Articles | Volume 21, issue 7
https://doi.org/10.5194/acp-21-5755-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-21-5755-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
16 Apr 2021
Research article |
| 16 Apr 2021
| 16 Apr 2021
Production of HONO from NO2 uptake on illuminated TiO2 aerosol particles and following the illumination of mixed TiO2∕ammonium nitrate particles
Joanna E. Dyson
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Graham A. Boustead
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Lauren T. Fleming
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Mark Blitz
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
National Centre of Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UK
Daniel Stone
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Stephen R. Arnold
School of Earth and Environment, University of Leeds, Leeds, LS2 9JT, UK
Lisa K. Whalley
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
National Centre of Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UK
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Related authors
No articles found.
Maria P. Veláquez-García, Richard J. Pope, Steven T. Turnock, Chetan Deva, David P. Moore, Guilherme Mataveli, Steve R. Arnold, Ruth M. Doherty, and Martyn P. Chiperffield
EGUsphere, https://doi.org/10.5194/egusphere-2025-3579, https://doi.org/10.5194/egusphere-2025-3579, 2025
This preprint is open for discussion and under review for Biogeosciences (BG).
Short summary
Short summary
Incorporating fire simulation into climate models is crucial for accurately representing the interactions between fires, ecosystems, and climate, thereby enhancing climate projections. In South America, the INFERNO fire model captures active fire zones, e.g. the Amazon Arc of Deforestation, but it overestimates emissions in other areas (mainly in tree-rich ecosystems). The model errors capturing seasonal emission cycles relate to the effects of soil moisture on plant flammability and growth.
Antonio Donateo, Gianluca Pappaccogli, Federico Scoto, Maurizio Busetto, Francesca Lucia Lovisco, Natalie Brett, Douglas Keller, Brice Barret, Elsa Dieudonné, Roman Pohorsky, Andrea Baccarini, Slimane Bekki, Jean-Christophe Raut, Julia Schmale, Kathy S. Law, Steve R. Arnold, Gilberto Javier Fochesatto, William R. Simpson, and Stefano Decesari
EGUsphere, https://doi.org/10.5194/egusphere-2025-1366, https://doi.org/10.5194/egusphere-2025-1366, 2025
Short summary
Short summary
A study in Fairbanks, Alaska, measured winter aerosol fluxes on snow. Both emission and deposition occurred, with larger particles settling faster. Weather influenced dispersion and deposition, while wind-driven turbulence enhanced deposition despite stable conditions. Results show aerosol accumulation in snow impacts pollution and snowmelt. Findings help improve aerosol models and pollution studies in cold cities.
Cynthia H. Whaley, Tim Butler, Jose A. Adame, Rupal Ambulkar, Steve R. Arnold, Rebecca R. Buchholz, Benjamin Gaubert, Douglas S. Hamilton, Min Huang, Hayley Hung, Johannes W. Kaiser, Jacek W. Kaminski, Christoph Knote, Gerbrand Koren, Jean-Luc Kouassi, Meiyun Lin, Tianjia Liu, Jianmin Ma, Kasemsan Manomaiphiboon, Elisa Bergas Masso, Jessica L. McCarty, Mariano Mertens, Mark Parrington, Helene Peiro, Pallavi Saxena, Saurabh Sonwani, Vanisa Surapipith, Damaris Y. T. Tan, Wenfu Tang, Veerachai Tanpipat, Kostas Tsigaridis, Christine Wiedinmyer, Oliver Wild, Yuanyu Xie, and Paquita Zuidema
Geosci. Model Dev., 18, 3265–3309, https://doi.org/10.5194/gmd-18-3265-2025, https://doi.org/10.5194/gmd-18-3265-2025, 2025
Short summary
Short summary
The multi-model experiment design of the HTAP3 Fires project takes a multi-pollutant approach to improving our understanding of transboundary transport of wildland fire and agricultural burning emissions and their impacts. The experiments are designed with the goal of answering science policy questions related to fires. The options for the multi-model approach, including inputs, outputs, and model setup, are discussed, and the official recommendations for the project are presented.
Xinyue Shao, Yaman Liu, Xinyi Dong, Minghuai Wang, Ruochong Xu, Joel A. Thornton, Duseong S. Jo, Man Yue, Wenxiang Shen, Manish Shrivastava, Stephen R. Arnold, and Ken S. Carslaw
EGUsphere, https://doi.org/10.5194/egusphere-2025-1526, https://doi.org/10.5194/egusphere-2025-1526, 2025
Short summary
Short summary
Highly Oxygenated Organic Molecules (HOMs) are key precursors of secondary organic aerosols (SOA). Incorporating the HOMs chemical mechanism into a global climate model allows for a reasonable reproduction of observed HOM characteristics. HOM-SOA constitutes a significant fraction of global SOA, and its distribution and formation pathways exhibit strong sensitivity to uncertainties in autoxidation processes and peroxy radical branching ratios.
Roman Pohorsky, Andrea Baccarini, Natalie Brett, Brice Barret, Slimane Bekki, Gianluca Pappaccogli, Elsa Dieudonné, Brice Temime-Roussel, Barbara D'Anna, Meeta Cesler-Maloney, Antonio Donateo, Stefano Decesari, Kathy S. Law, William R. Simpson, Javier Fochesatto, Steve R. Arnold, and Julia Schmale
Atmos. Chem. Phys., 25, 3687–3715, https://doi.org/10.5194/acp-25-3687-2025, https://doi.org/10.5194/acp-25-3687-2025, 2025
Short summary
Short summary
This study presents an analysis of vertical measurements of pollution in an Alaskan city during winter. It investigates the relationship between the atmospheric structure and the layering of aerosols and trace gases. Results indicate an overall very shallow surface mixing layer. The height of this layer is strongly influenced by a local shallow wind. The study also provides information on the pollution chemical composition at different altitudes, including pollution signatures from power plants.
Brice Barret, Patrice Medina, Natalie Brett, Roman Pohorsky, Kathy S. Law, Slimane Bekki, Gilberto J. Fochesatto, Julia Schmale, Steve R. Arnold, Andrea Baccarini, Maurizio Busetto, Meeta Cesler-Maloney, Barbara D'Anna, Stefano Decesari, Jingqiu Mao, Gianluca Pappaccogli, Joel Savarino, Federico Scoto, and William R. Simpson
Atmos. Meas. Tech., 18, 1163–1184, https://doi.org/10.5194/amt-18-1163-2025, https://doi.org/10.5194/amt-18-1163-2025, 2025
Short summary
Short summary
The Fairbanks area experiences severe pollution episodes in winter because of enhanced emissions of pollutants trapped near the surface by strong temperature inversions. Low-cost sensors were deployed on board a car and a tethered balloon to measure the concentrations of gaseous pollutants (CO, O3, and NOx) in Fairbanks during winter 2022. Data calibration with reference measurements and machine learning methods enabled us to document pollution at the surface and power plant plumes aloft.
Aishah I. Shittu, Kirsty J. Pringle, Stephen R. Arnold, Richard J. Pope, Ailish M. Graham, Carly Reddington, Richard Rigby, and James B. McQuaid
Atmos. Meas. Tech., 18, 817–828, https://doi.org/10.5194/amt-18-817-2025, https://doi.org/10.5194/amt-18-817-2025, 2025
Short summary
Short summary
The study highlighted the performance of Atmotube PRO sensor particulate matter (PM) data. The result showed inter-sensor variability among the Atmotube PRO sensor data. This study showed 62.5 % of the sensors used for the study exhibited greater precision in their PM2.5 measurements. The overall performance showed that sensors passed the base testing using 1 h averaged data and that a multiple linear regression model using relative humidity values improved the performance of the PM2.5 data.
Xinyue Shao, Minghuai Wang, Xinyi Dong, Yaman Liu, Stephen R. Arnold, Leighton A. Regayre, Duseong S. Jo, Wenxiang Shen, Hao Wang, Man Yue, Jingyi Wang, Wenxin Zhang, and Ken S. Carslaw
EGUsphere, https://doi.org/10.5194/egusphere-2024-4135, https://doi.org/10.5194/egusphere-2024-4135, 2025
Short summary
Short summary
This study uses a global chemistry-climate model to investigate how new particle formation (NPF) from highly oxygenated organic molecules (HOMs) contributes to cloud condensation nuclei (CCN) in both preindustrial (PI) and present-day (PD) environments, and its impact on aerosol indirect radiative forcing. The findings highlight the crucial role of biogenic emissions in climate change, providing new insights for carbon-neutral scenarios and enhancing understanding of aerosol-cloud interactions.
