Articles | Volume 25, issue 20
https://doi.org/10.5194/acp-25-13019-2025
© Author(s) 2025. 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-25-13019-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
20 Oct 2025
Research article |
| 20 Oct 2025
| 20 Oct 2025
Surface–bulk photochemical coupling of nonanoic acid and 4-benzoylbenzoic acid: the dual role of the photosensitizer and environmental influences
Ahmed Abdelmonem
CORRESPONDING AUTHOR
Institute of Meteorology and Climate Research, Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Dana Glikman
Institute of Physical Chemistry and Center for Soft Nanoscience, University of Münster, 48149 Münster, Germany
Yiwei Gong
Institute of Meteorology and Climate Research, Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Björn Braunschweig
Institute of Physical Chemistry and Center for Soft Nanoscience, University of Münster, 48149 Münster, Germany
Harald Saathoff
Institute of Meteorology and Climate Research, Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Johannes Lützenkirchen
Institute of Nuclear Wastes Disposal, Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Mohammed H. Fawey
Physics Department, Faculty of Science, Sohag University, 82524 Sohag, Egypt
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Simone Brunamonti, Harald Saathoff, Albert Hertzog, Glenn Diskin, Masatomo Fujiwara, Karen Rosenlof, Ottmar Möhler, Béla Tuzson, Lukas Emmenegger, Nadir Amarouche, Georges Durry, Fabien Frérot, Jean-Christophe Samake, Claire Cenac, Julio Lopez, Paul Monnier, and Mélanie Ghysels
Atmos. Meas. Tech., 18, 5321–5348, https://doi.org/10.5194/amt-18-5321-2025, https://doi.org/10.5194/amt-18-5321-2025, 2025
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Water vapor is a strong greenhouse gas, and accurate measurements of its concentration in the upper atmosphere (~8–25 km altitude) are crucial for reliable climate predictions. We investigated the performance of four airborne hygrometers, deployed on aircraft or stratospheric balloon platforms and based on different techniques, in a climate simulation chamber. The results demonstrate the high accuracy and reliability of the involved sensors for atmospheric monitoring and research applications.
Farhan R. Nursanto, Douglas A. Day, Roy Meinen, Rupert Holzinger, Harald Saathoff, Jinglan Fu, Jan Mulder, Ulrike Dusek, and Juliane L. Fry
Atmos. Meas. Tech., 18, 3051–3072, https://doi.org/10.5194/amt-18-3051-2025, https://doi.org/10.5194/amt-18-3051-2025, 2025
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It is of increasing importance to monitor nitrate pollution that can harm ecosystems. However, commonly used aerosol monitoring equipment cannot distinguish inorganic from organic forms of nitrate, which may have different consequences for the environment. We describe a method to differentiate types of nitrates that can be applied to ambient monitoring to improve understanding of its formation and impact.
Marco Zanatta, Pia Bogert, Patrick Ginot, Yiwei Gong, Gholam Ali Hoshyaripour, Yaqiong Hu, Feng Jiang, Paolo Laj, Yanxia Li, Claudia Linke, Ottmar Möhler, Harald Saathoff, Martin Schnaiter, Nsikanabasi Silas Umo, Franziska Vogel, and Robert Wagner
Aerosol Research Discuss., https://doi.org/10.5194/ar-2025-12, https://doi.org/10.5194/ar-2025-12, 2025
Revised manuscript accepted for AR
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Back carbon is an atmospheric pollutant from combustion, contributes to the Arctic warming. However, its properties change as it travels through the atmosphere, affecting its impact. We recreated Arctic transport conditions in a laboratory to study how black carbon evolves over time. Our findings show that temperature and altitude strongly influence its transformation, providing key insights for improving climate models and understanding Arctic pollution.
Feng Jiang, Harald Saathoff, Uzoamaka Ezenobi, Junwei Song, Hengheng Zhang, Linyu Gao, and Thomas Leisner
Atmos. Chem. Phys., 25, 1917–1930, https://doi.org/10.5194/acp-25-1917-2025, https://doi.org/10.5194/acp-25-1917-2025, 2025
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The chemical composition of brown carbon in the particle and gas phase was determined by mass spectrometry. BrC in the gas phase was mainly controlled by secondary formation and particle-to-gas partitioning. BrC in the particle phase was mainly from secondary formation. This work helps to get a better understanding of diurnal variations and the sources of brown carbon aerosol at a rural location in central Europe.
Junwei Song, Georgios I. Gkatzelis, Ralf Tillmann, Nicolas Brüggemann, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 13199–13217, https://doi.org/10.5194/acp-24-13199-2024, https://doi.org/10.5194/acp-24-13199-2024, 2024
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Biogenic volatile organic compounds (BVOCs) and organic aerosol (OA) particles were measured online in a stressed spruce-dominated forest. OA was mainly attributed to the monoterpene oxidation products. The mixing ratios of BVOCs were higher than the values previously measured in other temperate forests. The results demonstrate that BVOCs are influenced not only by meteorology and biogenic emissions but also by local anthropogenic emissions and subsequent chemical transformation processes.
Xiaoli Shen, David M. Bell, Hugh Coe, Naruki Hiranuma, Fabian Mahrt, Nicholas A. Marsden, Claudia Mohr, Daniel M. Murphy, Harald Saathoff, Johannes Schneider, Jacqueline Wilson, Maria A. Zawadowicz, Alla Zelenyuk, Paul J. DeMott, Ottmar Möhler, and Daniel J. Cziczo
Atmos. Chem. Phys., 24, 10869–10891, https://doi.org/10.5194/acp-24-10869-2024, https://doi.org/10.5194/acp-24-10869-2024, 2024
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Single-particle mass spectrometry (SPMS) is commonly used to measure the chemical composition and mixing state of aerosol particles. Intercomparison of SPMS instruments was conducted. All instruments reported similar size ranges and common spectral features. The instrument-specific detection efficiency was found to be more dependent on particle size than type. All differentiated secondary organic aerosol, soot, and soil dust but had difficulties differentiating among minerals and dusts.
