Gas-phase Precursors Research Articles

Oxidative aging and cloud condensation nuclei activation of laboratory combustion soot

Radiative forcing by aerosol particles containing black carbon (BC) may be positive or negative depending on specific atmospheric conditions. Black carbon itself absorbs solar radiation and thereby heats the surrounding environment. On the other hand, as a result of atmospheric aging, BC-containing particles may become hydrophilic due to oxidation, condensation, and/or coagulation of water-soluble material. The aged particles can act as cloud condensation nuclei (CCN) and contribute to cloud formation that may result either in cooling or heating. In this work, through a series of laboratory experiments, we investigate the transformation of soot particles from hydrophobic to hydrophilic and estimate the atmospheric residence time required for this transformation. Ethylene flame-generated soot particles were size-selected and exposed to OH radicals in a Potential Aerosol Mass flow reactor. Aging was simulated via OH exposures equivalent to atmospheric lifetimes over a range from hours to multiple days. The chemical composition of the organic coatings as a function of OH exposure was monitored with an Aerodyne Aerosol Mass Spectrometer. The CCN activity of the aged soot particles was measured as a function of OH exposure and chemical composition. Experimental measurements indicate that heterogeneous OH oxidation of initially CCN-inactive nascent soot produces CCN-active particles. Critical supersaturations at integrated OH exposures equivalent to 0.4, 2, and 10days are 2.1%, 0.82%, and 0.40%. Corresponding values for the effective hygroscopicity parameter, κeff, ranged from κeff<8×10−4 to κeff=0.09 as a function of OH exposure. Condensation of hydrophilic organic or inorganic coatings (produced from oxidation of gas-phase precursors introduced to the flow reactor) on soot particles speeds up the CCN activation by a factor of 6–50 depending on the nature and thickness of the coating. The results suggest that CCN activation of atmospheric BC-containing particles is primarily due to secondary coatings.

Aerosol fast flow reactor for laboratory studies of new particle formation

Understanding the fundamental mechanisms of new particle formation and growth (NPFG) is critical to the development of accurate quantitative models of atmospheric particulate matter. Challenges to elucidating the chemistry of these processes include accessing a variety of well-controlled experimental conditions approaching the point of new particle formation, and having an inexpensive system which can be reproducibly maintained with low levels of contaminants from previous runs and other sources. We describe here the design and characterization of a flow tube reactor for such studies, and its initial application to NPFG from the reaction of the gas phase precursors methanesulfonic acid and trimethylamine in the absence or presence of added water vapor. Insights into some of the fundamental processes involved in NPFG that could not be obtained in earlier studies using our large volume, slow flow system are described.

The Titan Haze Simulation experiment on COSmIC: Probing Titan’s atmospheric chemistry at low temperature

The aim of the Titan Haze Simulation (THS) experiment is to contribute to a better understanding of aerosol formation in Titan’s atmosphere through the study of the chemical formation pathways that link the simpler gas phase molecules resulting from the first steps of the N2–CH4 chemistry, to the more complex gas phase precursors of aerosols; and more specifically, to investigate the role of polycyclic aromatic hydrocarbons (PAHs) and nitrogenated polycyclic aromatic hydrocarbons (PANHs), among other hydrocarbons, in this process. In the THS experiment developed at the NASA Ames Cosmic simulation facility (COSmIC), Titan’s atmospheric chemistry is simulated by a pulsed plasma jet expansion at temperature conditions (∼150K) close to those found in Titan’s atmosphere in regions where aerosols are formed. In addition, because of the very short residence time of the gas in the plasma discharge, only the initial steps of the chemistry occur, making the COSmIC/THS a unique tool to study the first and intermediate (when adding heavier precursors to the initial N2–CH4 mixture) steps of Titan’s atmospheric chemistry at low temperature as shown in the study presented here. We further illustrate the potential of COSmIC/THS for the simulation of Titan’s atmospheric chemistry by presenting very promising results from a preliminary comparison of the laboratory data to data from the Cassini Plasma Spectrometer–Ion Beam Spectrometer (CAPS–IBS) instrument.

