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

Radiolytic Hydrogen Production in the Subseafloor Basaltic Aquifer

Hydrogen (H2) is produced in geological settings by dissociation of water due to radiation from radioactive decay of naturally occurring uranium (238U, 235U), thorium (232Th) and potassium (40K). To quantify the potential significance of radiolytic H2 as an electron donor for microbes within the South Pacific subseafloor basaltic aquifer, we use radionuclide concentrations of 43 basalt samples from IODP Expedition 329 to calculate radiolytic H2 production rates in basement fractures. The samples are from three sites with very different basement ages and a wide range of alteration types. U, Th, and K concentrations vary by up to an order of magnitude from sample to sample at each site. Comparison of our samples to each other and to the results of previous studies of unaltered East Pacific Rise basalt suggests that significant variations in radionuclide concentrations are due to differences in initial (unaltered basalt) concentrations (which can vary between eruptive events) and post-emplacement alteration. However, there is no clear relationship between alteration type and calculated radiolytic yields. Local maxima in U, Th, and K produce hotspots of H2production, causing calculated radiolytic rates to differ by up to a factor of 80 from sample to sample. Fracture width also greatly influences H2 production, where microfractures are hotspots for radiolytic H2 production. For example, H2 production rates normalized to water volume are 190 times higher in 1 μm wide fractures than in fractures that are 10 cm wide. To assess the importance of water radiolysis for microbial communities in subseafloor basaltic aquifers, we compare electron transfer rates from radiolysis to rates from iron oxidation in subseafloor basalt. Radiolysis appears likely to be a more important electron donor source than iron oxidation in old (\u3e10 Ma) basement basalt. Radiolytic H2 production in the volume of water adjacent to a square cm of the most radioactive SPG basalt may support as many as 1500 cells

Observations of heterogeneous reactions between Asian pollution and mineral dust over the Eastern North Pacific during INTEX-B

In-situ airborne measurements of trace gases, aerosol size distributions, chemistry and optical properties were conducted over Mexico and the Eastern North Pacific during MILAGRO and INTEX-B. Heterogeneous reactions between secondary aerosol precursor gases and mineral dust lead to sequestration of sulfur, nitrogen and chlorine in the supermicrometer particulate size range. Simultaneous measurements of aerosol size distributions and weak-acid soluble calcium result in an estimate of 11 wt% of CaCO_3 for Asian dust. During transport across the North Pacific, ~5–30% of the CaCO_3 is converted to CaSO_4 or Ca(NO_3)_2 with an additional ~4% consumed through reactions with HCl. The 1996 to 2008 record from the Mauna Loa Observatory confirm these findings, indicating that, on average, 19% of the CaCO_3 has reacted to form CaSO_4 and 7% has reacted to form Ca(NO_3)_2 and ~2% has reacted with HCl. In the nitrogen-oxide rich boundary layer near Mexico City up to 30% of the CaCO_3 has reacted to form Ca(NO_3)_2 while an additional 8% has reacted with HCl. These heterogeneous reactions can result in a ~3% increase in dust solubility which has an insignificant effect on their optical properties compared to their variability in-situ. However, competition between supermicrometer dust and submicrometer primary aerosol for condensing secondary aerosol species led to a 25% smaller number median diameter for the accumulation mode aerosol. A 10–25% reduction of accumulation mode number median diameter results in a 30–70% reduction in submicrometer light scattering at relative humidities in the 80–95% range. At 80% RH submicrometer light scattering is only reduced ~3% due to a higher mass fraction of hydrophobic refractory components in the dust-affected accumulation mode aerosol. Thus reducing the geometric mean diameter of the submicrometer aerosol has a much larger effect on aerosol optical properties than changes to the hygroscopic:hydrophobic mass fractions of the accumulation mode aerosol. In the presence of dust, nitric acid concentrations are reduced to 85% to 60–80% in the presence of dust. These observations support previous model studies which predict irreversible sequestration of reactive nitrogen species through heterogeneous reactions with mineral dust during long-range transport

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

Analysis of aircraft and satellite measurements from the Intercontinental Chemical Transport Experiment (INTEX-B) to quantify long-range transport of East Asian sulfur to Canada

