Articles | Volume 24, issue 6
https://doi.org/10.5194/acp-24-3729-2024
© Author(s) 2024. 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-24-3729-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
26 Mar 2024
Research article |
| 26 Mar 2024
| 26 Mar 2024
Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater
Delaney B. Kilgour
Department of Chemistry, University of Wisconsin–Madison, Madison, WI 53706, USA
Gordon A. Novak
Department of Chemistry, University of Wisconsin–Madison, Madison, WI 53706, USA
now at: NOAA Chemical Sciences Laboratory, Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO 80305, USA
Megan S. Claflin
Aerodyne Research Inc., Billerica, MA 01821, USA
Brian M. Lerner
Aerodyne Research Inc., Billerica, MA 01821, USA
Timothy H. Bertram
CORRESPONDING AUTHOR
Department of Chemistry, University of Wisconsin–Madison, Madison, WI 53706, USA
Related authors
Michael F. Link, Megan S. Claflin, Christina E. Cecelski, Ayomide A. Akande, Delaney Kilgour, Paul A. Heine, Matthew Coggon, Chelsea E. Stockwell, Andrew Jensen, Jie Yu, Han N. Huynh, Jenna C. Ditto, Carsten Warneke, William Dresser, Keighan Gemmell, Spiro Jorga, Rileigh L. Robertson, Joost de Gouw, Timothy Bertram, Jonathan P. D. Abbatt, Nadine Borduas-Dedekind, and Dustin Poppendieck
Atmos. Meas. Tech., 18, 1013–1038, https://doi.org/10.5194/amt-18-1013-2025, https://doi.org/10.5194/amt-18-1013-2025, 2025
Short summary
Short summary
Proton-transfer-reaction mass spectrometry (PTR-MS) is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. An analytical challenge for PTR-MS measurements is the formation of unintended measurement interferences, product ion distributions (PIDs), that may appear in the data as VOCs of interest. We developed a method for quantifying PID formation and use interlaboratory comparison data to put quantitative constraints on PID formation.
Delaney B. Kilgour, Christopher M. Jernigan, Olga Garmash, Sneha Aggarwal, Shengqian Zhou, Claudia Mohr, Matt E. Salter, Joel A. Thornton, Jian Wang, Paul Zieger, and Timothy H. Bertram
Atmos. Chem. Phys., 25, 1931–1947, https://doi.org/10.5194/acp-25-1931-2025, https://doi.org/10.5194/acp-25-1931-2025, 2025
Short summary
Short summary
We report simultaneous measurements of dimethyl sulfide (DMS) and hydroperoxymethyl thioformate (HPMTF) in the eastern North Atlantic. We use an observationally constrained box model to show that cloud loss is the dominant sink of HPMTF in this region over 6 weeks, resulting in large reductions in DMS-derived products that contribute to aerosol formation and growth. Our findings indicate that fast cloud processing of HPMTF must be included in global models to accurately capture the sulfur cycle.
Michael P. Vermeuel, Gordon A. Novak, Delaney B. Kilgour, Megan S. Claflin, Brian M. Lerner, Amy M. Trowbridge, Jonathan Thom, Patricia A. Cleary, Ankur R. Desai, and Timothy H. Bertram
Atmos. Chem. Phys., 23, 4123–4148, https://doi.org/10.5194/acp-23-4123-2023, https://doi.org/10.5194/acp-23-4123-2023, 2023
Short summary
Short summary
Reactive carbon species emitted from natural sources such as forests play an important role in the chemistry of the atmosphere. Predictions of these emissions are based on plant responses during the growing season and do not consider potential effects from seasonal changes. To address this, we made measurements of reactive carbon over a forest during the summer to autumn transition. We learned that observed concentrations and emissions for some key species are larger than model predictions.