Absorption electronic spectrum of gaseous FeO: in situ detection with intracavity laser absorption spectroscopy in a nanoparticle-generating flame reactor

Absorption measurement of a gas-phase iron oxide (FeO) electronic spectrum is reported for the first time. FeO was obtained in a methane/oxygen/nitrogen flame doped with iron pentacarbonyl and monitored via the 611-nm band of the orange system with intracavity laser absorption spectroscopy. The measured spectral range extends from 16,250 to 16,450 cm−1 for the appropriate intracavity tuning element position. The presented measurements demonstrate sensitive detection of the gas-phase precursor, playing a key role in flame synthesis of iron oxide nanoparticles. The sensitivity of the intracavity technique does not depend on broadband cavity losses and allows conducting measurements in a highly scattering, particle-laden flame environment.

Role of growth parameters in equalizing simultaneous growth of N‐ and Ga‐polar GaN by MOCVD

AbstractIn preparing periodically‐oriented gallium nitride (PO GaN) samples for optical applications, smooth surfaces are essential. Although post‐growth processing of these surfaces is possible, it is challenged by significantly different reactivity of the two polar surfaces. To this end, it would be highly desirable to grow PO GaN structures with smooth surfaces. In this paper, the influence of growth parameters on the morphology of PO GaN structures is investigated. The three primary parameters investigated include the V/III ratio of the gas phase precursors, the nature of the carrier gas, and the geometry of the structure. The V/III ratio was varied from 1100 to 5500. Substitution of N2 for the standard H2 carrier gas is investigated. Finally, the effects of changing the structure periodicity from 2 to 100 mm are studied. Smoother structures (resulting from more equal growth rates of the two polarities) are achieved with increases in V/III ratio, substitution of H2 with N2, and by reducing the stripe width. (© 2014 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Characteristics of heavy aerosol pollution during the 2012–2013 winter in Beijing, China

A comprehensive measurement was carried out to analyze the heavy haze events during 2012–2013 winter in Beijing. The measured variables include some important meteorological parameters, such wind directions, wind speeds, relative humidity (RH), planetary boundary layer (PBL), solar radiation, and visibility. The aerosol composition and concentrations (including particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)) as well as their gas-phase precursors (including nitrogen oxides (NOx) and sulfur dioxide (SO2)) were analyzed during the period between Nov. 16, 2012 and Jan. 15, 2013. The results show that the hourly mean concentrations of PM2.5 often exceeded 200 μg/m3, with a maximum concentration of 600 μg/m3 on Jan. 13, 2013. The relative humidity was increased during the haze events, indicating that both aerosol concentrations and RH had important effect on the reduction of visibility, causing the occurrence of the haze events. Because the wind speeds were generally low (less than 1 m/s) during the haze event, the vertical dispersion and the PBL heights were very important factors for causing the strong variability of aerosol concentrations. This study also finds that under the lower visibility condition, the conversion from the gas-phase of NOx and SO2 to the particle phase of NO3 and SO4 were higher than the values under the higher visibility condition. Because the lower visibility condition was corresponding to the lower photochemical activity than the higher visibility condition, the higher conversion from gas phase to particle phase in the lower visibility condition indicated that there was important heterogeneous formation of NO3 and SO4 during the heavy haze events.

Open-path, quantum cascade-laser-based sensor for high-resolution atmospheric ammonia measurements

Abstract. We demonstrate a compact, open-path, quantum cascade-laser-based atmospheric ammonia sensor operating at 9.06 μm for high-sensitivity, high temporal resolution, ground-based measurements. Atmospheric ammonia (NH3) is a gas-phase precursor to fine particulate matter, with implications for air quality and climate change. Currently, NH3 sensing challenges have led to a lack of widespread in situ measurements. Our open-path sensor configuration minimizes sampling artifacts associated with NH3 surface adsorption onto inlet tubing and reduced pressure sampling cells, as well as condensed-phase partitioning ambiguities. Multi-harmonic wavelength modulation spectroscopy allows for selective and sensitive detection of atmospheric pressure-broadened absorption features. An in-line ethylene reference cell provides real-time calibration (±20% accuracy) and normalization for instrument drift under rapidly changing field conditions. The sensor has a sensitivity and noise-equivalent limit (1σ) of 0.15 ppbv NH3 at 10 Hz, a mass of ~ 5 kg and consumes ~ 50 W of electrical power. The total uncertainty in NH3 measurements is 0.20 ppbv NH3 ± 10%, based on a spectroscopic calibration method. Field performance of this open-path NH3 sensor is demonstrated, with 10 Hz time resolution and a large dynamic response for in situ NH3 measurements. This sensor provides the capabilities for improved in situ gas-phase NH3 sensing relevant for emission source characterization and flux measurements.

