Takuma Miyakawa

Characterization of an Aerodyne Aerosol Mass Spectrometer (AMS): Intercomparison with other aerosol instruments

The Aerodyne Aerosol Mass Spectrometer (AMS) provides size-resolved chemical composition of non-refractory (vaporized at 600°C under vacuum) submicron aerosols with a time resolution of the order of minutes. Ambient measurements were performed in Tokyo between February 2003 and February 2004. We present intercomparisons of the AMS with a Particle-Into-Liquid Sampler combined with an Ion Chromatography analyzer (PILS-IC) and a Sunset Laboratory semi-continuous thermal-optical carbon analyzer. The temperature of the AMS inlet manifold was maintained at > 10 ˆ C above the ambient dew point to dry particles in the sample air (relative humidity (RH) in the inlet < 53%). Assuming a particle collection efficiency of 0.5 for the AMS, the mass concentrations of inorganic species (nitrate, sulfate, chloride, and ammonium) measured by the AMS agree with those measured by the PILS-IC to within 26%. The mass concentrations of organic compounds measured by the AMS correlate well with organic carbon (OC) mass measured by the Sunset Laboratory carbon analyzer (r 2 = 0.67–0.83). Assuming the same collection efficiency of 0.5 for the AMS organics, the linear regression slope is found to be 1.8 in summer and 1.6 in fall. These values are consistent with expected ratios of organic matter (OM) to OC in urban air.

Evolution of mixing state of black carbon particles : Aircraft measurements over the western Pacific in March 2004

0.63within12hours(h),namely2.3%h 1 ,afterbeingemitted from the Nagoya urban area in Japan. BC particles with a core diameter of 250 nm increased at the slower rate of 1.0% h 1 . The increase in coated BC particles was associated with increases in non-sea salt sulfate and water-soluble organic carbon by a factor of approximately two, indicating that these compounds contributed to the coating on the BC particles. These results give direct evidence that BC particles become internally mixed on a time scale of 12 h in urban plumes. Citation: Moteki, N., Y. Kondo, Y. Miyazaki, N. Takegawa, Y. Komazaki, G. Kurata, T. Shirai, D. R. Blake, T. Miyakawa, and M. Koike (2007), Evolution of mixing state of black carbon particles: Aircraft measurements over the western Pacific in March 2004,Geophys. Res. Lett., 34, L11803, doi:10.1029/2006GL028943.

Consistency and Traceability of Black Carbon Measurements Made by Laser-Induced Incandescence, Thermal-Optical Transmittance, and Filter-Based Photo-Absorption Techniques

In this study, we show that black carbon (BC) mass concentrations measured by different techniques are consistent and traceable. First, we present the volatilities of 13 organic compounds passed through a heated inlet. These data were used to quantify the interference of organic aerosols on the BC measurement techniques. The masses of the refractory particles that incandesce (m*ref) were used to calibrate BC mass measured by a single-particle soot photometer (SP2), which uses laser-induced incandescence. This calibration was influenced little by refractory organics and agreed well with that of fullerene soot, which indicates the consistency of the standards. We estimated the interference of pyrolyzed refractory organics on the BC measured with a filter-based absorption photometer continuous soot monitoring system (COSMOS) with a heated inlet to be small in Asia. This was also confirmed by the stable mass absorption cross section (MAC) obtained by the high correlations between BC mass concentrations measured by COSMOS (M COSMOS) and those measured by the thermal-optical transmittance method (M TOT) (Kondo et al. 2009). M COSMOS was also compared with total BC mass concentrations measured with an SP2 (M SP2) in Tokyo in 2009. M COSMOS and M SP2 were highly correlated (r 2= 0.97) and agreed to within about 10% on average. These results demonstrate that M SP2, M COSMOS, and M TOT were nearly identical. Use of the masses of incandescing refractory BC particles for calibration of BC mass concentrations determined by different techniques gave consistent results.

Contribution of Selected Dicarboxylic and ω-Oxocarboxylic Acids in Ambient Aerosol to the m/z 44 Signal of an Aerodyne Aerosol Mass Spectrometer

