| 1. |
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| 2. |
- Baduel, Christine, et al.
(författare)
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Summer/winter variability of the surfactants in aerosols from Grenoble, France
- 2012
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Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310 .- 1873-2844. ; 47, s. 413-420
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Tidskriftsartikel (refereegranskat)abstract
- Many atmospheric aerosols seem to contain strong organic surfactants likely to enhance their cloud-forming properties. Yet, few techniques allow for the identification and characterization of these compounds. Recently, we introduced a double extraction method to isolate the surfactant fraction of atmospheric aerosol samples, and evidenced their very low surface tension (<= 30 mN m(-1)). In this work, this analytical procedure was further optimized. In addition to an optimized extraction and a reduction of the analytical time, the improved method led to a high reproducibility in the surface tension curves obtained (shapes and minimal values), illustrated by the low uncertainties on the values, +/- 10% or less. The improved method was applied to PM10 aerosols from the urban area of Grenoble, France collected from June 2009 to January 2010. Significant variability was observed between the samples. The minimum surface tension obtained from the summer samples was systematically lower (30 mN m(-1)) than that of the winter samples (35-45 mN m(-1)). Sharp transitions in the curves together with the very low surface tensions suggested that the dominating surfactants in the summer samples were biosurfactants, which would be consistent with the high biogenic activity in that season. One group of samples from the winter also displayed sharp transitions, which, together with the slightly higher surface tension, suggested the presence of weaker, possibly man-made, surfactants. A second group of curves from the winter did not display any clear transition but were similar to those of macromolecular surfactants such as polysaccharides or humic substances from wood burning. These surfactants are thus likely to originate from wood burning, the dominating source for aerosols in Grenoble in winter. These observations thus confirm the presence of surfactants from combustion processes in urban aerosols reported by other groups and illustrates the ability of our method to distinguish between different types of surfactants in atmospheric samples.
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| 3. |
- Chatre, Clément, et al.
(författare)
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Influence of Surface-Active Substances and Substrates on the Wettability of Individual Aerosol Particles during Condensation by Environmental Scanning Electron Microscopy
- 2023
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 39:8, s. 2957-2965
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Tidskriftsartikel (refereegranskat)abstract
- The formation of liquid cloud droplets from aerosol particles in the Earth atmosphere is still under debate particularly because of the difficulties to quantify the importance of bulk and surface effects in these processes. Recently, single-particle techniques have been developed to access experimental key parameters at the scale of individual particles. Environmental scanning electron microscopy (ESEM) has the advantage to provide in situ monitoring of the water uptake of individual microscopic particles deposited on solid substrates. In this work, ESEM was used to compare droplet growth on pure ammonium sulfate (NH4)2SO4 and mixed sodium dodecyl sulfate/ammonium sulfate (SDS/(NH4)2SO4) particles and to explore the role of experimental parameters, such as the hydrophobic–hydrophilic character of the substrate, on this growth. With hydrophilic substrates, the growth on pure salt particles was strongly anisotropic, but this anisotropy was suppressed by the presence of SDS. With hydrophobic substrates, it is the wetting behavior of the liquid droplet that is impacted by the presence of SDS. The wetting behavior of the pure (NH4)2SO4 solution on a hydrophobic surface shows a step-by-step mechanism that can be attributed to successive pinning–depinning phenomena at the triple-phase line frontier. Unlike the pure (NH4)2SO4 solution, the mixed SDS/(NH4)2SO4 solution did not show such a mechanism. Therefore, the hydrophobic–hydrophilic character of the substrate plays an important role in the stability and dynamics of the liquid droplets’ nucleation by water vapor condensation. In particular, hydrophilic substrates are not suited for the investigation of the hygroscopic properties (deliquescence relative humidity (DRH) and hygroscopic growth factor (GF)) of particles. Using hydrophobic substrates, data show that the DRH of (NH4)2SO4 particles is measured within 3% accuracy on the RH and their GF could indicate a size-dependent effect in the micrometer range. The presence of SDS does not seem to modify the DRH and GF of (NH4)2SO4 particles. This study shows that the water uptake on deposited particles is a complex process but, once carefully taken into account, ESEM is a suitable technique to study them.
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| 4. |
- 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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| 5. |
- Ekström, Sanna, et al.
(författare)
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A possible role of ground-based microorganisms on cloud formation in the atmosphere
- 2010
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Ingår i: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 7:1, s. 387-394
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Tidskriftsartikel (refereegranskat)abstract
- The formation of clouds is an important process for the atmosphere, the hydrological cycle, and climate, but some aspects of it are not completely understood. In this work, we show that microorganisms might affect cloud formation without leaving the Earth’s surface by releasing biological surfactants (or biosurfactants) in the environment, that make their way into atmospheric aerosols and could significantly enhance their activation into cloud droplets. In the first part of this work, the cloud-nucleating efficiency of standard biosurfactants was characterized and found to be better than that of any aerosol material studied so far, including inorganic salts. These results identify molecular structures that give organic compounds exceptional cloud-nucleating properties. In the second part, atmospheric aerosols were sampled at different locations: a temperate coastal site, a marine site, a temperate forest, and a tropical forest. Their surface tension was measured and found to be below 30 mN/m, the lowest reported for aerosols, to our knowledge. This very low surface tension was attributed to the presence of biosurfactants, the only natural substances able to reach to such low values. The presence of strong microbial surfactants in aerosols would be consistent with the organic fractions of exceptional cloud-nucleating efficiency recently found in aerosols, and with the correlations between algae bloom and cloud cover reported in the Southern Ocean. The results of this work also suggest that biosurfactants might be common in aerosols and thus of global relevance. If this is confirmed, a new role for microorganisms on the atmosphere and climate could be identified.