Reductions in aircraft particulate emissions due to the use of Fischer–Tropsch fuels

Abstract. The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability, and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January–February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer–Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions in mass of 86% averaged over all powers) and blended fuels (66%) relative to the JP-8 baseline with the largest reductions at idle conditions. At 7% power, this corresponds to a reduction from 7.6 mg kg−1 for JP-8 to 1.2 mg kg−1 for the natural gas FT fuel. At full power, soot emissions were reduced from 103 to 24 mg kg−1 (JP-8 and natural gas FT, respectively). The alternative fuels also produced smaller soot (e.g., at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the natural gas FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the feedstock. As the plume cools downwind of the engine, nucleation-mode aerosols form. For the pure FT fuels, reductions (94% averaged over all powers) in downwind particle number emissions were similar to those measured at the exhaust plane (84%). However, the blended fuels had less of a reduction (reductions of 30–44%) than initially measured (64%). The likely explanation is that the reduced soot emissions in the blended fuel exhaust plume results in promotion of new particle formation microphysics, rather than coating on pre-existing soot particles, which is dominant in the JP-8 exhaust plume. Downwind particle volume emissions were reduced for both the pure (79 and 86% reductions) and blended FT fuels (36 and 46%) due to the large reductions in soot emissions. In addition, the alternative fuels had reduced particulate sulfate production (near zero for FT fuels) due to decreased fuel sulfur content. To study the formation of volatile aerosols (defined as any aerosol formed as the plume ages) in more detail, tests were performed at varying ambient temperatures (−4 to 20 °C). At idle, particle number and volume emissions were reduced linearly with increasing ambient temperature, with best fit slopes corresponding to −8 × 1014 particles (kg fuel)−1 °C−1 for particle number emissions and −10 mm3 (kg fuel)−1 °C−1 for particle volume emissions. The temperature dependency of aerosol formation can have large effects on local air quality surrounding airports in cold regions. Aircraft-produced aerosols in these regions will be much larger than levels expected based solely on measurements made directly at the engine exit plane. The majority (90% at idle) of the volatile aerosol mass formed as nucleation-mode aerosols, with a smaller fraction as a soot coating. Conversion efficiencies of up to 2.8% were measured for the partitioning of gas-phase precursors (unburned hydrocarbons and SO2) to form volatile aerosols. Highest conversion efficiencies were measured at 45% power.

Research and Development Aspects on Chemical Preparation Techniques of Photoanodes for Dye Sensitized Solar Cells

The importance of dye sensitized solar cells (DSSCs) as a low-cost and environmentally friendly photovoltaic (PV) technology has prompted many researchers to improve its efficiency and durability. The realization of these goals is impossible without taking into account the importance of the materials in DSSCs, so the focus on the preparation/deposition methods is essential. These methods can be either chemical or physical. In this study, the chemical applied methods that utilize chemical reaction to synthesize and deposit the materials are covered and categorized according to their gas phase and liquid phase precursors. Film processing techniques that can be used to enhance the materials' properties postpreparation are also included for further evaluation in this study. However, there is a variety of consideration, and certain criteria must be taken into account when selecting a specific deposition method, due to the fact that the fabrication conditions vary and are unoptimized.