Natalie Brett, Kathy S. Law, Steve R. Arnold, Javier G. Fochesatto, Jean-Christophe Raut, Tatsuo Onishi, Robert Gilliam, Kathleen Fahey, Deanna Huff, George Pouliot, Brice Barret, Elsa Dieudonné, Roman Pohorsky, Julia Schmale, Andrea Baccarini, Slimane Bekki, Gianluca Pappaccogli, Federico Scoto, Stefano Decesari, Antonio Donateo, Meeta Cesler-Maloney, William Simpson, Patrice Medina, Barbara D'Anna, Brice Temime-Roussel, Joel Savarino, Sarah Albertin, Jingqiu Mao, Becky Alexander, Allison Moon, Peter F. DeCarlo, Vanessa Selimovic, Robert Yokelson, and Ellis S. Robinson
Atmos. Chem. Phys., 25, 1063–1104, https://doi.org/10.5194/acp-25-1063-2025, https://doi.org/10.5194/acp-25-1063-2025, 2025
Short summary
Short summary
Processes influencing dispersion of local anthropogenic pollution in Arctic wintertime are investigated with Lagrangian dispersion modelling. Simulated power plant plume rise that considers temperature inversion layers improves results compared to observations (interior Alaska). Modelled surface concentrations are improved by representation of vertical mixing and emission estimates. Large increases in diesel vehicle emissions at temperatures reaching −35°C are required to reproduce observed NOx.
Alex T. Archibald, Bablu Sinha, Maria R. Russo, Emily Matthews, Freya A. Squires, N. Luke Abraham, Stephane J.-B. Bauguitte, Thomas J. Bannan, Thomas G. Bell, David Berry, Lucy J. Carpenter, Hugh Coe, Andrew Coward, Peter Edwards, Daniel Feltham, Dwayne Heard, Jim Hopkins, James Keeble, Elizabeth C. Kent, Brian A. King, Isobel R. Lawrence, James Lee, Claire R. Macintosh, Alex Megann, Bengamin I. Moat, Katie Read, Chris Reed, Malcolm J. Roberts, Reinhard Schiemann, David Schroeder, Timothy J. Smyth, Loren Temple, Navaneeth Thamban, Lisa Whalley, Simon Williams, Huihui Wu, and Mingxi Yang
Earth Syst. Sci. Data, 17, 135–164, https://doi.org/10.5194/essd-17-135-2025, https://doi.org/10.5194/essd-17-135-2025, 2025
Short summary
Short summary
Here, we present an overview of the data generated as part of the North Atlantic Climate System Integrated Study (ACSIS) programme that are available through dedicated repositories at the Centre for Environmental Data Analysis (CEDA; www.ceda.ac.uk) and the British Oceanographic Data Centre (BODC; bodc.ac.uk). The datasets described here cover the North Atlantic Ocean, the atmosphere above (it including its composition), and Arctic sea ice.
Ross J. Herbert, Alberto Sanchez-Marroquin, Daniel P. Grosvenor, Kirsty J. Pringle, Stephen R. Arnold, Benjamin J. Murray, and Kenneth S. Carslaw
Atmos. Chem. Phys., 25, 291–325, https://doi.org/10.5194/acp-25-291-2025, https://doi.org/10.5194/acp-25-291-2025, 2025
Short summary
Short summary
Aerosol particles that help form ice in clouds vary in number and type around the world and with time. However, in many weather and climate models cloud ice is not linked to aerosols that are known to nucleate ice. Here we report the first steps towards representing ice-nucleating particles within the UK Earth System Model. We conclude that in addition to ice nucleation by sea spray and mineral components of soil dust, we also need to represent ice nucleation by the organic components of soils.
Hazel Mooney, Stephen Arnold, Benjamin Silver, Piers Forster, and Catherine Scott
EGUsphere, https://doi.org/10.5194/egusphere-2024-3895, https://doi.org/10.5194/egusphere-2024-3895, 2025
Short summary
Short summary
We simulate the potential changes in natural emissions of volatile gases from the land surface in the UK following afforestation from present-day woodland cover of 13 % to 19 % by 2050. We estimate present-day annual UK emissions of isoprene at 40 kt yr-1 and total monoterpenes at 46 kt yr-1, but emissions from afforested experiments show between a 4 % decrease and 131 % increase in emissions, explained by the variation in emissions activity between and within needleleaf and broadleaf trees.
Amna Ijaz, Brice Temime-Roussel, Benjamin Chazeau, Sarah Albertin, Stephen R. Arnold, Brice Barrett, Slimane Bekki, Natalie Brett, Meeta Cesler-Maloney, Elsa Dieudonne, Kayane K. Dingilian, Javier G. Fochesatto, Jingqiu Mao, Allison Moon, Joel Savarino, William Simpson, Rodney J. Weber, Kathy S. Law, and Barbara D'Anna
EGUsphere, https://doi.org/10.5194/egusphere-2024-3789, https://doi.org/10.5194/egusphere-2024-3789, 2024
Short summary
Short summary
Fairbanks is among the most polluted cities with the highest particulate matter (PM) levels in the US during winters. Highly time-resolved measurements of the sub-micron PM elucidated residential heating with wood and oil and hydrocarbon-like organics from traffic, as well as sulphur-containing organic aerosol, to be the key pollution sources. Remarkable differences existed between complementary instruments, warranting the deployment of multiple tools at sites with wide-ranging influences.
Xinyue Shao, Minghuai Wang, Xinyi Dong, Yaman Liu, Wenxiang Shen, Stephen R. Arnold, Leighton A. Regayre, Meinrat O. Andreae, Mira L. Pöhlker, Duseong S. Jo, Man Yue, and Ken S. Carslaw
Atmos. Chem. Phys., 24, 11365–11389, https://doi.org/10.5194/acp-24-11365-2024, https://doi.org/10.5194/acp-24-11365-2024, 2024
Short summary
Short summary
Highly oxygenated organic molecules (HOMs) play an important role in atmospheric new particle formation (NPF). By semi-explicitly coupling the chemical mechanism of HOMs and a comprehensive nucleation scheme in a global climate model, the updated model shows better agreement with measurements of nucleation rate, growth rate, and NPF event frequency. Our results reveal that HOM-driven NPF leads to a considerable increase in particle and cloud condensation nuclei burden globally.
Victoria A. Flood, Kimberly Strong, Cynthia H. Whaley, Kaley A. Walker, Thomas Blumenstock, James W. Hannigan, Johan Mellqvist, Justus Notholt, Mathias Palm, Amelie N. Röhling, Stephen Arnold, Stephen Beagley, Rong-You Chien, Jesper Christensen, Makoto Deushi, Srdjan Dobricic, Xinyi Dong, Joshua S. Fu, Michael Gauss, Wanmin Gong, Joakim Langner, Kathy S. Law, Louis Marelle, Tatsuo Onishi, Naga Oshima, David A. Plummer, Luca Pozzoli, Jean-Christophe Raut, Manu A. Thomas, Svetlana Tsyro, and Steven Turnock
Atmos. Chem. Phys., 24, 1079–1118, https://doi.org/10.5194/acp-24-1079-2024, https://doi.org/10.5194/acp-24-1079-2024, 2024
Short summary
Short summary
It is important to understand the composition of the Arctic atmosphere and how it is changing. Atmospheric models provide simulations that can inform policy. This study examines simulations of CH4, CO, and O3 by 11 models. Model performance is assessed by comparing results matched in space and time to measurements from five high-latitude ground-based infrared spectrometers. This work finds that models generally underpredict the concentrations of these gases in the Arctic troposphere.
Robert Woodward-Massey, Roberto Sommariva, Lisa K. Whalley, Danny R. Cryer, Trevor Ingham, William J. Bloss, Stephen M. Ball, Sam Cox, James D. Lee, Chris P. Reed, Leigh R. Crilley, Louisa J. Kramer, Brian J. Bandy, Grant L. Forster, Claire E. Reeves, Paul S. Monks, and Dwayne E. Heard
Atmos. Chem. Phys., 23, 14393–14424, https://doi.org/10.5194/acp-23-14393-2023, https://doi.org/10.5194/acp-23-14393-2023, 2023
Short summary
Short summary
Measurements of OH, HO2 and RO2 radicals and also OH reactivity were made at a UK coastal site and compared to calculations from a constrained box model utilising the Master Chemical Mechanism. The model agreement displayed a strong dependence on the NO concentration. An experimental budget analysis for OH, HO2, RO2 and total ROx demonstrated significant imbalances between HO2 and RO2 production rates. Ozone production rates were calculated from measured radicals and compared to modelled values.
