ALBERT

Description: A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3.

Description: Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are of concern due to their effects on climate and health. The main goal of this research is to provide the first estimate of emissions of BC and particle-phase PAHs (PPAHs) from motor vehicles in Mexico City. The emissions of other pollutants including carbon monoxide (CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs), and particulate matter of diameter 2.5 μm and less (PM2.5) are also estimated. As a part of the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003), a mobile laboratory was driven throughout the city. The laboratory was equipped with a comprehensive suite of gas and particle analyzers, including an aethalometer that measured BC and a photoionization aerosol sensor that measured PPAHs. While driving through traffic, the mobile lab continuously sampled exhaust plumes from the vehicles around it. We have developed a method of automatically identifying exhaust plumes, which are then used as the basis for calculation of fleet-average emissions. In the approximately 75 h of on-road sampling during the field campaign, we have identified ~30 000 exhaust measurement points that represent a variety of vehicle types and driving conditions. The large sample provides a basis for estimating fleet-average emission factors and thus the emission inventory. Motor vehicles in the Mexico City area are estimated to emit 1700±200 metric tons BC, 57±6 tons PPAHs, 1 190 000±40 000 tons CO, 120 000±3000 tons NOx, 240 000±50 000 tons VOCs, and 4400±400 tons PM2.5 per year, not including cold start emissions. The estimates for CO, NOx, and PPAHs may be low by up to 10% due to the slower response time of analyzers used to measure these species. Compared to the government's official motor vehicle emission inventory for the year 2002, the estimates for CO, NOx, VOCs, and PM2.5 are 38% lower, 23% lower, 27% higher, and 25% higher, respectively. The distributions of emission factors of BC, PPAHs, and PM2.5 are highly skewed, i.e. asymmetric, while those for benzene, measured as a surrogate for total VOCs, and NOx are less skewed. As a result, the total emissions of BC, PPAHs, and PM2.5 could be reduced by approximately 50% if the highest 20% of data points were removed, but "super polluters" are less influential on overall NOx and VOC emissions.

Description: A mobile laboratory was used to measure on-road vehicle emission ratios during the MCMA-2003 field campaign held during the spring of 2003 in the Mexico City Metropolitan Area (MCMA). The measured emission ratios represent a sample of emissions of in-use vehicles under real world driving conditions for the MCMA. From the relative amounts of NOx and selected VOC's sampled, the results indicate that the technique is capable of differentiating among vehicle categories and fuel type in real world driving conditions. Emission ratios for NOx, NOy, NH3, H2CO, CH3CHO, and other selected volatile organic compounds (VOCs) are presented for chase sampled vehicles in the form of frequency distributions as well as estimates for the fleet averaged emissions. Our measurements of emission ratios for both CNG and gasoline powered "colectivos" (public transportation buses that are intensively used in the MCMA) indicate that – in a mole per mole basis – have significantly larger NOx and aldehydes emissions ratios as compared to other sampled vehicles in the MCMA. Similarly, ratios of selected VOCs and NOy showed a strong dependence on traffic mode. These results are compared with the vehicle emissions inventory for the MCMA, other vehicle emissions measurements in the MCMA, and measurements of on-road emissions in U.S. cities. We estimate NOx emissions as 100 600±29 200 metric tons per year for light duty gasoline vehicles in the MCMA for 2003. According to these results, annual NOx emissions estimated in the emissions inventory for this category are within the range of our estimated NOx annual emissions. Our estimates for motor vehicle emissions of benzene, toluene, formaldehyde, and acetaldehyde in the MCMA indicate these species are present in concentrations higher than previously reported. The high motor vehicle aldehyde emissions may have an impact on the photochemistry of urban areas.

Description: There is an emerging need for regional applications of sea ice projections to provide more accuracy and greater detail to scientists, national, state and local planners, and other stakeholders. The present study offers a prototype for a comprehensive, interdisciplinary study to bridge observational data, climate model simulations, and user needs. The study's first component is an observationally-based evaluation of Arctic sea ice trends during 1980–2008, with an emphasis on seasonal and regional differences relative to the overall pan-Arctic trend. Regional sea ice los has varied, with a significantly larger decline of winter maximum (January–March) extent in the Atlantic region than in other sectors. A lead-lag regression analysis of Atlantic sea ice extent and ocean temperatures indicates that reduced sea ice extent is associated with increased Atlantic Ocean temperatures. Correlations between the two variables are greater when ocean temperatures lag rather than lead sea ice. The performance of 13 global climate models is evaluated using three metrics to compare sea ice simulations with the observed record. We rank models over the pan-Arctic domain and regional quadrants, and synthesize model performance across several different studies. The best performing models project reduced ice cover across key access routes in the Arctic through 2100, with a lengthening of seasons for marine operations by 1–3 months. This assessment suggests that the Northwest and Northeast Passages hold potential for enhanced marine access to the Arctic in the future, including shipping and resource development opportunities.

