Articles | Volume 15, issue 23
https://doi.org/10.5194/acp-15-13627-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/acp-15-13627-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| Highlight paper
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10 Dec 2015
Research article | Highlight paper |
| 10 Dec 2015
Updated ozone absorption cross section will reduce air quality compliance
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UK
M. J. Evans
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UK
National Centre for Atmospheric Science, Department of Chemistry, University of York, York, YO10 5DD, UK
A. C. Lewis
Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UK
National Centre for Atmospheric Science, Department of Chemistry, University of York, York, YO10 5DD, UK
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Becky Alexander, Tomás Sherwen, Christopher D. Holmes, Jenny A. Fisher, Qianjie Chen, Mat J. Evans, and Prasad Kasibhatla
Atmos. Chem. Phys., 20, 3859–3877, https://doi.org/10.5194/acp-20-3859-2020, https://doi.org/10.5194/acp-20-3859-2020, 2020
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Nitrogen oxides are important for the formation of tropospheric oxidants and are removed from the atmosphere mainly through the formation of nitrate. We compare observations of the oxygen isotopes of nitrate with a global model to test our understanding of the chemistry nitrate formation. We use the model to quantify nitrate formation pathways in the atmosphere and identify key uncertainties and their relevance for the oxidation capacity of the atmosphere.
Sophie L. Haslett, Jonathan W. Taylor, Mathew Evans, Eleanor Morris, Bernhard Vogel, Alima Dajuma, Joel Brito, Anneke M. Batenburg, Stephan Borrmann, Johannes Schneider, Christiane Schulz, Cyrielle Denjean, Thierry Bourrianne, Peter Knippertz, Régis Dupuy, Alfons Schwarzenböck, Daniel Sauer, Cyrille Flamant, James Dorsey, Ian Crawford, and Hugh Coe
Atmos. Chem. Phys., 19, 15217–15234, https://doi.org/10.5194/acp-19-15217-2019, https://doi.org/10.5194/acp-19-15217-2019, 2019
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Tomás Sherwen, Rosie J. Chance, Liselotte Tinel, Daniel Ellis, Mat J. Evans, and Lucy J. Carpenter
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Mark O. Battle, J. William Munger, Margaret Conley, Eric Sofen, Rebecca Perry, Ryan Hart, Zane Davis, Jacob Scheckman, Jayme Woogerd, Karina Graeter, Samuel Seekins, Sasha David, and John Carpenter
Atmos. Chem. Phys., 19, 8687–8701, https://doi.org/10.5194/acp-19-8687-2019, https://doi.org/10.5194/acp-19-8687-2019, 2019
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Predictions of global warming require predictions of how much CO2 will be taken up by the oceans, how much by land plants, and how much will stay in the atmosphere. Measurements of atmospheric oxygen (O2) help with these predictions if we also know the ratio of O2 release to CO2 uptake in land plants. We have measured this ratio in a midlatitude forest and find a lower value than the one in wide use. If truly applicable, our results call for a modest adjustment in the global carbon budget.
Lei Zhu, Daniel J. Jacob, Sebastian D. Eastham, Melissa P. Sulprizio, Xuan Wang, Tomás Sherwen, Mat J. Evans, Qianjie Chen, Becky Alexander, Theodore K. Koenig, Rainer Volkamer, L. Gregory Huey, Michael Le Breton, Thomas J. Bannan, and Carl J. Percival
Atmos. Chem. Phys., 19, 6497–6507, https://doi.org/10.5194/acp-19-6497-2019, https://doi.org/10.5194/acp-19-6497-2019, 2019
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We quantify the effect of sea salt aerosol on tropospheric bromine chemistry with a new mechanistic description of the halogen chemistry in a global atmospheric chemistry model. For the first time, we are able to reproduce the observed levels of bromide activation from the sea salt aerosol in a manner consistent with bromine oxide radical measured from various platforms. Sea salt aerosol plays a far more complex role in global tropospheric chemistry than previously recognized.
Christoph A. Keller and Mat J. Evans
Geosci. Model Dev., 12, 1209–1225, https://doi.org/10.5194/gmd-12-1209-2019, https://doi.org/10.5194/gmd-12-1209-2019, 2019
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Xuan Wang, Daniel J. Jacob, Sebastian D. Eastham, Melissa P. Sulprizio, Lei Zhu, Qianjie Chen, Becky Alexander, Tomás Sherwen, Mathew J. Evans, Ben H. Lee, Jessica D. Haskins, Felipe D. Lopez-Hilfiker, Joel A. Thornton, Gregory L. Huey, and Hong Liao
Atmos. Chem. Phys., 19, 3981–4003, https://doi.org/10.5194/acp-19-3981-2019, https://doi.org/10.5194/acp-19-3981-2019, 2019
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Kate R. Smith, Peter M. Edwards, Peter D. Ivatt, James D. Lee, Freya Squires, Chengliang Dai, Richard E. Peltier, Mat J. Evans, Yele Sun, and Alastair C. Lewis
Atmos. Meas. Tech., 12, 1325–1336, https://doi.org/10.5194/amt-12-1325-2019, https://doi.org/10.5194/amt-12-1325-2019, 2019
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Clusters of low-cost, low-power atmospheric gas sensors were built into a sensor instrument to monitor NO2 and O3 in Beijing, alongside reference instruments, aiming to improve the reliability of sensor measurements. Clustering identical sensors and using the median sensor signal was used to minimize drift over short and medium timescales. Three different machine learning techniques were used for all the sensor data in an attempt to correct for cross-interferences, which worked to some degree.
Federica Pacifico, Claire Delon, Corinne Jambert, Pierre Durand, Eleanor Morris, Mat J. Evans, Fabienne Lohou, Solène Derrien, Venance H. E. Donnou, Arnaud V. Houeto, Irene Reinares Martínez, and Pierre-Etienne Brilouet
Atmos. Chem. Phys., 19, 2299–2325, https://doi.org/10.5194/acp-19-2299-2019, https://doi.org/10.5194/acp-19-2299-2019, 2019
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Biogenic fluxes from soil at a local and regional scale are crucial to study air pollution and climate. Here we present field measurements of soil fluxes of nitric oxide (NO) and ammonia (NH3) observed over four different land cover types, i.e. bare soil, grassland, maize field, and forest, at an inland rural site in Benin, West Africa, during the DACCIWA field campaign in
June and July 2016.
Lu Hu, Christoph A. Keller, Michael S. Long, Tomás Sherwen, Benjamin Auer, Arlindo Da Silva, Jon E. Nielsen, Steven Pawson, Matthew A. Thompson, Atanas L. Trayanov, Katherine R. Travis, Stuart K. Grange, Mat J. Evans, and Daniel J. Jacob
Geosci. Model Dev., 11, 4603–4620, https://doi.org/10.5194/gmd-11-4603-2018, https://doi.org/10.5194/gmd-11-4603-2018, 2018
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We present a full-year online global simulation of tropospheric chemistry at 12.5 km resolution. To the best of our knowledge, such a resolution in a state-of-the-science global simulation of tropospheric chemistry is unprecedented. This simulation will serve as the Nature Run for observing system simulation experiments to support the future geostationary satellite constellation for tropospheric chemistry, and can also be used for various air quality applications.
Qianjie Chen, Tomás Sherwen, Mathew Evans, and Becky Alexander
Atmos. Chem. Phys., 18, 13617–13637, https://doi.org/10.5194/acp-18-13617-2018, https://doi.org/10.5194/acp-18-13617-2018, 2018
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Uncertainty in the natural tropospheric sulfur cycle represents the largest source of uncertainty in radiative forcing estimates of sulfate aerosol. This study investigates the natural sulfur cycle in the marine troposphere using the GEOS-Chem model. We found that BrO is important for DMS oxidation and multiphase chemistry is important for MSA production and loss, which have implications for the yield of SO2 and MSA from DMS oxidation and the radiative effect of DMS-derived sulfate aerosol.