Hengheng Zhang, Wei Huang, Xiaoli Shen, Ramakrishna Ramisetty, Junwei Song, Olga Kiseleva, Christopher Claus Holst, Basit Khan, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 10617–10637, https://doi.org/10.5194/acp-24-10617-2024, https://doi.org/10.5194/acp-24-10617-2024, 2024
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Our study unravels how stagnant winter conditions elevate aerosol levels in Stuttgart. Cloud cover at night plays a pivotal role, impacting morning air quality. Validating a key model, our findings aid accurate air quality predictions, crucial for effective pollution mitigation in urban areas.
Junwei Song, Harald Saathoff, Feng Jiang, Linyu Gao, Hengheng Zhang, and Thomas Leisner
Atmos. Chem. Phys., 24, 6699–6717, https://doi.org/10.5194/acp-24-6699-2024, https://doi.org/10.5194/acp-24-6699-2024, 2024
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This study presents concurrent online measurements of organic gas and particles (VOCs and OA) at a forested site in summer. Both VOCs and OA were largely contributed by oxygenated organic compounds. Semi-volatile oxygenated OA and organic nitrate formed from monoterpenes and sesquiterpenes contributed significantly to nighttime particle growth. The results help us to understand the causes of nighttime particle growth regularly observed in summer in central European rural forested environments.
Hengheng Zhang, Christian Rolf, Ralf Tillmann, Christian Wesolek, Frank Gunther Wienhold, Thomas Leisner, and Harald Saathoff
Aerosol Research, 2, 135–151, https://doi.org/10.5194/ar-2-135-2024, https://doi.org/10.5194/ar-2-135-2024, 2024
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Our study employs advanced tools, including scanning lidar, balloons, and UAVs, to explore aerosol particles in the atmosphere. The scanning lidar offers distinctive near-ground-level insights, enriching our comprehension of aerosol distribution from ground level to the free troposphere. This research provides valuable data for comparing remote sensing and in situ aerosol measurements, advancing our understanding of aerosol impacts on radiative transfer, clouds, and air quality.
Feng Jiang, Kyla Siemens, Claudia Linke, Yanxia Li, Yiwei Gong, Thomas Leisner, Alexander Laskin, and Harald Saathoff
Atmos. Chem. Phys., 24, 2639–2649, https://doi.org/10.5194/acp-24-2639-2024, https://doi.org/10.5194/acp-24-2639-2024, 2024
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We investigated the optical properties, chemical composition, and formation mechanisms of secondary organic aerosol (SOA) and brown carbon (BrC) from the oxidation of indole with and without NO2 in the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) simulation chamber. This work is one of the very few to link the optical properties and chemical composition of indole SOA with and without NO2 by simulation chamber experiments.
Wei Huang, Cheng Wu, Linyu Gao, Yvette Gramlich, Sophie L. Haslett, Joel Thornton, Felipe D. Lopez-Hilfiker, Ben H. Lee, Junwei Song, Harald Saathoff, Xiaoli Shen, Ramakrishna Ramisetty, Sachchida N. Tripathi, Dilip Ganguly, Feng Jiang, Magdalena Vallon, Siegfried Schobesberger, Taina Yli-Juuti, and Claudia Mohr
Atmos. Chem. Phys., 24, 2607–2624, https://doi.org/10.5194/acp-24-2607-2024, https://doi.org/10.5194/acp-24-2607-2024, 2024
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We present distinct molecular composition and volatility of oxygenated organic aerosol particles in different rural, urban, and mountain environments. We do a comprehensive investigation of the relationship between the chemical composition and volatility of oxygenated organic aerosol particles across different systems and environments. This study provides implications for volatility descriptions of oxygenated organic aerosol particles in different model frameworks.
Yiwei Gong, Feng Jiang, Yanxia Li, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 167–184, https://doi.org/10.5194/acp-24-167-2024, https://doi.org/10.5194/acp-24-167-2024, 2024
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This study investigates the role of the important atmospheric reactive intermediates in the formation of dimers and aerosol in monoterpene ozonolysis at different temperatures. Through conducting a series of chamber experiments and utilizing chemical kinetic and aerosol dynamic models, the SOA formation processes are better described, especially for colder regions. The results can be used to improve the chemical mechanism modeling of monoterpenes and SOA parameterization in transport models.
Jessica Lessing, Julia Neumann, Frank Bok, Johannes Lützenkirchen, Vinzenz Brendler, Moritz Schmidt, and Thorsten Stumpf
Saf. Nucl. Waste Disposal, 2, 161–162, https://doi.org/10.5194/sand-2-161-2023, https://doi.org/10.5194/sand-2-161-2023, 2023
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The immobilization of trivalent actinides (Am, Cm) and their less toxic homologue (Eu) in feldspar, a very common mineral in our earth crust, was studied by sorption experiments and spectroscopic studies. The speciation was identified and used to gain thermodynamic parameters to develop a surface complexation model. To sum up, feldspar, a main component of crystalline rock, is suitable for retaining radionuclides in a deep radioactive waste repository.
Robert Wagner, Alexander D. James, Victoria L. Frankland, Ottmar Möhler, Benjamin J. Murray, John M. C. Plane, Harald Saathoff, Ralf Weigel, and Martin Schnaiter
Atmos. Chem. Phys., 23, 6789–6811, https://doi.org/10.5194/acp-23-6789-2023, https://doi.org/10.5194/acp-23-6789-2023, 2023
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Polar stratospheric clouds (PSCs) play an important role in the depletion of stratospheric ozone. They can consist of different chemical species, including crystalline nitric acid hydrates. We found that mineral dust or meteoric ablation material can efficiently catalyse the formation of a specific phase of nitric acid dihydrate crystals. We determined predominant particle shapes and infrared optical properties of these crystals, which are important inputs for remote sensing detection of PSCs.
