Articles | Volume 22, issue 24
https://doi.org/10.5194/acp-22-16003-2022
© Author(s) 2022. 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-22-16003-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| Highlight paper
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20 Dec 2022
Research article | Highlight paper |
| 20 Dec 2022
| 20 Dec 2022
Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes
Department of Civil and Environmental Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts 02139, United States
now at: Atmospheric Chemistry Observations and Modeling, National Center for Atmospheric Research, Boulder, Colorado
80301, United States
Matthew B. Goss
Department of Civil and Environmental Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts 02139, United States
Jordan E. Krechmer
Center for Aerosol and Cloud Chemistry, Aerodyne Research
Incorporated, Billerica, Massachusetts 01821, United States
Francesca Majluf
Center for Aerosol and Cloud Chemistry, Aerodyne Research
Incorporated, Billerica, Massachusetts 01821, United States
Alexander Zaytsev
John A. Paulson School of Engineering and Applied Sciences, Harvard
University, Cambridge, Massachusetts 02138, United States
Yaowei Li
John A. Paulson School of Engineering and Applied Sciences, Harvard
University, Cambridge, Massachusetts 02138, United States
Joseph R. Roscioli
Center for Atmospheric and Environmental Chemistry, Aerodyne Research
Incorporated, Billerica, Massachusetts 01821, United States
Manjula Canagaratna
Center for Aerosol and Cloud Chemistry, Aerodyne Research
Incorporated, Billerica, Massachusetts 01821, United States
Frank N. Keutsch
John A. Paulson School of Engineering and Applied Sciences, Harvard
University, Cambridge, Massachusetts 02138, United States
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
Colette L. Heald
Department of Civil and Environmental Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts 02139, United States
Department of Civil and Environmental Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts 02139, United States
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Therese S. Carter, Colette L. Heald, Jesse H. Kroll, Eric C. Apel, Donald Blake, Matthew Coggon, Achim Edtbauer, Georgios Gkatzelis, Rebecca S. Hornbrook, Jeff Peischl, Eva Y. Pfannerstill, Felix Piel, Nina G. Reijrink, Akima Ringsdorf, Carsten Warneke, Jonathan Williams, Armin Wisthaler, and Lu Xu
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Vigneshkumar Balamurugan, Jia Chen, Zhen Qu, Xiao Bi, and Frank N. Keutsch
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Andrew J. Lindsay, Daniel C. Anderson, Rebecca A. Wernis, Yutong Liang, Allen H. Goldstein, Scott C. Herndon, Joseph R. Roscioli, Christoph Dyroff, Ed C. Fortner, Philip L. Croteau, Francesca Majluf, Jordan E. Krechmer, Tara I. Yacovitch, Walter B. Knighton, and Ezra C. Wood
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This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
Ka Ming Fung, Colette L. Heald, Jesse H. Kroll, Siyuan Wang, Duseong S. Jo, Andrew Gettelman, Zheng Lu, Xiaohong Liu, Rahul A. Zaveri, Eric C. Apel, Donald R. Blake, Jose-Luis Jimenez, Pedro Campuzano-Jost, Patrick R. Veres, Timothy S. Bates, John E. Shilling, and Maria Zawadowicz
Atmos. Chem. Phys., 22, 1549–1573, https://doi.org/10.5194/acp-22-1549-2022, https://doi.org/10.5194/acp-22-1549-2022, 2022
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Understanding the natural aerosol burden in the preindustrial era is crucial for us to assess how atmospheric aerosols affect the Earth's radiative budgets. Our study explores how a detailed description of dimethyl sulfide (DMS) oxidation (implemented in the Community Atmospheric Model version 6 with chemistry, CAM6-chem) could help us better estimate the present-day and preindustrial concentrations of sulfate and other relevant chemicals, as well as the resulting aerosol radiative impacts.
Juliana Gil-Loaiza, Joseph R. Roscioli, Joanne H. Shorter, Till H. M. Volkmann, Wei-Ren Ng, Jordan E. Krechmer, and Laura K. Meredith
Biogeosciences, 19, 165–185, https://doi.org/10.5194/bg-19-165-2022, https://doi.org/10.5194/bg-19-165-2022, 2022
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We evaluated a new diffusive soil probe integrated with high-resolution gas analyzers to measure soil gases in real time at a centimeter scale. Using columns with simple silica and soil, we captured changes in carbon dioxide (CO2), volatile organic compounds (VOCs), and nitrous oxide (N2O) with its isotopes to distinguish potential nutrient sources and microbial metabolism. This approach will advance the use of soil gases as important signals to understand and monitor soil fertility and health.