Prasad Kasibhatla, Tomás Sherwen, Mathew J. Evans, Lucy J. Carpenter, Chris Reed, Becky Alexander, Qianjie Chen, Melissa P. Sulprizio, James D. Lee, Katie A. Read, William Bloss, Leigh R. Crilley, William C. Keene, Alexander A. P. Pszenny, and Alma Hodzic
Atmos. Chem. Phys., 18, 11185–11203, https://doi.org/10.5194/acp-18-11185-2018, https://doi.org/10.5194/acp-18-11185-2018, 2018
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Recent measurements of NOx and HONO suggest that photolysis of particulate nitrate in sea-salt aerosols is important in terms of marine boundary layer oxidant chemistry. We present the first global-scale assessment of the significance of this new chemical pathway for NOx, O3, and OH in the marine boundary layer. We also present a preliminary assessment of the potential impact of photolysis of particulate nitrate associated with other aerosol types on continental boundary layer chemistry.
Mike J. Newland, Andrew R. Rickard, Tomás Sherwen, Mathew J. Evans, Luc Vereecken, Amalia Muñoz, Milagros Ródenas, and William J. Bloss
Atmos. Chem. Phys., 18, 6095–6120, https://doi.org/10.5194/acp-18-6095-2018, https://doi.org/10.5194/acp-18-6095-2018, 2018
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Stabilised Criegee intermediates (SCIs) are formed in the reaction of alkenes with ozone, both of which are ubiquitous throughout the troposphere. We determine the fate and global distribution of SCI from monoterpene ozonolysis. One major fate of SCI is reaction with H2O, but for a fraction of SCIs, unimolecular reactions dominate. Concentrations of SCIs are high enough regionally to play a key role in the conversion of sulfur dioxide to aerosol, affecting air quality and climate.
Daniel Stone, Tomás Sherwen, Mathew J. Evans, Stewart Vaughan, Trevor Ingham, Lisa K. Whalley, Peter M. Edwards, Katie A. Read, James D. Lee, Sarah J. Moller, Lucy J. Carpenter, Alastair C. Lewis, and Dwayne E. Heard
Atmos. Chem. Phys., 18, 3541–3561, https://doi.org/10.5194/acp-18-3541-2018, https://doi.org/10.5194/acp-18-3541-2018, 2018
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Halogen chemistry in the troposphere impacts oxidising capacity, but model studies assessing the nature of these impacts can vary according to the model framework used. In this work we present simulations of OH and HO2 radicals using both box and global model frameworks, and compare to observations made at the Cape Verde Atmospheric Observatory. We highlight, and rationalise, differences between the model frameworks.
Theodore K. Koenig, Rainer Volkamer, Sunil Baidar, Barbara Dix, Siyuan Wang, Daniel C. Anderson, Ross J. Salawitch, Pamela A. Wales, Carlos A. Cuevas, Rafael P. Fernandez, Alfonso Saiz-Lopez, Mathew J. Evans, Tomás Sherwen, Daniel J. Jacob, Johan Schmidt, Douglas Kinnison, Jean-François Lamarque, Eric C. Apel, James C. Bresch, Teresa Campos, Frank M. Flocke, Samuel R. Hall, Shawn B. Honomichl, Rebecca Hornbrook, Jørgen B. Jensen, Richard Lueb, Denise D. Montzka, Laura L. Pan, J. Michael Reeves, Sue M. Schauffler, Kirk Ullmann, Andrew J. Weinheimer, Elliot L. Atlas, Valeria Donets, Maria A. Navarro, Daniel Riemer, Nicola J. Blake, Dexian Chen, L. Gregory Huey, David J. Tanner, Thomas F. Hanisco, and Glenn M. Wolfe
Atmos. Chem. Phys., 17, 15245–15270, https://doi.org/10.5194/acp-17-15245-2017, https://doi.org/10.5194/acp-17-15245-2017, 2017
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Tropospheric inorganic bromine (BrO and Bry) shows a C-shaped profile over the tropical western Pacific Ocean, and supports previous speculation that marine convection is a source for inorganic bromine from sea salt to the upper troposphere. The Bry profile in the tropical tropopause layer (TTL) is complex, suggesting that the total Bry budget in the TTL is not closed without considering aerosol bromide. The implications for atmospheric composition and bromine sources are discussed.
Ben Newsome and Mat Evans
Atmos. Chem. Phys., 17, 14333–14352, https://doi.org/10.5194/acp-17-14333-2017, https://doi.org/10.5194/acp-17-14333-2017, 2017
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We explore the uncertainty in the predictions of a chemical transport model (GEOS-Chem) from uncertainty in 60 inorganic rate constants and photolysis rates. We find uncertainty in the global mean ozone burden of 10 %, in global mean OH of 16 %, methane lifetimes of 16 %, and tropospheric ozone radiative forcings of 13 %. Reductions in the uncertainty of rate constants of these simple reactions would reduce uncertainty in our understanding of atmospheric composition.
Peter M. Edwards and Mathew J. Evans
Atmos. Chem. Phys., 17, 13669–13680, https://doi.org/10.5194/acp-17-13669-2017, https://doi.org/10.5194/acp-17-13669-2017, 2017
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Understanding tropospheric ozone chemistry has been at the centre of the field of atmospheric chemistry for the last 30 years. However, our conceptual approach to diagnosing ozone production in global models has not advanced in this time. Our work presents a new and powerful approach for diagnosing tropospheric ozone production, providing a significant enhancement in our ability to understand the processes controlling ozone and how we can validate our assessment of these processes.
Peter Knippertz, Andreas H. Fink, Adrien Deroubaix, Eleanor Morris, Flore Tocquer, Mat J. Evans, Cyrille Flamant, Marco Gaetani, Christophe Lavaysse, Celine Mari, John H. Marsham, Rémi Meynadier, Abalo Affo-Dogo, Titike Bahaga, Fabien Brosse, Konrad Deetz, Ridha Guebsi, Issaou Latifou, Marlon Maranan, Philip D. Rosenberg, and Andreas Schlueter
Atmos. Chem. Phys., 17, 10893–10918, https://doi.org/10.5194/acp-17-10893-2017, https://doi.org/10.5194/acp-17-10893-2017, 2017
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In June–July 2016 DACCIWA (Dynamics–Aerosol–Chemistry–Cloud Interactions in West Africa), a large, EU-funded European–African project, organised an international field campaign in densely populated southern West Africa, including measurements from ground sites, research aircraft, weather balloons and urban sites. This paper gives an overview of the atmospheric evolution during this period focusing on meteorological (precipitation, cloudiness, winds) and composition (gases, particles) aspects.
Katie A. Read, Luis M. Neves, Lucy J. Carpenter, Alastair C. Lewis, Zoe L. Fleming, and John Kentisbeer
Atmos. Chem. Phys., 17, 5393–5406, https://doi.org/10.5194/acp-17-5393-2017, https://doi.org/10.5194/acp-17-5393-2017, 2017
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This paper presents 4 years of total gaseous mercury data obtained from measurements made at the Cape Verde Atmospheric Observatory, a subtropical site in the Atlantic Ocean. The data show a clear decreasing trend in the overall concentrations but in air from sub-Saharan Africa the trend is less significant and the data more variable. We attribute this result to an influence from artisanal small-scale gold mining in this region, a source for which there is uncertain information.