Richard J. Pope, Brian J. Kerridge, Martyn P. Chipperfield, Richard Siddans, Barry G. Latter, Lucy J. Ventress, Matilda A. Pimlott, Wuhu Feng, Edward Comyn-Platt, Garry D. Hayman, Stephen R. Arnold, and Ailish M. Graham
Atmos. Chem. Phys., 23, 13235–13253, https://doi.org/10.5194/acp-23-13235-2023, https://doi.org/10.5194/acp-23-13235-2023, 2023
Short summary
Short summary
In the summer of 2018, Europe experienced several persistent large-scale ozone (O3) pollution episodes. Satellite tropospheric O3 and surface O3 data recorded substantial enhancements in 2018 relative to other years. Targeted model simulations showed that meteorological processes and emissions controlled the elevated surface O3, while mid-tropospheric O3 enhancements were dominated by stratospheric O3 intrusion and advection of North Atlantic O3-rich air masses into Europe.
Frank A. F. Winiberg, William J. Warman, Charlotte A. Brumby, Graham Boustead, Iustinian G. Bejan, Thomas H. Speak, Dwayne E. Heard, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 16, 4375–4390, https://doi.org/10.5194/amt-16-4375-2023, https://doi.org/10.5194/amt-16-4375-2023, 2023
Short summary
Short summary
OH and HO2 are key reactive intermediates in the Earth's atmosphere. Accurate measurements in either the field or simulation chambers provide a good test for chemical mechanisms. Fluorescence techniques have the appropriate sensitivity for detection but require calibration. This paper compares different methods of calibration and specifically how calibration factors vary across a temperature range relevant to atmospheric and chamber determinations.
Joanna E. Dyson, Lisa K. Whalley, Eloise J. Slater, Robert Woodward-Massey, Chunxiang Ye, James D. Lee, Freya Squires, James R. Hopkins, Rachel E. Dunmore, Marvin Shaw, Jacqueline F. Hamilton, Alastair C. Lewis, Stephen D. Worrall, Asan Bacak, Archit Mehra, Thomas J. Bannan, Hugh Coe, Carl J. Percival, Bin Ouyang, C. Nicholas Hewitt, Roderic L. Jones, Leigh R. Crilley, Louisa J. Kramer, W. Joe F. Acton, William J. Bloss, Supattarachai Saksakulkrai, Jingsha Xu, Zongbo Shi, Roy M. Harrison, Simone Kotthaus, Sue Grimmond, Yele Sun, Weiqi Xu, Siyao Yue, Lianfang Wei, Pingqing Fu, Xinming Wang, Stephen R. Arnold, and Dwayne E. Heard
Atmos. Chem. Phys., 23, 5679–5697, https://doi.org/10.5194/acp-23-5679-2023, https://doi.org/10.5194/acp-23-5679-2023, 2023
Short summary
Short summary
The hydroxyl (OH) and closely coupled hydroperoxyl (HO2) radicals are vital for their role in the removal of atmospheric pollutants. In less polluted regions, atmospheric models over-predict HO2 concentrations. In this modelling study, the impact of heterogeneous uptake of HO2 onto aerosol surfaces on radical concentrations and the ozone production regime in Beijing in the summertime is investigated, and the implications for emissions policies across China are considered.
Cynthia H. Whaley, Kathy S. Law, Jens Liengaard Hjorth, Henrik Skov, Stephen R. Arnold, Joakim Langner, Jakob Boyd Pernov, Garance Bergeron, Ilann Bourgeois, Jesper H. Christensen, Rong-You Chien, Makoto Deushi, Xinyi Dong, Peter Effertz, Gregory Faluvegi, Mark Flanner, Joshua S. Fu, Michael Gauss, Greg Huey, Ulas Im, Rigel Kivi, Louis Marelle, Tatsuo Onishi, Naga Oshima, Irina Petropavlovskikh, Jeff Peischl, David A. Plummer, Luca Pozzoli, Jean-Christophe Raut, Tom Ryerson, Ragnhild Skeie, Sverre Solberg, Manu A. Thomas, Chelsea Thompson, Kostas Tsigaridis, Svetlana Tsyro, Steven T. Turnock, Knut von Salzen, and David W. Tarasick
Atmos. Chem. Phys., 23, 637–661, https://doi.org/10.5194/acp-23-637-2023, https://doi.org/10.5194/acp-23-637-2023, 2023
Short summary
Short summary
This study summarizes recent research on ozone in the Arctic, a sensitive and rapidly warming region. We find that the seasonal cycles of near-surface atmospheric ozone are variable depending on whether they are near the coast, inland, or at high altitude. Several global model simulations were evaluated, and we found that because models lack some of the ozone chemistry that is important for the coastal Arctic locations, they do not accurately simulate ozone there.
Simone T. Andersen, Beth S. Nelson, Katie A. Read, Shalini Punjabi, Luis Neves, Matthew J. Rowlinson, James Hopkins, Tomás Sherwen, Lisa K. Whalley, James D. Lee, and Lucy J. Carpenter
Atmos. Chem. Phys., 22, 15747–15765, https://doi.org/10.5194/acp-22-15747-2022, https://doi.org/10.5194/acp-22-15747-2022, 2022
Short summary
Short summary
The cycling of NO and NO2 is important to understand to be able to predict O3 concentrations in the atmosphere. We have used long-term measurements from the Cape Verde Atmospheric Observatory together with model outputs to investigate the cycling of nitrogen oxide (NO) and nitrogen dioxide (NO2) in very clean marine air. This study shows that we understand the processes occurring in very clean air, but with small amounts of pollution in the air, known chemistry cannot explain what is observed.
Matilda A. Pimlott, Richard J. Pope, Brian J. Kerridge, Barry G. Latter, Diane S. Knappett, Dwayne E. Heard, Lucy J. Ventress, Richard Siddans, Wuhu Feng, and Martyn P. Chipperfield
Atmos. Chem. Phys., 22, 10467–10488, https://doi.org/10.5194/acp-22-10467-2022, https://doi.org/10.5194/acp-22-10467-2022, 2022
Short summary
Short summary
We present a new method to derive global information of the hydroxyl radical (OH), an important atmospheric oxidant. OH controls the lifetime of trace gases important to air quality and climate. We use satellite observations of ozone, carbon monoxide, methane and water vapour in a simple expression to derive OH around 3–4 km altitude. The derived OH compares well to model and aircraft OH data. We then apply the method to 10 years of satellite data to study the inter-annual variability of OH.
Marios Panagi, Roberto Sommariva, Zoë L. Fleming, Paul S. Monks, Gongda Lu, Eloise A. Marais, James R. Hopkins, Alastair C. Lewis, Qiang Zhang, James D. Lee, Freya A. Squires, Lisa K. Whalley, Eloise J. Slater, Dwayne E. Heard, Robert Woodward-Massey, Chunxiang Ye, and Joshua D. Vande Hey
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-379, https://doi.org/10.5194/acp-2022-379, 2022
Revised manuscript not accepted
Short summary
Short summary
A dispersion model and a box model were combined to investigate the evolution of VOCs in Beijing once they are emitted from anthropogenic sources. It was determined that during the winter time the VOC concentrations in Beijing are driven predominantly by sources within Beijing and by a combination of transport and chemistry during the summer. Furthermore, the results in the paper highlight the need for a season specific policy.
Zara S. Mir, Matthew Jamieson, Nicholas R. Greenall, Paul W. Seakins, Mark A. Blitz, and Daniel Stone
Atmos. Meas. Tech., 15, 2875–2887, https://doi.org/10.5194/amt-15-2875-2022, https://doi.org/10.5194/amt-15-2875-2022, 2022
Short summary
Short summary
In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. This work has significance for the identification and measurement of reactive trace species in complex systems.
Cynthia H. Whaley, Rashed Mahmood, Knut von Salzen, Barbara Winter, Sabine Eckhardt, Stephen Arnold, Stephen Beagley, Silvia Becagli, Rong-You Chien, Jesper Christensen, Sujay Manish Damani, Xinyi Dong, Konstantinos Eleftheriadis, Nikolaos Evangeliou, Gregory Faluvegi, Mark Flanner, Joshua S. Fu, Michael Gauss, Fabio Giardi, Wanmin Gong, Jens Liengaard Hjorth, Lin Huang, Ulas Im, Yugo Kanaya, Srinath Krishnan, Zbigniew Klimont, Thomas Kühn, Joakim Langner, Kathy S. Law, Louis Marelle, Andreas Massling, Dirk Olivié, Tatsuo Onishi, Naga Oshima, Yiran Peng, David A. Plummer, Olga Popovicheva, Luca Pozzoli, Jean-Christophe Raut, Maria Sand, Laura N. Saunders, Julia Schmale, Sangeeta Sharma, Ragnhild Bieltvedt Skeie, Henrik Skov, Fumikazu Taketani, Manu A. Thomas, Rita Traversi, Kostas Tsigaridis, Svetlana Tsyro, Steven Turnock, Vito Vitale, Kaley A. Walker, Minqi Wang, Duncan Watson-Parris, and Tahya Weiss-Gibbons
Atmos. Chem. Phys., 22, 5775–5828, https://doi.org/10.5194/acp-22-5775-2022, https://doi.org/10.5194/acp-22-5775-2022, 2022
Short summary
Short summary
Air pollutants, like ozone and soot, play a role in both global warming and air quality. Atmospheric models are often used to provide information to policy makers about current and future conditions under different emissions scenarios. In order to have confidence in those simulations, in this study we compare simulated air pollution from 18 state-of-the-art atmospheric models to measured air pollution in order to assess how well the models perform.