Dongyu S. Wang, Chuan Ping Lee, Jordan E. Krechmer, Francesca Majluf, Yandong Tong, Manjula R. Canagaratna, Julia Schmale, André S. H. Prévôt, Urs Baltensperger, Josef Dommen, Imad El Haddad, Jay G. Slowik, and David M. Bell
Atmos. Meas. Tech., 14, 6955–6972, https://doi.org/10.5194/amt-14-6955-2021, https://doi.org/10.5194/amt-14-6955-2021, 2021
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To understand the sources and fate of particulate matter in the atmosphere, the ability to quantitatively describe its chemical composition is essential. In this work, we developed a calibration method for a state-of-the-art measurement technique without the need for chemical standards. Statistical analyses identified the driving factors behind instrument sensitivity variability towards individual components of particulate matter.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6835–6850, https://doi.org/10.5194/amt-14-6835-2021, https://doi.org/10.5194/amt-14-6835-2021, 2021
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Iodide-adduct chemical ionization mass spectrometry (I-CIMS) has been widely used to analyze airborne organics. In this study, I-CIMS sensitivities of isomers within a formula are found to generally vary by 1 and up to 2 orders of magnitude. Comparisons between measured and predicted moles, obtained using a voltage-scanning calibration approach, show that predictions for individual compounds or formulas might carry high uncertainty, yet the summed moles of analytes agree reasonably well.
Dandan Wei, Hariprasad D. Alwe, Dylan B. Millet, Brandon Bottorff, Michelle Lew, Philip S. Stevens, Joshua D. Shutter, Joshua L. Cox, Frank N. Keutsch, Qianwen Shi, Sarah C. Kavassalis, Jennifer G. Murphy, Krystal T. Vasquez, Hannah M. Allen, Eric Praske, John D. Crounse, Paul O. Wennberg, Paul B. Shepson, Alexander A. T. Bui, Henry W. Wallace, Robert J. Griffin, Nathaniel W. May, Megan Connor, Jonathan H. Slade, Kerri A. Pratt, Ezra C. Wood, Mathew Rollings, Benjamin L. Deming, Daniel C. Anderson, and Allison L. Steiner
Geosci. Model Dev., 14, 6309–6329, https://doi.org/10.5194/gmd-14-6309-2021, https://doi.org/10.5194/gmd-14-6309-2021, 2021
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Over the past decade, understanding of isoprene oxidation has improved, and proper representation of isoprene oxidation and isoprene-derived SOA (iSOA) formation in canopy–chemistry models is now recognized to be important for an accurate understanding of forest–atmosphere exchange. The updated FORCAsT version 2.0 improves the estimation of some isoprene oxidation products and is one of the few canopy models currently capable of simulating SOA formation from monoterpenes and isoprene.
Chenyang Bi, Jordan E. Krechmer, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6551–6560, https://doi.org/10.5194/amt-14-6551-2021, https://doi.org/10.5194/amt-14-6551-2021, 2021
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Calibration techniques have been recently developed to log-linearly correlate analyte sensitivity with CIMS operating conditions particularly for compounds without authentic standards. In this work, we examine the previously ignored bias in the log-linear-based calibration method and estimate an average bias of 30 %, with 1 order of magnitude for less sensitive compounds in some circumstances. A step-by-step guide was provided to reduce and even remove the bias.
Mao Xiao, Christopher R. Hoyle, Lubna Dada, Dominik Stolzenburg, Andreas Kürten, Mingyi Wang, Houssni Lamkaddam, Olga Garmash, Bernhard Mentler, Ugo Molteni, Andrea Baccarini, Mario Simon, Xu-Cheng He, Katrianne Lehtipalo, Lauri R. Ahonen, Rima Baalbaki, Paulus S. Bauer, Lisa Beck, David Bell, Federico Bianchi, Sophia Brilke, Dexian Chen, Randall Chiu, António Dias, Jonathan Duplissy, Henning Finkenzeller, Hamish Gordon, Victoria Hofbauer, Changhyuk Kim, Theodore K. Koenig, Janne Lampilahti, Chuan Ping Lee, Zijun Li, Huajun Mai, Vladimir Makhmutov, Hanna E. Manninen, Ruby Marten, Serge Mathot, Roy L. Mauldin, Wei Nie, Antti Onnela, Eva Partoll, Tuukka Petäjä, Joschka Pfeifer, Veronika Pospisilova, Lauriane L. J. Quéléver, Matti Rissanen, Siegfried Schobesberger, Simone Schuchmann, Yuri Stozhkov, Christian Tauber, Yee Jun Tham, António Tomé, Miguel Vazquez-Pufleau, Andrea C. Wagner, Robert Wagner, Yonghong Wang, Lena Weitz, Daniela Wimmer, Yusheng Wu, Chao Yan, Penglin Ye, Qing Ye, Qiaozhi Zha, Xueqin Zhou, Antonio Amorim, Ken Carslaw, Joachim Curtius, Armin Hansel, Rainer Volkamer, Paul M. Winkler, Richard C. Flagan, Markku Kulmala, Douglas R. Worsnop, Jasper Kirkby, Neil M. Donahue, Urs Baltensperger, Imad El Haddad, and Josef Dommen
Atmos. Chem. Phys., 21, 14275–14291, https://doi.org/10.5194/acp-21-14275-2021, https://doi.org/10.5194/acp-21-14275-2021, 2021
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Experiments at CLOUD show that in polluted environments new particle formation (NPF) is largely driven by the formation of sulfuric acid–base clusters, stabilized by amines, high ammonia concentrations or lower temperatures. While oxidation products of aromatics can nucleate, they play a minor role in urban NPF. Our experiments span 4 orders of magnitude variation of observed NPF rates in ambient conditions. We provide a framework based on NPF and growth rates to interpret ambient observations.