We interpret a suite of satellite, aircraft, and ground-based measurements over the North Pacific Ocean and western North America during April&amp;ndash;May 2006 as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign to understand the implications of long-range transport of East Asian emissions to North America. The Canadian component of INTEX-B included 33 vertical profiles from a Cessna 207 aircraft equipped with an aerosol mass spectrometer. Long-range transport of organic aerosols was insignificant, contrary to expectations. Measured sulfate plumes in the free troposphere over British Columbia exceeded 2 μg/m&lt;sup&gt;3&lt;/sup&gt;. We update the global anthropogenic emission inventory in a chemical transport model (GEOS-Chem) and use it to interpret the observations. Aerosol Optical Depth (AOD) retrieved from two satellite instruments (MISR and MODIS) for 2000&amp;ndash;2006 are analyzed with GEOS-Chem to estimate an annual growth in Chinese sulfur emissions of 6.2% and 9.6%, respectively. Analysis of aircraft sulfate measurements from the NASA DC-8 over the central Pacific, the NSF C-130 over the east Pacific and the Cessna over British Columbia indicates most Asian sulfate over the ocean is in the lower free troposphere (800&amp;ndash;600 hPa), with a decrease in pressure toward land due to orographic effects. We calculate that 56% of the measured sulfate between 500&amp;ndash;900 hPa over British Columbia is due to East Asian sources. We find evidence of a 72&amp;ndash;85% increase in the relative contribution of East Asian sulfate to the total burden in spring off the northwest coast of the United States since 1985. Campaign-average simulations indicate anthropogenic East Asian sulfur emissions increase mean springtime sulfate in Western Canada at the surface by 0.31 μg/m&lt;sup&gt;3&lt;/sup&gt; (~30%) and account for 50% of the overall regional sulfate burden between 1 and 5 km. Mean measured daily surface sulfate concentrations taken in the Vancouver area increase by 0.32 μg/m&lt;sup&gt;3&lt;/sup&gt; per 10% increase in the simulated fraction of Asian sulfate, and suggest current East Asian emissions episodically degrade local air quality by more than 1.5 μg/m&lt;sup&gt;3&lt;/sup&gt;

A regional scale modeling analysis of aerosol and trace gas distributions over the eastern Pacific during the INTEX-B field campaign

The Sulfur Transport and dEposition Model (STEM) is applied to the analysis of observations obtained during the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), conducted over the eastern Pacific Ocean during spring 2006. Predicted trace gas and aerosol distributions over the Pacific are presented and discussed in terms of transport and source region contributions. Trace species distributions show a strong west (high) to east (low) gradient, with the bulk of the pollutant transport over the central Pacific occurring between similar to 20 degrees N and 50 degrees N in the 2-6 km altitude range. These distributions are evaluated in the eastern Pacific by comparison with the NASA DC-8 and NSF/NCAR C-130 airborne measurements along with observations from the Mt. Bachelor (MBO) surface site. Thirty different meteorological, trace gas and aerosol parameters are compared. In general the meteorological fields are better predicted than gas phase species, which in turn are better predicted than aerosol quantities. PAN is found to be significantly overpredicted over the eastern Pacific, which is attributed to uncertainties in the chemical reaction mechanisms used in current atmospheric chemistry models in general and to the specifically high PAN production in the SAPRC-99 mechanism used in the regional model. A systematic underprediction of the elevated sulfate layer in the eastern Pacific observed by the C-130 is another issue that is identified and discussed. Results from source region tagged CO simulations are used to estimate how the different source regions around the Pacific contribute to the trace gas species distributions. During this period the largest contributions were from China and from fires in South/Southeast and North Asia. For the C-130 flights, which operated off the coast of the Northwest US, the regional CO contributions range as follows: China (35%), South/Southeast Asia fires (35%), North America anthropogenic (20%), and North Asia fires (10%). The transport of pollution into the western US is studied at MBO and a variety of events with elevated Asian dust, and periods with contributions from China and fires from both Asia and North America are discussed. The role of heterogeneous chemistry on the composition over the eastern Pacific is also studied. The impacts of heterogeneous reactions at specific times can be significant, increasing sulfate and nitrate aerosol production and reducing gas phase nitric acid levels appreciably (~50%)

Total Observed Organic Carbon (TOOC): A synthesis of North American observations

Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m^−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink

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

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP-3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ∼10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in the springtime troposphere of the North Pacific is responsible for this increased O3. This change is evidenced in the eastern North Pacific ITCT 2K2 study region by (1) larger increases in the minimum observed ozone levels compared to more modest increases in the maximum levels, (2) increased peroxyacetyl nitrate (PAN) levels that parallel trends in NOx, emissions, and (3) decreased efficiency of photochemical O3 destruction, i.e., less negative O3 photochemical tendency (or net rate of O3 photochemical production; P(O3)). This change photochemical environment is hypothesized to be due to anthropogenic emissions from Asia, which are believed to have substantially increased over the two decades preceding the study. We propose that their influence has changed the springtime Pacific tropospheric photochemistry from predominately ozone destroying to more nearly ozone producing. However, chemical transport model calculations indicate the possible influence of a confounding factor; unusual transport of tropical air to the western North Pacific during one early field study may have played a role in this apparent change in the photochemistry. Copyright 2004 by the American Geophysical Union