Insights to the 3D internal morphology and metal oxidation states of single atmospheric aerosol particles by synchrotron-based methodology.

The morphology and metal oxidation states of atmospheric aerosols are pertinent to their formation processes and ensuing interactions with surrounding gases, vapors and other environments upon deposition, such as human respiratory tract, soil and water. Although much progress has been made in recent years through single-particle techniques, considerably less is known with respect to the three-dimensional (3D) internal morphology of single atmospheric aerosol particles due to the limited penetration depth of electron microscopy. In this study, for the first time, a novel synchrotron-based transmission X-ray microscopy (TXM) methodology has been developed to visualize the 3D internal chemical mixing state and structure of single particles. The results show that the TXM is more applicable to the imaging of solid particles containing high-density elements, e.g., iron (Fe), aluminum (Al), silicone (Si), carbon (C) and sulfur (S), and/or solid particles of sizes larger than about 100 nm. In addition, the TXM is capable to reveal the fine 3D topographic features of single particles. The derived 3D internal and external information would be difficult to discern in the 2D images from electron microscopy. The TXM 3D images illustrate that aerosol particles exhibit complex internal mixing state and structure, e.g., homogeneously-, heterogeneously-mixed, multiple inclusions, fibrous, porous, and core-shell configuration. When coupled with the synchrotron-based X-ray fluorescence spectrometry (XRF) and absorption near-edge spectroscopy (XANES) of an X-ray nanoprobe in the energy range of 4-15 keV, the 3D morphology of single particles is further supplemented with the spatial distribution and oxidation sates of selected elements, including Fe, vanadium (V), manganese (Mn), chromium (Cr) and arsenic (As). The presented cross-platform, synchrotron-based methodology shows promise in complementing existing single-particle techniques and providing new insights to the heterogeneity of single-particle micro-physicochemical states relevant to the aerosol chemistry, optical properties, and their environmental and health impacts.

Elevated emissions of volatile and nonvolatile nanoparticles from heavy-duty diesel engine running on diesel-gas co-fuels.

This study experimentally examines the effects of four diesel-gas co-fuels, two engine loads and an aftertreatment on regulated and unregulated emissions from a 6-cylinder natural-aspirated direct-injection heavy-duty diesel engine (HDDE) with an engine dynamometer. Fuel energy of ultra-low-sulfur diesel was substituted with 10% and 20% of gas fuels, including pure H2, CH4, and two CH4-CO2 blends. The particle number size distributions of volatile and nonvolatile nanoparticles were measured under ambient temperature and after 300 °C heating, respectively. The results show that the gas fuels caused increases of hydrocarbon emission, slight changes of NOx emission, and decreases of opacity. All four gas fuels resulted in elevated emissions of both volatile and nonvolatile nanoparticles at 25% and 75% load, in the range of 29% to 390%. The increased emissions of volatile nanoparticles were variable and without obvious trends. Special attentions should be given to the addition of H2 under high load, during which significant increases of volatile nanoparticles could be formed not only post-combustion (up to 1376%), but also post-diesel oxidation catalyst plus diesel particulate filter (DOC + DPF). The nonvolatile nanoparticles, on the other hand, could be effectively removed by the retrofitted DOC + DPF, with efficiency >98.2%. A noteworthy fraction of solid particles of sizes <23 nm were found in the exhaust, not being accounted for by current regulatory emission standard.