Louise N. Jensen, Manjula R. Canagaratna, Kasper Kristensen, Lauriane L. J. Quéléver, Bernadette Rosati, Ricky Teiwes, Marianne Glasius, Henrik B. Pedersen, Mikael Ehn, and Merete Bilde
Atmos. Chem. Phys., 21, 11545–11562, https://doi.org/10.5194/acp-21-11545-2021, https://doi.org/10.5194/acp-21-11545-2021, 2021
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This work targets the chemical composition of α-pinene-derived secondary organic aerosol (SOA) formed in the temperature range from -15 to 20°C. Experiments were conducted in an atmospheric simulation chamber. Positive matrix factorization analysis of data obtained by a high-resolution time-of-flight aerosol mass spectrometer shows that the elemental aerosol composition is controlled by the initial α-pinene concentration and temperature during SOA formation.
Benjamin A. Nault, Duseong S. Jo, Brian C. McDonald, Pedro Campuzano-Jost, Douglas A. Day, Weiwei Hu, Jason C. Schroder, James Allan, Donald R. Blake, Manjula R. Canagaratna, Hugh Coe, Matthew M. Coggon, Peter F. DeCarlo, Glenn S. Diskin, Rachel Dunmore, Frank Flocke, Alan Fried, Jessica B. Gilman, Georgios Gkatzelis, Jacqui F. Hamilton, Thomas F. Hanisco, Patrick L. Hayes, Daven K. Henze, Alma Hodzic, James Hopkins, Min Hu, L. Greggory Huey, B. Thomas Jobson, William C. Kuster, Alastair Lewis, Meng Li, Jin Liao, M. Omar Nawaz, Ilana B. Pollack, Jeffrey Peischl, Bernhard Rappenglück, Claire E. Reeves, Dirk Richter, James M. Roberts, Thomas B. Ryerson, Min Shao, Jacob M. Sommers, James Walega, Carsten Warneke, Petter Weibring, Glenn M. Wolfe, Dominique E. Young, Bin Yuan, Qiang Zhang, Joost A. de Gouw, and Jose L. Jimenez
Atmos. Chem. Phys., 21, 11201–11224, https://doi.org/10.5194/acp-21-11201-2021, https://doi.org/10.5194/acp-21-11201-2021, 2021
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Secondary organic aerosol (SOA) is an important aspect of poor air quality for urban regions around the world, where a large fraction of the population lives. However, there is still large uncertainty in predicting SOA in urban regions. Here, we used data from 11 urban campaigns and show that the variability in SOA production in these regions is predictable and is explained by key emissions. These results are used to estimate the premature mortality associated with SOA in urban regions.
Eleni Dovrou, Kelvin H. Bates, Jean C. Rivera-Rios, Joshua L. Cox, Joshua D. Shutter, and Frank N. Keutsch
Atmos. Chem. Phys., 21, 8999–9008, https://doi.org/10.5194/acp-21-8999-2021, https://doi.org/10.5194/acp-21-8999-2021, 2021
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We examined the mechanism and products of oxidation of dissolved sulfur dioxide with the main isomers of isoprene hydroxyl hydroperoxides, via laboratory and model analysis. Two chemical mechanism pathways are proposed and the results provide an improved understanding of the broader atmospheric chemistry and role of multifunctional organic hydroperoxides, which should be the dominant VOC oxidation products under low-NO conditions, highlighting their significant contribution to sulfate formation.
Jack C. Hensley, Adam W. Birdsall, Gregory Valtierra, Joshua L. Cox, and Frank N. Keutsch
Atmos. Chem. Phys., 21, 8809–8821, https://doi.org/10.5194/acp-21-8809-2021, https://doi.org/10.5194/acp-21-8809-2021, 2021
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We measured reactions of butenedial, an atmospheric dicarbonyl, in aqueous mixtures that mimic the conditions of aerosol particles. Major reaction products and rates were determined to assess their atmospheric relevance and to compare against other well-studied dicarbonyls. We suggest that the structure of the carbon backbone, not just the dominant functional group, plays a major role in dicarbonyl reactivity, influencing the fate and ability of dicarbonyls to produce brown carbon.
