous nation, is considering extensive development of its automotive transportation infrastructure. Upper limits to the associated pollution increases can be defined through scenarios with Western style vehicles and vehicle-to-person ratios. Here we construct estimates of fundamental changes to chemistry of the Pacific ocean/atmosphere system through simple budgeting procedures. Regional increases in tropospheric ozone could reach tens of parts per billion. Observations/experiments suggest that enhanced nitrogen oxides will react with sea salt aerosols to yield chlorine atoms in the marine boundary layer. Nitrate deposition onto the open sea surface would support several percent of exported North Pacific carbon production. Transport of biologically active iron to surface waters may follow from increases in mineral dust and acid sulfate aerosols. Altered plankton ecodynamics will feed back into climate processes through sea to air flux of reduced sulfur gases and through carbon dioxide drawdown.

Spatial inhomogeneity in pollutant concentrations, and their implications for air quality model evaluation

Abstract The Southern California Air Quality Study database provides a valuable resource with which to test urban-scale photochemical models and to achieve a better understanding of the atmospheric dynamics of pollutant formation. The CIT model was evaluated using the SCAQS database according to traditional model performance guidelines. A first application, reported previously, focused on model enhancement and application of the model to the 27–29 August 1987 episode. This study evaluates the CIT model using the 24–25 June SCAQS episode, providing further evaluation of the model. Results show that the CIT airshed model can follow the diurnal variations of reactive species and the transport for relatively unreactive species. The normalized gross error for ozone was 31 % in June compared to 38% in August. However, to fully judge model performance in proper perspective, a question arises: “How well do the measurements reflect the air quality surrounding the monitoring station, not just in that location?” This is an important but seldom quantitatively considered factor, not only in model evaluation but in the study of health effects as well. Analyses indicate that individual concentration measurements only approximately represent the true volume-averaged concentrations within a computational grid cell and that significant spatial variations exist. Thus any evaluation of models using these data sets should take these local variations into consideration. A series of tests found that the local inhomogeneities had a normalized gross error in the range of 25–45% depending on the pollutant. In this context, the performance of the CIT model is consistent with known modeling limitations such as emissions inventories and sub-grid scale variation of observations.

Ventilation of liquefied petroleum gas components from the Valley of Mexico

The saturated hydrocarbons propane and the butane isomers are both indirect greenhouse gases and key species in liquefied petroleum gas (LPG). Leakage of LPG and its component alkanes/alkenes is now thought to explain a significant fraction of the volatile organic burden and oxidative potential in the basin which confines Mexico City. Propane and the butanes, however, are stable enough to escape from the basin. The gas Chromatographie measurements which have drawn attention to their sources within the urban area are used here to estimate rates of ventilation into the free troposphere. The calculations are centered on several well studied February/March pollution episodes. Carbon monoxide observations and emissions data are first exploited to provide a rough time constant for the removal of typical inert pollutant species from the valley. The timescale obtained is validated through an examination of meteorological simulations of three-dimensional flow. Heuristic arguments and transport modeling establish that propane and the butanes are distributed through the basin in a manner analogous to CO despite differing emissions functions. Ventilation rates and mass loadings yield outbound fluxes in a box model type computation. Estimated in this fashion, escape from the Valley of Mexico constitutes of the order of half of 1% of the northern hemispheric inputs for both propane and n-butane. Uncertainties in the calculations are detailed and include factors such as flow into the basin via surface winds and the size of the polluted regime. General quantification of the global propane and butane emissions from large cities will entail studies of this type in a variety of locales.

Airshed calculation of the sensitivity of pollutant formation to organic compound classes and oxygenates associated with alternative fuels

This study uses a 3-D Eulerian photochemical model and an advanced chemical reaction mechanism to evaluate the sensitivity of pollutant levels to changes in emissions. In particular, the ozone forming potentials of classes of organic compounds are calculated, with particular emphasis on oxygenated organics associated with alternative fuels. Methanol, ethanol, MTBE, alkane and toluene emissions were found to add about one-fifth the ozone (on a carbon mass basis) as alkenes, aldehydes, non-toluene aromatics and ethene. On a per-carbon basis, formaldehyde added about ten times as much ozone as the least reactive organics tested. The results of the trajectory model-based study usually compare well with those found here. The pollution formation potentials can now be used in assessing the relative impact of various exhaust gas compositions.

