| 1. |
- Ahlberg, Erik, et al.
(författare)
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Effect of salt seed particle surface area, composition and phase on secondary organic aerosol mass yields in oxidation flow reactors
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:4, s. 2701-2712
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Tidskriftsartikel (refereegranskat)abstract
- Atmospheric particulate water is ubiquitous, affecting particle transport and uptake of gases. Yet, research on the effect of water on secondary organic aerosol (SOA) mass yields is not consistent. In this study, the SOA mass yields of an α-pinene and m-xylene mixture, at a concentration of 60 μgm-3, were examined using an oxidation flow reactor operated at a relative humidity (RH) of 60% and a residence time of 160 s. Wet or dried ammonium sulfate and ammonium nitrate seed particles were used. By varying the amount of seed particle surface area, the underestimation of SOA formation induced by the short residence time in flow reactors was confirmed. Starting at a SOA mass concentration of 5 μgm-3, the maximum yield increased by a factor of 2 with dry seed particles and on average a factor of 3.2 with wet seed particles. Hence, wet particles increased the SOA mass yield by 60% compared to the dry experiment. Maximum yield in the reactor was achieved using a surface area concentration of 1600 μm2 cm-3. This corresponded to a condensational lifetime of 20 s for low-volatility organics. The O V C ratio of SOA on wet ammonium sulfate was significantly higher than when using ammonium nitrate or dry ammonium sulfate seed particles, probably due to differences in heterogeneous chemistry.
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| 2. |
- Ahlberg, Erik, et al.
(författare)
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Measurement report : Black carbon properties and concentrations in southern Sweden urban and rural air-the importance of long-range transport
- 2023
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 23:5, s. 3051-3064
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Tidskriftsartikel (refereegranskat)abstract
- Soot, or black carbon (BC), aerosol is a major climate forcer with severe health effects. The impacts depend strongly on particle number concentration, size and mixing state. This work reports on two field campaigns at nearby urban and rural sites, 65gkm apart, in southern Sweden during late summer 2018. BC was measured using a single-particle soot photometer (SP2) and Aethalometers (AE33). Differences in BC concentrations between the sites are driven primarily by local traffic emissions. Equivalent and refractory BC mass concentrations at the urban site were on average a factor 2.2 and 2.5, with peaks during rush hour up to a factor g1/44, higher than the rural background levels. The number fraction of particles containing a soot core was significantly higher in the city. BC particles at the urban site were on average smaller by mass and had less coating owing to fresh traffic emissions. The organic components of the fresh traffic plumes were similar in mass spectral signature to hydrocarbon-like organic aerosol (HOA), commonly associated with traffic. Despite the intense local traffic (g1/4g30g000 vehicles passing per day), PM1, including organic aerosol, was dominated by aged continental air masses even at the curbside site. The fraction of thickly coated particles at the urban site was highly correlated with the mass concentrations of all measured chemical species of PM1, consistent with aged, internally mixed aerosol. Trajectory analysis for the whole year showed that air masses arriving at the rural site from eastern Europe contained approximately double the amount of BC compared to air masses from western Europe. Furthermore, the largest regional emissions of BC transported to the rural site, from the Malmö-Copenhagen urban area, are discernible above background levels only when precipitation events are excluded. We show that continental Europe and not the Malmö-Copenhagen region is the major contributor to the background BC mass concentrations in southern Sweden.
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| 3. |
- Ahlberg, Erik, et al.
(författare)
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No particle mass enhancement from induced atmospheric ageing at a rural site in northern Europe
- 2019
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Ingår i: Atmosphere. - : MDPI AG. - 2073-4433. ; 10:7
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Tidskriftsartikel (refereegranskat)abstract
- A large portion of atmospheric aerosol particles consists of secondary material produced by oxidation reactions. The relative importance of secondary organic aerosol (SOA) can increase with improved emission regulations. A relatively simple way to study potential particle formation in the atmosphere is by using oxidation flow reactors (OFRs) which simulate atmospheric ageing. Here we report on the first ambient OFR ageing experiment in Europe, coupled with scanning mobility particle sizer (SMPS), aerosol mass spectrometer (AMS) and proton transfer reaction (PTR)-MS measurements. We found that the simulated ageing did not produce any measurable increases in particle mass or number concentrations during the two months of the campaign due to low concentrations of precursors. Losses in the reactor increased with hydroxyl radical (OH) exposure and with increasing difference between ambient and reactor temperatures, indicating fragmentation and evaporation of semivolatile material.
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| 4. |
- Ahlberg, Erik, et al.
(författare)
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Secondary organic aerosol from VOC mixtures in an oxidation flow reactor
- 2017
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Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310. ; 161, s. 210-220
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Tidskriftsartikel (refereegranskat)abstract
- The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (α-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor.
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| 5. |
- Ahlberg, Erik, et al.
(författare)
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"Vi klimatforskare stödjer Greta och skolungdomarna"
- 2019
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Ingår i: Dagens nyheter (DN debatt). - 1101-2447.
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Tidskriftsartikel (populärvet., debatt m.m.)abstract
- DN DEBATT 15/3. Sedan industrialiseringens början har vi använt omkring fyra femtedelar av den mängd fossilt kol som får förbrännas för att vi ska klara Parisavtalet. Vi har bara en femtedel kvar och det är bråttom att kraftigt reducera utsläppen. Det har Greta Thunberg och de strejkande ungdomarna förstått. Därför stödjer vi deras krav, skriver 270 klimatforskare.
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| 6. |
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| 7. |
- Bianchi, Federico, et al.
(författare)
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Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals : A Key Contributor to Atmospheric Aerosol
- 2019
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Ingår i: Chemical Reviews. - : American Chemical Society (ACS). - 0009-2665 .- 1520-6890. ; 119:6, s. 3472-3509
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Forskningsöversikt (refereegranskat)abstract
- Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earths radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.