Chenshuo Ye, Bin Yuan, Yi Lin, Zelong Wang, Weiwei Hu, Tiange Li, Wei Chen, Caihong Wu, Chaomin Wang, Shan Huang, Jipeng Qi, Baolin Wang, Chen Wang, Wei Song, Xinming Wang, E Zheng, Jordan E. Krechmer, Penglin Ye, Zhanyi Zhang, Xuemei Wang, Douglas R. Worsnop, and Min Shao
Atmos. Chem. Phys., 21, 8455–8478, https://doi.org/10.5194/acp-21-8455-2021, https://doi.org/10.5194/acp-21-8455-2021, 2021
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We performed measurements of gaseous and particulate organic compounds using a state-of-the-art online mass spectrometer in urban air. Using the dataset, we provide a holistic chemical characterization of oxygenated organic compounds in the polluted urban atmosphere, which can serve as a reference for the future field measurements of organic compounds in cities.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 3895–3907, https://doi.org/10.5194/amt-14-3895-2021, https://doi.org/10.5194/amt-14-3895-2021, 2021
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Measurement techniques that can achieve molecular characterizations are necessary to understand the differences of fate and transport within isomers produced in the atmospheric oxidation process. In this work, we develop an instrument to conduct isomer-resolved measurements of particle-phase organics. We assess the number of isomers per chemical formula in atmospherically relevant samples and examine the feasibility of extending the use of an existing instrument to a broader range of analytes.
Mutian Ma, Laura-Hélèna Rivellini, YuXi Cui, Megan D. Willis, Rio Wilkie, Jonathan P. D. Abbatt, Manjula R. Canagaratna, Junfeng Wang, Xinlei Ge, and Alex K. Y. Lee
Atmos. Meas. Tech., 14, 2799–2812, https://doi.org/10.5194/amt-14-2799-2021, https://doi.org/10.5194/amt-14-2799-2021, 2021
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Chemical characterization of organic coatings is important to advance our understanding of the physio-chemical properties and atmospheric processing of black carbon (BC) particles. This work develops two approaches to improve the elemental analysis of oxygenated organic coatings using a soot-particle aerosol mass spectrometer. Analyzing ambient data with the new approaches indicated that secondary organics that coated on BC were likely less oxygenated compared to those externally mixed with BC.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
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We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
Ruud H. H. Janssen, Colette L. Heald, Allison L. Steiner, Anne E. Perring, J. Alex Huffman, Ellis S. Robinson, Cynthia H. Twohy, and Luke D. Ziemba
Atmos. Chem. Phys., 21, 4381–4401, https://doi.org/10.5194/acp-21-4381-2021, https://doi.org/10.5194/acp-21-4381-2021, 2021
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Bioaerosols are ubiquitous in the atmosphere and have the potential to affect cloud formation, as well as human and ecosystem health. However, their emissions are not well quantified, which hinders the assessment of their role in atmospheric processes. Here, we develop two new emission schemes for fungal spores based on multi-annual datasets of spore counts. We find that our modeled global emissions and burden are an order of magnitude lower than previous estimates.
Haiyan Li, Manjula R. Canagaratna, Matthieu Riva, Pekka Rantala, Yanjun Zhang, Steven Thomas, Liine Heikkinen, Pierre-Marie Flaud, Eric Villenave, Emilie Perraudin, Douglas Worsnop, Markku Kulmala, Mikael Ehn, and Federico Bianchi
Atmos. Chem. Phys., 21, 4123–4147, https://doi.org/10.5194/acp-21-4123-2021, https://doi.org/10.5194/acp-21-4123-2021, 2021
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For the first time, we performed binPMF analysis on the complex mass spectra acquired with the Vocus PTR-TOF in two European pine forests and identified various primary emission sources and secondary oxidation processes of atmospheric organic vapors, i.e., terpenes and their oxidation products, with varying oxidation degrees. Further insights were gained regarding monoterpene and sesquiterpene reactions based on the interpretation results.
Demetrios Pagonis, Pedro Campuzano-Jost, Hongyu Guo, Douglas A. Day, Melinda K. Schueneman, Wyatt L. Brown, Benjamin A. Nault, Harald Stark, Kyla Siemens, Alex Laskin, Felix Piel, Laura Tomsche, Armin Wisthaler, Matthew M. Coggon, Georgios I. Gkatzelis, Hannah S. Halliday, Jordan E. Krechmer, Richard H. Moore, David S. Thomson, Carsten Warneke, Elizabeth B. Wiggins, and Jose L. Jimenez
Atmos. Meas. Tech., 14, 1545–1559, https://doi.org/10.5194/amt-14-1545-2021, https://doi.org/10.5194/amt-14-1545-2021, 2021
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We describe the airborne deployment of an extractive electrospray time-of-flight mass spectrometer (EESI-MS). The instrument provides a quantitative 1 Hz measurement of the chemical composition of organic aerosol up to altitudes of
7 km, with single-compound detection limits as low as 50 ng per standard cubic meter.
