Michihiro Mochida

Hygroscopic properties of levoglucosan and related organic compounds characteristic to biomass burning aerosol particles

[1] Biomass burning, which is characterized by pyrolysis as well as vaporization and condensation of biomass constituents, is a significant source of atmospheric organic aerosols. In this study, hygroscopic properties of five organic compounds (levoglucosan, D-glucose, and vanillic, syringic, and 4-hydroxybenozoic acids), which are major pyrolysis products of wood, were measured using a tandem differential mobility analyzer. Levoglucosan, which is typically the most abundant species in wood burning aerosols, showed a significant hygroscopic growth for particles with a diameter of 100 nm. No efflorescence was observed under the measured relative humidity, and a supersaturated condition of levoglucosan-water particles was observed. The growth factors of levoglucosan are 1.08, 1.18, 1.23, and 1.38 at relative humidity (RH) of 60, 80, 85, and 90%, respectively. The measured hygroscopic curves are in general consistent with those estimated from ideal solution theory and Uniquac Functional-Group Activity Coefficient (UNIFAC) and Conductor-Like Screening Model for Real Solvent (COSMO-RS) methods. Significant hygroscopic growth was also observed for D-glucose, whose growth factor is quite similar to that of levoglucosan. However, three model pyrolysis products of lignin (i.e., vanillic-, syringic-, and 4-hydroxybenzoic acids) did not show any hygroscopic growth under the RH conditions up to 95%. On the basis of the organic composition of wood burning aerosols, the water absorption attributed to levoglucosan in wood burning aerosols is calculated to be up to 30% of the organic mass at 90% RH. This study demonstrates that oxygenated organics emitted from biomass burning could significantly enhance the hygroscopic properties of atmospheric aerosols.

Organic and inorganic compositions of marine aerosols from East Asia: Seasonal variations of water-soluble dicarboxylic acids, major ions, total carbon and nitrogen, and stable C and N isotopic composition

Atmospheric particles were collected for 1 year (2001–2002) at a site Gosan on Jeju Island, South Korea. The samples were analyzed for water-soluble dicarboxylic acids and related compounds using a capillary GC and GC/MS. Total carbon and nitrogen contents, as well as their stable isotopic ratios, were also determined using elemental analyzer (EA) and EA/IR/MS, respectively. Elemental and isotopic analyses were also performed after the HC1 fume treatment of aerosol samples. The results demonstrate that calcium carbonate of dust origin was not a significant component, except for a few dust event samples. Carbonates most likely reacted with acidic species (such as H2SO4, HNO3 and organic acids) in the atmosphere during a long-range transport, and did not contribute to the total aerosol carbon, except for few strong dust episodes that occurred in spring. This study also demonstrates that nitrate and ammonium largely contribute to aerosol nitrogen, and organic nitrogen is a minor component in the Asian aerosols. Acidic aerosols enriched with sulfate likely adsorb NH3 gas that is emitted from soils in Asia whereas mineral dust particles containing carbonate may adsorb HNO3 and volatile organic acids. Homologous series of dicarboxylic acids (C2–C12) including unsaturated structures as well as ketocarboxylic acids (C2–C9) were detected in the aerosol samples with oxalic (C2) acid being the most abundant species followed by malonic (C3) or succinic (C4) acids. Total concentrations of diacids (130–2070 ng m-3) are one or two orders of magnitude greater than those reported for remote marine aerosols in the North Pacific, but are equivalent to those reported for urban aerosols. Very high concentrations of dusts (up to 880 μg m-3) and water- soluble dicarboxylic acids were often observed in early spring. However, their correlation (r = 0.27) is not strong throughout the campaign. Although both mineral dusts and diacids are derived from the Asian continent, they originate from different sources and source regions. Diacids are probably emitted from urban sources in East Asia and produced by secondary photochemical oxidation of their precursors, whereas dusts are derived from the arid interior regions. This study provides evidence for photochemical production of water-soluble organic acids in East Asia and the western North Pacific rim.

Aerosol particles collected on aircraft flights over the northwestern Pacific region during the ACE‐Asia campaign: Composition and major sources of the organic compounds

Interestingly, the water-soluble compounds (72–133 ng m 3 ) were found to account for 16–50% (average 34%) of the total identified compound mass (TCM). Organic compounds were further categorized into several groups to suggest their sources. Fossil fuel combustion was recognized as the most significant source for the TCM (contributing 33–80% of TCM, average 50%), followed by soil resuspension (5–25%, average 19%) and secondary oxidation products (4–15%, average 9%). In contrast, the contribution of natural sources such as terrestrial plant wax and marine lipids (fatty acids and alkanols) was relatively small (3.4% and 9.4% on average, respectively). Biomass burning was suggested to contribute only a minor portion to the TCM of the Asian aerosols during the spring season (1.4% on average based on levoglucosan). However, levoglucosan may have been hydrolyzed and/or oxidized in part during long-range transport, and therefore this value represents a lower limit. The organic compound compositions of these samples are very different from those reported for aerosol particles of the Atlantic Ocean and from the earlier data for the mid-Pacific in terms of the abundant presence of water-soluble compounds consisting of saccharides, anhydrosaccharides, and the secondary dicarboxylic acids. This study demonstrated that the organic tracer approach can be carried out on small samples acquired on aircraft and is useful to better understand the sources of organic aerosols over the Asia/Pacific region. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0315 Atmospheric Composition and Structure: Biosphere/ atmosphere interactions; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 1055 Geochemistry: Organic geochemistry; 9320 Information Related to Geographic Region: Asia;

