Articles | Volume 14, issue 3
https://doi.org/10.5194/amt-14-2501-2021
© 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/amt-14-2501-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
31 Mar 2021
Research article |
| 31 Mar 2021
| 31 Mar 2021
Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase
Alexander Zaytsev
CORRESPONDING AUTHOR
John A. Paulson School of Engineering and Applied Sciences, Harvard
University, Cambridge, MA 02138, USA
Martin Breitenlechner
John A. Paulson School of Engineering and Applied Sciences, Harvard
University, Cambridge, MA 02138, USA
now at: NOAA Chemical Sciences Laboratory, Boulder, CO 80305, USA
Anna Novelli
Institute of Energy and Climate Research – Troposphere (IEK-8),
Forschungszentrum Jülich GmbH, 52428 Jülich, Germany
Hendrik Fuchs
Institute of Energy and Climate Research – Troposphere (IEK-8),
Forschungszentrum Jülich GmbH, 52428 Jülich, Germany
Daniel A. Knopf
School of Marine and Atmospheric Sciences, Stony Brook University,
Stony Brook, NY 11794, USA
Jesse H. Kroll
Department of Civil and Environmental Engineering, Massachusetts
Institute of Technology, Cambridge, MA 02139, USA
Frank N. Keutsch
CORRESPONDING AUTHOR
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
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Atmos. Chem. Phys., 24, 3445–3528, https://doi.org/10.5194/acp-24-3445-2024, https://doi.org/10.5194/acp-24-3445-2024, 2024
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Matthew B. Goss and Jesse H. Kroll
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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
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Rodanthi-Elisavet Mamouri, Albert Ansmann, Kevin Ohneiser, Daniel A. Knopf, Argyro Nisantzi, Johannes Bühl, Ronny Engelmann, Annett Skupin, Patric Seifert, Holger Baars, Dragos Ene, Ulla Wandinger, and Diofantos Hadjimitsis
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Marc von Hobe, Domenico Taraborrelli, Sascha Alber, Birger Bohn, Hans-Peter Dorn, Hendrik Fuchs, Yun Li, Chenxi Qiu, Franz Rohrer, Roberto Sommariva, Fred Stroh, Zhaofeng Tan, Sergej Wedel, and Anna Novelli
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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
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Vigneshkumar Balamurugan, Jia Chen, Adrian Wenzel, and Frank N. Keutsch
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Daniel A. Knopf, Peiwen Wang, Benny Wong, Jay M. Tomlin, Daniel P. Veghte, Nurun N. Lata, Swarup China, Alexander Laskin, Ryan C. Moffet, Josephine Y. Aller, Matthew A. Marcus, and Jian Wang
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boundary layer and free troposphere in the eastern North Atlantic during
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particle populations seasonally and with sampling altitudes, which are
reflected in the INP types. Freezing parameterizations are derived for
implementation in cloud-resolving and climate models.
Kevin J. Nihill, Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Bin Yuan, Jordan E. Krechmer, Kanako Sekimoto, Jose L. Jimenez, Joost de Gouw, Christopher D. Cappa, Colette L. Heald, Carsten Warneke, and Jesse H. Kroll
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Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
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Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime oxidant, forms many highly oxygenated organic molecules (HOMs), including C10-20 compounds. HOMs play an important role in new particle formation and growth. HOM formation can be explained by the chemistry of peroxy radicals. We found that a minor branching ratio initial pathway plays an unexpected, significant role. Considering this pathway enables accurate simulations of HOMs and other concentrations.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
Changmin Cho, Hendrik Fuchs, Andreas Hofzumahaus, Frank Holland, William J. Bloss, Birger Bohn, Hans-Peter Dorn, Marvin Glowania, Thorsten Hohaus, Lu Liu, Paul S. Monks, Doreen Niether, Franz Rohrer, Roberto Sommariva, Zhaofeng Tan, Ralf Tillmann, Astrid Kiendler-Scharr, Andreas Wahner, and Anna Novelli
Atmos. Chem. Phys., 23, 2003–2033, https://doi.org/10.5194/acp-23-2003-2023, https://doi.org/10.5194/acp-23-2003-2023, 2023
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With this study, we investigated the processes leading to the formation, destruction, and recycling of radicals for four seasons in a rural environment. Complete knowledge of their chemistry is needed if we are to predict the formation of secondary pollutants from primary emissions. The results highlight a still incomplete understanding of the paths leading to the formation of the OH radical, which has been observed in several other environments as well and needs to be further investigated.
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
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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.
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
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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.
Zhaofeng Tan, Hendrik Fuchs, Andreas Hofzumahaus, William J. Bloss, Birger Bohn, Changmin Cho, Thorsten Hohaus, Frank Holland, Chandrakiran Lakshmisha, Lu Liu, Paul S. Monks, Anna Novelli, Doreen Niether, Franz Rohrer, Ralf Tillmann, Thalassa S. E. Valkenburg, Vaishali Vardhan, Astrid Kiendler-Scharr, Andreas Wahner, and Roberto Sommariva
Atmos. Chem. Phys., 22, 13137–13152, https://doi.org/10.5194/acp-22-13137-2022, https://doi.org/10.5194/acp-22-13137-2022, 2022
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During the 2019 JULIAC campaign, ClNO2 was measured at a rural site in Germany in different seasons. The highest ClNO2 level was 1.6 ppbv in September. ClNO2 production was more sensitive to the availability of NO2 than O3. The average ClNO2 production efficiency was up to 18 % in February and September and down to 3 % in December. These numbers are at the high end of the values reported in the literature, indicating the importance of ClNO2 chemistry in rural environments in midwestern Europe.
Therese S. Carter, Colette L. Heald, Jesse H. Kroll, Eric C. Apel, Donald Blake, Matthew Coggon, Achim Edtbauer, Georgios Gkatzelis, Rebecca S. Hornbrook, Jeff Peischl, Eva Y. Pfannerstill, Felix Piel, Nina G. Reijrink, Akima Ringsdorf, Carsten Warneke, Jonathan Williams, Armin Wisthaler, and Lu Xu
Atmos. Chem. Phys., 22, 12093–12111, https://doi.org/10.5194/acp-22-12093-2022, https://doi.org/10.5194/acp-22-12093-2022, 2022
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Fires emit many gases which can contribute to smog and air pollution. However, the amount and properties of these chemicals are not well understood, so this work updates and expands their representation in a global atmospheric model, including by adding new chemicals. We confirm that this updated representation generally matches measurements taken in several fire regions. We then show that fires provide ~15 % of atmospheric reactivity globally and more than 75 % over fire source regions.
Albert Ansmann, Kevin Ohneiser, Alexandra Chudnovsky, Daniel A. Knopf, Edwin W. Eloranta, Diego Villanueva, Patric Seifert, Martin Radenz, Boris Barja, Félix Zamorano, Cristofer Jimenez, Ronny Engelmann, Holger Baars, Hannes Griesche, Julian Hofer, Dietrich Althausen, and Ulla Wandinger
Atmos. Chem. Phys., 22, 11701–11726, https://doi.org/10.5194/acp-22-11701-2022, https://doi.org/10.5194/acp-22-11701-2022, 2022
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For the first time we present a systematic study on the impact of wildfire smoke on ozone depletion in the Arctic (2020) and Antarctic stratosphere (2020, 2021). Two major fire events in Siberia and Australia were responsible for the observed record-breaking stratospheric smoke pollution. Our analyses were based on lidar observations of smoke parameters (Polarstern, Punta Arenas) and NDACC Arctic and Antarctic ozone profiles as well as on Antarctic OMI satellite observations of column ozone.