Gordon A. Novak, Delaney B. Kilgour, Christopher M. Jernigan, Michael P. Vermeuel, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 6309–6325, https://doi.org/10.5194/acp-22-6309-2022, https://doi.org/10.5194/acp-22-6309-2022, 2022
Short summary
Short summary
We describe field measurements of the mixing ratio and oceanic emission flux of dimethyl sulfide (DMS) and methanethiol (MeSH) from a coastal ocean site. DMS is known to impact aerosol formation and growth in the marine atmosphere, influencing cloud formation and climate. Measurements of MeSH, which is produced by the same oceanic source as DMS, are rare. We show that MeSH emissions are large and must be measured alongside DMS to understand marine sulfur chemistry and aerosol formation.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
Short summary
Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Yugo Kanaya, Roberto Sommariva, Alfonso Saiz-Lopez, Andrea Mazzeo, Theodore K. Koenig, Kaori Kawana, James E. Johnson, Aurélie Colomb, Pierre Tulet, Suzie Molloy, Ian E. Galbally, Rainer Volkamer, Anoop Mahajan, John W. Halfacre, Paul B. Shepson, Julia Schmale, Hélène Angot, Byron Blomquist, Matthew D. Shupe, Detlev Helmig, Junsu Gil, Meehye Lee, Sean C. Coburn, Ivan Ortega, Gao Chen, James Lee, Kenneth C. Aikin, David D. Parrish, John S. Holloway, Thomas B. Ryerson, Ilana B. Pollack, Eric J. Williams, Brian M. Lerner, Andrew J. Weinheimer, Teresa Campos, Frank M. Flocke, J. Ryan Spackman, Ilann Bourgeois, Jeff Peischl, Chelsea R. Thompson, Ralf M. Staebler, Amir A. Aliabadi, Wanmin Gong, Roeland Van Malderen, Anne M. Thompson, Ryan M. Stauffer, Debra E. Kollonige, Juan Carlos Gómez Martin, Masatomo Fujiwara, Katie Read, Matthew Rowlinson, Keiichi Sato, Junichi Kurokawa, Yoko Iwamoto, Fumikazu Taketani, Hisahiro Takashima, Mónica Navarro-Comas, Marios Panagi, and Martin G. Schultz
Earth Syst. Sci. Data, 17, 4901–4932, https://doi.org/10.5194/essd-17-4901-2025, https://doi.org/10.5194/essd-17-4901-2025, 2025
Short summary
Short summary
The first comprehensive dataset of tropospheric ozone over oceans/polar regions is presented, including 77 ship/buoy and 48 aircraft campaign observations (1977–2022, 0–5000 m altitude), supplemented by ozonesonde and surface data. Air masses isolated from land for 72+ hours are systematically selected as essentially oceanic. Among the 11 global regions, they show daytime decreases of 11–16 % in the tropics, while near-zero depletions are rare, unlike in the Arctic, implying different mechanisms.
Ying Zhang, Yuwei Wang, Chuang Li, Yueyang Li, Sijia Yin, Megan S. Claflin, Brian M. Lerner, Douglas Worsnop, and Lin Wang
Atmos. Meas. Tech., 18, 3547–3568, https://doi.org/10.5194/amt-18-3547-2025, https://doi.org/10.5194/amt-18-3547-2025, 2025
Short summary
Short summary
This study provides insight into how individual ions measured by proton-transfer-reaction (PTR) mass spectrometry are produced by multiple volatile organic compounds (VOCs). A reference table is provided for attributing the PTR signal to contributing VOC species. The signals are grouped according to the complexity of their potential identities. We find that a number of signal ions such as C6H7+ for benzene and C5H9+ for isoprene merely give an upper limit of their corresponding concentrations.
Michael F. Link, Megan S. Claflin, Christina E. Cecelski, Ayomide A. Akande, Delaney Kilgour, Paul A. Heine, Matthew Coggon, Chelsea E. Stockwell, Andrew Jensen, Jie Yu, Han N. Huynh, Jenna C. Ditto, Carsten Warneke, William Dresser, Keighan Gemmell, Spiro Jorga, Rileigh L. Robertson, Joost de Gouw, Timothy Bertram, Jonathan P. D. Abbatt, Nadine Borduas-Dedekind, and Dustin Poppendieck
Atmos. Meas. Tech., 18, 1013–1038, https://doi.org/10.5194/amt-18-1013-2025, https://doi.org/10.5194/amt-18-1013-2025, 2025
Short summary
Short summary
Proton-transfer-reaction mass spectrometry (PTR-MS) is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. An analytical challenge for PTR-MS measurements is the formation of unintended measurement interferences, product ion distributions (PIDs), that may appear in the data as VOCs of interest. We developed a method for quantifying PID formation and use interlaboratory comparison data to put quantitative constraints on PID formation.
Delaney B. Kilgour, Christopher M. Jernigan, Olga Garmash, Sneha Aggarwal, Shengqian Zhou, Claudia Mohr, Matt E. Salter, Joel A. Thornton, Jian Wang, Paul Zieger, and Timothy H. Bertram
Atmos. Chem. Phys., 25, 1931–1947, https://doi.org/10.5194/acp-25-1931-2025, https://doi.org/10.5194/acp-25-1931-2025, 2025
Short summary
Short summary
We report simultaneous measurements of dimethyl sulfide (DMS) and hydroperoxymethyl thioformate (HPMTF) in the eastern North Atlantic. We use an observationally constrained box model to show that cloud loss is the dominant sink of HPMTF in this region over 6 weeks, resulting in large reductions in DMS-derived products that contribute to aerosol formation and growth. Our findings indicate that fast cloud processing of HPMTF must be included in global models to accurately capture the sulfur cycle.
Josie K. Radtke, Benjamin N. Kies, Whitney A. Mottishaw, Sydney M. Zeuli, Aidan T. H. Voon, Kelly L. Koerber, Grant W. Petty, Michael P. Vermeuel, Timothy H. Bertram, Ankur R. Desai, Joseph P. Hupy, R. Bradley Pierce, Timothy J. Wagner, and Patricia A. Cleary
Atmos. Meas. Tech., 17, 2833–2847, https://doi.org/10.5194/amt-17-2833-2024, https://doi.org/10.5194/amt-17-2833-2024, 2024
Short summary
Short summary
The use of uncrewed aircraft systems (UASs) to conduct a vertical profiling of ozone and meteorological variables was evaluated using comparisons between tower or ground observations and UAS-based measurements. Changes to the UAS profiler showed an improvement in performance. The profiler was used to see the impact of Chicago pollution plumes on a shoreline area near Lake Michigan.
