Articles | Volume 21, issue 11
https://doi.org/10.5194/acp-21-8999-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-21-8999-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
14 Jun 2021
Research article |
| 14 Jun 2021
| 14 Jun 2021
Towards a chemical mechanism of the oxidation of aqueous sulfur dioxide via isoprene hydroxyl hydroperoxides (ISOPOOH)
John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA
now at: Multiphase Chemistry Department, Max Planck Institute for Chemistry, 55128 Mainz, Germany
Kelvin H. Bates
Harvard University Center for the Environment, Cambridge, MA 02138, USA
Jean C. Rivera-Rios
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
now at: School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
Joshua L. Cox
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
Joshua D. Shutter
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
Frank N. Keutsch
John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA
Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, USA
Related authors
Olga Zografou, Maria Gini, Prodromos Fetfatzis, Konstantinos Granakis, Romanos Foskinis, Manousos Ioannis Manousakas, Fotios Tsopelas, Evangelia Diapouli, Eleni Dovrou, Christina N. Vasilakopoulou, Alexandros Papayannis, Spyros N. Pandis, Athanasios Nenes, and Konstantinos Eleftheriadis
Atmos. Chem. Phys., 24, 8911–8926, https://doi.org/10.5194/acp-24-8911-2024, https://doi.org/10.5194/acp-24-8911-2024, 2024
Short summary
Short summary
Characterization of PM1 and positive matrix factorization (PMF) source apportionment of organic and inorganic fractions were conducted at the high-altitude station (HAC)2. Cloud presence reduced PM1, affecting sulfate more than organics. Free-troposphere (FT) conditions showed more black carbon (eBC) than planetary boundary layer (PBL) conditions.
Eleni Dovrou, Christopher Y. Lim, Manjula R. Canagaratna, Jesse H. Kroll, Douglas R. Worsnop, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 5303–5315, https://doi.org/10.5194/amt-12-5303-2019, https://doi.org/10.5194/amt-12-5303-2019, 2019
Short summary
Short summary
Measurement techniques commonly used to analyze particulate matter composition can result in the possible misidentification of sulfur-containing species, especially for the case of sulfate and hydroxymethanesulfonate (HMS). The efficiency and limitations of these techniques, along with a method that enables further studies of the contribution of sulfur-containing species, S(IV) versus S(VI), to particulate matter under low-light atmospheric conditions, are described in this work.
Sandro Vattioni, Rahel Weber, Aryeh Feinberg, Andrea Stenke, John A. Dykema, Beiping Luo, Georgios A. Kelesidis, Christian A. Bruun, Timofei Sukhodolov, Frank N. Keutsch, Thomas Peter, and Gabriel Chiodo
Geosci. Model Dev., 17, 7767–7793, https://doi.org/10.5194/gmd-17-7767-2024, https://doi.org/10.5194/gmd-17-7767-2024, 2024
Short summary
Short summary
We quantified impacts and efficiency of stratospheric solar climate intervention via solid particle injection. Microphysical interactions of solid particles with the sulfur cycle were interactively coupled to the heterogeneous chemistry scheme and the radiative transfer code of an aerosol–chemistry–climate model. Compared to injection of SO2 we only find a stronger cooling efficiency for solid particles when normalizing to the aerosol load but not when normalizing to the injection rate.
Ursula A. Jongebloed, Jacob I. Chalif, Linia Tashmim, William C. Porter, Kelvin H. Bates, Qianjie Chen, Erich C. Osterberg, Bess G. Koffman, Jihong Cole-Dai, Dominic A. Winksi, David G. Ferris, Karl J. Kreutz, Cameron P. Wake, and Becky Alexander
EGUsphere, https://doi.org/10.5194/egusphere-2024-3026, https://doi.org/10.5194/egusphere-2024-3026, 2024
Short summary
Short summary
Marine phytoplankton emit dimethyl sulfide (DMS), which forms methanesulfonic acid (MSA) and sulfate. MSA concentrations in ice cores decreased over the industrial era, which has been attributed to pollution-driven changes in DMS chemistry. We use a models to investigate DMS chemistry compared to observations of DMS, MSA, and sulfate. We find that modeled DMS, MSA, and sulfate are influenced by pollution-sensitive oxidant concentrations, characterization of DMS chemistry, and other variables.
Hendrik Fuchs, Aaron Stainsby, Florian Berg, René Dubus, Michelle Färber, Andreas Hofzumahaus, Frank Holland, Kelvin H. Bates, Steven S. Brown, Matthew M. Coggon, Glenn S. Diskin, Georgios I. Gkatzelis, Christopher M. Jernigan, Jeff Peischl, Michael A. Robinson, Andrew W. Rollins, Nell B. Schafer, Rebecca H. Schwantes, Chelsea E. Stockwell, Patrick R. Veres, Carsten Warneke, Eleanor M. Waxman, Lu Xu, Kristen Zuraski, Andreas Wahner, and Anna Novelli
EGUsphere, https://doi.org/10.5194/egusphere-2024-2752, https://doi.org/10.5194/egusphere-2024-2752, 2024
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
Short summary
Short summary
Significant improvements have been made to the instruments used to measure OH reactivity, which is equivalent to the sum of air pollutant concentrations. Accurate and precise measurements with a high time resolution have been achieved, allowing use on aircraft, as demonstrated during flights in the USA.
Katherine R. Travis, Benjamin A. Nault, James H. Crawford, Kelvin H. Bates, Donald R. Blake, Ronald C. Cohen, Alan Fried, Samuel R. Hall, L. Gregory Huey, Young Ro Lee, Simone Meinardi, Kyung-Eun Min, Isobel J. Simpson, and Kirk Ullman
Atmos. Chem. Phys., 24, 9555–9572, https://doi.org/10.5194/acp-24-9555-2024, https://doi.org/10.5194/acp-24-9555-2024, 2024
Short summary
Short summary
Human activities result in the emission of volatile organic compounds (VOCs) that contribute to air pollution. Detailed VOC measurements were taken during a field study in South Korea. When compared to VOC inventories, large discrepancies showed underestimates from chemical products, liquefied petroleum gas, and long-range transport. Improved emissions and chemistry of these VOCs better described urban pollution. The new chemical scheme is relevant to urban areas and other VOC sources.
Olga Zografou, Maria Gini, Prodromos Fetfatzis, Konstantinos Granakis, Romanos Foskinis, Manousos Ioannis Manousakas, Fotios Tsopelas, Evangelia Diapouli, Eleni Dovrou, Christina N. Vasilakopoulou, Alexandros Papayannis, Spyros N. Pandis, Athanasios Nenes, and Konstantinos Eleftheriadis
Atmos. Chem. Phys., 24, 8911–8926, https://doi.org/10.5194/acp-24-8911-2024, https://doi.org/10.5194/acp-24-8911-2024, 2024
Short summary
Short summary
Characterization of PM1 and positive matrix factorization (PMF) source apportionment of organic and inorganic fractions were conducted at the high-altitude station (HAC)2. Cloud presence reduced PM1, affecting sulfate more than organics. Free-troposphere (FT) conditions showed more black carbon (eBC) than planetary boundary layer (PBL) conditions.
Bryan Duncan, Daniel Anderson, Arlene Fiore, Joanna Joiner, Nickolay Krotkov, Can Li, Dylan Millet, Julie Nicely, Luke Oman, Jason St. Clair, Joshua Shutter, Amir Souri, Sarah Strode, Brad Weir, Glenn Wolfe, Helen Worden, and Qindan Zhu
EGUsphere, https://doi.org/10.5194/egusphere-2024-2331, https://doi.org/10.5194/egusphere-2024-2331, 2024
Short summary
Short summary
Trace gases emitted to or formed within the atmosphere may be chemically or physically removed from the atmosphere. One trace gas, the hydroxyl radical (OH), is responsible for initiating the chemical removal of many trace gases, including some climate gases. Despite its importance, scientists have not been able to adequately measure OH. In this opinion piece, we discuss promising new methods to indirectly constrain OH using satellite data of trace gases that control the abundance of OH.
Matthew J. Rowlinson, Mat J. Evans, Lucy J. Carpenter, Katie A. Read, Shalini Punjabi, Adedayo Adedeji, Luke Fakes, Ally Lewis, Ben Richmond, Neil Passant, Tim Murrells, Barron Henderson, Kelvin H. Bates, and Detlev Helmig
Atmos. Chem. Phys., 24, 8317–8342, https://doi.org/10.5194/acp-24-8317-2024, https://doi.org/10.5194/acp-24-8317-2024, 2024
Short summary
Short summary
Ethane and propane are volatile organic compounds emitted from human activities which help to form ozone, a pollutant and greenhouse gas, and also affect the chemistry of the lower atmosphere. Atmospheric models tend to do a poor job of reproducing the abundance of these compounds in the atmosphere. By using regional estimates of their emissions, rather than globally consistent estimates, we can significantly improve the simulation of ethane in the model and make some improvement for propane.