Yindong Guo, Hongru Shen, Iida Pullinen, Hao Luo, Sungah Kang, Luc Vereecken, Hendrik Fuchs, Mattias Hallquist, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Astrid Kiendler-Scharr, Andreas Wahner, Defeng Zhao, and Thomas F. Mentel
Atmos. Chem. Phys., 22, 11323–11346, https://doi.org/10.5194/acp-22-11323-2022, https://doi.org/10.5194/acp-22-11323-2022, 2022
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The oxidation of limonene, a common volatile emitted by trees and chemical products, by NO3, a nighttime oxidant, forms many highly oxygenated organic molecules (HOM), including C10-30 compounds. Most of the HOM are second-generation organic nitrates, in which carbonyl-substituted C10 nitrates accounted for a major fraction. Their formation can be explained by chemistry of peroxy radicals. HOM, especially low-volatile ones, play an important role in nighttime new particle formation and growth.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Kevin Ohneiser, Albert Ansmann, Bernd Kaifler, Alexandra Chudnovsky, Boris Barja, Daniel A. Knopf, Natalie Kaifler, Holger Baars, Patric Seifert, Diego Villanueva, Cristofer Jimenez, Martin Radenz, Ronny Engelmann, Igor Veselovskii, and Félix Zamorano
Atmos. Chem. Phys., 22, 7417–7442, https://doi.org/10.5194/acp-22-7417-2022, https://doi.org/10.5194/acp-22-7417-2022, 2022
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We present and discuss 2 years of long-term lidar observations of the largest stratospheric perturbation by wildfire smoke ever observed. The smoke originated from the record-breaking Australian fires in 2019–2020 and affects climate conditions and even the ozone layer in the Southern Hemisphere. The obvious link between dense smoke occurrence in the stratosphere and strong ozone depletion found in the Arctic and in the Antarctic in 2020 can be regarded as a new aspect of climate change.
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
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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.
Daniel A. Knopf, Joseph C. Charnawskas, Peiwen Wang, Benny Wong, Jay M. Tomlin, Kevin A. Jankowski, Matthew Fraund, Daniel P. Veghte, Swarup China, Alexander Laskin, Ryan C. Moffet, Mary K. Gilles, Josephine Y. Aller, Matthew A. Marcus, Shira Raveh-Rubin, and Jian Wang
Atmos. Chem. Phys., 22, 5377–5398, https://doi.org/10.5194/acp-22-5377-2022, https://doi.org/10.5194/acp-22-5377-2022, 2022
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Marine boundary layer aerosols collected in the remote region of the eastern North Atlantic induce immersion freezing and deposition ice nucleation under typical mixed-phase and cirrus cloud conditions. Corresponding ice nucleation parameterizations for model applications have been derived. Chemical imaging of ambient aerosol and ice-nucleating particles demonstrates that the latter is dominated by sea salt and organics while also representing a major particle type in the particle population.
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
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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.
Ka Ming Fung, Colette L. Heald, Jesse H. Kroll, Siyuan Wang, Duseong S. Jo, Andrew Gettelman, Zheng Lu, Xiaohong Liu, Rahul A. Zaveri, Eric C. Apel, Donald R. Blake, Jose-Luis Jimenez, Pedro Campuzano-Jost, Patrick R. Veres, Timothy S. Bates, John E. Shilling, and Maria Zawadowicz
Atmos. Chem. Phys., 22, 1549–1573, https://doi.org/10.5194/acp-22-1549-2022, https://doi.org/10.5194/acp-22-1549-2022, 2022
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Understanding the natural aerosol burden in the preindustrial era is crucial for us to assess how atmospheric aerosols affect the Earth's radiative budgets. Our study explores how a detailed description of dimethyl sulfide (DMS) oxidation (implemented in the Community Atmospheric Model version 6 with chemistry, CAM6-chem) could help us better estimate the present-day and preindustrial concentrations of sulfate and other relevant chemicals, as well as the resulting aerosol radiative impacts.
Lukas Fischer, Martin Breitenlechner, Eva Canaval, Wiebke Scholz, Marcus Striednig, Martin Graus, Thomas G. Karl, Tuukka Petäjä, Markku Kulmala, and Armin Hansel
Atmos. Meas. Tech., 14, 8019–8039, https://doi.org/10.5194/amt-14-8019-2021, https://doi.org/10.5194/amt-14-8019-2021, 2021
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Ecosystems emit biogenic volatile organic compounds (BVOCs), which are then oxidized in the atmosphere, contributing to ozone and secondary aerosol formation. While flux measurements of BVOCs are state of the art, flux measurements of the less volatile oxidation products are difficult to achieve due to inlet losses. Here we present first flux measurements, utilizing a novel PTR3 instrument in combination with a specially designed wall-less inlet we put on top of the Hyytiälä tower in Finland.
Clara M. Nussbaumer, John N. Crowley, Jan Schuladen, Jonathan Williams, Sascha Hafermann, Andreas Reiffs, Raoul Axinte, Hartwig Harder, Cheryl Ernest, Anna Novelli, Katrin Sala, Monica Martinez, Chinmay Mallik, Laura Tomsche, Christian Plass-Dülmer, Birger Bohn, Jos Lelieveld, and Horst Fischer
Atmos. Chem. Phys., 21, 18413–18432, https://doi.org/10.5194/acp-21-18413-2021, https://doi.org/10.5194/acp-21-18413-2021, 2021
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HCHO is an important atmospheric trace gas influencing the photochemical processes in the Earth’s atmosphere, including the budget of HOx and the abundance of tropospheric O3. This research presents the photochemical calculations of HCHO and O3 based on three field campaigns across Europe. We show that HCHO production via the oxidation of only four volatile organic compound precursors, i.e., CH4, CH3CHO, C5H8 and CH3OH, can balance the observed loss at all sites well.
