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Diesel engines are known to emit high number concentrations of nanoparticles (diameter < 50 nm), but the physical and chemical mechanisms by which they form are not understood. Information on chemical composition is lacking because the small size, low mass concentration, and potential for contamination of samples obtained by standard techniques make nanoparticles difficult to analyze. A nano-differential mobility analyzer was used to size-select nanoparticles (mass median diameter approximately 25-60 nm) from diesel engine exhaust for subsequent chemical analysis by thermal desorption particle beam mass spectrometry. Mass spectra were used to identify and quantify nanoparticle components, and compound molecular weights and vapor pressures were estimated from calibrated desorption temperatures. Branched alkanes and alkyl-substituted cycloalkanes from unburned fuel and/or lubricating oil appear to contribute most of the diesel nanoparticle mass. The volatility of the organic fraction of the aerosol increases as the engine load decreases and as particle size increases. Sulfuric acid was also detected at estimated concentrations of a few percent of the total nanoparticle mass. The results are consistent with a mechanism of nanoparticle formation involving nucleation of sulfuric acid and water, followed by particle growth by condensation of organic species.

Mixing characteristics of particles of different volatilities from a diesel engine were studied with two tandem differential mobility analyzers (TDMAs) and an aerosol particle mass analyzer (APM). In both TDMA systems, a heater was located in the aerosol path between the first and second DMAs. Diesel exhaust particles that were size-selected in the first DMA were passed through the heater, and the change in particle size due to loss of volatile components was determined by the second DMA. On the basis of the volatility measurements, the particles could be separated into two overlapping modes that varied in peak diameter and magnitude depending on the engine operating conditions. Particles in the smaller size mode were almost completely volatile, while those in the larger size mode contained a nonvolatile core. The TDMA data inversion technique used here allowed accurate determination of the mixing ratios of the two types of particles. These data were in turn used to validate a simple fitting method that uses two log-normal curves to obtain the mixing ratios. In some experiments, the APM was used downstream of a TDMA to directly measure the particle mass loss due to evaporation. The loss determined by the TDMA−APM system was significantly greater than that calculated from mobility size changes measured solely with the TDMA. The TDMA−APM results were used to calculate the size-dependent mass concentrations of volatile and nonvolatile components for particles in the size range from 70 to 200 nm.

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