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| 8. |
- Boy, M., et al.
(författare)
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Interactions between the atmosphere, cryosphere, and ecosystems at northern high latitudes
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:3, s. 2015-2061
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Tidskriftsartikel (refereegranskat)abstract
- The Nordic Centre of Excellence CRAICC (Cryosphere-Atmosphere Interactions in a Changing Arctic Climate), funded by NordForsk in the years 2011-2016, is the largest joint Nordic research and innovation initiative to date, aiming to strengthen research and innovation regarding climate change issues in the Nordic region. CRAICC gathered more than 100 scientists from all Nordic countries in a virtual centre with the objectives of identifying and quantifying the major processes controlling Arctic warming and related feedback mechanisms, outlining strategies to mitigate Arctic warming, and developing Nordic Earth system modelling with a focus on short-lived climate forcers (SLCFs), including natural and anthropogenic aerosols. The outcome of CRAICC is reflected in more than 150 peer-reviewed scientific publications, most of which are in the CRAICC special issue of the journal Atmospheric Chemistry and Physics. This paper presents an overview of the main scientific topics investigated in the centre and provides the reader with a state-of-the-art comprehensive summary of what has been achieved in CRAICC with links to the particular publications for further detail. Faced with a vast amount of scientific discovery, we do not claim to completely summarize the results from CRAICC within this paper, but rather concentrate here on the main results which are related to feedback loops in climate change-cryosphere interactions that affect Arctic amplification.
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| 9. |
- Boy, Michael, et al.
(författare)
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Positive feedback mechanism between biogenic volatile organic compounds and the methane lifetime in future climates
- 2022
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Ingår i: npj Climate and Atmospheric Science. - : Springer Science and Business Media LLC. - 2397-3722. ; 5:1
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Tidskriftsartikel (refereegranskat)abstract
- A multitude of biogeochemical feedback mechanisms govern the climate sensitivity of Earth in response to radiation balance perturbations. One feedback mechanism, which remained missing from most current Earth System Models applied to predict future climate change in IPCC AR6, is the impact of higher temperatures on the emissions of biogenic volatile organic compounds (BVOCs), and their subsequent effects on the hydroxyl radical (OH) concentrations. OH, in turn, is the main sink term for many gaseous compounds including methane, which is the second most important human-influenced greenhouse gas in terms of climate forcing. In this study, we investigate the impact of this feedback mechanism by applying two models, a one-dimensional chemistry-transport model, and a global chemistry-transport model. The results indicate that in a 6 K temperature increase scenario, the BVOC-OH-CH4 feedback increases the lifetime of methane by 11.4% locally over the boreal region when the temperature rise only affects chemical reaction rates, and not both, chemistry and BVOC emissions. This would lead to a local increase in radiative forcing through methane (ΔRFCH4) of approximately 0.013 Wm−2 per year, which is 2.1% of the current ΔRFCH4. In the whole Northern hemisphere, we predict an increase in the concentration of methane by 0.024% per year comparing simulations with temperature increase only in the chemistry or temperature increase in chemistry and BVOC emissions. This equals approximately 7% of the annual growth rate of methane during the years 2008–2017 (6.6 ± 0.3 ppb yr−1) and leads to an ΔRFCH4 of 1.9 mWm−2 per year.
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| 10. |
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| 11. |
- Chen, Dean, et al.
(författare)
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A modelling study of OH, NO3 and H2SO4 in 2007- 2018 at SMEAR II, Finland : Analysis of long-term trends
- 2021
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Ingår i: Environmental Science: Atmospheres. - : Royal Society of Chemistry (RSC). - 2634-3606. ; 1:6, s. 449-472
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Tidskriftsartikel (refereegranskat)abstract
- Major atmospheric oxidants (OH,O3 and NO3) dominate the atmospheric oxidation capacity, while H2SO4 is considered as a main driver for new particle formation. Although numerous studies have investigated the long-term trend of ozone in Europe, the trends of OH, NO3 and H2SO4 at specific sites are to a large extent unknown. The one-dimensional model SOSAA has been applied in several studies at the SMEAR II station and has been validated by measurements in several projects. Here, we applied the SOSAA model for the years 2007-2018 to simulate the atmospheric chemical components, especially the atmospheric oxidants OH and NO3, as well as H2SO4 at SMEAR II. The simulations were evaluated with observations from several shorter and longer campaigns at SMEAR II. Our results show that daily OH increased by 2.39% per year and NO3 decreased by 3.41% per year, with different trends of these oxidants during day and night. On the contrary, daytime sulfuric acid concentrations decreased by 2.78% per year, which correlated with the observed decreasing concentration of newly formed particles in the size range of 3- 25 nm with 1.4% per year at SMEAR II during the years 1997-2012. Additionally, we compared our simulated OH, NO3 and H2SO4 concentrations with proxies, which are commonly applied in case a limited number of parameters are measured and no detailed model simulations are available.
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| 12. |
- Clusius, Petri, et al.
(författare)
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Atmospherically Relevant Chemistry and Aerosol box model - ARCA box (version 1.2)
- 2022
-
Ingår i: Geoscientific Model Development. - : Copernicus GmbH. - 1991-959X .- 1991-9603. ; 15:18, s. 7257-7286
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Tidskriftsartikel (refereegranskat)abstract
- We introduce the Atmospherically Relevant Chemistry and Aerosol box model ARCA box (v.1.2.2). It is a zero-dimensional process model with a focus on atmospheric chemistry and submicron aerosol processes, including cluster formation. A novel feature in the model is its comprehensive graphical user interface, allowing for detailed configuration and documentation of the simulation settings, flexible model input, and output visualization. Additionally, the graphical interface contains tools for module customization and input data acquisition. These properties - customizability, ease of implementation and repeatability - make ARCA an invaluable tool for any atmospheric scientist who needs a view on the complex atmospheric aerosol processes. ARCA is based on previous models (MALTE-BOX, ADiC and ADCHEM), but the code has been fully rewritten and reviewed. The gas-phase chemistry module incorporates the Master Chemical Mechanism (MCMv3.3.1) and Peroxy Radical Autoxidation Mechanism (PRAM) but can use any compatible chemistry scheme. ARCA's aerosol module couples the ACDC (Atmospheric Cluster Dynamics Code) in its particle formation module, and the discrete particle size representation includes the fully stationary and fixed-grid moving average methods. ARCA calculates the gas-particle partitioning of low-volatility organic vapours for any number of compounds included in the chemistry, as well as the Brownian coagulation of the particles. The model has parametrizations for vapour and particle wall losses but accepts user-supplied time- and size-resolved input. ARCA is written in Fortran and Python (user interface and supplementary tools), can be installed on any of the three major operating systems and is licensed under GPLv3.