Matthew M. Coggon, Chelsea E. Stockwell, Megan S. Claflin, Eva Y. Pfannerstill, Lu Xu, Jessica B. Gilman, Julia Marcantonio, Cong Cao, Kelvin Bates, Georgios I. Gkatzelis, Aaron Lamplugh, Erin F. Katz, Caleb Arata, Eric C. Apel, Rebecca S. Hornbrook, Felix Piel, Francesca Majluf, Donald R. Blake, Armin Wisthaler, Manjula Canagaratna, Brian M. Lerner, Allen H. Goldstein, John E. Mak, and Carsten Warneke
Atmos. Meas. Tech., 17, 801–825, https://doi.org/10.5194/amt-17-801-2024, https://doi.org/10.5194/amt-17-801-2024, 2024
Short summary
Short summary
Mass spectrometry is a tool commonly used to measure air pollutants. This study evaluates measurement artifacts produced in the proton-transfer-reaction mass spectrometer. We provide methods to correct these biases and better measure compounds that degrade air quality.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
Short summary
Short summary
We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
Michael P. Vermeuel, Gordon A. Novak, Delaney B. Kilgour, Megan S. Claflin, Brian M. Lerner, Amy M. Trowbridge, Jonathan Thom, Patricia A. Cleary, Ankur R. Desai, and Timothy H. Bertram
Atmos. Chem. Phys., 23, 4123–4148, https://doi.org/10.5194/acp-23-4123-2023, https://doi.org/10.5194/acp-23-4123-2023, 2023
Short summary
Short summary
Reactive carbon species emitted from natural sources such as forests play an important role in the chemistry of the atmosphere. Predictions of these emissions are based on plant responses during the growing season and do not consider potential effects from seasonal changes. To address this, we made measurements of reactive carbon over a forest during the summer to autumn transition. We learned that observed concentrations and emissions for some key species are larger than model predictions.
Lu Xu, Matthew M. Coggon, Chelsea E. Stockwell, Jessica B. Gilman, Michael A. Robinson, Martin Breitenlechner, Aaron Lamplugh, John D. Crounse, Paul O. Wennberg, J. Andrew Neuman, Gordon A. Novak, Patrick R. Veres, Steven S. Brown, and Carsten Warneke
Atmos. Meas. Tech., 15, 7353–7373, https://doi.org/10.5194/amt-15-7353-2022, https://doi.org/10.5194/amt-15-7353-2022, 2022
Short summary
Short summary
We describe the development and operation of a chemical ionization mass spectrometer using an ammonium–water cluster (NH4+·H2O) as a reagent ion. NH4+·H2O is a highly versatile reagent ion for measurements of a wide range of oxygenated organic compounds. The major product ion is the cluster with NH4+ produced via ligand-switching reactions. The instrumental sensitivities of analytes depend on the binding energy of the analyte–NH4+ cluster; sensitivities can be estimated using voltage scanning.
Rachel A. Bergin, Monica Harkey, Alicia Hoffman, Richard H. Moore, Bruce Anderson, Andreas Beyersdorf, Luke Ziemba, Lee Thornhill, Edward Winstead, Tracey Holloway, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 15449–15468, https://doi.org/10.5194/acp-22-15449-2022, https://doi.org/10.5194/acp-22-15449-2022, 2022
Short summary
Short summary
Correctly predicting aerosol surface area concentrations is important for determining the rate of heterogeneous reactions in chemical transport models. Here, we compare aircraft measurements of aerosol surface area with a regional model. In polluted air masses, we show that the model underpredicts aerosol surface area by a factor of 2. Despite this disagreement, the representation of heterogeneous chemistry still dominates the overall uncertainty in the loss rate of molecules such as N2O5.
Sungwoo Kim, Brian M. Lerner, Donna T. Sueper, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 15, 5061–5075, https://doi.org/10.5194/amt-15-5061-2022, https://doi.org/10.5194/amt-15-5061-2022, 2022
Short summary
Short summary
Atmospheric samples can be complex, and current analysis methods often require substantial human interaction and discard potentially important information. To improve analysis accuracy and computational cost of these large datasets, we developed an automated analysis algorithm that utilizes a factor analysis approach coupled with a decision tree. We demonstrate that this algorithm cataloged approximately 10 times more analytes compared to a manual analysis and in a quarter of the analysis time.
Gordon A. Novak, Delaney B. Kilgour, Christopher M. Jernigan, Michael P. Vermeuel, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 6309–6325, https://doi.org/10.5194/acp-22-6309-2022, https://doi.org/10.5194/acp-22-6309-2022, 2022
Short summary
Short summary
We describe field measurements of the mixing ratio and oceanic emission flux of dimethyl sulfide (DMS) and methanethiol (MeSH) from a coastal ocean site. DMS is known to impact aerosol formation and growth in the marine atmosphere, influencing cloud formation and climate. Measurements of MeSH, which is produced by the same oceanic source as DMS, are rare. We show that MeSH emissions are large and must be measured alongside DMS to understand marine sulfur chemistry and aerosol formation.
