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  • 1
    Publication Date: 2016-07-14
    Description: In the atmosphere night time removal of volatile organic compounds (VOC) is initiated to a large extent by reaction with the nitrate radical (NO 3 ) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model (CTM) indicate that most of the measured particulate organic nitrates are formed by NO 3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM 1 ) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.
    Print ISSN: 0094-8276
    Electronic ISSN: 1944-8007
    Topics: Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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  • 2
    Publication Date: 2015-12-06
    Description: Secondary organic aerosol components (SOA) contribute significantly to the activation of cloud condensation nuclei (CCN) in the atmosphere. The CCN activity of internally-mixed submicron SOA particles is often parameterized assuming a size-independent single hygroscopicity parameter κ. In the experiments done in a large atmospheric reactor (SAPHIR, Jülich), we consistently observed size-dependent κ and particle composition for SOA from different precursors in the size range of 50 nm-200 nm. Smaller particles had higher κ and a higher degree of oxidation, although all particles were formed from the same reaction mixture. Since decreasing volatility and increasing hygroscopicity often co-vary with the degree of oxidation, the size dependence of composition and hence of CCN activity can be understood by enrichment of higher oxygenated, low volatility hygroscopic compounds in smaller particles. Neglecting the size dependence of κ can lead to significant bias in the prediction of the activated fraction of particles during cloud formation.
    Print ISSN: 0094-8276
    Electronic ISSN: 1944-8007
    Topics: Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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  • 3
    Publication Date: 2012-02-10
    Description: Recent studies have shown that measured OH under NOx-limited, high-isoprene conditions are many times higher than modeled OH. In this study, a detailed analysis of the HOx radical budgets under low-NOx, rural conditions was performed employing a box model based on the Master Chemical Mechanism (MCMv3.2). The model results were compared with HOx radical measurements performed during the international HOxComp campaign carried out in Jülich, Germany, during summer 2005. Two different air masses influenced the measurement site denoted as high-NOx (NO, 1–3 ppbv) and low-NOx (NO, 〈 1 ppbv) periods. Both modeled OH and HO2 diurnal profiles lay within the measurement range of all HOx measurement techniques, with correlation slopes between measured and modeled OH and HO2 around unity. Recently discovered interference in HO2 measurements caused by RO2 cross sensitivity was found to cause a 30% increase in measured HO2 during daytime on average. After correction of the measured HO2 data, the model HO2 is still in good agreement with the observations at high NOx but overpredicts HO2 by a factor of 1.3 to 1.8 at low NOx. In addition, for two different set of measurements, a missing OH source of 3.6 ± 1.6 and 4.9 ± 2.2 ppb h−1 was estimated from the experimental OH budget during the low-NOx period using the corrected HO2 data. The measured diurnal profile of the HO2/OH ratio, calculated using the corrected HO2, is well reproduced by the MCM at high NOx but is significantly overestimated at low NOx. Thus, the cycling between OH and HO2 is better described by the model at high NOx than at low NOx. Therefore, similar comprehensive field measurements accompanied by model studies are urgently needed to investigate HOx recycling under low-NOx conditions.
    Print ISSN: 0148-0227
    Topics: Geosciences , Physics
    Published by Wiley on behalf of American Geophysical Union (AGU).
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  • 4
    Publication Date: 2013-11-29
    Description: Nature Geoscience 6, 1023 (2013). doi:10.1038/ngeo1964 Authors: H. Fuchs, A. Hofzumahaus, F. Rohrer, B. Bohn, T. Brauers, H-P. Dorn, R. Häseler, F. Holland, M. Kaminski, X. Li, K. Lu, S. Nehr, R. Tillmann, R. Wegener & A. Wahner Most pollutants in the Earth’s atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain. Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.
