Articles | Volume 16, issue 19
https://doi.org/10.5194/amt-16-4375-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-16-4375-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
05 Oct 2023
Research article |
| 05 Oct 2023
| 05 Oct 2023
Comparison of temperature-dependent calibration methods of an instrument to measure OH and HO2 radicals using laser-induced fluorescence spectroscopy
Frank A. F. Winiberg
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
now at: NASA's Jet Propulsion Laboratory, California Institute of
Technology, Pasadena, 91109, USA
William J. Warman
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Charlotte A. Brumby
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Graham Boustead
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Iustinian G. Bejan
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
now at: Faculty of Chemistry and Integrated Center of Environmental
Science Studies in the North-East Development Region – CERNESIM, Al. I.
Cuza University of Iasi, Iaşi, Romania
Thomas H. Speak
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Dwayne E. Heard
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
Daniel Stone
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
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Finja Löher, Mark A. Blitz, Paul W. Seakins, Nicola Carslaw, and Terry J. Dillon
EGUsphere, https://doi.org/10.5194/egusphere-2026-1660, https://doi.org/10.5194/egusphere-2026-1660, 2026
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Ethyl butyrate and its methylated derivatives are volatile and commonly used aroma compounds, yet their gas-phase chemistry and air quality impact remain poorly characterised. In this work, we investigated the reactivity of these compounds experimentally. We determined temperature-dependent rate coefficients for their reaction with the main atmospheric oxidant, OH, and found that this was the dominant tropospheric loss process. In contrast, direct photolysis is negligible under most conditions.
Hendrik Fuchs, Niklas Illmann, Amalia Muñoz, Mila Ródenas, Bénédicte Picquet-Varrault, M. Rami Alfarra, Cecilia Arsene, Iustinian G. Bejan, David M. Bell, Merete Bilde, Alexander Böhmländer, Mixtli Campos-Pineda, Mathieu Cazaunau, Patrice Coll, Véronique Daële, Claudia Di Biagio, Michael Flynn, Paola Formenti, Hartmut Herrmann, Kristina Höhler, Thorsten Hohaus, Matthew S. Johnson, Eija Juurola, Niku Kivekäs, Jan Kaiser, Christos Kaltsonoudis, Paolo Laj, Dario Massabò, Federico Mazzei, Gordon McFiggans, Max R. McGillen, Abdelwahid Mellouki, Peter Mettke, Ottmar Möhler, Falk Mothes, Dennis Niedermeier, Anna Novelli, Romeo I. Olariu, Spyros N. Pandis, Iulia Patroescu-Klotz, Rosa Maria Petracca Altieri, Paolo Prati, Claudiu Roman, Albert A. Ruth, Harald Saathoff, Silvio Schmalfuß, Frank Stratmann, Virginia Vernocchi, Aristeidis Voliotis, Jens Voigtländer, Annele Virtanen, Andreas Wahner, Robert Wagner, John Wenger, Sören Zorn, Peter Wiesen, and Jean-Francois Doussin
EGUsphere, https://doi.org/10.5194/egusphere-2026-1612, https://doi.org/10.5194/egusphere-2026-1612, 2026
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
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Atmospheric simulation chambers enable experiments to be conducted under controlled conditions, improving our understanding of, and ability to predict, changes in the composition of the atmosphere. This is important for assessing air quality and its effects on human health, climate, the environment, and the economy. This paper describes the chambers of the European ACTRIS research infrastructure and discusses topics and directions that can be addressed in future chamber experiments.
Ruth M. Doherty, Zhenze Liu, Massimo Vieno, Oliver Wild, Fiona M. O'Connor, Steven T. Turnock, Christina M. Hood, Jenny R. Stocker, Mathew R. Heal, Dwayne E. Heard, Emma G. Sands, David J. Carruthers, and Lisa K. Whalley
EGUsphere, https://doi.org/10.5194/egusphere-2025-6407, https://doi.org/10.5194/egusphere-2025-6407, 2026
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This study developed a coupled model approach to investigate key processes determining how climate change impacts 21st-century air quality. Elevated isoprene emissions drive summer ozone and fine particulate matter increases over continental Europe; but their response to climate change is uncertain. Unabated climate change, without emission reductions, poses a challenge for achieving ozone, fine particulate matter and nitrogen dioxide long-term air quality guidelines over much of Europe by 2100.