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| 13. |
- de Jonge, Robin Wollesen, et al.
(författare)
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Natural Marine Precursors Boost Continental New Particle Formation and Production of Cloud Condensation Nuclei
- 2024
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Ingår i: Environmental Science and Technology. - Malmö : IVL Svenska Miljöinstitutet. - 0013-936X .- 1520-5851. ; 58:25, s. 10956-10968
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Tidskriftsartikel (refereegranskat)abstract
- Marine dimethyl sulfide (DMS) emissions are the dominant source of natural sulfur in the atmosphere. DMS oxidizes to produce low-volatility acids that potentially nucleate to form particles that may grow into climatically important cloud condensation nuclei (CCN). In this work, we utilize the chemistry transport model ADCHEM to demonstrate that DMS emissions are likely to contribute to the majority of CCN during the biological active period (May-August) at three different forest stations in the Nordic countries. DMS increases CCN concentrations by forming nucleation and Aitken mode particles over the ocean and land, which eventually grow into the accumulation mode by condensation of low-volatility organic compounds from continental vegetation. Our findings provide a new understanding of the exchange of marine precursors between the ocean and land, highlighting their influence as one of the dominant sources of CCN particles over the boreal forest.
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| 14. |
- Du, Yaxing, et al.
(författare)
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Large-eddy simulation of aerosol concentrations in a realistic urban environment: Model validation and transport mechanism
- 2024
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Ingår i: Environmental Pollution. - Malmö : IVL Svenska Miljöinstitutet. - 0269-7491 .- 1873-6424. ; 358, s. 124475-124475
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Tidskriftsartikel (refereegranskat)abstract
- Air pollution in urban environments exhibits large spatial and temporal variations due to high heterogeneous air flow and emissions. To address the complexity of local air pollutant dynamics, a comprehensive large-eddy simulation using the PALM model system v6.0 was conducted. The distribution of flow and vehicle emitted aerosol particles in a realistic urban environment in Malmö, Sweden, was studied and evaluated against on-site measurements made using portable instrumentation on a spring morning in 2021.The canyon transport mechanisms were investigated, and the convective and turbulent mass-transport rates compared to clarify their role in aerosol transport. The horizontal distribution of aerosols showed acceptable evaluation metrics for both mass and number. Flow and pollutant concentrations were more complex than those in idealized street canyon networks. Vertical turbulent mass-transport rate was found to dominate the mass transport process compared with the convective transport rate, contributing more than 70% of the pollutant transport process.Our findings highlight the necessity of examining various aerosol metric due their distinct dispersion behaviour. This study introduces a comprehensive high-resolution modelling framework that accounts for dynamic meteorological and aerosol background boundary conditions, real-time traffic emission, and detailed building features, offering a robust toll for local urban air quality assessment.
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| 15. |
- Du, Yaxing, et al.
(författare)
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Large-eddy simulation of aerosol concentrations in a realistic urban environment : Model validation and transport mechanism
- 2024
-
Ingår i: Environmental Pollution. - Malmö : IVL Svenska Miljöinstitutet. - 0269-7491 .- 1873-6424. ; 358
-
Tidskriftsartikel (refereegranskat)abstract
- Air pollution in urban environments exhibits large spatial and temporal variations due to high heterogeneous air flow and emissions. To address the complexity of local air pollutant dynamics, a comprehensive large-eddy simulation using the PALM model system v6.0 was conducted. The distribution of flow and vehicle emitted aerosol particles in a realistic urban environment in Malmö, Sweden, was studied and evaluated against on-site measurements made using portable instrumentation on a spring morning in 2021. The canyon transport mechanisms were investigated, and the convective and turbulent mass-transport rates compared to clarify their role in aerosol transport. The horizontal distribution of aerosols showed acceptable evaluation metrics for both mass and number. Flow and pollutant concentrations were more complex than those in idealized street canyon networks. Vertical turbulent mass-transport rate was found to dominate the mass transport process compared with the convective transport rate, contributing more than 70% of the pollutant transport process. Our findings highlight the necessity of examining various aerosol metric due their distinct dispersion behaviour. This study introduces a comprehensive high-resolution modelling framework that accounts for dynamic meteorological and aerosol background boundary conditions, real-time traffic emission, and detailed building features, offering a robust toll for local urban air quality assessment.
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| 16. |
- Eriksson, Axel, et al.
(författare)
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Diesel soot aging in urban plumes within hours under cold dark and humid conditions
- 2017
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322.
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Tidskriftsartikel (refereegranskat)abstract
- Fresh and aged diesel soot particles have different impacts on climate and human health. While fresh diesel soot particles are highly aspherical and non-hygroscopic, aged particles are spherical and hygroscopic. Aging and its effect on water uptake also controls the dispersion of diesel soot in the atmosphere. Understanding the timescales on which diesel soot ages in the atmosphere is thus important, yet knowledge thereof is lacking. We show that under cold, dark and humid conditions the atmospheric transformation from fresh to aged soot occurs on a timescale of less than five hours. Under dry conditions in the laboratory, diesel soot transformation is much less efficient. While photochemistry drives soot aging, our data show it is not always a limiting factor. Field observations together with aerosol process model simulations show that the rapid ambient diesel soot aging in urban plumes is caused by coupled ammonium nitrate formation and water uptake.
