| 1. |
- Lundén, Jenny, et al.
(författare)
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The vertical distribution of atmospheric DMS in the high Arctic summer
- 2010
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Ingår i: Tellus. Series B, Chemical and physical meteorology. - : Stockholm University Press. - 0280-6509 .- 1600-0889. ; 62:3, s. 160-171
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Tidskriftsartikel (refereegranskat)abstract
- The vertical structure of gas-phase dimethyl sulfide, DMS(g), in the high Arctic atmosphere is investigated during a summer season. The model results show that the near-surface DMS(g) concentration over open ocean is very variable both in time and space, depending on the local atmospheric conditions. Profiles over ocean have typically highest concentration near the surface and decrease exponentially with height. Over the pack-ice, the concentrations are typically lower and the vertical structure changes as the air is advected northward. Modeled DMS(g) maxima above the local boundary layer were present in about 3\% of the profiles found over the pack-ice. These maxima were found in association to frontal zones. Our results also show that DMS(g) can be mixed downward by turbulence into the local boundary layer and act as a local near--surface DMS(g) source over the pack-ice and may hence influence the growth of cloud condensation nuclei and cloud formation in the boundary layer. Profile observations are presented in support to the model results. They show that significant DMS(g) concentrations exist in the Arctic atmosphere at altitudes not to be expected when only considering vertical mixing in the boundary layer.
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| 2. |
- Antonsen, Simen, et al.
(författare)
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Atmospheric Chemistry of tert-butylamine and AMP
- 2017
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Ingår i: Energy Procedia. Volume 114, 2017, Pages 1026-103213th International Conference on Greenhouse Gas Control Technologies, GHGT 2016; Lausanne; Switzerland; 14 November 2016 through 18 November 2016. - : Elsevier BV. - 1876-6102.
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Konferensbidrag (refereegranskat)abstract
- © 2017 The Authors. The atmospheric chemistry of (CH 3 ) 3 CNH 2 (tert-butylamine, tBA) and (CH 3 ) 2 (CH 2 OH)CNH 2 (2-amino-2-methyl-1-propanol, AMP) has been studied by quantum chemistry methods and in photo-oxidation experiments in the EUPHORE chamber in Valencia (Spain). Aerosol formation and composition has been quantified. Yields of nitramines and other products in the photo-oxidations have been determined and complete photo-oxidation schemes including branching between the major reaction routes have been obtained. Published by Elsevier Ltd.
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| 3. |
- Durif, Olivier, et al.
(författare)
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Strong Uptake of Gas-Phase Organic Peroxy Radicals (ROO•) by Solid Surfaces Driven by Redox Reactions
- 2024
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Ingår i: JACS Au. - : American Chemical Society (ACS). - 2691-3704. ; 4:5, s. 1875-1882
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Tidskriftsartikel (refereegranskat)abstract
- Organic peroxy radicals (ROO•) are key oxidants in a wide range of chemical systems such as living organisms, chemical synthesis and polymerization systems, combustion systems, the natural environment, and the Earth’s atmosphere. Although surfaces are ubiquitous in all of these systems, the interactions of organic peroxy radicals with these surfaces have not been studied until today because of a lack of adequate detection techniques. In this work, the uptake and reaction of gas-phase organic peroxy radicals (CH3OO• and i-C3H7OO•) with solid surfaces was studied by monitoring each radical specifically and in real-time with mass spectrometry. Our results show that the uptake of organic peroxy radicals varies widely with the surface material. While their uptake by borosilicate glass and perfluoroalkoxy alkanes (PFA) was negligible, it was substantial with metals and even dominated over the gas-phase reactions with stainless steel and aluminum. The results also indicate that these uptakes are controlled by redox reactions at the surfaces for which the products were analyzed. Our results show that the reactions of organic peroxy radicals with metal surfaces have to be carefully considered in all the experimental investigations of these radicals as they could directly impact the kinetic and mechanistic knowledge derived from such studies.
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| 4. |
- Elihn, Karine, et al.
