A13I-01 INVITED
Top-down constraints of volatile organic compound (VOC) emissions
The ability to measure volatile organic compound (VOC) fluxes on tower and airborne platforms is assessed. Airborne flux measurements are compared with anthropogenic emission estimates for the Mexico City Basin. We have tested the feasibility of airborne flux measurements to investigate area sources over regional urban footprints, such as encountered in many Mega-cities, where bottom-up emission estimates are particularly uncertain. We demonstrate that these measurements could provide a useful top-down constraint on bottom-up emission estimates. Complementary to ground based flux measurements, airborne flux measurements could also play a key role in reducing uncertainties when mapping biogenic VOC emission models on to different land-cover databases in the future.
A13I-02
Eddy Covariance Flux Measurements of Pollutant Gases in the Mexico City Urban Area: a Useful Technique to Evaluate Emissions inventories
Direct measurements of emissions of pollutant gases that include all major and minor emissions sources in urban areas are a missing requirement to improve and evaluate emissions inventories. The quality of an urban emissions inventory relies on the accuracy of the information of anthropogenic activities, which in many cases is not available, in particular in urban areas of developing countries. As part of the MCMA-2003 field campaign, we demonstrated the feasibility of using eddy covariance (EC) techniques coupled with fast-response sensors to measure fluxes of volatile organic compounds (VOCs) and CO2 from a residential district of Mexico City. Those flux measurements demonstrated to be also a valuable tool to evaluate the emissions inventory used for air quality modeling. With the objective to confirm the representativeness of the 2003 flux measurements in terms of magnitude, composition and diurnal distribution, as well to evaluate the most recent emissions inventory, a second flux system was deployed in a different district of Mexico City during the 2006 MILAGRO field campaign. This system was located in a busy district surrounded by congested avenues close to the center of the city. In 2003 and 2006 fluxes of olefins and CO2 were measured by the EC technique using a Fast Isoprene Sensor calibrated with a propylene standard and an open path Infrared Gas Analyzer (IRGA), respectively. Fluxes of aromatic and oxygenated VOCs were analyzed by Proton Transfer Reaction-Mass Spectroscopy (PTR-MS) and the disjunct eddy covariance (DEC) technique. In 2006 the number of VOCs was extended using a disjunct eddy accumulation (DEA) system. This system collected whole air samples as function of the direction of the vertical wind component, and the samples were analyzed on site by gas chromatography / flame ionization detection (GC-FID). In both studies we found that the urban surface is a net source of CO2 and VOCs. The diurnal patterns were similar, but the 2006 fluxes showed higher magnitudes. This difference was due to the different characteristics of the monitored sites rather than an increment of the emissions over a 3-year period. The diurnal patterns of VOCs and CO2 fluxes were strongly related to vehicular traffic. Toluene and methanol fluxes also exhibited a strong influence from non-mobile sources; in particular the 2006 flux measurements were influenced on some days by the application of a resin to the sidewalks in the neighborhood near the flux tower. The fluxes of individual hydrocarbons measured by DEA showed good agreement with the fluxes measured by EC and DEC which demonstrates that the DEA method is valuable for flux measurements of additional individual species. Finally, the comparisons between the measured fluxes of VOCs and the emissions reported by the emissions inventory for the monitored sector of the city showed that these last were within the observed variability of the measured fluxes.