Hannah Walker, Daniel Stone, Trevor Ingham, Sina Hackenberg, Danny Cryer, Shalini Punjabi, Katie Read, James Lee, Lisa Whalley, Dominick V. Spracklen, Lucy J. Carpenter, Steve R. Arnold, and Dwayne E. Heard
Atmos. Chem. Phys., 22, 5535–5557, https://doi.org/10.5194/acp-22-5535-2022, https://doi.org/10.5194/acp-22-5535-2022, 2022
Short summary
Short summary
Glyoxal is a ubiquitous reactive organic compound in the atmosphere, which may form organic aerosol and impact the atmosphere's oxidising capacity. There are limited measurements of glyoxal's abundance in the remote marine atmosphere. We made new measurements of glyoxal using a highly sensitive technique over two 4-week periods in the tropical Atlantic atmosphere. We show that daytime measurements are mostly consistent with our chemical understanding but a potential missing source at night.
Robert Woodward-Massey, Roberto Sommariva, Lisa K. Whalley, Danny R. Cryer, Trevor Ingham, William J1 Bloss, Sam Cox, James D. Lee, Chris P. Reed, Leigh R. Crilley, Louisa J. Kramer, Brian J. Bandy, Grant L. Forster, Claire E. Reeves, Paul S. Monks, and Dwayne E. Heard
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-207, https://doi.org/10.5194/acp-2022-207, 2022
Preprint withdrawn
Short summary
Short summary
We measured radicals (OH, HO2, RO2) and OH reactivity at a UK coastal site and compared our observations to the predictions of an MCMv3.3.1 box model. We find variable agreement between measured and modelled radical concentrations and OH reactivity, where the levels of agreement for individual species display strong dependences on NO concentrations. The most substantial disagreement is found for RO2 at high NO (> 1 ppbv), when RO2 levels are underpredicted by a factor of ~10–30.
Richard J. Pope, Rebecca Kelly, Eloise A. Marais, Ailish M. Graham, Chris Wilson, Jeremy J. Harrison, Savio J. A. Moniz, Mohamed Ghalaieny, Steve R. Arnold, and Martyn P. Chipperfield
Atmos. Chem. Phys., 22, 4323–4338, https://doi.org/10.5194/acp-22-4323-2022, https://doi.org/10.5194/acp-22-4323-2022, 2022
Short summary
Short summary
Nitrogen oxides (NOx) are potent air pollutants which directly impact on human health. In this study, we use satellite nitrogen dioxide (NO2) data to evaluate the spatial distribution and temporal evolution of the UK official NOx emissions inventory, with reasonable agreement. We also derived satellite-based NOx emissions for several UK cities. In the case of London and Birmingham, the NAEI NOx emissions are potentially too low by >50%.
Jessica L. McCarty, Juha Aalto, Ville-Veikko Paunu, Steve R. Arnold, Sabine Eckhardt, Zbigniew Klimont, Justin J. Fain, Nikolaos Evangeliou, Ari Venäläinen, Nadezhda M. Tchebakova, Elena I. Parfenova, Kaarle Kupiainen, Amber J. Soja, Lin Huang, and Simon Wilson
Biogeosciences, 18, 5053–5083, https://doi.org/10.5194/bg-18-5053-2021, https://doi.org/10.5194/bg-18-5053-2021, 2021
Short summary
Short summary
Fires, including extreme fire seasons, and fire emissions are more common in the Arctic. A review and synthesis of current scientific literature find climate change and human activity in the north are fuelling an emerging Arctic fire regime, causing more black carbon and methane emissions within the Arctic. Uncertainties persist in characterizing future fire landscapes, and thus emissions, as well as policy-relevant challenges in understanding, monitoring, and managing Arctic fire regimes.
Beth S. Nelson, Gareth J. Stewart, Will S. Drysdale, Mike J. Newland, Adam R. Vaughan, Rachel E. Dunmore, Pete M. Edwards, Alastair C. Lewis, Jacqueline F. Hamilton, W. Joe Acton, C. Nicholas Hewitt, Leigh R. Crilley, Mohammed S. Alam, Ülkü A. Şahin, David C. S. Beddows, William J. Bloss, Eloise Slater, Lisa K. Whalley, Dwayne E. Heard, James M. Cash, Ben Langford, Eiko Nemitz, Roberto Sommariva, Sam Cox, Shivani, Ranu Gadi, Bhola R. Gurjar, James R. Hopkins, Andrew R. Rickard, and James D. Lee
Atmos. Chem. Phys., 21, 13609–13630, https://doi.org/10.5194/acp-21-13609-2021, https://doi.org/10.5194/acp-21-13609-2021, 2021
Short summary
Short summary
Ozone production at an urban site in Delhi is sensitive to volatile organic compound (VOC) concentrations, particularly those of the aromatic, monoterpene, and alkene VOC classes. The change in ozone production by varying atmospheric pollutants according to their sources, as defined in an emissions inventory, is investigated. The study suggests that reducing road transport emissions alone does not reduce reactive VOCs in the atmosphere enough to perturb an increase in ozone production.
Claire E. Reeves, Graham P. Mills, Lisa K. Whalley, W. Joe F. Acton, William J. Bloss, Leigh R. Crilley, Sue Grimmond, Dwayne E. Heard, C. Nicholas Hewitt, James R. Hopkins, Simone Kotthaus, Louisa J. Kramer, Roderic L. Jones, James D. Lee, Yanhui Liu, Bin Ouyang, Eloise Slater, Freya Squires, Xinming Wang, Robert Woodward-Massey, and Chunxiang Ye
Atmos. Chem. Phys., 21, 6315–6330, https://doi.org/10.5194/acp-21-6315-2021, https://doi.org/10.5194/acp-21-6315-2021, 2021
Short summary
Short summary
The impact of isoprene on atmospheric chemistry is dependent on how its oxidation products interact with other pollutants, specifically nitrogen oxides. Such interactions can lead to isoprene nitrates. We made measurements of the concentrations of individual isoprene nitrate isomers in Beijing and used a model to test current understanding of their chemistry. We highlight areas of uncertainty in understanding, in particular the chemistry following oxidation of isoprene by the nitrate radical.
Thomas Thorp, Stephen R. Arnold, Richard J. Pope, Dominick V. Spracklen, Luke Conibear, Christoph Knote, Mikhail Arshinov, Boris Belan, Eija Asmi, Tuomas Laurila, Andrei I. Skorokhod, Tuomo Nieminen, and Tuukka Petäjä
Atmos. Chem. Phys., 21, 4677–4697, https://doi.org/10.5194/acp-21-4677-2021, https://doi.org/10.5194/acp-21-4677-2021, 2021
Short summary
Short summary
We compare modelled near-surface pollutants with surface and satellite observations to better understand the controls on the regional concentrations of pollution in western Siberia for late spring and summer in 2011. We find two commonly used emission inventories underestimate human emissions when compared to observations. Transport emissions are the main source of pollutants within the region during this period, whilst fire emissions peak during June and are only significant south of 60° N.
Lisa K. Whalley, Eloise J. Slater, Robert Woodward-Massey, Chunxiang Ye, James D. Lee, Freya Squires, James R. Hopkins, Rachel E. Dunmore, Marvin Shaw, Jacqueline F. Hamilton, Alastair C. Lewis, Archit Mehra, Stephen D. Worrall, Asan Bacak, Thomas J. Bannan, Hugh Coe, Carl J. Percival, Bin Ouyang, Roderic L. Jones, Leigh R. Crilley, Louisa J. Kramer, William J. Bloss, Tuan Vu, Simone Kotthaus, Sue Grimmond, Yele Sun, Weiqi Xu, Siyao Yue, Lujie Ren, W. Joe F. Acton, C. Nicholas Hewitt, Xinming Wang, Pingqing Fu, and Dwayne E. Heard
Atmos. Chem. Phys., 21, 2125–2147, https://doi.org/10.5194/acp-21-2125-2021, https://doi.org/10.5194/acp-21-2125-2021, 2021
Short summary
Short summary
To understand how emission controls will impact ozone, an understanding of the sources and sinks of OH and the chemical cycling between peroxy radicals is needed. This paper presents measurements of OH, HO2 and total RO2 taken in central Beijing. The radical observations are compared to a detailed chemistry model, which shows that under low NO conditions, there is a missing OH source. Under high NOx conditions, the model under-predicts RO2 and impacts our ability to model ozone.
