Chris A. Jakober

Size and Composition Distributions of Particulate Matter Emissions: Part 1—Light-Duty Gasoline Vehicles

Abstract Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965–2003; odometer readings 1264–207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-μm aerodynamic diameter) and fine PM1.8 (≤1.8-μm aerodynamic diame ter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emis sions of 51 μg/km and 371 μg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1-and 0.18-μm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 μm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.

Size and Composition Distributions of Particulate Matter Emissions: Part 2-Heavy-Duty Diesel Vehicles

Abstract Particulate matter (PM) emissions from heavy-duty diesel vehicles (HDDVs) were collected using a chassis dynamometer/dilution sampling system that employed filter-based samplers, cascade impactors, and scanning mobility particle size (SMPS) measurements. Four diesel vehicles with different engine and emission control technologies were tested using the California Air Resources Board Heavy Heavy-Duty Diesel Truck (HHDDT) 5 mode driving cycle. Vehicles were tested using a simulated inertial weight of either 56,000 or 66,000 lb. Exhaust particles were then analyzed for total carbon, elemental carbon (EC), organic matter (OM), and water-soluble ions. HDDV fine (≤1.8 μm aerodynamic diameter; PM1.8) and ultra fine (0.056–0.1 μm aerodynamic diameter; PM0.1) PM emission rates ranged from 181–581 mg/km and 25–72 mg/km, respectively, with the highest emission rates in both size fractions associated with the oldest vehicle tested. Older diesel vehicles produced fine and ultrafine exhaust particles with higher EC/OM ratios than newer vehicles. Transient modes produced very high EC/OM ratios whereas idle and creep modes produced very low EC/OM ratios. Calcium was the most abundant water-soluble ion with smaller amounts of magnesium, sodium, ammonium ion, and sulfate also detected. Particle mass distributions emitted during the full 5-mode HDDV tests peaked between 100–180 nm and their shapes were not a function of vehicle age. In contrast, particle mass distributions emitted during the idle and creep driving modes from the newest diesel vehicle had a peak diameter of approximately 70 nm, whereas mass distributions emitted from older vehicles had a peak diameter larger than 100 nm for both the idle and creep modes. Increasing inertial loads reduced the OM emissions, causing the residual EC emissions to shift to smaller sizes. The same HDDV tested at 56,000 and 66,000 lb had higher PM0.1 EC emissions (+22%) and lower PM0.1 OM emissions (–38%) at the higher load condition.

Emission Factors for High-Emitting Vehicles Based on On-Road Measurements of Individual Vehicle Exhaust with a Mobile Measurement Platform.

ABSTRACT Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NOx), and particle mass with aerodynamic diameter below 2.5 μm (PM2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NOx, black carbon (BC), PM2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NOx and CO fleet-average emission factors and more than 60% of PM2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM2.5, and NOx tended to cluster among the same vehicles. IMPLICATIONS This study presents the characterization of on-road vehicle emissions in Wilmington, CA, by sampling individual vehicle plumes. Approximately 5% of the vehicles were high emitters, whose emissions were more than 5 times the fleet-average values. These high emitters were responsible for 30% and more than 50% of the average emission factors of LDGVs and HDDVs, respectively. It is likely that as the overall fleet becomes cleaner due to more stringent regulations, a small fraction of the fleet may contribute a growing and disproportionate share of the overall emissions. Therefore, long-term changes in on-road emissions need to be monitored.

Mobile measurements of climate forcing agents: Application to methane emissions from landfill and natural gas compression.

Measuring greenhouse gas (GHG) source emissions provides data for validation of GHG inventories, which provide the foundation for climate change mitigation. Two Toyota RAV4 electric vehicles were outfitted with high-precision instrumentation to determine spatial and temporal resolution of GHGs (e.g., nitrous oxide, methane [CH4], and carbon dioxide [CO2]), and other gaseous species and particulate metrics found near emission sources. Mobile measurement platform (MMP) analytical performance was determined over relevant measurement time scales. Pollutant residence times through the sampling configuration were measured, ranging from 3 to 11 sec, enabling proper time alignment for spatial measurement of each respective analyte. Linear response range for GHG analytes was assessed across expected mixing ratio ranges, showing minimal regression and standard error differences between 5, 10, 30, and 60 sec sampling intervals and negligible differences between the two MMPs. GHG instrument drift shows deviation of less than 0.8% over a 24-hr measurement period. These MMPs were utilized in tracer-dilution experiments at a California landfill and natural gas compressor station (NGCS) to quantify CH4 emissions. Replicate landfill measurements during October 2009 yielded annual CH4 emissions estimates of 0.10 ± 0.01, 0.11 ± 0.01, and 0.12 ± 0.02 million tonnes of CO2 equivalent (MTCO2E). These values compare favorably to California GHG Emissions Inventory figures for 2007, 2008, and 2009 of 0.123, 0.125, and 0.126 MTCO2E/yr, respectively, for this facility. Measurements to quantify NGCS boosting facility-wide emissions, during June 2010 yielded an equivalent of 5400 ± 100 TCO2E/yr under steady-state operation. However, measurements during condensate transfer without operational vapor recovery yield an instantaneous emission rate of 2–4 times greater, but was estimated to only add 12 TCO2E/yr overall. This work displays the utility for mobile GHG measurements to validate existing measurement and modeling approaches, so emission inventory values can be confirmed and associated uncertainties reduced. Implications: Measuring greenhouse gas (GHG) source emissions provides data and validation for GHG inventories, the foundation for climate change mitigation. Mobile measurement platforms with robust analytical instrumentation completed tracer-dilution experiments in California at a landfill and natural gas compressor station (NGCS) to quantify CH4 emissions. Data collected for landfill CH4 agree with the current California emissions inventory, while NGCS data show the possible variability from this type of facility. This work displays the utility of mobile GHG measurements to validate existing measurement and modeling approaches, such that emission inventory values can be confirmed, associated uncertainties reduced, and mitigation efforts quantified.

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles.

Abstract A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.