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| 17. |
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| 18. |
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| 19. |
- Gunthe, S. S., et al.
(författare)
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Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity
- 2009
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Ingår i: Atmospheric Chemistry and Physics. - 1680-7324. ; 9:19, s. 7551-7575
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Tidskriftsartikel (refereegranskat)abstract
- Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of kappa approximate to 0.1-0.4 (0.16+/-0.06 arithmetic mean and standard deviation). The overall median value of kappa approximate to 0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (kappa approximate to 0.1 at D approximate to 50 nm; kappa approximate to 0.2 at D approximate to 200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (f(org)) was on average as high as similar to 90% in the Aitken mode (D <= 100 nm) and decreased with increasing particle diameter in the accumulation mode (similar to 80% at D approximate to 200 nm). The kappa values exhibited a negative linear correlation with f(org) (R-2=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: kappa(org)approximate to 0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and kappa(inorg)approximate to 0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (kappa(p)=kappa(org) x f(org)+kappa(inorg) x f(inorg)). The CCN number concentrations predicted with kappa(p) were in fair agreement with the measurement results (similar to 20% average deviation). The median CCN number concentrations at S=0.1-0.82% ranged from N-CCN,N-0.10 approximate to 35 cm(-3) to N-CCN,N-0.82 approximate to 160 cm(-3), the median concentration of aerosol particles larger than 30 nm was N-CN,N-30 approximate to 200 cm(-3), and the corresponding integral CCN efficiencies were in the range of N-CCN,N-0.10/NCN,N-30 approximate to 0.1 to N-CCN,N-0.82/NCN,N-30 approximate to 0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of N-CCN,N-S assuming an approximate global average value of kappa approximate to 0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded similar to 50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (<= 100 cm(-3)). Model calculations assuming aconstant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: similar to 60% for the campaign average distribution and similar to 1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.
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| 20. |
- Hao, Liqing, et al.
(författare)
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Combined effects of boundary layer dynamics and atmospheric chemistry on aerosol composition during new particle formation periods
- 2018
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:23, s. 17705-17716
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Tidskriftsartikel (refereegranskat)abstract
- Characterizing aerosol chemical composition in response to meteorological changes and atmospheric chemistry is important to gain insights into new particle formation mechanisms. A BAECC (Biogenic Aerosols - Effects on Clouds and Climate) campaign was conducted during the spring 2014 at the SMEAR II station (Station for Measuring Forest Ecosystem-Aerosol Relations) in Finland. The particles were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A PBL (planetary boundary layer) dilution model was developed to assist interpreting the measurement results. Right before nucleation events, the mass concentrations of organic and sulfate aerosol species were both decreased rapidly along with the growth of PBL heights. However, the mass fraction of sulfate aerosol of the total aerosol mass was increased, in contrast to a decrease for the organic mass fraction. Meanwhile, an increase in LVOOA (low-volatility oxygenated organic aerosol) mass fraction of the total organic mass was observed, in distinct comparison to a reduction of SVOOA (semi-volatile OOA) mass fraction. Our results demonstrate that, at the beginning of nucleation events, the observed sulfate aerosol mass was mainly driven by vertical turbulent mixing of sulfate-rich aerosols between the residual layer and the newly formed boundary layer, while the condensation of sulfuric acid (SA) played a minor role in interpreting the measured sulfate mass concentration. For the measured organic aerosols, their temporal profiles were mainly driven by dilution from PBL development, organic aerosol mixing in different boundary layers and/or partitioning of organic vapors, but accurate measurements of organic vapor concentrations and characterization on the spatial aerosol chemical composition are required. In general, the observed aerosol particles by AMS are subjected to joint effects of PBL dilution, atmospheric chemistry and aerosol mixing in different boundary layers. During aerosol growth periods in the nighttime, the mass concentrations of organic aerosols and organic nitrate aerosols were both increased. The increase in SVOOA mass correlated well with the calculated increase in condensed HOMs' (highly oxygenated organic molecules) mass. To our knowledge, our results are the first atmospheric observations showing a connection between increase in SVOOA and condensed HOMs during the nighttime.
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| 21. |
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| 22. |
- Kalivitis, Nikos, et al.
(författare)
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Formation and growth of atmospheric nanoparticles in the eastern Mediterranean : Results from long-term measurements and process simulations
- 2019
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:4, s. 2671-2686
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Tidskriftsartikel (refereegranskat)abstract
- Atmospheric new particle formation (NPF) is a common phenomenon all over the world. In this study we present the longest time series of NPF records in the eastern Mediterranean region by analyzing 10 years of aerosol number size distribution data obtained with a mobility particle sizer. The measurements were performed at the Finokalia environmental research station on Crete, Greece, during the period June 2008-June 2018. We found that NPF took place on 27 % of the available days, undefined days were 23 % and non-event days 50 %. NPF is more frequent in April and May probably due to the terrestrial biogenic activity and is less frequent in August. Throughout the period under study, nucleation was observed also during the night. Nucleation mode particles had the highest concentration in winter and early spring, mainly because of the minimum sinks, and their average contribution to the total particle number concentration was 8 %. Nucleation mode particle concentrations were low outside periods of active NPF and growth, so there are hardly any other local sources of sub-25 nm particles. Additional atmospheric ion size distribution data simultaneously collected for more than 2 years were also analyzed. Classification of NPF events based on ion spectrometer measurements differed from the corresponding classification based on a mobility spectrometer, possibly indicating a different representation of local and regional NPF events between these two measurement data sets. We used the MALTE-Box model for simulating a case study of NPF in the eastern Mediterranean region. Monoterpenes contributing to NPF can explain a large fraction of the observed NPF events according to our model simulations. However the adjusted parameterization resulting from our sensitivity tests was significantly different from the initial one that had been determined for the boreal environment.