Mike J. Newland, Daniel J. Bryant, Rachel E. Dunmore, Thomas J. Bannan, W. Joe F. Acton, Ben Langford, James R. Hopkins, Freya A. Squires, William Dixon, William S. Drysdale, Peter D. Ivatt, Mathew J. Evans, Peter M. Edwards, Lisa K. Whalley, Dwayne E. Heard, Eloise J. Slater, Robert Woodward-Massey, Chunxiang Ye, Archit Mehra, Stephen D. Worrall, Asan Bacak, Hugh Coe, Carl J. Percival, C. Nicholas Hewitt, James D. Lee, Tianqu Cui, Jason D. Surratt, Xinming Wang, Alastair C. Lewis, Andrew R. Rickard, and Jacqueline F. Hamilton
Atmos. Chem. Phys., 21, 1613–1625, https://doi.org/10.5194/acp-21-1613-2021, https://doi.org/10.5194/acp-21-1613-2021, 2021
Short summary
Short summary
We report the formation of secondary pollutants in the urban megacity of Beijing that are typically associated with remote regions such as rainforests. This is caused by extremely low levels of nitric oxide (NO), typically expected to be high in urban areas, observed in the afternoon. This work has significant implications for how we understand atmospheric chemistry in the urban environment and thus for how to implement effective policies to improve urban air quality.
Huan Song, Xiaorui Chen, Keding Lu, Qi Zou, Zhaofeng Tan, Hendrik Fuchs, Alfred Wiedensohler, Daniel R. Moon, Dwayne E. Heard, María-Teresa Baeza-Romero, Mei Zheng, Andreas Wahner, Astrid Kiendler-Scharr, and Yuanhang Zhang
Atmos. Chem. Phys., 20, 15835–15850, https://doi.org/10.5194/acp-20-15835-2020, https://doi.org/10.5194/acp-20-15835-2020, 2020
Short summary
Short summary
Accurate calculation of the HO2 uptake coefficient is one of the key parameters to quantify the co-reduction of both aerosol and ozone pollution. We modelled various lab measurements of γHO2 based on a gas-liquid phase kinetic model and developed a state-of-the-art parameterized equation. Based on a dataset from a comprehensive field campaign in the North China Plain, we proposed that the determination of the heterogeneous uptake process for HO2 should be included in future field campaigns.
Eloise J. Slater, Lisa K. Whalley, Robert Woodward-Massey, Chunxiang Ye, James D. Lee, Freya Squires, James R. Hopkins, Rachel E. Dunmore, Marvin Shaw, Jacqueline F. Hamilton, Alastair C. Lewis, Leigh R. Crilley, Louisa Kramer, William Bloss, Tuan Vu, Yele Sun, Weiqi Xu, Siyao Yue, Lujie Ren, W. Joe F. Acton, C. Nicholas Hewitt, Xinming Wang, Pingqing Fu, and Dwayne E. Heard
Atmos. Chem. Phys., 20, 14847–14871, https://doi.org/10.5194/acp-20-14847-2020, https://doi.org/10.5194/acp-20-14847-2020, 2020
Short summary
Short summary
The paper details atmospheric chemistry in a megacity (Beijing), focussing on radicals which mediate the formation of secondary pollutants such as ozone and particles. Highly polluted conditions were experienced, including the highest ever levels of nitric oxide (NO), with simultaneous radical measurements. Radical concentrations were large during "haze" events, demonstrating active photochemistry. Modelling showed that our understanding of the chemistry at high NOx levels is incomplete.
Ben Silver, Luke Conibear, Carly L. Reddington, Christoph Knote, Steve R. Arnold, and Dominick V. Spracklen
Atmos. Chem. Phys., 20, 11683–11695, https://doi.org/10.5194/acp-20-11683-2020, https://doi.org/10.5194/acp-20-11683-2020, 2020
Short summary
Short summary
China suffers from serious air pollution, which is thought to cause millions of early deaths each year. Measurements on the ground show that overall air quality is improving. Air quality is also affected by weather conditions, which can vary from year to year. We conduct computer simulations to show it is the reduction of the amount of pollution emitted, rather than weather conditions, which caused air quality to improve during 2015–2017. We then estimate that 150 000 fewer people die early.
Matthew J. Rowlinson, Alexandru Rap, Douglas S. Hamilton, Richard J. Pope, Stijn Hantson, Steve R. Arnold, Jed O. Kaplan, Almut Arneth, Martyn P. Chipperfield, Piers M. Forster, and Lars Nieradzik
Atmos. Chem. Phys., 20, 10937–10951, https://doi.org/10.5194/acp-20-10937-2020, https://doi.org/10.5194/acp-20-10937-2020, 2020
Short summary
Short summary
Tropospheric ozone is an important greenhouse gas which contributes to anthropogenic climate change; however, the effect of human emissions is uncertain because pre-industrial ozone concentrations are not well understood. We use revised inventories of pre-industrial natural emissions to estimate the human contribution to changes in tropospheric ozone. We find that tropospheric ozone radiative forcing is up to 34 % lower when using improved pre-industrial biomass burning and vegetation emissions.
Thomas R. Lewis, Juan Carlos Gómez Martín, Mark A. Blitz, Carlos A. Cuevas, John M. C. Plane, and Alfonso Saiz-Lopez
Atmos. Chem. Phys., 20, 10865–10887, https://doi.org/10.5194/acp-20-10865-2020, https://doi.org/10.5194/acp-20-10865-2020, 2020
Short summary
Short summary
Iodine-bearing gasses emitted from the sea surface are chemically processed in the atmosphere, leading to iodine accumulation in aerosol and transport to continental ecosystems. Such processing involves light-induced break-up of large, particle-forming iodine oxides into smaller, ozone-depleting molecules. We combine experiments and theory to report the photolysis efficiency of iodine oxides required to assess the impact of iodine on ozone depletion and particle formation.
Cited articles
Alicke, B., Platt, U., and Stutz, J.: Impact of nitrous acid photolysis on
the total hydroxyl radical budget during the Limitation of Oxidant
Production/Pianura Padana Produzione di Ozono study in Milan, J. Geophys.
Res.-Atmos., 107, 8196, https://doi.org/10.1029/2000JD000075, 2002.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004.
Beckers, H., Zeng, X., and Willner, H.: Intermediates involved in the
oxidation of nitrogen monoxide: Photochemistry of the
cis-N2O2⋅ O2 complex and of sym-N2O4 in
Solid Ne Matrices, Chemistry, 16, 1506–1520,
https://doi.org/10.1002/chem.200902406, 2010.
Bedjanian, Y. and El Zein, A.: Interaction of NO2 with TiO2
Surface Under UV Irradiation: Products Study, J. Phys. Chem. A, 116,
1758–1764, https://doi.org/10.1021/jp210078b, 2012.
Boustead, G. A.: Measurement of nitrous acid production from aerosol
surfaces using Photo-Fragmentation Laser-Induced Fluorescence, School of
Chemistry, University of Leeds, 2019.
Bröske, R., Kleffmann, J., and Wiesen, P.: Heterogeneous conversion of NO2 on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO) in the atmosphere?, Atmos. Chem. Phys., 3, 469–474, https://doi.org/10.5194/acp-3-469-2003, 2003.
Cantrell, C., Zimmer, A., and Tyndall, G. S.: Adsorption cross sections for
water vapor from 183 to 193 nm, Geophys. Res. Lett., 24, 2195–2198,
https://doi.org/10.1029/97GL02100, 1997.
Carpenter, L. J., Fleming, Z. L., Read, K. A., Lee, J. D., Moller, S. J.,
Hopkins, J. R., Purvis, R. M., Lewis, A. C., Müller, K., Heinold, B.,
Herrmann, H., Fomba, K. W., van Pinxteren, D., Müller, C., Tegen, I.,
Wiedensohler, A., Müller, T., Niedermeier, N., Achterberg, E. P., Patey,
M. D., Kozlova, E. A., Heimann, M., Heard, D. E., Plane, J. M. C., Mahajan,
A., Oetjen, H., Ingham, T., Stone, D., Whalley, L. K., Evans, M. J.,
Pilling, M. J., Leigh, R. J., Monks, P. S., Karunaharan, A., Vaughan, S.,
Arnold, S. R., Tschritter, J., Pöhler, D., Frieß, U., Holla, R.,
Mendes, L. M., Lopez, H., Faria, B., Manning, A. J., and Wallace, D. W. R.:
Seasonal characteristics of tropical marine boundary layer air measured at
the Cape Verde Atmospheric Observatory, J. Atmos. Chem.,
67, 87–140, https://doi.org/10.1007/s10874-011-9206-1, 2010.
