| 41. |
- Qi, Ximeng, et al.
(författare)
-
Modelling studies of HOMs and their contributions to new particle formation and growth : Comparison of boreal forest in Finland and a polluted environment in China
- 2018
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:16, s. 11779-11791
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Tidskriftsartikel (refereegranskat)abstract
- Highly oxygenated multifunctional compounds (HOMs) play a key role in new particle formation (NPF), but their quantitative roles in different environments of the globe have not been well studied yet. Frequent NPF events were observed at two flagship stations under different environmental conditions, i.e. a remote boreal forest site (SMEAR II) in Finland and a suburban site (SORPES) in polluted eastern China. The averaged formation rate of 6 nm particles and the growth rate of 6-30 nm particles were 0.3 cm-3 s-1 and 4.5 nm h-1 at SMEAR II compared to 2.3 cm-3 s-1 and 8.7 nm h-1 at SORPES, respectively. To explore the differences of NPF at the two stations, the HOM concentrations and NPF events at two sites were simulated with the MALTE-BOX model, and their roles in NPF and particle growth in the two distinctly different environments are discussed. The model provides an acceptable agreement between the simulated and measured concentrations of sulfuric acid and HOMs at SMEAR II. The sulfuric acid and HOM organonitrate concentrations are significantly higher but other HOM monomers and dimers from monoterpene oxidation are lower at SORPES compared to SMEAR II. The model simulates the NPF events at SMEAR II with a good agreement but underestimates the growth of new particles at SORPES, indicating a dominant role of anthropogenic processes in the polluted environment. HOMs from monoterpene oxidation dominate the growth of ultrafine particles at SMEAR II while sulfuric acid and HOMs from aromatics oxidation play a more important role in particle growth. This study highlights the distinct roles of sulfuric acid and HOMs in NPF and particle growth in different environmental conditions and suggests the need for molecular-scale measurements in improving the understanding of NPF mechanisms in polluted areas like eastern China.
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| 42. |
- Quelever, Lauriane L.J., et al.
(författare)
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Effect of temperature on the formation of highly oxygenated organic molecules (HOMs) from alpha-pinene ozonolysis
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:11, s. 7609-7625
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Tidskriftsartikel (refereegranskat)abstract
- Highly oxygenated organic molecules (HOMs) are important contributors to secondary organic aerosol (SOA) and new-particle formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOCs), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during α-pinene ozonolysis experiments performed at three different temperatures, 20, 0 and -15 ĝC, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb α-pinene and 100 ppb ozone), decreased considerably at lower temperature, with molar yields dropping by around a factor of 50 when experiments were performed at 0 ĝC, compared to 20 ĝC. At -15 ĝC, the HOM signals were already close to the detection limit of the nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOMs. Surprisingly, comparing spectra measured at 0 and 20 ĝC, ratios between HOMs of different oxidation levels, e.g., the typical HOM products C10H14O7, C10H14O9, and C10H14O11, changed considerably less than the total HOM yields. More oxidized species have undergone more isomerization steps; yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is that the primary rate-limiting steps forming these HOMs occur before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e., typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant to the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, both the magnitude and complexity of this effect clearly deserve more consideration in future studies in order to estimate the ultimate role of HOMs on SOA and NPF under different atmospheric conditions.
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| 43. |
- Reddington, C. L., et al.
(författare)
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Primary versus secondary contributions to particle number concentrations in the European boundary layer
- 2011
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 11:23, s. 12007-12036
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Tidskriftsartikel (refereegranskat)abstract
- It is important to understand the relative contribution of primary and secondary particles to regional and global aerosol so that models can attribute aerosol radiative forcing to different sources. In large-scale models, there is considerable uncertainty associated with treatments of particle formation (nucleation) in the boundary layer (BL) and in the size distribution of emitted primary particles, leading to uncertainties in predicted cloud condensation nuclei (CCN) concentrations. Here we quantify how primary particle emissions and secondary particle formation influence size-resolved particle number concentrations in the BL using a global aerosol microphysics model and aircraft and ground site observations made during the May 2008 campaign of the European Integrated Project on Aerosol Cloud Climate Air Quality Interactions (EUCAARI). We tested four different parameterisations for BL nucleation and two assumptions for the emission size distribution of anthropogenic and wildfire carbonaceous particles. When we emit carbonaceous particles at small sizes (as recommended by the Aerosol Inter-comparison project, AEROCOM), the spatial distributions of campaign-mean number concentrations of particles with diameter >50 nm (N(50)) and >100 nm (N(100)) were well captured by the model (R(2)>= 0.8) and the normalised mean bias (NMB) was also small (-18% for N(50) and -1% for N(100)). Emission of carbonaceous particles at larger sizes, which we consider to be more realistic for low spatial resolution global models, results in equally good correlation but larger bias (R(2)>= 0.8, NMB = -52% and -29%), which could be partly but not entirely compensated by BL nucleation. Within the uncertainty of the observations and accounting for the uncertainty in the size of emitted primary particles, BL nucleation makes a statistically significant contribution to CCN-sized particles at less than a quarter of the ground sites. Our results show that a major source of uncertainty in CCN-sized particles in polluted European air is the emitted size of primary carbonaceous particles. New information is required not just from direct observations, but also to determine the effective emission size and composition of primary particles appropriate for different resolution models.