On the nucleation of dust in oxygen-rich stellar outflows

Understanding the nature of dust condensation in the outflow from oxygen-rich asymptotic giant branch stars is a continuing problem. A kinetic model has been developed to describe the formation of gas-phase precursors from Ca, Mg, Fe, SiO and TiO in an outflow cooling from 1500 to 1000 K. Electronic structure calculations are used to identify efficient reaction pathways that lead to the formation of metal titanates and silicates. The molecular properties of the stationary points on the relevant potential energy surfaces are then used in a multi-well master equation solver to calculate pertinent rate coefficients. The outflow model couples an explicit treatment of gas-phase chemistry to a volume-conserving particle growth model. CaTiO₃ is shown to be the overwhelming contributor to the formation of condensation nuclei (CN), with less than 0.01 per cent provided by CaSiO₃, (TiO₂)₂ and FeTiO₃. Magnesium species make a negligible contribution. Defining CN as particles with radii greater than 2 nm, the model shows that for stellar mass loss rates above 3×10⁻⁵ M⊙ yr⁻¹, more than 10⁻¹³ CN per H nucleus will be produced when the outflow temperature is still well above 1000 K. This is sufficient to explain the observed number density of grains in circumstellar dust shells.

Relationship between Oxidation Level and Optical Properties of Secondary Organic Aerosol

Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo[5.2.1.0(2,6)]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level.

The Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS): model description and application to a temperate deciduous forest canopy

Abstract. Forest canopies are primary emission sources of biogenic volatile organic compounds (BVOCs) and have the potential to significantly influence the formation and distribution of secondary organic aerosol (SOA) mass. Biogenically-derived SOA formed as a result of emissions from the widespread forests across the globe may affect air quality in populated areas, degrade atmospheric visibility, and affect climate through direct and indirect forcings. In an effort to better understand the formation of SOA mass from forest emissions, a 1-D column model of the multiphase physical and chemical processes occurring within and just above a vegetative canopy is being developed. An initial, gas-phase-only version of this model, the Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS), includes processes accounting for the emission of BVOCs from the canopy, turbulent vertical transport within and above the canopy and throughout the height of the planetary boundary layer (PBL), near-explicit representation of chemical transformations, mixing with the background atmosphere and bi-directional exchange between the atmosphere and canopy and the atmosphere and forest floor. The model formulation of ACCESS is described in detail and results are presented for an initial application of the modeling system to Walker Branch Watershed, an isoprene-emission-dominated forest canopy in the southeastern United States which has been the focal point for previous chemical and micrometeorological studies. Model results of isoprene profiles and fluxes are found to be consistent with previous measurements made at the simulated site and with other measurements made in and above mixed deciduous forests in the southeastern United States. Sensitivity experiments are presented which explore how canopy concentrations and fluxes of gas-phase precursors of SOA are affected by background anthropogenic nitrogen oxides (NOx). Results from these experiments suggest that the level of ambient NOx influences the pathways by which SOA is formed by affecting the relative magnitudes and fluxes of isoprene oxidation products emitted from the canopy. Future versions of the ACCESS model are planned to be multiphase, including gas- and aerosol-phase chemical and physical processes, to more fully explore these preliminary results.

Characteristics of gas–phase nitric acid and ammonium–nitrate– sulfate aerosol, and their gas–phase precursors in a suburban area in Cairo, Egypt

Simultaneous measurements of gaseous SO2, NO2, HNO3, NH3 and particulate SO42–, NO3– and NH4+ were carried out in a suburban area in Cairo during summer 2009 and winter 2009–2010. PTFE membrane filters were used to collect particulate SO42–, NH4+ and NO3–, followed by the impregnated filter to collect HNO3. Colorimetric methods were used for determination of NO2, SO2, NH3, SO42–, NH4+ NO3–, and HNO3 levels. The mean concentrations of NO2, SO2 and NH3 were 75.0, 40.1 and 29.1 µg/m3 in winter and 54.1, 25.1 and 44.9 µg/m3 in summer, respectively. The daytime/nighttime concentration ratios were 1.3 and 1.2 for NO2, 1.3 and 1.2 for SO2 and 0.6, and 0.8 for NH3 during the winter and summer, respectively. The mean values of NH4+, SO42–, NO3–, HNO3 and total NO3– were 4.4, 19.0, 3.4, 1.1 and 4.5 µg/m3 in winter and 7.5, 28.0, 4.2, 3.1 and 7.3 µg/m3 in summer, respectively. The levels of NH4+, SO42–, NO3– and HNO3 were relatively higher in daytime than in nighttime. Sulfur conversion (Fs) and nitrogen conversion ratios (Fn) in summer were about 1.78 and 2.15 times higher than in winter, respectively. Fs and Fn were higher in daytime than in nighttime. Significant positive correlation was found between Fs and relative humidity. The positive correlation between Fn and relative humidity was insignificant. The correlation between the concentration of NH4+ and NO3– indicates that NO3– may be found in fine mode (NH4NO3) in winter and it may be present predominantly as a coarse mode, such as Ca(NO3)2, Mg(NO3)2 and NaNO3 in summer. The concentration of SO42– was significantly correlated with NH4+ concentration, suggesting neutralization by NH3 and indicating that the forms of (NH4)2SO4 and/or NH4HSO4 exist in the aerosol. The NH4+/SO42– molar ratio indicates that SO42– in aerosol may be present as (NH4)2SO4, (NH4)2SO4.CaSO4.2H2O and CaSO4.