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| 6. |
- Ekström, Sanna, et al.
(författare)
-
Biosurfactants as CCN : comparison between on-line and off-line measurements
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- We are presenting the CCN properties for the bacterial compounds rhamnolipid and surfactin, which are extremely strong surfactants. Three organic:sodium chloride mixtures with mass percentages of 80:20, 50:50 and 20:80 were measured for each biosurfactant. Both on-line Cloud Condensation Nuclei Counter (CCNC) and off-line osmolality combined with surface tension measurements were performed to obtain two sets of critical supersaturations for various dry particle diameters. The critical supersaturations measured by the CCNC were systematically higher than the corresponding supersaturations derived from osmolality/surface tension measurements. A simple surface partitioning-adaption was applied to the off-line data and resulted in a correlation with the results from CCNC measurements for both mixtures with 20 wt% biosurfactant and the 50 wt% rhamnolipid mixture but not for the mixtures with 80 wt% biosurfactant and the 50 wt% surfactin mixture. An explanation can be unreliable CCNC results from the surfactin mixtures as we suspect poor dissolvement of the organic crystals. The choice of the assumed biosurfactant density also has an effect which should not be ignored. However, this indicate that the experimental method using osmolality and surface tension measurements together with a simple surface partitioning model can be used for strongly surfactant compounds as long as they do not dominate the particle mass. We also conclude that biosurfactants in mixed potential CCN particles can activate at relatively low supersaturation compared to other organic mixtures. Still, the critical supersaturation increases with increasing surfactant fraction.
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| 7. |
- Ekström, Sanna, et al.
(författare)
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First direct measurements of the CCN properties of 2-methyltetrols and polyols
- 2008
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Ingår i: Geophysical Research Abstracts.
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Konferensbidrag (refereegranskat)abstract
- 2-methyltetrols and polyols have received a lot of attention in recent years. 2-methyltetrols have been found in aerosols in various regions are believed to be formed by the oxidation of isoprene. Polyols are produced by fungi and have been measuredin large concentrations in aerosols. The main reason of interest of both 2-methyltetrols and polyols as efficient cloud condensation nuclei (CCN) is due to their high solubility.This presentation will report for the first time the experimental determination of complete Köhler curves for 2-methyltetrols (2-methylerythritol and 2-methylthreitol), C3 to C6 polyols (glycerol, erythritol, arabitol, and mannitol), and for comparison theiranalogue di-acids (malonic acid, succinic acid and, adipic acid). The original Köhler equations were determined from osmolality and tensiometry measurements of the compounds both in water and salt solutions (sodium chloride and ammonium sulphate).The results indicate that the polyols generally have similar CCN properties as the dicarboxylic acids. The critical supersaturation for aerosol particles with a 30 nm radius were: 2-methyltetrol; 0.68%, mannitol; 0.62%, arabitol; 0.60%, 2-methylerythritol;0.57%, erythritol; 0.56%, glycerol; 0.53%, adipic acid; 0.52%, succinic acid; 0.49%, and malonic acid; 0.44%. Mixtures of salts had lower critical supersaturation than water solutions, especially for the polyols. One exception was 2-methylerythritol, which interestingly was less efficient as CCN in salt solutions.The CCN efficiency of the polyols is believed to result mostly from their large water affinity, enforcing the Raoult effect, while organic acids lower the Kelvin effect. The very large solubility of polyols compared to the di-acids mean that they could positive effect in the initial phase of the droplet growth while the di-acids cannot. 2-methyltetrols were found to have both a Kelvin and a Raoult effect.In addition, these results establish for the first time that the 3-dimensional structure of molecules can have an effect on their CCN properties. The two isomers of the 2-methyltetrols have significantly different CCN properties that are also influencedoppositely in the presence of salts.
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| 8. |
- Ekström, Sanna, et al.
(författare)
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Of Bacteria and clouds: when microbial substances trigger cloud formation in Earth’s atmosphere
- 2008
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Ingår i: American Geophysical Union Fall Meeting 2008.
-
Konferensbidrag (refereegranskat)abstract
- This presentation reports the discovery that substances produced by microorganisms might trigger the formation of cloud in the atmosphere, at least under certain conditions.The Cloud Condensation Nuclei (CCN) efficiency of substances produced by microorganisms (bacteria, fungi, micro-algae …) that are common at Earth’s surface and in the oceans were studied. Their Köhler curves were determined experimentally by surface tension and osmometry measurements and found to have much lower critical supersaturations than any material studied so far, including inorganic salts.The presence of these substances was evidenced in aerosols from four different origins (coastal, marine, temperate forest, and Amazonian forest) by LC/MS/MS analyses and by their unique signature on the surface tension. These substances lowered the surface tension of the aerosols below 40 mN/m, allowing them to be activated into cloud droplets before inorganic particles.Microorganisms would thus be able to control cloud formation in Earth’s atmosphere under certain conditions. This would explain many previous observations such as correlations between algae bloom and cloud cover. Most importantly, this work identifies a potentially important component of Earth’s hydrological cycle and a new direct link between biosphere and climate.
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| 9. |
- Ekström, Sanna, et al.