Chris Reed, Mathew J. Evans, Leigh R. Crilley, William J. Bloss, Tomás Sherwen, Katie A. Read, James D. Lee, and Lucy J. Carpenter
Atmos. Chem. Phys., 17, 4081–4092, https://doi.org/10.5194/acp-17-4081-2017, https://doi.org/10.5194/acp-17-4081-2017, 2017
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The source of ozone-depleting compounds in the remote troposphere has been thought to be long-range transport of secondary pollutants such as organic nitrates. Processing of organic nitrates to nitric acid and subsequent deposition on surfaces in the atmosphere was thought to remove these nitrates from the ozone–NOx–HOx cycle. We found through observation of NOx in the remote tropical troposphere at the Cape Verde Observatory that surface nitrates can be released back into the atmosphere.
Tomás Sherwen, Mat J. Evans, Lucy J. Carpenter, Johan A. Schmidt, and Loretta J. Mickley
Atmos. Chem. Phys., 17, 1557–1569, https://doi.org/10.5194/acp-17-1557-2017, https://doi.org/10.5194/acp-17-1557-2017, 2017
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We model pre-industrial to present day changes using the GEOS-Chem global chemical transport model with halogens (Cl, Br, I). The model better captures pre-industrial O3 observations with halogens included. Halogens buffer the tropospheric forcing of O3 (RFTO3) from pre-industrial to present day, reducing RFTO3 by 0.087 Wm−2. This reduction is greater than that from halogens on stratospheric O3 (−0.05 Wm−2). This suggests that models that do not include halogens will overestimate RFTO3by ~ 25%.
Stephen J. Andrews, Lucy J. Carpenter, Eric C. Apel, Elliot Atlas, Valeria Donets, James R. Hopkins, Rebecca S. Hornbrook, Alastair C. Lewis, Richard T. Lidster, Richard Lueb, Jamie Minaeian, Maria Navarro, Shalini Punjabi, Daniel Riemer, and Sue Schauffler
Atmos. Meas. Tech., 9, 5213–5225, https://doi.org/10.5194/amt-9-5213-2016, https://doi.org/10.5194/amt-9-5213-2016, 2016
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We present a comparison of aircraft measurements of important trace gases from a co-ordinated campaign in Jan–Feb 2014 in the tropical west Pacific involving the NASA Global Hawk, NCAR GV and FAAM BAe-146 aircraft.
The paper studies the comparability of separate measurements across platforms and demonstrates that aircraft measurements are relevant for characterising the vertical uplift of important gases, such as those with ozone-depleting potential, to the upper troposphere–lower stratosphere.
Tomás Sherwen, Johan A. Schmidt, Mat J. Evans, Lucy J. Carpenter, Katja Großmann, Sebastian D. Eastham, Daniel J. Jacob, Barbara Dix, Theodore K. Koenig, Roman Sinreich, Ivan Ortega, Rainer Volkamer, Alfonso Saiz-Lopez, Cristina Prados-Roman, Anoop S. Mahajan, and Carlos Ordóñez
Atmos. Chem. Phys., 16, 12239–12271, https://doi.org/10.5194/acp-16-12239-2016, https://doi.org/10.5194/acp-16-12239-2016, 2016
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We present a simulation of tropospheric Cl, Br, I chemistry within the GEOS-Chem CTM. We find a decrease in tropospheric ozone burden of 18.6 % and a 8.2 % decrease in global mean OH concentrations. Cl oxidation of some VOCs range from 15 to 27 % of the total loss. Bromine plays a small role in oxidising oVOCs. Surface ozone, ozone sondes, and methane lifetime are in general improved by the inclusion of halogens. We argue that simulated bromine and chlorine represent a lower limit.
Dene R. Bowdalo, Mathew J. Evans, and Eric D. Sofen
Atmos. Chem. Phys., 16, 8295–8308, https://doi.org/10.5194/acp-16-8295-2016, https://doi.org/10.5194/acp-16-8295-2016, 2016
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We introduce a new methodology for the assessment of atmospheric models with observations. We apply a spectral analysis methodology to hourly ozone observations and the equivalent model output. The spectrally transformed observational data show significant peaks on daily and annual timescales. Comparison between the amplitude and phase of these peaks introduces a new comparison methodology between model and measurements. We find the model shows significant biases on an annual timescale.
Hannah Sonderfeld, Iain R. White, Iain C. A. Goodall, James R. Hopkins, Alastair C. Lewis, Ralf Koppmann, and Paul S. Monks
Atmos. Chem. Phys., 16, 6303–6318, https://doi.org/10.5194/acp-16-6303-2016, https://doi.org/10.5194/acp-16-6303-2016, 2016
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Unknown sinks of OH and oxidation processes in the atmosphere have been attributed to what has been termed "missing" OH reactivity. Often overlooked are the differences in timescales over which the diverse measurement techniques operate. The effect of the sampling time and thus the contribution of unmeasured VOC variability on OH reactivity is investigated.
Alicia Gressent, Bastien Sauvage, Daniel Cariolle, Mathew Evans, Maud Leriche, Céline Mari, and Valérie Thouret
Atmos. Chem. Phys., 16, 5867–5889, https://doi.org/10.5194/acp-16-5867-2016, https://doi.org/10.5194/acp-16-5867-2016, 2016
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In chemical transport models, NOx emitted by lightning (LNOx) is instantaneously diluted into the grid. A plume-in-grid parameterization to account for the sub-grid chemistry of LNOx is presented. This approach was implemented into the GEOS-Chem model and leads to a relative increase of NOx and O3 (18 % and 2 %, respectively, in July) on a large scale downwind of lightning emissions and a relative decrease (25 % and 8 %, respectively, over central Africa in July) over the regions of emissions.
Chris Reed, Mathew J. Evans, Piero Di Carlo, James D. Lee, and Lucy J. Carpenter
Atmos. Chem. Phys., 16, 4707–4724, https://doi.org/10.5194/acp-16-4707-2016, https://doi.org/10.5194/acp-16-4707-2016, 2016
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The self-cleaning capacity of the atmosphere in places like Antarctica can be measured by quantifying very low amounts of combustion products that exist in a well-known ratio. When this ratio deviates from 1 it points to the existence of unknown compounds. Several unknown compounds have been theorized to exist but never measured. We have found the method for measuring the ratio of combustion products suffers a bias in remote places, which when taken into account disproves any unknown compounds.
Frank A. F. Winiberg, Terry J. Dillon, Stephanie C. Orr, Christoph B. M Groß, Iustinian Bejan, Charlotte A. Brumby, Matthew J. Evans, Shona C. Smith, Dwayne E. Heard, and Paul W. Seakins
Atmos. Chem. Phys., 16, 4023–4042, https://doi.org/10.5194/acp-16-4023-2016, https://doi.org/10.5194/acp-16-4023-2016, 2016
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OH radicals are important intermediates in the atmosphere, and the high concentrations observed in tropical regions are yet to be fully explained. Radical-radical reactions such as the title reaction can contribute to OH formation. This is the most fully comprehensive study of the CH3C(O)O2 + HO2 reaction with direct observation of products in all reaction channels. The implications of the new measurements on OH, PAN and NOx concentrations are considered via global models.
Maria Zatko, Lei Geng, Becky Alexander, Eric Sofen, and Katarina Klein
Atmos. Chem. Phys., 16, 2819–2842, https://doi.org/10.5194/acp-16-2819-2016, https://doi.org/10.5194/acp-16-2819-2016, 2016
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We have incorporated an idealized snowpack with a nitrate photolysis parameterization into a global chemical transport model (GEOS-Chem) to examine the implications of snow nitrate photolysis for boundary layer chemistry, the recycling and redistribution of reactive nitrogen, and the preservation of ice-core nitrate in ice cores across Antarctica and Greenland. We also examine the sensitivity of these processes to meteorological parameters and chemical, optical, and physical snow properties.