Jay M. Tomlin, Kevin A. Jankowski, Daniel P. Veghte, Swarup China, Peiwen Wang, Matthew Fraund, Johannes Weis, Guangjie Zheng, Yang Wang, Felipe Rivera-Adorno, Shira Raveh-Rubin, Daniel A. Knopf, Jian Wang, Mary K. Gilles, Ryan C. Moffet, and Alexander Laskin
Atmos. Chem. Phys., 21, 18123–18146, https://doi.org/10.5194/acp-21-18123-2021, https://doi.org/10.5194/acp-21-18123-2021, 2021
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Analysis of individual atmospheric particles shows that aerosol transported from North America during meteorological dry intrusion episodes may have a substantial impact on the mixing state and particle-type population over the mid-Atlantic, as organic contribution and particle-type diversity are significantly enhanced during these periods. These observations need to be considered in current atmospheric models.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091, https://doi.org/10.5194/acp-21-16067-2021, https://doi.org/10.5194/acp-21-16067-2021, 2021
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The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Dandan Wei, Hariprasad D. Alwe, Dylan B. Millet, Brandon Bottorff, Michelle Lew, Philip S. Stevens, Joshua D. Shutter, Joshua L. Cox, Frank N. Keutsch, Qianwen Shi, Sarah C. Kavassalis, Jennifer G. Murphy, Krystal T. Vasquez, Hannah M. Allen, Eric Praske, John D. Crounse, Paul O. Wennberg, Paul B. Shepson, Alexander A. T. Bui, Henry W. Wallace, Robert J. Griffin, Nathaniel W. May, Megan Connor, Jonathan H. Slade, Kerri A. Pratt, Ezra C. Wood, Mathew Rollings, Benjamin L. Deming, Daniel C. Anderson, and Allison L. Steiner
Geosci. Model Dev., 14, 6309–6329, https://doi.org/10.5194/gmd-14-6309-2021, https://doi.org/10.5194/gmd-14-6309-2021, 2021
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Over the past decade, understanding of isoprene oxidation has improved, and proper representation of isoprene oxidation and isoprene-derived SOA (iSOA) formation in canopy–chemistry models is now recognized to be important for an accurate understanding of forest–atmosphere exchange. The updated FORCAsT version 2.0 improves the estimation of some isoprene oxidation products and is one of the few canopy models currently capable of simulating SOA formation from monoterpenes and isoprene.
Daniel A. Knopf and Markus Ammann
Atmos. Chem. Phys., 21, 15725–15753, https://doi.org/10.5194/acp-21-15725-2021, https://doi.org/10.5194/acp-21-15725-2021, 2021
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Adsorption on and desorption of gas molecules from solid or liquid surfaces or interfaces represent the initial interaction of gas-to-condensed-phase processes that can define the physicochemical evolution of the condensed phase. We apply a thermodynamic and microscopic treatment of these multiphase processes to evaluate how adsorption and desorption rates and surface accommodation depend on the choice of adsorption model and standard states with implications for desorption energy and lifetimes.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685, https://doi.org/10.5194/acp-21-12665-2021, https://doi.org/10.5194/acp-21-12665-2021, 2021
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The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Yang Wang, Guangjie Zheng, Michael P. Jensen, Daniel A. Knopf, Alexander Laskin, Alyssa A. Matthews, David Mechem, Fan Mei, Ryan Moffet, Arthur J. Sedlacek, John E. Shilling, Stephen Springston, Amy Sullivan, Jason Tomlinson, Daniel Veghte, Rodney Weber, Robert Wood, Maria A. Zawadowicz, and Jian Wang
Atmos. Chem. Phys., 21, 11079–11098, https://doi.org/10.5194/acp-21-11079-2021, https://doi.org/10.5194/acp-21-11079-2021, 2021
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This paper reports the vertical profiles of trace gas and aerosol properties over the eastern North Atlantic, a region of persistent but diverse subtropical marine boundary layer (MBL) clouds. We examined the key processes that drive the cloud condensation nuclei (CCN) population and how it varies with season and synoptic conditions. This study helps improve the model representation of the aerosol processes in the remote MBL, reducing the simulated aerosol indirect effects.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824, https://doi.org/10.5194/acp-21-10799-2021, https://doi.org/10.5194/acp-21-10799-2021, 2021
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Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
Albert Ansmann, Kevin Ohneiser, Rodanthi-Elisavet Mamouri, Daniel A. Knopf, Igor Veselovskii, Holger Baars, Ronny Engelmann, Andreas Foth, Cristofer Jimenez, Patric Seifert, and Boris Barja
Atmos. Chem. Phys., 21, 9779–9807, https://doi.org/10.5194/acp-21-9779-2021, https://doi.org/10.5194/acp-21-9779-2021, 2021
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We present retrievals of tropospheric and stratospheric height profiles of particle mass, volume, surface area concentration of wildfire smoke layers, and related cloud condensation nuclei (CCN) and ice-nucleating particle (INP) concentrations. The new analysis scheme is applied to ground-based lidar observations of stratospheric Australian smoke over southern South America and to spaceborne lidar observations of tropospheric North American smoke.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704, https://doi.org/10.5194/acp-21-9681-2021, https://doi.org/10.5194/acp-21-9681-2021, 2021
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The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Eleni Dovrou, Kelvin H. Bates, Jean C. Rivera-Rios, Joshua L. Cox, Joshua D. Shutter, and Frank N. Keutsch
Atmos. Chem. Phys., 21, 8999–9008, https://doi.org/10.5194/acp-21-8999-2021, https://doi.org/10.5194/acp-21-8999-2021, 2021
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We examined the mechanism and products of oxidation of dissolved sulfur dioxide with the main isomers of isoprene hydroxyl hydroperoxides, via laboratory and model analysis. Two chemical mechanism pathways are proposed and the results provide an improved understanding of the broader atmospheric chemistry and role of multifunctional organic hydroperoxides, which should be the dominant VOC oxidation products under low-NO conditions, highlighting their significant contribution to sulfate formation.
Jack C. Hensley, Adam W. Birdsall, Gregory Valtierra, Joshua L. Cox, and Frank N. Keutsch
Atmos. Chem. Phys., 21, 8809–8821, https://doi.org/10.5194/acp-21-8809-2021, https://doi.org/10.5194/acp-21-8809-2021, 2021
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We measured reactions of butenedial, an atmospheric dicarbonyl, in aqueous mixtures that mimic the conditions of aerosol particles. Major reaction products and rates were determined to assess their atmospheric relevance and to compare against other well-studied dicarbonyls. We suggest that the structure of the carbon backbone, not just the dominant functional group, plays a major role in dicarbonyl reactivity, influencing the fate and ability of dicarbonyls to produce brown carbon.
Marvin Glowania, Franz Rohrer, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Meas. Tech., 14, 4239–4253, https://doi.org/10.5194/amt-14-4239-2021, https://doi.org/10.5194/amt-14-4239-2021, 2021
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Three instruments that use different techniques to measure gaseous formaldehyde concentrations were compared in experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. The results demonstrated the need to correct the baseline in measurements by instruments that use the Hantzsch reaction or make use of cavity ring-down spectroscopy. After applying corrections, all three methods gave accurate and precise measurements within their specifications.
Israel Silber, Ann M. Fridlind, Johannes Verlinde, Andrew S. Ackerman, Grégory V. Cesana, and Daniel A. Knopf
Atmos. Chem. Phys., 21, 3949–3971, https://doi.org/10.5194/acp-21-3949-2021, https://doi.org/10.5194/acp-21-3949-2021, 2021
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Long-term ground-based radar and sounding measurements over Alaska (Antarctica) indicate that more than 85 % (75 %) of supercooled clouds are precipitating at cloud base and that 75 % (50 %) are precipitating to the surface. Such high prevalence is reconciled with lesser spaceborne estimates by considering radar sensitivity. Results provide a strong observational constraint for polar cloud processes in large-scale models.