Kara D. Lamb, Jerry Y. Harrington, Benjamin W. Clouser, Elisabeth J. Moyer, Laszlo Sarkozy, Volker Ebert, Ottmar Möhler, and Harald Saathoff
Atmos. Chem. Phys., 23, 6043–6064, https://doi.org/10.5194/acp-23-6043-2023, https://doi.org/10.5194/acp-23-6043-2023, 2023
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This study investigates how ice grows directly from vapor in cirrus clouds by comparing observations of populations of ice crystals growing in a cloud chamber against models developed in the context of single-crystal laboratory studies. We demonstrate that previous discrepancies between different experimental measurements do not necessarily point to different physical interpretations but are rather due to assumptions that were made in terms of how experiments were modeled in previous studies.
Feng Jiang, Junwei Song, Jonas Bauer, Linyu Gao, Magdalena Vallon, Reiner Gebhardt, Thomas Leisner, Stefan Norra, and Harald Saathoff
Atmos. Chem. Phys., 22, 14971–14986, https://doi.org/10.5194/acp-22-14971-2022, https://doi.org/10.5194/acp-22-14971-2022, 2022
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We studied brown carbon aerosol during typical summer and winter periods in downtown Karlsruhe in southwestern Germany. The chromophore and chemical composition of brown carbon was determined by excitation–emission spectroscopy and mass spectrometry. The chromophore types and sources were substantially different in winter and summer. Humic-like chromophores of different degrees of oxidation dominated and were associated with molecules of different molecular weight and nitrogen content.
Linyu Gao, Junwei Song, Claudia Mohr, Wei Huang, Magdalena Vallon, Feng Jiang, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 22, 6001–6020, https://doi.org/10.5194/acp-22-6001-2022, https://doi.org/10.5194/acp-22-6001-2022, 2022
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We study secondary organic aerosol (SOA) from β-caryophyllene (BCP) ozonolysis with and without nitrogen oxides over 213–313 K in the simulation chamber. The yields and the rate constants were determined at 243–313 K. Chemical compositions varied at different temperatures, indicating a strong impact on the BCP ozonolysis pathways. This work helps to better understand the SOA from BCP ozonolysis for conditions representative of the real atmosphere from the boundary layer to the upper troposphere.
Magdalena Vallon, Linyu Gao, Feng Jiang, Bianca Krumm, Jens Nadolny, Junwei Song, Thomas Leisner, and Harald Saathoff
Atmos. Meas. Tech., 15, 1795–1810, https://doi.org/10.5194/amt-15-1795-2022, https://doi.org/10.5194/amt-15-1795-2022, 2022
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A LED-based light source has been constructed for the AIDA simulation chamber at the Karlsruhe Institute of Technology. It allows aerosol formation and ageing studies under atmospherically relevant illumination intensities and spectral characteristics at temperatures from –90 °C to 30 °C with the possibility of changing the photon flux and irradiation spectrum at any point. The first results of photolysis experiments with 2,3-pentanedione, iron oxalate and a brown carbon component are shown.
Lucía Caudillo, Birte Rörup, Martin Heinritzi, Guillaume Marie, Mario Simon, Andrea C. Wagner, Tatjana Müller, Manuel Granzin, Antonio Amorim, Farnoush Ataei, Rima Baalbaki, Barbara Bertozzi, Zoé Brasseur, Randall Chiu, Biwu Chu, Lubna Dada, Jonathan Duplissy, Henning Finkenzeller, Loïc Gonzalez Carracedo, Xu-Cheng He, Victoria Hofbauer, Weimeng Kong, Houssni Lamkaddam, Chuan P. Lee, Brandon Lopez, Naser G. A. Mahfouz, Vladimir Makhmutov, Hanna E. Manninen, Ruby Marten, Dario Massabò, Roy L. Mauldin, Bernhard Mentler, Ugo Molteni, Antti Onnela, Joschka Pfeifer, Maxim Philippov, Ana A. Piedehierro, Meredith Schervish, Wiebke Scholz, Benjamin Schulze, Jiali Shen, Dominik Stolzenburg, Yuri Stozhkov, Mihnea Surdu, Christian Tauber, Yee Jun Tham, Ping Tian, António Tomé, Steffen Vogt, Mingyi Wang, Dongyu S. Wang, Stefan K. Weber, André Welti, Wang Yonghong, Wu Yusheng, Marcel Zauner-Wieczorek, Urs Baltensperger, Imad El Haddad, Richard C. Flagan, Armin Hansel, Kristina Höhler, Jasper Kirkby, Markku Kulmala, Katrianne Lehtipalo, Ottmar Möhler, Harald Saathoff, Rainer Volkamer, Paul M. Winkler, Neil M. Donahue, Andreas Kürten, and Joachim Curtius
Atmos. Chem. Phys., 21, 17099–17114, https://doi.org/10.5194/acp-21-17099-2021, https://doi.org/10.5194/acp-21-17099-2021, 2021
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We performed experiments in the CLOUD chamber at CERN at low temperatures to simulate new particle formation in the upper free troposphere (at −30 ºC and −50 ºC). We measured the particle and gas phase and found that most of the compounds present in the gas phase are detected as well in the particle phase. The major compounds in the particles are C8–10 and C18–20. Specifically, we showed that C5 and C15 compounds are detected in a mixed system with isoprene and α-pinene at −30 ºC, 20 % RH.