Arttu Ylisirniö, Luis M. F. Barreira, Iida Pullinen, Angela Buchholz, John Jayne, Jordan E. Krechmer, Douglas R. Worsnop, Annele Virtanen, and Siegfried Schobesberger
Atmos. Meas. Tech., 14, 355–367, https://doi.org/10.5194/amt-14-355-2021, https://doi.org/10.5194/amt-14-355-2021, 2021
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FIGAERO-ToF-CIMS enables online volatility measurements of chemical compounds in ambient aerosols. Previously published volatility calibration results however differ from each other significantly. In this study we investigate the reason for this discrepancy. We found a major source of error in the widely used syringe deposition method and propose a new method for volatility calibration by using atomized calibration compounds.
Cited articles
Arsene, C., Barnes, I., Becker, K. H., Schneider, W. F., Wallington, T. T.,
Mihalopoulos, N., and Patroescu-Klotz, I. V.: Formation of methane sulfinic
acid in the gas-phase OH-radical initiated oxidation of dimethyl
sulfoxide, Environ. Sci. Technol, 36, 5155–5163, 2002.
Barnes, I., Becker, K. H., and Patroescu, I.: The tropospheric oxidation of
dimethy sulfide: a new source of carbonyl sulfide, Geophys. Res. Lett.,
21, 2389–2392, 1994.
Barnes, I., Hjorth, J., and Mihalapoulos, N.: Dimethyl sulfide and dimethyl
sulfoxide and their oxidation in the atmosphere, Chem. Rev., 106,
940–975, https://doi.org/10.1021/cr020529+, 2006.
Berndt, T., Scholz, W., Mentler, B., Fischer, L., Hoffmann, E. H., Tilgner,
A., Hyttinen, N., Prisle, N. L., Hansel, A., and Herrmann, H.: Fast Peroxy
Radical Isomerization and OH Recycling in the Reaction of OH Radicals with
Dimethyl Sulfide, J. Phys. Chem. Lett., 10, 6478–6483,
https://doi.org/10.1021/acs.jpclett.9b02567, 2019.
Charlson, R. J., Lovelock, J. E., Andreae, M. O., and Warren, S. G.: Oceanic
phytoplankton, atmospheric sulphur, cloud albedo and climate, Nature, 326,
665–661, 1987.
Chen, Q., Sherwen, T., Evans, M., and Alexander, B.: DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry, Atmos. Chem. Phys., 18, 13617–13637, https://doi.org/10.5194/acp-18-13617-2018, 2018.
Chen, T. and Jang, M.: Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NOx, Atmos. Chem. Phys., 12, 10257–10269, https://doi.org/10.5194/acp-12-10257-2012, 2012.
Chin, M., Jacob, D. J., Gardner, G. M., Foreman-fowler, M. S., Spiro, P. A., and Savoie, D. L.: A global three-dimensional model of tropospheric sulfate,
J. Geophys. Res., 101, 18667–18690, 1996.
Crounse, J. D., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., and
Wennberg, P. O.: Autoxidation of organic compounds in the atmosphere, J.
Phys. Chem. Lett., 4, 3513–3520, 2013.
Decarlo, P. F., Kimmel, J. R., Trimborn, A., Northway, M. J., Jayne, J. T., Aiken, A. C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K. S., Worsnop, D. R., and Jimenez, J. L.: Aerosol Mass Spectrometer, Anal. Chem., 78, 8281–8289, https://doi.org/10.1021/ac061249n, 2006.
Fung, K. M., Heald, C. L., Kroll, J. H., Wang, S., Jo, D. S., Gettelman, A., Lu, Z., Liu, X., Zaveri, R. A., Apel, E. C., Blake, D. R., Jimenez, J.-L., Campuzano-Jost, P., Veres, P. R., Bates, T. S., Shilling, J. E., and Zawadowicz, M.: Exploring dimethyl sulfide (DMS) oxidation and implications for global aerosol radiative forcing, Atmos. Chem. Phys., 22, 1549–1573, https://doi.org/10.5194/acp-22-1549-2022, 2022.
Hodshire, A. L., Campuzano-Jost, P., Kodros, J. K., Croft, B., Nault, B. A., Schroder, J. C., Jimenez, J. L., and Pierce, J. R.: The potential role of methanesulfonic acid (MSA) in aerosol formation and growth and the associated radiative forcings, Atmos. Chem. Phys., 19, 3137–3160, https://doi.org/10.5194/acp-19-3137-2019, 2019.
Hoffmann, E. H., Tilgner, A., Schrödner, R., Bräuer, P., Wolke, R., and Herrmann, H.: An advanced modeling study on the impacts and atmospheric
implications of multiphase dimethyl sulfide chemistry, P. Natl. Acad.
Sci. USA, 113, 11776–11781, https://doi.org/10.1073/pnas.1606320113, 2016.
Hoffmann, E. H., Heinold, B., Kubin, A., Tegen, I., and Herrmann, H.: The
Importance of the Representation of DMS Oxidation in Global
Chemistry-Climate Simulations, Geophys. Res. Lett., 48, e2021GL094068, https://doi.org/10.1029/2021GL094068, 2021.