Changmin Cho, Andreas Hofzumahaus, Hendrik Fuchs, Hans-Peter Dorn, Marvin Glowania, Frank Holland, Franz Rohrer, Vaishali Vardhan, Astrid Kiendler-Scharr, Andreas Wahner, and Anna Novelli
Atmos. Meas. Tech., 14, 1851–1877, https://doi.org/10.5194/amt-14-1851-2021, https://doi.org/10.5194/amt-14-1851-2021, 2021
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This study describes the implementation and characterization of the chemical modulation reactor (CMR) used in the laser-induced fluorescence instrument of the Forschungszentrum Jülich. The CMR allows for interference-free OH radical measurement in ambient air. During a field campaign in a rural environment, the observed interference was mostly below the detection limit of the instrument and fully explained by the known ozone interference.
Huan Song, Xiaorui Chen, Keding Lu, Qi Zou, Zhaofeng Tan, Hendrik Fuchs, Alfred Wiedensohler, Daniel R. Moon, Dwayne E. Heard, María-Teresa Baeza-Romero, Mei Zheng, Andreas Wahner, Astrid Kiendler-Scharr, and Yuanhang Zhang
Atmos. Chem. Phys., 20, 15835–15850, https://doi.org/10.5194/acp-20-15835-2020, https://doi.org/10.5194/acp-20-15835-2020, 2020
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Accurate calculation of the HO2 uptake coefficient is one of the key parameters to quantify the co-reduction of both aerosol and ozone pollution. We modelled various lab measurements of γHO2 based on a gas-liquid phase kinetic model and developed a state-of-the-art parameterized equation. Based on a dataset from a comprehensive field campaign in the North China Plain, we proposed that the determination of the heterogeneous uptake process for HO2 should be included in future field campaigns.
David H. Hagan and Jesse H. Kroll
Atmos. Meas. Tech., 13, 6343–6355, https://doi.org/10.5194/amt-13-6343-2020, https://doi.org/10.5194/amt-13-6343-2020, 2020
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Assessing the error of low-cost particulate matter (PM) sensors has been difficult as each empirical study presents unique limitations. Here, we present a new, open-sourced, physics-based model (opcsim) and use it to understand how the properties of different particle sensors alter their accuracy. We offer a summary of likely sources of error for different sensor types, environmental conditions, and particle classes and offer recommendations for the choice of optimal calibrant.
Michael Rolletter, Marion Blocquet, Martin Kaminski, Birger Bohn, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Xin Li, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 13701–13719, https://doi.org/10.5194/acp-20-13701-2020, https://doi.org/10.5194/acp-20-13701-2020, 2020
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The photooxidation of pinonaldehyde is investigated in a chamber study under natural sunlight and low NO conditions with and without an added hydroxyl radical (OH) scavenger. The experimentally determined pinonaldehyde photolysis frequency is faster by a factor of 3.5 than currently used parameterizations in atmospheric models. Yields of degradation products are measured in the presence and absence of OH. Measurements are compared to current atmospheric models and a theory-based mechanism.
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
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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.
Patrick Dewald, Jonathan M. Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, Franz Rohrer, David Reimer, Ralf Tillmann, Anna Novelli, Changmin Cho, Kangming Xu, Rupert Holzinger, François Bernard, Li Zhou, Wahid Mellouki, Steven S. Brown, Hendrik Fuchs, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 10459–10475, https://doi.org/10.5194/acp-20-10459-2020, https://doi.org/10.5194/acp-20-10459-2020, 2020
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We present direct measurements of NO3 reactivity resulting from the oxidation of isoprene by NO3 during an intensive simulation chamber study. Measurements were in excellent agreement with values calculated from measured isoprene amounts and the rate coefficient for the reaction of NO3 with isoprene. Comparison of the measurement with NO3 reactivities from non-steady-state and model calculations suggests that isoprene-derived RO2 and HO2 radicals account to ~ 50 % of overall NO3 losses.
Christopher D. Cappa, Christopher Y. Lim, David H. Hagan, Matthew Coggon, Abigail Koss, Kanako Sekimoto, Joost de Gouw, Timothy B. Onasch, Carsten Warneke, and Jesse H. Kroll
Atmos. Chem. Phys., 20, 8511–8532, https://doi.org/10.5194/acp-20-8511-2020, https://doi.org/10.5194/acp-20-8511-2020, 2020
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Smoke from combustion of a wide range of biomass fuels (e.g., leaves, twigs, logs, peat, and dung) was photochemically aged in a small chamber for up to 8 d of equivalent atmospheric aging. Upon aging, the particle chemical composition and ability to absorb sunlight changed owing to reactions in both the gas and particulate phases. We developed a model to explain the observations and used this to derive insights into the aging of smoke in the atmosphere.
Jienan Li, Seanna M. Forrester, and Daniel A. Knopf
Atmos. Chem. Phys., 20, 6055–6080, https://doi.org/10.5194/acp-20-6055-2020, https://doi.org/10.5194/acp-20-6055-2020, 2020
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Organic aerosol is ubiquitous in the atmosphere and can change its phase state from liquid to solid in response to temperature. Our laboratory measurements demonstrate that the chemical reactivity of typical organic aerosol species with atmospheric oxidants is modulated by the species’ phase state. We find that under temperatures typical of the middle and upper troposphere the chemical lifetime of organic aerosol can be significantly extended due to the reduced reactive uptake of gas oxidants.
Anna Novelli, Luc Vereecken, Birger Bohn, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, David Reimer, Franz Rohrer, Simon Rosanka, Domenico Taraborrelli, Ralf Tillmann, Robert Wegener, Zhujun Yu, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 3333–3355, https://doi.org/10.5194/acp-20-3333-2020, https://doi.org/10.5194/acp-20-3333-2020, 2020
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Experimental evidence from a simulation chamber study shows that the regeneration efficiency of the hydroxyl radical is maintained globally at values higher than 0.5 for a wide range of nitrogen oxide concentrations as a result of isomerizations of peroxy radicals originating from the OH oxidation of isoprene. The available models were tested, and suggestions on how to improve their ability to reproduce the measured radical and oxygenated volatile organic compound concentrations are provided.
Crystal D. McClure, Christopher Y. Lim, David H. Hagan, Jesse H. Kroll, and Christopher D. Cappa
Atmos. Chem. Phys., 20, 1531–1547, https://doi.org/10.5194/acp-20-1531-2020, https://doi.org/10.5194/acp-20-1531-2020, 2020
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We characterized various optical, chemical, and physical properties of particles produced from combustion of a variety of different biomass fuels, many representative of those found in the western US. We find that many properties scale with the ratio between bulk average organic aerosol and black carbon mass concentrations, although there are some properties that do not.
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
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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
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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.
Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Kanako Sekimoto, Bin Yuan, Jessica B. Gilman, David H. Hagan, Vanessa Selimovic, Kyle J. Zarzana, Steven S. Brown, James M. Roberts, Markus Müller, Robert Yokelson, Armin Wisthaler, Jordan E. Krechmer, Jose L. Jimenez, Christopher Cappa, Jesse H. Kroll, Joost de Gouw, and Carsten Warneke
Atmos. Chem. Phys., 19, 14875–14899, https://doi.org/10.5194/acp-19-14875-2019, https://doi.org/10.5194/acp-19-14875-2019, 2019
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Wildfire emissions significantly contribute to adverse air quality; however, the chemical processes that lead to hazardous pollutants, such as ozone, are not fully understood. In this study, we describe laboratory experiments where we simulate the atmospheric chemistry of smoke emitted from a range of biomass fuels. We show that certain understudied compounds, such as furans and phenolic compounds, are significant contributors to pollutants formed as a result of typical atmospheric oxidation.