The Aerodyne aerosol mass spectrometer (AMS) employs flash vaporization (600°C) followed by 70-eV electron impact ionization (EI) to detect organic and inorganic aerosols. The signal at mass-to-charge ratio (m/z) 44 (mainly CO 2 + ) is considered the most reliable marker of oxygenated organic aerosol. This study is the first to evaluate the contribution of selected low molecular weight dicarboxylic acids (diacids) and ω-oxocarboxylic acids (ω-oxoacids) to the particle-phase m/z 44 signal of the AMS mass spectrum. Ambient measurements were conducted at a surface site in Tokyo (35°39 ′ N, 139°40 ′ E) during August 3–8, 2003. Diacids and ω-oxoacids were measured using a filter sampling followed by extraction, derivation, and gas chromatograph-flame ionization detector (GC-FID) analysis. The mass concentrations of diacids and ω-oxoacids show tight correlation with the m/z 44 signal (r 2 = 0.85–0.94) during the measurement period. Laboratory experiments were also performed to determine the fragment patterns of selected diacids (C2–C6 diacids and phthalic acids) and ω-oxoacid (glyoxylic acid) in ambient aerosols. Here, we report for the first time that the selected organic acids could account for 14 ± 5% of the observed m/z 44 signal on average during the measurement period. Oxalic acid (C2) is the largest contributor, accounting for 10 ± 4% of the observed m/z 44 signal. These results would be useful for interpreting the m/z 44 signals obtained from ambient measurements in various locations.

Performance of an Aerodyne Aerosol Mass Spectrometer (AMS) during Intensive Campaigns in China in the Summer of 2006

An Aerodyne quadrupole aerosol mass spectrometer (AMS) was deployed in China in the summer of 2006. The measurements were made in the Pearl River Delta region in July 2006 (PRD campaign) and also in Beijing in August–September 2006 (CAREBEIJING campaign). The AMS successfully measured size-resolved chemical composition of submicron non-refractory aerosol (vaporized at 600°C in vacuum) with a time resolution of 10 min, although some quantification issues have been identified. We observed extremely large signals at m/z 39 ( 39 K + ) and 41 (41K + ), which significantly exceeded m/z 28 (N + 2 ) signals. We also found large signals of m/z 85 ( 85 Rb + ), 87 (87Rb + ), and 133 (Cs + ). Laboratory experiments suggest that the large enhancement of K + could have been due to the presence of K-containing particles in ambient air. The interferences of alkali metals at m/z 41, 85, 87, and 133 were significant and need to be corrected for better quantification of organic aerosol. The AMS measurements are compared with other, collocated measurements: a particle-into-liquid sampler combined with an ion chromatograph (PILS-IC), a Sunset Laboratory semi-continuous carbonaceous aerosol analyzer, and a Berner impactor sampler followed by off-line ion chromatography analysis (for major inorganic ions). We have found good agreement between the AMS and the other instruments when we assume an AMS particle collection efficiency (CE) of 0.5 for the PRD data and CE = 1.0 for the CAREBEIJING data. These results suggest that the AMS CE could be significantly different in different locations. Possible factors affecting the variability in the CE values are discussed.

Laboratory measurements of emission factors of nonmethane volatile organic compounds from burning of Chinese crop residues

The emission factors (EFs) of nonmethane volatile organic compounds (NMVOCs) emitted during the burning of Chinese crop residue were investigated as a function of modified combustion efficiency in laboratory experiments. NMVOCs, including acetonitrile, aldehydes/ketones, furan, and aromatic hydrocarbons, were monitored by proton-transfer-reaction mass spectrometry. Rape plant was burned in dry conditions and wheat straw was burned in both wet and dry conditions to simulate the possible burning of damp crop residue in regions of high temperature and humidity. We compared the present data to field data reported by Kudo et al. (2014). Good agreement between field and laboratory data was obtained for aromatics under relatively more smoldering combustion of dry samples, but laboratory data were slightly overestimated compared to field data for oxygenated VOC (OVOC). When EFs from the burning of wet samples were investigated, the consistency between the field and laboratory data for OVOCs was stronger than for dry samples. This may be caused by residual moisture in crop residue that has been stockpiled in humid regions. Comparison of the wet laboratory data with field data suggests that Kudo et al. (2014) observed the biomass burning plumes under relatively more smoldering conditions in which approximately a few tens of percentages of burned fuel materials were wet.

Ground‐based measurement of fluorescent aerosol particles in Tokyo in the spring of 2013: Potential impacts of nonbiological materials on autofluorescence measurements of airborne particles