(författare)
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The Cloud Condensation Nuclei (CCN) properties of 2-methyltetrols and C3-C6 polyols from osmolality and surface tension measurements
- 2009
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 9:3, s. 973-980
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Tidskriftsartikel (refereegranskat)abstract
- A significant fraction of the organic material in aerosols is made of highly soluble compounds such as sugars (mono-and polysaccharides) and polyols such as the 2-methyltetrols, methylerythritol and methyltreitol. Because of their high solubility these compounds are considered as potentially efficient CCN material. For the 2-methyltetrols, this would have important implications for cloud formation at global scale because they are thought to be produced by the atmospheric oxidation of isoprene. To investigate this question, the complete Kohler curves for C3-C6 polyols and the 2-methyltetrols have been determined experimentally from osmolality and surface tension measurements. Contrary to what was expected, none of these compounds displayed a higher CCN efficiency than organic acids. Their Raoult terms show that this limited CCN efficiency is due to their absence of dissociation in water, this in spite of slight surface-tension effects for the 2-methyltetrols. Thus, compounds such as saccharides and polyols would not contribute more to cloud formation than other organic compounds studied so far. In particular, the presence of 2-methyltetrols in aerosols would not particularly enhance cloud formation in the atmosphere, in contrary to recently suggested
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| 10. |
- Ekström, Sanna, et al.
(författare)
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The Cloud Condensation Nuclei (CCN) properties of 2-methyltetrols and C3–C6 polyols from osmolality and surface tension measurements (Discussion paper)
- 2008
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Ingår i: Atmospheric Chemistry and Physics Discussion. - : Copernicus GmbH. - 1680-7367. ; 8:5, s. 17237-17256
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Tidskriftsartikel (refereegranskat)abstract
- A significant fraction of the organic material in aerosols is made of highly soluble compounds such as sugars (mono- and polysaccharides) and polyols, including the 2-methyltetrols, methylerythritol and methyltreitol. The high solubility of these compounds has brought the question of their potentially high CCN efficiency. For the 2-methyltetrols, this would have important implications for cloud formation at global scale because they are thought to be produced by the atmospheric oxidation of isoprene. To investigate this question, the complete Köhler curves for C3–C6 polyols and the 2-methyltetrols have been determined experimentally from osmolality and surface tension measurements. Contrary to what expected, none of these compounds displayed a critical supersaturation lower than those of inorganic salts or organic acids. Their Raoult terms show that this limited CCN efficiency is due to their absence of dissociation in water, this in spite of slight surface-tension effects for the 2-methyltetrols. Thus, compounds such as sugars and polyols would not contribute more to cloud formation in the atmosphere than any other organic compounds studied so far. In particular, the presence of 2-methyltetrols in aerosols would not particularly enhance cloud formation in the atmosphere, contrary to what has been suggested.
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| 11. |
- Ekström, Sanna, 1980-
(författare)
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The influence of biogenic organic compounds on cloud formation
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Aerosols and clouds provide the largest uncertainty in the atmospheric radiation budget. The main focus of this thesis was to investigate the ability of organic compounds in aerosol particles to form clouds, and more specifically those emitted by living organisms. The cloud forming properties of the highly water-soluble methyltetrols and polyols, which are compounds produced by plants and fungi that are common in aerosol, were studied. All compounds and their salt mixtures have a moderate potential to serve as cloud condensation nuclei (CCN). They are thus not likely to have a significant global impact on cloudiness. The potential presence of surfactants released by microorganisms was investigated for aerosols sampled at different locations. Very low surface tension values were measured for these aerosol extracts (30 mN/m), which implies that these aerosols have good CCN properties and indicate the presence of biosurfactants. Their occurrence in aerosols still needs to be confirmed directly by chemical identification. Reactions of organic compounds in sulfate salt solutions exposed to UV-light were studied and found to produce surface active compounds. Thus, mixed sulfate/organic aerosol could have more favourable CCN properties after exposure to light than when kept in the dark. The surface active compounds were proposed to be long-chained organosulfates with hydrophilic and hydrophobic parts, similar to other amphiphilic surfactants. Mixtures of salt and strong surfactants formed by bacteria were studied using two different techniques for determining their CCN properties. There were inconsistencies between the two methods which could be accounted for by surface partitioning. The studied mixtures were determined to be good potential CCN material in both techniques. All these aspects require further investigation, but if the impact of strong biogenic surfactants on cloud formation is confirmed, a new link between living organisms and climate would be identified.
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| 12. |
- El Haber, Manuella, et al.
(författare)
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Salting out, non-ideality and synergism enhance surfactant efficiency in atmospheric aerosols
- 2023
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Ingår i: Scientific Reports. - : Springer Nature. - 2045-2322. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- In Earth’s atmosphere, the surface tension of sub-micron aerosol particles is suspected to affect their efficiency in becoming cloud droplets. But this quantity cannot be measured directly and is inferred from the chemical compounds present in aerosols. Amphiphilic surfactants have been evidenced in aerosols but experimental information on the surface properties of their mixtures with other aerosol components is lacking. This work explores experimentally the surface properties of aqueous mixtures of amphiphilic surfactants (SDS, Brij35, TritonX100, TritonX114, and CTAC) with inorganic salts (NaCl, (NH4)2SO4) and soluble organic acids (oxalic and glutaric acid) using pendant droplet tensiometry. Contrary to what could be expected, inorganic salts and organic acids systematically enhanced the efficiency of the surfactants rather than reduced it, by further lowering the surface tension and, in some cases, the CMC. Furthermore, all the mixtures studied were strongly non-ideal, some even displaying some synergism, thus demonstrating that the common assumption of ideality for aerosol mixtures is not valid. The molecular interactions between the mixture components were either in the bulk (salting out), in the mixed surface monolayer (synergy on the surface tension) or in the micelles (synergy on the CMC) and need to be included when describing such aerosol mixtures.