A13I-03
New Approaches for Estimating Motor Vehicle Emissions in Megacities
The rapid proliferation of megacities and their air quality problems is producing unprecedented air pollution health risks and management challenges. Quantifying motor vehicle emissions in the developing world's megacities, where vehicle ownership is skyrocketing, is critical for evaluating the cities' impacts on the atmosphere at urban, regional, and global scales. The main goal of this research is to quantify gasoline- and diesel-powered motor vehicle emissions within the Mexico City Metropolitan Area (MCMA). We apply positive matrix factorization to fast measurements of gaseous and particulate pollutants made by the Aerodyne Mobile Laboratory as it drove throughout the MCMA in 2006. We consider carbon dioxide; carbon monoxide; volatile organic compounds including benzene and formaldehyde; nitrogen oxides; ammonia; fine particulate matter; particulate polycyclic aromatic hydrocarbons; and black carbon. Analysis of the video record confirms the apportionment of emissions to different engine types. From the derived source profiles, we calculate fuel-based fleet-average emission factors and then estimate the total motor vehicle emission inventory. The advantages of this method are that it can capture a representative sample of vehicles in a variety of on-road driving conditions and can separate emissions from gasoline versus diesel engines. The results of this research can be used to help assess the accuracy of emission inventories and to guide the development of strategies for reducing vehicle emissions.
A13I-04
Air quality modeling in the Valley of Mexico: meteorology, emissions and forecasting
The Valley of Mexico presents important challenges for air quality modeling: complex terrain, a great variety of anthropogenic and natural emissions sources, and high altitude and low latitude increasing the amount of radiation flux. The modeling group at the CCA-UNAM is using and merging state of the art models to study the different aspects that influence the air quality phenomenon in the Valley of Mexico. The air quality model MCCM that uses MM5 as its meteorological input has been a valuable tool to study important features of the complex and intricate atmospheric flows on the valley, such as local confluences and vertical fumigation. Air quality modeling has allowed studying the interaction between the atmospheres of the valleys surrounding the Valley of Mexico, prompting the location of measurement stations during the MILAGRO campaign. These measurements confirmed the modeling results and expanded our knowledge of the transport of pollutants between the Valleys of Cuernavaca, Puebla and Mexico. The urban landscape of Mexico City complicates meteorological modeling. Urban-MM5, a model that explicitly takes into account the influence of buildings, houses, streets, parks and anthropogenic heat, is being implemented. Preliminary results of urban-MM5 on a small area of the city have been obtained. The current emissions inventory uses traffic database that includes hourly vehicular activity in more than 11,000 street segments, includes 23 area emissions categories, more than 1,000 industrial sources and biogenic emissions. To improve mobile sources emissions a system consisting of a traffic model and a car simulator is underway. This system will allow for high time and space resolution and takes into account motor stress due to different driving regimes. An important source of emissions in the Valley of Mexico is erosion dust. The erosion model WEPS has been integrated with MM5 and preliminary results showing dust episodes over Mexico City have been obtained. A real time Ozone forecast model is being implemented for the Valley of Mexico whose performance is being evaluated.
A13I-05 INVITED
Measurements of industrial emissions of VOCs, NH3, NO2 and SO2 in Texas using the Solar Occultation Flux method and mobile DOAS
Solar Occultation Flux (SOF) measurements of olefines and alkanes have been conducted to pin-point and quantify the largest sources of olefines and alkanes in the vicinity of Houston and in south eastern Texas during September 2006. The SOF measurements were part of the extensive summer campaign TexAQS 2006, included in the Second Texas Air Quality Study (TexAQS II). The SOF technique is an optical method utilizing the absorption of direct solar infrared radiation in the 1.8-14 micrometer range for retrieval of total columns of various species such as ethylene, propylene, ammonia and alkanes. The instrument is carried on a mobile platform, making it possible to conduct transects of the emission plume downwind an industry, and thus integrate all the molecules of the plume cross section in real time. By multiplying with the plume wind speed, the total flux emerging from the source is obtained. Flux estimates with SOF were obtained for the large petrochemical and refining complexes around the Houston area. This was done in parallell with airborne plume studies by other parties. The primary research goal was to supply a data set for emission inventory comparisons and for input to models looking at the strong ozone production in Texas. The SOF measurements show that the hourly gas emissions from the Houston Ship channel area correspond to about 1 metric ton of ethylene, 1.5 tons of propylene, 12 tons of alkanes, 1/4 ton of NH3 and about 5 tons of SO2 and NO2. For the VOCs this is an order of magnitude or greater than reported VOC emissions in the 2004 inventory.