Reasearch on the Formation Mechanisms of New Particles in the Atmosphere

New particle formation (NPF) in the atmosphere i.e. nucleation of gas phase precursors and continuing condensa- tional growth is a crucial secondary transformation process. The freshly nucleated particles can grow into sizes where they can act as cloud condensation nuclei (CCN) and further influence cloud and climate-relevant properties. Hence, the detailed knowledge on the formation mechanisms of new particles and their subsequent growth will help us to improve our under- standing on the regional air pollution and global climate change. Recent-developed measurement techniques enable to ex- plore atmospheric nucleation by measuring particles/clusters down to 1 nm. NPF events have been observed in a variety of atmospheric environments. Several methods including field observation, laboratory simulations and model calculations are implemented to investigate the nucleation mechanisms and growth properties. Good agreement between particle formation rates and gaseous sulfuric acid concentrations is observed, indicating that sulfuric acid is a key compnent in the atmospheric nucleation process. In addition, the low-volatile organic vapors are found to be involved in new particle formation. However, the huge variations of the particle formation and growth rates in diverse atmospheric environments suggest that a consistent picture on formation mechanisms of new particles does not achieve. Long-term continuous measurements of NPF events have been first performed in the urban atmosphere of Beijing since 2004. Up to now, NPF events have been observed in many different environments, including coastal area, high-elevation mountain, rural site as well as urban region in China. The cur- rent nucleation mechanisms are developed based on the observation in clean environment. Hence, whether it could well ex- plain the NPF events occurred in the polluted atmosphere with strong oxidation capacity is a key issue to be addressed in further studies. This paper reviews the measurement techniques for investigating atmospheric new particle formation and growth, summarizes the observation results in various typical environments, introduces the current understanding of the nu- cleation mechanisms and discusses the main scientific questions that need further researches. Keywords new particle formation; nucleation mechanism; growth property; measurement technique; precursor 1 引言

Modeling Forced Flow Chemical Vapor Infiltration Fabrication of SiC-SiC Composites for Advanced Nuclear Reactors

Silicon carbide fiber/silicon carbide matrix (SiC-SiC) composites exhibit remarkable material properties, including high temperature strength and stability under irradiation. These qualities have made SiC-SiC composites extremely desirable for use in advanced nuclear reactor concepts, where higher operating temperatures and longer lives require performance improvements over conventional metal alloys. However, fabrication efficiency advances need to be achieved. SiC composites are typically produced using chemical vapor infiltration (CVI), where gas phase precursors flow into the fiber preform and react to form a solid SiC matrix. Forced flow CVI utilizes a pressure gradient to more effectively transport reactants into the composite, reducing fabrication time. The fabrication parameters must be well understood to ensure that the resulting composite has a high density and good performance. To help optimize this process, a computer model was developed. This model simulates the transport of the SiC precursors, the deposition of SiC matrix on the fiber surfaces, and the effects of byproducts on the process. Critical process parameters, such as the temperature and reactant concentration, were simulated to identify infiltration conditions which maximize composite density while minimizing the fabrication time.