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| 13. |
- Gérard, Violaine, et al.
(författare)
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Anionic, Cationic, and Nonionic Surfactants in Atmospheric Aerosols from the Baltic Coast at Asko, Sweden : Implications for Cloud Droplet Activation
- 2016
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 50:6, s. 2974-2982
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Tidskriftsartikel (refereegranskat)abstract
- Recent analyses of atmospheric aerosols from different regions have demonstrated the ubiquitous presence of strong surfactants and evidenced surface tension values, sigma, below 40 mN m(-1), suspected to enhance the cloud-forming potential of these aerosols. In this work, this approach was further improved and combined with absolute concentration measurements of aerosol surfactants by colorimetric titration. This analysis was applied to PM2.5 aerosols collected at the Baltic station of Asko, Sweden, from July to October 2010. Strong surfactants were found in all the sampled aerosols, with sigma = (32-40) +/- 1 mN m(-1) and concentrations of at least 27 +/- 6 mM or 104 +/- 21 pmol m(-3). The absolute surface tension curves and critical micelle concentrations (CMC) determined for these aerosol surfactants show that (1) surfactants are concentrated enough in atmospheric particles to strongly depress the surface tension until activation, and (2) the surface tension does not follow the Szyszkowski equation during activation but is nearly constant and minimal, which provides new insights on cloud droplet activation. In addition, both the CMCs determined and the correlation (R-2 similar to 0.7) between aerosol surfactant concentrations and chlorophyll-a seawater concentrations suggest a marine and biological origin for these compounds.
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| 14. |
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| 15. |
- Gonzalez, Nelida J. D., et al.
(författare)
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New method for resolving the enantiomeric composition of 2-methyltetrols in atmospheric organic aerosols
- 2011
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Ingår i: Journal of Chromatography A. - : Elsevier BV. - 0021-9673 .- 1873-3778. ; 1218:51, s. 9288-9294
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Tidskriftsartikel (refereegranskat)abstract
- In order to facilitate the determination of the primary and secondary origin of atmospheric organic aerosols, a novel method involving chiral capillary gas chromatography coupled with mass spectrometry has been developed and validated. The method was focused on the analysis of 2-methylerythritol and 2-methylthreitol, considered to be tracers of secondary organic aerosols from the oxidation of atmospheric isoprene. The method was validated by performing various tests using authentic standards, including pure enantiomeric standards. The result showed that the analytical method itself does not affect the enantiomeric composition of the samples analyzed. The method was applied on atmospheric aerosols from a boreal forest collected in Aspvreten, Sweden and on laboratory samples obtained from liquid phase oxidation of isoprene and smog chamber experiments. Aerosol samples contained one enantiomer of 2-methylerythritol in significantly larger quantities than the others. In contrast, the liquid-phase oxidation of isoprene and its gas-phase oxidation in the smog chamber produced all enantiomers in equal quantities. The results obtained where the enantiomer fraction, EF, is larger than 0.50 suggest that 2-methyltetrols in atmospheric aerosols may also have biological origin. Information about the differences between enantiomer fractions obtained using this method brings new insights in the area of atmospheric aerosols.
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| 16. |
- Gonzalez, N. J. D., et al.
(författare)
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Primary and secondary organics in the tropical Amazonian rainforest aerosols : chiral analysis of 2-methyltetraols
- 2014
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Ingår i: ENVIRON SCI-PROC IMP. - : Royal Society of Chemistry (RSC). - 2050-7887 .- 2050-7895. ; 16:6, s. 1413-1421
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Tidskriftsartikel (refereegranskat)abstract
- This work presents the application of a new method to facilitate the distinction between biologically produced (primary) and atmospherically produced (secondary) organic compounds in ambient aerosols based on their chirality. The compounds chosen for this analysis were the stereomers of 2-methyltetraols, (2R, 3S)- and (2S, 3R)-methylerythritol, (L- and D-form, respectively), and (2S, 3S)- and (2R, 3R)-methylthreitol (L- and D-form), shown previously to display some enantiomeric excesses in atmospheric aerosols, thus to have at least a partial biological origin. In this work PM10 aerosol fractions were collected in a remote tropical rainforest environment near Manaus, Brazil, between June 2008 and June 2009 and analysed. Both 2-methylerythritol and 2-methylthreitol displayed a net excess of one enantiomer (either the L- or the D-form) in 60 to 72% of these samples. These net enantiomeric excesses corresponded to compounds entirely biological but accounted for only about 5% of the total 2-methyltetrol mass in all the samples. Further analysis showed that, in addition, a large mass of the racemic fractions (equal mixtures of D- and L-forms) was also biological. Estimating the contribution of secondary reactions from the isomeric ratios measured in the samples (=ratios 2-methylthreitol over 2-methylerythritol), the mass fraction of secondary methyltetrols in these samples was estimated to a maximum of 31% and their primary fraction to a minimum of 69%. Such large primary fractions could have been expected in PM10 aerosols, largely influenced by biological emissions, and would now need to be investigated in finer aerosols. This work demonstrates the effectiveness of chiral and isomeric analyses as the first direct tool to assess the primary and secondary fractions of organic aerosols.
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| 17. |
- Kleinheins, Judith, et al.