Lisa K. Whalley, Daniel Stone, Brian Bandy, Rachel Dunmore, Jacqueline F. Hamilton, James Hopkins, James D. Lee, Alastair C. Lewis, and Dwayne E. Heard
Atmos. Chem. Phys., 16, 2109–2122, https://doi.org/10.5194/acp-16-2109-2016, https://doi.org/10.5194/acp-16-2109-2016, 2016
E. D. Sofen, D. Bowdalo, M. J. Evans, F. Apadula, P. Bonasoni, M. Cupeiro, R. Ellul, I. E. Galbally, R. Girgzdiene, S. Luppo, M. Mimouni, A. C. Nahas, M. Saliba, and K. Tørseth
Earth Syst. Sci. Data, 8, 41–59, https://doi.org/10.5194/essd-8-41-2016, https://doi.org/10.5194/essd-8-41-2016, 2016
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We have brought together all publicly available surface ozone observations from online databases from 1971–2015, with 2200 sites representing regional background conditions appropriate for the evaluation of chemical transport and chemistry-climate models for projects such as the Chemistry-Climate Model Initiative. Gridded data sets of ozone metrics (mean, percentiles, MDA8, SOMO35, etc.) are available from the British Atmospheric Data Centre.
E. D. Sofen, D. Bowdalo, and M. J. Evans
Atmos. Chem. Phys., 16, 1445–1457, https://doi.org/10.5194/acp-16-1445-2016, https://doi.org/10.5194/acp-16-1445-2016, 2016
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We explore the global representativeness of a global surface ozone data set from a range of perspectives (area, biomes, chemical regimes, model uncertainty, model trends). We conclude that the current network fails to provide sufficient constraints for important regions/regimes, leading to uncertainty for a range of atmospheric composition challenges. We suggest 20 new locations for making surface ozone observations, which would significantly enhance our observational capability.
T. Sherwen, M. J. Evans, L. J. Carpenter, S. J. Andrews, R. T. Lidster, B. Dix, T. K. Koenig, R. Sinreich, I. Ortega, R. Volkamer, A. Saiz-Lopez, C. Prados-Roman, A. S. Mahajan, and C. Ordóñez
Atmos. Chem. Phys., 16, 1161–1186, https://doi.org/10.5194/acp-16-1161-2016, https://doi.org/10.5194/acp-16-1161-2016, 2016
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Using a global chemical transport model (GEOS-Chem) with additional iodine emissions, chemistry, and deposition we show that iodine is responsible for ~ 9 % of global ozone loss but has negligible impacts on global OH. Uncertainties are large in the chemistry and emissions and future research is needed in both. Measurements of iodine species (especially HOI) would be useful. We believe iodine chemistry should be considered in future chemistry-climate and in air quality modelling.
R. E. Dunmore, J. R. Hopkins, R. T. Lidster, J. D. Lee, M. J. Evans, A. R. Rickard, A. C. Lewis, and J. F. Hamilton
Atmos. Chem. Phys., 15, 9983–9996, https://doi.org/10.5194/acp-15-9983-2015, https://doi.org/10.5194/acp-15-9983-2015, 2015
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Technological shifts between fuel sources have had unexpected impacts on atmospheric composition and these significant changes can go undetected if source-specific monitoring infrastructure is not in place. We present chemically comprehensive, continuous measurements of organic compounds in a developed megacity (London), that show diesel-related hydrocarbons can dominate reactive carbon and ozone formation potential, highlighting a serious underestimation of this source in emission inventories.
J. G. Levine, A. R. MacKenzie, O. J. Squire, A. T. Archibald, P. T. Griffiths, N. L. Abraham, J. A. Pyle, D. E. Oram, G. Forster, J. F. Brito, J. D. Lee, J. R. Hopkins, A. C. Lewis, S. J. B. Bauguitte, C. F. Demarco, P. Artaxo, P. Messina, J. Lathière, D. A. Hauglustaine, E. House, C. N. Hewitt, and E. Nemitz
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acpd-15-24251-2015, https://doi.org/10.5194/acpd-15-24251-2015, 2015
Revised manuscript has not been submitted
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This study explores our ability to simulate atmospheric chemistry stemming from isoprene emissions—a reactive gas emitted from vegetation—in pristine and polluted regions of the Amazon basin. We explore how two contrasting models fare in reproducing recent airborne measurements in the region. Their differing treatments of transport and mixing are found to: profoundly affect their performance; and yield very different pictures of the exposure of the rainforest to harmful ozone concentrations.
H. M. Walker, D. Stone, T. Ingham, S. Vaughan, M. Cain, R. L. Jones, O. J. Kennedy, M. McLeod, B. Ouyang, J. Pyle, S. Bauguitte, B. Bandy, G. Forster, M. J. Evans, J. F. Hamilton, J. R. Hopkins, J. D. Lee, A. C. Lewis, R. T. Lidster, S. Punjabi, W. T. Morgan, and D. E. Heard
Atmos. Chem. Phys., 15, 8179–8200, https://doi.org/10.5194/acp-15-8179-2015, https://doi.org/10.5194/acp-15-8179-2015, 2015
M. D. Shaw, J. D. Lee, B. Davison, A. Vaughan, R. M. Purvis, A. Harvey, A. C. Lewis, and C. N. Hewitt
Atmos. Chem. Phys., 15, 5083–5097, https://doi.org/10.5194/acp-15-5083-2015, https://doi.org/10.5194/acp-15-5083-2015, 2015
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This paper presents the first highly spatially resolved simultaneous mixing ratios of VOCs, NOx and O3 in the atmospheric boundary layer above Greater London (UK) using an research aircraft. Average mixing ratios measured at 360±10 m agl over outer London were always lower than over inner London, indicative of strong local vehicular sources. The comparison of airborne mixing ratio with LAQN air quality ground monitoring stations suggests that the mixing ratios were characteristic of the surface.