Zhaojin An, Rujing Yin, Xinyan Zhao, Xiaoxiao Li, Yi Yuan, Junchen Guo, Yuyang Li, Xue Li, Dandan Li, Yaowei Li, Dongbin Wang, Chao Yan, Kebin He, Douglas R. Worsnop, Frank N. Keutsch, and Jingkun Jiang
EGUsphere, https://doi.org/10.5194/egusphere-2024-1325, https://doi.org/10.5194/egusphere-2024-1325, 2024
Short summary
Short summary
Online Vocus-PTR measurements show the compositions and seasonal variations of organic vapors in urban Beijing. With enhanced sensitivity and mass resolution, various sub-ppt level species and organics with multiple oxygens (≥3) were discovered. The fast photooxidation process in summer leads to an increase in both concentration and proportion of organics with multiple oxygens. While in other seasons, the variations of them could be influenced by primary emissions.
Kelvin H. Bates, Mathew J. Evans, Barron H. Henderson, and Daniel J. Jacob
Geosci. Model Dev., 17, 1511–1524, https://doi.org/10.5194/gmd-17-1511-2024, https://doi.org/10.5194/gmd-17-1511-2024, 2024
Short summary
Short summary
Accurate representation of rates and products of chemical reactions in atmospheric models is crucial for simulating concentrations of pollutants and climate forcers. We update the widely used GEOS-Chem atmospheric chemistry model with reaction parameters from recent compilations of experimental data and demonstrate the implications for key atmospheric chemical species. The updates decrease tropospheric CO mixing ratios and increase stratospheric nitrogen oxide mixing ratios, among other changes.
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.
Yaowei Li, Corey Pedersen, John Dykema, Jean-Paul Vernier, Sandro Vattioni, Amit Kumar Pandit, Andrea Stenke, Elizabeth Asher, Troy Thornberry, Michael A. Todt, Thao Paul Bui, Jonathan Dean-Day, and Frank N. Keutsch
Atmos. Chem. Phys., 23, 15351–15364, https://doi.org/10.5194/acp-23-15351-2023, https://doi.org/10.5194/acp-23-15351-2023, 2023
Short summary
Short summary
In 2021, the eruption of La Soufrière released sulfur dioxide into the stratosphere, resulting in a spread of volcanic aerosol over the Northern Hemisphere. We conducted extensive aircraft and balloon-borne measurements after that, revealing enhanced particle concentration and altered size distribution due to the eruption. The eruption's impact on ozone depletion was minimal, contributing ~0.6 %, and its global radiative forcing effect was modest, mainly affecting tropical and midlatitude areas.
Brandon Bottorff, Michelle M. Lew, Youngjun Woo, Pamela Rickly, Matthew D. Rollings, Benjamin Deming, Daniel C. Anderson, Ezra Wood, Hariprasad D. Alwe, Dylan B. Millet, Andrew Weinheimer, Geoff Tyndall, John Ortega, Sebastien Dusanter, Thierry Leonardis, James Flynn, Matt Erickson, Sergio Alvarez, Jean C. Rivera-Rios, Joshua D. Shutter, Frank Keutsch, Detlev Helmig, Wei Wang, Hannah M. Allen, Johnathan H. Slade, Paul B. Shepson, Steven Bertman, and Philip S. Stevens
Atmos. Chem. Phys., 23, 10287–10311, https://doi.org/10.5194/acp-23-10287-2023, https://doi.org/10.5194/acp-23-10287-2023, 2023
Short summary
Short summary
The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2) radicals play important roles in atmospheric chemistry and have significant air quality implications. Here, we compare measurements of OH, HO2, and total peroxy radicals (XO2) made in a remote forest in Michigan, USA, to predictions from a series of chemical models. Lower measured radical concentrations suggest that the models may be missing an important radical sink and overestimating the rate of ozone production in this forest.
Vigneshkumar Balamurugan, Jia Chen, Adrian Wenzel, and Frank N. Keutsch
Atmos. Chem. Phys., 23, 10267–10285, https://doi.org/10.5194/acp-23-10267-2023, https://doi.org/10.5194/acp-23-10267-2023, 2023
Short summary
Short summary
In this study, machine learning models are employed to model NO2 and O3 concentrations. We employed a wide range of sources of data, including meteorological and column satellite measurements, to model NO2 and O3 concentrations. The spatial and temporal variability, and their drivers, were investigated. Notably, the machine learning model established the relationship between NOx and O3. Despite the fact that metropolitan regions are NO2 hotspots, rural areas have high O3 concentrations.
Laura Hyesung Yang, Daniel J. Jacob, Nadia K. Colombi, Shixian Zhai, Kelvin H. Bates, Viral Shah, Ellie Beaudry, Robert M. Yantosca, Haipeng Lin, Jared F. Brewer, Heesung Chong, Katherine R. Travis, James H. Crawford, Lok N. Lamsal, Ja-Ho Koo, and Jhoon Kim
Atmos. Chem. Phys., 23, 2465–2481, https://doi.org/10.5194/acp-23-2465-2023, https://doi.org/10.5194/acp-23-2465-2023, 2023
Short summary
Short summary
A geostationary satellite can now provide hourly NO2 vertical columns, and obtaining the NO2 vertical columns from space relies on NO2 vertical distribution from the chemical transport model (CTM). In this work, we update the CTM to better represent the chemistry environment so that the CTM can accurately provide NO2 vertical distribution. We also find that the changes in NO2 vertical distribution driven by a change in mixing depth play an important role in the NO2 column's diurnal variation.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
Short summary
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.
Vigneshkumar Balamurugan, Jia Chen, Zhen Qu, Xiao Bi, and Frank N. Keutsch
Atmos. Chem. Phys., 22, 7105–7129, https://doi.org/10.5194/acp-22-7105-2022, https://doi.org/10.5194/acp-22-7105-2022, 2022
Short summary
Short summary
In this study, we investigated the response of secondary pollutants to changes in precursor emissions, focusing on the formation of secondary PM, during the COVID-19 lockdown period. We show that, due to the decrease in primary NOx emissions, atmospheric oxidizing capacity is increased. The nighttime increase in ozone, caused by less NO titration, results in higher NO3 radicals, which contribute significantly to the formation of PM nitrates. O3 should be limited in order to control PM pollution.
Lu Shen, Daniel J. Jacob, Mauricio Santillana, Kelvin Bates, Jiawei Zhuang, and Wei Chen
Geosci. Model Dev., 15, 1677–1687, https://doi.org/10.5194/gmd-15-1677-2022, https://doi.org/10.5194/gmd-15-1677-2022, 2022
Short summary
Short summary
The high computational cost of chemical integration is a long-standing limitation in global atmospheric chemistry models. Here we present an adaptive and efficient algorithm that can reduce the computational time of atmospheric chemistry by 50 % and maintain the error below 2 % for important species, inspired by machine learning clustering techniques and traditional asymptotic analysis ideas.
Kelvin H. Bates, Guy J. P. Burke, James D. Cope, and Tran B. Nguyen
Atmos. Chem. Phys., 22, 1467–1482, https://doi.org/10.5194/acp-22-1467-2022, https://doi.org/10.5194/acp-22-1467-2022, 2022
Short summary
Short summary
The main nighttime sink of α-pinene, a hydrocarbon abundantly emitted by plants, is reaction with NO3 to form nitrooxy peroxy radicals (nRO2). Using uniquely designed chamber experiments, we show that this reaction is a major source of organic aerosol when nRO2 reacts with other nRO2 and forms a nitrooxy hydroperoxide when nRO2 reacts with HO2. Under ambient conditions these pathways are key loss processes of atmospheric reactive nitrogen in areas with mixed biogenic and anthropogenic influence.
Kelvin H. Bates, Daniel J. Jacob, Ke Li, Peter D. Ivatt, Mat J. Evans, Yingying Yan, and Jintai Lin
Atmos. Chem. Phys., 21, 18351–18374, https://doi.org/10.5194/acp-21-18351-2021, https://doi.org/10.5194/acp-21-18351-2021, 2021
Short summary
Short summary
Simple aromatic compounds (benzene, toluene, xylene) have complex gas-phase chemistry that is inconsistently represented in atmospheric models. We compile recent experimental and theoretical insights to develop a new mechanism for gas-phase aromatic oxidation that is sufficiently compact for use in multiscale models. We compare our new mechanism to chamber experiments and other mechanisms, and implement it in a global model to quantify the impacts of aromatic oxidation on tropospheric chemistry.
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
Short summary
Short summary
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.
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
Short summary
Short summary
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.
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
Short summary
Short summary
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.
Lei Zhu, Gonzalo González Abad, Caroline R. Nowlan, Christopher Chan Miller, Kelly Chance, Eric C. Apel, Joshua P. DiGangi, Alan Fried, Thomas F. Hanisco, Rebecca S. Hornbrook, Lu Hu, Jennifer Kaiser, Frank N. Keutsch, Wade Permar, Jason M. St. Clair, and Glenn M. Wolfe
Atmos. Chem. Phys., 20, 12329–12345, https://doi.org/10.5194/acp-20-12329-2020, https://doi.org/10.5194/acp-20-12329-2020, 2020
Short summary
Short summary
We develop a validation platform for satellite HCHO retrievals using in situ observations from 12 aircraft campaigns. The platform offers an alternative way to quickly assess systematic biases in HCHO satellite products over large domains and long periods, facilitating optimization of retrieval settings and the minimization of retrieval biases. Application to the NASA operational HCHO product indicates that relative biases range from −44.5 % to +112.1 % depending on locations and seasons.