(författare)
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Surface tension models for binary aqueous solutions: a review and intercomparison : a review and intercomparison
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 25:16, s. 11055-11074
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Tidskriftsartikel (refereegranskat)abstract
- The liquid-air surface tension of aqueous solutions is a fundamental quantity in multi-phase thermodynamics and fluid dynamics and thus relevant in many scientific and engineering fields. Various models have been proposed for its quantitative description. This Perspective gives an overview of the most popular models and their ability to reproduce experimental data of ten binary aqueous solutions of electrolytes and organic molecules chosen to be representative of different solute types. In addition, we propose a new model which reproduces sigmoidal curve shapes (Sigmoid model) to empirically fit experimental surface tension data. The surface tension of weakly surface-active substances is well reproduced by all models. In contrast, only few models successfully model the surface tension of aqueous solutions with strongly surface-active substances. For substances with a solubility limit, usually no experimental data is available for the surface tension of supersaturated solutions and the pure liquid solute. We discuss ways in which these can be estimated and emphasize the need for further research. The newly developed Sigmoid model best reproduces the surface tension of all tested solutions and can be recommended as a model for a broad range of binary mixtures and over the entire concentration range.
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| 18. |
- Maxut, A., et al.
(författare)
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Formation mechanisms and yields of small imidazoles from reactions of glyoxal with NH4+ in water at neutral pH
- 2015
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 17:31, s. 20416-20424
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Tidskriftsartikel (refereegranskat)abstract
- Imidazoles have numerous applications in pharmacology, chemistry, optics and electronics, making the development of their environmentally-friendly synthetic procedures worthwhile. In this work, the formation of imidazole, imidazole-2-carboxaldehyde, and 2,2-bis-1H-imidazole was investigated in the self-reaction of glyoxal and its cross-reactions with each of these compounds in aqueous solutions of inorganic ammonium salts at pH =7. Such conditions are relevant both as cheap and environmentally-friendly synthetic procedures and for the chemistry of natural environments where NH4+ is abundant, such as in atmospheric aerosols. These reactions were investigated both by 1H-NMR and UV-Vis absorption spectroscopy at room temperature with the objective to determine the formation pathways of the three imidazoles and the parameters affecting their yields, to identify the optimal conditions for their synthesis. The results show that only the simplest imidazole is produced by the self-reaction of glyoxal and that imidazole-2-carboxaldehyde and 2,2-bis-1H-imidazole are produced by cross-reactions of glyoxal with imidazole and imidazole-2-carboxaldehyde, respectively. The yields of imidazole-2-carboxaldehyde and 2,2-bis-1H-imidazole formed by the cross-reactions were close to unity, but the yield of imidazole formed by the self-reaction of glyoxal, YIm, was small and varied inversely with the initial glyoxal concentration, [G]0: YIm > 10% only for [G]0 < 0.1 M. The latter result was attributed to the kinetic competition between the imidazole-forming condensation pathway and the acetal/oligomer formation pathway of the glyoxal self-reaction and constitutes a bottleneck for the formation of higher imidazoles. Other parameters such as pH and the NH4+ concentration did not affect the yields. Thus, by maintaining small glyoxal concentrations, high imidazole yields can be achieved in environmentally-friendly aqueous ammonium solutions at neutral pH. Under the same conditions, higher yields are expected expected from substituted carbonyl compounds, regardless of their concentration, as they produce less acetals.
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| 19. |
- Nozière, Barbara, et al.
(författare)
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A Kinetic and Mechanistic Study of the Amino Acid Catalyzed Aldol Condensation of Acetaldehyde in Aqueous and Salt Solutions
- 2008
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 112:13, s. 2827-2837
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Tidskriftsartikel (refereegranskat)abstract
- The amino acid-catalyzed aldol condensation is of great interest in organic synthesis and natural environments such as atmospheric particles. But kinetic and mechanistic information on these reactions is limited. In this work, the kinetics of the aldol condensation of acetaldehyde in water and aqueous salt solutions (NaCl, CaCl2, Na2SO4, MgSO4), catalyzed by five amino acids (glycine, alanine, serine, arginine, and proline) at room temperature (295 ± 2K) has been studied. Monitoring the formation of three products, crotonaldehyde, 2,4-hexadienal, and 2,4,6-octatrienal by UV-Visible absorption over 200 – 1100 nm revealed two distinct kinetic regimes: at low amino acid concentrations (in all cases, below 0.1 M) the overall reaction was first order with respect to acetaldehyde and kinetically limited by the formation of the enamine intermediate. At larger amino acid concentrations (at least 0.3 M) the kinetics was second order and controlled by the C-C bond-forming step. The first-order rate constants increased linearly with amino acid concentration, consistent with the enamine formation. Inorganic salts further accelerated the enamine formation according to their pKb plausibly by facilitating the iminium and/or enamine formation. The rate constant of the C-C bond-forming step varied with the square of amino acid concentration, suggesting the involvement of two amino acid molecules. Thus, the reaction proceeded via a Mannich pathway. However, the contribution of an aldol pathway, first-order in amino acid, could not be excluded. Our results show that the rate constant for the self-condensation of acetaldehyde in aqueous atmospheric aerosols (up to 10 of mM of amino acids) is identical as in sulfuric acid 10 - 15 M (kI ~ 10-7 - 10-6 s-1), clearly illustrating the potential importance of amino acid catalysis in natural environments. This work also demonstrates that under usual laboratory conditions and in natural environments aldol condensation is likely to be kinetically controlled by the enamine formation. Notably, kinetic investigations of the C-C bond-forming addition step would only be possible with high concentrations of amino acids.