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| 23. |
- Kivekäs, Niku, et al.
(författare)
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Coupling an aerosol box model with one-dimensional flow : A tool for understanding observations of new particle formation events
- 2016
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Ingår i: Tellus. Series B: Chemical and Physical Meteorology. - : Stockholm University Press. - 1600-0889 .- 0280-6509. ; 68:1
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Tidskriftsartikel (refereegranskat)abstract
- Field observations of new particle formation and the subsequent particle growth are typically only possible at a fixed measurement location, and hence do not follow the temporal evolution of an air parcel in a Lagrangian sense. Standard analysis for determining formation and growth rates requires that the time-dependent formation rate and growth rate of the particles are spatially invariant; air parcel advection means that the observed temporal evolution of the particle size distribution at a fixed measurement location may not represent the true evolution if there are spatial variations in the formation and growth rates. Here we present a zerodimensional aerosol box model coupled with one-dimensional atmospheric flow to describe the impact of advection on the evolution of simulated new particle formation events. Wind speed, particle formation rates and growth rates are input parameters that can vary as a function of time and location, using wind speed to connect location to time. The output simulates measurements at a fixed location; formation and growth rates of the particle mode can then be calculated from the simulated observations at a stationary point for different scenarios and be compared with the 'true' input parameters. Hence, we can investigate how spatial variations in the formation and growth rates of new particles would appear in observations of particle number size distributions at a fixed measurement site. We show that the particle size distribution and growth rate at a fixed location is dependent on the formation and growth parameters upwind, even if local conditions do not vary. We also show that different input parameters used may result in very similar simulated measurements. Erroneous interpretation of observations in terms of particle formation and growth rates, and the time span and areal extent of new particle formation, is possible if the spatial effects are not accounted for.
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| 24. |
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| 25. |
- Kurppa, Mona, et al.
(författare)
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Implementation of the sectional aerosol module SALSA2.0 into the PALM model system 6.0 : Model development and first evaluation
- 2019
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Ingår i: Geoscientific Model Development. - : Copernicus GmbH. - 1991-959X .- 1991-9603. ; 12:4, s. 1403-1422
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Tidskriftsartikel (refereegranskat)abstract
- Urban pedestrian-level air quality is a result of an interplay between turbulent dispersion conditions, background concentrations, and heterogeneous local emissions of air pollutants and their transformation processes. Still, the complexity of these interactions cannot be resolved by the commonly used air quality models. By embedding the sectional aerosol module SALSA2.0 into the large-eddy simulation model PALM, a novel, high-resolution, urban aerosol modelling framework has been developed. The first model evaluation study on the vertical variation of aerosol number concentration and size distribution in a simple street canyon without vegetation in Cambridge, UK, shows good agreement with measurements, with simulated values mainly within a factor of 2 of observations. Dispersion conditions and local emissions govern the pedestrian-level aerosol number concentrations. Out of different aerosol processes, dry deposition is shown to decrease the total number concentration by over 20 %, while condensation and dissolutional increase the total mass by over 10 %. Following the model development, the application of PALM can be extended to local- and neighbourhood-scale air pollution and aerosol studies that require a detailed solution of the ambient flow field.
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| 26. |
- Kurppa, Mona, et al.
(författare)
-
Sensitivity of spatial aerosol particle distributions to the boundary conditions in the PALM model system 6.0
- 2020
-
Ingår i: Geoscientific Model Development. - : Copernicus GmbH. - 1991-959X .- 1991-9603. ; 13:11, s. 5663-5685
-
Tidskriftsartikel (refereegranskat)abstract
- High-resolution modelling is needed to understand urban air quality and pollutant dispersion in detail. Recently, the PALM model system 6.0, which is based on large-eddy simulation (LES), was extended with the detailed Sectional Aerosol module for Large Scale Applications (SALSA) v2.0 to enable studying the complex interactions between the turbulent flow field and aerosol dynamic processes. This study represents an extensive evaluation of the modelling system against the horizontal and vertical distributions of aerosol particles measured using a mobile laboratory and a drone in an urban neighbourhood in Helsinki, Finland. Specific emphasis is on the model sensitivity of aerosol particle concentrations, size distributions and chemical compositions to boundary conditions of meteorological variables and aerosol background concentrations. The meteorological boundary conditions are taken from both a numerical weather prediction model and observations, which occasionally differ strongly. Yet, the model shows good agreement with measurements (fractional bias < 0.67, normalised mean squared error < 6, fraction of the data within a factor of 2 > 0.3, normalised mean bias factor < 0.25 and normalised mean absolute error factor < 0.35) with respect to both horizontal and vertical distribution of aerosol particles, their size distribution and chemical composition. The horizontal distribution is most sensitive to the wind speed and atmospheric stratification, and vertical distribution to the wind direction. The aerosol number size distribution is mainly governed by the flow field along the main street with high traffic rates and in its surroundings by the background concentrations. The results emphasise the importance of correct meteorological and aerosol background boundary conditions, in addition to accurate emission estimates and detailed model physics, in quantitative high-resolution air pollution modelling and future urban LES studies.
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| 27. |
- Kurtén, Theo, et al.
