Evaluation of mobile emissions contributions to Mexico City's emissions inventory using on-road and cross-road emission measurements and ambient data

Mobile emissions represent a significant fraction of the total anthropogenic emissions burden in the Mexico City Metropolitan Area (MCMA) and, therefore, it is crucial to use top-down techniques informed by on-road exhaust measurements to evaluate and improve traditional bottom-up official emissions inventory (EI) for the city. We present the measurements of on-road fleet-average emission factors obtained using the Aerodyne mobile laboratory in the MCMA in March 2006 as part of the MILAGRO/MCMA-2006 field campaign. A comparison of our on-road emission measurements with those obtained in 2003 using essentially the same measurement techniques and analysis methods indicates that, in the three year span, NO emission factors remain within the measured variability ranges whereas emission factors of aldehydes and aromatics species were reduced for all sampled driving conditions. We use a top-down fuel-based approach to evaluate the mobile emissions from the gasoline fleet estimated in the bottom-up official 2006 MCMA mobile sources. Within the range of measurement uncertainties, we found probable slight overpredictions of mean EI estimates on the order of 20–28% for CO and 14–20% for NO. However, we identify a probable EI underprediction of VOC mobile emissions between 1.4 and 1.9; although estimated benzene and toluene mobile emissions in the inventory seem to be well within the uncertainties of the corresponding emissions estimates. Aldehydes mobile emissions in the inventory, however, seem to be under predicted by factors of 3 for HCHO and 2 for CH3CHO [CH subscript 3 CHO]. Our on-road measurement based estimate of annual emissions of organic mass from PM1 particles suggests a severe underprediction (larger than a factor of 4) of PM2.5 [PM subscript 2.5] mobile emissions in the inventory. Analyses of ambient CO, NOx [NO subscript x] and CO/NOx [CO/NO subscript x] concentration trends in the MCMA indicate that the early morning ambient CO/NOx [CO/NO subscript x] ratio has decreased at a rate of about 1.9 ppm/ppm/year over the last two decades and that the decrease has been driven by reductions in CO levels rather than by NOx [NO subscript x] concentration changes, suggesting that the relative contribution of diesel vehicles to overall NOx [NO subscript x] levels has increased over time in the city. Despite the impressive increases in the size of the vehicle fleet between 2000 and 2006, the early morning ambient concentrations of CO and NOx [NO subscript x] have not increased accordingly, probably due to the reported low removal rates of older vehicles, which do not have emissions control technologies, and partially due to the much lower emissions from newer gasoline vehicles. This indicates that an emission-based air quality control strategy targeting large reductions of emissions from mobile sources should be directed towards a significant increase of the removal rate of older, highly-polluting, vehicles.Atmospheric Sciences Program (U.S.) (DE-FG02-05ER63980)Atmospheric Sciences Program (U.S.) (DE-FG02-05ER63982)United States. Dept. of EnergyNational Science Foundation (U.S.) (Atmospheric chemistry program ATM-0528170)National Science Foundation (U.S.) (Atmospheric chemistry program ATM-528227

Mobile laboratory measurements of black carbon, polycyclic aromatic hydrocarbons and other vehicle emissions in Mexico City

International audienceBlack 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

Comparison of emission ratios from on-road sources using a mobile laboratory under various driving and operational sampling modes

International audienceMobile sources produce a significant fraction of the total anthropogenic emissions burden in large cities and have harmful effects on air quality at multiple spatial scales. Mobile emissions are intrinsically difficult to estimate due to the large number of parameters affecting the emissions variability within and across vehicles types. The MCMA-2003 Campaign in Mexico City has showed the utility of using a mobile laboratory to sample and characterize specific classes of motor vehicles to better quantify their emissions characteristics as a function of their driving cycles. The technique clearly identifies "high emitter" vehicles via individual exhaust plumes, and also provides fleet average emission rates. We have applied this technique to Mexicali during the Border Ozone Reduction and Air Quality Improvement Program for the Mexicali-Imperial Valley in 2005. In this paper we analyze the variability of measured emission ratios for emitted NOx, CO, specific VOCs, NH3, and some primary fine particle components and properties obtained during the Border Ozone Reduction and Air Quality Improvement Program for the Mexicali-Imperial Valley in 2005 by deploying a mobile laboratory in roadside stationary sampling, chase and fleet average operational sampling modes. The measurements reflect various driving modes characteristic of the urban fleets. The observed variability for all measured gases and particle emission ratios is greater for the chase and roadside stationary sampling than for fleet average measurements. The fleet average sampling mode captured the effects of traffic conditions on the measured on-road emission ratios, allowing the use of fuel-based emission ratios to assess the validity of traditional "bottom-up" emissions inventories. Using the measured on-road emission ratios, we estimate CO and NOx mobile emissions of 175±62 and 10.4±1.3 metric tons/day, respectively, for the gasoline vehicle fleet in Mexicali. Comparisons with similar on-road emissions data from Mexico City indicated that fleet average NO emission ratios were around 20% higher in Mexicali than in Mexico City whereas HCHO and NH3 emission ratios were higher by a factor of 2 in Mexico City than in Mexicali. Acetaldehyde emission ratios did not differ significantly whereas selected aromatics VOCs emissions were similar or smaller in Mexicali. On-road heavy-duty diesel truck (HDDT) nitrogen oxides emissions were measured near Austin, Texas, as well as in both Mexican cities, with NOy emission ratios in Austin < Mexico City < Mexicali