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| 20. |
- Noziere, Barbara, et al.
(författare)
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Abiotic C-C bond formation under environmental conditions : kinetics of the aldol condensation of acetaldehyde in water catalyzed by carbonate ions (CO32-)
- 2010
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Ingår i: International Journal of Chemical Kinetics. - : Wiley. - 0538-8066 .- 1097-4601. ; 42:11, s. 676-686
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Tidskriftsartikel (refereegranskat)abstract
- The role of CC bond-forming reactions such as aldol condensation in the degradation of organic matter in natural environments is receiving a renewed interest because naturally occurring ions, ammonium ions, NH+4, and carbonate ions, CO32−, have recently been reported to catalyze these reactions. While the catalysis of aldol condensation by OH− has been widely studied, the catalytic properties of carbonate ions, CO32−, have been little studied, especially under environmental conditions. This work presents a study of the catalysis of the aldol condensation of acetaldehyde in aqueous solutions of sodium carbonate (0.1–50 mM) at T = 295 ± 2 K. By monitoring the absorbance of the main product, crotonaldehyde, instead of that of acetaldehyde, interferences from other reaction products and from side reactions, in particular a known Cannizzaro reaction, were avoided. The rate constant was found to be first order in acetaldehyde in the presence of both CO32− and OH−, suggesting that previous studies reporting a second order for this base-catalyzed reaction were flawed. Comparisons between the rate constants in carbonate solutions and in sodium hydroxide solutions ([NaOH] = 0.3–50 mM) showed that, among the three bases present in carbonate solutions, CO32−, HCO3−, and OH−, OH− was the main catalyst for pH ≤ 11. CO32− became the main catalyst at higher pH, whereas the catalytic contribution of HCO3− was negligible over the range of conditions studied (pH 10.3–11.3). Carbonate-catalyzed condensation reactions could contribute significantly to the degradation of organic matter in hyperalkaline natural environments (pH ≥ 11) and be at the origin of the macromolecular matter found in these environments.
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| 21. |
- Nozière, Barbara, et al.
(författare)
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Atmospheric chemistry in stereo : A new look at secondary organic aerosols from isoprene
- 2011
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Ingår i: Geophysical Research Letters. - 0094-8276 .- 1944-8007. ; 38, s. L11807-
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Tidskriftsartikel (refereegranskat)abstract
- Isoprene, a compound emitted by vegetation, could be a major contributor to secondary organic aerosols (SOA) in the atmosphere. The main evidence for this contribution were the 2-methylbutane-1,2,3,4-tetraols, or 2-methyltetrols (2-methylerythritol and 2-methylthreitol) present in ambient aerosols. In this work, the four stereoisomers of these tetraols were analyzed in aerosols from Aspvreten, Sweden. 2-C-methyl-D-erythritol was found in excess over its enantiomer in the Spring/Summer, by up to 29% in July. This clearly indicated some biological origins for this enantiomer, consistent with its well-documented production by plants and other living organisms. In addition, a minimum of 20 to 60% of the mass of racemic tetraols appeared from biological origin. Thus, the SOA mass produced by isoprene in the atmosphere is less than what indicated by the 2-methyltetrols in aerosols. Our results also demonstrate that stereochemical speciation can distinguish primary and secondary organic material in atmospheric aerosols.
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| 22. |
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| 23. |
- Nozière, Barbara, et al.
(författare)
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Common inorganic ions are efficient catalysts for organic reactions in atmospheric aerosols and other natural environments
- 2009
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Ingår i: Atmospheric Chemistry and Physics Discussion. ; 9:1, s. 1-21
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Tidskriftsartikel (populärvet., debatt m.m.)abstract
- In this work, inorganic ammonium ions, NH4+, and carbonate ions, CO32-, are reported for the first time as catalysts for organic reactions in atmospheric aerosols and other natural environments at the Earth’s surface. These reactions include the formation of C-C and C-O bonds by aldol condensation and acetal formation, and reveal a new aspect of the interactions between organic and inorganic materials in natural environments. The catalytic properties of inorganic ammonium ions, in particular, were not previously known in chemistry. The reactions were found to be as fast in tropospheric ammonium sulfate composition as in concentrated sulfuric acid. The ubiquitous presence and large concentrations of ammonium ions in tropospheric aerosols would make of ammonium catalysis a main consumption pathway for organic compounds in these aerosols, while acid catalysis would have a minor contribution. In particular, ammonium catalysis would account quantitatively for the aging of carbonyl compounds into secondary “fulvic” compounds in tropospheric aerosols, a transformation affecting the optical properties of these aerosols. In general, ammonium catalysis is likely to be responsible for many observations previously attributed to acid catalysis in the troposphere.
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| 24. |
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| 25. |
- Nozière, Barbara, et al.
(författare)
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Direct Observation of Aliphatic Peroxy Radical Autoxidation and Water Effects: An Experimental and Theoretical Study
- 2019
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 58:39, s. 13976-13982
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Tidskriftsartikel (refereegranskat)abstract
- The autoxidation of organic peroxy radicals (RO2) into hydroperoxy-alkyl radicals (QOOH), then hydroperoxy-peroxy radicals (HOOQO2) is now considered to be important in the Earth's atmosphere. To avoid mechanistic uncertainties these reactions are best studied by monitoring the radicals. But for the volatile and aliphatic RO2 radicals playing key roles in the atmosphere this has long been an instrumental challenge. This work reports the first study of the autoxidation of aliphatic RO2 radicals and is based on monitoring RO2 and HOOQO2 radicals. The rate coefficients, kiso (s−1), were determined both experimentally and theoretically using MC-TST kinetic theory based on CCSD(T)//M06-2X quantum chemical methodologies. The results were in excellent agreement and confirmed that the first H-migration is strongly rate-limiting in the oxidation of non-oxygenated volatile organic compounds (VOCs). At higher relative humidity (2–30 %) water complexes were evidenced for HOOQO2 radicals, which could be an important fate for HOO-substituted RO2 radicals in the atmosphere.