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
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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
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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.
Christopher Y. Lim, David H. Hagan, Matthew M. Coggon, Abigail R. Koss, Kanako Sekimoto, Joost de Gouw, Carsten Warneke, Christopher D. Cappa, and Jesse H. Kroll
Atmos. Chem. Phys., 19, 12797–12809, https://doi.org/10.5194/acp-19-12797-2019, https://doi.org/10.5194/acp-19-12797-2019, 2019
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Wildfires are a large source of gases and particles to the atmosphere, both of which impact human health and climate. The amount and composition of particles from wildfires can change with time in the atmosphere; however, the impact of aging is not well understood. In a series of controlled laboratory experiments, we show that the particles are oxidized and a significant fraction of the gas-phase carbon (24 %–56 %) is converted to particle mass over the course of several days in the atmosphere.
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
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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.
Horst Fischer, Raoul Axinte, Heiko Bozem, John N. Crowley, Cheryl Ernest, Stefan Gilge, Sascha Hafermann, Hartwig Harder, Korbinian Hens, Ruud H. H. Janssen, Rainer Königstedt, Dagmar Kubistin, Chinmay Mallik, Monica Martinez, Anna Novelli, Uwe Parchatka, Christian Plass-Dülmer, Andrea Pozzer, Eric Regelin, Andreas Reiffs, Torsten Schmidt, Jan Schuladen, and Jos Lelieveld
Atmos. Chem. Phys., 19, 11953–11968, https://doi.org/10.5194/acp-19-11953-2019, https://doi.org/10.5194/acp-19-11953-2019, 2019
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We use in situ observations of H2O2 to study the interplay between photochemistry, transport and deposition processes. The data were obtained during five ground-based field campaigns across Europe. A budget calculation indicates that the photochemical production rate was much larger than photochemical loss and that dry deposition is the dominant loss process. To reproduce the change in H2O2 mixing ratios after sunrise, a variable contribution of entrainment from the residual layer is required.
Michael Rolletter, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Hans-Peter Dorn, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 19, 11635–11649, https://doi.org/10.5194/acp-19-11635-2019, https://doi.org/10.5194/acp-19-11635-2019, 2019
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Here we present a study of the photooxidation of alpha-pinene, the most abundant monoterpene, by hydroxyl radicals (OH) conducted in the simulation chamber SAPHIR under low NOx and atmospheric alpha-pinene concentrations. Yields of the main degradation products acetone, formaldehyde, and pinonaldehyde were determined and the HOx (OH + HO2) radical budget was investigated. Measurements were used to test current atmospheric models and a theory-based mechanism.
Zhaofeng Tan, Keding Lu, Andreas Hofzumahaus, Hendrik Fuchs, Birger Bohn, Frank Holland, Yuhan Liu, Franz Rohrer, Min Shao, Kang Sun, Yusheng Wu, Limin Zeng, Yinsong Zhang, Qi Zou, Astrid Kiendler-Scharr, Andreas Wahner, and Yuanhang Zhang
Atmos. Chem. Phys., 19, 7129–7150, https://doi.org/10.5194/acp-19-7129-2019, https://doi.org/10.5194/acp-19-7129-2019, 2019
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Atmospheric OH, HO2, and RO2 radicals; OH reactivity; and trace gases measured in the Pearl River Delta in autumn 2014 are used for radical budget analyses. The RO2 budget suggests that unexplained OH reactivity is due to unmeasured volatile organic compounds. The OH budget points to a missing OH source and that of RO2 to a missing RO2 sink at low NO. This could indicate a common, unknown process that converts RO2 to OH without the involvement of NO, which would reduce ozone production by 30 %.
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
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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.
Rachel E. O'Brien, Kelsey J. Ridley, Manjula R. Canagaratna, John T. Jayne, Philip L. Croteau, Douglas R. Worsnop, Sri Hapsari Budisulistiorini, Jason D. Surratt, Christopher L. Follett, Daniel J. Repeta, and Jesse H. Kroll
Atmos. Meas. Tech., 12, 1659–1671, https://doi.org/10.5194/amt-12-1659-2019, https://doi.org/10.5194/amt-12-1659-2019, 2019
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Analysis of the elemental composition of organic mixtures can provide insights into the sources and aging of environmental samples. Here we describe a method that allows characterization of this type of material using micrograms of material by a combination of a small-volume ultrasonic nebulizer and an aerosol mass spectrometer. This technique enables rapid analysis of complex organic mixtures using approximately an order of magnitude less sample than standard analyses.
Sascha R. Albrecht, Anna Novelli, Andreas Hofzumahaus, Sungah Kang, Yare Baker, Thomas Mentel, Andreas Wahner, and Hendrik Fuchs
Atmos. Meas. Tech., 12, 891–902, https://doi.org/10.5194/amt-12-891-2019, https://doi.org/10.5194/amt-12-891-2019, 2019
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Within this study we demonstrate reliable measurement of hydroperoxy (HO2) radicals via chemical ionisation mass spectrometry. HO2 is detected as an ion cluster with bromide ions, which allows a selective detection. This direct and sensitive measurement provides reliable data of HO2 radical concentrations in the atmosphere as demonstrated in the first application in simulation chamber experiments.
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
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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.
John N. Crowley, Nicolas Pouvesle, Gavin J. Phillips, Raoul Axinte, Horst Fischer, Tuukka Petäjä, Anke Nölscher, Jonathan Williams, Korbinian Hens, Hartwig Harder, Monica Martinez-Harder, Anna Novelli, Dagmar Kubistin, Birger Bohn, and Jos Lelieveld
Atmos. Chem. Phys., 18, 13457–13479, https://doi.org/10.5194/acp-18-13457-2018, https://doi.org/10.5194/acp-18-13457-2018, 2018
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Simultaneous observations of PAA, PAN and H2O2 are used to provide insight into processes influencing the HOx chemistry of the boreal forest, including two biomass-burning-impacted periods. A significant contribution from photolytic HOx sources was included in a box model analysis to align model predictions with measurements. The model predicts high levels of organic peroxy radicals, also at night-time.
Anna L. Hodshire, Brett B. Palm, M. Lizabeth Alexander, Qijing Bian, Pedro Campuzano-Jost, Eben S. Cross, Douglas A. Day, Suzane S. de Sá, Alex B. Guenther, Armin Hansel, James F. Hunter, Werner Jud, Thomas Karl, Saewung Kim, Jesse H. Kroll, Jeong-Hoo Park, Zhe Peng, Roger Seco, James N. Smith, Jose L. Jimenez, and Jeffrey R. Pierce
Atmos. Chem. Phys., 18, 12433–12460, https://doi.org/10.5194/acp-18-12433-2018, https://doi.org/10.5194/acp-18-12433-2018, 2018
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We investigate the nucleation and growth processes that shape the aerosol size distribution inside oxidation flow reactors (OFRs) that sampled ambient air from Colorado and the Amazon rainforest. Results indicate that organics are important for both nucleation and growth, vapor uptake was limited to accumulation-mode particles, fragmentation reactions were important to limit particle growth at higher OH exposures, and an H2SO4-organics nucleation mechanism captured new particle formation well.