L. K. Whalley, D. Stone, I. J. George, S. Mertes, D. van Pinxteren, A. Tilgner, H. Herrmann, M. J. Evans, and D. E. Heard
Atmos. Chem. Phys., 15, 3289–3301, https://doi.org/10.5194/acp-15-3289-2015, https://doi.org/10.5194/acp-15-3289-2015, 2015
E. D. Sofen, B. Alexander, E. J. Steig, M. H. Thiemens, S. A. Kunasek, H. M. Amos, A. J. Schauer, M. G. Hastings, J. Bautista, T. L. Jackson, L. E. Vogel, J. R. McConnell, D. R. Pasteris, and E. S. Saltzman
Atmos. Chem. Phys., 14, 5749–5769, https://doi.org/10.5194/acp-14-5749-2014, https://doi.org/10.5194/acp-14-5749-2014, 2014
D. Stone, M. J. Evans, H. Walker, T. Ingham, S. Vaughan, B. Ouyang, O. J. Kennedy, M. W. McLeod, R. L. Jones, J. Hopkins, S. Punjabi, R. Lidster, J. F. Hamilton, J. D. Lee, A. C. Lewis, L. J. Carpenter, G. Forster, D. E. Oram, C. E. Reeves, S. Bauguitte, W. Morgan, H. Coe, E. Aruffo, C. Dari-Salisburgo, F. Giammaria, P. Di Carlo, and D. E. Heard
Atmos. Chem. Phys., 14, 1299–1321, https://doi.org/10.5194/acp-14-1299-2014, https://doi.org/10.5194/acp-14-1299-2014, 2014
P. M. Edwards, M. J. Evans, K. L. Furneaux, J. Hopkins, T. Ingham, C. Jones, J. D. Lee, A. C. Lewis, S. J. Moller, D. Stone, L. K. Whalley, and D. E. Heard
Atmos. Chem. Phys., 13, 9497–9514, https://doi.org/10.5194/acp-13-9497-2013, https://doi.org/10.5194/acp-13-9497-2013, 2013
J. R. Pierce, M. J. Evans, C. E. Scott, S. D. D'Andrea, D. K. Farmer, E. Swietlicki, and D. V. Spracklen
Atmos. Chem. Phys., 13, 3163–3176, https://doi.org/10.5194/acp-13-3163-2013, https://doi.org/10.5194/acp-13-3163-2013, 2013
A. C. Lewis, M. J. Evans, J. R. Hopkins, S. Punjabi, K. A. Read, R. M. Purvis, S. J. Andrews, S. J. Moller, L. J. Carpenter, J. D. Lee, A. R. Rickard, P. I. Palmer, and M. Parrington
Atmos. Chem. Phys., 13, 851–867, https://doi.org/10.5194/acp-13-851-2013, https://doi.org/10.5194/acp-13-851-2013, 2013
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Rate coefficients for the reactions of OH radicals with C3–C11 alkanes determined by the relative-rate technique
Formation and temperature dependence of highly oxygenated organic molecules (HOMs) from Δ3-carene ozonolysis
Mechanistic insight into the kinetic fragmentation of norpinonic acid in the gas phase: an experimental and density functional theory (DFT) study
Exploring HONO production from particulate nitrate photolysis in Chinese representative regions: characteristics, influencing factors and environmental implications
Secondary reactions of aromatics-derived oxygenated organic molecules lead to plentiful highly oxygenated organic molecules within an intraday OH exposure
Impact of HO2∕RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential
Formation of Reactive Nitrogen Species Promoted by Iron Ions Through the Photochemistry of Neonicotinoid Insecticide
Negligible temperature dependence of the ozone–iodide reaction and implications for oceanic emissions of iodine
Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework
On the potential use of highly oxygenated organic molecules (HOMs) as indicators for ozone formation sensitivity
Oxygenated organic molecules produced by low-NOx photooxidation of aromatic compounds: contributions to secondary organic aerosol and steric hindrance
Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis
Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants
Quantifying primary oxidation products in the OH-initiated reaction of benzyl alcohol
Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures
Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules
Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals
Compilation of Henry's law constants (version 5.0.0) for water as solvent
Measurement report: Carbonyl sulfide production during dimethyl sulfide oxidation in the atmospheric simulation chamber SAPHIR
An aldehyde as a rapid source of secondary aerosol precursors: theoretical and experimental study of hexanal autoxidation
Measuring and modeling investigation of the net photochemical ozone production rate via an improved dual-channel reaction chamber technique
Evolution of organic carbon in the laboratory oxidation of biomass-burning emissions
Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone
On the formation of highly oxidized pollutants by autoxidation of terpenes under low-temperature-combustion conditions: the case of limonene and α-pinene
Selective deuteration as a tool for resolving autoxidation mechanisms in α-pinene ozonolysis
Comparison of isoprene chemical mechanisms under atmospheric night-time conditions in chamber experiments: evidence of hydroperoxy aldehydes and epoxy products from NO3 oxidation
Measurement of Henry's law and liquid-phase loss rate constants of peroxypropionic nitric anhydride (PPN) in deionized water and in n-octanol
Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes
Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cooking
Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes
Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)
Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicals
An experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radical
Oxidation product characterization from ozonolysis of the diterpene ent-kaurene
Kinetics of OH + SO2 + M: temperature-dependent rate coefficients in the fall-off regime and the influence of water vapour
Formation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface
Stable carbon isotopic composition of biomass burning emissions – implications for estimating the contribution of C3 and C4 plants
Evaluation of the daytime tropospheric loss of 2-methylbutanal
Investigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviour
Reproducing Arctic springtime tropospheric ozone and mercury depletion events in an outdoor mesocosm sea ice facility
N2O5 uptake onto saline mineral dust: a potential missing source of tropospheric ClNO2 in inland China
NO3 chemistry of wildfire emissions: a kinetic study of the gas-phase reactions of furans with the NO3 radical
Marine gas-phase sulfur emissions during an induced phytoplankton bloom
Biomass burning plume chemistry: OH-radical-initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanal
Atmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgets
Characterization of ambient volatile organic compounds, source apportionment, and the ozone–NOx–VOC sensitivities in a heavily polluted megacity of central China: effect of sporting events and emission reductions
Atmospheric oxidation of α,β-unsaturated ketones: kinetics and mechanism of the OH radical reaction
Reactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reaction
Atmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yields
Yanyan Xin, Chengtang Liu, Xiaoxiu Lun, Shuyang Xie, Junfeng Liu, and Yujing Mu
Atmos. Chem. Phys., 24, 11409–11429, https://doi.org/10.5194/acp-24-11409-2024, https://doi.org/10.5194/acp-24-11409-2024, 2024
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Rate coefficients for the reactions of OH radicals with C3–C11 alkanes were determined using the multivariate relative-rate technique. A total of 25 relative-rate coefficients at room temperature and 24 Arrhenius expressions in the temperature range of 273–323 K were obtained, which expanded the data available.
Yuanyuan Luo, Ditte Thomsen, Emil Mark Iversen, Pontus Roldin, Jane Tygesen Skønager, Linjie Li, Michael Priestley, Henrik B. Pedersen, Mattias Hallquist, Merete Bilde, Marianne Glasius, and Mikael Ehn
Atmos. Chem. Phys., 24, 9459–9473, https://doi.org/10.5194/acp-24-9459-2024, https://doi.org/10.5194/acp-24-9459-2024, 2024
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∆3-carene is abundantly emitted from vegetation, but its atmospheric oxidation chemistry has received limited attention. We explored highly oxygenated organic molecule (HOM) formation from ∆3-carene ozonolysis in chambers and investigated the impact of temperature and relative humidity on HOM formation. Our findings provide new insights into ∆3-carene oxidation pathways and their potential to impact atmospheric aerosols.
Izabela Kurzydym, Agata Błaziak, Kinga Podgórniak, Karol Kułacz, and Kacper Błaziak
Atmos. Chem. Phys., 24, 9309–9322, https://doi.org/10.5194/acp-24-9309-2024, https://doi.org/10.5194/acp-24-9309-2024, 2024
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This paper outlines a unique scientific strategy for studying the reactivity of atmospherically relevant norpinonic acid (NA). The publication offers a new toolbox, illustrating NA's fragmentation and pattern of kinetic degradation leading to the formation of new small molecules. Furthermore, the research strategy presented here demonstrates how a mass spectrometer can function as a gas-phase reactor and the quantum chemistry method can serve as a reaction model builder.
Bowen Li, Jian Gao, Chun Chen, Liang Wen, Yuechong Zhang, Junling Li, Yuzhe Zhang, Xiaohui Du, Kai Zhang, and Jiaqi Wang
EGUsphere, https://doi.org/10.5194/egusphere-2024-2141, https://doi.org/10.5194/egusphere-2024-2141, 2024
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The photolysis rate constants of particulate nitrate for HONO production (JHONO) with PM2.5 samples collected from five representative sites in China varied over a wide range. The parameterization equation between JHONO and OC/NO3− has been established and can be used to estimate JHONO in different environments. Our work provided an important reference for the research in other areas in the world with high proportion of organic components in aerosol samples, such as United States and Europe.