Chen, H., Nanayakkara, C. E., and Grassian, V. H.: Titanium dioxide
photocatalysis in atmospheric chemistry, Chem. Rev., 112, 5919–5948,
https://doi.org/10.1021/cr3002092, 2012.
Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: Thermodynamic model of
the system H+- NH
Crilley, L. R., Kramer, L. J., Ouyang, B., Duan, J., Zhang, W., Tong, S., Ge, M., Tang, K., Qin, M., Xie, P., Shaw, M. D., Lewis, A. C., Mehra, A., Bannan, T. J., Worrall, S. D., Priestley, M., Bacak, A., Coe, H., Allan, J., Percival, C. J., Popoola, O. A. M., Jones, R. L., and Bloss, W. J.: Intercomparison of nitrous acid (HONO) measurement techniques in a megacity (Beijing), Atmos. Meas. Tech., 12, 6449–6463, https://doi.org/10.5194/amt-12-6449-2019, 2019.
de Jesus Madeiros, D. and Pimentel, A. S.: New insights in the atmospheric
HONO formation: new pathways for N2O4 isomerisaton and NO2
dimerisation in the presence of water, J. Phys. Chem. A, 115, 6357–6365,
https://doi.org/10.1021/jp1123585, 2011.
Dupart, Y., Fine, L., D'Anna, B., and George, C.: Heterogeneous uptake of
NO2 on Arizona Test Dust under UV-A irradiation: an aerosol flow tube
study, Aeolian Res., 15, 45–51,
https://doi.org/10.1016/j.aeolia.2013.10.001, 2014.
El Zein, A. and Bedjanian, Y.: Reactive Uptake of HONO to TiO2
Surface: “Dark” Reaction, J. Phys. Chem. A, 116, 3665–3672,
https://doi.org/10.1021/jp300859w, 2012a.
El Zein, A. and Bedjanian, Y.: Interaction of NO2 with TiO2 surface under UV irradiation: measurements of the uptake coefficient, Atmos. Chem. Phys., 12, 1013–1020, https://doi.org/10.5194/acp-12-1013-2012, 2012b.
El Zein, A., Bedjanian, Y., and Romanias, M. N.: Kinetics and products of
HONO interaction with TiO2 surface under UV irradiation, Atmos.
Environ., 67, 203–210, https://doi.org/10.1016/j.atmosenv.2012.11.016, 2013.
Fateley, W. G., Bent, H. A., and Crawford Jr., B.: Infrared spectra of the
frozen oxides of nitrogen, J. Chem. Phys., 31, 204–217,
https://doi.org/10.1063/1.1730296, 1959.
Finlayson-Pitts, B. J., Wingen, L. M., Summer, A. L., Syomin, D., and
Ramazan, K. A.: The heterogeneous hydrolysis of NO2 in laboratory
systems in outdoor and indoor atmospheres: An intergrated mechanism,
Phys. Chem. Phys. Chem, 5, 223–242, https://doi.org/10.1039/b208564j, 2003.
Forney, D., Thompson, W. E., and Jacox, M. E.: The vibrational spectra of
molecular ions isolated in solid neon. XI. NO
Gandolfo, A., Bartolomei, V., Gomez Alvarez, E., Tlili, S., Gligorovski, S.,
Kleffmann, J., and Wortham, H.: The effectiveness of indoor photocatalytic
paints on NOx and HONO levels, Appl. Catal. B-Environ., 166–167,
84–90, https://doi.org/10.1016/j.apcatb.2014.11.011, 2015.
Gandolfo, A., Rouyer, L., Wortham, H., and Gligorovski, S.: The influence of
wall temperature on NO2 removal and HONO levels released by indoor
photocatalytic paints, Appl. Catal. B-Environ., 209, 429–436,
https://doi.org/10.1016/j.apcatb.2017.03.021, 2017.
George, C., Strekowski, R. S., Kleffmann, J., Stemmler, K., and Ammann, M.:
Photoenhanced uptake of gaseous NO2 on solid organic compounds: a
photochemical source of HONO?, Faraday Discuss., 130, 195–210,
https://doi.org/10.1039/b417888m, 2005.
George, I. J., Matthews, P. S. J., Whalley, L. K., Brooks, B., Goddard, A.,
Baeza-Romero, M., and Heard, D. E.: Measurements of uptake coefficients for
heterogeneous loss of HO2 onto submicron inorganic salt aerosols,
Phys. Chem. Chem. Phys., 15, 12829–12845,
https://doi.org/10.1039/c3cp51831k, 2013.
Ginoux, P., Chin, M., Tegen, I., Prospero, J. M., Holben, B., Dubovik, O.,
and Lin, S. J.: Sources and distributions of dust aerosols simulated with
the GOCART model, J. Geophys. Res.-Atmos., 106, 20255–20273,
https://doi.org/10.1029/2000JD000053, 2001.
Givan, A. and Loewenschuss, A.: Fourier transform infrared and Raman
studies on solid nitrogen dioxide: Temperature cycling of ordered,
disordered, and multicomponent layers, J. Chem. Phys., 90,
6135–6142, https://doi.org/10.1063/1.456379, 1989a.
Givan, A. and Loewenschuss, A.: On the intermolecularity or
intramolecularity of nitrosonium nitrate formation in thin films of nitrogen
dioxide: A Fourier transform infrared study, J. Chem.
Phys., 91, 5126–5127, https://doi.org/10.1063/1.457609, 1989b.
Givan, A. and Loewenschuss, A.: Fourier transform infrared study of
amorphous N2O4 solid: Destabilization with inert impurities,
J. Chem. Phys., 94, 7562–7563,
https://doi.org/10.1063/1.460192, 1991.
Goodman, A. L., Bernard, E. T., and Grassian, V. H.: Spectroscopic study of
nitric acid and water adsorption on oxide particles: enhanced nitric acid
uptake kinetics in the presence of adsorbed water, J. Phys. Chem. A, 105,
6443–6457, https://doi.org/10.1021/jp0037221, 2001.
Gustafsson, R. J., Orlov, A., Griffiths, P. T., Cox, R. A., and Lambert, R.
M.: Reduction of NO2 to nitrous acid on illuminated titanium dioxide
aerosol surfaces: implications for photocatalysis and atmospheric chemistry,
Chem. Commun., 37, 3936–3938, https://doi.org/10.1039/b609005b, 2006.
Hanisch, F. and Crowley, J. N.: Ozone decomposition on Saharan dust: an experimental investigation, Atmos. Chem. Phys., 3, 119–130, https://doi.org/10.5194/acp-3-119-2003, 2003.
Harrison, R. M., Peak, J. D., and Collins, G. M.: Tropospheric cycle of
nitrous acid, J. Geophys. Res.-Atmos., 101, 14429–14439,
https://doi.org/10.1029/96JD00341, 1996.
Heard, D. E.: Atmospheric field measurements of the hydroxyl radical using
Laser-Induced Fluorescence spectroscopy, Annu. Rev. Phys. Chem., 57,
191–216, https://doi.org/10.1146/annurev.physchem.57.032905.104516, 2006.
Jeong, M.-G., Park, E. J., Seo, H. O., Kim, K.-D., Kim, Y. D., and Lim, D.
C.: Humidity effect on photocatalytic activity of TiO2 and regeneration
of deactivated photocatalysts, Appl. Surf. Sci., 271, 164–170,
https://doi.org/10.1016/j.apsusc.2013.01.155, 2013.
Kleffmann, J.: Daytime sources of nitrous acid (HONO) in the atmospheric
boundary layer, Chem. Phys. Chem., 8, 1137–1144,
https://doi.org/10.1002/cphc.200700016, 2007.
Kurtenbach, R., Becker, K. H., Gomes, J. A. G., Kleffmann, J., Lörzer,
J. C., Spittler, M., Wiesen, P., Ackermann, R., Geyer, A., and Platt, U.:
Investigations of emissions and heterogeneous formation of HONO in road
traffic tunnel, Atmos. Environ., 35, 3385–3394,
https://doi.org/10.1016/S1352-2310(01)00138-8, 2001.
Langridge, J. M., Gustafsson, R. J., Griffiths, P. T., Cox, R. A., Lambert,
R. M., and Jones, R. L.: Solar driven nitrous acid formation on building
material surfaces containing titanium dioxide: A concern for air quality in
urban areas?, Atmos. Environ., 43, 5128–5131,
https://doi.org/10.1016/j.atmosenv.2009.06.046, 2009.