Zhaofeng Tan, Franz Rohrer, Keding Lu, Xuefei Ma, Birger Bohn, Sebastian Broch, Huabin Dong, Hendrik Fuchs, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, Xin Li, Ying Liu, Yuhan Liu, Anna Novelli, Min Shao, Haichao Wang, Yusheng Wu, Limin Zeng, Min Hu, Astrid Kiendler-Scharr, Andreas Wahner, and Yuanhang Zhang
Atmos. Chem. Phys., 18, 12391–12411, https://doi.org/10.5194/acp-18-12391-2018, https://doi.org/10.5194/acp-18-12391-2018, 2018
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We present the first wintertime OH, HO2, and RO2 measurements in Beijing, China. OH concentrations are nearly 2-fold larger than those observed in foreign cities during wintertime. The high OH and large OH reactivities indicate photochemical processes can be effective even during wintertime. A box model largely underestimated HO2 and RO2 concentrations during pollution episodes correlated with high NOx, indicating a deficit current chemistry in the high NOx regime.
Anna Novelli, Martin Kaminski, Michael Rolletter, Ismail-Hakki Acir, Birger Bohn, Hans-Peter Dorn, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Frank Holland, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 18, 11409–11422, https://doi.org/10.5194/acp-18-11409-2018, https://doi.org/10.5194/acp-18-11409-2018, 2018
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The impact of photooxidation of 2-methyl-3-butene-2-ol (MBO) on the concentration of radical species was studied in the atmospheric simulation chamber SAPHIR. MBO is a volatile organic compound mainly emitted by ponderosa and lodgepole pines which are very abundant in forests in the central-west USA. A very good agreement between measured and modelled radical concentrations and products from the oxidation of MBO was observed in an environment with NO of ~ 200 pptv.
Chinmay Mallik, Laura Tomsche, Efstratios Bourtsoukidis, John N. Crowley, Bettina Derstroff, Horst Fischer, Sascha Hafermann, Imke Hüser, Umar Javed, Stephan Keßel, Jos Lelieveld, Monica Martinez, Hannah Meusel, Anna Novelli, Gavin J. Phillips, Andrea Pozzer, Andreas Reiffs, Rolf Sander, Domenico Taraborrelli, Carina Sauvage, Jan Schuladen, Hang Su, Jonathan Williams, and Hartwig Harder
Atmos. Chem. Phys., 18, 10825–10847, https://doi.org/10.5194/acp-18-10825-2018, https://doi.org/10.5194/acp-18-10825-2018, 2018
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OH and HO2 control the transformation of air pollutants and O3 formation. Their implication for air quality over the climatically sensitive Mediterranean region was studied during a field campaign in Cyprus. Production of OH, HO2, and recycled OH was lower in aged marine air masses. Box model simulations of OH and HO2 agreed with measurements except at high terpene concentrations when model RO2 due to terpenes caused large HO2 loss. Autoxidation schemes for RO2 improved the agreement.
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
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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
Defeng Zhao, Sebastian H. Schmitt, Mingjin Wang, Ismail-Hakki Acir, Ralf Tillmann, Zhaofeng Tan, Anna Novelli, Hendrik Fuchs, Iida Pullinen, Robert Wegener, Franz Rohrer, Jürgen Wildt, Astrid Kiendler-Scharr, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 18, 1611–1628, https://doi.org/10.5194/acp-18-1611-2018, https://doi.org/10.5194/acp-18-1611-2018, 2018
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Air pollutants emitted by human activities such as NOx and SO2 can influence the abundance of secondary organic aerosol (SOA) from biogenic volatile organic compounds (VOCs). We found that NOx suppressed new particle formation and SOA mass formation. When both SO2 and NOx are present, the suppressing effect of NOx on SOA mass formation was counteracted by SO2. High NOx changed SOA chemical composition, forming more organic nitrate, because NOx changed radical chemistry during VOC oxidation.
David H. Hagan, Gabriel Isaacman-VanWertz, Jonathan P. Franklin, Lisa M. M. Wallace, Benjamin D. Kocar, Colette L. Heald, and Jesse H. Kroll
Atmos. Meas. Tech., 11, 315–328, https://doi.org/10.5194/amt-11-315-2018, https://doi.org/10.5194/amt-11-315-2018, 2018
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The use of low-cost sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions. Here we describe the deployment, calibration and evaluation of electrochemical sensors on the Island of Hawai‘i. We obtain excellent performance (RMSE < 7 ppb, r2 = 0.997) across a wide dynamic range (1 ppb–2 ppm). We introduce a hybrid regression algorithm which works across a large dynamic range and shows little decay in sensitivity over time.
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
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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.
Hendrik Fuchs, Anna Novelli, Michael Rolletter, Andreas Hofzumahaus, Eva Y. Pfannerstill, Stephan Kessel, Achim Edtbauer, Jonathan Williams, Vincent Michoud, Sebastien Dusanter, Nadine Locoge, Nora Zannoni, Valerie Gros, Francois Truong, Roland Sarda-Esteve, Danny R. Cryer, Charlotte A. Brumby, Lisa K. Whalley, Daniel Stone, Paul W. Seakins, Dwayne E. Heard, Coralie Schoemaecker, Marion Blocquet, Sebastien Coudert, Sebastien Batut, Christa Fittschen, Alexander B. Thames, William H. Brune, Cheryl Ernest, Hartwig Harder, Jennifer B. A. Muller, Thomas Elste, Dagmar Kubistin, Stefanie Andres, Birger Bohn, Thorsten Hohaus, Frank Holland, Xin Li, Franz Rohrer, Astrid Kiendler-Scharr, Ralf Tillmann, Robert Wegener, Zhujun Yu, Qi Zou, and Andreas Wahner
Atmos. Meas. Tech., 10, 4023–4053, https://doi.org/10.5194/amt-10-4023-2017, https://doi.org/10.5194/amt-10-4023-2017, 2017
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Hydroxyl radical reactivity (k(OH)) is closely related to processes that lead to the formation of oxidised, secondary pollutants such as ozone and aerosol. In order to compare the performances of instruments measuring k(OH), experiments were conducted in the simulation chamber SAPHIR. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. Overall, the results show that instruments are capable of measuring k(OH).
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
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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.
Bettina Derstroff, Imke Hüser, Efstratios Bourtsoukidis, John N. Crowley, Horst Fischer, Sergey Gromov, Hartwig Harder, Ruud H. H. Janssen, Jürgen Kesselmeier, Jos Lelieveld, Chinmay Mallik, Monica Martinez, Anna Novelli, Uwe Parchatka, Gavin J. Phillips, Rolf Sander, Carina Sauvage, Jan Schuladen, Christof Stönner, Laura Tomsche, and Jonathan Williams
Atmos. Chem. Phys., 17, 9547–9566, https://doi.org/10.5194/acp-17-9547-2017, https://doi.org/10.5194/acp-17-9547-2017, 2017
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The aim of the study was to examine aged air masses being transported from the European continent towards Cyprus. Longer-lived oxygenated volatile organic compounds (OVOCs) such as methanol were mainly impacted by long-distance transport and showed higher values in air masses from eastern Europe than in a flow regime from the west. The impact of the transport through the marine boundary layer as well as the influence of the residual layer/free troposphere on OVOCs were studied.