Huang, D. D., Li, Y. J., Lee, B. P., and Chan, C. K.: Analysis of Organic
Sulfur Compounds in Atmospheric Aerosols at the HKUST Supersite in Hong Kong
Using HR-ToF-AMS, Environ. Sci. Technol., 49, 3672–3679,
https://doi.org/10.1021/es5056269, 2015.
Huijnen, V., Williams, J., van Weele, M., van Noije, T., Krol, M., Dentener, F., Segers, A., Houweling, S., Peters, W., de Laat, J., Boersma, F., Bergamaschi, P., van Velthoven, P., Le Sager, P., Eskes, H., Alkemade, F., Scheele, R., Nédélec, P., and Pätz, H.-W.: The global chemistry transport model TM5: description and evaluation of the tropospheric chemistry version 3.0, Geosci. Model Dev., 3, 445–473, https://doi.org/10.5194/gmd-3-445-2010, 2010.
Hunter, J. F., Carrasquillo, A. J., Daumit, K. E., and Kroll, J. H.:
Secondary Organic Aerosol Formation from Acyclic, Monocyclic, and Polycyclic
Alkanes, Environ. Sci. Technol., 48, 10227–10234, 2014.
Jenkin, M. E., Saunders, S. M., and Pilling, M. J.: The tropospheric
degradation of volatile organic compounds: a protocol for mechanism
development, Atmos. Environ., 31, 81–104, 1997.
Jernigan, C. M., Fite, C. H., Vereecken, L., Berkelhammer, M. B., Rollins,
A. W., Rickly, P. S., Novelli, A., Taraborrelli, D., Holmes, C. D., and
Bertram, T. H.: Efficient production of carbonyl sulfide in the low-NOx
oxidation of dimethyl sulfide, Geophys. Res. Lett., 49, https://doi.org/10.1029/2021GL096838, 2022a.
Jernigan, C. M., Christopher, D. C., and Timothy H. B.: Reactive Uptake of
Hydroperoxymethyl Thioformate to Sodium Chloride and Sodium Iodide Aerosol
Particles, J. Phys. Chem. A, 126, 4476–4481, 2022b.
Khan, M. A. H., Bannan, T. J., Holland, R., Shallcross, D. E., Archibald, A.
T., Matthews, E., Back, A., Allan, J., Coe, H., Artaxo, P., and Percival, C.
J.: Impacts of Hydroperoxymethyl Thioformate on the Global Marine Sulfur
Budget, ACS Earth Sp. Chem., 5, 2577–2586, 2021.
Kloster, S., Feichter, J., Maier-Reimer, E., Six, K. D., Stier, P., and Wetzel, P.: DMS cycle in the marine ocean-atmosphere system – a global model study, Biogeosciences, 3, 29–51, https://doi.org/10.5194/bg-3-29-2006, 2006.
Krechmer, E. J., Lopez-Hilfiker, F., Koss, A., Hutterli, M., Stoermer, C.,
Deming, B., Kimmel, J., Warneke, C., Holzinger, R., Jayne, J., Worsnop, D.,
Fuhrer, K., Gonin, M., and Gouw, J. De: Evaluation of a New Reagent-Ion
Source and Focusing Ion- Molecule Reactor for Use in
Proton-Transfer-Reaction Mass Spectrometry, Anal. Chem., 90, 12011–12018,
https://doi.org/10.1021/acs.analchem.8b02641, 2018.
Kroll Group: Chamber data and species concentrations, http://krollgroup.mit.edu/publications.html, last access: 2022.
Lamarque, J.-F., Emmons, L. K., Hess, P. G., Kinnison, D. E., Tilmes, S., Vitt, F., Heald, C. L., Holland, E. A., Lauritzen, P. H., Neu, J., Orlando, J. J., Rasch, P. J., and Tyndall, G. K.: CAM-chem: description and evaluation of interactive atmospheric chemistry in the Community Earth System Model, Geosci. Model Dev., 5, 369–411, https://doi.org/10.5194/gmd-5-369-2012, 2012.
Lucas, D. D. and Prinn, R. G.: Mechanistic studies of dimethylsulfide
oxidation products using an observationally constrained model, J. Geophys. Res.-Atmos., 107, ACH-12, https://doi.org/10.1029/2001JD000843, 2002.
Lana, A., Bell, T. G., Simo, R., Vallina, S. M., Ballabrera-Poy, J., Kettle,
A. J., Dachs, J., Bopp, L., Saltzman, E. S., Stefels, J., Johnson, J. E.,
and Liss, P. S.: An updated climatology of surface dimethlysulfide
concentrationsand emission fluxes in the global ocean, Global Biogeochem.
Cycles, 25, GB1004, https://doi.org/10.1029/2010GB003850, 2011.
Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Kurtén, T., Worsnop, D. R., and Thornton, J. A.: An iodide-adduct high-resolution time-of-flight
chemical-ionization mass spectrometer: Application to atmospheric inorganic
and organic compounds, Environ. Sci. Technol., 48, 6309–6317,
https://doi.org/10.1021/es500362a, 2014.
McManus, J. B., Kebabian, P. L., and Zahniser, M.S.: Astigmatic mirror
multipass absorption cells for long-path-length spectroscopy, Appl.
Optics, 34, 3336–3348, 1995.
McManus, J. B., Zahniser, M. S., Nelson, D. D., McGovern, R. M., Agnese, M., and Brown, W. F.: Compact Quantum Cascade Laser Instrument for High Precision
Trace Gas Measurements, in: Optical Instrumentation for Energy and
Environmental Applications (p. EThC2), Optica Publishing Group, https://doi.org/10.1364/E2.2011.EThC2, 2011.
Mihalopoulos, N., Barnes, I., and Becker, K. H.: Infrared absorption spectra
and integrated band intensities for gaseous methanesulphonic acid (MSA),
Atmos. Environ., 25, 807–812, 1992.
Novak, G. A., Fite, C. H., Holmes, C. D., Veres, P. R., Neuman, J. A.,
Faloona, I., Thornton, J. A., Wolfe, G. M., Vermeuel, M. P., Jernigan, C.
M., Peischl, J., Ryerson, T. B., Thompson, C. R., Bourgeois, I., Warneke,
C., Gkatzelis, G. I., Coggon, M. M., Sekimoto, K., Bui, T. P., Dean-Day, J.,
Diskin, G. S., DiGangi, J. P., Nowak, J. B., Moore, R. H., Wiggins, E. B.,
Winstead, E. L., Robinson, C., Thornhill, K. L., Sanchez, K. J., Hall, S.
R., Ullmann, K., Dollner, M., Weinzierl, B., Blake, D. R., and Bertram, T.
H.: Rapid cloud removal of dimethyl sulfide oxidation products limits
SO2 and cloud condensation nuclei production in the marine atmosphere,
P. Natl. Acad. Sci., 118, e2110472118, https://doi.org/10.1073/PNAS.2110472118,
2021.
Patroescu, I. V., Barnes, I., and Becker, K. H.: FTIR kinetic and mechanistic
study of the atmospheric chemistry of methyl thiolformate, J. Phys. Chem.,
100, 17207–17217, https://doi.org/10.1021/jp961452u, 1996.
Rap, A., Scott, C. E., Spracklen, D. V., Bellouin, N., Forster, P. M.,
Carslaw, K. S., Schmidt, A., and Mann, G.: Natural aerosol direct and
indirect radiative effects, Geophys. Res. Lett., 40, 3297–3301,
https://doi.org/10.1002/grl.50441, 2013.
Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, https://doi.org/10.5194/acp-3-161-2003, 2003.
Shen, J., Scholz, W., He, X. C., Zhou, P., Marie, G., Wang, M., Marten, R.,
Surdu, M., Rörup, B., Baalbaki, R. and Amorim, A, Ataei,
F., Bell, D. M., Bertozzi, B., Brasseur, Z., Caudillo, L., Chen, D., Chu,
B., Dada, L., Duplissy, J., Finkenzeller, H., Granzin, M., Guida, R.,
Heinritzi, M., Hofbauer, V., Iyer, S., Kemppainen, D., Kong, W., Krechmer,
J. E., Kürten, A., Lamkaddam, H., Lee. C. P., Lopez, B., Mahfouz, N. G.,
Manninen, H. E., Massabò, D., Mauldin, R. L., Mentler, B., Müller,
T., Pfeifer, J., Phillppov, M., Piedehierro, A. A., Roldin, P.,
Schobesberger, S., Simon, M., Stolzenburg, D., Tham, Y. J., Tomé, A.,
Umo, N. S., Wang, D., Wang, Y., Weber, S. K., Welti, A., Wollesen de Jonge,
R., Wu, Y., Zauner-Wieczorek, M., Zust, F., Baltensperger, U., Curtius, J.,
Flagan, R. C., Hansel, A., Möhler, O., Petäjä,
T., Volkamer, R., Kulmala, M., Lehtipalo, K., Rissanen, M., Kirkby, J.,
El-Haddad, I., Bianchi, F., Silipä, M., Donahue, N. M., and Worsnop, D.
R.: High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated
Oxidation of Dimethyl Sulfide at Low Temperatures, Environ. Sci. Technol.,
56, 13931–13944, 2022.
Veres, P. R., Andrew Neuman, J., Bertram, T. H., Assaf, E., Wolfe, G. M.,
Williamson, C. J., Weinzierl, B., Tilmes, S., Thompson, C. R., Thames, A.