Abigail R. Koss, Manjula R. Canagaratna, Alexander Zaytsev, Jordan E. Krechmer, Martin Breitenlechner, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joseph R. Roscioli, Frank N. Keutsch, and Jesse H. Kroll
Atmos. Chem. Phys., 20, 1021–1041, https://doi.org/10.5194/acp-20-1021-2020, https://doi.org/10.5194/acp-20-1021-2020, 2020
Short summary
Short summary
Oxidation chemistry of organic compounds in the atmosphere produces a diverse spectrum of products. This diversity is difficult to represent in air quality and climate models, and in laboratory experiments it results in large and complex datasets. This work evaluates several methods to simplify the chemistry of oxidation systems in environmental chambers, including positive matrix factorization, hierarchical clustering analysis, and gamma kinetics parameterization.
Alexander Zaytsev, Abigail R. Koss, Martin Breitenlechner, Jordan E. Krechmer, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joshua L. Cox, Joshua Moss, Joseph R. Roscioli, Manjula R. Canagaratna, Douglas R. Worsnop, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Chem. Phys., 19, 15117–15129, https://doi.org/10.5194/acp-19-15117-2019, https://doi.org/10.5194/acp-19-15117-2019, 2019
Short summary
Short summary
Aromatic hydrocarbons contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Here later-generation low-volatility oxygenated products from toluene and 1,2,4-TMB oxidation by OH are detected in the gas and particle phases. We show that these products, previously identified as highly oxygenated molecules (HOMs), are formed in more than one pathway with differing numbers of reaction steps with OH. They also make up a significant fraction of SOA.
Rupert Holzinger, W. Joe F. Acton, William J. Bloss, Martin Breitenlechner, Leigh R. Crilley, Sébastien Dusanter, Marc Gonin, Valerie Gros, Frank N. Keutsch, Astrid Kiendler-Scharr, Louisa J. Kramer, Jordan E. Krechmer, Baptiste Languille, Nadine Locoge, Felipe Lopez-Hilfiker, Dušan Materić, Sergi Moreno, Eiko Nemitz, Lauriane L. J. Quéléver, Roland Sarda Esteve, Stéphane Sauvage, Simon Schallhart, Roberto Sommariva, Ralf Tillmann, Sergej Wedel, David R. Worton, Kangming Xu, and Alexander Zaytsev
Atmos. Meas. Tech., 12, 6193–6208, https://doi.org/10.5194/amt-12-6193-2019, https://doi.org/10.5194/amt-12-6193-2019, 2019
Adam W. Birdsall, Jack C. Hensley, Paige S. Kotowitz, Andrew J. Huisman, and Frank N. Keutsch
Atmos. Chem. Phys., 19, 14195–14209, https://doi.org/10.5194/acp-19-14195-2019, https://doi.org/10.5194/acp-19-14195-2019, 2019
Short summary
Short summary
We have measured the evaporation rates of butenedial, a four-carbon dialdehyde produced in the atmosphere, from individual levitated particles. Effective vapor pressures and Henry's law constants, which characterize the compound's gas-particle partitioning behavior, were determined. The important role of hydration reactions was observed under both dry and humid conditions, as well as a salting-out effect in the presence of sodium chloride or sodium sulfate.
Joshua D. Shutter, Norton T. Allen, Thomas F. Hanisco, Glenn M. Wolfe, Jason M. St. Clair, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 6079–6089, https://doi.org/10.5194/amt-12-6079-2019, https://doi.org/10.5194/amt-12-6079-2019, 2019
Short summary
Short summary
A new mid-infrared and ultra-portable formaldehyde (HCHO) sensor from Aeris Technologies is characterized and evaluated against well-established laser-induced fluorescence (LIF) instrumentation. The Aeris sensor displays linear behavior (R squared > 0.94) and shows good agreement with LIF instruments. While the compact sensor is not currently a replacement for the most sensitive research-grade instrumentation available, its sub-ppbv precision is sufficient for indoor and outdoor HCHO monitoring.
Eleni Dovrou, Christopher Y. Lim, Manjula R. Canagaratna, Jesse H. Kroll, Douglas R. Worsnop, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 5303–5315, https://doi.org/10.5194/amt-12-5303-2019, https://doi.org/10.5194/amt-12-5303-2019, 2019
Short summary
Short summary
Measurement techniques commonly used to analyze particulate matter composition can result in the possible misidentification of sulfur-containing species, especially for the case of sulfate and hydroxymethanesulfonate (HMS). The efficiency and limitations of these techniques, along with a method that enables further studies of the contribution of sulfur-containing species, S(IV) versus S(VI), to particulate matter under low-light atmospheric conditions, are described in this work.
Alexander Zaytsev, Martin Breitenlechner, Abigail R. Koss, Christopher Y. Lim, James C. Rowe, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 1861–1870, https://doi.org/10.5194/amt-12-1861-2019, https://doi.org/10.5194/amt-12-1861-2019, 2019
Short summary
Short summary
We present the development of a chemical ionization mass spectrometer which can be operated with either ammonium (NH4+) or hydronium (H3O+) as the reagent ion. We describe a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of detected ammonium–organic ions and hence constrain the sensitivity of the instrument to a wide range of organic compounds that cannot be calibrated directly.
Azimeh Zare, Paul S. Romer, Tran Nguyen, Frank N. Keutsch, Kate Skog, and Ronald C. Cohen
Atmos. Chem. Phys., 18, 15419–15436, https://doi.org/10.5194/acp-18-15419-2018, https://doi.org/10.5194/acp-18-15419-2018, 2018
Short summary
Short summary
Organic nitrates play an important role in concentrations and distribution of NOx, ozone and aerosol as the most important air pollutants. We develop a state-of-the-science detailed chemical mechanism representing individual organic nitrates, which is appropriate to use in air quality models and results in a more accurate simulation of atmospheric chemistry. Using this mechanism we explore production and removal processes of organic nitrates in a rural environment that are poorly constrained.
Hendrik Fuchs, Sascha Albrecht, Ismail–Hakki Acir, Birger Bohn, Martin Breitenlechner, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, Martin Kaminski, Frank N. Keutsch, Anna Novelli, David Reimer, Franz Rohrer, Ralf Tillmann, Luc Vereecken, Robert Wegener, Alexander Zaytsev, Astrid Kiendler-Scharr, and Andreas Wahner
Atmos. Chem. Phys., 18, 8001–8016, https://doi.org/10.5194/acp-18-8001-2018, https://doi.org/10.5194/acp-18-8001-2018, 2018
Short summary
Short summary
The photooxidation of methyl vinyl ketone MVK, one of the most important products of isoprene that is emitted by plants, was investigated in the atmospheric simulation chamber SAPHIR for conditions found in forested areas. The comparison of measured trace gas time series with model calculations shows a gap in the understanding of radical chemistry in the MVK oxidation scheme. The possibility of unimolecular isomerization reactions were investigated by means of quantum-chemical calculations.
Shouming Zhou, Jean C. Rivera-Rios, Frank N. Keutsch, and Jonathan P. D. Abbatt
Atmos. Meas. Tech., 11, 3081–3089, https://doi.org/10.5194/amt-11-3081-2018, https://doi.org/10.5194/amt-11-3081-2018, 2018
Adam W. Birdsall, Ulrich K. Krieger, and Frank N. Keutsch
Atmos. Meas. Tech., 11, 33–47, https://doi.org/10.5194/amt-11-33-2018, https://doi.org/10.5194/amt-11-33-2018, 2018
Short summary
Short summary
We have developed a laboratory system that provides mass spectra of individual particles, roughly 20 microns in diameter, after they have been levitated in an electric field. Measured evaporation of polyethylene glycol particles was found to agree with a kinetic model. The system can be used to study fundamental chemical and physical processes involving particles that are difficult to isolate and study with other techniques, and hence improve our understanding of atmospheric particles.
Abigail Koss, Bin Yuan, Carsten Warneke, Jessica B. Gilman, Brian M. Lerner, Patrick R. Veres, Jeff Peischl, Scott Eilerman, Rob Wild, Steven S. Brown, Chelsea R. Thompson, Thomas Ryerson, Thomas Hanisco, Glenn M. Wolfe, Jason M. St. Clair, Mitchell Thayer, Frank N. Keutsch, Shane Murphy, and Joost de Gouw
Atmos. Meas. Tech., 10, 2941–2968, https://doi.org/10.5194/amt-10-2941-2017, https://doi.org/10.5194/amt-10-2941-2017, 2017
Short summary
Short summary
Oil and gas extraction activity can cause air quality issues through emission of reactive chemicals. VOCs related to extraction operations in the United States were measured by PTR-ToF-MS from aircraft during the SONGNEX campaign in March–April 2015. The detailed analysis in this work provides a guide to interpreting PTR-ToF measurements in oil- and gas-producing regions, and it includes fundamental observations of VOC speciation and mixing ratios.