Yuwei Wang, Chuang Li, Ying Zhang, Yueyang Li, Gan Yang, Xueyan Yang, Yizhen Wu, Lei Yao, Hefeng Zhang, and Lin Wang
Atmos. Chem. Phys., 24, 7961–7981, https://doi.org/10.5194/acp-24-7961-2024, https://doi.org/10.5194/acp-24-7961-2024, 2024
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The formation and evolution mechanisms of aromatics-derived highly oxygenated organic molecules (HOMs) are essential to understand the formation of secondary organic aerosol pollution. Our conclusion highlights an underappreciated formation pathway of aromatics-derived HOMs and elucidates detailed formation mechanisms of certain HOMs, which advances our understanding of HOMs and potentially explains the existing gap between model prediction and ambient measurement of the HOMs' concentrations.
Yarê Baker, Sungah Kang, Hui Wang, Rongrong Wu, Jian Xu, Annika Zanders, Quanfu He, Thorsten Hohaus, Till Ziehm, Veronica Geretti, Thomas J. Bannan, Simon P. O'Meara, Aristeidis Voliotis, Mattias Hallquist, Gordon McFiggans, Sören R. Zorn, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 24, 4789–4807, https://doi.org/10.5194/acp-24-4789-2024, https://doi.org/10.5194/acp-24-4789-2024, 2024
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Highly oxygenated organic molecules are important contributors to secondary organic aerosol. Their yield depends on detailed atmospheric chemical composition. One important parameter is the ratio of hydroperoxy radicals to organic peroxy radicals (HO2/RO2), and we show that higher HO2/RO2 ratios lower the secondary organic aerosol yield. This is of importance as laboratory studies are often biased towards organic peroxy radicals.
Zhu Ran, Yanan Hu, Yuanzhe Li, Xiaoya Gao, Can Ye, Shuai Li, Xiao Lu, Yongming Luo, Sasho Gligorovski, and Jiangping Liu
EGUsphere, https://doi.org/10.5194/egusphere-2024-1116, https://doi.org/10.5194/egusphere-2024-1116, 2024
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We report eruptive production of nitrous acid (HONO) and NOx (NO + NO2) triggered by iron ions during the photolysis of neonicotinoid insecticide in the air-water interface. This novel previously overlooked source of atmospheric HONO and NOx, may be an important contribution to the global nitrogen cycle and affects the atmospheric oxidizing capacity as well as the climate change.
Lucy V. Brown, Ryan J. Pound, Lyndsay S. Ives, Matthew R. Jones, Stephen J. Andrews, and Lucy J. Carpenter
Atmos. Chem. Phys., 24, 3905–3923, https://doi.org/10.5194/acp-24-3905-2024, https://doi.org/10.5194/acp-24-3905-2024, 2024
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Ozone is deposited from the lower atmosphere to the surface of the ocean; however, the chemical reactions which drive this deposition are currently not well understood. Of particular importance is the reaction between ozone and iodide, and this work measures the kinetics of this reaction and its temperature dependence, which we find to be negligible. We then investigate the subsequent emissions of iodine-containing species from the surface ocean, which can further impact ozone.
Lorrie Simone Denise Jacob, Chiara Giorio, and Alexander Thomas Archibald
Atmos. Chem. Phys., 24, 3329–3347, https://doi.org/10.5194/acp-24-3329-2024, https://doi.org/10.5194/acp-24-3329-2024, 2024
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Recent studies on DMS have provided new challenges to our mechanistic understanding. Here we synthesise a number of recent studies to further develop and extend a state-of-the-art mechanism. Our new mechanism is shown to outperform all existing mechanisms when compared over a wide set of conditions. The development of an improved DMS mechanism will help lead the way to better the understanding the climate impacts of DMS emissions in past, present, and future atmospheric conditions.
Jiangyi Zhang, Jian Zhao, Yuanyuan Luo, Valter Mickwitz, Douglas Worsnop, and Mikael Ehn
Atmos. Chem. Phys., 24, 2885–2911, https://doi.org/10.5194/acp-24-2885-2024, https://doi.org/10.5194/acp-24-2885-2024, 2024
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Due to the intrinsic connection between the formation pathways of O3 and HOMs, the ratio of HOM dimers or non-nitrate monomers to HOM organic nitrates could be used to determine O3 formation regimes. Owing to the fast formation and short lifetimes of HOMs, HOM-based indicating ratios can describe O3 formation in real time. Despite the success of our approach in this simple laboratory system, applicability to the much more complex atmosphere remains to be determined.
Xi Cheng, Yong Jie Li, Yan Zheng, Keren Liao, Theodore K. Koenig, Yanli Ge, Tong Zhu, Chunxiang Ye, Xinghua Qiu, and Qi Chen
Atmos. Chem. Phys., 24, 2099–2112, https://doi.org/10.5194/acp-24-2099-2024, https://doi.org/10.5194/acp-24-2099-2024, 2024
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In this study we conducted laboratory measurements to investigate the formation of gas-phase oxygenated organic molecules (OOMs) from six aromatic volatile organic compounds (VOCs). We provide a thorough analysis on the effects of precursor structure (substituents and ring numbers) on product distribution and highlight from a laboratory perspective that heavy (e.g., double-ring) aromatic VOCs are important in initial particle growth during secondary organic aerosol formation.
Yiwei Gong, Feng Jiang, Yanxia Li, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 167–184, https://doi.org/10.5194/acp-24-167-2024, https://doi.org/10.5194/acp-24-167-2024, 2024
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This study investigates the role of the important atmospheric reactive intermediates in the formation of dimers and aerosol in monoterpene ozonolysis at different temperatures. Through conducting a series of chamber experiments and utilizing chemical kinetic and aerosol dynamic models, the SOA formation processes are better described, especially for colder regions. The results can be used to improve the chemical mechanism modeling of monoterpenes and SOA parameterization in transport models.
María Asensio, Sergio Blázquez, María Antiñolo, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 23, 14115–14126, https://doi.org/10.5194/acp-23-14115-2023, https://doi.org/10.5194/acp-23-14115-2023, 2023
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In this work, we focus on the atmospheric chemistry and consequences for air quality of 2-methylpentanal (2MP), which is widely used as a flavoring ingredient and as an intermediate in the synthesis of dyes, resins, and pharmaceuticals. Measurements are presented on how fast 2MP is degraded by sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms and what products are generated. We conclude that 2MP will be degraded in a few hours, affecting local air quality.
Reina S. Buenconsejo, Sophia M. Charan, John H. Seinfeld, and Paul O. Wennberg
EGUsphere, https://doi.org/10.5194/egusphere-2023-2483, https://doi.org/10.5194/egusphere-2023-2483, 2023
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We look at the atmospheric chemistry of a volatile chemical product (VCP), benzyl alcohol. Benzyl alcohol and other VCPs may play a significant role in the formation of urban smog. By better understanding the chemistry of VCPs like benzyl alcohol, we may better understand observed data and how VCPs affect air quality. We identify products formed from benzyl alcohol chemistry and use this chemistry to understand how benzyl alcohol forms a key component of smog, secondary organic aerosol.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
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We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
Han Zang, Dandan Huang, Jiali Zhong, Ziyue Li, Chenxi Li, Huayun Xiao, and Yue Zhao
Atmos. Chem. Phys., 23, 12691–12705, https://doi.org/10.5194/acp-23-12691-2023, https://doi.org/10.5194/acp-23-12691-2023, 2023
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Acylperoxy radicals (RO2) are key intermediates in the atmospheric oxidation of organic compounds, yet our knowledge of their identities and chemistry remains poor. Using direct measurements and kinetic modeling, we identify the composition and formation pathways of acyl RO2 and quantify their contribution to highly oxygenated organic molecules during α-pinene ozonolysis, which will help to understand oxidation chemistry of monoterpenes and sources of low-volatility organics in the atmosphere.