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| 26. |
- Nozière, Barbara, et al.
(författare)
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Formation of secondary light-absorbing "fulvic-like'' oligomers : A common process in aqueous and ionic atmospheric particles?
- 2007
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Ingår i: Geophysical Research Letters. - 0094-8276 .- 1944-8007. ; 34:21, s. L21812-
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Tidskriftsartikel (refereegranskat)abstract
- Light-absorbing ''humic-like'' compounds of secondary origin have been consistently reported in partly inorganic aerosols and in fog waters but their formation could not be explained until now. In this work, we demonstrate that amino acid- and ammonium sulfate-catalyzed reactions in water and ionic solutions produce compounds of identical molecular and optical properties and account well for the quantities found in atmospheric particles. For typical aerosol concentrations of amino acids or ammonium sulfate the rate constants of reaction are found to be identical to the one in concentrated sulfuric acid (10-15 M), clearly demonstrating the efficiency of these catalysts. Our results also show that these reactions should be common in aqueous and ionic aerosols, as confirmed by the observations, and significantly impact their absorption index. In particular, previous radiative calculations indicate that they should substantially reduce current estimates of the cooling contribution of sulfate aerosols on climate.
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| 27. |
- Nozière, Barbara, et al.
(författare)
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Inorganic ammonium salts and carbonate salts are efficient catalysts for aldol condensation in atmospheric aerosols
- 2010
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 12:15, s. 3864-3872
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Tidskriftsartikel (refereegranskat)abstract
- In natural environments such as atmospheric aerosols, organic compounds coexist with inorganic salts but, until recently, were not thought to interact chemically. We have recently shown that inorganic ammonium ions, NH4+, act as catalysts for acetal formation from glyoxal, a common atmospheric gas. In this work, we report that inorganic ammonium ions, NH4+, and carbonate ions, CO32−, are also efficient catalysts for the aldol condensation of carbonyl compounds. In the case of NH4+ this was not previously known, and was patented prior to this article. The kinetic results presented in this work show that, for the concentrations of ammonium and carbonate ions present in tropospheric aerosols, the aldol condensation of acetaldehyde and acetone could be as fast as in concentrated sulfuric acid and might compete with their reactions with OH radicals. These catalytic processes could produce significant amounts of polyconjugated, light-absorbing compounds in aerosols, and thus affect their direct forcing on climate. For organic gases with large Henry's law coefficients, these reactions could also result in a significant uptake and in the formation of secondary organic aerosols (SOA). This work reinforces the recent findings that inorganic salts are not inert towards organic compounds in aerosols and shows, in particular, that common ones, such as ammonium and carbonate salts, might even play important roles in their chemical transformations.
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| 28. |
- Nozière, Barbara, et al.
(författare)
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Light-absorbing aldol condensation products in acidic aerosols : Spectra, kinetics, and contribution to the absorption index
- 2007
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Ingår i: Atmospheric environment. - : Elsevier BV. - 1352-2310. ; 41:6, s. 1150-1163
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Tidskriftsartikel (refereegranskat)abstract
- The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot.In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190–1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation.The products are oligomers absorbing light in the 300–500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols.Kinetic experiments in 96–75 wt% H2SO4 solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of −(70±15) kJ mol−1 in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H2SO4 and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10−4, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.
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| 29. |
- Nozière, Barbara, et al.
(författare)
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Products and Kinetics of the Liquid-Phase Reaction of Glyoxal Catalyzed by Ammonium Ions (NH4+)
- 2009
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society. - 1089-5639 .- 1520-5215. ; 113:1, s. 231-237
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Tidskriftsartikel (refereegranskat)abstract
- Glyoxal, a common atmospheric gas, has been reported to be depleted in some regions of the atmosphere. The corresponding sink could be accounted for by reactions in or at the surface of atmospheric particles, but these reactions were not identified. Recently, we showed that inorganic ammonium ions, NH4+, are efficient catalysts for reactions of carbonyl compounds, including glyoxal, in the liquid phase. To determine whether ammonium-catalyzed reactions can contribute to depletion of glyoxal in the atmosphere, the reactivity of this compound in aqueous solutions containing ammonium salts (ammonium sulfate, chloride, fluoride, and phosphate) at 298 K has been studied. The products identified by LC-HRMS and UV absorption revealed a mechanism involving two distinct pathways: a Bronsted acid pathway and an iminium pathway. The kinetics of the iminium pathway was studied by monitoring formation of a specific product. This pathway was second order in glyoxal in most of the solutions studied and should therefore be second order in most ammonium containing aerosols in the atmosphere. The corresponding rate constant, kII (M-1 s-1), increased strongly with ammonium ion activity, aNH4+, and pH:kII (M-1 s-1) ) (2 ( 1) × 10-10 exp(1.5 ( 0.8)aNH4+ exp(2.5 ( 0.2)pH.This iminium pathway is a lower limit for the ammonium-catalyzed consumption of glyoxal, but the contribution of the acid pathway is expected to be small in tropospheric aerosols. With these results the reactive uptake of glyoxal on ammonium-containing aerosols was estimated and shown to be a possible explanation for the depletion of this compound in Mexico City.