(författare)
-
α-Pinene Autoxidation Products May Not Have Extremely Low Saturation Vapor Pressures Despite High O : C Ratios
- 2016
-
Ingår i: The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. - : American Chemical Society (ACS). - 1089-5639. ; 120:16, s. 2569-2582
-
Tidskriftsartikel (refereegranskat)abstract
- COSMO-RS (conductor-like screening model for real solvents) and three different group-contribution methods were used to compute saturation (subcooled) liquid vapor pressures for 16 possible products of ozone-initiated α-pinene autoxidation, with elemental compositions C10H16O4-10 and C20H30O10-12. The saturation vapor pressures predicted by the different methods varied widely. COSMO-RS predicted relatively high saturation vapor pressures values in the range of 10-6 to 10-10 bar for the C10H16O4-10 "monomers", and 10-11 to 10-16 bar for the C20H30O10-12 "dimmers". The group-contribution methods predicted significantly (up to 8 order of magnitude) lower saturation vapor pressures for most of the more highly oxidized monomers. For the dimers, the COSMO-RS predictions were within the (wide) range spanned by the three group-contribution methods. The main reason for the discrepancies between the methods is likely that the group-contribution methods do not contain the necessary parameters to accurately treat autoxidation products containing multiple hydroperoxide, peroxy acid or peroxide functional groups, which form intramolecular hydrogen bonds with each other. While the COSMO-RS saturation vapor pressures for these systems may be overestimated, the results strongly indicate that despite their high O:C ratios, the volatilities of the autoxidation products of α-pinene (and possibly other atmospherically relevant alkenes) are not necessarily extremely low. In other words, while autoxidation products are able to adsorb onto aerosol particles, their evaporation back into the gas phase cannot be assumed to be negligible, especially from the smallest nanometer-scale particles. Their observed effective contribution to aerosol particle growth may therefore involve rapid heterogeneous reactions (reactive uptake) rather than effectively irreversible physical absorption.
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| 28. |
- Li, Linjie, et al.
(författare)
-
Gas-to-Particle Partitioning of Products from Ozonolysis of Δ3-Carene and the Effect of Temperature and Relative Humidity
- 2024
-
Ingår i: JOURNAL OF PHYSICAL CHEMISTRY A. - 1089-5639 .- 1520-5215. ; 128:5, s. 918-928
-
Tidskriftsartikel (refereegranskat)abstract
- Formation of oxidized products from Delta(3)-carene (C10H16) ozonolysis and their gas-to-particle partitioning at three temperatures (0, 10, and 20 degrees C) under dry conditions (<2% RH) and also at 10 degrees C under humid (78% RH) conditions were studied using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) combined with a filter inlet for gases and aerosols (FIGAERO). The Delta(3)-carene ozonolysis products detected by the FIGAERO-ToF-CIMS were dominated by semivolatile organic compounds (SVOCs). The main effect of increasing temperature or RH on the product distribution was an increase in fragmentation of monomer compounds (from C-10 to C-7 compounds), potentially via alkoxy scission losing a C-3 group. The equilibrium partitioning coefficient estimated according to equilibrium partitioning theory shows that the measured SVOC products distribute more into the SOA phase as the temperature decreases from 20 to 10 and 0 degrees C and for most products as the RH increases from <2 to 78%. The temperature dependency of the saturation vapor pressure (above an assumed liquid state), derived from the partitioning method, also allows for a direct way to obtain enthalpy of vaporization for the detected species without accessibility of authentic standards of the pure substances. This method can provide physical properties, beneficial for, e.g., atmospheric modeling, of complex multifunctional oxidation products.
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| 29. |
- Li, Linjie, et al.
(författare)
-
Gas-to-Particle Partitioning of Products from Ozonolysis of Δ3-Carene and the Effect of Temperature and Relative Humidity
- 2024
-
Ingår i: Journal of Physical Chemistry A. - Malmö : IVL Svenska Miljöinstitutet. - 1089-5639 .- 1520-5215. ; 128:5, s. 918-928
-
Tidskriftsartikel (refereegranskat)abstract
- Formation of oxidized products from Δ3-carene (C10H16) ozonolysis and their gas-to-particle partitioning at three temperatures (0, 10, and 20 °C) under dry conditions (<2% RH) and also at 10 °C under humid (78% RH) conditions were studied using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) combined with a filter inlet for gases and aerosols (FIGAERO). The Δ3-carene ozonolysis products detected by the FIGAERO-ToF-CIMS were dominated by semivolatile organic compounds (SVOCs). The main effect of increasing temperature or RH on the product distribution was an increase in fragmentation of monomer compounds (from C10 to C7 compounds), potentially via alkoxy scission losing a C3 group.The equilibrium partitioning coefficient estimated according to equilibrium partitioning theory shows that the measured SVOC products distribute more into the SOA phase as the temperature decreases from 20 to 10 and 0 °C and for most products as the RH increases from <2 to 78%. The temperature dependency of the saturation vapor pressure (above an assumed liquid state), derived from the partitioning method, also allows for a direct way to obtain enthalpy of vaporization for the detected species without accessibility of authentic standards of the pure substances. This method can provide physical properties, beneficial for, e.g., atmospheric modeling, of complex multifunctional oxidation products.
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| 30. |
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| 31. |
- Moberg, Christina, et al.
(författare)
-
De unga gör helt rätt när de stämmer staten
- 2022
-
Ingår i: Aftonbladet. - 1103-9000.
-
Tidskriftsartikel (populärvet., debatt m.m.)abstract
- 1 620 forskare och lärare i forskarvärlden: Vi ställer oss bakom Auroras klimatkrav
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| 32. |
- Nie, Wei, et al.
(författare)
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NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere
- 2023
-
Ingår i: Nature Communications. - Malmö : IVL Svenska Miljöinstitutet AB. - 2041-1723. ; 14:1
-
Tidskriftsartikel (refereegranskat)abstract
- The interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated organic molecules (HOM), the key precursors of secondary organic aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on HOM formation from monoterpenes at low NO concentrations (0 – 82 pptv). We demonstrate that such low NO can enhance HOM production by modulating the RO2 loss and favoring the formation of alkoxy radicals that can continue to autoxidize through isomerization.These insights suggest that HOM yields from typical boreal forest emissions can vary between 2.5%-6.5%, and HOM formation will not be completely inhibited even at high NO concentrations. Our findings challenge the notion that NO monotonically reduces HOM yields by extending the knowledge of RO2-NO interactions to the low-NO regime. This represents a major advance towards an accurate assessment of HOM budgets, especially in low-NO environments, which prevails in the preindustrial atmosphere, pristine areas, and the upper boundary layer.