Larissa Lacher, Hans-Christian Clemen, Xiaoli Shen, Stephan Mertes, Martin Gysel-Beer, Alireza Moallemi, Martin Steinbacher, Stephan Henne, Harald Saathoff, Ottmar Möhler, Kristina Höhler, Thea Schiebel, Daniel Weber, Jann Schrod, Johannes Schneider, and Zamin A. Kanji
Atmos. Chem. Phys., 21, 16925–16953, https://doi.org/10.5194/acp-21-16925-2021, https://doi.org/10.5194/acp-21-16925-2021, 2021
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We investigate ice-nucleating particle properties at Jungfraujoch during the 2017 joint INUIT/CLACE field campaign, to improve the knowledge about those rare particles in a cloud-relevant environment. By quantifying ice-nucleating particles in parallel to single-particle mass spectrometry measurements, we find that mineral dust and aged sea spray particles are potential candidates for ice-nucleating particles. Our findings are supported by ice residual analysis and source region modeling.
Julia Schneider, Kristina Höhler, Robert Wagner, Harald Saathoff, Martin Schnaiter, Tobias Schorr, Isabelle Steinke, Stefan Benz, Manuel Baumgartner, Christian Rolf, Martina Krämer, Thomas Leisner, and Ottmar Möhler
Atmos. Chem. Phys., 21, 14403–14425, https://doi.org/10.5194/acp-21-14403-2021, https://doi.org/10.5194/acp-21-14403-2021, 2021
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Homogeneous freezing is a relevant mechanism for the formation of cirrus clouds in the upper troposphere. Based on an extensive set of homogeneous freezing experiments at the AIDA chamber with aqueous sulfuric acid aerosol, we provide a new fit line for homogeneous freezing onset conditions of sulfuric acid aerosol focusing on cirrus temperatures. In the atmosphere, homogeneous freezing thresholds have important implications on the cirrus cloud occurrence and related cloud radiative effects.
Naruki Hiranuma, Brent W. Auvermann, Franco Belosi, Jack Bush, Kimberly M. Cory, Dimitrios G. Georgakopoulos, Kristina Höhler, Yidi Hou, Larissa Lacher, Harald Saathoff, Gianni Santachiara, Xiaoli Shen, Isabelle Steinke, Romy Ullrich, Nsikanabasi S. Umo, Hemanth S. K. Vepuri, Franziska Vogel, and Ottmar Möhler
Atmos. Chem. Phys., 21, 14215–14234, https://doi.org/10.5194/acp-21-14215-2021, https://doi.org/10.5194/acp-21-14215-2021, 2021
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We present laboratory and field studies showing that an open-lot livestock facility is a substantial source of atmospheric ice-nucleating particles (INPs). The ambient concentration of INPs from livestock facilities in Texas is very high. It is up to several thousand INPs per liter below –20 °C and may impact regional aerosol–cloud interactions. About 50% of feedlot INPs were supermicron in diameter. No notable amount of known ice-nucleating microorganisms was found in our feedlot samples.
Hengheng Zhang, Frank Wagner, Harald Saathoff, Heike Vogel, Gholam Ali Hoshyaripour, Vanessa Bachmann, Jochen Förstner, and Thomas Leisner
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2021-193, https://doi.org/10.5194/amt-2021-193, 2021
Revised manuscript not accepted
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The evolution and the properties of Saharan dust plume were characterized by LIDARs, a sun photometer, and a regional transport model. Comparison between LIDAR measurements, sun photometer and ICON-ART predictions shows a good agreement for dust arrival time, dust layer height, and dust structure but also that the model overestimates the backscatter coefficients by a factor of (2.2 ± 0.16) and underestimate aerosol optical depth by a factor of (1.5 ± 0.11).
Barbara Bertozzi, Robert Wagner, Junwei Song, Kristina Höhler, Joschka Pfeifer, Harald Saathoff, Thomas Leisner, and Ottmar Möhler
Atmos. Chem. Phys., 21, 10779–10798, https://doi.org/10.5194/acp-21-10779-2021, https://doi.org/10.5194/acp-21-10779-2021, 2021
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Internally mixed particles composed of sulfate and organics are among the most abundant aerosol types. Their ice nucleation (IN) ability influences the formation of cirrus and, thus, the climate. We show that the presence of a thin organic coating suppresses the heterogeneous IN ability of crystalline ammonium sulfate particles. However, the IN ability of the same particle can substantially change if subjected to atmospheric processing, mainly due to differences in the resulting morphology.
Robert Wagner, Baptiste Testa, Michael Höpfner, Alexei Kiselev, Ottmar Möhler, Harald Saathoff, Jörn Ungermann, and Thomas Leisner
Atmos. Meas. Tech., 14, 1977–1991, https://doi.org/10.5194/amt-14-1977-2021, https://doi.org/10.5194/amt-14-1977-2021, 2021
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During the Asian summer monsoon period, air pollutants are transported from layers near the ground to high altitudes of 13 to 18 km in the atmosphere. Infrared measurements have shown that particles composed of solid ammonium nitrate are a major part of these pollutants. To enable the quantitative analysis of the infrared spectra, we have determined for the first time accurate optical constants of ammonium nitrate for the low-temperature conditions of the upper atmosphere.
Cited articles
Alpert, P. A., Ciuraru, R., Rossignol, S., Passananti, M., Tinel, L., Perrier, S., Dupart, Y., Steimer, S. S., Ammann, M., Donaldson, D. J., and George, C.: Fatty Acid Surfactant Photochemistry Results in New Particle Formation, Sci. Rep.-UK, 7, https://doi.org/10.1038/s41598-017-12601-2, 2017.
Atkinson, R.: Atmospheric chemistry of VOCs and NOx, Atmos. Environ., 34, 2063–2101, https://doi.org/10.1016/S1352-2310(99)00460-4, 2000.