James D'Souza Metcalf, Ruth K. Winkless, Caterina Mapelli, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 25, 9169–9181, https://doi.org/10.5194/acp-25-9169-2025, https://doi.org/10.5194/acp-25-9169-2025, 2025
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Oxymethylene ethers are a class of sustainable compounds that could be used to replace harmful organic solvents in a range of applications. In this work, we use lab-based experiments to identify the main breakdown routes of these compounds in the atmosphere. We have determined that they likely contribute less to air pollution than the compounds that they replace.
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
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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.
Barbara Ervens, Andrew Rickard, Bernard Aumont, William P. L. Carter, Max McGillen, Abdelwahid Mellouki, John Orlando, Bénédicte Picquet-Varrault, Paul Seakins, William R. Stockwell, Luc Vereecken, and Timothy J. Wallington
Atmos. Chem. Phys., 24, 13317–13339, https://doi.org/10.5194/acp-24-13317-2024, https://doi.org/10.5194/acp-24-13317-2024, 2024
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Chemical mechanisms describe the chemical processes in atmospheric models that are used to describe the changes in the atmospheric composition. Therefore, accurate chemical mechanisms are necessary to predict the evolution of air pollution and climate change. The article describes all steps that are needed to build chemical mechanisms and discusses the advances and needs of experimental and theoretical research activities needed to build reliable chemical mechanisms.
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
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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.
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
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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.
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.
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
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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
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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.
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.
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
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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.
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
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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
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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.
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.
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.
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
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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.
Esther Borrás, Luis A. Tortajada-Genaro, Milagro Ródenas, Teresa Vera, Thomas Speak, Paul Seakins, Marvin D. Shaw, Alastair C. Lewis, and Amalia Muñoz
Atmos. Meas. Tech., 14, 4989–4999, https://doi.org/10.5194/amt-14-4989-2021, https://doi.org/10.5194/amt-14-4989-2021, 2021
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This work presents promising results in the characterization of specific atmospheric pollutants (oxygenated VOCs) present at very low but highly relevant concentrations.
We carried out this research at EUPHORE facilities within the framework of the EUROCHAMP project. A new analytical method, with high robustness and precision, also clean in the use of solvents, low cost, and easily adaptable for use in mobile laboratories for air quality monitoring, is presented.
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
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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.
Joanna E. Dyson, Graham A. Boustead, Lauren T. Fleming, Mark Blitz, Daniel Stone, Stephen R. Arnold, Lisa K. Whalley, and Dwayne E. Heard
Atmos. Chem. Phys., 21, 5755–5775, https://doi.org/10.5194/acp-21-5755-2021, https://doi.org/10.5194/acp-21-5755-2021, 2021
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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.
Cited articles
Atkinson, R.: Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes, Atmos. Chem. Phys., 3, 2233–2307, https://doi.org/10.5194/acp-3-2233-2003, 2003.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, https://doi.org/10.5194/acp-6-3625-2006, 2006.
Bailey, A. E., Heard, D. E., Paul, P. H., and Pilling, M. J.: Collisional
Quenching of OH by N2, O2 and CO2, Journal of the Chemical
Society, Faraday Trans., 93, 2915–2920, 1997.
Bailey, A. E., Heard, D. E., Henderson, D. A., and Paul, P. H.: Collisional
quenching of OH(A2Σ+,
Bejan, I. G., Winiberg, F. A. F., Mortimer, N., Medeiros, D. J., Brumby, C.
A., Orr, S. C., Kelly, J., and Seakins, P. W.: Gas-phase rate coefficients
for a series of alkyl cyclohexanes with OH radicals and Cl atoms,
Int. J. Chem. Kinet., 50, 544–555, https://doi.org/10.1002/kin.21179,
2018.
Brown, A. C., Canosamas, C. E., Parr, A. D., and Wayne, R. P.: Laboratory
studies of some halogenated ethanes and ethers – measurements of rates of
reaction with OH and of infrared-absorption cross-sections, Atmos.
Environ. A, 24, 2499–2511,
https://doi.org/10.1016/0960-1686(90)90341-j, 1990.
Cantrell, C. A., Tyndall, G., and Zimmer, A.: Absorption cross sections for
water vapour from 183 to 193 nm, Geophys. Res. Lett., 24,
2195–2198, 1997.
Commane, R., Floquet, C. F. A., Ingham, T., Stone, D., Evans, M. J., and Heard, D. E.: Observations of OH and HO2 radicals over West Africa, Atmos. Chem. Phys., 10, 8783–8801, https://doi.org/10.5194/acp-10-8783-2010, 2010.