Vehicle fleet emissions of black carbon, polycyclic aromatic hydrocarbons, and other pollutants measured by a mobile laboratory in Mexico City

International audienceBlack 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 ?m 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

Application of positive matrix factorization to on-road measurements for source apportionment of diesel- and gasoline-powered vehicle emissions in Mexico City

The goal of this research is to quantify diesel- and gasoline-powered motor vehicle emissions within the Mexico City Metropolitan Area (MCMA) using on-road measurements captured by a mobile laboratory combined with positive matrix factorization (PMF) receptor modeling. During the MCMA-2006 ground-based component of the MILAGRO field campaign, the Aerodyne Mobile Laboratory (AML) measured many gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitrogen oxides (NOx) [(NO subscript x)], benzene, toluene, alkylated aromatics, formaldehyde, acetaldehyde, acetone, ammonia, particle number, fine particulate mass (PM2.5) [(PM subscript 2.5)], and black carbon (BC). These serve as inputs to the receptor model, which is able to resolve three factors corresponding to gasoline engine exhaust, diesel engine exhaust, and the urban background. Using the source profiles, we calculate fuel-based emission factors for each type of exhaust. The MCMA's gasoline-powered vehicles are considerably dirtier, on average, than those in the US with respect to CO and aldehydes. Its diesel-powered vehicles have similar emission factors of NOx [NO subscript x] and higher emission factors of aldehydes, particle number, and BC. In the fleet sampled during AML driving, gasoline-powered vehicles are found to be responsible for 97% of total vehicular emissions of CO, 22% of NOx [NO subscript x], 95–97% of each aromatic species, 72–85% of each carbonyl species, 74% of ammonia, negligible amounts of particle number, 26% of PM2.5 [PM subscript 2.5], and 2% of BC; diesel-powered vehicles account for the balance. Because the mobile lab spent 17% of its time waiting at stoplights, the results may overemphasize idling conditions, possibly resulting in an underestimate of NOx [NO subscript x] and overestimate of CO emissions. On the other hand, estimates of the inventory that do not correctly account for emissions during idling are likely to produce bias in the opposite direction.The resulting fuel-based estimates of emissions are lower than in the official inventory for CO and NOx [NO subscript x] and higher for VOCs. For NOx [NO subscript x], the fuel-based estimates are lower for gasoline-powered vehicles but higher for diesel-powered ones compared to the official inventory. While conclusions regarding the inventory should be interpreted with care because of the small sample size, 3.5 h of driving, the discrepancies with the official inventory agree with those reported in other studies.National Science Foundation (U.S.) (Grant ATM-0528170)National Science Foundation (U.S.) (Grant ATM-0528227)United States. Dept. of Energy (Grant DE-FG02-05ER63982)United States. National Aeronautics and Space AdministrationMolina Center for Energy and the Environmen

Reach-scale bankfull channel types can exist independently of catchment hydrology