Backus, E. H. G., Bonn, D., Cantin, S., Roke, S., and Bonn, M.: Laser-Heating-Induced Displacement of Surfactants on the Water Surface, J. Phys. Chem. B, 116, 2703–2712, https://doi.org/10.1021/jp2074545, 2012.
Badban, S., Hyde, A. E., and Phan, C. M.: Hydrophilicity of Nonanoic Acid and Its Conjugate Base at the Air/Water Interface, ACS Omega, 2, 5565–5573, https://doi.org/10.1021/acsomega.7b00960, 2017.
Bernard, F., Ciuraru, R., Boréave, A., and George, C.: Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface, Environ. Sci. Technol., 50, 8678–8686, https://doi.org/10.1021/acs.est.6b03520, 2016.
Boucher, O.: Atmospheric Aerosols, in: Atmospheric Aerosols: Properties and Climate Impacts, edited by: Boucher, O., Springer Netherlands, Dordrecht, https://doi.org/10.1007/978-94-017-9649-1_2, 9–24, 2015.
Brüggemann, M., Hayeck, N., and George, C.: Interfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols, Nat. Commun., 9, 2101, https://doi.org/10.1038/s41467-018-04528-7, 2018.
Carlson, D. J.: Dissolved organic materials in surface microlayers: Temporal and spatial variability and relation to sea state, Limnol. Oceanogr., 28, 415–431, https://doi.org/10.4319/lo.1983.28.3.0415, 1983.
Carlson, D. J. and Mayer, L. M.: Enrichment of dissolved phenolic material in the surface microlayer of coastal waters, Nature, 286, 482–483, https://doi.org/10.1038/286482a0, 1980.
Carpenter, L. J. and Nightingale, P. D.: Chemistry and Release of Gases from the Surface Ocean, Chem. Rev., 115, 4015–4034, https://doi.org/10.1021/cr5007123, 2015.
Ciuraru, R., Fine, L., van Pinxteren, M., D'Anna, B., Herrmann, H., and George, C.: Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface, Sci. Rep.-UK, 5, 12741, https://doi.org/10.1038/srep12741, 2015.
Covington, A. K. and Whitfield, M.: Recommendations for the determination of pH in sea water and estuarine waters, Pure Appl. Chem., 60, 865–870, https://doi.org/10.1351/pac198860060865, 1988.
Cui, G., Liu, Y., and Tong, S.: Hydrogeochemical processes controlling the salinity of surface water and groundwater in an inland saline-alkali wetland in western Jilin, China, Front. Ecol. Evol., 10, https://doi.org/10.3389/fevo.2022.993849, 2022.
Dalton, E. Z., Wang, X., Wappes, S. C., Petersen-Sonn, E. A., Hagan, S. N., George, C., and Raff, J. D.: Photosensitizers Regulate Nitrate Photoproduct Yields in Bulk Aqueous Matrices, Environ. Sci. Technol., 59, 6142–6154, https://doi.org/10.1021/acs.est.4c09491, 2025.
Dickson, A. G.: The measurement of sea water pH, Mar. Chem., 44, 131–142, https://doi.org/10.1016/0304-4203(93)90198-W, 1993.
Dommer, A. C., Rogers, M. M., Carter-Fenk, K. A., Wauer, N. A., Rubio, P., Davasam, A., Allen, H. C., and Amaro, R. E.: Interfacial Enrichment of Lauric Acid Assisted by Long-Chain Fatty Acids, Acidity and Salinity at Sea Spray Aerosol Surfaces, J. Phys. Chem. A, 128, 7195–7207, https://doi.org/10.1021/acs.jpca.4c03335, 2024.
Doughty, B., Yin, P. C., and Ma, Y. Z.: Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air-Water Interface, Langmuir, 32, 8116–8122, https://doi.org/10.1021/acs.langmuir.6b01643, 2016.
Freeman-Gallant, G., Davis, E. J., Scholer, E., Alija, O., and Navea, J. G.: Photooxidation of Nonanoic Acid by Molecular and Complex Environmental Photosensitizers, J. Phys. Chem. A, 128, 9792–9803, https://doi.org/10.1021/acs.jpca.4c05608, 2024.
Gantt, B. and Meskhidze, N.: The physical and chemical characteristics of marine primary organic aerosol: a review, Atmos. Chem. Phys., 13, 3979–3996, https://doi.org/10.5194/acp-13-3979-2013, 2013.
García Rey, N., Weißenborn, E., Schulze-Zachau, F., Gochev, G., and Braunschweig, B.: Quantifying Double-Layer Potentials at Liquid–Gas Interfaces from Vibrational Sum-Frequency Generation, J. Phys. Chem. C, 123, 1279–1286, https://doi.org/10.1021/acs.jpcc.8b10097, 2019.
Gautam, K. S., Schwab, A. D., Dhinojwala, A., Zhang, D., Dougal, S. M., and Yeganeh, M. S.: Molecular Structure of Polystyrene at Air/Polymer and Solid/Polymer Interfaces, Phys. Rev. Lett., 85, 3854–3857, https://doi.org/10.1103/PhysRevLett.85.3854, 2000.
Ghosh, A., Campen, R. K., Sovago, M., and Bonn, M.: Structure and dynamics of interfacial water in model lung surfactants, Faraday Discuss., 141, 145–159, https://doi.org/10.1039/b805858j, 2009.
Goswami, P. C., Mayo, P. de, Ramnath, N., Bernard, G., Omkaram, N., Scheffer, J. R., and Wong, Y.-F.: Modification of photochemical reactivity through the use of clathrates: the Norrish type I and type II reactions in Dianin's compound, Can. J. Chem., 63, 2719–2725, https://doi.org/10.1139/v85-451, 1985.