(författare)
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Air quality impacts of a large waste fire in Stockholm, Sweden
- 2023
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Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310 .- 1873-2844. ; 315
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Tidskriftsartikel (refereegranskat)abstract
- Fires in waste facilities are a common occurrence. Since many waste facilities are located adjacent to densely populated areas, these fires could potentially expose large populations to the emitted pollutants. However, at the moment there are only few field studies investigating the impact of waste fire emissions on air quality since the unpredictable nature of these events makes them challenging to capture. This study investigated the impact of a large and persistent un-prescribed fire in a waste storage facility in Stockholm county, Sweden, on the local air quality of two residential areas in close proximity to the fire. In-situ measurements of particulate matter, black carbon and nitrogen oxide concentrations were conducted both during open burning and after the fire was fully covered. In addition, filter samples were collected for offline analysis of organic composition, metal content and toxicity. Strongly increased concentrations of PM10, PM2.5 and black carbon were found during the open burning period, especially when the wind was coming from the direction of the fire. In addition, elevated concentrations of particulate heavy metals and polycyclic aromatic hydrocarbons were observed in the air during the open burning period. These results show that waste fires can have a strong impact on the air quality of nearby residential areas.
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| 5. |
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| 6. |
- Nozière, Barbara, et al.
(författare)
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The Reaction of Organic Peroxy Radicals with Unsaturated Compounds Controlled by a non-Epoxide Pathway under Atmospheric Conditions
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 25:11, s. 7772-7782
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Tidskriftsartikel (refereegranskat)abstract
- Today, the reactions of gas-phase organic peroxy radicals (RO2) with unsaturated Volatile Organic Compounds (VOC) are expected to be negligible at room temperature and ignored in atmospheric chemistry. This assumption is based on combustion studies (T ³ 360 K), which were the only experimental data available for these reactions until recently. These studies also reported epoxide formation as the only reaction channel. In this work, the products of the reactions of 1-pentylperoxy (C5H11O2) and methylperoxy (CH3O2) with 2,3-Dimethyl-2-butene (“2,3DM2B”) and isoprene were investigated at T = 300 ± 5 K with Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) and Gas Chromatography/Electron Impact Mass Spectrometry. Unlike what was expected, the experiments showed no measurable formation of epoxide. However, RO2 + alkene was found to produce compounds retaining the alkene structure, such as 3-hydroxy-3-methyl-2-butanone (C5H10O2) with 2,3DM2B and 2-hydroxy-2-methyl-3-butenal (C5H8O2) and methyl vinyl ketone with isoprene, suggesting that these reactions proceed through another reaction pathway under atmospheric conditions. We propose that, instead of forming an epoxide, the alkyl radical produced by the addtion of RO2 onto the alkene reacts with oxygen, producing a peroxy radical. The corresponding mechanisms are consistent with the products observed in the experiments. This alternative pathway implies that, under atmospheric conditions, RO2 + alkene reactions are kinetically limited by the initial addition step and not by the epoxide formation proposed until now for combustion systems. Extrapolating the combustion data to room temperature thus underestimates the rate coefficients, which is consistent with those recently reported for these reactions at room temperature. While slow for many classes of RO2, these reactions could be non-negligible at room temperature for some functionalized RO2. They might thus need to be considered in laboratory studies using large alkene concentrations and in biogenically-dominated regions of the atmosphere.
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| 7. |
- Tan, Wen, et al.
(författare)
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Theoretical and Experimental Study on the Reaction of tert-Butylamine with OH Radicals in the Atmosphere
- 2018
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 122:18, s. 4470-4480
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Tidskriftsartikel (refereegranskat)abstract
- © 2018 American Chemical Society. The OH-initiated atmospheric degradation of tert-butylamine (tBA), (CH 3 ) 3 CNH 2 , was investigated in a detailed quantum chemistry study and in laboratory experiments at the European Photoreactor (EUPHORE) in Spain. The reaction was found to mainly proceed via hydrogen abstraction from the amino group, which in the presence of nitrogen oxides (NO x ), generates tert-butylnitramine, (CH 3 ) 3 CNHNO 2 , and acetone as the main reaction products. Acetone is formed via the reaction of tert-butylnitrosamine, (CH 3 ) 3 CNHNO, and/or its isomer tert-butylhydroxydiazene, (CH 3 ) 3 CN=NOH, with OH radicals, which yield nitrous oxide (N 2 O) and the (CH 3 ) 3 Ċ radical. The latter is converted to acetone and formaldehyde. Minor predicted and observed reaction products include formaldehyde, 2-methylpropene, acetamide and propan-2-imine. The reaction in the EUPHORE chamber was accompanied by strong particle formation which was induced by an acid-base reaction between photochemically formed nitric acid and the reagent amine. The tert-butylaminium nitrate salt was found to be of low volatility, with a vapor pressure of 5.1 × 10 -6 Pa at 298 K. The rate of reaction between tert-butylamine and OH radicals was measured to be 8.4 (±1.7) × 10 -12 cm 3 molecule -1 s -1 at 305 ± 2 K and 1015 ± 1 hPa.
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