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| 44. |
- Rizzo, L. V., et al.
(författare)
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Long term measurements of aerosol optical properties at a primary forest site in Amazonia
- 2013
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7324. ; 13:5, s. 2391-2413
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Tidskriftsartikel (refereegranskat)abstract
- A long term experiment was conducted in a primary forest area in Amazonia, with continuous in-situ measurements of aerosol optical properties between February 2008 and April 2011, comprising, to our knowledge, the longest database ever in the Amazon Basin. Two major classes of aerosol particles, with significantly different optical properties were identified: coarse mode predominant biogenic aerosols in the wet season (January-June), naturally released by the forest metabolism, and fine mode dominated biomass burning aerosols in the dry season (July-December), transported from regional fires. Dry particle median scattering coefficients at the wavelength of 550 nm increased from 6.3 Mm(-1) to 22 Mm(-1), whereas absorption at 637 nm increased from 0.5 Mm(-1) to 2.8 Mm(-1) from wet to dry season. Most of the scattering in the dry season was attributed to the predominance of fine mode (PM2) particles (40-80% of PM10 mass), while the enhanced absorption coefficients are attributed to the presence of light absorbing aerosols from biomass burning. As both scattering and absorption increased in the dry season, the single scattering albedo (SSA) did not show a significant seasonal variability, in average 0.86 +/- 0.08 at 637 nm for dry aerosols. Measured particle optical properties were used to estimate the aerosol forcing efficiency at the top of the atmosphere. Results indicate that in this primary forest site the radiative balance was dominated by the cloud cover, particularly in the wet season. Due to the high cloud fractions, the aerosol forcing efficiency absolute values were below -3.5 Wm(-2) in 70% of the wet season days and in 46% of the dry season days. Besides the seasonal variation, the influence of out-of-Basin aerosol sources was observed occasionally. Periods of influence of the Manaus urban plume were detected, characterized by a consistent increase on particle scattering (factor 2.5) and absorption coefficients (factor 5). Episodes of biomass burning and mineral dust particles advected from Africa were observed between January and April, characterized by enhanced concentrations of crustal elements (Al, Si, Ti, Fe) and potassium in the fine mode. During these episodes, median particle absorption coefficients increased by a factor of 2, whereas median SSA values decreased by 7 %, in comparison to wet season conditions.
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| 45. |
- Rizzo, Luciana Varanda, et al.
(författare)
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Multi-year statistical and modeling analysis of submicrometer aerosol number size distributions at a rain forest site in Amazonia
- 2018
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:14, s. 10255-10274
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Tidskriftsartikel (refereegranskat)abstract
- The Amazon Basin is a unique region to study atmospheric aerosols, given their relevance for the regional hydrological cycle and the large uncertainty of their sources. Multi-year datasets are crucial when contrasting periods of natural conditions and periods influenced by anthropogenic emissions. In the wet season, biogenic sources and processes prevail, and the Amazonian atmospheric composition resembles preindustrial conditions. In the dry season, the basin is influenced by widespread biomass burning emissions. This work reports multi-year observations of high time resolution submicrometer (10-600 nm) particle number size distributions at a rain forest site in Amazonia (TT34 tower, 60 km NW from Manaus city), between 2008 and 2010 and 2012 and 2014. The median particle number concentration was 403 cm(-3) in the wet season and 1254 cm(-3) in the dry season. The Aitken mode (similar to 30-100 nm in diameter) was prominent during the wet season, while the accumulation mode (similar to 100-600 nm in diameter) dominated the particle size spectra during the dry season. Cluster analysis identified groups of aerosol number size distributions influenced by convective downdrafts, nucleation events and fresh biomass burning emissions. New particle formation and subsequent growth was rarely observed during the 749 days of observations, similar to previous observations in the Amazon Basin. A stationary 1-D column model (ADCHEM Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer model) was used to assess the importance of the processes behind the observed diurnal particle size distribution trends. Three major particle source types are required in the model to reproduce the observations: (i) a surface source of particles in the evening, possibly related to primary biological emissions; (ii) entrainment of accumulation mode aerosols in the morning; and (iii) convective downdrafts transporting Aitken mode particles into the boundary layer mostly during the afternoon. The latter process has the largest influence on the modeled particle number size distributions. However, convective downdrafts are often associated with rain and, thus, act as both a source of Aitken mode particles and a sink of accumulation mode particles, causing a net reduction in the median total particle number concentrations in the surface layer. Our study shows that the combination of the three mentioned particle sources is essential to sustain particle number concentrations in Amazonia.