Gragson, D. E. and Richmond, G. L.: Investigations of the Structure and Hydrogen Bonding of Water Molecules at Liquid Surfaces by Vibrational Sum Frequency Spectroscopy, J. Phys. Chem. B, 102, 3847–3861, https://doi.org/10.1021/jp9806011, 1998.
Hardt, M., Honnigfort, C., Carrascosa-Tejedor, J., Braun, M. G., Winnall, S., Glikman, D., Gutfreund, P., Campbell, R. A., and Braunschweig, B.: Photoresponsive arylazopyrazole surfactant/PDADMAC mixtures: reversible control of bulk and interfacial properties, Nanoscale, 16, 9975–9984, https://doi.org/10.1039/D3NR05414D, 2024.
Hendrickson, B. N., Brooks, S. D., Thornton, D. C. O., Moore, R. H., Crosbie, E., Ziemba, L. D., Carlson, C. A., Baetge, N., Mirrielees, J. A., and Alsante, A. N.: Role of Sea Surface Microlayer Properties in Cloud Formation, Front. Mar. Sci., 7, https://doi.org/10.3389/fmars.2020.596225, 2021.
Henry, M. C., Yang, Y. J., Pizzolatto, R. L., and Messmer, M. C.: Competitive adsorption of 2,4,7,9-tetramethyl-5-decyn-4,7-diol and linear alkane surfactants at the air/water interface, Langmuir, 19, 2592–2598, https://doi.org/10.1021/la026812l, 2003.
Jiang, L. Q., Carter, B. R., Feely, R. A., Lauvset, S. K., and Olsen, A.: Surface ocean pH and buffer capacity: past, present and future, Sci. Rep.-UK, 9, 18624, https://doi.org/10.1038/s41598-019-55039-4, 2019.
Jiménez, M. C. and Miranda, M. A.: Organic aspects. Oxygen-containing functions, Royal Society of Chemistry, 169–193, https://doi.org/10.1039/9781788013598-00169, 2018.
Kroll, J. H., Lim, C. Y., Kessler, S. H., and Wilson, K. R.: Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon, J. Phys. Chem. A, 119, 10767–10783, https://doi.org/10.1021/acs.jpca.5b06946, 2015.
Kusaka, R., Ishiyama, T., Nihonyanagi, S., Morita, A., and Tahara, T.: Structure at the air/water interface in the presence of phenol: a study using heterodyne-detected vibrational sum frequency generation and molecular dynamics simulation, Phys. Chem. Chem. Phys., 20, 3002–3009, https://doi.org/10.1039/C7CP05150F, 2018.
Lankone, R. S., Deline, A. R., Barclay, M., and Fairbrother, D. H.: UV–Vis quantification of hydroxyl radical concentration and dose using principal component analysis, Talanta, 218, 121148, https://doi.org/10.1016/j.talanta.2020.121148, 2020.
Liss, P. S. and Duce, R. A.: The Sea Surface and Global Change, Cambridge University Press, ISBN 9780521017459, ISBN 0521017459, 2005.
Lu, R., Gan, W., Wu, B., Zhang, Z., Guo, Y., and Wang, H.: C-H Stretching Vibrations of Methyl, Methylene and Methine Groups at the Vapor/Alcohol (n= 1–8) Interfaces, J. Phys. Chem. B, 109, 14118–14129, https://doi.org/10.1021/jp051565q, 2005.
MacPhail, R. A., Strauss, H. L., Snyder, R. G., and Elliger, C. A.: Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 2. Long, all-trans chains, J. Phys. Chem., 88, 334–341, https://doi.org/10.1021/j150647a002, 1984.
Marion, G. M., Millero, F. J., Camões, M. F., Spitzer, P., Feistel, R., and Chen, C. T. A.: pH of seawater, Mar. Chem., 126, 89–96, https://doi.org/10.1016/j.marchem.2011.04.002, 2011.
Meerkötter, R. and Vázquez-Navarro, M.: Earth's Radiation Budget: The Driver for Weather and Climate, in: Atmospheric Physics: Background – Methods – Trends, edited by: Schumann, U., Springer Berlin Heidelberg, Berlin, Heidelberg, https://doi.org/10.1007/978-3-642-30183-4_4, 55–67, 2012.
Milinković, A., Penezić, A., Kušan, A. C., Gluščić, V., Žužul, S., Skejić, S., Šantić, D., Godec, R., Pehnec, G., Omanović, D., Engel, A., and Frka, S.: Variabilities of biochemical properties of the sea surface microlayer: Insights to the atmospheric deposition impacts, Sci. Total Environ., 838, 156440, https://doi.org/10.1016/j.scitotenv.2022.156440, 2022.
Millero, F. J., Feistel, R., Wright, D. G., and McDougall, T. J.: The composition of Standard Seawater and the definition of the Reference-Composition Salinity Scale, Deep-Sea Res. Part I Oceanogr. Res. Pap., 55, 50–72, https://doi.org/10.1016/j.dsr.2007.10.001, 2008.
Miranda, P. B. and Shen, Y. R.: Liquid interfaces: A study by sum-frequency vibrational spectroscopy, J. Phys. Chem. B, 103, 3292–3307, https://doi.org/10.1021/jp9843757, 1999.
Mmereki, B. T. and Donaldson, D. J.: Laser induced fluorescence of pyrene at an organic coated air–water interface, Phys. Chem. Chem. Phys., 4, 4186–4191, https://doi.org/10.1039/b204754c, 2002.