Copeland, R. A. and Crosley, D.: Temperature dependent electronic quenching
of OH A2Σ, v'=0 between 230 and 310 K, J. Chem.
Phys., 84, 3099–3105, 1986.
Creasey, D. J., Halford-Maw, P. A., Heard, D. E., Pilling, M. J., and
Whitaker, B. J.: Implementation and initial deployment of a field instrument
for measurement of OH and HO2 in the troposphere by laser-induced
fluorescence, J. Chem. Soc.-Faraday Trans., 93, 2907–2913, 1997a.
Creasey, D. J., Heard, D. E., Pilling, M. J., Whitaker, B. J., Berzins, M.,
and Fairlie, R.: Visualisation of a supersonic free-jet expansion using
laser-induced fluorescence spectroscopy: Application to the measurement of
rate constants at ultralow temperatures, Appl. Phys. B, 65, 375–391, https://doi.org/10.1007/s003400050285, 1997b.
Creasey, D. J., Heard, D. E., and Lee, J. D.: Absorption cross-section
measurements of water vapour and oxygen at 185 nm. Implications for the
calibration of field instruments to measure OH, HO2 and RO2
radicals, Geophys. Res. Lett., 27, 1651–1654, https://doi.org/10.1029/1999gl011014,
2000.
Edwards, G. D., Cantrell, C., Stephens, S., Hill, B., Goyea, O., Shetter,
R., Mauldin, R. L., Kosciuch, E., Tanner, D., and Eisele, F.: Chemical
Ionization Mass Spectrometer Instrument for the Measurement of Tropospheric
HO2 and RO2, Anal. Chem., 75, 5317–5327, 2003.
Faloona, I. C., Tan, D., Lesher, R. L., Hazen, N. L., Frame, C. L., Simpas,
J. B., Harder, H., Martinez, M., Di Carlo, P., Ren, X. R., and Brune, W. H.:
A laser-induced fluorescence instrument for detecting tropospheric OH and
HO2: Characteristics and calibration, J. Atmos. Chem., 47, 139–167,
https://doi.org/10.1023/B:JOCH.0000021036.53185.0e, 2004.
Fittschen, C., Al Ajami, M., Batut, S., Ferracci, V., Archer-Nicholls, S., Archibald, A. T., and Schoemaecker, C.: ROOOH: a missing piece of the puzzle for OH measurements in low-NO environments?, Atmos. Chem. Phys., 19, 349–362, https://doi.org/10.5194/acp-19-349-2019, 2019.
Fuchs, H., Bohn, B., Hofzumahaus, A., Holland, F., Lu, K. D., Nehr, S., Rohrer, F., and Wahner, A.: Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals, Atmos. Meas. Tech., 4, 1209–1225, https://doi.org/10.5194/amt-4-1209-2011, 2011.
Fuchs, H., Tan, Z., Hofzumahaus, A., Broch, S., Dorn, H.-P., Holland, F., Künstler, C., Gomm, S., Rohrer, F., Schrade, S., Tillmann, R., and Wahner, A.: Investigation of potential interferences in the detection of atmospheric ROx radicals by laser-induced fluorescence under dark conditions, Atmos. Meas. Tech., 9, 1431–1447, https://doi.org/10.5194/amt-9-1431-2016, 2016.
Gligorovski, S., Strekowski, R., Barbati, S., and Vione, D.: Environmental
Implications of Hydroxyl Radicals (center dot OH), Chem. Rev., 115,
13051–13092, https://doi.org/10.1021/cr500310b, 2015.
Glowacki, D. R., Goddard, A., Hemavibool, K., Malkin, T. L., Commane, R., Anderson, F., Bloss, W. J., Heard, D. E., Ingham, T., Pilling, M. J., and Seakins, P. W.: Design of and initial results from a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC), Atmos. Chem. Phys., 7, 5371–5390, https://doi.org/10.5194/acp-7-5371-2007, 2007.
Hard, T. M., Obrien, R. J., Chan, C. Y., and Mehrabzadeh, A. A.:
Tropospheric free-radical determination by FAGE, Environ. Sci.
Technol., 18, 768–777, https://doi.org/10.1021/es00128a009, 1984.
Heard, D. E. and Pilling, M. J.: Measurement of OH and HO2 in the
troposphere, Chem. Rev., 103, 5163–5198, 2003.