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
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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.
Anna Novelli, Korbinian Hens, Cheryl Tatum Ernest, Monica Martinez, Anke C. Nölscher, Vinayak Sinha, Pauli Paasonen, Tuukka Petäjä, Mikko Sipilä, Thomas Elste, Christian Plass-Dülmer, Gavin J. Phillips, Dagmar Kubistin, Jonathan Williams, Luc Vereecken, Jos Lelieveld, and Hartwig Harder
Atmos. Chem. Phys., 17, 7807–7826, https://doi.org/10.5194/acp-17-7807-2017, https://doi.org/10.5194/acp-17-7807-2017, 2017
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The ambient concentration of stabilised Criegee intermediates (SCIs) was estimated for two
environments using field data. The low concentrations predicted indicate that SCIs are
unlikely to have a large impact on atmospheric chemistry. Concurrent measurements of an OH background signal using the Mainz IPI-LIF-FAGE instrument were found to be consistent with the chemistry of SCIs during the measurement campaigns.
Martin Kaminski, Hendrik Fuchs, Ismail-Hakki Acir, Birger Bohn, Theo Brauers, Hans-Peter Dorn, Rolf Häseler, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Luc Vereecken, Robert Wegener, and Andreas Wahner
Atmos. Chem. Phys., 17, 6631–6650, https://doi.org/10.5194/acp-17-6631-2017, https://doi.org/10.5194/acp-17-6631-2017, 2017
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Monoterpenes emitted by trees are among the volatile organic compounds with the highest global emission rates. The atmospheric degradation of the monoterpene β-pinene was investigated in the atmosphere simulation chamber SAPHIR in Jülich under low NOx and atmospheric β-pinene concentrations. While the budget of OH was balanced, both OH and HO2 concentrations were underestimated in the simulation results. These observations suggest the existence of unaccounted sources of HO2.
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
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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.
Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Herrmann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert McLaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, and Rahul A. Zaveri
Atmos. Chem. Phys., 17, 2103–2162, https://doi.org/10.5194/acp-17-2103-2017, https://doi.org/10.5194/acp-17-2103-2017, 2017
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Oxidation of biogenic volatile organic compounds by NO3 is an important interaction between anthropogenic
and natural emissions. This review results from a June 2015 workshop and includes the recent literature
on kinetics, mechanisms, organic aerosol yields, and heterogeneous chemistry; advances in analytical
instrumentation; the current state NO3-BVOC chemistry in atmospheric models; and critical needs for
future research in modeling, field observations, and laboratory studies.
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
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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.
Zhaofeng Tan, Hendrik Fuchs, Keding Lu, Andreas Hofzumahaus, Birger Bohn, Sebastian Broch, Huabin Dong, Sebastian Gomm, Rolf Häseler, Lingyan He, Frank Holland, Xin Li, Ying Liu, Sihua Lu, Franz Rohrer, Min Shao, Baolin Wang, Ming Wang, Yusheng Wu, Limin Zeng, Yinsong Zhang, Andreas Wahner, and Yuanhang Zhang
Atmos. Chem. Phys., 17, 663–690, https://doi.org/10.5194/acp-17-663-2017, https://doi.org/10.5194/acp-17-663-2017, 2017
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In this study, we performed accurate OH measurements as well as selective HO2 and RO2 measurements at a rural site in North China Plain with state-of-the-art instruments newly developed. We confirmed the previous discovery on the enhancement of the OH in low NOx with which little O3 production was associated, and we found a missing RO2 source in high NOx which promoted higher O3 production. Our results are of vital importance for ozone abatement strategies currently under discussion for China.
Hendrik Fuchs, Zhaofeng Tan, Keding Lu, Birger Bohn, Sebastian Broch, Steven S. Brown, Huabin Dong, Sebastian Gomm, Rolf Häseler, Lingyan He, Andreas Hofzumahaus, Frank Holland, Xin Li, Ying Liu, Sihua Lu, Kyung-Eun Min, Franz Rohrer, Min Shao, Baolin Wang, Ming Wang, Yusheng Wu, Limin Zeng, Yinson Zhang, Andreas Wahner, and Yuanhang Zhang
Atmos. Chem. Phys., 17, 645–661, https://doi.org/10.5194/acp-17-645-2017, https://doi.org/10.5194/acp-17-645-2017, 2017
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OH reactivity was measured during a 1-month long campaign at a rural site in the North China Plain in 2014. OH reactivity measurements are compared to calculations using OH reactant measurements. Good agreement is found indicating that all important OH reactants were measured. In addition, the chemical OH budget is analyzed. In contrast to previous campaigns in China in 2006, no significant imbalance between OH production and destruction is found.
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
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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.
Ryan C. Moffet, Rachel E. O'Brien, Peter A. Alpert, Stephen T. Kelly, Don Q. Pham, Mary K. Gilles, Daniel A. Knopf, and Alexander Laskin
Atmos. Chem. Phys., 16, 14515–14525, https://doi.org/10.5194/acp-16-14515-2016, https://doi.org/10.5194/acp-16-14515-2016, 2016
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Atmospheric black carbon (BC), commonly known as soot, is an important constituent of the earth that imparts a warming similar to that of carbon dioxide. However, BC is much shorter lived and has uncertain warming due to its mixture with other solid and liquid components. Here, advanced microscopic methods have provided a detailed look at thousands of BC particles sampled from central California; these measurements will lead towards a better understanding of the effects that BC has on climate.
Hannah Meusel, Uwe Kuhn, Andreas Reiffs, Chinmay Mallik, Hartwig Harder, Monica Martinez, Jan Schuladen, Birger Bohn, Uwe Parchatka, John N. Crowley, Horst Fischer, Laura Tomsche, Anna Novelli, Thorsten Hoffmann, Ruud H. H. Janssen, Oscar Hartogensis, Michael Pikridas, Mihalis Vrekoussis, Efstratios Bourtsoukidis, Bettina Weber, Jos Lelieveld, Jonathan Williams, Ulrich Pöschl, Yafang Cheng, and Hang Su
Atmos. Chem. Phys., 16, 14475–14493, https://doi.org/10.5194/acp-16-14475-2016, https://doi.org/10.5194/acp-16-14475-2016, 2016
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There are many studies which show discrepancies between modeled and measured nitrous acid (HONO, precursor of OH radical) in the troposphere but with no satisfactory explanation. Ideal conditions to study the unknown sources of HONO were found on Cyprus, a remote Mediterranean island. Budget analysis of trace gas measurements indicates a common source of NO and HONO, which is not related to anthropogenic activity and is most likely derived from biologic activity in soils and subsequent emission.