© 2020 John Wiley &amp; Sons, Ltd. Reach-scale morphological channel classifications are underpinned by the theory that each channel type is related to an assemblage of reach- and catchment-scale hydrologic, topographic, and sediment supply drivers. However, the relative importance of each driver on reach morphology is unclear, as is the possibility that different driver assemblages yield the same reach morphology. Reach-scale classifications have never needed to be predicated on hydrology, yet hydrology controls discharge and thus sediment transport capacity. The scientific question is: do two or more regions with quantifiable differences in hydrologic setting end up with different reach-scale channel types, or do channel types transcend hydrologic setting because hydrologic setting is not a dominant control at the reach scale? This study answered this question by isolating hydrologic metrics as potential dominant controls of channel type. Three steps were applied in a large test basin with diverse hydrologic settings (Sacramento River, California) to: (1) create a reach-scale channel classification based on local site surveys, (2) categorize sites by flood magnitude, dimensionless flood magnitude, and annual hydrologic regime type, and (3) statistically analyze two hydrogeomorphic linkages. Statistical tests assessed the spatial distribution of channel types and the dependence of channel type morphological attributes by hydrologic setting. Results yielded 10 channel types. Nearly all types existed across all hydrologic settings, which is perhaps a surprising development for hydrogeomorphology. Downstream hydraulic geometry relationships were statistically significant. In addition, cobble-dominated uniform streams showed a consistent inverse relationship between slope and dimensionless flood magnitude, an indication of dynamic equilibrium between transport capacity and sediment supply. However, most morphological attributes showed no sorting by hydrologic setting. This study suggests that median hydraulic geometry relations persist across basins and within channel types, but hydrologic influence on geomorphic variability is likely due to local influences rather than catchment-scale drivers. © 2020 John Wiley &amp; Sons, Ltd

An Instruction on the In Vivo Shell-Less Chorioallantoic Membrane 3-Dimensional Tumor Spheroid Model

The traditional shell chicken chorioallantoic membrane (CAM) model has been used extensively in cancer research to study tumor growth and angiogenesis. Here we present a combined in vivo tumor spheroid and shell-less CAM three-dimensional model for use in quantitative and qualitative analysis. With this model, the angiogenic and tumorigenic environments can be generated locally without exogenous growth factors. This physiological model offers a stable, static and flat environment that features a large working area and wider field of view useful for imaging and biomedical engineering applications. The short experimental time frame allows for rapid data acquisition, screening and validation of biomedical devices. The method and application of this shell-less model are discussed in detail, providing a useful tool for biomedical engineering research

Comparison of emissions from on-road sources using a mobile laboratory under various driving and operational sampling modes

Mobile sources produce a significant fraction of the total anthropogenic emissions burden in large cities and have harmful effects on air quality at multiple spatial scales. Mobile emissions are intrinsically difficult to estimate due to the large number of parameters affecting the emissions variability within and across vehicles types. The MCMA-2003 Campaign in Mexico City has showed the utility of using a mobile laboratory to sample and characterize specific classes of motor vehicles to better quantify their emissions characteristics as a function of their driving cycles. The technique clearly identifies "high emitter" vehicles via individual exhaust plumes, and also provides fleet average emission rates. We have applied this technique to Mexicali during the Border Ozone Reduction and Air Quality Improvement Program (BORAQIP) for the Mexicali-Imperial Valley in 2005. We analyze the variability of measured emission ratios for emitted NOx [NO subscript x], CO, specific VOCs, NH3 [NH subscript 3], and some primary fine particle components and properties by deploying a mobile laboratory in roadside stationary sampling, chase and fleet average operational sampling modes. The measurements reflect various driving modes characteristic of the urban fleets. The observed variability for all measured gases and particle emission ratios is greater for the chase and roadside stationary sampling than for fleet average measurements. The fleet average sampling mode captured the effects of traffic conditions on the measured on-road emission ratios, allowing the use of fuel-based emission ratios to assess the validity of traditional "bottom-up" emissions inventories. Using the measured on-road emission ratios, we estimate CO and NOx [NO subscript x] mobile emissions of 175±62 and 10.4±1.3 metric tons/day, respectively, for the gasoline vehicle fleet in Mexicali. Comparisons with similar on-road emissions data from Mexico City indicated that fleet average NO emission ratios were around 20% higher in Mexicali than in Mexico City whereas HCHO and NH3 [NH subscript 3] emission ratios were higher by a factor of 2 in Mexico City than in Mexicali. Acetaldehyde emission ratios did not differ significantly whereas selected aromatics VOCs emissions were similar or smaller in Mexicali. Nitrogen oxides emissions for on-road heavy-duty diesel truck (HDDT) were measured near Austin, Texas, as well as in both Mexican cities, with NOy [NO subscript y] emission ratios in Austin < Mexico City < Mexicali.Mexico. Comisión Ambiental MetropolitanaNational Science Foundation (U.S.) (Grant ATM-0528227)Molina Center for Energy and the EnvironmentUniversity of Texas at AustinLatin American Scholarship Program of American Universitie

Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns

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