Christopher Chan Miller, Daniel J. Jacob, Eloise A. Marais, Karen Yu, Katherine R. Travis, Patrick S. Kim, Jenny A. Fisher, Lei Zhu, Glenn M. Wolfe, Thomas F. Hanisco, Frank N. Keutsch, Jennifer Kaiser, Kyung-Eun Min, Steven S. Brown, Rebecca A. Washenfelder, Gonzalo González Abad, and Kelly Chance
Atmos. Chem. Phys., 17, 8725–8738, https://doi.org/10.5194/acp-17-8725-2017, https://doi.org/10.5194/acp-17-8725-2017, 2017
Short summary
Short summary
The use of satellite glyoxal observations for estimating isoprene emissions has been limited by knowledge of the glyoxal yield from isoprene. We use SENEX aircraft observations over the southeast US to evaluate glyoxal yields from isoprene in a 3-D atmospheric model. The SENEX observations support a pathway for glyoxal formation in pristine regions that we propose here, which may have implications for improving isoprene emissions estimates from upcoming high-resolution geostationary satellites.
Anne-Kathrin Bernhammer, Martin Breitenlechner, Frank N. Keutsch, and Armin Hansel
Atmos. Chem. Phys., 17, 4053–4062, https://doi.org/10.5194/acp-17-4053-2017, https://doi.org/10.5194/acp-17-4053-2017, 2017
Short summary
Short summary
Isoprene is the predominant non-methane compound emitted by the biosphere. In the atmosphere oxidation by OH under low NOx produces isoprene hydroxy hydroperoxides (ISOPOOHs). This work has found an effective conversion of ISOPOOHs to volatile carbonyls on metal environmental simulation chamber walls. Likely catalyzed decomposition reactions also occur for other hydroxyl hydroperoxides on metal surfaces.
Anusha P. S. Hettiyadura, Thilina Jayarathne, Karsten Baumann, Allen H. Goldstein, Joost A. de Gouw, Abigail Koss, Frank N. Keutsch, Kate Skog, and Elizabeth A. Stone
Atmos. Chem. Phys., 17, 1343–1359, https://doi.org/10.5194/acp-17-1343-2017, https://doi.org/10.5194/acp-17-1343-2017, 2017
Short summary
Short summary
Organosulfates are components of secondary organic aerosol (SOA) formed in the presence of sulfate. Herein, their abundance, identity, and potential to form as sampling artifacts were studied in Centreville, AL, USA. The 10 most abundant signals accounted for 58–78 % of the total, with at least 20–200 other species accounting for the remainder. These major species were largely associated with biogenic gases, like isoprene and monoterpenes, and are proposed targets for future standard development.
Emma L. D'Ambro, Ben H. Lee, Jiumeng Liu, John E. Shilling, Cassandra J. Gaston, Felipe D. Lopez-Hilfiker, Siegfried Schobesberger, Rahul A. Zaveri, Claudia Mohr, Anna Lutz, Zhenfa Zhang, Avram Gold, Jason D. Surratt, Jean C. Rivera-Rios, Frank N. Keutsch, and Joel A. Thornton
Atmos. Chem. Phys., 17, 159–174, https://doi.org/10.5194/acp-17-159-2017, https://doi.org/10.5194/acp-17-159-2017, 2017
Short summary
Short summary
We studied the formation and properties of secondary organic aerosol produced from isoprene. We find that a significant fraction (~50 %) of the mass is composed of low-volatility, highly oxidized compounds such as C5H12O6. A significant fraction of the remainder appears to be in the form of oligomeric material. Adding NOx maintained or decreased SOA yields while increasing the fraction of low-volatility material, possibly due to oligomers.
Jason M. St. Clair, Jean C. Rivera-Rios, John D. Crounse, Eric Praske, Michelle J. Kim, Glenn M. Wolfe, Frank N. Keutsch, Paul O. Wennberg, and Thomas F. Hanisco
Atmos. Meas. Tech., 9, 4561–4568, https://doi.org/10.5194/amt-9-4561-2016, https://doi.org/10.5194/amt-9-4561-2016, 2016
Short summary
Short summary
Global isoprene emissions are the largest source of atmospheric non-methane hydrocarbons. Lab results show that ISOPOOH, a low-NOx isoprene oxidation product, can decompose on instrument surfaces to form high-NOx isoprene oxidation products, causing misinterpretation of oxidation conditions. This study investigated the potential formaldehyde artifact from ISOPOOH for the NASA ISAF instrument, and found that it does not significantly affect the accuracy of the ISAF field measurements.
J. Kaiser, K. M. Skog, K. Baumann, S. B. Bertman, S. B. Brown, W. H. Brune, J. D. Crounse, J. A. de Gouw, E. S. Edgerton, P. A. Feiner, A. H. Goldstein, A. Koss, P. K. Misztal, T. B. Nguyen, K. F. Olson, J. M. St. Clair, A. P. Teng, S. Toma, P. O. Wennberg, R. J. Wild, L. Zhang, and F. N. Keutsch
Atmos. Chem. Phys., 16, 9349–9359, https://doi.org/10.5194/acp-16-9349-2016, https://doi.org/10.5194/acp-16-9349-2016, 2016
Short summary
Short summary
OH reactivity can be used to assess the amount of reactive carbon in an air mass. “Missing” reactivity is commonly found in forested environments and is attributed to either direct emissions of unmeasured volatile organic compounds or to unmeasured/underpredicted oxidation products. Using a box model and measurements from the 2013 SOAS campaign, we find only small discrepancies in measured and calculated reactivity. Our results suggest the discrepancies stem from unmeasured direct emissions.
Carsten Warneke, Michael Trainer, Joost A. de Gouw, David D. Parrish, David W. Fahey, A. R. Ravishankara, Ann M. Middlebrook, Charles A. Brock, James M. Roberts, Steven S. Brown, Jonathan A. Neuman, Brian M. Lerner, Daniel Lack, Daniel Law, Gerhard Hübler, Iliana Pollack, Steven Sjostedt, Thomas B. Ryerson, Jessica B. Gilman, Jin Liao, John Holloway, Jeff Peischl, John B. Nowak, Kenneth C. Aikin, Kyung-Eun Min, Rebecca A. Washenfelder, Martin G. Graus, Mathew Richardson, Milos Z. Markovic, Nick L. Wagner, André Welti, Patrick R. Veres, Peter Edwards, Joshua P. Schwarz, Timothy Gordon, William P. Dube, Stuart A. McKeen, Jerome Brioude, Ravan Ahmadov, Aikaterini Bougiatioti, Jack J. Lin, Athanasios Nenes, Glenn M. Wolfe, Thomas F. Hanisco, Ben H. Lee, Felipe D. Lopez-Hilfiker, Joel A. Thornton, Frank N. Keutsch, Jennifer Kaiser, Jingqiu Mao, and Courtney D. Hatch
Atmos. Meas. Tech., 9, 3063–3093, https://doi.org/10.5194/amt-9-3063-2016, https://doi.org/10.5194/amt-9-3063-2016, 2016
Short summary
Short summary
In this paper we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign, which was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants.
During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN. The SENEX flights included day- and nighttime flights in the Southeast as well as flights over areas with intense shale gas extraction.
Amy P. Sullivan, Natasha Hodas, Barbara J. Turpin, Kate Skog, Frank N. Keutsch, Stefania Gilardoni, Marco Paglione, Matteo Rinaldi, Stefano Decesari, Maria Cristina Facchini, Laurent Poulain, Hartmut Herrmann, Alfred Wiedensohler, Eiko Nemitz, Marsailidh M. Twigg, and Jeffrey L. Collett Jr.
Atmos. Chem. Phys., 16, 8095–8108, https://doi.org/10.5194/acp-16-8095-2016, https://doi.org/10.5194/acp-16-8095-2016, 2016
Short summary
Short summary
This paper presents the results from our measurements and approach for the investigation of aqueous secondary organic aerosol (aqSOA) formation in the ambient atmosphere. When local aqSOA formation was observed, a correlation of water-soluble organic carbon with organic aerosol, aerosol liquid water, relative humidity, and aerosol nitrate was found. Key factors of local aqSOA production include air mass stagnation, formation of local nitrate overnight, and significant amounts of ammonia.
Luping Su, Edward G. Patton, Jordi Vilà-Guerau de Arellano, Alex B. Guenther, Lisa Kaser, Bin Yuan, Fulizi Xiong, Paul B. Shepson, Li Zhang, David O. Miller, William H. Brune, Karsten Baumann, Eric Edgerton, Andrew Weinheimer, Pawel K. Misztal, Jeong-Hoo Park, Allen H. Goldstein, Kate M. Skog, Frank N. Keutsch, and John E. Mak
Atmos. Chem. Phys., 16, 7725–7741, https://doi.org/10.5194/acp-16-7725-2016, https://doi.org/10.5194/acp-16-7725-2016, 2016
Markus Müller, Bruce E. Anderson, Andreas J. Beyersdorf, James H. Crawford, Glenn S. Diskin, Philipp Eichler, Alan Fried, Frank N. Keutsch, Tomas Mikoviny, Kenneth L. Thornhill, James G. Walega, Andrew J. Weinheimer, Melissa Yang, Robert J. Yokelson, and Armin Wisthaler
Atmos. Chem. Phys., 16, 3813–3824, https://doi.org/10.5194/acp-16-3813-2016, https://doi.org/10.5194/acp-16-3813-2016, 2016
Short summary
Short summary
Atmospheric emissions from small forest fires and their impact on regional air quality are still poorly characterized. We used an instrumented NASA P-3B aircraft to study emissions from a small forest understory fire in Georgia (USA) and to investigate chemical transformations in the fire plume in the 1 h downwind region. A state-of-the-art chemical model was able to accurately simulate key chemical processes in the aging plume.