    Print ISSN: 1752-0894
    Electronic ISSN: 1752-0908
    Topics: Geosciences
    Published by Springer Nature
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  • 5
    Publication Date: 2009-09-18
    Description: It has been suggested that volatile organic compounds (VOCs) are involved in organic aerosol formation, which in turn affects radiative forcing and climate. The most abundant VOCs emitted by terrestrial vegetation are isoprene and its derivatives, such as monoterpenes and sesquiterpenes. New particle formation in boreal regions is related to monoterpene emissions and causes an estimated negative radiative forcing of about -0.2 to -0.9 W m(-2). The annual variation in aerosol growth rates during particle nucleation events correlates with the seasonality of monoterpene emissions of the local vegetation, with a maximum during summer. The frequency of nucleation events peaks, however, in spring and autumn. Here we present evidence from simulation experiments conducted in a plant chamber that isoprene can significantly inhibit new particle formation. The process leading to the observed decrease in particle number concentration is linked to the high reactivity of isoprene with the hydroxyl radical (OH). The suppression is stronger with higher concentrations of isoprene, but with little dependence on the specific VOC mixture emitted by trees. A parameterization of the observed suppression factor as a function of isoprene concentration suggests that the number of new particles produced depends on the OH concentration and VOCs involved in the production of new particles undergo three to four steps of oxidation by OH. Our measurements simulate conditions that are typical for forested regions and may explain the observed seasonality in the frequency of aerosol nucleation events, with a lower number of nucleation events during summer compared to autumn and spring. Biogenic emissions of isoprene are controlled by temperature and light, and if the relative isoprene abundance of biogenic VOC emissions increases in response to climate change or land use change, the new particle formation potential may decrease, thus damping the aerosol negative radiative forcing effect.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Kiendler-Scharr, Astrid -- Wildt, Jurgen -- Dal Maso, Miikka -- Hohaus, Thorsten -- Kleist, Einhard -- Mentel, Thomas F -- Tillmann, Ralf -- Uerlings, Ricarda -- Schurr, Uli -- Wahner, Andreas -- England -- Nature. 2009 Sep 17;461(7262):381-4. doi: 10.1038/nature08292.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Institut ICG-2, Troposphare. a.kiendler-scharr@fz-juelich.de〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19759617" target="_blank"〉PubMed〈/a〉
    Keywords: Aerosols/analysis/metabolism ; Air/analysis ; Betula/drug effects/metabolism ; Butadienes/analysis/*pharmacology ; Carbon/analysis ; Environment, Controlled ; Fagus/drug effects/metabolism ; Hemiterpenes/analysis/*pharmacology/*secretion ; Hydroxyl Radical/analysis/metabolism ; Light ; Monoterpenes/metabolism/pharmacology ; Oxidation-Reduction ; Pentanes/analysis/*pharmacology ; Picea/drug effects/metabolism ; Seasons ; Temperature ; Time Factors ; Trees/*drug effects/*metabolism ; Volatile Organic Compounds/analysis/*metabolism
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 6
    Publication Date: 2009-06-06
    Description: The degradation of trace gases and pollutants in the troposphere is dominated by their reaction with hydroxyl radicals (OH). The importance of OH rests on its high reactivity, its ubiquitous photochemical production in the sunlit atmosphere, and most importantly on its regeneration in the oxidation chain of the trace gases. In the current understanding, the recycling of OH proceeds through HO2 reacting with NO, thereby forming ozone. A recent field campaign in the Pearl River Delta, China, quantified tropospheric OH and HO2 concentrations and turnover rates by direct measurements. We report that concentrations of OH were three to five times greater than expected, and we propose the existence of a pathway for the regeneration of OH independent of NO, which amplifies the degradation of pollutants without producing ozone.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hofzumahaus, Andreas -- Rohrer, Franz -- Lu, Keding -- Bohn, Birger -- Brauers, Theo -- Chang, Chih-Chung -- Fuchs, Hendrik -- Holland, Frank -- Kita, Kazuyuki -- Kondo, Yutaka -- Li, Xin -- Lou, Shengrong -- Shao, Min -- Zeng, Limin -- Wahner, Andreas -- Zhang, Yuanhang -- New York, N.Y. -- Science. 2009 Jun 26;324(5935):1702-4. doi: 10.1126/science.1164566. Epub 2009 Jun 4.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Forschungszentrum Julich, Institut fur Chemie und Dynamik der Geosphare-2: Troposphare, 52425 Julich, Germany.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19498111" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 7
    Publication Date: 2014-04-20