Variation on the atmospheric concentrations of biogenic carbonyl compounds and their removal processes in the northern forest at Moshiri, Hokkaido Island in Japan

[1] Biogenic aldehydes, hydroxycarbonyls, and dicarbonyls in gas and particle phases were collected with an annular denuder sampling system (ADSS) in a Quercus crispula and Picea glehnii mast mixed forest. Eighty samples were collected from 22 to 29 August 2002. The size distributions of aerosols were also observed concurrently with a scanning mobility particle sizer (SMPS). The gaseous concentrations of these carbonyl compounds ranged from the detection limit (approximately 1 pptv) to 154 pptv (630 ng m -3 , 4-oxopentanal), and the particulate concentrations ranged from the detection limit (approximately 3 ng m -3 ) to 200 ng m -3 (4-oxopentanal). Although the production processes of these compounds are different from each other, the temporal variations of the gaseous concentrations were quite similar. In addition, the variation was also similar to that of the ambient temperature. Furthermore, gas-to-particle conversion was suggested to be an important removal process of these compounds. We could evaluate the importance of the gas-to-particle conversion as a removal process of the gaseous species by an ADSS measurement. In addition, the results of our experiment indicated that the conversion includes two processes. The first is an adsorption onto the aerosols which have already existed in the atmosphere. The next is dissolution into the water phases in the aerosols. The latter process was particular to water soluble compounds. The measurement allowed us to identify the most likely removal processes of biogenic semivolatile organic compounds (SOCs). In this study, we discuss about these processes of semivolatile and biogenic carbonyls in the forest atmosphere.

In situ measurement of isoprene in the marine air and surface seawater from the western North Pacific

Isoprene (2-methyl-1,3-butadiene) was measured on board of R/V Mirai for eight air samples and 14 seawater samples collected in the western North Pacific during ACE-Asia campaign (from 18 to 26 May 2001). The measurements were conducted in situ using a cryo-focus/gas chromatography/mass spectrometry (Cryo/GC/MS). Concentrations of isoprene ranged from 7.2 to 110 parts-per-trillion (pptv) in the marine air, and ranged from below 12 to 94 pmol l � 1 in the seawater. Based on these results, sea-to-air fluxes of isoprene were calculated to be 184 and 300 nmol m � 2 day � 1 for two samples, and the upper limits of the fluxes were also calculated to be from 32 to 300 nmol m � 2 day � 1 . Atmospheric isoprene concentrations cannot be explained only by the flux from the seawater. Thus, the concentrations of isoprene in the marine air in western North Pacific should be significantly affected by terrestrial vegetational emission and subsequent long-range atmospheric transport of isoprene. r 2002 Elsevier Science Ltd. All rights reserved.

Laboratory studies of sources of HONO in polluted urban atmospheres

Laboratory studies reported here and in previous work show that the reaction of NO(g) with surface adsorbed HNO3 may be a significant source of HONO in polluted urban atmospheres. If these laboratory studies can be extrapolated to ambient conditions, this heterogeneous reaction may generate HONO to about the same extent as the hydrolysis of NO2 on surfaces, which is greater than the heterogeneous reaction of NO, NO2 and water. It may also be involved in generating HONO in snowpacks, and important in reconciling the discrepancy between measured and modeled HNO3/NOx ratios in the troposphere.

Hygroscopicity and cloud condensation nucleus activity of marine aerosol particles over the western North Pacific

Received 14 July 2010; revised 12 October 2010; accepted 27 October 2010; published 19 March 2011. [1] Hygroscopic growth of aerosol particles at 85% relative humidity and the number fraction of cloud condensation nuclei (CCN; 0.42%, 0.23%, and 0.10% supersaturation) as a function of dry diameter (24.1–359 nm) were measured simultaneously on board R/V Hakuho‐Maru over the western North Pacific during August–September 2008. Highly hygroscopic and unimodal growth distributions were observed, except for aerosols, which showed lower hygroscopic growth over the northern Pacific. The measured particle hygroscopicity, CCN activation diameters, and chemical composition data suggest the dominance of internally mixed sulfate aerosols. Backward air mass trajectory analysis exhibits an intrusion of free tropospheric aerosol, which was likely influenced by Kasatochi’s volcanic plume and which was linked to the low‐hygroscopicity event. Frequent observation of the Hoppel minimum suggests that in‐cloud processing over the Pacific enhanced and/or maintained the high hygroscopicity of accumulation mode particles. The CCN activation diameters predicted from median hygroscopic growth factors (gmedian) agreed well with those determined from the CCN efficiency spectra, without assuming surface tension reduction caused by organics or enhancement of bulk hygroscopicity at high RH caused by sparingly soluble or polymeric compounds. The CCN spectra predicted from gmedian and measured CCN activation diameters suggest that the high CCN activities of particles over the North Pacific are sustained by high hygroscopicity, while sporadic changes of aerosol origins produce the diversity of the aerosol properties.