G. M. Wolfe, J. Kaiser, T. F. Hanisco, F. N. Keutsch, J. A. de Gouw, J. B. Gilman, M. Graus, C. D. Hatch, J. Holloway, L. W. Horowitz, B. H. Lee, B. M. Lerner, F. Lopez-Hilifiker, J. Mao, M. R. Marvin, J. Peischl, I. B. Pollack, J. M. Roberts, T. B. Ryerson, J. A. Thornton, P. R. Veres, and C. Warneke
Atmos. Chem. Phys., 16, 2597–2610, https://doi.org/10.5194/acp-16-2597-2016, https://doi.org/10.5194/acp-16-2597-2016, 2016
Short summary
Short summary
This study uses airborne trace gas observations acquired over the southeast US to examine how both natural (isoprene) and anthropogenic (NOx) emissions influence the production of formaldehyde (HCHO). We find a 3-fold increase in HCHO yield between rural and polluted environments. State-of-the-science chemical mechanisms are generally able to reproduce this behavior. These results add confidence to global hydrocarbon emission inventories constrained by spaceborne HCHO observations.
J. Kaiser, G. M. Wolfe, K. E. Min, S. S. Brown, C. C. Miller, D. J. Jacob, J. A. deGouw, M. Graus, T. F. Hanisco, J. Holloway, J. Peischl, I. B. Pollack, T. B. Ryerson, C. Warneke, R. A. Washenfelder, and F. N. Keutsch
Atmos. Chem. Phys., 15, 7571–7583, https://doi.org/10.5194/acp-15-7571-2015, https://doi.org/10.5194/acp-15-7571-2015, 2015
R. Thalman, M. T. Baeza-Romero, S. M. Ball, E. Borrás, M. J. S. Daniels, I. C. A. Goodall, S. B. Henry, T. Karl, F. N. Keutsch, S. Kim, J. Mak, P. S. Monks, A. Muñoz, J. Orlando, S. Peppe, A. R. Rickard, M. Ródenas, P. Sánchez, R. Seco, L. Su, G. Tyndall, M. Vázquez, T. Vera, E. Waxman, and R. Volkamer
Atmos. Meas. Tech., 8, 1835–1862, https://doi.org/10.5194/amt-8-1835-2015, https://doi.org/10.5194/amt-8-1835-2015, 2015
Short summary
Short summary
Measurements of α-dicarbonyl compounds, like glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO), are informative about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation in the atmosphere. We have compared nine instruments and seven techniques to measure α-dicarbonyl, using simulation chamber facilities in the US and Europe. We assess our understanding of calibration, precision, accuracy and detection limits, as well as possible sampling biases.
J. Kaiser, G. M. Wolfe, B. Bohn, S. Broch, H. Fuchs, L. N. Ganzeveld, S. Gomm, R. Häseler, A. Hofzumahaus, F. Holland, J. Jäger, X. Li, I. Lohse, K. Lu, A. S. H. Prévôt, F. Rohrer, R. Wegener, R. Wolf, T. F. Mentel, A. Kiendler-Scharr, A. Wahner, and F. N. Keutsch
Atmos. Chem. Phys., 15, 1289–1298, https://doi.org/10.5194/acp-15-1289-2015, https://doi.org/10.5194/acp-15-1289-2015, 2015
Short summary
Short summary
Using measurements acquired from a Zeppelin airship during the PEGASOS 2012 campaign, we show that VOC oxidation alone cannot account for the formaldehyde concentrations observed in the morning over rural Italy. Vertical profiles suggest a ground-level source of HCHO. Incorporating this additional HCHO source into a photochemical model increases calculated O3 production by as much as 12%.
T. B. Nguyen, J. D. Crounse, R. H. Schwantes, A. P. Teng, K. H. Bates, X. Zhang, J. M. St. Clair, W. H. Brune, G. S. Tyndall, F. N. Keutsch, J. H. Seinfeld, and P. O. Wennberg
Atmos. Chem. Phys., 14, 13531–13549, https://doi.org/10.5194/acp-14-13531-2014, https://doi.org/10.5194/acp-14-13531-2014, 2014
J. Ortega, A. Turnipseed, A. B. Guenther, T. G. Karl, D. A. Day, D. Gochis, J. A. Huffman, A. J. Prenni, E. J. T. Levin, S. M. Kreidenweis, P. J. DeMott, Y. Tobo, E. G. Patton, A. Hodzic, Y. Y. Cui, P. C. Harley, R. S. Hornbrook, E. C. Apel, R. K. Monson, A. S. D. Eller, J. P. Greenberg, M. C. Barth, P. Campuzano-Jost, B. B. Palm, J. L. Jimenez, A. C. Aiken, M. K. Dubey, C. Geron, J. Offenberg, M. G. Ryan, P. J. Fornwalt, S. C. Pryor, F. N. Keutsch, J. P. DiGangi, A. W. H. Chan, A. H. Goldstein, G. M. Wolfe, S. Kim, L. Kaser, R. Schnitzhofer, A. Hansel, C. A. Cantrell, R. L. Mauldin, and J. N. Smith
Atmos. Chem. Phys., 14, 6345–6367, https://doi.org/10.5194/acp-14-6345-2014, https://doi.org/10.5194/acp-14-6345-2014, 2014
J. Kaiser, X. Li, R. Tillmann, I. Acir, F. Holland, F. Rohrer, R. Wegener, and F. N. Keutsch
Atmos. Meas. Tech., 7, 1571–1580, https://doi.org/10.5194/amt-7-1571-2014, https://doi.org/10.5194/amt-7-1571-2014, 2014
G. M. Wolfe, C. Cantrell, S. Kim, R. L. Mauldin III, T. Karl, P. Harley, A. Turnipseed, W. Zheng, F. Flocke, E. C. Apel, R. S. Hornbrook, S. R. Hall, K. Ullmann, S. B. Henry, J. P. DiGangi, E. S. Boyle, L. Kaser, R. Schnitzhofer, A. Hansel, M. Graus, Y. Nakashima, Y. Kajii, A. Guenther, and F. N. Keutsch
Atmos. Chem. Phys., 14, 4715–4732, https://doi.org/10.5194/acp-14-4715-2014, https://doi.org/10.5194/acp-14-4715-2014, 2014
T. B. Nguyen, M. M. Coggon, K. H. Bates, X. Zhang, R. H. Schwantes, K. A. Schilling, C. L. Loza, R. C. Flagan, P. O. Wennberg, and J. H. Seinfeld
Atmos. Chem. Phys., 14, 3497–3510, https://doi.org/10.5194/acp-14-3497-2014, https://doi.org/10.5194/acp-14-3497-2014, 2014
L. Kaser, T. Karl, A. Guenther, M. Graus, R. Schnitzhofer, A. Turnipseed, L. Fischer, P. Harley, M. Madronich, D. Gochis, F. N. Keutsch, and A. Hansel
Atmos. Chem. Phys., 13, 11935–11947, https://doi.org/10.5194/acp-13-11935-2013, https://doi.org/10.5194/acp-13-11935-2013, 2013
S. Kundu, T. A. Quraishi, G. Yu, C. Suarez, F. N. Keutsch, and E. A. Stone
Atmos. Chem. Phys., 13, 4865–4875, https://doi.org/10.5194/acp-13-4865-2013, https://doi.org/10.5194/acp-13-4865-2013, 2013
Related subject area
Subject: Clouds and Precipitation | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Retention of α-pinene oxidation products and nitro-aromatic compounds during riming
Direct formation of HONO through aqueous-phase photolysis of organic nitrates
On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal
Effects of pH and light exposure on the survival of bacteria and their ability to biodegrade organic compounds in clouds: implications for microbial activity in acidic cloud water
On the importance of atmospheric loss of organic nitrates by aqueous-phase ●OH oxidation
Lignin's ability to nucleate ice via immersion freezing and its stability towards physicochemical treatments and atmospheric processing
Biodegradation of phenol and catechol in cloud water: comparison to chemical oxidation in the atmospheric multiphase system
Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 2: Quartz and amorphous silica
Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 3: Aluminosilicates
Aqueous reactions of organic triplet excited states with atmospheric alkenes
The quasi-liquid layer of ice revisited: the role of temperature gradients and tip chemistry in AFM studies
Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions – Part 1: The K-feldspar microcline
Direct molecular-level characterization of different heterogeneous freezing modes on mica – Part 1
Chemistry of riming: the retention of organic and inorganic atmospheric trace constituents
Surface-charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001)
Screening of cloud microorganisms isolated at the Puy de Dôme (France) station for the production of biosurfactants
Comparing contact and immersion freezing from continuous flow diffusion chambers
A better understanding of hydroxyl radical photochemical sources in cloud waters collected at the puy de Dôme station – experimental versus modelled formation rates
Deposition and immersion-mode nucleation of ice by three distinct samples of volcanic ash
Organic matter matters for ice nuclei of agricultural soil origin
Effect of atmospheric organic complexation on iron-bearing dust solubility
Are sesquiterpenes a good source of secondary organic cloud condensation nuclei (CCN)? Revisiting β-caryophyllene CCN
Ice nucleation efficiency of clay minerals in the immersion mode
Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry
Yields of hydrogen peroxide from the reaction of hydroxyl radical with organic compounds in solution and ice
In-cloud processes of methacrolein under simulated conditions – Part 1: Aqueous phase photooxidation
In-cloud processes of methacrolein under simulated conditions – Part 2: Formation of secondary organic aerosol
Christine Borchers, Jackson Seymore, Martanda Gautam, Konstantin Dörholt, Yannik Müller, Andreas Arndt, Laura Gömmer, Florian Ungeheuer, Miklós Szakáll, Stephan Borrmann, Alexander Theis, Alexander Lucas Vogel, and Thorsten Hoffmann
EGUsphere, https://doi.org/10.5194/egusphere-2024-1443, https://doi.org/10.5194/egusphere-2024-1443, 2024
Short summary
Short summary
Riming, a crucial process in cloud dynamics, influences the vertical distribution of compounds in the atmosphere. Experiments in Mainz's wind tunnel investigated retention coefficients of organic compounds under varying conditions. Findings suggest a correlation between Henry's law constant and retention, applicable even to complex organic molecules.
