Deriving fuel-based emission factor thresholds to interpret heavy-duty vehicle roadside plume measurements.

Remote sensing devices have been used for decades to measure gaseous emissions from individual vehicles at the roadside. Systems have also been developed that entrain diluted exhaust and can also measure particulate matter (PM) emissions. In 2015, the California Air Resources Board (CARB) reported that 8% of in-field diesel particulate filters (DPF) on heavy-duty (HD) vehicles were malfunctioning and emitted about 70% of total diesel PM emissions from the DPF-equipped fleet. A new high-emitter problem in the heavy-duty vehicle fleet had emerged. Roadside exhaust plume measurements reflect a snapshot of real-world operation, typically lasting several seconds. In order to relate roadside plume measurements to laboratory emission tests, we analyzed carbon dioxide (CO2), oxides of nitrogen (NOX), and PM emissions collected from four HD vehicles during several driving cycles on a chassis dynamometer. We examined the fuel-based emission factors corresponding to possible exceedances of emission standards as a function of vehicle power. Our analysis suggests that a typical HD vehicle will exceed the model year (MY) 2010 emission standards (of 0.2 g NOX/bhp-hr and 0.01 g PM/bhp-hr) by three times when fuel-based emission factors are 9.3 g NOX/kg fuel and 0.11 g PM/kg using the roadside plume measurement approach. Reported limits correspond to 99% confidence levels, which were calculated using the detection uncertainty of emissions analyzers, accuracy of vehicle power calculations, and actual emissions variability of fixed operational parameters. The PM threshold was determined for acceleration events between 0.47 and 1.4 mph/sec only, and the NOX threshold was derived from measurements where after-treatment temperature was above 200°C. Anticipating a growing interest in real-world driving emissions, widespread implementation of roadside exhaust plume measurements as a compliment to in-use vehicle programs may benefit from expanding this analysis to a larger sample of in-use HD vehicles. IMPLICATIONS: Regulatory agencies, civil society, and the public at large have a growing interest in vehicle emission compliance in the real world. Leveraging roadside plume measurements to identify vehicles with malfunctioning emission control systems is emerging as a viable new and useful method to assess in-use performance. This work proposes fuel-based emission factor thresholds for PM and NOx that signify exceedances of emission standards on a work-specific basis by analyzing real-time emissions in the laboratory. These thresholds could be used to prescreen vehicles before roadside enforcement inspection or other inquiry, enhance and further develop emission inventories, and potentially develop new requirements for heavy-duty inspection and maintenance (I/M) programs, including but not limited to identifying vehicles for further testing.

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions.

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.

Effect of advanced aftertreatment for PM and NO(x) control on heavy-duty diesel truck emissions.

Emissions from four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreatment configurations using a chassis dynamometer. The aftertreatment included four different diesel particle filters (DPF) and two prototype selective catalytic reduction (SCR) devices for NO(x) control. The goal of the project was to fully characterize emissions from various in-use vehicles meeting the 2007 particulate matter (PM) standard for the United States and California and to provide a snapshot of emissions from 2010 compliant vehicles. The aftertreatment devices all worked as designed, realizing significant reductions of PM and NO(x). The DPF realized > 95% PM reductions irrespective of cycle and the SCRs > 75% NO(x) reductions during cruise and transient modes, but no NO(x) reductions during idle. Because of the large test matrix of vehicles and aftertreatment devices, we were able to characterize effects on additional emission species (CO, organics, and nucleation mode particles) from these devices as a function of their individual characteristics. The two predicting parameters were found to be exhaust temperature and available catalytic surface in the aftertreatment, which combine to create varying degrees of oxidizing conditions. The aftertreatments were not found to incur a fuel penalty.

A new approach to determining gas-particle reaction probabilities and application to the heterogeneous reaction of deliquesced sodium chloride particles with gas-phase hydroxyl radicals.

The reaction kinetics for gaseous hydroxyl radicals (OH) with deliquesced sodium chloride particles (NaCl(aq)) were investigated using a novel experimental approach. The technique utilizes the exposure of substrate-deposited aerosol particles to reactive gases followed by chemical analysis of the particles using computer-controlled scanning electron microscopy with energy-dispersive analysis of X-rays (CCSEM/EDX) capability. Experiments were performed at room temperature and atmospheric pressure with deliquesced NaCl particles in the micron size range at 70-80% RH and with OH concentrations in the range of 1 to 7 x 10(9) cm(-3). The apparent, pseudo first-order rate constant for the reaction was determined from measurements of changes in the chloride concentration of individual particles upon reaction with OH as a function of the particle loading on the substrate. Quantitative treatment of the data using a model that incorporates both diffusion and reaction kinetics yields a lower limit to the net reaction probability of gamma(net) > or = 0.1, with an overall uncertainty of a factor of 2.

Molecular aspects of halide ion hydration: the cluster approach.

This review provides a historical context for our understanding of the hydration shell surrounding halide ions and illustrates how the cluster systems can be used, in combination with theory, to elucidate the behavior of water molecules in direct contact with the anion. We discuss how vibrational predissociation spectroscopy, carried out with weakly bound argon atoms, has been employed to deduce the morphology of the small water networks attached to anions in the primary steps of hydration. We emphasize the importance of charge-transfer in the binary interaction, and discuss how this process affects the structures of the larger networks. Finally, we survey how the negatively charged water clusters (H2O)n(-) are providing a molecular-level perspective on how diffuse excess electrons interact with the water networks.

Spectroscopic determination of the OH- solvation shell in the OH-.(H2O)n clusters.

There has been long-standing uncertainty about the number of water molecules in the primary coordination environment of the OH- and F- ions in aqueous chemistry. We report the vibrational spectra of the OH-.(H2O)n and F-.(H2O)n clusters and interpret the pattern of OH stretching fundamentals with ab initio calculations. The spectra of the cold complexes are obtained by first attaching weakly bound argon atoms to the clusters and then monitoring the photoinduced evaporation of these atoms when an infrared laser is tuned to a vibrational resonance. The small clusters (n