Lee, J. D., Whalley, L. K., Heard, D. E., Stone, D., Dunmore, R. E., Hamilton, J. F., Young, D. E., Allan, J. D., Laufs, S., and Kleffmann, J.: Detailed budget analysis of HONO in central London reveals a missing daytime source, Atmos. Chem. Phys., 16, 2747–2764, https://doi.org/10.5194/acp-16-2747-2016, 2016.
Levy, H.: Normal atmosphere: large radical and formaldehyde concentrations
predicted, Science, 173, 141–143,
https://doi.org/10.1126/science.173.3992.141, 1971.
Li, S., Matthews, J., and Sinha, A.: Atmospheric hydroxyl radical production
from electronically excited NO2 and H2O, Science, 319, 1657–1660,
https://doi.org/10.1126/science.1151443, 2008.
Liao, W., Hecobian, A., Mastromarino, J., and Tan, D.: Development of a
photo-fragmentation/laser-induced fluorescence measurement of atmospheric
nitrous acid, Atmos. Environ., 40, 17–26,
https://doi.org/10.1016/j.atmosenv.2005.07.001, 2006.
Liao, W., Hecobian, A., Mastromarino, J., and Tan, D.: Development of a
photo-fragmentation/laser-induced fluorescence measurement of atmospheric
nitrous acid, Atmos. Envrion., 40, 17–26,
https://doi.org/10.1016/j.atmosenv.2005.07.001, 2007.
Liu, W. G. and Goddard, W. A.: First-principle study of the role of
interconversion between NO2, N2O4, cis-ONO-NO2, and
trans-ONO-NO2 in chemical processes, J. Am. Chem. Soc., 134, 12970–12978,
https://doi.org/10.1021/ja300545e, 2012.
Lu, K., Fuchs, H., Hofzumahaus, A., Tan, Z., Wang, H., Zhang, L., Schmitt,
S. H., Rohrer, F., Bohn, B., Broch, S., Dong, H., Gkatzelis, G. I., Hohaus,
T., Holland, F., Li, X., Liu, Y., Liu, Y., Ma, X., Novelli, A., Schlag, P.,
Shao, M., Wu, Y., Wu, Z., Zeng, L., Hu, M., Kiendler-Scharr, A., Wahner, A.,
and Zhang, Y.: Fast Photochemistry in Wintertime Haze: Consequences for
Pollution Mitigation Strategies, Environ. Sci. Technol., 53, 10676–10684,
https://doi.org/10.1021/acs.est.9b02422, 2019.
Lu, X., Park, J., and Lin, M. C.: Gas phase reactions of HONO with NO2,
O3 and HCl: Ab initio and TST study, J. Phys. Chem. A, 104,
8730–8738, https://doi.org/10.1021/jp001610o, 2000.
Matthews, P. S. J., Baeza-Romero, M. T., Whalley, L. K., and Heard, D. E.: Uptake of HO2 radicals onto Arizona test dust particles using an aerosol flow tube, Atmos. Chem. Phys., 14, 7397–7408, https://doi.org/10.5194/acp-14-7397-2014, 2014.
MCPA Software Ltd.: Facsimile integrator software package, MCPA Software Ltd.: Facsimile, 2020
Michoud, V., Colomb, A., Borbon, A., Miet, K., Beekmann, M., Camredon, M., Aumont, B., Perrier, S., Zapf, P., Siour, G., Ait-Helal, W., Afif, C., Kukui, A., Furger, M., Dupont, J. C., Haeffelin, M., and Doussin, J. F.: Study of the unknown HONO daytime source at a European suburban site during the MEGAPOLI summer and winter field campaigns, Atmos. Chem. Phys., 14, 2805–2822, https://doi.org/10.5194/acp-14-2805-2014, 2014.
Moon, D. R., Ingham, T., Whalley, L. K., Seakins, P. W., Baeza-Romero, M.
T., and Heard, D. E.: Production of OH and HO2 radicals from near-UV
irradiated airborne TiO2 nanoparticles, Phys. Chem. Phys. Chem, 21,
2325–2336, https://doi.org/10.1039/C8CP06889E, 2019.
Murdachaew, G., Varner, M. E., Philips, L. F., Finlayson-Pitts, B. J., and
Gerber, R. B.: Nitrogen dioxide at the air-water interface: trapping,
adsorption, and solvation in the bulk and at the surface, Phys. Chem. Chem.
Phys., 15, 204–212, https://doi.org/10.1039/c2cp42810e, 2013.
Nakamura, I., Sugihara, S., and Takeuchi, K.: Mechanism for NO
photooxidation over the oxygen-deficient TiO2 powder under visible
light irradiation, Chem. Lett., 29, 1276–1277,
https://doi.org/10.1246/cl.2000.1276, 2000.
Ndour, M., D'Anna, B., George, C., Ka, O., Balkanski, Y., Kleffman, J.,
Stemmler, K., and Ammann, M.: Photoenhanced uptake of NO2 on mineral
dust: Laboratory experiments and model simulations, Geophys. Res. Lett., 35,
L05812, https://doi.org/10.1029/2007GL032006, 2008.
Oswald, R., Behrendt, T., Ermel, M., Wu, D., Su, H., Cheng, Y., Breuninger,
C., Moravek, A., Mougin, E., Delon, C., Loubet, B., Pommerening-Röser,
A., Sörgel, M., Pöschl, U., Hoffmann, T., Andeae, M. O., Meixner, F.
X., and Trebs, I.: HONO emissions from soil bacteria as a major source of
atmospheric reactive nitrogen, Science, 341, 1233–1235,
https://doi.org/10.1126/science.1242266, 2013.
Pimental, A. S., Lima, F. C. A., and da Silva, A. B. F.: The isomerization of dinitrogen tetraoxide:
Pinnick, D., Agnew, S., and Swanson, B.: Fluid dinitrogen tetroxide at very
high pressure and high temperature: observation of the nitrite isomer,
J. Phys. Chem., 96, 7092–7096,
https://doi.org/10.1021/j100196a046, 1992.
Pitts, J. N., Sanhueza, E., Atkinson, R., Carter, W. P. L., Winer, A. M.,
Harris, G. W., and Plum, C. N.: An investigation of the dark formation of
nitrous acid in environmental chambers, Int. J. Chem. Kinet., 16, 919–939,
https://doi.org/10.1002/kin.550160712, 1984.
Platt, U., Perner, D., Harris, G. W., Winer, A. M., and Pitts, J. N.:
Observations of nitrous acid in an urban atmosphere by differential optical
absorption, Nature, 285, 312–314, https://doi.org/10.1038/285312a0, 1980.
Ramazan, K. A., Syomin, D., and Finlayson-Pitts, B. J.: The photochemical
production of HONO during the heterogeneous hydrolysis of NO2, Phys. Chem.
Chem. Phys., 6, 3836–3843, https://doi.org/10.1039/B402195A, 2004.
Ramazan, K. A., Wingen, L. M., Miller, Y., Chaban, G. M., Gerber, R. B.,
Xantheas, S. S., and Finlayson-Pitts, B. J.: New experimental and
theoretical approach to the heterogeneous hydrolysis of NO2: key role
of molecular nitric acid and its complexes, J. Phys. Chem. A, 110,
6886–6897, https://doi.org/10.1021/jp056426n, 2006.
Reed, C., Evans, M. J., Crilley, L. R., Bloss, W. J., Sherwen, T., Read, K.
A., Lee, J. D., and Carpenter, L. J.: Evidence for renoxification in the
tropical marine boundary layer, Atmos. Chem. Phys., 17, 4081–4092,
https://doi.org/10.5194/acp-17-4081-2017, 2017.
Sakamaki, F., Hatakeyama, S., and Akimoto, H.: Formation of nitrous acid and
nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and
water vapor in a smog chamber, Int. J. Chem. Kinet., 15, 1013–1029,
https://doi.org/10.1002/kin.550151006, 1983.
Saliba, N. A., Moussa, S. G., and El Tayyar, G.: Contribution of airborne dust particles to HONO sources, Atmos. Chem. Phys. Discuss., 14, 4827–4839, https://doi.org/10.5194/acpd-14-4827-2014, 2014.
Sander, S., Friedl, R., Barker, J., Golden, D., Kurylo, M., Wine, P., Abbatt, J., Burkholder, J., Kolb, C., and Moortgat, G.: Chemical kinetics and photochemical data for use in atmospheric studies, evaluation number 14, JPL Publ. 02-25, 2003.
Schleicher, N., Norra, S., Chai, F., Chen, Y., Wang, S., and Stüben, D.:
Anthropogenic versus geogenic contribution to total suspended atmospheric
particulate matter and its variations during a two-year sampling period in
Beijing, China, J. Environ. Monit., 12, 434–441,
https://doi.org/10.1039/B914739J, 2010.