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| 33. |
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| 34. |
- Nordin, Erik, et al.
(författare)
-
Influence of ozone initiated processing on the toxicity of aerosol particles from small scale wood combustion
- 2015
-
Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310 .- 1873-2844. ; 102, s. 282-289
-
Tidskriftsartikel (refereegranskat)abstract
- Black carbon containing emissions from biomass combustion are being transformed in the atmosphere upon processing induced by tropospheric ozone and UV. The knowledge today is very limited on how atmospheric processing affects the toxicological properties of the emissions. The aim of this study was to investigate the influence of ozone initiated (dark) atmospheric processing on the physicochemical and toxicological properties of particulate emissions from wood combustion. Emissions from a conventional wood stove operated at two combustion conditions (nominal and hot air starved) were diluted and transferred to a chamber. Particulate matter (PM) was collected before and after ozone addition to the chamber using an impactor. Detailed chemical and physical characterization was performed on chamber air and collected PM. The collected PM was investigated toxicologically in vitro with a mouse macrophage model, endpoints included: cell cycle analysis, viability, inflammation and genotoxicity. The results suggest that changes in the organic fraction, including polycyclic aromatic hydrocarbons (PAHs) are the main driver for differences in obtained toxicological effects. Fresh hot air starved emissions containing a higher organic and PAH mass-fraction affected cell viability stronger than fresh emissions from nominal combustion. The PAH mass fractions decreased upon aging due to chemical degradation. Dark aging increased genotoxicity, reduced viability and reduced release of inflammatory markers. These differences were statistically significant for single doses and typically less pronounced. We hypothesize that the alterations in toxicity upon simulated dark aging in the atmosphere may be caused by reaction products that form when PAHs and other organic compounds react with ozone and nitrate radicals. (C) 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).
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| 35. |
- Nordin, Erik, et al.
(författare)
-
Smog Chamber Experiments of SOA Formation from Gasoline Exhaust and Light Aromatics
- 2010
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)abstract
- Experiments where gasoline exhaust was exposed to UV-radiation to examine Secondary Organic Aerosol (SOA) formation were performed in a smog chamber. The Aerosol Mass Yield (formed SOA/reacted precursor mass) was determined and compared with the yield from a pure precursor experiment in the chamber and from results reported in literature. Preliminary results show that the majority of the organic aerosol mass emitted from idling gasoline cars is secondary. Further, the SOA yields when taking only C6-C10 light aromatics into account are within a similar range to pure precursor experiments, suggesting that light aromatics are dominating precursors in gasoline exhaust SOA.
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| 36. |
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| 37. |
- Nordin, E. Z., et al.
(författare)
-
Secondary organic aerosol formation from gasoline passenger vehicle emissions investigated in a smog chamber
- 2012
-
Ingår i: Atmospheric Chemistry and Physics Discussions. - : Copernicus Publications. - 1680-7367 .- 1680-7375. ; 12:12, s. 31725-31765
-
Tidskriftsartikel (refereegranskat)abstract
- Gasoline vehicles have elevated emissions of volatile organic compounds during cold starts and idling and have recently been pointed out as potentially the main source of anthropogenic secondary organic aerosol (SOA) in megacities. However, there is a lack of laboratory studies to systematically investigate SOA formation in real-world exhaust. In this study, SOA formation from pure aromatic precursors, idling and cold start gasoline exhaust from one Euro II, one Euro III and one Euro IV passenger vehicles were investigated using photo-oxidation experiments in a 6 m3 smog chamber. The experiments were carried out at atmospherically relevant organic aerosol mass concentrations. The characterization methods included a high resolution aerosol mass spectrometer and a proton transfer mass spectrometer. It was found that gasoline exhaust readily forms SOA with a signature aerosol mass spectrum similar to the oxidized organic aerosol that commonly dominates the organic aerosol mass spectra downwind urban areas. After 4 h aging the formed SOA was 1–2 orders of magnitude higher than the Primary OA emissions. The SOA mass spectrum from a relevant mixture of traditional light aromatic precursors gave f43 (mass fraction at m/z = 4 3) approximately two times higher than to the gasoline SOA. However O : C and H : C ratios were similar for the two cases. Classical C6–C9 light aromatic precursors were responsible for up to 60% of the formed SOA, which is significantly higher than for diesel exhaust. Important candidates for additional precursors are higher order aromatic compounds such as C10, C11 light aromatics, naphthalene and methyl-naphthalenes.
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| 38. |
- Olenius, Tinja, et al.
(författare)
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Modeling of exhaust gas cleaning by acid pollutant conversion to aerosol particles
- 2021
-
Ingår i: Fuel. - : Elsevier BV. - 0016-2361 .- 1873-7153. ; 290
-
Tidskriftsartikel (refereegranskat)abstract
- Sulfur and nitrogen oxides (SOx and NOx) are harmful pollutants emitted into the atmosphere by industry and transport sectors. In addition to being hazardous gases, SOx and NOx form sulfuric and nitric acids which contribute to the formation of airborne particulate matter through nucleation and condensation, hence magnifying the environmental impact of these species. In this work, we build a modeling framework for utilizing this phenomenon for low-temperature exhaust gas cleaning. It has been reported that ammonia gas can be used to facilitate particle formation from the aforementioned acids, and thus remove these gaseous pollutants by converting them into ammonium sulfate and nitrate particles. Here we provide comprehensive modeling tools for applying this idea to exhaust gas cleaning by combining detailed models for nucleation, gas-particle mass exchange and particle population dynamics. We demonstrate how these models can be used to find advantageous operating conditions for a cleaning unit. In particular, the full model is computationally cheap and enables optimization of the particle formation efficiency and particle growth, hence ensuring sufficient conversion of gaseous pollutants into collectable particulate matter. This constitutes a ground for future engineering tools for designing next-generation sustainable exhaust gas cleaners.