We present results from the observation of fluorescent (FL) aerosols in Tokyo in the spring of 2013. Ambient aerosol particles were analyzed using a single-particle laser-induced fluorescence instrument. The fluorescent emission from a single particle excited by a pulsed UV laser (excitation wavelength of 263 nm) was detected by three photomultiplier tubes with band-pass filters (fluorescence wavelength of 335–379, 420–500, and 500–600 nm). Fluorescence patterns from single particles were analyzed for investigating fluorophores and their sources using backward trajectory analysis, factor analysis, and a comparison with other tracer observations. The backward trajectory analysis suggested possible influences of long-range transport from northern China in some cases. Observed supermicron FL aerosols were classified into two types: combustion- and dust-type particles. The detection of combustion-type FL aerosols, which showed temporal variations similar to nitrogen oxides and elemental carbon, implied the presence of polyaromatic hydrocarbons (PAHs) and their derivatives. Dust-type FL aerosols, which were well correlated with the lidar-derived dust-aerosol optical depth near the surface (<1 km) and with mineral ions, were dominant in the supermicron size range. The number concentrations of coarse FL aerosols (≥2 µm), with which nonnegligible levels of fluorescence were recorded in all three channels, increased during Asian dust events (relative to a local dust event). It is suggested that PAHs and/or biological materials mixed with dust particles were transported from the North China Plain to the outflow region in East Asia during the observation period. Moreover, the autofluorescence measurement of airborne particles can be substantially affected by nonbiological materials in this region.

Evaluation of a New Particle Trap in a Laser Desorption Mass Spectrometer for Online Measurement of Aerosol Composition

We have developed a new analyzer for the online measurement of aerosol composition: a particle trap laser desorption mass spectrometer (PT-LDMS). The main components of the instrument include an aerodynamic lens, a particle trap enclosed by a quartz cell, a quadrupole mass spectrometer (QMS), a vacuum chamber incorporating the above components, and a carbon dioxide (CO2) laser (wavelength 10.6 μm). The aerodynamic lens generates a beam of submicron particles, which is focused on a small area on the particle trap. The particle trap consists of custom-made mesh layers, the structure of which was newly designed using engineering techniques for micro electro mechanical systems (MEMS). A large number of mesh frames are well arranged in the trap, and particles can be efficiently captured after multiple impactions on the frames. The CO2 laser is used to vaporize aerosol compounds captured on the particle trap. The evolved gas confined within the quartz cell is analyzed using an electron impact ionization (EI) QMS to quantify the chemical composition of the particles. The concept of the PT-LDMS and first evaluation of its performance are presented, specifically focusing on the structure and performance of the particle trap.

Evaluation of a Heated-Inlet for Calibration of the SP2

Black carbon (BC) calibration standards, such as fullerene soot, are routinely used to calibrate single-particle soot photometer (SP2) instruments. Impurities in BC standards create uncertainties in these calibrations, and thus it is desirable to remove non-BC compounds from the aerosol, though removal processes must not significantly alter BC microphysical properties. We present a series of experiments using mobility- and mass-selected fullerene soot particles to assess the performance of a high-temperature denuder system for treating BC prior to SP2 analysis. Particle mass, incandescence, and scattering properties were measured by tandem aerosol particle mass analyzers and an SP2, after thermal treatment at a range of temperatures and residence times (RT). For a longer RT (e.g., ∼6 s at 300°C), monodisperse fullerene soot particles of initial mass 1.4 fg decreased in mass with increasing temperature, by 3% at 300°C to 15% at 600°C. Mass losses were similar for fullerene soot particles of initial mass 10.7 fg. The peak height of the particle laser-induced incandescence (LII) and scattering intensities of the 10.7 fg fullerene soot increased by 7% and 3%, respectively, at 300°C, and by over 15% and 10% at 400°C, possibly due to microphysical changes after heating. When sampling through a 300°C denuder with a particle RT of 2.5 s, the LII intensity of ambient BC particles of initial mass 1.1 fg increased by 8%. In light of these results, denuder temperatures of ∼300°C with 0.4 s ≤ RT ≤ 2.5 s are recommended for SP2 calibration. Copyright 2013 American Association for Aerosol Research

Reconsidering Adhesion and Bounce of Submicron Particles Upon High-Velocity Impact

Adhesion and bounce of liquid and solid particles upon high-velocity impact with a surface has been investigated using semi-empirical and explicit hydrodynamic simulations. Ammonium nitrate (AN) and sodium chloride (NaCl) were selected as test compounds for the liquid and solid particles, respectively, and tungsten (W) as the target surface. Changes in the shape, temperature, strain, and rebound velocity of these particles upon high-velocity impact are investigated assuming operational conditions (particle diameter, and velocity) of Aerodyne aerosol mass spectrometer (AMS). The simulations show that the AN particles adhere to the W surface, which is consistent with previous experimental studies. In the case of NaCl, the collection efficiencies depend significantly on the stress–strain characteristics of the crystal. Our results suggest that, in addition to particle phase and impact velocity, anisotropy of the elastic properties and brittleness are key factors in controlling the adhesion and bounce of solid particles. Copyright 2013 American Association for Aerosol Research