Martin Breitenlechner, Gordon A. Novak, J. Andrew Neuman, Andrew W. Rollins, and Patrick R. Veres
Atmos. Meas. Tech., 15, 1159–1169, https://doi.org/10.5194/amt-15-1159-2022, https://doi.org/10.5194/amt-15-1159-2022, 2022
Short summary
Short summary
We coupled a new ion source to a commercially available state-of-the-art trace gas analyzer. The instrument is particularly well suited for conducting high-altitude observations, addressing the challenges of low ambient pressures and a complex sample matrix. The new instrument and ion source provides significant advantages to more traditional modes of operation, without sacrificing the sensitivity and flexibility of this technique.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
Short summary
Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
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
Short summary
Short summary
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.
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
Short summary
Short summary
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.
Megan S. Claflin, Demetrios Pagonis, Zachary Finewax, Anne V. Handschy, Douglas A. Day, Wyatt L. Brown, John T. Jayne, Douglas R. Worsnop, Jose L. Jimenez, Paul J. Ziemann, Joost de Gouw, and Brian M. Lerner
Atmos. Meas. Tech., 14, 133–152, https://doi.org/10.5194/amt-14-133-2021, https://doi.org/10.5194/amt-14-133-2021, 2021
Short summary
Short summary
We have developed a field-deployable gas chromatograph with thermal desorption preconcentration and detector switching between two high-resolution mass spectrometers for in situ measurements of volatile organic compounds (VOCs). This system combines chromatography with both proton transfer and electron ionization to offer fast time response and continuous molecular speciation. This technique was applied during the 2018 ATHLETIC campaign to characterize VOC emissions in an indoor environment.
Cited articles
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004.
Bates, T. S., Lamb, B. K., Guenther, A., Dignon, J., and Stoiber, R. E.: Sulfur emissions to the atmosphere from natural sourees, J. Atmos. Chem., 14, 315–337, https://doi.org/10.1007/BF00115242, 1992.
Berkelhammer, M., Steen-Larsen, H. C., Cosgrove, A., Peters, A. J., Johnson, R., Hayden, M., and Montzka, S. A.: Radiation and atmospheric circulation controls on carbonyl sulfide concentrations in the marine boundary layer, J. Geophys. Res.-Atmos., 121, 13113–13128, https://doi.org/10.1002/2016JD025437, 2016.
Bertram, T. H., Kimmel, J. R., Crisp, T. A., Ryder, O. S., Yatavelli, R. L. N., Thornton, J. A., Cubison, M. J., Gonin, M., and Worsnop, D. R.: A field-deployable, chemical ionization time-of-flight mass spectrometer, Atmos. Meas. Tech., 4, 1471–1479, https://doi.org/10.5194/amt-4-1471-2011, 2011.
Bowman, J. H., Barket, D. J., and Shepson, P. B.: Atmospheric Chemistry of Nonanal, Environ. Sci. Technol., 37, 2218–2225, https://doi.org/10.1021/es026220p, 2003.
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.
Burkholder, J. B., Sander, S. P., Abbatt, J., Barker, J. R., Huie, R. E., Kolb, C. E., Kurylo, M. J., Orkin, V. L., Wilmouth, D. M., and Wine, P. H.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation No. 18, JPL Publication 15-10, Jet Propulsion Laboratory, Pasadena, http://jpldataeval.jpl.nasa.gov (last access: 27 September 2023), 2015.
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.
Carpenter, L. J., Archer, S. D., and Beale, R.: Ocean-atmosphere trace gas exchange, Chem. Soc. Rev., 41, 6473, https://doi.org/10.1039/c2cs35121h, 2012.
Carpenter, L. J., Chance, R. J., Sherwen, T., Adams, T. J., Ball, S. M., Evans, M. J., Hepach, H., Hollis, L. D. J., Hughes, C., Jickells, T. D., Mahajan, A., Stevens, D. P., Tinel, L., and Wadley, M. R.: Marine iodine emissions in a changing world, Proc. R. Soc. A., 477, 20200824, https://doi.org/10.1098/rspa.2020.0824, 2021.
Chacon-Madrid, H. J. and Donahue, N. M.: Fragmentation vs. functionalization: chemical aging and organic aerosol formation, Atmos. Chem. Phys., 11, 10553–10563, https://doi.org/10.5194/acp-11-10553-2011, 2011.
Chacon-Madrid, H. J., Presto, A. A., and Donahue, N. M.: Functionalization vs. fragmentation: n-aldehyde oxidation mechanisms and secondary organic aerosol formation, Phys. Chem. Chem. Phys., 12, 13975, https://doi.org/10.1039/c0cp00200c, 2010.
Chacon-Madrid, H. J., Henry, K. M., and Donahue, N. M.: Photo-oxidation of pinonaldehyde at low NOx: from chemistry to organic aerosol formation, Atmos. Chem. Phys., 13, 3227–3236, https://doi.org/10.5194/acp-13-3227-2013, 2013.