Mora Garcia, S. L., Pandit, S., Navea, J. G., and Grassian, V. H.: Nitrous Acid (HONO) Formation from the Irradiation of Aqueous Nitrate Solutions in the Presence of Marine Chromophoric Dissolved Organic Matter: Comparison to Other Organic Photosensitizers, ACS Earth Sp. Chem., 5, 3056–3064, https://doi.org/10.1021/acsearthspacechem.1c00292, 2021.
Morgan, J. J.: Aquatic Chemistry-Chemical Equilibria and Rates in Natural Waters, John Wiley, USA, ISBN 9780471511854, ISBN 0471511854, 1995.
Nihonyanagi, S., Mondal, J. A., Yamaguchi, S., and Tahara, T.: Structure and dynamics of interfacial water studied by heterodyne-detected vibrational sum-frequency generation, Annu. Rev. Phys. Chem., 64, 579–603, https://doi.org/10.1146/annurev-physchem-040412-110138, 2013.
Numadate, N., Saito, S., Nojima, Y., Ishibashi, T., Enami, S., and Hama, T.: Direct Observation and Quantitative Measurement of OH Radical Desorption During the Ultraviolet Photolysis of Liquid Nonanoic Acid, J. Phys. Chem. Lett., 13, 8290–8297, https://doi.org/10.1021/acs.jpclett.2c02199, 2022.
Ouafo-Leumbe, M. R., Galy-Lacaux, C., Liousse, C., Pont, V., Akpo, A., Doumbia, T., Gardrat, E., Zouiten, C., Sigha-Nkamdjou, L., and Ekodeck, G. E.: Chemical composition and sources of atmospheric aerosols at Djougou (Benin), Meteorol. Atmos. Phys., 130, 591–609, https://doi.org/10.1007/s00703-017-0538-5, 2018.
Rao, Y., Li, X., Lei, X. G., Jockusch, S., George, M. W., Turro, N. J., and Eisenthal, K. B.: Observations of Interfacial Population and Organization of Surfactants with Sum Frequency Generation and Surface Tension, J. Phys. Chem. C, 115, 12064–12067, https://doi.org/10.1021/jp201799z, 2011.
Riva, M., Rantala, P., Krechmer, J. E., Peräkylä, O., Zhang, Y., Heikkinen, L., Garmash, O., Yan, C., Kulmala, M., Worsnop, D., and Ehn, M.: Evaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic species, Atmos. Meas. Tech., 12, 2403–2421, https://doi.org/10.5194/amt-12-2403-2019, 2019.
Schultz, M. J., Baldelli, S., Schnitzer, C., and Simonelli, D.: Aqueous Solution/Air Interfaces Probed with Sum Frequency Generation Spectroscopy, J. Phys. Chem. B, 106, 5313–5324, https://doi.org/10.1021/jp014466v, 2002.
Sellegri, K., O'Dowd, C. D., Yoon, Y. J., Jennings, S. G., and de Leeuw, G.: Surfactants and submicron sea spray generation, J. Geophys. Res., 111, https://doi.org/10.1029/2005jd006658, 2006.
Sellegri, K., Simó, R., Wang, B., Alpert, P. A., Altieri, K., Burrows, S., Hopkins, F. E., Koren, I., McCoy, I. L., Ovadnevaite, J., Salter, M., and Schmale, J.: Influence of open ocean biogeochemistry on aerosol and clouds: Recent findings and perspectives, Elementa Sci. Anth., 12, https://doi.org/10.1525/elementa.2023.00058, 2024.
Shen, Y. R.: Surface Properties Probed by Second-Harmonic and Sum-Frequency Generation, Nature, 337, 519–525, https://doi.org/10.1038/337519a0, 1989.
Shultz, M. J., Schnitzer, C., Simonelli, D., and Baldelli, S.: Sum frequency generation spectroscopy of the aqueous interface: ionic and soluble molecular solutions, Int. Rev. Phys. Chem., 19, 123–153, https://doi.org/10.1080/014423500229882, 2000.
Snyder, R. G., Strauss, H. L., and Elliger, C. A.: Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains, J. Phys. Chem., 86, 5145–5150, https://doi.org/10.1021/j100223a018, 1982.
Sovago, M., Campen, R. K., Wurpel, G. W. H., Müller, M., Bakker, H. J., and Bonn, M.: Vibrational Response of Hydrogen-Bonded Interfacial Water is Dominated by Intramolecular Coupling, Phys. Rev. Lett., 100, 173901, https://doi.org/10.1103/PhysRevLett.100.173901, 2008.
Stolle, C., Ribas-Ribas, M., Badewien, T. H., Barnes, J., Carpenter, L. J., Chance, R., Damgaard, L. R., Durán Quesada, A. M., Engel, A., Frka, S., Galgani, L., Gašparović, B., Gerriets, M., Hamizah Mustaffa, N. I., Herrmann, H., Kallajoki, L., Pereira, R., Radach, F., Revsbech, N. P., Rickard, P., Saint, A., Salter, M., Striebel, M., Triesch, N., Uher, G., Upstill-Goddard, R. C., van Pinxteren, M., Zäncker, B., Zieger, P., and Wurl, O.: The MILAN Campaign: Studying Diel Light Effects on the Air–Sea Interface, B. Am. Meteorol. Soc., 101, E146–E166, https://doi.org/10.1175/BAMS-D-17-0329.1, 2020.
Tilstone, G. H., Airs, ruth L., Vicente, V. M., Widdicombe, C., and Llewellyn, C.: High concentrations of mycosporine-like amino acids and colored dissolved organic matter in the sea surface microlayer off the Iberian Peninsula, Limnol. Oceanogr., 55, 1835–1850, https://doi.org/10.4319/lo.2010.55.5.1835, 2010.
Tinel, L., Rossignol, S., Bianco, A., Passananti, M., Perrier, S., Wang, X., Brigante, M., Donaldson, D. J., and George, C.: Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface, Environ. Sci. Technol., 50, 11041–11048, https://doi.org/10.1021/acs.est.6b03165, 2016.