Description: There is an emerging need for regional applications of sea ice projections to provide more accuracy and greater detail to scientists, national, state and local planners, and other stakeholders. The present study offers a prototype for a comprehensive, interdisciplinary study to bridge observational data, climate model simulations, and user needs. The study's first component is an observationally based evaluation of Arctic sea ice trends during 1980–2008, with an emphasis on seasonal and regional differences relative to the overall pan-Arctic trend. Regional sea ice loss has varied, with a significantly larger decline of winter maximum (January–March) extent in the Atlantic region than in other sectors. A lead–lag regression analysis of Atlantic sea ice extent and ocean temperatures indicates that reduced sea ice extent is associated with increased Atlantic Ocean temperatures. Correlations between the two variables are greater when ocean temperatures lag rather than lead sea ice. The performance of 13 global climate models is evaluated using three metrics to compare sea ice simulations with the observed record. We rank models over the pan-Arctic domain and regional quadrants and synthesize model performance across several different studies. The best performing models project reduced ice cover across key access routes in the Arctic through 2100, with a lengthening of seasons for marine operations by 1–3 months. This assessment suggests that the Northwest and Northeast Passages hold potential for enhanced marine access to the Arctic in the future, including shipping and resource development opportunities.

Description: Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are of concern due to their effects on climate and health. The main goal of this research is to provide the first estimate of emissions of BC and particle-phase PAHs (PPAHs) from motor vehicles in Mexico City. The emissions of other pollutants including carbon monoxide (CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs), and particulate matter of diameter 2.5 µm and less (PM2.5) are also estimated. As a part of the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003), a mobile laboratory was driven throughout the city. The laboratory was equipped with a comprehensive suite of gas and particle analyzers, including an aethalometer that measured BC and a photoionization aerosol sensor that measured PPAHs. While driving through traffic, the mobile lab is continuously sampling exhaust plumes from the vehicles around it. We have developed a method of automatically identifying exhaust plumes, which are then used as the basis for calculation of fleet-average emission factors. In the approximately 75 h of on-road sampling during the field campaign, we have identified ~30 000 exhaust measurement points that represent a variety of vehicle types and driving conditions. The large sample provides a basis for estimating fleet-average emission factors and thus the emission inventory. Motor vehicles in the Mexico City area are estimated to emit 1700±200 metric tons BC, 57±6 tons PPAHs, 1 190 000±40 000 tons CO, 120 000±3000 tons NOx, 202 000±4000 tons VOCs, and 4400±400 tons PM2.5 per year, not including cold start emissions. The estimates for CO, NOx, and PPAHs may be low by up to 10% due to the slower response time of analyzers used to measure these species. Compared to the government's official motor vehicle emission inventory for the year 2002, the estimates for CO, NOx, VOCs, and PM2.5 are 38% lower, 23% lower, 7% higher, and 26% higher, respectively. The distributions of emission factors of BC, PPAHs, and PM2.5 are highly skewed, i.e. asymmetric, while those for benzene, measured as a surrogate for total VOCs, and NOx are less skewed. As a result, the total emissions of BC, PPAHs, and PM2.5 could be reduced by approximately 50% if the highest 20% of data points were removed, but ''super polluters'' are less influential on overall NOx and VOC emissions.

Description: A mobile laboratory was used to measure on-road vehicle emission ratios during the MCMA-2003 field campaign held during the spring of 2003 in the Mexico City Metropolitan Area (MCMA). The measured emission ratios represent a sample of emissions of in-use vehicles under real world driving conditions for the MCMA. From the relative amounts of NOx and selected VOC's sampled, the results indicate that the technique is capable of differentiating among vehicle categories and fuel type in real world driving conditions. Emission ratios for NOx, NOy, NH3, H2CO, CH3CHO, and other selected volatile organic compounds (VOCs) are presented for chase sampled vehicles and fleet averaged emissions. Results indicate that colectivos, particularly CNG-powered colectivos, are potentially significant contributors of NOx and aldehydes in the MCMA. Similarly, ratios of selected VOCs and NOy showed a strong dependence on traffic mode. These results are compared with the vehicle emissions inventory for the MCMA, other vehicle emissions measurements in the MCMA, and measurements of on-road emissions in US cities. Our estimates for motor vehicle emissions of benzene, toluene, formaldehyde, and acetaldehyde in the MCMA indicate these species are present in concentrations higher than previously reported. The high motor vehicle aldehyde emissions may have an impact on the photochemistry of urban areas.

Description: A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some alkanes are underestimated in the emissions inventory, while some olefins and aromatics are overestimated.