Chance, R. J., Tinel, L., Sherwen, T., Baker, A. R., Bell, T., Brindle, J., Campos, M. L. A. M., Croot, P., Ducklow, H., Peng, H., Hopkins, F., Hoogakker, B., Hughes, C., Jickells, T. D., Loades, D., Macaya, D. A. R., Mahajan, A. S., Malin, G., Phillips, D., Roberts, I., Roy, R., Sarkar, A., Sinha, A. K., Song, X., Winkelbauer, H., Wuttig, K., Yang, M., Peng, Z., and Carpenter, L. J.: Global sea-surface iodide observations, 1967–2018, Sci. Data, 6, 286, https://doi.org/10.1038/s41597-019-0288-y, 2019.
Chang, W., Heikes, B. G., and Lee, M.: Ozone deposition to the sea surface: chemical enhancement and wind speed dependence, Atmos. Environ., 38, 1053–1059, https://doi.org/10.1016/j.atmosenv.2003.10.050, 2004.
Charlson, R. J., Lovelock, J. E., Andreae, M. O., and Warren, S. G.: Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate, Nature, 326, 655–661, https://doi.org/10.1038/326655a0, 1987.
Chhabra, P. S., Ng, N. L., Canagaratna, M. R., Corrigan, A. L., Russell, L. M., Worsnop, D. R., Flagan, R. C., and Seinfeld, J. H.: Elemental composition and oxidation of chamber organic aerosol, Atmos. Chem. Phys., 11, 8827–8845, https://doi.org/10.5194/acp-11-8827-2011, 2011.
Chiu, R., Tinel, L., Gonzalez, L., Ciuraru, R., Bernard, F., George, C., and Volkamer, R.: UV photochemistry of carboxylic acids at the air-sea boundary: A relevant source of glyoxal and other oxygenated VOC in the marine atmosphere: Glyoxal Source From Carboxylic Acids, Geophys. Res. Lett., 44, 1079–1087, https://doi.org/10.1002/2016GL071240, 2017.
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., 5, 12741, https://doi.org/10.1038/srep12741, 2015a.
Ciuraru, R., Fine, L., van Pinxteren, M., D'Anna, B., Herrmann, H., and George, C.: Unravelling New Processes at Interfaces: Photochemical Isoprene Production at the Sea Surface, Environ. Sci. Technol., 49, 13199–13205, https://doi.org/10.1021/acs.est.5b02388, 2015b.
Claflin, M. S., Pagonis, D., Finewax, Z., Handschy, A. V., Day, D. A., Brown, W. L., Jayne, J. T., Worsnop, D. R., Jimenez, J. L., Ziemann, P. J., de Gouw, J., and Lerner, B. M.: An in situ gas chromatograph with automatic detector switching between PTR- and EI-TOF-MS: isomer-resolved measurements of indoor air, Atmos. Meas. Tech., 14, 133–152, https://doi.org/10.5194/amt-14-133-2021, 2021.
Clifford, D., Donaldson, D. J., Brigante, M., D'Anna, B., and George, C.: Reactive Uptake of Ozone by Chlorophyll at Aqueous Surfaces, Environ. Sci. Technol., 42, 1138–1143, https://doi.org/10.1021/es0718220, 2008.
Coburn, S., Ortega, I., Thalman, R., Blomquist, B., Fairall, C. W., and Volkamer, R.: Measurements of diurnal variations and eddy covariance (EC) fluxes of glyoxal in the tropical marine boundary layer: description of the Fast LED-CE-DOAS instrument, Atmos. Meas. Tech., 7, 3579–3595, https://doi.org/10.5194/amt-7-3579-2014, 2014.
Coggon, M. M., McDonald, B. C., Vlasenko, A., Veres, P. R., Bernard, F., Koss, A. R., Yuan, B., Gilman, J. B., Peischl, J., Aikin, K. C., DuRant, J., Warneke, C., Li, S.-M., and de Gouw, J. A.: Diurnal Variability and Emission Pattern of Decamethylcyclopentasiloxane (D5) from the Application of Personal Care Products in Two North American Cities, Environ. Sci. Technol., 52, 5610–5618, https://doi.org/10.1021/acs.est.8b00506, 2018.
Coggon, M. M., Stockwell, C. E., Claflin, M. S., Pfannerstill, E. Y., Xu, L., Gilman, J. B., Marcantonio, J., Cao, C., Bates, K., Gkatzelis, G. I., Lamplugh, A., Katz, E. F., Arata, C., Apel, E. C., Hornbrook, R. S., Piel, F., Majluf, F., Blake, D. R., Wisthaler, A., Canagaratna, M., Lerner, B. M., Goldstein, A. H., Mak, J. E., and Warneke, C.: Identifying and correcting interferences to PTR-ToF-MS measurements of isoprene and other urban volatile organic compounds, Atmos. Meas. Tech., 17, 801–825, https://doi.org/10.5194/amt-17-801-2024, 2024.
Donahue, N. M. and Prinn, R. G.: Nonmethane hydrocarbon chemistry in the remote marine boundary layer, J. Geophys. Res., 95, 18387, https://doi.org/10.1029/JD095iD11p18387, 1990.