Properties of light‐absorbing aerosols in the Nagoya urban area, Japan, in August 2011 and January 2012: Contributions of brown carbon and lensing effect

The optical properties of aerosols at 405 and 781 nm were measured in an urban site in Nagoya, Japan, in August 2011 and in January 2012 using a photoacoustic spectrometer. Comparison of the absorption coefficient at 781 nm of aerosols that did and did not pass through a thermo-denuder showed that an increase in black carbon (BC) light absorption due to the coating of non-refractory materials (i.e., the lensing effect) was small (on average, 10%) in August and negligible in January. The effective density distributions for the particles that did and did not pass through the thermo-denuder, which were measured simultaneously in August, suggested that the majority of BC particles sampled had a minimal coating. The small lensing effect observed can be explained partly by assuming that a large portion of non-refractory materials was mixed externally with BC. The contribution of direct light absorption by organic matter (OM) that vaporized at temperatures below 300°C to the total light absorption at 405 nm was negligible in August, but those by OM that vaporized below 300 and 400°C averaged 11 and 17%, respectively, in January. The larger contribution of light-absorbing OM in January is likely due to the greater contribution of OM originating from the burning of biomass, including biofuel and agricultural residue, in Japan, northern China, or Siberia, during the winter.

Chemical Structural Characteristics of HULIS and Other Fractionated Organic Matter in Urban Aerosols: Results from Mass Spectral and FT-IR Analysis.

The chemical characteristics of complex organic matter in atmospheric aerosols remain poorly understood. Water-insoluble organic matter (WISOM) and water-soluble organic matter (WSOM) in the total suspended particulates collected in the city of Nagoya in summer/early autumn and winter were extracted using multiple solvents. Two fractions of humic-like substances, showing neutral and acidic behavior (HULIS-n and HULIS-a, respectively), and the remaining highly polar part (HP-WSOM) were fractionated from WSOM using solid phase extraction. The chemical structural characteristics and concentrations of the organic matter were investigated using mass spectrometry and Fourier transform infrared (FT-IR) spectroscopy. WISOM and HULIS-n had low O/C ratios (0.1 and 0.4, respectively) and accounted for a large fraction of the organics in aerosols (70%). HULIS-a and HP-WSOM had higher O/C ratios (0.7 and 1.0, respectively), and their concentrations in summer and early autumn were on average ∼2 times higher than those in winter. The mass spectrum and FT-IR analyses suggest the following: (1) WISOM were high-molecular-weight aliphatics (primarily C27-C32) with small proportions of -CH3, -OH, and C═O groups; (2) HULIS-n was abundant in aliphatic structures and hydroxyl groups (primarily C9-C18) and by branched structures; (3) HULIS-a and HP-WSOM contained relatively large amounts of low-molecular-weight carboxylic acids and alcohols (primarily C4-C10); and (4) WISOM and HULIS-n were relatively abundant in amines and organic nitrates.

Characterization of solvent-extractable organics in urban aerosols based on mass spectrum analysis and hygroscopic growth measurement.

To characterize atmospheric particulate organics with respect to polarity, aerosol samples collected on filters in the urban area of Nagoya, Japan, in 2009 were extracted using water, methanol, and ethyl acetate. The extracts were atomized and analyzed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a hygroscopicity tandem differential mobility analyzer. The atmospheric concentrations of the extracted organics were determined using phthalic acid as a reference material. Comparison of the organic carbon concentrations measured using a carbon analyzer and the HR-ToF-AMS suggests that organics extracted with water (WSOM) and ethyl acetate (EASOM) or those extracted with methanol (MSOM) comprise the greater part of total organics. The oxygen-carbon ratios (O/C) of the extracted organics varied: 0.51-0.75 (WSOM), 0.37-0.48 (MSOM), and 0.27-0.33 (EASOM). In the ion-group analysis, WSOM, MSOM, and EASOM were clearly characterized by the different fractions of the CH and CO(2) groups. On the basis of the hygroscopic growth measurements of the extracts, κ of organics at 90% relative humidity (κ(org)) were estimated. Positive correlation of κ(org) with O/C (r 0.70) was found for MSOM and EASOM, but no clear correlation was found for WSOM.