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| 30. |
- Noziere, Barbara, et al.
(författare)
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Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols
- 2010
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Ingår i: Geophysical Research Letters. - 0094-8276 .- 1944-8007. ; 37:L05806
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Tidskriftsartikel (refereegranskat)abstract
- Many atmospheric aerosols contain both organic compounds and inorganic material, such as sulfate salts. In this work, we show that these sulfates could trigger some chemical transformations of the organic compounds by producing sulfate radicals, SO4−, when exposed to UV light (280–320 nm). In particular, we show by mass spectrometry (LC/ESI-MSMS) that isoprene, methyl vinyl ketone, methacrolein, and α-pinene in irradiated sulfate solutions (ammonium and sodium sulfate) produce the same organosulfates as previously identified in aerosols, and even some that had remained unidentified until now. With a typical time constant of 9 h instead of 4600 days for esterifications, these radical reactions would be a plausible origin for the atmospheric organosulfates. These reactions also produced efficient surfactants, possibly resembling the long-chain organosulfates found in the experiments. Thus, photochemistry in mixed sulfate/organic aerosols could increase cloud condensation nuclei (CCN) numbers, which would be supported by previous atmospheric observations
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| 31. |
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| 32. |
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| 33. |
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| 34. |
- Nozière, Barbara, et al.
(författare)
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The dynamic surface tension of atmospheric aerosol surfactants reveals new aspects of cloud activation
- 2014
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 5, s. 3335-
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Tidskriftsartikel (refereegranskat)abstract
- The activation of aerosol particles into cloud droplets in the Earth's atmosphere is both a key process for the climate budget and a main source of uncertainty. Its investigation is facing major experimental challenges, as no technique can measure the main driving parameters, the Raoult's term and surface tension, sigma, for sub-micron atmospheric particles. In addition, the surfactant fraction of atmospheric aerosols could not be isolated until recently. Here we present the first dynamic investigation of the total surfactant fraction of atmospheric aerosols, evidencing adsorption barriers that limit their gradient (partitioning) in particles and should enhance their cloud-forming efficiency compared with current models. The results also show that the equilibration time of surfactants in sub-micron atmospheric particles should be beyond the detection of most on-line instruments. Such instrumental and theoretical shortcomings would be consistent with atmospheric and laboratory observations and could have limited the understanding of cloud activation until now.
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| 35. |
- Nozière, Barbara, et al.
(författare)
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The hydrolysis of epoxides catalyzed by inorganic ammonium salts in water: kinetic evidence for hydrogen bond catalysis
- 2018
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 20:3, s. 1583-1590
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Tidskriftsartikel (refereegranskat)abstract
- Naturally-occurring inorganic ammonium ions have been recently reported as efficient catalysts for some organic reactions in water, which contributes to the understanding of the chemistry in some natural environments (soils, seawater, atmospheric aerosols, .) and biological systems, and is also potentially interesting for green chemistry as many of their salts are cheap and non-toxic. In this work, the effect of NH4+ ions on the hydrolysis of small epoxides in water was studied kinetically. The presence of NH4+ increased the hydrolysis rate by a factor of 6 to 25 compared to pure water and these catalytic effects were shown not to result from other ions, counter-ions or from acid or base catalysis, general or specific. The small amounts of amino alcohols produced in the reactions were identified as the actual catalysts by obtaining a strong acceleration of the reactions when adding these compounds directly to the epoxides in water. Replacing the amino alcohols by other strong hydrogen-bond donors, such as trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) gave the same results, demonstrating that the kinetics of these reactions was driven by hydrogen-bond catalysis. Because of the presence of many hydrogen-bond donors in natural environments (for instance amines and hydroxy-containing compounds), hydrogen-bond catalysis is likely to contribute to many reaction rates in these environments.
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| 36. |
- 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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| 37. |
- Vereecken, Luc, et al.
(författare)
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H migration in peroxy radicals under atmospheric conditions
- 2020
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Ingår i: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 20:12, s. 7429-7458
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Tidskriftsartikel (refereegranskat)abstract
- A large data set of rate coefficients for H migration in peroxy radicals is presented and supplemented with literature data to derive a structure-activity relationship (SAR) for the title reaction class. The SAR supports aliphatic RO2 radicals; unsaturated bonds and iβ/i-oxo substitutions both endocyclic and exocyclic to the transition state ring; and iα/i-oxo (aldehyde), -OH, -OOH, and -ONO2 substitutions, including migration of O-based hydrogen atoms. Also discussed are -C( Combining double low line O)OH and -OR substitutions. The SAR allows predictions of rate coefficients ik/i(iT/i) for a temperature range of 200 to 450 K, with migrations spans ranging from 1,4 to 1,9-H shifts depending on the functionalities. The performance of the SAR reflects the uncertainty of the underlying data, reproducing the scarce experimental data on average to a factor of 2 and the wide range of theoretical data to a factor of 10 to 100, depending also on the quality of the data. The SAR evaluation discusses the performance in multi-functionalized species. For aliphatic RO2, we also present some experimental product identification that validates the expected mechanisms. The proposed SAR is a valuable tool for mechanism development and experimental design and guides future theoretical work, which should allow for rapid improvements of the SAR in the future. Relative multi-conformer transition state theory (rel-MC-TST) kinetic theory is introduced as an aid for systematic kinetic studies.
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