Real-Time Measurements of Engine-Out Trace Elements: Application of a Novel Soot Particle Aerosol Mass Spectrometer for Emissions Characterization

Lubricant-derived trace element emissions are the largest contributors to the accumulation of incombustible ash in diesel particulate filters (DPF), eventually leading to filter plugging and an increase in engine fuel consumption. Particulate trace element emissions also pose adverse health effects and are the focus of increasingly stringent air quality regulations. To date, the rates and physical and chemical properties of lubricant-derived additive emissions are not well characterized, largely due to the difficulties associated with conducting the measurements. This work investigated the potential for conducting real-time measurements of lubricant-derived particle emissions. The experiment used the Soot Particle Aerosol Mass Spectrometer (SP-AMS) developed by Aerodyne Research to measure the size, mass and composition of submicron particles in the exhaust. Results confirm the ability of the SP-AMS to measure engine-out emissions of calcium, zinc, magnesium, phosphorous, and sulfur. Further, emissions of previously difficult to detect elements, such as boron, and low-level engine wear metals, such as lead, were also measured. This paper provides an overview of the results obtained with the SP-AMS, and demonstrates the utility of applying real-time techniques to engine-out and tailpipe-out trace element emissions. The SP-AMS used in this study was developed for real-time characterization of refractory particles (i.e. black carbon or soot) in the ambient atmosphere. The instrument consists of an intra-cavity laser (1064 nm) for particle vaporization followed by electron impact ionization and ion detection via a time-of-flight mass spectrometer. Application of the SP-AMS for engine exhaust characterization followed a two-part approach: (1) measurement validation, and (2) measurement of engine-out exhaust. Measurement validation utilized a diesel burner with precise control of lubricant consumption. Results showed a good correlation between CJ-4 oil consumption and measured levels of lubricant-derived trace elements in the particle phase. Following measurement validation, the SP-AMS measured engine-out emissions from a medium-duty diesel engine, operated over a standard speed/load matrix. This work demonstrates the utility of state-of-the-art online techniques (such as the SP-AMS) to measure engine-out emissions, including trace species derived from lubricant additives. Results help optimize the combined engine-lubricant-aftertreatment system and provide a real-time characterization of emissions. As regulations become more stringent and emission controls more complex, advanced measurement techniques with high sensitivity and fast time response will become an increasingly important part of engine characterization studies.United States. Environmental Protection Agency (grant RD834560)United States. Department of Energy (Contract DE-FG02-07ER84890 SBIR)United States. National Aeronautics and Space Administration (Contract NNX10CA32C SBIR)nited States. National Aeronautics and Space Administration (Contract NA09OAR4310125)Camille and Henry Dreyfus Foundation (environmental chemistry postdoctoral fellowship