Jacky Y. S. Pang, Florian Berg, Anna Novelli, Birger Bohn, Michelle Färber, Philip T. M. Carlsson, René Dubus, Georgios I. Gkatzelis, Franz Rohrer, Sergej Wedel, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 12631–12649, https://doi.org/10.5194/acp-23-12631-2023, https://doi.org/10.5194/acp-23-12631-2023, 2023
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In this study, the oxidations of sabinene by OH radicals and ozone were investigated with an atmospheric simulation chamber. Reaction rate coefficients of the OH-oxidation reaction at temperatures between 284 to 340 K were determined for the first time in the laboratory by measuring the OH reactivity. Product yields determined in chamber experiments had good agreement with literature values, but discrepancies were found between experimental yields and expected yields from oxidation mechanisms.
Rolf Sander
Atmos. Chem. Phys., 23, 10901–12440, https://doi.org/10.5194/acp-23-10901-2023, https://doi.org/10.5194/acp-23-10901-2023, 2023
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According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry’s law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 46 434 values of Henry's law constants for 10 173 species, collected from 995 references. It is also available on the internet at https://www.henrys-law.org.
Marc von Hobe, Domenico Taraborrelli, Sascha Alber, Birger Bohn, Hans-Peter Dorn, Hendrik Fuchs, Yun Li, Chenxi Qiu, Franz Rohrer, Roberto Sommariva, Fred Stroh, Zhaofeng Tan, Sergej Wedel, and Anna Novelli
Atmos. Chem. Phys., 23, 10609–10623, https://doi.org/10.5194/acp-23-10609-2023, https://doi.org/10.5194/acp-23-10609-2023, 2023
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The trace gas carbonyl sulfide (OCS) transports sulfur from the troposphere to the stratosphere, where sulfate aerosols are formed that influence climate and stratospheric chemistry. An uncertain OCS source in the troposphere is chemical production form dimethyl sulfide (DMS), a gas released in large quantities from the oceans. We carried out experiments in a large atmospheric simulation chamber to further elucidate the chemical mechanism of OCS production from DMS.
Shawon Barua, Siddharth Iyer, Avinash Kumar, Prasenjit Seal, and Matti Rissanen
Atmos. Chem. Phys., 23, 10517–10532, https://doi.org/10.5194/acp-23-10517-2023, https://doi.org/10.5194/acp-23-10517-2023, 2023
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This work illustrates how a common volatile hydrocarbon, hexanal, has the potential to undergo atmospheric autoxidation that leads to prompt formation of condensable material that subsequently contributes to aerosol formation, deteriorating the air quality of urban atmospheres. We used the combined state-of-the-art quantum chemical modeling and experimental flow reactor experiments under atmospheric conditions to resolve the autoxidation mechanism of hexanal initiated by a common oxidant.
Yixin Hao, Jun Zhou, Jie-Ping Zhou, Yan Wang, Suxia Yang, Yibo Huangfu, Xiao-Bing Li, Chunsheng Zhang, Aiming Liu, Yanfeng Wu, Yaqing Zhou, Shuchun Yang, Yuwen Peng, Jipeng Qi, Xianjun He, Xin Song, Yubin Chen, Bin Yuan, and Min Shao
Atmos. Chem. Phys., 23, 9891–9910, https://doi.org/10.5194/acp-23-9891-2023, https://doi.org/10.5194/acp-23-9891-2023, 2023
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By employing an improved net photochemical ozone production rate (NPOPR) detection system based on the dual-channel reaction chamber technique, we measured the net photochemical ozone production rate in the Pearl River Delta in China. The photochemical ozone formation mechanisms in the reaction and reference chambers were investigated using the observation-data-constrained box model, which helped us to validate the NPOPR detection system and understand photochemical ozone formation mechanism.
Kevin J. Nihill, Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Bin Yuan, Jordan E. Krechmer, Kanako Sekimoto, Jose L. Jimenez, Joost de Gouw, Christopher D. Cappa, Colette L. Heald, Carsten Warneke, and Jesse H. Kroll
Atmos. Chem. Phys., 23, 7887–7899, https://doi.org/10.5194/acp-23-7887-2023, https://doi.org/10.5194/acp-23-7887-2023, 2023
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In this work, we collect emissions from controlled burns of biomass fuels that can be found in the western United States into an environmental chamber in order to simulate their oxidation as they pass through the atmosphere. These findings provide a detailed characterization of the composition of the atmosphere downwind of wildfires. In turn, this will help to explore the effects of these changing emissions on downwind populations and will also directly inform atmospheric and climate models.
Caterina Mapelli, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
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Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
Roland Benoit, Nesrine Belhadj, Zahraa Dbouk, Maxence Lailliau, and Philippe Dagaut
Atmos. Chem. Phys., 23, 5715–5733, https://doi.org/10.5194/acp-23-5715-2023, https://doi.org/10.5194/acp-23-5715-2023, 2023
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We observed a surprisingly similar set of oxidation product chemical formulas from limonene and α-pinene, including oligomers, formed under cool-flame (present experiments) and simulated atmospheric oxidation (literature). Data analysis indicated that a subset of chemical formulas is common to all experiments independently of experimental conditions. Also, this study indicates that many detected chemical formulas can be ascribed to an autooxidation reaction.
Melissa Meder, Otso Peräkylä, Jonathan G. Varelas, Jingyi Luo, Runlong Cai, Yanjun Zhang, Theo Kurtén, Matthieu Riva, Matti Rissanen, Franz M. Geiger, Regan J. Thomson, and Mikael Ehn
Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, https://doi.org/10.5194/acp-23-4373-2023, 2023
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We discuss and show the viability of a method where multiple isotopically labelled precursors are used for probing the formation pathways of highly oxygenated organic molecules (HOMs) from the oxidation of the monoterpene a-pinene. HOMs are very important for secondary organic aerosol (SOA) formation in forested regions, and monoterpenes are the single largest source of SOA globally. The fast reactions forming HOMs have thus far remained elusive despite considerable efforts over the last decade.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
Kevin D. Easterbrook, Mitchell A. Vona, Kiana Nayebi-Astaneh, Amanda M. Miller, and Hans D. Osthoff
Atmos. Chem. Phys., 23, 311–322, https://doi.org/10.5194/acp-23-311-2023, https://doi.org/10.5194/acp-23-311-2023, 2023
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The trace gas peroxypropionyl nitrate (PPN) is generated in photochemical smog, phytotoxic, a strong eye irritant, and possibly mutagenic. Here, its solubility and reactivity in water and in octanol were investigated using a bubble flow apparatus, yielding its Henry's law constant and octanol–water partition coefficient (Kow). The results allow the fate of PPN to be more accurately constrained in atmospheric chemical transport models, including its uptake on clouds, organic aerosol, and leaves.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
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The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
Caterina Mapelli, Juliette V. Schleicher, Alex Hawtin, Conor D. Rankine, Fiona C. Whiting, Fergal Byrne, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 22, 14589–14602, https://doi.org/10.5194/acp-22-14589-2022, https://doi.org/10.5194/acp-22-14589-2022, 2022
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Solvents represent an important source of pollution from the chemical industry. New "green" solvents aim to replace toxic solvents with new molecules made from renewable sources and designed to be less harmful. Whilst these new molecules are selected according to toxicity and other characteristics, no consideration has yet been included on air quality. Studying the solvent breakdown in air, we found that TMO has a lower impact on air quality than traditional solvents with similar properties.