Donaldson, D. J. and Vaida, V.: The Influence of Organic Films at the Air-Aqueous Boundary on Atmospheric Processes, Chem. Rev., 106, 1445–1461, https://doi.org/10.1021/cr040367c, 2006.
dos Santos, D. J. V. A., Müller-Plathe, F., and Weiss, V. C.: Consistency of Ion Adsorption and Excess Surface Tension in Molecular Dynamics Simulations of Aqueous Salt Solutions, J. Phys. Chem. C, 112, 19431–19442, https://doi.org/10.1021/jp804811u, 2008.
Franklin, E. B., Alves, M. R., Moore, A. N., Kilgour, D. B., Novak, G. A., Mayer, K., Sauer, J. S., Weber, R. J., Dang, D., Winter, M., Lee, C., Cappa, C. D., Bertram, T. H., Prather, K. A., Grassian, V. H., and Goldstein, A. H.: Atmospheric Benzothiazoles in a Coastal Marine Environment, Environ. Sci. Technol., 55, 15705–15714, https://doi.org/10.1021/acs.est.1c04422, 2021.
Fu, H., Ciuraru, R., Dupart, Y., Passananti, M., Tinel, L., Rossignol, S., Perrier, S., Donaldson, D. J., Chen, J., and George, C.: Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface, J. Am. Chem. Soc., 137, 8348–8351, https://doi.org/10.1021/jacs.5b04051, 2015.
Ganzeveld, L., Helmig, D., Fairall, C. W., Hare, J., and Pozzer, A.: Atmosphere-ocean ozone exchange: A global modeling study of biogeochemical, atmospheric, and waterside turbulence dependencies: Global Oceanic Ozone Deposition, Global Biogeochem. Cy., 23, GB4021, https://doi.org/10.1029/2008GB003301, 2009.
Griffin, R. J., Cocker III, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res.-Atmos., 104, 3555–3567, https://doi.org/10.1029/1998JD100049, 1999.
Hackenberg, S. C., Andrews, S. J., Airs, R., Arnold, S. R., Bouman, H. A., Brewin, R. J. W., Chance, R. J., Cummings, D., Dall'Olmo, G., Lewis, A. C., Minaeian, J. K., Reifel, K. M., Small, A., Tarran, G. A., Tilstone, G. H., and Carpenter, L. J.: Potential controls of isoprene in the surface ocean, Global Biogeochem. Cy., 31, 644–662, https://doi.org/10.1002/2016GB005531, 2017.
Halsey, K. H. and Giovannoni, S. J.: Biological controls on marine volatile organic compound emissions: A balancing act at the sea-air interface, Earth-Sci. Rev., 240, 104360, https://doi.org/10.1016/j.earscirev.2023.104360, 2023.
Hulswar, S., Simó, R., Galí, M., Bell, T. G., Lana, A., Inamdar, S., Halloran, P. R., Manville, G., and Mahajan, A. S.: Third revision of the global surface seawater dimethyl sulfide climatology (DMS-Rev3), Earth Syst. Sci. Data, 14, 2963–2987, https://doi.org/10.5194/essd-14-2963-2022, 2022.
Jiménez, E., Lanza, B., Martínez, E., and Albaladejo, J.: Daytime tropospheric loss of hexanal and trans-2-hexenal: OH kinetics and UV photolysis, Atmos. Chem. Phys., 7, 1565–1574, https://doi.org/10.5194/acp-7-1565-2007, 2007.
Johnson, M. T.: A numerical scheme to calculate temperature and salinity dependent air-water transfer velocities for any gas, Ocean Sci., 6, 913–932, https://doi.org/10.5194/os-6-913-2010, 2010.
Kiene, R. P. and Linn, L. J.: The fate of dissolved dimethylsulfoniopropionate (DMSP) in seawater: tracer studies using 35S-DMSP, Geochim. Cosmochim. Ac., 64, 2797–2810, https://doi.org/10.1016/S0016-7037(00)00399-9, 2000.
Kilgour, D. B., Novak, G. A., and Bertram, T. H.: Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater, MINDS@UW [data set], http://digital.library.wisc.edu/1793/84597, 2023.
Kim, M. J., Novak, G. A., Zoerb, M. C., Yang, M., Blomquist, B. W., Huebert, B. J., Cappa, C. D., and Bertram, T. H.: Air-Sea exchange of biogenic volatile organic compounds and the impact on aerosol particle size distributions: Air-Sea Exchange of Biogenic VOCs, Geophys. Res. Lett., 44, 3887–3896, https://doi.org/10.1002/2017GL072975, 2017.
Kim, S., Karl, T., Guenther, A., Tyndall, G., Orlando, J., Harley, P., Rasmussen, R., and Apel, E.: Emissions and ambient distributions of Biogenic Volatile Organic Compounds (BVOC) in a ponderosa pine ecosystem: interpretation of PTR-MS mass spectra, Atmos. Chem. Phys., 10, 1759–1771, https://doi.org/10.5194/acp-10-1759-2010, 2010.