Mexico City and the biogeochemistry of global urbanization

Mexico City is far advanced in its urban evolution, and cities in currently developing nations may soon follow a similar course. This paper investigates the strengths and weaknesses of infrastructures for the emerging megacities. The major driving force for infrastructure change in Mexico City is concern over air quality. Air chemistry data from recent field campaigns have been used to calculate fluxes in the atmosphere of the Valley of Mexico, for compounds that are important to biogeochemistry including methane (CH4), carbon monoxide (CO), nonmethane hydrocarbons (NMHCs), ammonia (NH3), sulfur dioxide (SO2), nitrogen oxides (NOx and NOy), soot, and dust. Leakage of liquified petroleum gas approached 10% during sampling periods, and automotive pollutant sources in Mexico City were found to match those in developed cities, despite a lower vehicle-to-person ratio of 0.1. Ammonia is released primarily from residential areas, at levels sufficient to titrate pollutant acids into particles across the entire basin. Enhancements of reduced nitrogen and hydrocarbons in the vapor phase skew the distribution of NOy species towards lower average deposition velocities. Partly as a result, downwind nutrient deposition occurs on a similar scale as nitrogen fixation across Central America, and augments marine nitrate upwelling. Dust suspension from unpaved roads and from the bed of Lake Texcoco was found to be comparable to that occurring on the periphery of the Sahara, Arabian, and Gobi deserts. In addition, sodium chloride (NaCl) in the dust may support heterogeneous chlorine oxide (ClOx) chemistry. The insights from our Mexico City analysis have been tentatively applied to the upcoming urbanization of Asia.

ECODYNAMICS AND DISSOLVED GAS CHEMISTRY ROUTINES FOR OCEAN CIRCULATION MODELS

Abstract Interactions between oceanic nitrate ecology and circulation determine the marine distribution of dissolved, climate relevant trace gases such as dimethyl sulfide (DMS) and carbonyl sulfide (OCS), and a variety of hydrocarbons. Our group is constructing a suite of ecosystem/reaction/transport models, which link nitrate to the chemistry of volatiles near the sea–air interface. In this paper, we describe programs which will be inserted into the high resolution Parallel Ocean Program. Major features of the coding include: (1) ecodynamics represented in seven biological compartments (phytoplankton, zooplankton, bacteria, detritus, nitrate, ammonium and dissolved organic nitrogen). Light limited primary production is computed, along with nitrogen cycling among the bioentities. (2) Photochemistry for the volatile species DMS, OCS, the methyl halides, nonmethane hydrocarbons (NMHC) and ammonia. DMS and the halides are emitted by phytoplankton, while OCS and NMHC are produced by photolysis of dissolved organic material. Ammonia is exuded by animals and bacteria. Removal mechanisms for the gases include consumption by organisms, hydrolysis, chlorination and interfacial transfer. (3) Explicit, efficient and mass conserving numerical solutions for the biological and chemical continuity equations. Production and loss forms are generalized and automated so that they are readily applied to new constituents. Ecology and the chemical transformations are exposed qualitatively to begin, and are then expressed as differential and differencing equations. The structure of the program is described in terms of the major subroutines and their purposes. Results are provided from both one- and three-dimensional sample runs. Computational aspects such as performance and code availability are discussed.

Airshed model evaluation of reactivity adjustment factors calculated with the maximum incremental reactivity scale for transitional-low emission vehicles

Abstract The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactiv...

Pathways for the oxidation of sarin in urban atmospheres

The nerve agent sarin has recently been deployed by terrorists in a major city. The molecule is volatile and made its way to many victims by passing as vapor through a highly reactive medium. Here we estimate rates and pathways for the removal of gas phase sarin from a generalized urban atmosphere. Only information from the open scientific literature is used. By structure reactivity comparisons with the organophosphorus pesticides, hydroxyl radical hydrogen abstraction may occur in as little as one hour. Decomposition of side chains after hydroxyl attack leads to organic oxygenates which preserve the phosphonofluoridate and so toxicity. The aqueous aerosol surface is contacted in minutes and offers access to a range of dissolved nucleophiles. Substitution displaces the fluoride leaving group, giving safe phosphoric acid analogs. Because of uncertainties in the electron distribution and in aqueous decay mechanisms, the time constants must be viewed as lower limits.