Formation of secondary organic aerosol marker compounds from the photooxidation of isoprene and isoprene-derived alkene diols under low-NOx conditions

In the present work, we have evaluated whether isomeric C5-alkene diols (1,2-dihydroxy-2-methyl-3-butene, 1,2-dihydroxy-3-methyl-3-butene, and 1,4-dihydroxy-2-methyl-2-butene (cis + trans)), which have first been detected upon photooxidation of isoprene in the absence of NO and are known to be formed in the ambient atmosphere, can serve as precursors for the 2-methyltetrols, C5-alkene triols, and 2-methylglyceric acid under low-NO(x) conditions. The C5-alkene diols were prepared following published synthesis procedures. It is shown that under the applied chamber conditions the isomeric C5-alkene diols give rise to 2-methyltetrols with different threo/erythro abundance ratios and that certain diols produce 2-methylglyceric acid, but that they do not form C5-alkene triols. Furthermore, it is shown that the photooxidation of isoprene under the applied chamber conditions employing photolysis of H2O2 under dry conditions yields relatively small amounts of C5-alkene triols compared to those of the 2-methyltetrols, unlike under ambient conditions. It is argued that the chamber conditions are not optimal for the formation of C5-epoxydiols, which serve as gas-phase precursors for the C5-alkene triols, and likely as in some previous studies favor the formation of C5-alkene diols as a result of RO2 + RO2 reactions.

Modelling of secondary organic aerosol formation from isoprene photooxidation chamber studies using different approaches

Environmental context Fine particulate matter (PM2.5) in the Earth’s atmosphere plays an important role in climate change and human health, in which secondary organic aerosol (SOA) that forms from the photooxidation of volatile organic compounds (VOCs) has a significant contribution. SOA derived from isoprene, the most abundant non-methane VOC emitted into the Earth’s atmosphere, has been widely studied to interpret its formation mechanisms. However, the ability to predict isoprene SOA using current models remains difficult due to the lack of understanding of isoprene chemistry. Abstract Secondary organic aerosol (SOA) formation from the photooxidation of isoprene was simulated against smog chamber experiments with varied concentrations of isoprene, nitrogen oxides (NOx=NO + NO2) and ammonium sulfate seed aerosols. A semi-condensed gas-phase isoprene chemical mechanism (ISO-UNC) was coupled with different aerosol-phase modelling frameworks to simulate SOA formation, including: (1) the Odum two-product approach, (2) the 1-D volatility basis-set (VBS) approach and (3) a new condensed kinetic model based upon the gas-particle partitioning theory and reactive uptake processes. The first two approaches are based upon empirical parameterisations from previous studies. The kinetic model uses a gas-phase mechanism to explicitly predict the major intermediate precursors, namely the isoprene-derived epoxides, and hence simulate SOA formation. In general, they all tend to significantly over predict SOA formation when semivolatile concentrations are higher because more semivolatiles are forced to produce SOA in the models to maintain gas-particle equilibrium; yet the data indicate otherwise. Consequently, modified dynamic parameterised models, assuming non-equilibrium partitioning, were incorporated and could improve the model performance. In addition, the condensed kinetic model was expanded by including an uptake limitation representation so that reactive uptake processes slow down or even stop; this assumes reactive uptake reactions saturate seed aerosols. The results from this study suggest that isoprene SOA formation by reactive uptake of gas-phase precursors is likely limited by certain particle-phase features, and at high gas-phase epoxide levels, gas-particle equilibrium is not obtained. The real cause of the limitation needs further investigation; however, the modified kinetic model in this study could tentatively be incorporated in large-scale SOA models given its predictive ability.

The lofting of Western Pacific regional aerosol by island thermodynamics as observed around Borneo