    Description: Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth's surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Li, Xin -- Rohrer, Franz -- Hofzumahaus, Andreas -- Brauers, Theo -- Haseler, Rolf -- Bohn, Birger -- Broch, Sebastian -- Fuchs, Hendrik -- Gomm, Sebastian -- Holland, Frank -- Jager, Julia -- Kaiser, Jennifer -- Keutsch, Frank N -- Lohse, Insa -- Lu, Keding -- Tillmann, Ralf -- Wegener, Robert -- Wolfe, Glenn M -- Mentel, Thomas F -- Kiendler-Scharr, Astrid -- Wahner, Andreas -- New York, N.Y. -- Science. 2014 Apr 18;344(6181):292-6. doi: 10.1126/science.1248999.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Institut fur Energie-und Klimaforschung: Troposphare (IEK-8), Forschungszentrum Julich, Julich, Germany.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/24744373" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 8
    Publication Date: 2014-02-28
    Description: Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene alpha-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ehn, Mikael -- Thornton, Joel A -- Kleist, Einhard -- Sipila, Mikko -- Junninen, Heikki -- Pullinen, Iida -- Springer, Monika -- Rubach, Florian -- Tillmann, Ralf -- Lee, Ben -- Lopez-Hilfiker, Felipe -- Andres, Stefanie -- Acir, Ismail-Hakki -- Rissanen, Matti -- Jokinen, Tuija -- Schobesberger, Siegfried -- Kangasluoma, Juha -- Kontkanen, Jenni -- Nieminen, Tuomo -- Kurten, Theo -- Nielsen, Lasse B -- Jorgensen, Solvejg -- Kjaergaard, Henrik G -- Canagaratna, Manjula -- Maso, Miikka Dal -- Berndt, Torsten -- Petaja, Tuukka -- Wahner, Andreas -- Kerminen, Veli-Matti -- Kulmala, Markku -- Worsnop, Douglas R -- Wildt, Jurgen -- Mentel, Thomas F -- England -- Nature. 2014 Feb 27;506(7489):476-9. doi: 10.1038/nature13032.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉1] Institute for Energy and Climate Research (IEK-8), Forschungszentrum Julich, 52425 Julich, Germany [2] Department of Physics, PO Box 64, 00014 University of Helsinki, Finland. ; 1] Department of Physics, PO Box 64, 00014 University of Helsinki, Finland [2] Department of Atmospheric Sciences, University of Washington, Seattle, Washington 98195, USA. ; Institute of Bio- and Geosciences (IBG-2), Forschungszentrum Julich, 52425 Julich, Germany. ; Department of Physics, PO Box 64, 00014 University of Helsinki, Finland. ; Institute for Energy and Climate Research (IEK-8), Forschungszentrum Julich, 52425 Julich, Germany. ; Department of Atmospheric Sciences, University of Washington, Seattle, Washington 98195, USA. ; 1] Department of Physics, PO Box 64, 00014 University of Helsinki, Finland [2] Institute for Tropospheric Research (TROPOS), 04318 Leipzig, Germany. ; 1] Department of Physics, PO Box 64, 00014 University of Helsinki, Finland [2] Helsinki Institute of Physics, PO Box 64, 00014 University of Helsinki, Finland. ; Department of Chemistry, PO Box 55, 00014 University of Helsinki, Finland. ; Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen O, Denmark. ; Aerodyne Research, Inc., 45 Manning Road, Billerica, Massachusetts 01821, USA. ; Department of Physics, Tampere University of Technology, PO Box 692, 33101 Tampere, Finland. ; Institute for Tropospheric Research (TROPOS), 04318 Leipzig, Germany. ; 1] Department of Physics, PO Box 64, 00014 University of Helsinki, Finland [2] Aerodyne Research, Inc., 45 Manning Road, Billerica, Massachusetts 01821, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/24572423" target="_blank"〉PubMed〈/a〉
    Keywords: Aerosols/analysis/*chemistry/metabolism ; Atmosphere/chemistry ; Climate ; Ecosystem ; Finland ; Gases/analysis/chemistry ; *Models, Chemical ; Monoterpenes/chemistry ; Oxidation-Reduction ; Ozone/chemistry ; Particle Size ; Trees/metabolism ; Volatile Organic Compounds/analysis/*chemistry/metabolism ; Volatilization
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 9
    Publication Date: 2015-06-20
    Description: Ye et al. have determined a maximum nitrous acid (HONO) yield of 3% for the reaction HO2.H2O + NO2, which is much lower than the yield used in our work. This finding, however, does not affect our main result that HONO in the investigated Po Valley region is mainly from a gas-phase source that consumes nitrogen oxides.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Li, Xin -- Rohrer, Franz -- Hofzumahaus, Andreas -- Brauers, Theo -- Haseler, Rolf -- Bohn, Birger -- Broch, Sebastian -- Fuchs, Hendrik -- Gomm, Sebastian -- Holland, Frank -- Jager, Julia -- Kaiser, Jennifer -- Keutsch, Frank N -- Lohse, Insa -- Lu, Keding -- Tillmann, Ralf -- Wegener, Robert -- Wolfe, Glenn M -- Mentel, Thomas F -- Kiendler-Scharr, Astrid -- Wahner, Andreas -- New York, N.Y. -- Science. 2015 Jun 19;348(6241):1326. doi: 10.1126/science.aaa3777.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Institut fur Energie und Klimaforschung, Troposphare (IEK-8), Forschungszentrum Julich, Julich, Germany. f.rohrer@fz-juelich.de x.li@fz-juelich.de. ; Institut fur Energie und Klimaforschung, Troposphare (IEK-8), Forschungszentrum Julich, Julich, Germany. ; Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/26089508" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 10
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Photochemistry 17 (1981), S. 142 
    ISSN: 0047-2670
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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