Juan Miguel González-Sánchez, Miquel Huix-Rotllant, Nicolas Brun, Julien Morin, Carine Demelas, Amandine Durand, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 23, 15135–15147, https://doi.org/10.5194/acp-23-15135-2023, https://doi.org/10.5194/acp-23-15135-2023, 2023
Short summary
Short summary
Organic nitrates play a crucial role in air pollution, as they are nitrogen oxide (NOx) reservoirs. This work investigated the reaction products and mechanisms of their reactivity with light in the aqueous phase (cloud and fog conditions and wet aerosol). Our findings reveal that this chemistry leads to the formation of atmospheric nitrous acid (HONO).
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 23, 5851–5866, https://doi.org/10.5194/acp-23-5851-2023, https://doi.org/10.5194/acp-23-5851-2023, 2023
Short summary
Short summary
Organic nitrates play a crucial role in air pollution, as they are NOx reservoirs. This work investigated for the first time their reactivity with light in the aqueous phase (cloud and fog and wet aerosol), proving it slower than in the gas phase. Therefore, our findings reveal that partitioning of organic nitrates in the aqueous phase leads to longer atmospheric lifetimes of these compounds and thus a broader spatial distribution of their related pollution.
Yushuo Liu, Chee Kent Lim, Zhiyong Shen, Patrick K. H. Lee, and Theodora Nah
Atmos. Chem. Phys., 23, 1731–1747, https://doi.org/10.5194/acp-23-1731-2023, https://doi.org/10.5194/acp-23-1731-2023, 2023
Short summary
Short summary
We investigated how cloud water pH and solar radiation impact the survival and energetic metabolism of two neutrophilic bacteria species and their biodegradation of organic acids. Experiments were performed using artificial cloud water that mimicked the pH and composition of cloud water in South China. We found that there is a minimum cloud water pH threshold at which neutrophilic bacteria will survive and biodegrade organic compounds in cloud water during the daytime and/or nighttime.
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Julien Morin, Brice Temime-Roussel, Sylvain Ravier, Camille Mouchel-Vallon, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 21, 4915–4937, https://doi.org/10.5194/acp-21-4915-2021, https://doi.org/10.5194/acp-21-4915-2021, 2021
Short summary
Short summary
Organic nitrates play a crucial role in air pollution as they are considered NOx reservoirs. This work lights up the importance of their reactions with OH radicals in the aqueous phase (cloud/fog, wet aerosol), which is slower than in the gas phase. For compounds that significantly partition in water such as polyfunctional biogenic nitrates, these aqueous-phase reactions should drive their atmospheric removal, leading to a broader spatial distribution of NOx than previously accounted for.
Sophie Bogler and Nadine Borduas-Dedekind
Atmos. Chem. Phys., 20, 14509–14522, https://doi.org/10.5194/acp-20-14509-2020, https://doi.org/10.5194/acp-20-14509-2020, 2020
Short summary
Short summary
To study the role of organic matter in ice crystal formation, we investigated the ice nucleation ability of a subcomponent of organic aerosols, the biopolymer lignin, using a droplet-freezing technique. We found that lignin is an ice-active macromolecule with changing abilities based on dilutions. The effects of atmospheric processing and of physicochemical treatments on the ability of lignin solutions to freeze were negligible. Thus, lignin is a recalcitrant ice-nucleating macromolecule.
Saly Jaber, Audrey Lallement, Martine Sancelme, Martin Leremboure, Gilles Mailhot, Barbara Ervens, and Anne-Marie Delort
Atmos. Chem. Phys., 20, 4987–4997, https://doi.org/10.5194/acp-20-4987-2020, https://doi.org/10.5194/acp-20-4987-2020, 2020
Short summary
Short summary
Current atmospheric multiphase models do not include biotransformations of organic compounds by bacteria, although many previous studies of our and other research groups have shown microbial activity in cloud water. The current lab/model study shows that for water-soluble aromatic compounds, biodegradation by bacteria may be as efficient as chemical reactions in cloud water.
Anand Kumar, Claudia Marcolli, and Thomas Peter
Atmos. Chem. Phys., 19, 6035–6058, https://doi.org/10.5194/acp-19-6035-2019, https://doi.org/10.5194/acp-19-6035-2019, 2019
Short summary
Short summary
This paper not only interests the atmospheric science community but has a potential to cater to a broader audience. We discuss both long- and
short-term effects of various
atmospherically relevantchemical species on a fairly abundant mineral surface
Quartz. We of course discuss these chemical interactions from the perspective of fate of airborne mineral dust but the same interactions could be interesting for studies on minerals at the ground level.
Anand Kumar, Claudia Marcolli, and Thomas Peter
Atmos. Chem. Phys., 19, 6059–6084, https://doi.org/10.5194/acp-19-6059-2019, https://doi.org/10.5194/acp-19-6059-2019, 2019
Short summary
Short summary
This paper not only interests the Atmospheric Science community but has a potential to cater to a broader audience. We discuss both long- and short-term effects of various
atmospherically relevantchemical species on fairly abundant mineral surfaces like feldspars and clays. We of course discuss these chemical interactions from the perspective of fate of airborne mineral dust but the same interactions could be interesting for studies on minerals at the ground level.
Richie Kaur, Brandi M. Hudson, Joseph Draper, Dean J. Tantillo, and Cort Anastasio
Atmos. Chem. Phys., 19, 5021–5032, https://doi.org/10.5194/acp-19-5021-2019, https://doi.org/10.5194/acp-19-5021-2019, 2019
Short summary
Short summary
Organic triplets are an important class of aqueous photooxidants, but little is known about their reactions with most atmospheric organic compounds. We measured the reaction rate constants of a model triplet with 17 aliphatic alkenes; using their correlation with oxidation potential, we predicted rate constants for some atmospherically relevant alkenes. Depending on their reactivities, triplets can be minor to important sinks for isoprene- and limonene-derived alkenes in cloud or fog drops.
Julián Gelman Constantin, Melisa M. Gianetti, María P. Longinotti, and Horacio R. Corti
Atmos. Chem. Phys., 18, 14965–14978, https://doi.org/10.5194/acp-18-14965-2018, https://doi.org/10.5194/acp-18-14965-2018, 2018
Short summary
Short summary
Numerous studies have shown that ice surface is actually coated by a thin layer of water even for temperatures below melting temperature. This quasi-liquid layer is relevant in the atmospheric chemistry of clouds, polar regions, glaciers, and other cold regions. We present new results of atomic force microscopy on pure ice, which suggests a thickness for this layer below 1 nm between -7 ºC and -2 ºC. We propose that in many cases previous authors have overestimated this thickness.
Anand Kumar, Claudia Marcolli, Beiping Luo, and Thomas Peter
Atmos. Chem. Phys., 18, 7057–7079, https://doi.org/10.5194/acp-18-7057-2018, https://doi.org/10.5194/acp-18-7057-2018, 2018
Short summary
Short summary
We have performed immersion freezing experiments with microcline (most active ice nucleation, IN, K-feldspar polymorph) and investigated the effect of ammonium and non-ammonium solutes on its IN efficiency. We report increased IN efficiency of microcline in dilute ammonia- or ammonium-containing solutions, which opens up a pathway for condensation freezing occurring at a warmer temperature than immersion freezing.
Ahmed Abdelmonem
Atmos. Chem. Phys., 17, 10733–10741, https://doi.org/10.5194/acp-17-10733-2017, https://doi.org/10.5194/acp-17-10733-2017, 2017
Short summary
Short summary
On the basis of supercooled SHG spectroscopy, I report molecular-level evidence for the existence of one- and two-step deposition freezing depending on the surface type and the supersaturation conditions. In addition, immersion freezing shows a transient ice phase with a lifetime of c. 1 min. This study provides new insights into atmospheric processes and can impact various industrial and research branches, particularly climate change, weather modification, and tracing water in the hydrosphere.