Abstract. Vertical profiles of aerosol chemical composition, number concentration and size were measured throughout the lower troposphere of Borneo, a large tropical island in the western Pacific Ocean. Aerosol composition, size and number concentration measurements (using an Aerodyne Aerosol Mass Spectrometer, Passive Cavity Aerosol Spectrometer Probe and Condensation Particle Counter, respectively) were made both upwind and downwind of Borneo, as well as over the island itself, on board the UK BAe-146 research aircraft as part of the OP3 project. Two meteorological regimes were identified – one dominated by isolated terrestrial convection (ITC) which peaked in the afternoon, and the other characterised by more regionally active mesoscale convective systems (MCS). Upwind profiles show aerosol to be confined to a shallow marine boundary layer below 930 ± 10 hPa (~760 m above sea level, a.s.l.). As this air mass advects over the island with the mean free troposphere synoptic flow during the ITC-dominated regime, it is convectively lofted above the terrestrial surface mixed layer to heights of between 945 ± 22 (~630 m a.s.l.) and 740 ± 44 hPa (~2740 m a.s.l.), consistent with a coupling between the synoptic steering level flow and island sea breeze circulations. Terrestrial aerosol was observed to be lofted into this higher layer through both moist convective uplift and transport through turbulent diurnal sea-breeze cells. At the peak of convective activity in the mid-afternoons, organic aerosol loadings in the lofted layer were observed to be substantially higher than in the morning (by a mean factor of three). This organic matter is dominated by secondary aerosol from processing of biogenic gas phase precursors. Aerosol number concentration profiles suggest formation of new particles aloft in the atmosphere. By the time the air mass reaches the west coast of the island, terrestrial aerosol is enhanced in the lofted layer. Such uplift of aerosol in Borneo is expected to increase aerosol lifetimes in the lower free troposphere downwind, as they are above the boundary layer and therefore less likely to be lost by wet or dry deposition. It is also likely to change the role they play in the semi-direct and direct aerosol effects. The long chain of islands extending from Malaysia to Australia may all similarly be expected to present an orographic barrier to low level mean flow. This would lead to significant transport of aerosol into the tropical free troposphere across the Western Pacific region.

Effect of isothermal dilution on emission factors of organic carbon and n-alkanes in the particle and gas phases of diesel exhaust

To investigate the effect of isothermal dilution (30 °C) on emission factors (EFs) of semivolatile and nonvolatile compounds of heavy-duty diesel exhaust, we measured EFs for particulate matter (PM), organic carbon (OC), and elemental carbon (EC) in the particle phase, and EFs for n-alkanes in both the particle phase and the gas phase of exhaust produced under high-idle engine operating conditions at dilution ratios (DRs) ranging from 8 to 1027. The EC EFs did not vary with DR, whereas the OC EFs in the particle phase determined at DR = 1027 were 13% of the EFs determined at DR = 8, owing to evaporation of organic compounds. Using partitioning theory and n-alkane EFs measured at DR = 14 and 238, we calculated the distributions of compounds between the particle and gas phases at DR = 1760, which corresponds to the DR for tailpipe emissions as they move from the tailpipe to the roadside atmosphere. The gas-phase EF of a compound with a vapor pressure of 10−7 Pa was 0.01 μg kg−1-fuel at DR = 14, and this value is 1/330 the value derived at DR = 1760. Our results suggest that the EFs of high-volatility compounds in the particle phase will be overestimated and that the EFs of low-volatility compounds in the gas phase will be underestimated if the estimates are derived from data obtained at the low DRs and they are applied to the real world. Therefore, extrapolation from EFs derived at low DR values to EFs at atmospherically relevant DRs will be a source of error in predictions of the concentrations of particulate matter and gas-phase precursors to secondary organic aerosols in air quality models.

Relationship between water-soluble ions in PM2.5 and their precursor gases in Seoul megacity

In this study, fine-particle (PM2.5) ionic composition in the city of Seoul was investigated using short-term measurement data (1 h interval) collected during the year 2010. The partitioning of semi-volatile inorganic species and phase state of aerosols were studied using ISORROPIA II thermodynamic equilibrium model. The analysis of ionic composition identified the relative dominance of NO3−, SO42−, and NH4+ in the fine particles. The presence of strong correlation between these components indicates similarity of their formation pathways. Seasonal patterns of these ionic components and their gas-phase precursors were somewhat different from each other. The observed SO42−/SO2 mass ratio indicated a significant role of the gas-phase oxidation of SO2 (to H2SO4) in the SO42− formation. Moreover, both SO42− and NO3− were almost completely neutralized by NH4+ to form (NH4)2SO4 and NH4NO3. The formation of NO3− aerosol would be ammonia-sensitive (i.e., deficit ammonia), as evidenced by smaller total ammonia concentration than the sum of total sulfate and nitrate concentrations. The uptake of SO2 on dust particles during Asian dust event is also likely to exert controls on SO42− concentrations.