B., Schroder, J. C., Saiz-Lopez, A., Rollins, A. W., Roberts, J. M., Price,
D., Peischl, J., Nault, B. A., Møller, K. H., Miller, D. O., Meinardi,
S., Li, Q., Lamarque, J. F., Kupc, A., Kjaergaard, H. G., Kinnison, D.,
Jimenez, J. L., Jernigan, C. M., Hornbrook, R. S., Hills, A., Dollner, M.,
Day, D. A., Cuevas, C. A., Campuzano-Jost, P., Burkholder, J., Paul Bui, T.,
Brune, W. H., Brown, S. S., Brock, C. A., Bourgeois, I., Blake, D. R., Apel,
E. C., and Ryerson, T. B.: Global airborne sampling reveals a previously
unobserved dimethyl sulfide oxidation mechanism in the marine atmosphere,
P. Natl. Acad. Sci. USA, 117, 4505–4510,
https://doi.org/10.1073/pnas.1919344117, 2020.
Vermeuel, M. P., Novak, G. A., Jernigan, C. M., and Bertram, T. H.: Diel
profile of hydroperoxymethyl thioformate: Evidence for surface deposition
and multiphase chemistry, Environ. Sci. Technol, 54, 12521–12529,
2020.
von Glasow, R. and Crutzen, P. J.: Model study of multiphase DMS oxidation with a focus on halogens, Atmos. Chem. Phys., 4, 589–608, https://doi.org/10.5194/acp-4-589-2004, 2004.
Wallace, J. M. and Hobbs, P. V.: Atmospheric science: an introductory
survey, U. K. Elsevier Inc., ISBN 9780127329512, 2006.
Wolfe, G.: F0AM model, https://github.com/AirChem/F0AM/releases/tag/v3.2, last access: 2019.
Wolfe, G. M., Marvin, M. R., Roberts, S. J., Travis, K. R., and Liao, J.: The Framework for 0-D Atmospheric Modeling (F0AM) v3.1, Geosci. Model Dev., 9, 3309–3319, https://doi.org/10.5194/gmd-9-3309-2016, 2016.
Wolfe, G., Haskins, J., and srobe: AirChem/F0AM: v4.2.2 (v4.2.2), Zenodo [code], https://doi.org/10.5281/zenodo.6984581, 2022.
Wollesen de Jonge, R., Elm, J., Rosati, B., Christiansen, S., Hyttinen, N., Lüdemann, D., Bilde, M., and Roldin, P.: Secondary aerosol formation from dimethyl sulfide – improved mechanistic understanding based on smog chamber experiments and modelling, Atmos. Chem. Phys., 21, 9955–9976, https://doi.org/10.5194/acp-21-9955-2021, 2021.
Wu, R., Wang, S., and Wang, L.: New mechanism for the atmospheric oxidation
of dimethyl sulfide. The importance of intramolecular hydrogen shift in a
CH3SCH2OO radical, J. Phys. Chem. A, 119, 112–117,
https://doi.org/10.1021/jp511616j, 2015.
Xu, L., Møller, K. H., Crounse, J. D., Otkjær, R. V., Kjaergaard, H.
G., and Wennberg, P. O.: Unimolecular reactions of peroxy radicals formed in
the oxidation of α-Pinene and β-Pinene by hydroxyl radicals,
J. Phys. Chem. A, 123, 1661–1674, https://doi.org/10.1021/acs.jpca.8b11726, 2019.
Ye, Q., Goss, M. B., Isaacman-Vanwertz, G., Zaytsev, A., Massoli, P., Lim,
C., Croteau, P., Canagaratna, M., Knopf, D. A., Keutsch, F. N., Heald, C. L., and Kroll, J. H.: Organic Sulfur Products and Peroxy Radical Isomerization
in the OH Oxidation of Dimethyl Sulfide, ACS Earth Sp. Chem., 5,
2013–2020, https://doi.org/10.1021/acsearthspacechem.1c00108, 2021.
Yin, F., Grosjean, D., and Seinfeld, J. H.: Photooxidation of Dimethyl
Sulfide and Dimethyl Disulfide. I: Mechanism Development, J. Atmos. Chem., 11, 309–365, 1990.
Zaytsev, A., Breitenlechner, M., Koss, A. R., Lim, C. Y., Rowe, J. C., Kroll, J. H., and Keutsch, F. N.: Using collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH
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This paper is a significant advancement in the understanding of the chemistry of dimethyl sulfide (DMS) and its oxidation products in the atmosphere. DMS is mainly emitted by marine phytoplankton and forms a relevant natural source of non-sea salt sulfate aerosols which plays an important role in global aerosol climate effects. However, the chemistry by which DMS oxidizes to form sulfate aerosols is highly complex. This work represents a next important step in the understanding of chemical processes within the reaction of OH with DMS. The results of this study allow to include a better, because less simplified, inclusion of DMS chemistry in large-scale models which can reduce errors in predicted aerosol radiative effects in past, present and future atmospheres.
This paper is a significant advancement in the understanding of the chemistry of dimethyl...
Short summary
The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate...
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