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841, https://doi.org/10.5194/acp-22-9827-2022, https://doi.org/10.5194/acp-22-9827-2022, 2022
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Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031, https://doi.org/10.5194/acp-22-9017-2022, https://doi.org/10.5194/acp-22-9017-2022, 2022
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We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004, https://doi.org/10.5194/acp-22-6989-2022, https://doi.org/10.5194/acp-22-6989-2022, 2022
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This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, https://doi.org/10.5194/acp-22-6411-2022, 2022
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Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637, https://doi.org/10.5194/acp-22-5619-2022, https://doi.org/10.5194/acp-22-5619-2022, 2022
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Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984, https://doi.org/10.5194/acp-22-4969-2022, https://doi.org/10.5194/acp-22-4969-2022, 2022
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The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Haoyu Jiang, Yingyao He, Yiqun Wang, Sheng Li, Bin Jiang, Luca Carena, Xue Li, Lihua Yang, Tiangang Luan, Davide Vione, and Sasho Gligorovski
Atmos. Chem. Phys., 22, 4237–4252, https://doi.org/10.5194/acp-22-4237-2022, https://doi.org/10.5194/acp-22-4237-2022, 2022
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Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890, https://doi.org/10.5194/acp-22-2871-2022, https://doi.org/10.5194/acp-22-2871-2022, 2022
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Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701, https://doi.org/10.5194/acp-22-2689-2022, https://doi.org/10.5194/acp-22-2689-2022, 2022
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The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
Claudiu Roman, Cecilia Arsene, Iustinian Gabriel Bejan, and Romeo Iulian Olariu
Atmos. Chem. Phys., 22, 2203–2219, https://doi.org/10.5194/acp-22-2203-2022, https://doi.org/10.5194/acp-22-2203-2022, 2022
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Gas-phase reaction rate coefficients of OH radicals with four nitrocatechols have been investigated for the first time by using ESC-Q-UAIC chamber facilities. The reactivity of all investigated nitrocatechols is influenced by the formation of the intramolecular H-bonds that are connected to the deactivating electromeric effect of the NO2 group. For the 3-nitrocatechol compounds, the electromeric effect of the
freeOH group is diminished by the deactivating E-effect of the NO2 group.
Zhiyuan Gao, Nicolas-Xavier Geilfus, Alfonso Saiz-Lopez, and Feiyue Wang
Atmos. Chem. Phys., 22, 1811–1824, https://doi.org/10.5194/acp-22-1811-2022, https://doi.org/10.5194/acp-22-1811-2022, 2022
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Every spring in the Arctic, a series of photochemical events occur over the ice-covered ocean, known as bromine explosion events, ozone depletion events, and mercury depletion events. Here we report the re-creation of these events at an outdoor sea ice facility in Winnipeg, Canada, far away from the Arctic. The success provides a new platform with new opportunities to uncover fundamental mechanisms of these Arctic springtime phenomena and how they may change in a changing climate.
Haichao Wang, Chao Peng, Xuan Wang, Shengrong Lou, Keding Lu, Guicheng Gan, Xiaohong Jia, Xiaorui Chen, Jun Chen, Hongli Wang, Shaojia Fan, Xinming Wang, and Mingjin Tang
Atmos. Chem. Phys., 22, 1845–1859, https://doi.org/10.5194/acp-22-1845-2022, https://doi.org/10.5194/acp-22-1845-2022, 2022
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Via combining laboratory and modeling work, we found that heterogeneous reaction of N2O5 with saline mineral dust aerosol could be an important source of tropospheric ClNO2 in inland regions.
Mike J. Newland, Yangang Ren, Max R. McGillen, Lisa Michelat, Véronique Daële, and Abdelwahid Mellouki
Atmos. Chem. Phys., 22, 1761–1772, https://doi.org/10.5194/acp-22-1761-2022, https://doi.org/10.5194/acp-22-1761-2022, 2022
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Wildfires are increasing in extent and severity, driven by climate change. Such fires emit large amounts of volatile organic compounds (VOCs) to the atmosphere. Many of these, such as the furans studied here, are very reactive and are rapidly converted to other VOCs, which are expected to have negative health effects and to further impact the climate. Here, we establish the importance of the nitrate radical for removing these compounds both during the night and during the day.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
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We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572, https://doi.org/10.5194/acp-21-18557-2021, https://doi.org/10.5194/acp-21-18557-2021, 2021
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Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091, https://doi.org/10.5194/acp-21-16067-2021, https://doi.org/10.5194/acp-21-16067-2021, 2021
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The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Shijie Yu, Fangcheng Su, Shasha Yin, Shenbo Wang, Ruixin Xu, Bing He, Xiangge Fan, Minghao Yuan, and Ruiqin Zhang
Atmos. Chem. Phys., 21, 15239–15257, https://doi.org/10.5194/acp-21-15239-2021, https://doi.org/10.5194/acp-21-15239-2021, 2021
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This study measured 106 VOC species using a GC-MS/FID. Meanwhile, the WRF-CMAQ model was used to investigate the nonlinearity of the O3 response to precursor reductions. This study highlights the effectiveness of stringent emission controls in relation to solvent utilization and coal combustion. However, unreasonable emission reduction may aggravate ozone pollution during control periods. It is suggested that emission-reduction ratios of the precursors (VOC : NOx) should be more than 2.
Niklas Illmann, Rodrigo Gastón Gibilisco, Iustinian Gabriel Bejan, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 13667–13686, https://doi.org/10.5194/acp-21-13667-2021, https://doi.org/10.5194/acp-21-13667-2021, 2021
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Within this work we determined the rate coefficients and products of the reaction of unsaturated ketones with OH radicals in an effort to complete the gaps in the knowledge needed for modelling chemistry in the atmosphere. Both substances are potentially emitted by biomass burning, industrial activities or formed in the troposphere by oxidation of terpenes. As products we identified aldehydes and ketones which in turn are known to be responsible for the transportation of NOx species.
Yangang Ren, Li Zhou, Abdelwahid Mellouki, Véronique Daële, Mahmoud Idir, Steven S. Brown, Branko Ruscic, Robert S. Paton, Max R. McGillen, and A. R. Ravishankara
Atmos. Chem. Phys., 21, 13537–13551, https://doi.org/10.5194/acp-21-13537-2021, https://doi.org/10.5194/acp-21-13537-2021, 2021
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Aromatic aldehydes are a family of compounds emitted into the atmosphere from both anthropogenic and biogenic sources that are formed from the degradation of aromatic hydrocarbons. Their atmospheric degradation may impact air quality. We report on their atmospheric degradation through reaction with NO3, which is useful to estimate their atmospheric lifetimes. We have also attempted to elucidate the mechanism of these reactions via studies of isotopic substitution and quantum chemistry.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685, https://doi.org/10.5194/acp-21-12665-2021, https://doi.org/10.5194/acp-21-12665-2021, 2021
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The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Cited articles
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Short summary
As an air pollutant, O3 is monitored photometrically to assess compliance with air quality legislation. A recent study found a 1.8% reduction in its absorption cross section, which would lead to an equivalent increase in observed O3 concentrations. We estimate this would increase the number of sites out of compliance with air quality regulations in the EU and US by 20%. We draw attention to how small changes in gas metrology impacts attainment and compliance with legal air quality standards.
As an air pollutant, O3 is monitored photometrically to assess compliance with air quality...
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