Tinel, L., Abbatt, J., Saltzman, E., Engel, A., Fernandez, R., Li, Q., Mahajan, A. S., Nicewonger, M., Novak, G., Saiz-Lopez, A., Schneider, S., and Wang, S.: Impacts of ocean biogeochemistry on atmospheric chemistry, Elementa Sci. Anth., 11, https://doi.org/10.1525/elementa.2023.00032, 2023.
Truong, V. N. T., Wang, X. M., Dang, L. X., and Miller, J. D.: Interfacial Water Features at Air-Water Interfaces as Influenced by Charged Surfactants, J. Phys. Chem. B, 123, 2397–2404, https://doi.org/10.1021/acs.jpcb.9b01246, 2019.
van Pinxteren, M., Fomba, K. W., Triesch, N., Stolle, C., Wurl, O., Bahlmann, E., Gong, X., Voigtländer, J., Wex, H., Robinson, T.-B., Barthel, S., Zeppenfeld, S., Hoffmann, E. H., Roveretto, M., Li, C., Grosselin, B., Daële, V., Senf, F., van Pinxteren, D., Manzi, M., Zabalegui, N., Frka, S., Gašparović, B., Pereira, R., Li, T., Wen, L., Li, J., Zhu, C., Chen, H., Chen, J., Fiedler, B., von Tümpling, W., Read, K. A., Punjabi, S., Lewis, A. C., Hopkins, J. R., Carpenter, L. J., Peeken, I., Rixen, T., Schulz-Bull, D., Monge, M. E., Mellouki, A., George, C., Stratmann, F., and Herrmann, H.: Marine organic matter in the remote environment of the Cape Verde islands – an introduction and overview to the MarParCloud campaign, Atmos. Chem. Phys., 20, 6921–6951, https://doi.org/10.5194/acp-20-6921-2020, 2020.
Varga, I., Keszthelyi, T., Meszaros, R., Hakkel, O., and Gilanyi, T.: Observation of a liquid-gas phase transition in monolayers of alkyltrimethylammonium alkyl sulfates adsorbed at the air/water interface, J. Phys. Chem. B, 109, 872–878, https://doi.org/10.1021/jp048006o, 2005.
Wang, Y., Zeng, J., Wu, B., Song, W., Hu, W., Liu, J., Yang, Y., Yu, Z., Wang, X., and Gligorovski, S.: Production of Volatile Organic Compounds by Ozone Oxidation Chemistry at the South China Sea Surface Microlayer, ACS Earth Sp. Chem., 7, 1306–1313, https://doi.org/10.1021/acsearthspacechem.3c00102, 2023.
Wilson, T. W., Ladino, L. A., Alpert, P. A., Breckels, M. N., Brooks, I. M., Browse, J., Burrows, S. M., Carslaw, K. S., Huffman, J. A., Judd, C., Kilthau, W. P., Mason, R. H., McFiggans, G., Miller, L. A., Najera, J. J., Polishchuk, E., Rae, S., Schiller, C. L., Si, M., Temprado, J. V, Whale, T. F., Wong, J. P. S., Wurl, O., Yakobi-Hancock, J. D., Abbatt, J. P. D., Aller, J. Y., Bertram, A. K., Knopf, D. A., and Murray, B. J.: A marine biogenic source of atmospheric ice-nucleating particles, Nature, 525, https://doi.org/10.1038/nature14986, 2015.
Xing, J., Zheng, S., Li, S., Huang, L., Wang, X., Kelly, J. T., Wang, S., Liu, C., Jang, C., Zhu, Y., Zhang, J., Bian, J., Liu, T.-Y., and Hao, J.: Mimicking atmospheric photochemical modeling with a deep neural network, Atmos. Res., 265, 105919, https://doi.org/10.1016/j.atmosres.2021.105919, 2022.
Yan, S., Liu, Y., Lian, L., Li, R., Ma, J., Zhou, H., and Song, W.: Photochemical formation of carbonate radical and its reaction with dissolved organic matters, Water Res., 161, 288–296, https://doi.org/10.1016/j.watres.2019.06.002, 2019.
Yang, L., Zhang, J., Engel, A., and Yang, G.-P.: Spatio-temporal distribution, photoreactivity and environmental control of dissolved organic matter in the sea-surface microlayer of the eastern marginal seas of China, Biogeosciences, 19, 5251–5268, https://doi.org/10.5194/bg-19-5251-2022, 2022.
You, B., Li, S., Tsona, N. T., Li, J., Xu, L., Yang, Z., Cheng, S., Chen, Q., George, C., Ge, M., and Du, L.: Environmental Processing of Short-Chain Fatty Alcohols Induced by Photosensitized Chemistry of Brown Carbons, ACS Earth Sp. Chem., 4, 631–640, https://doi.org/10.1021/acsearthspacechem.0c00023, 2020.
Zhang, D., Gutow, J., and Eisenthal, K. B.: Vibrational-spectra, orientations, and phase-transitions in long-chain amphiphiles at the air-water-interface – probing the head and tail groups by sum-frequency generation, J. Phys. Chem., 98, 13729–13734, https://doi.org/10.1021/j100102a045, 1994.
Short summary
This study examines how environmental factors (sunlight, pH, salinity, and surface chemistry) affect air–water interface reactions. Using a surface-specific technique, sum-frequency generation (SFG) spectroscopy, we found that compounds like 4-benzoylbenzoic acid (4-BBA) not only act as photosensitizers but also generate new surface-active products under UV light. These reactions have implications for oceans, lakes, and clouds, providing crucial insights for modeling natural processes.
This study examines how environmental factors (sunlight, pH, salinity, and surface chemistry)...
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