Alexander Jost, Miklós Szakáll, Karoline Diehl, Subir K. Mitra, and Stephan Borrmann
Atmos. Chem. Phys., 17, 9717–9732, https://doi.org/10.5194/acp-17-9717-2017, https://doi.org/10.5194/acp-17-9717-2017, 2017
Short summary
Short summary
During riming of graupel and hail, soluble chemical trace constituents contained in the liquid droplets could be retained while freezing onto the glaciated particle, or released back to the air potentially at other altitudes as retained. Quantification of retention constitutes a major uncertainty in numerical models for atmospheric chemistry and improvements hinge upon experimental determination of retention for carboxylic acids, aldehydes, SO2, H2O2, NH2, and others, as presented in this paper.
Ahmed Abdelmonem, Ellen H. G. Backus, Nadine Hoffmann, M. Alejandra Sánchez, Jenée D. Cyran, Alexei Kiselev, and Mischa Bonn
Atmos. Chem. Phys., 17, 7827–7837, https://doi.org/10.5194/acp-17-7827-2017, https://doi.org/10.5194/acp-17-7827-2017, 2017
Short summary
Short summary
We report the effect of surface charge on heterogeneous immersion freezing for the atmospherically relevant sapphire surface. Combining linear and nonlinear optical techniques and investigating isolated drops, we find that charge-induced surface templating is detrimental for ice nucleation on α-alumina surface. This study provides new insights into atmospheric processes and can impact various industrial and research branches, particularly climate change and tracing of water in the hydrosphere.
Pascal Renard, Isabelle Canet, Martine Sancelme, Nolwenn Wirgot, Laurent Deguillaume, and Anne-Marie Delort
Atmos. Chem. Phys., 16, 12347–12358, https://doi.org/10.5194/acp-16-12347-2016, https://doi.org/10.5194/acp-16-12347-2016, 2016
Short summary
Short summary
A total of 480 microorganisms collected from 39 clouds sampled in France were isolated and identified. This unique collection was screened for biosurfactant production by measuring the surface tension. 41 % of the tested strains were active producers. Pseudomonas, the most frequently detected genus in clouds, was the dominant group for the production of biosurfactants. Further, the potential impact of the production of biosurfactants by cloud microorganisms on atmospheric processes is discussed.
Baban Nagare, Claudia Marcolli, André Welti, Olaf Stetzer, and Ulrike Lohmann
Atmos. Chem. Phys., 16, 8899–8914, https://doi.org/10.5194/acp-16-8899-2016, https://doi.org/10.5194/acp-16-8899-2016, 2016
Short summary
Short summary
The relative importance of contact freezing and immersion freezing at mixed-phase cloud temperatures is the subject of debate. We performed experiments using continuous-flow diffusion chambers to compare the freezing efficiency of ice-nucleating particles for both these nucleation modes. Silver iodide, kaolinite and Arizona Test Dust were used as ice-nucleating particles. We could not confirm the dominance of contact freezing over immersion freezing for our experimental conditions.
A. Bianco, M. Passananti, H. Perroux, G. Voyard, C. Mouchel-Vallon, N. Chaumerliac, G. Mailhot, L. Deguillaume, and M. Brigante
Atmos. Chem. Phys., 15, 9191–9202, https://doi.org/10.5194/acp-15-9191-2015, https://doi.org/10.5194/acp-15-9191-2015, 2015
G. P. Schill, K. Genareau, and M. A. Tolbert
Atmos. Chem. Phys., 15, 7523–7536, https://doi.org/10.5194/acp-15-7523-2015, https://doi.org/10.5194/acp-15-7523-2015, 2015
Short summary
Short summary
Fine volcanic ash can influence cloud glaciation and, therefore, global climate. In this work we examined the heterogeneous ice nucleation properties of three distinct types of volcanic ash. We find that, in contrast to previous studies, these volcanic ash samples have different ice nucleation properties in the immersion mode. In the deposition mode, however, they nucleate ice with similar efficiency. We show that this behavior may be due to their mineralogy.
Y. Tobo, P. J. DeMott, T. C. J. Hill, A. J. Prenni, N. G. Swoboda-Colberg, G. D. Franc, and S. M. Kreidenweis
Atmos. Chem. Phys., 14, 8521–8531, https://doi.org/10.5194/acp-14-8521-2014, https://doi.org/10.5194/acp-14-8521-2014, 2014
R. Paris and K. V. Desboeufs
Atmos. Chem. Phys., 13, 4895–4905, https://doi.org/10.5194/acp-13-4895-2013, https://doi.org/10.5194/acp-13-4895-2013, 2013
X. Tang, D. R. Cocker III, and A. Asa-Awuku
Atmos. Chem. Phys., 12, 8377–8388, https://doi.org/10.5194/acp-12-8377-2012, https://doi.org/10.5194/acp-12-8377-2012, 2012
V. Pinti, C. Marcolli, B. Zobrist, C. R. Hoyle, and T. Peter
Atmos. Chem. Phys., 12, 5859–5878, https://doi.org/10.5194/acp-12-5859-2012, https://doi.org/10.5194/acp-12-5859-2012, 2012
M. Vaïtilingom, T. Charbouillot, L. Deguillaume, R. Maisonobe, M. Parazols, P. Amato, M. Sancelme, and A.-M. Delort
Atmos. Chem. Phys., 11, 8721–8733, https://doi.org/10.5194/acp-11-8721-2011, https://doi.org/10.5194/acp-11-8721-2011, 2011
T. Hullar and C. Anastasio
Atmos. Chem. Phys., 11, 7209–7222, https://doi.org/10.5194/acp-11-7209-2011, https://doi.org/10.5194/acp-11-7209-2011, 2011
Yao Liu, I. El Haddad, M. Scarfogliero, L. Nieto-Gligorovski, B. Temime-Roussel, E. Quivet, N. Marchand, B. Picquet-Varrault, and A. Monod
Atmos. Chem. Phys., 9, 5093–5105, https://doi.org/10.5194/acp-9-5093-2009, https://doi.org/10.5194/acp-9-5093-2009, 2009
I. El Haddad, Yao Liu, L. Nieto-Gligorovski, V. Michaud, B. Temime-Roussel, E. Quivet, N. Marchand, K. Sellegri, and A. Monod
Atmos. Chem. Phys., 9, 5107–5117, https://doi.org/10.5194/acp-9-5107-2009, https://doi.org/10.5194/acp-9-5107-2009, 2009
Cited articles
Alexander, B., Allman, D. J., Amos, H. M., Fairlie, T. D., Dachs, J., Hegg, D. A., and Sletten, R. S.:
Isotopic constraints on the formation pathways of sulfate aerosol in the marine boundary layer of the subtropical northeast Atlantic Ocean,
J. Geophys. Res.,
117, 1–17, https://doi.org/10.1029/2011JD016773, 2012.
Bates, K. H., Crounse, J. D., St. Clair, J. M., Bennett, N. B., Nguyen, T. B., Seinfeld, J. H., Stoltz, B. M., and Wennberg, P. O.: Gas phase production and loss of isoprene epoxydiols, J. Phys. Chem. A, 118, 1237–1246, https://doi.org/10.1021/jp4107958, 2014.
Bey, I., Jacob, J., Yantosca, R. M., Logan, A., Field, B. D., Fiore, A. M., Li, Q., Liu, H. Y., Mickley, J., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res.-Atmos., 106, 73–95, https://doi.org/10.1029/2001JD000807, 2001.
Darer, A. I., Cole-Filipiak, N. C., O'Connor, A. E., and Elrod, M. J.:
Formation and stability of atmospherically relevant isoprene-derived organosulfates and organonitrates,
Environ. Sci. Technol.,
45, 1895–1902, https://doi.org/10.1021/es103797z, 2011.
Dovrou, E., Lim, C. Y., Canagaratna, M. R., Kroll, J. H., Worsnop, D. R., and Keutsch, F. N.: Measurement techniques for identifying and quantifying hydroxymethanesulfonate (HMS) in an aqueous matrix and particulate matter using aerosol mass spectrometry and ion chromatography, Atmos. Meas. Tech., 12, 5303–5315, https://doi.org/10.5194/amt-12-5303-2019, 2019a.
Dovrou, E., Rivera-Rios, J. C., Bates, K. H., and Keutsch, F. N.:
Sulfate Formation via Cloud Processing from Isoprene Hydroxyl Hydroperoxides (ISOPOOH),
Environ. Sci. Technol.,
53, 12476–12484, https://doi.org/10.1021/acs.est.9b04645, 2019b.
Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, https://doi.org/10.5194/acp-6-3181-2006, 2006.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Hoffmann, M. R. and Edwards, J. O.: Kinetics of the oxidation of sulfite by hydrogen peroxide in acidic solution, J. Phys. Chem., 79, 2096–2098, https://doi.org/10.1021/j100587a005, 1975.