Hofzumahaus, A., Brauers, T., Aschmutat, U., Brandenburger, U., Dorn, H. P.,
Hausmann, M., Hessling, M., Holland, F., PlassDulmer, C., Sedlacek, M.,
Weber, M., and Ehhalt, D. H.: The measurement of tropospheric OH radicals by
laser-induced fluorescence spectroscopy during the POPCORN field campaign
and Intercomparison of tropospheric OH radical measurements by multiple
folded long-path laser absorption and laser induced fluorescence – Reply,
Geophys. Res. Lett., 24, 3039–3040, https://doi.org/10.1029/97gl02947, 1997.
Howard, C. J.: Kinetic measurements using flow tubes, J. Phys.
Chem., 83, 3–9, https://doi.org/10.1021/j100464a001, 1979.
IUPAC: Evaluated Kinetic Data: Task Group on Atmospheric Chemical Kinetic Data Evaluation, https://iupac-aeris.ipsl.fr/ (last access: 28 May 2023), 2007.
Karl, M., Brauers, T., Dorn, H. P., Holland, F., Komenda, M., Poppe, D.,
Rohrer, F., Rupp, L., Schaub, A., and Wahner, A.: Kinetic Study of the
OH-isoprene and O3-isoprene reaction in the atmosphere simulation
chamber, SAPHIR, Geophys. Res. Lett., 31, L05117, https://doi.org/10.1029/2003gl019189,
2004.
Malkin, T. L., Goddard, A., Heard, D. E., and Seakins, P. W.: Measurements of OH and HO2 yields from the gas phase ozonolysis of isoprene, Atmos. Chem. Phys., 10, 1441–1459, https://doi.org/10.5194/acp-10-1441-2010, 2010.
Mao, J., Ren, X., Zhang, L., Van Duin, D. M., Cohen, R. C., Park, J.-H., Goldstein, A. H., Paulot, F., Beaver, M. R., Crounse, J. D., Wennberg, P. O., DiGangi, J. P., Henry, S. B., Keutsch, F. N., Park, C., Schade, G. W., Wolfe, G. M., Thornton, J. A., and Brune, W. H.: Insights into hydroxyl measurements and atmospheric oxidation in a California forest, Atmos. Chem. Phys., 12, 8009–8020, https://doi.org/10.5194/acp-12-8009-2012, 2012.
Marno, D., Ernest, C., Hens, K., Javed, U., Klimach, T., Martinez, M., Rudolf, M., Lelieveld, J., and Harder, H.: Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE), Atmos. Meas. Tech., 13, 2711–2731, https://doi.org/10.5194/amt-13-2711-2020, 2020.
Novelli, A., Hens, K., Tatum Ernest, C., Kubistin, D., Regelin, E., Elste, T., Plass-Dülmer, C., Martinez, M., Lelieveld, J., and Harder, H.: Characterisation of an inlet pre-injector laser-induced fluorescence instrument for the measurement of atmospheric hydroxyl radicals, Atmos. Meas. Tech., 7, 3413–3430, https://doi.org/10.5194/amt-7-3413-2014, 2014.
Novelli, A., Hens, K., Tatum Ernest, C., Martinez, M., Nölscher, A. C., Sinha, V., Paasonen, P., Petäjä, T., Sipilä, M., Elste, T., Plass-Dülmer, C., Phillips, G. J., Kubistin, D., Williams, J., Vereecken, L., Lelieveld, J., and Harder, H.: Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument, Atmos. Chem. Phys., 17, 7807–7826, https://doi.org/10.5194/acp-17-7807-2017, 2017.
Onel, L., Brennan, A., Gianella, M., Ronnie, G., Lawry Aguila, A., Hancock, G., Whalley, L., Seakins, P. W., Ritchie, G. A. D., and Heard, D. E.: An intercomparison of HO2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry), Atmos. Meas. Tech., 10, 4877–4894, https://doi.org/10.5194/amt-10-4877-2017, 2017a.
Onel, L., Brennan, A., Seakins, P. W., Whalley, L., and Heard, D. E.: A new method for atmospheric detection of the CH3O2 radical, Atmos. Meas. Tech., 10, 3985–4000, https://doi.org/10.5194/amt-10-3985-2017, 2017b.
Onel, L., Brennan, A., Gianella, M., Hooper, J., Ng, N., Hancock, G., Whalley, L., Seakins, P. W., Ritchie, G. A. D., and Heard, D. E.: An intercomparison of CH3O2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry), Atmos. Meas. Tech., 13, 2441–2456, https://doi.org/10.5194/amt-13-2441-2020, 2020.