Krechmer, 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 de Gouw, J.: 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, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary Organic Aerosol Formation from Isoprene Photooxidation, Environ. Sci. Technol., 40, 1869–1877, https://doi.org/10.1021/es0524301, 2006.
Lana, A., Bell, T. G., Simó, 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 concentrations and emission fluxes in the global ocean, Global Biogeochem. Cy., 25, GB1004, https://doi.org/10.1029/2010GB003850, 2011.
Lee, J. D., Moller, S. J., Read, K. A., Lewis, A. C., Mendes, L., and Carpenter, L. J.: Year-round measurements of nitrogen oxides and ozone in the tropical North Atlantic marine boundary layer, J. Geophys. Res.-Atmos., 114, D21302, https://doi.org/10.1029/2009JD011878, 2009.
Li, X.-J., Liang, H.-R., Zhuang, G.-C., Wu, Y.-C., Li, S.-T., Zhang, H.-H., Montgomery, A., and Yang, G.-P.: Annual Variations of Isoprene and Other Non-Methane Hydrocarbons in the Jiaozhou Bay on the East Coast of North China, J. Geophys. Res.-Biogeo., 127, e2021JG006531, https://doi.org/10.1029/2021JG006531, 2022.
Lim, C. Y., Hagan, D. H., Coggon, M. M., Koss, A. R., Sekimoto, K., de Gouw, J., Warneke, C., Cappa, C. D., and Kroll, J. H.: Secondary organic aerosol formation from the laboratory oxidation of biomass burning emissions, Atmos. Chem. Phys., 19, 12797–12809, https://doi.org/10.5194/acp-19-12797-2019, 2019.
Luo, G. and Yu, F.: A numerical evaluation of global oceanic emissions of α-pinene and isoprene, Atmos. Chem. Phys., 10, 2007–2015, https://doi.org/10.5194/acp-10-2007-2010, 2010.
Meskhidze, N., Xu, J., Gantt, B., Zhang, Y., Nenes, A., Ghan, S. J., Liu, X., Easter, R., and Zaveri, R.: Global distribution and climate forcing of marine organic aerosol: 1. Model improvements and evaluation, Atmos. Chem. Phys., 11, 11689–11705, https://doi.org/10.5194/acp-11-11689-2011, 2011.
Mungall, E. L., Abbatt, J. P. D., Wentzell, J. J. B., Lee, A. K. Y., Thomas, J. L., Blais, M., Gosselin, M., Miller, L. A., Papakyriakou, T., Willis, M. D., and Liggio, J.: Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer, P. Natl. Acad. Sci. USA, 114, 6203–6208, https://doi.org/10.1073/pnas.1620571114, 2017.
Nightingale, P. D., Malin, G., Law, C. S., Watson, A. J., Liss, P. S., Liddicoat, M. I., Boutin, J., and Upstill-Goddard, R. C.: In situ evaluation of air-sea gas exchange parameterizations using novel conservative and volatile tracers, Global Biogeochem. Cy., 14, 373–387, https://doi.org/10.1029/1999GB900091, 2000.
Novak, G. A. and Bertram, T. H.: Reactive VOC Production from Photochemical and Heterogeneous Reactions Occurring at the Air–Ocean Interface, Acc. Chem. Res., 53, 1014–1023, https://doi.org/10.1021/acs.accounts.0c00095, 2020.
Novak, G. A., Vermeuel, M. P., and Bertram, T. H.: Simultaneous detection of ozone and nitrogen dioxide by oxygen anion chemical ionization mass spectrometry: a fast-time-response sensor suitable for eddy covariance measurements, Atmos. Meas. Tech., 13, 1887–1907, https://doi.org/10.5194/amt-13-1887-2020, 2020.
Novak, G. A., Kilgour, D. B., Jernigan, C. M., Vermeuel, M. P., and Bertram, T. H.: Oceanic emissions of dimethyl sulfide and methanethiol and their contribution to sulfur dioxide production in the marine atmosphere, Atmos. Chem. Phys., 22, 6309–6325, https://doi.org/10.5194/acp-22-6309-2022, 2022.
Pagonis, D., Sekimoto, K., and de Gouw, J.: A Library of Proton-Transfer Reactions of H3O+ Ions Used for Trace Gas Detection, J. Am. Soc. Mass Spectr., 30, 1330–1335, https://doi.org/10.1007/s13361-019-02209-3, 2019.
Papagni, C., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of a series of C3–C6 aldehydes with OH and NO3 radicals, Int. J. Chem. Kinet., 32, 79–84, https://doi.org/10.1002/(SICI)1097-4601(2000)32:2<79::AID-KIN2>3.0.CO;2-A, 2000.
Penezić, A., Wang, X., Perrier, S., George, C., and Frka, S.: Interfacial photochemistry of marine diatom lipids: Abiotic production of volatile organic compounds and new particle formation, Chemosphere, 313, 137510, https://doi.org/10.1016/j.chemosphere.2022.137510, 2023.
Phillips, D. P., Hopkins, F. E., Bell, T. G., Liss, P. S., Nightingale, P. D., Reeves, C. E., Wohl, C., and Yang, M.: Air–sea exchange of acetone, acetaldehyde, DMS and isoprene at a UK coastal site, Atmos. Chem. Phys., 21, 10111–10132, https://doi.org/10.5194/acp-21-10111-2021, 2021.