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| 46. |
- Roldin, Pontus, et al.
(författare)
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Aerosol ageing in an urban plume - implication for climate
- 2011
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7324. ; 11:12, s. 5897-5915
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Tidskriftsartikel (refereegranskat)abstract
- The climate effects downwind of an urban area resulting from gaseous and particulate emissions within the city are as yet inadequately quantified. The aim of this work was to estimate these effects for Malmo city in southern Sweden (population 280 000). The chemical and physical particle properties were simulated with a model for Aerosol Dynamics, gas phase CHEMistry and radiative transfer calculations (ADCHEM) following the trajectory movement from upwind of Malmo, through the urban background environment and finally tens and hundreds of kilometers downwind of Malmo. The model results were evaluated using measurements of the particle number size distribution and chemical composition. The total particle number concentration 50 km (similar to 3 h) downwind, in the center of the Malmo plume, is about 3700 cm(-3) of which the Malmo contribution is roughly 30%. Condensation of nitric acid, ammonium and to a smaller extent oxidized organic compounds formed from the emissions in Malmo increases the secondary aerosol formation with a maximum of 0.7-0.8 mu gm(-3) 6 to 18 h downwind of Malmo. The secondary mass contribution dominates over the primary soot contribution from Malmo already 3 to 4 h downwind of the emission sources and contributes to an enhanced total surface direct or indirect aerosol shortwave radiative forcing in the center of the urban plume ranging from -0.3 to -3.3 Wm(-2) depending on the distance from Malmo, and the specific cloud properties.
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| 47. |
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| 48. |
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| 49. |
- Roldin, Pontus, et al.
(författare)
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Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM
- 2011
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7324. ; 11:12, s. 5867-5896
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Tidskriftsartikel (refereegranskat)abstract
- The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1x1 km(2)) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (AD-CHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as in-put to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmo in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm, while the moving-center method is preferable when only a few size bins are selected. The particle number size distribution in the center of the urban plume from Malmo was mainly affected by dry deposition, coagulation and vertical dilution. The modeled PM2.5 mass was dominated by organic material, nitrate, sulfate and ammonium. If the condensation of HNO3 and NH3 was treated as a coupled process (pH independent) the model gave lower nitrate PM2.5 mass than if considering uncoupled condensation. Although the time of ageing from that SOA precursors are emitted until condensable products are formed is substantially different with the 2D-VBS and two product model, the models gave similar total organic mass concentrations.
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| 50. |
- Roldin, Pontus, et al.
(författare)
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Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM
- 2014
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7324. ; 14:15, s. 7953-7993
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Tidskriftsartikel (refereegranskat)abstract
- We have developed the novel Aerosol Dynamics, gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas-phase Master Chemical Mechanism version 3.2 (MCMv3.2), an aerosol dynamics and particle-phase chemistry module (which considers acid-catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion-limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study (1) the evaporation of liquid dioctyl phthalate (DOP) particles, (2) the slow and almost particle-size-independent evaporation of alpha-pinene ozonolysis secondary organic aerosol (SOA) particles, (3) the mass-transfer-limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), and (4) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed alpha-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. In the smog chamber experiments, these salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating alpha-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar-like amorphous-phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if the concentration of low-volatility and viscous oligomerized SOA material at the particle surface increases upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass-transfer-limited uptake of condensable organic compounds onto wall-deposited particles or directly onto the Teflon chamber walls of smog chambers can have a profound influence on the observed SOA formation. During the early stage of the SOA formation the wall-deposited particles and walls themselves serve as an SOA sink from the air to the walls. However, at the end of smog chamber experiments the semi-volatile SOA material may start to evaporate from the chamber walls. With these four model applications, we demonstrate that several poorly quantified processes (i.e. mass transport limitations within the particle phase, oligomerization, heterogeneous oxidation, organic salt formation, and chamber wall effects) can have a substantial influence on the SOA formation, lifetime, chemical and physical particle properties, and their evolution. In order to constrain the uncertainties related to these processes, future experiments are needed in which as many of the influential variables as possible are varied. ADCHAM can be a valuable model tool in the design and analysis of such experiments.
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