Seifert, N. A., Zaleski, D. P., Fehnel, R., Goswami, M., Pate, B. H.,
Lehmann, K. K., Leung, H. O., Marshall, M. D., and Stanton, J. F.: The
gas-phase structure of the asymmetric, trans-dinitrogen tetroxide
(N2O4), formed by dimerization of nitrogen dioxide (NO2),
from rotational spectroscopy and ab initio quantum chemistry, J.
Chem. Phys., 146, 134305, https://doi.org/10.1063/1.4979182, 2017.
Shan, J. H., Wategaonkar, S. J., and Vasudev, R.: Vibrational state
dependence of the A state lifetime of HONO, Chem. Phys. Lett., 158, 317–320,
https://doi.org/10.1016/0009-2614(89)87343-9, 1989.
Slater, E. J., Whalley, L. K., Woodward-Massey, R., Ye, C., Lee, J. D., Squires, F., Hopkins, J. R., Dunmore, R. E., Shaw, M., Hamilton, J. F., Lewis, A. C., Crilley, L. R., Kramer, L., Bloss, W., Vu, T., Sun, Y., Xu, W., Yue, S., Ren, L., Acton, W. J. F., Hewitt, C. N., Wang, X., Fu, P., and Heard, D. E.: Elevated levels of OH observed in haze events during wintertime in central Beijing, Atmos. Chem. Phys., 20, 14847–14871, https://doi.org/10.5194/acp-20-14847-2020, 2020.
Spataro, F. and Ianniello, A.: Sources of atmospheric nitrous acid: State
of the science, current research needs, and future prospects, J. Air Waste
Ma., 64, 1232–1250, https://doi.org/10.1080/10962247.2014.952846,
2014.
Stemmler, K., Ndour, M., Elshorbany, Y., Kleffmann, J., D'Anna, B., George, C., Bohn, B., and Ammann, M.: Light induced conversion of nitrogen dioxide into nitrous acid on submicron humic acid aerosol, Atmos. Chem. Phys., 7, 4237–4248, https://doi.org/10.5194/acp-7-4237-2007, 2007.
Su, H., Cheng, Y., Oswald, R., Behrendt, T., Trebs, I., Meixner, F. C.,
Andreae, M. O., Cheng, P., Zhang, Y., and Pöschl, U.: Soil nitrate as a
source of atmospheric HONO and OH radicals, Science, 333, 1616–1618,
https://doi.org/10.1126/science.1207687, 2011.
Syomin, D. A. and Finlayson-Pitts, B. J.: HONO decomposition on
borosilicate glass surfaces: implications for environmental chamber studies
and field experiments, Phys. Chem. Chem. Phys., 5, 5236–5242,
https://doi.org/10.1039/b309851f, 2003.
Takeuchi, M., Sakamoto, K., Martra, G., Coluccia, S., and Anpo, M.:
Mechanism of photoinduced superhydrophilicity on the TiO2 photocatalyst
surface, J. Phys. Chem. B, 109, 15422–15428,
https://doi.org/10.1021/jp058075i, 2005.
Varner, M. E., Finlayson-Pitts, B. J., and Gerber, R. B.: Reaction of a
charge-separated ONONO2 species with water in the formation of HONO: an
MP2 molecular dynamics study, Phys. Chem. Chem. Phys., 16, 4483–4487,
https://doi.org/10.1039/c3cp55024a, 2014.
Wang, C., Bottorff, B., Reidy, E., Rosales, C. M. F., Collins, D. B.,
Novoselac, A., Farmer, D. K., Vance, M. E., Stevens, P. S., and Abbatt, J.
P. D.: Cooking, Bleach Cleaning, and Air Conditioning Strongly Impact Levels
of HONO in a House, Environ. Sci. Technol., 54, 13488–13497,
10.1021/acs.est.0c05356, 2020.
Wang, J. and Koel, B. E.: IRAS studies of NO2, N2O3, and
N2O4 adsorbed on Au (111) surfaces and reactions with coadsorbed
H2O, J. Phys. Chem. A, 102, 8573–8579,
https://doi.org/10.1021/jp982061d, 1998.
Wang, J. and Koel, B. E.: Reactions of N2O4 with ice at low
temperatures on the Au (111) surface, Surf. Sci., 436, 15–28,
https://doi.org/10.1016/S0039-6028(99)00457-4, 1999.
Wexler, A. S. and Clegg, S. L.: Atmospheric aerosol models for systems
including the ions H+, NH
Whalley, L. K., Furneaux, K. L., Goddard, A., Lee, J. D., Mahajan, A., Oetjen, H., Read, K. A., Kaaden, N., Carpenter, L. J., Lewis, A. C., Plane, J. M. C., Saltzman, E. S., Wiedensohler, A., and Heard, D. E.: The chemistry of OH and HO2 radicals in the boundary layer over the tropical Atlantic Ocean, Atmos. Chem. Phys., 10, 1555–1576, https://doi.org/10.5194/acp-10-1555-2010, 2010.
Whalley, L. K., Stone, D., Dunmore, R., Hamilton, J., Hopkins, J. R., Lee, J. D., Lewis, A. C., Williams, P., Kleffmann, J., Laufs, S., Woodward-Massey, R., and Heard, D. E.: Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo), Atmos. Chem. Phys., 18, 2547–2571, https://doi.org/10.5194/acp-18-2547-2018, 2018.
Whalley, L. K., Slater, E. J., Woodward-Massey, R., Ye, C., Lee, J. D., Squires, F., Hopkins, J. R., Dunmore, R. E., Shaw, M., Hamilton, J. F., Lewis, A. C., Mehra, A., Worrall, S. D., Bacak, A., Bannan, T. J., Coe, H., Percival, C. J., Ouyang, B., Jones, R. L., Crilley, L. R., Kramer, L. J., Bloss, W. J., Vu, T., Kotthaus, S., Grimmond, S., Sun, Y., Xu, W., Yue, S., Ren, L., Acton, W. J. F., Hewitt, C. N., Wang, X., Fu, P., and Heard, D. E.: Evaluating the sensitivity of radical chemistry and ozone formation to ambient VOCs and NOx in Beijing, Atmos. Chem. Phys., 21, 2125–2147, https://doi.org/10.5194/acp-21-2125-2021, 2021.
Winer, A. M. and Biermann, H. W.: Long pathlength differential optical
absorption spectroscopy (DOAS) measurements of gaseous HONO, NO2 and
HCNO in the California South Coast Air Basin, Res. Chem. Intermed., 20,
423–445, https://doi.org/10.1163/156856794X00405, 1994.
Wu, L., Li, X., and Ro, C.: Hygroscopic behavior of ammonium sulfate,
ammonium nitrate, and their mixture particles, Asian J. Atmos. Environ.,
13.3, 196–211, https://doi.org/10.5572/ajae.2019.13.3.196, 2019.
Ye, C., Zhou, X., Pu, D., Stutz, J., Festa, J., Spolaor, M., Tsai, C.,
Cantrell, C., Mauldin, R. L., Campos, T., Weinheimer, A., Hornbrook, R. S.,
Apel, E. C., Guenther, A., Kaser, L., Yuan, B., Karl, T., Haggerty, J.,
Hall, S., Ullmann, K., Smith, J. N., Ortega, J., and Knote, C.: Rapid
cycling of reactive nitrogen in the marine boundary layer, Nature, 532,
489–491, https://doi.org/10.1038/nature17195, 2016.
Ye, C., Heard, D. E., and Whalley, L. K.: Evaluation of novel routes for
NOx formation in remote regions, Environ. Sci. Technol.,
51, 7442–7449, ht 2017a.
Ye, C., Zhang, N., Gao, H., and Zhou, X.: Photolysis of particulate nitrate
as a source of HONO and NOx, Environ. Sci. Technol., 51, 6849–6856,
https://doi.org/10.1021/acs.est.7b00387, 2017b.
Zhou, X., Gao, H., He, Y., Huang, G., Bertman, S. B., Civerolo, K., and
Schwab, J.: Nitric acid photolysis on surfaces in low NOx environments:
Significant atmospheric implications, Geophys. Res. Lett., 30, 2217,
https://doi.org/10.1029/2003GL018620, 2003.
Short summary
The hydroxyl radical (OH) dominates the removal of atmospheric pollutants, with nitrous acid (HONO) recognised as a major OH source. For remote regions HONO production through the action of sunlight on aerosol surfaces can provide a source of nitrogen oxides. In this study, HONO production rates at illuminated aerosol surfaces are measured under atmospheric conditions, a model consistent with the data is developed and aerosol production of HONO in the atmosphere is shown to be significant.
The hydroxyl radical (OH) dominates the removal of atmospheric pollutants, with nitrous acid...
Altmetrics
Final-revised paper
Preprint