Prophet, A. M., Polley, K., Van Berkel, G. J., Limmer, D. T., and Wilson, K. R.: Iodide oxidation by ozone at the surface of aqueous microdroplets, Chem. Sci., 15, 736–756, https://doi.org/10.1039/D3SC04254E, 2024.
Rinaldi, M., Decesari, S., Finessi, E., Giulianelli, L., Carbone, C., Fuzzi, S., O'Dowd, C. D., Ceburnis, D., and Facchini, M. C.: Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies, Adv. Meteorol., 2010, 1–10, https://doi.org/10.1155/2010/310682, 2010.
Ruzsanyi, V., Fischer, L., Herbig, J., Ager, C., and Amann, A.: Multi-capillary-column proton-transfer-reaction time-of-flight mass spectrometry, J. Chromatogr. A, 1316, 112–118, https://doi.org/10.1016/j.chroma.2013.09.072, 2013.
Schneider, S. R., Collins, D. B., Lim, C. Y., Zhu, L., and Abbatt, J. P. D.: Formation of Secondary Organic Aerosol from the Heterogeneous Oxidation by Ozone of a Phytoplankton Culture, ACS Earth Space Chem., 3, 2298–2306, https://doi.org/10.1021/acsearthspacechem.9b00201, 2019.
Schneider, S. R., Lakey, P. S. J., Shiraiwa, M., and Abbatt, J. P. D.: Reactive Uptake of Ozone to Simulated Seawater: Evidence for Iodide Depletion, J. Phys. Chem. A, 124, 9844–9853, https://doi.org/10.1021/acs.jpca.0c08917, 2020.
Shaw, M. D. and Carpenter, L. J.: Modification of Ozone Deposition and I 2 Emissions at the Air–Aqueous Interface by Dissolved Organic Carbon of Marine Origin, Environ. Sci. Technol., 47, 10947–10954, https://doi.org/10.1021/es4011459, 2013.
Shaw, S. L., Gantt, B., and Meskhidze, N.: Production and Emissions of Marine Isoprene and Monoterpenes: A Review, Adv. Meteorol., 2010, 1–24, https://doi.org/10.1155/2010/408696, 2010.
Tokarek, T. W., Brownsey, D. K., Jordan, N., Garner, N. M., Ye, C. Z., and Osthoff, H. D.: Emissions of C9–C16 hydrocarbons from kelp species on Vancouver Island: Alaria marginata (winged kelp) and Nereocystis luetkeana (bull kelp) as an atmospheric source of limonene, Atmos. Environ. X, 2, 100007, https://doi.org/10.1016/j.aeaoa.2019.100007, 2019.
Vermeuel, M. P., Novak, G. A., Kilgour, D. B., Claflin, M. S., Lerner, B. M., Trowbridge, A. M., Thom, J., Cleary, P. A., Desai, A. R., and Bertram, T. H.: Observations of biogenic volatile organic compounds over a mixed temperate forest during the summer to autumn transition, Atmos. Chem. Phys., 23, 4123–4148, https://doi.org/10.5194/acp-23-4123-2023, 2023.
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 Space Chem., 7, 1306–1313, https://doi.org/10.1021/acsearthspacechem.3c00102, 2023.
Wurl, O., Wurl, E., Miller, L., Johnson, K., and Vagle, S.: Formation and global distribution of sea-surface microlayers, Biogeosciences, 8, 121–135, https://doi.org/10.5194/bg-8-121-2011, 2011.
Zhao, D. F., Buchholz, A., Kortner, B., Schlag, P., Rubach, F., Kiendler-Scharr, A., Tillmann, R., Wahner, A., Flores, J. M., Rudich, Y., Watne, Å. K., Hallquist, M., Wildt, J., and Mentel, T. F.: Size-dependent hygroscopicity parameter (κ) and chemical composition of secondary organic cloud condensation nuclei, Geophys. Res. Lett., 42, 10920–10928, https://doi.org/10.1002/2015GL066497, 2015.
Zhou, S., Gonzalez, L., Leithead, A., Finewax, Z., Thalman, R., Vlasenko, A., Vagle, S., Miller, L. A., Li, S.-M., Bureekul, S., Furutani, H., Uematsu, M., Volkamer, R., and Abbatt, J.: Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air–water interface and of the sea surface microlayer, Atmos. Chem. Phys., 14, 1371–1384, https://doi.org/10.5194/acp-14-1371-2014, 2014.
Short summary
Laboratory experiments with seawater mimics suggest ozone deposition to the surface ocean can be a source of reactive carbon to the marine atmosphere. We conduct both field and laboratory measurements to assess abiotic VOC composition and yields from ozonolysis of real surface seawater. We show that C5–C11 aldehydes contribute to the observed VOC emission flux. We estimate that VOCs generated by the ozonolysis of surface seawater are competitive with biological VOC production and emission.
Laboratory experiments with seawater mimics suggest ozone deposition to the surface ocean can be...
Altmetrics
Final-revised paper
Preprint