A13I-06
Quantification of Ethene Emissions from Petrochemical Industries in Houston, Texas: Large Disagreements with Emission Inventories
Reactive alkenes from petrochemical industries are known to play an important role in the formation of ozone in Houston, Texas. In this work we developed a fast-response detector of ethene based on laser photo-acoustic spectroscopy (LPAS) and used it onboard the NOAA WP-3D aircraft to measure ethene in industrial plumes around Houston in the summer of 2006. The new LPAS instrument was evaluated by comparison with measurement results from the whole air sampler (WAS), and the two measurements were found to agree within the combined measurement uncertainties of +/- (200 pptv + 15%). Emission fluxes of ethene were estimated (1) by integrating the measured ethene concentration across the width of industrial plumes, (2) by multiplying the concentration with the orthogonal wind speed measured from the aircraft, and (3) by assuming that the emissions are homogeneously distributed across the height of the boundary layer as estimated using aircraft ascents and descents. The estimated ethene fluxes were compared with the results of simultaneous Solar Occultation Flux (SOF) measurements inside a mobile laboratory, and agreement within a factor of 2 was obtained. Previous work had indicated that current emission inventories underestimate reactive alkene emissions in Houston by 1-2 orders of magnitude. These findings were confirmed both by the LPAS measurements onboard the NOAA WP-3D and the SOF measurements. Finally, the measured mixing ratios of ethene were compared between the results from 2006 and an earlier mission in 2000. In contrast with CO and ethyne, which are predominantly from traffic, ethene and its photoproduct formaldehyde showed the largest decreases between 2000 and 2006, suggesting possible reductions of approximately 40% in the industrial emissions of ethene.
A13I-07
Impact of Emissions from Commercial Shipping During TexAQS 2006
Commercial marine vessels range in size from small fishing boats (20-30 meters in length) to extremely large container ships (over 300 meters in length). These ships almost without exception use diesel engines for propulsion and auxiliary power generation. The larger ships, comprising bulk carriers, tankers and container carriers, utilize diesel engines that produce power in the 10 MW to 100 MW range. These engines typically consume heavy fuel oils which are high in sulfur content (1%-4.5% by weight). These engines are also extremely efficient, converting essentially all of the carbon in the fuel to CO2, but also emitting NOx, CO, SO2, VOCs, and PM. During TexAQS 2006 our measurements on board the NOAA research ship Ronald H. Brown allowed us to characterize the emissions from a large number of commercial marine vessels. The measurements provided the means to calculate mass-based emission factors for many of the compounds noted above. With the information broadcast by these vessels over the Automated Information System, we have unequivocally determined the emission factors for over 200 vessels both at dock and underway. Our data largely confirm published average emission factors, but also show significant variability especially with NOx. This talk will present those results and then use the data to show that emissions of NOx and SO2 from these vessels are not negligible in the Houston-Galveston region.
A13I-08
Emissions of SO2, NOx, and CO2 from the Houston Ship Channel Measured by the NOAA WP-3
The Port of Houston is made up of the Houston Ship Channel and Galveston Bay. Together these comprise a 25- mile long complex of diversified public and private facilities, including a petrochemical complex that is among the largest in the world. The Houston Ship Channel is a major source of industrial pollution, emitting sulfur dioxide (SO2), nitrogen oxides (NOx), carbon monoxide (CO), carbon dioxide (CO2), and volatile organic compounds (VOC). Unlike a single large power plant, the Houston Ship Channel consists of numerous sources that can be difficult to quantify in inventories. In order to evaluate and predict air quality in the Houston area, it is important to understand the magnitude and variability of sources in the Houston Ship Channel, and how these sources are evolving over time. We examine fluxes of SO2, NOx, and CO2 from the Houston Ship Channel observed onboard the NOAA WP-3 during September - October 2006. We report the magnitude of these sources, and compare these results to aircraft measurements from 2000 to identify trends.