Hu, K. S., Darer, A. I., and Elrod, M. J.: Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates, Atmos. Chem. Phys., 11, 8307–8320, https://doi.org/10.5194/acp-11-8307-2011, 2011.
Iraci, L. T., Baker, B. M., Tyndall, G. S., and Orlando, J. J.:
Measurements of the Henry's law coefficients of 2-methyl-3-buten-2-ol, methacrolein, and methylvinyl ketone,
J. Atmos. Chem.,
33, 321–330, https://doi.org/10.1023/A:1006169029230, 1999.
Kok, G. L., Gitlin, S. N., and Lazrus, A. L.: Kinetics of the Formation and Decomposition of Hydroxymethanesulfonate, J. Geophys. Res., 91, 2801–2804, https://doi.org/10.1029/JD091iD02p02801, 1986.
Krechmer, J. E., Coggon, M. M., Massoli, P., Nguyen, T. B., Crounse, J. D., Hu, W., Day, D. A., Tyndall, G. S., Henze, D. K., Rivera-Rios, J. C., Nowak, J. B., Kimmel, J. R., Mauldin, R. L., Stark, H., Jayne, J. T., Sipilä, M., Junninen, H., St. Clair, J. M., Zhang, X., Feiner, P. A., Zhang, L., Miller, D. O., Brune, W. H., Keutsch, F. N., Wennberg, P. O., Seinfeld, J. H., Worsnop, D. R., Jimenez, J. L., and Canagaratna, M. R.:
Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation,
Environ. Sci. Technol.,
49, 10330–10339, https://doi.org/10.1021/acs.est.5b02031, 2015.
Lin, Y. H., Zhang, Z., Docherty, K. S., Zhang, H., Budisulistiorini, S. H., Rubitschun, C. L., Shaw, S. L., Knipping, E. M., Edgerton, E. S., Kleindienst, T. E., Gold, A., and Surratt, J. D.:
Isoprene epoxydiols as precursors to secondary organic aerosol formation: Acid-catalyzed reactive uptake studies with authentic compounds,
Environ. Sci. Technol.,
46, 250–258, https://doi.org/10.1021/es202554c, 2012.
Lind, J. A., Lazrus, A. L., and Kok, G. L.:
Aqueous Phase Oxidation of Sulfur(Iv) By Hydrogen-Peroxide, Methylhydroperoxide, and Peroxyacetic Acid,
J. Geophys. Res.,
92, 4171–4177, https://doi.org/10.1029/JD092iD04p04171, 1987.
Liu, Y., Brito, J., Dorris, M. R., Rivera-Rios, J. C., Seco, R., Bates, K. H., Artaxo, P., Duvoisin Jr., S., Keutsch, F. N., Kim, S., Goldstein, A. H., Guenther, A. B., Manzi, A. O., Souza, R. A. F., Springston, S. R., Watson, T. B., McKinney, K. A., and Martin, A. T.:
Isoprene photochemistry over the Amazon rainforest,
P. Natl. Acad. Sci. USA,
113, 6125-6130, https://doi.org/10.1073/pnas.1524136113, 2016.
McNeill, V. F.:
Aqueous organic chemistry in the atmosphere: Sources and chemical processing of organic aerosols,
Environ. Sci. Technol.,
49, 1237–1244, https://doi.org/10.1021/es5043707, 2015.
Munger, J. W., Jacob, D. J., and Hoffmann, M. R.:
The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater,
J. Atmos. Chem.,
1, 335–350, https://doi.org/10.1007/BF00053799, 1984.
Munger, J. W., Tiller, C., and Hoffmann, M. R.:
Identification of hydroxymethanesulfonate in fog water,
Science,
231, 247–249, https://doi.org/10.1126/science.231.4735.247, 1986.
Neta, P. and Huie, R. E.:
Free-radical chemistry of sulfite,
Environ. Health Persp.,
64, 209–217, https://doi.org/10.2307/3430011, 1985.
Nguyen, T. B., Coggon, M. M., Bates, K. H., Zhang, X., Schwantes, R. H., Schilling, K. A., Loza, C. L., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.: Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds, Atmos. Chem. Phys., 14, 3497–3510, https://doi.org/10.5194/acp-14-3497-2014, 2014.
Park, R. J., Jacob, D. J., Field, B. D., and Yantosca, R. M.:
Natural and transboundary pollution influences on sulfate-nitrate- ammonium aerosols in the United States: Implications for policy,
J. Geophys. Res.,
109, 1–17, https://doi.org/10.1029/2003JD004473, 2004.
Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kürten, A., Clair, J. M. S., Seinfeld, J. H., and Wennberg, P. O.:
Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene,
Science,
325, 730–734, 2009a.
Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, https://doi.org/10.5194/acp-9-1479-2009, 2009b.
Rivera-Rios, J. C.:
Atmospheric Chemistry of Isoprene Hydroxyhydroperoxides,
PhD dissertation,
Harvard University, Cambridge MA, May 2018.
Rivera-Rios, J. C., Nguyen, T. B., Crounse, J. D., Jud, W., St. Clair, J. M., Mikoviny, T., Gilman, J. B., Lerner, B. M., Kaiser, J. B., De Gouw, J., Wisthaler, A., Hansel, A., Wennberg, P. O., Seinfeld, J. H., and Keutsch, F. N.:
Conversion of hydroperoxides to carbonyls in field and laboratory instrumentation: Observational bias in diagnosing pristine versus anthropogenically controlled atmospheric chemistry,
Geophys. Res. Lett.,
41, 8645–8651, https://doi.org/10.1002/2014GL061919, 2014.
St. Clair, J. M., Rivera-Rios, J. C., Crounse, J. D., Praske, E., Kim, M. J., Wolfe, G. M., Keutsch, F. N., Wennberg, P. O., and Hanisco, T. F.: Investigation of a potential HCHO measurement artifact from ISOPOOH, Atmos. Meas. Tech., 9, 4561–4568, https://doi.org/10.5194/amt-9-4561-2016, 2016.
Surratt, J. D., Chan, A. W. H., Eddingsaas, N. C., Chan, M. N., Loza, C. L., Kwan, A. J., Hersey, S. P., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.:
Reactive intermediates revealed in secondary organic aerosol formation from isoprene,
P. Natl. Acad. Sci. USA,
107, 6640–6645, https://doi.org/10.1073/pnas.0911114107, 2010.
Wennberg, P. O., Bates, K. H., Crounse, J. D., Dodson, L. G., Mcvay, R. C., Mertens, L. A., Nguyen, T. B., Praske, E., Schwantes, R. H., Smarte, M. D., Clair, J. M. S., Teng, A. P., Zhang, X., and Seinfeld, J. H.:
Gas-Phase Reactions of Isoprene and Its Major Oxidation Products,
Chem. Rev.,
118, 3337–3390, https://doi.org/10.1021/acs.chemrev.7b00439, 2018.
Worton, D. R., Surratt, J. D., Lafranchi, B. W., Chan, A. W. H., Zhao, Y., Weber, R. J., Park, J. H., Gilman, J. B., De Gouw, J., Park, C., Schade, G., Beaver, M., Clair, J. M. S., Crounse, J., Wennberg, P., Wolfe, G. M., Harrold, S., Thornton, J. A., Farmer, D. K., Docherty, K. S., Cubison, M. J., Jimenez, J. L., Frossard, A. A., Russell, L. M., Kristensen, K., Glasius, M., Mao, J., Ren, X., Brune, W., Browne, E. C., Pusede, S. E., Cohen, R. C., Seinfeld, J. H., and Goldstein, A. H.:
Observational insights into aerosol formation from isoprene,
Environ. Sci. Technol.,
47, 11403–11413, https://doi.org/10.1021/es4011064, 2013.
Yang, Y., Jiang, J., Lu, X., Ma, J., and Liu, Y.:
Production of Sulfate Radical and Hydroxyl Radical by Reaction of Ozone with Peroxymonosulfate: A Novel Advanced Oxidation Process,
Environ. Sci. Technol.,
49, 73307339, https://doi.org/10.1021/es506362e, 2015.
Zhang, Y., Chen, Y., Lambe, A. T., Olson, N. E., Lei, Z., Craig, R. L., Zhang, Z., Gold, A., Onasch, T. B., Jayne, J. T., Worsnop, D. R., Gaston, C. J., Thornton, J. A., Vizuete, W., Ault, A. P., and Surratt, J. D.:
Effect of the Aerosol-Phase State on Secondary Organic Aerosol Formation from the Reactive Uptake of Isoprene-Derived Epoxydiols (IEPOX),
Environ. Sci. Tech. Let.,
5, 167–174, https://doi.org/10.1021/acs.estlett.8b00044, 2018.
Zhang, Z., Lin, Y. H., Zhang, H., Surratt, J. D., Ball, L. M., and Gold, A.: Technical Note: Synthesis of isoprene atmospheric oxidation products: Isomeric epoxydiols and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran, Atmos. Chem. Phys., 12, 8529–8535, https://doi.org/10.5194/acp-12-8529-2012, 2012.
Short summary
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.
We examined the mechanism and products of oxidation of dissolved sulfur dioxide with the main...
Altmetrics
Final-revised paper
Preprint