No abstract

The effective density and volatility of particulate emissions from five gasoline direct injection (GDI) passenger vehicles were measured using a tandem differential mobility analyzer (DMA) and centrifugal particle mass analyzer (CPMA) system. The measurements were conducted on a chassis dynamometer at three steady-state operating conditions. A thermodenuder was employed to find the volatility and mixing state of the particles as well as the effective density of nascent and non-volatile particles (defined as particle phase remaining after denuding at 200 C). The mass-mobility exponent ranged between 2.4 and 2.7 for nascent (or undenuded) particles and between 2.5 and 2.7 for non-volatile particles; higher than typical diesel soot. The effective density function was 4278d m ¡0.438 § 76.3 kg/m 3 (for mobility diameter, d m , in nm) for nascent particles and 3215d m ¡0.395 § 37.9 kg/m 3 for non-volatile particles. The effective density functions of the non-volatile particles were fairly similar for the conditions studied. The uncertainty in using the effective density and mixing state data to determine the mass concentration of the aerosol by integrating mobility size distributions was examined. The uncertainty in mass concentration is minimized when only the non-volatile component is measured. However, the uncertainty in the mass concentration increases substantially if nascent particles are measured due to uncertainties in the particle mixing state and their associated effective densities. Furthermore, transient vehicle operation (cold-starts, accelerations, and decelerations) would likely change the mixing state of the exhaust particles suggesting it is difficult to accurately measure the mass concentration of undenuded GDI exhaust particulate using integrated size distribution methods.

Mixing state refers to the relative proportions of chemical species in an aerosol, and the way these species are combined; either as a population where each particle consists of a single species ('externally mixed') or where all particles individually consist of two or more species ('internally mixed') or the case where some particles are pure and some particles consist of multiple species. The mixing state affects optical and hygroscopic properties, and quantifying it is therefore important for studying an aerosol's climate impact. In this article, we describe a method to quantify the volatile mixing state of an aerosol using a differential mobility analyzer, centrifugal particle mass analyzer, catalytic denuder, and condensation particle counter by measuring the mass distributions of the volatile and non-volatile components of an aerosol and determining how the material is mixed within and between particles as a function of mobility diameter. The method is demonstrated using two aerosol samples from a miniCAST soot generator, one with a high elemental carbon (EC) content, and one with a high organic carbon (OC) content. The measurements are presented in terms of the mass distribution of the volatile and non-volatile material, as well as measures of diversity and mixing state parameter. It was found that the high-EC soot nearly consisted of only pure particles where 86% of the total mass was non-volatile. The high-OC soot consisted of either pure volatile particles or particles that contained a mixture of volatile and non-volatile material where 8% of the total mass was pure volatile particles and 70% was non-volatile material (with the remaining 22% being volatile material condensed on non-volatile particles).

The effective density and size-resolved volatility of particles emitted from a Rolls-Royce Gnome helicopter turboshaft engine are measured at two engine speed settings (13,000 and 22,000 RPM). The effective density of denuded and undenuded particles were measured. The denuded effective densities are similar to the effective densities of particles from a gas turbine with a ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT 2 double annular combustor as well as a wide variety of internal combustion engines. The denuded effective density measurements were also used to estimate the size and number of primary particles in the soot aggregates. The primary particle size estimates show that the primary particle size was smaller at lower engine speed (in agreement with transmission electron microscopy analysis). As a demonstration, the size-resolved volatility of particles emitted from the engine are measured with a system consisting of a differential mobility analyzer, centrifugal particle mass analyzer, condensation particle counter, and catalytic stripper. This system determines the number distributions of particles that contain or do not contain non-volatile material, and the mass distributions of non-volatile material, volatile material condensed onto the surface of non-volatile particles, and volatile material forming independent particles (e.g. nucleated volatile material). It was found that the particulate at 13,000 RPM contained a measurable fraction of purely volatile material with diameters below ~25 nm and had a higher mass fraction of volatile material condensed on the surface of the soot (6-12%) compared to the 22,000 RPM condition (1-5%). This study demonstrates the potential to quantify the distribution of volatile particulate matter and gives additional information to characterize sampling effects with regulatory measurement procedures.

The effective density and mixing state of particles emitted from a natural gas–diesel dual fuel engine are investigated. Measurements were conducted at three different fuel compositions including 100% diesel fuel (0% NG), 75% diesel–25% natural gas (25% NG) and 50% diesel–50% NG (50% NG). The particle effective density was measured using a differential mobility analyzer in series with a centrifugal particle mass analyzer. A catalytic stripper at 350 °C was employed upstream of the centrifugal particle mass analyzer in order to remove the semi-volatile material from the solid particles to measure the effective density of non-volatile particles as well as the particle mixing state. A scanning mobility particle sizer was used to measure the particle size distribution. The particle mass concentration was also measured using several techniques including cavity-attenuated phase-shift particulate matter single-scattering albedo, laser-induced incandescence, thermal-optical analysis, photoacoustic spectroscopy, and integrated particle size distribution. The semi-volatile number and mass fractions are found to be lower than 15%. The effective density functions of particles at 0% and 25% NG are within 6% of each other; however, the effective density values of particles at 50% NG are lower than those of the 0% NG by up to 35%. The mass-mobility exponent varies in the range of 2.42–2.51 and 2.38–2.54 for undenuded and denuded particles, respectively. For the mass concentration measurements, photoacoustic spectroscopy agrees with thermal-optical analysis within 5%, while all the other techniques measure up to 50% deviations relative to thermal-optical analysis.