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| 39. |
- Olenius, Tinja, et al.
(författare)
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Role of gas–molecular cluster–aerosol dynamics in atmospheric new-particle formation
- 2022
-
Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 12:1
-
Tidskriftsartikel (refereegranskat)abstract
- New-particle formation from vapors through molecular cluster formation is a central process affecting atmospheric aerosol and cloud condensation nuclei numbers, and a significant source of uncertainty in assessments of aerosol radiative forcing. While advances in experimental and computational methods provide improved assessments of particle formation rates from different species, the standard approach to implement these data in aerosol models rests on highly simplifying assumptions concerning gas–cluster–aerosol dynamics. To quantify the effects of the simplifications, we develop an open-source tool for explicitly simulating the dynamics of the complete particle size spectrum from vapor molecules and molecular clusters to larger aerosols for multi-compound new-particle formation. We demonstrate that the simplified treatment is a reasonable approximation for particle formation from weakly clustering chemical compounds, but results in overprediction of particle numbers and of the contribution of new-particle formation to cloud condensation nuclei for strongly clustering, low-concentration trace gases. The new explicit approach circumvents these issues, thus enabling robust model–measurement comparisons, improved assessment of the importance of different particle formation agents, and construction of optimal simplifications for large-scale models.
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| 40. |
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| 41. |
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| 42. |
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| 43. |
- Peräkylä, Otso, et al.
(författare)
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Experimental investigation into the volatilities of highly oxygenated organic molecules (HOMs)
- 2020
-
Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 20:2, s. 649-669
-
Tidskriftsartikel (refereegranskat)abstract
- Secondary organic aerosol (SOA) forms a major part of the tropospheric submicron aerosol. Still, the exact formation mechanisms of SOA have remained elusive. Recently, a newly discovered group of oxidation products of volatile organic compounds (VOCs), highly oxygenated organic molecules (HOMs), have been proposed to be responsible for a large fraction of SOA formation. To assess the potential of HOMs to form SOA and to even take part in new particle formation, knowledge of their exact volatilities is essential. However, due to their exotic, and partially unknown, structures, estimating their volatility is challenging. In this study, we performed a set of continuous flow chamber experiments, supported by box modelling, to study the volatilities of HOMs, along with some less oxygenated compounds, formed in the ozonolysis of a-pinene, an abundant VOC emitted by boreal forests. Along with gaseous precursors, we periodically injected inorganic seed aerosol into the chamber to vary the condensation sink (CS) of low-volatility vapours. We monitored the decrease of oxidation products in the gas phase in response to increasing CS, and were able to relate the responses to the volatilities of the compounds. We found that HOM monomers are mainly of low volatility, with a small fraction being semi-volatile. HOM dimers were all at least low volatility, but probably extremely low volatility; however, our method is not directly able to distinguish between the two. We were able to model the volatility of the oxidation products in terms of their carbon, hydrogen, oxygen and nitrogen numbers. We found that increasing levels of oxygenation correspond to lower volatilities, as expected, but that the decrease is less steep than would be expected based on many existing models for volatility, such as SIMPOL. The hydrogen number of a compound also predicted its volatility, independently of the carbon number, with higher hydrogen numbers corresponding to lower volatilities. This can be explained in terms of the functional groups making up a molecule: high hydrogen numbers are associated with, e.g. hydroxy groups, which lower volatility more than, e.g. carbonyls, which are associated with a lower hydrogen number. The method presented should be applicable to systems other than a-pinene ozonolysis, and with different organic loadings, in order to study different volatility ranges.
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| 44. |
- Pichelstorfer, Lukas, et al.
(författare)
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Towards automated inclusion of autoxidation chemistry in models: from precursors to atmospheric implications
- 2024
-
Ingår i: Environmental Science. - Malmö : IVL Svenska Miljöinstitutet. - 2634-3606. ; 4:8, s. 879-896
-
Tidskriftsartikel (refereegranskat)abstract
- In the last few decades, atmospheric formation of secondary organic aerosols (SOA) has gained increasing attention due to their impact on air quality and climate. However, methods to predict their abundance are mainly empirical and may fail under real atmospheric conditions. In this work, a close-to-mechanistic approach allowing SOA quantification is presented, with a focus on a chainlike chemical reaction called “autoxidation”. A novel framework is employed to (a) describe the gasphase chemistry, (b) predict the products' molecular structures and (c) explore the contribution of autoxidation chemistry on SOA formation under various conditions. As a proof of concept, the method is applied to benzene, an important anthropogenic SOA precursor. Our results suggest autoxidation to explain up to 100% of the benzene-SOA formed under low-NOx laboratory conditions. Under atmospheric-like day-time conditions, the calculated benzene-aerosol mass continuously forms, as expected based on prior work. Additionally, a prompt increase, driven by the NO3 radical, is predicted by the model at dawn. This increase has not yet been explored experimentally and stresses the potential for atmospheric SOA formation via secondary oxidation of benzene by O3 and NO3.
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| 45. |
- Poeschl, U., et al.
(författare)
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Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon
- 2010
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 1095-9203 .- 0036-8075. ; 329:5998, s. 1513-1516
-
Tidskriftsartikel (refereegranskat)abstract
- The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.
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| 46. |
- 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
-
Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 18:16, s. 11779-11791
-
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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| 47. |
- Quelever, Lauriane L.J., et al.
(författare)
-
Effect of temperature on the formation of highly oxygenated organic molecules (HOMs) from alpha-pinene ozonolysis
- 2019
-
Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 19:11, s. 7609-7625
-
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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| 48. |
- 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
-
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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| 49. |
- 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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- 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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