A. A. Mensah

Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol

In the atmosphere night time removal of volatile organic compounds (VOC) is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model (CTM) indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

Measurement of Aircraft Engine Non-Volatile PM Emissions: Results of the Aviation-Particle Regulatory Instrumentation Demonstration Experiment (A-PRIDE) 4 Campaign

This study reports the first of a kind data on aircraft engine non-volatile particulate matter (nvPM) number- and mass-based emissions using standardized systems. Two compliant sampling and measurement systems operated by Missouri University of Science and Technology (Missouri S&T) and Empa were evaluated during the Aviation - Particle Regulatory Instrumentation Demonstration Experiment (A-PRIDE) 4 campaign at the SR Technics facilities in Zürich, Switzerland, in November 2012. The Missouri S&T and Empa systems were compared during a series of dedicated engine tests using a CFM56-5B4/2P engine source, and maintenance engine testing using CFM56-7B24/3 and PW4168A engine sources at a range of engine operating conditions. These two compliant systems were found to agree within 6% of each other in terms of nvPM number-based emissions, and within 15% for nvPM mass-based emissions. For the three engine sources studied, at several engine power conditions the mass instruments approached their limit of detection, resulting in high measurement uncertainties. Ancillary instrumentation was used to determine PM size distributions, chemical composition, and effective density from mass-mobility experiments. Particle geometric mean mobility diameter ranged 20–45 nm, and geometric standard deviation varied from 1.55 to 1.9 for the three engine types studied. The fraction of PM organic content measured in the emissions from the CFM56-5B4/2P engine was ∼4% while the size-dependent particle effective density was parameterized with a mass-mobility exponent of 2.57 and a pre-factor of 0.606. Results of this study will contribute to the development of the new nvPM emissions certification standard and emissions inventories from commercial aviation operations.

Organic Emissions from a Wood Stove and a Pellet Stove Before and After Simulated Atmospheric Aging

Logwood and pellet stoves are popular heating sources around the world. The particulate matter emitted from such stoves contains organic particulate matter (OM), soot, and ash, each of which may have significant effects on climate and health. In this study, the primary OM (POM) emitted from a wood stove and a pellet stove operated according to standard Swiss testing protocols were characterized using aerosol mass spectrometry. The POM mass spectra were found to be highly reproducible, and contained CO+ as the dominant ion. Because the POM emitted by such stoves is typically enhanced by the condensation of gaseous organics following atmospheric aging, the secondary OM (SOM) formation potential of these stoves was simulated using the Micro Smog Chamber (MSC) designed by Keller and Burtscher in 2012. In general, OM emission factors from MSC-aged aerosols were comparable to lower-time-resolution results from the literature, although the MSC exposed aerosols to much higher concentrations of oxidants and therefore produced OM that was more oxidized than expected for atmospheric samples. In addition, the logwood-stove particles remained highly aspherical even after oxidation, indicating that mixing with an external aerosol is required for these particles to become spherical. The one exception to this observation occurred when the wood failed to ignite and appeared to generate tar-ball OM particles.

Investigations of SP-AMS Carbon Ion Distributions as a Function of Refractory Black Carbon Particle Type

The soot particle aerosol mass spectrometer (SP-AMS) instrument combines continuous wave laser vaporization with electron ionization aerosol mass spectrometry to characterize airborne, refractory black carbon (rBC) particles. The laser selectively vaporizes absorbing rBC-containing particles, allowing the SP-AMS to provide direct chemical information on the refractory and non-refractory chemical components, providing the potential to fingerprint various rBC particle types. In this study, SP-AMS mass spectra were measured for 12 types of rBC particles produced by industrial and combustion processes to explore differences in the carbon cluster (Cn+) mass spectra. The Cn+ mass spectra were classified into three categories based on their ion distributions, which varied with rBC particle type. The carbon ion distributions were investigated as a function of laser power, electron ionization (on/off), and ion charge (positive or negative). Results indicate that the dominant positive ion-formation mechanism is likely the vaporization of small, neutral carbon clusters followed by electron ionization (C1+ to C5+). Significant ion signal from larger carbon cluster ions (and their fragment ions in the small carbon cluster range), including mid carbon (C6+ to C29+) and fullerene (greater than C30+) ions, were observed in soot produced under incomplete combustion conditions, including biomass burning, as well as in fullerene-enriched materials. Fullerene ions were also observed at high laser power with electron ionization turned off, formed via an additional ionization mechanism. We expect this SP-AMS technique to find application in the identification of the source and atmospheric history of airborne ambient rBC particles. Copyright 2015 American Association for Aerosol Research

Particle Emission Characteristics of a Gas Turbine with a Double Annular Combustor

The total climate, air quality, and health impact of aircraft black carbon (BC) emissions depend on quantity (mass and number concentration) as well as morphology (fractal dimension and surface area) of emitted BC aggregates. This study examines multiple BC emission metrics from a gas turbine with a double annular combustor, CFM56-5B4-2P. As a part of the SAMPLE III.2 campaign, concurrent measurements of particle mobility, particle mass, particle number concentration, and mass concentration, as well as collection of transmission electron microscopy (TEM) samples, allowed for characterization of the BC emissions. Mass- and number-based emission indices were strongly influenced by thrust setting during pilot combustion and ranged from <1 to 208 mg/kg-fuel and 3 ×× 1012 to 3 ×× 1016 particles/kg-fuel, respectively. Mobility measurements indicated that mean diameters ranged from 7 to 44 nm with a strong dependence on thrust during pilot-only combustion. Using aggregation and sintering theory with empirical effective density relationships, a power-law relationship between primary particle diameter and mobility diameter is presented. Mean primary particle diameter ranged from 6 to 19 nm; however, laser-induced incandescence (LII) and mass-mobility-calculated primary particle diameters demonstrated opposite trends with thrust setting. Similarly, mass-mobility-calculated aggregate mass specific surface area and LII-measured surface area were not in agreement, indicating both methods need further development and validation before use as quantitative indicators of primary particle diameter and mass-specific surface area. Copyright 2015 American Association for Aerosol Research