Regelin, E., Harder, H., Martinez, M., Kubistin, D., Tatum Ernest, C., Bozem, H., Klippel, T., Hosaynali-Beygi, Z., Fischer, H., Sander, R., Jöckel, P., Königstedt, R., and Lelieveld, J.: HOx measurements in the summertime upper troposphere over Europe: a comparison of observations to a box model and a 3-D model, Atmos. Chem. Phys., 13, 10703–10720, https://doi.org/10.5194/acp-13-10703-2013, 2013.
Savitzky, A. and Golay, M. J. E.: Smoothing and Differentiation of Data by
Simplified Least Squares Procedures, Anal. Chem., 36, 1627–1639,
https://doi.org/10.1021/ac60214a047, 1964.
Schlosser, E., Brauers, T., Dorn, H.-P., Fuchs, H., Häseler, R., Hofzumahaus, A., Holland, F., Wahner, A., Kanaya, Y., Kajii, Y., Miyamoto, K., Nishida, S., Watanabe, K., Yoshino, A., Kubistin, D., Martinez, M., Rudolf, M., Harder, H., Berresheim, H., Elste, T., Plass-Dülmer, C., Stange, G., and Schurath, U.: Technical Note: Formal blind intercomparison of OH measurements: results from the international campaign HOxComp, Atmos. Chem. Phys., 9, 7923–7948, https://doi.org/10.5194/acp-9-7923-2009, 2009.
Stone, D., Whalley, L. K., and Heard, D. E.: Tropospheric OH and HO2
radicals: field measurements and model comparisons, Chem. Soc.
Rev., 41, 6348–6404, https://doi.org/10.1039/c2cs35140d, 2012.
Wang, G. Y., Iradukunda, Y., Shi, G. F., Sanga, P., Niu, X. L., and Wu, Z.
J.: Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere
and troposphere, J. Environ. Sci., 99, 324–335, https://doi.org/10.1016/j.jes.2020.06.038,
2021.
Whalley, L. K., Furneaux, K. L., Gravestock, T. J., Atkinson, H. M., Bale,
C. S. E., Ingham, T., Bloss, W. J., and Heard, D. E.: Detection of iodine
monoxide radicals in the marine boundary layer using laser induced
fluorescence spectroscopy, J. Atmos. Chem., 58, 19–39, 2007.
Whalley, L. K., Blitz, M. A., Desservettaz, M., Seakins, P. W., and Heard, D. E.: Reporting the sensitivity of laser-induced fluorescence instruments used for HO2 detection to an interference from RO2 radicals and introducing a novel approach that enables HO2 and certain RO2 types to be selectively measured, Atmos. Meas. Tech., 6, 3425–3440, https://doi.org/10.5194/amt-6-3425-2013, 2013.
Winiberg, F. A. F.: Characterisation of FAGE apparatus for HOx detection and
application in an environmental chamber, PhD, School of Chemistry,
University of Leeds, Leeds, 232 pp., 2014.
Winiberg, F. A. F., Smith, S. C., Bejan, I., Brumby, C. A., Ingham, T., Malkin, T. L., Orr, S. C., Heard, D. E., and Seakins, P. W.: Pressure-dependent calibration of the OH and HO2 channels of a FAGE HOx instrument using the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC), Atmos. Meas. Tech., 8, 523–540, https://doi.org/10.5194/amt-8-523-2015, 2015.
Winiberg, F. A. F., Dillon, T. J., Orr, S. C., Groß, C. B. M., Bejan, I., Brumby, C. A., Evans, M. J., Smith, S. C., Heard, D. E., and Seakins, P. W.: Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction, Atmos. Chem. Phys., 16, 4023–4042, https://doi.org/10.5194/acp-16-4023-2016, 2016.
Woodward-Massey, R., Slater, E. J., Alen, J., Ingham, T., Cryer, D. R., Stimpson, L. M., Ye, C., Seakins, P. W., Whalley, L. K., and Heard, D. E.: Implementation of a chemical background method for atmospheric OH measurements by laser-induced fluorescence: characterisation and observations from the UK and China, Atmos. Meas. Tech., 13, 3119–3146, https://doi.org/10.5194/amt-13-3119-2020, 2020.
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.
OH and HO2 are key reactive intermediates in the Earth's atmosphere. Accurate measurements in...