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
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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
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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
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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
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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
Hendrik Fuchs, Zhaofeng Tan, Andreas Hofzumahaus, Sebastian Broch, Hans-Peter Dorn, Frank Holland, Christopher Künstler, Sebastian Gomm, Franz Rohrer, Stephanie Schrade, Ralf Tillmann, and Andreas Wahner
Atmos. Meas. Tech., 9, 1431–1447, https://doi.org/10.5194/amt-9-1431-2016, https://doi.org/10.5194/amt-9-1431-2016, 2016
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The hydroxyl radical is the key reactant that controls the chemical transformation of pollutants in the atmosphere. Observations of nighttime radicals concentrations were larger than predicted by models in field campaigns in forested and urban environments. Here, we investigated, if measurements could have been affected by artifacts. No significant interferences were found for atmospheric concentrations of reactants in ozonolysis experiments, but small artificats from nitrate radicals.
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
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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.
Brett B. Palm, Pedro Campuzano-Jost, Amber M. Ortega, Douglas A. Day, Lisa Kaser, Werner Jud, Thomas Karl, Armin Hansel, James F. Hunter, Eben S. Cross, Jesse H. Kroll, Zhe Peng, William H. Brune, and Jose L. Jimenez
Atmos. Chem. Phys., 16, 2943–2970, https://doi.org/10.5194/acp-16-2943-2016, https://doi.org/10.5194/acp-16-2943-2016, 2016
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Ambient pine forest air was oxidized by OH radicals in a PAM oxidation flow reactor during the BEACHON-RoMBAS campaign to study secondary organic aerosol formation. Approximately 4.4 times more secondary organic aerosol was formed in the reactor than could be explained by the volatile organic gases (VOCs) measured in ambient air. The organic aerosol formation can be explained by including an SOA yield from typically unmeasured semivolatile and intermediate-volatility organic gases (S/IVOCs).
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
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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.
Peter A. Alpert and Daniel A. Knopf
Atmos. Chem. Phys., 16, 2083–2107, https://doi.org/10.5194/acp-16-2083-2016, https://doi.org/10.5194/acp-16-2083-2016, 2016
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A stochastic immersion freezing model is introduced capable of reproducing laboratory data for a variety of experimental methods using a time and surface area dependent ice nucleation process. The assumption that droplets contain identical surface area is evaluated. A quantitative uncertainty analysis of the laboratory observed freezing process is presented. Our results imply that ice nuclei surface area assumptions are crucial for interpretation of experimental immersion freezing results.
D. F. Zhao, A. Buchholz, B. Kortner, P. Schlag, F. Rubach, H. Fuchs, A. Kiendler-Scharr, R. Tillmann, A. Wahner, Å. K. Watne, M. Hallquist, J. M. Flores, Y. Rudich, K. Kristensen, A. M. K. Hansen, M. Glasius, I. Kourtchev, M. Kalberer, and Th. F. Mentel
Atmos. Chem. Phys., 16, 1105–1121, https://doi.org/10.5194/acp-16-1105-2016, https://doi.org/10.5194/acp-16-1105-2016, 2016
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This study investigated the cloud droplet activation behavior and hygroscopic growth of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Cloud droplet activation behaviors of different types of SOA were similar. In contrast, the hygroscopicity of ASOA was higher than BSOA and ABSOA. ASOA components enhanced the hygroscopicity of the ABSOA. Yet this enhancement cannot be described by a linear mixing of pure SOA systems.
J. H. Slade, R. Thalman, J. Wang, and D. A. Knopf
Atmos. Chem. Phys., 15, 10183–10201, https://doi.org/10.5194/acp-15-10183-2015, https://doi.org/10.5194/acp-15-10183-2015, 2015
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Aerosol particles undergo chemical modification during atmospheric transport due to reactions with trace gas species such as OH radicals affecting cloud formation and, thus, prediction of climate. Here, the cloud formation potential of surrogate biomass burning aerosol (BBA) is studied as a function of particle composition and OH exposure. We find that OH oxidation can alter the cloud formation potential of BBA, but its significance depends on the available water-soluble particulate material.
F. D. Lopez-Hilfiker, C. Mohr, M. Ehn, F. Rubach, E. Kleist, J. Wildt, Th. F. Mentel, A. J. Carrasquillo, K. E. Daumit, J. F. Hunter, J. H. Kroll, D. R. Worsnop, and J. A. Thornton
Atmos. Chem. Phys., 15, 7765–7776, https://doi.org/10.5194/acp-15-7765-2015, https://doi.org/10.5194/acp-15-7765-2015, 2015
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We measured a large suite organic compounds using a recently developed Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a (HR-ToF-CIMS). The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We find that approximately 50% of the detected particle phase mass is associated with compounds having effective vapor pressures 4, or more, orders of magnitude lower than commonly measured products.
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
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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.
A. T. Lambe, P. S. Chhabra, T. B. Onasch, W. H. Brune, J. F. Hunter, J. H. Kroll, M. J. Cummings, J. F. Brogan, Y. Parmar, D. R. Worsnop, C. E. Kolb, and P. Davidovits
Atmos. Chem. Phys., 15, 3063–3075, https://doi.org/10.5194/acp-15-3063-2015, https://doi.org/10.5194/acp-15-3063-2015, 2015
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We compared the chemistry and yields of SOA generated from OH oxidation of gas-phase precursors in a flow reactor (high OH, short residence time) and environmental chambers (low OH, long residence time). We find that chemical composition of SOA produced in the flow reactor and in chambers is similar. SOA yields measured in the flow reactor are lower than in chambers. Seed particles increase the yield of SOA produced in the flow reactor and may account in part for higher SOA yields in chambers.
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
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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%.
R. Oswald, M. Ermel, K. Hens, A. Novelli, H. G. Ouwersloot, P. Paasonen, T. Petäjä, M. Sipilä, P. Keronen, J. Bäck, R. Königstedt, Z. Hosaynali Beygi, H. Fischer, B. Bohn, D. Kubistin, H. Harder, M. Martinez, J. Williams, T. Hoffmann, I. Trebs, and M. Sörgel
Atmos. Chem. Phys., 15, 799–813, https://doi.org/10.5194/acp-15-799-2015, https://doi.org/10.5194/acp-15-799-2015, 2015
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Nitrous acid (HONO) is a key species in atmospheric photochemistry since the photolysis leads to the important hydroxyl radical (OH). Although the importance of HONO as a precursor of OH is known, the formation pathways of HONO, especially during daytime, are a major challenge in atmospheric science. We present a detailed analysis of sources and sinks for HONO in the atmosphere for a field measurement campaign in the boreal forest in Finland and wonder if there is really a source term missing.
M. R. Canagaratna, J. L. Jimenez, J. H. Kroll, Q. Chen, S. H. Kessler, P. Massoli, L. Hildebrandt Ruiz, E. Fortner, L. R. Williams, K. R. Wilson, J. D. Surratt, N. M. Donahue, J. T. Jayne, and D. R. Worsnop
Atmos. Chem. Phys., 15, 253–272, https://doi.org/10.5194/acp-15-253-2015, https://doi.org/10.5194/acp-15-253-2015, 2015
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Atomic oxygen-to-carbon (O:C), hydrogen-to-carbon (H:C), and organic mass-to-organic carbon (OM:OC) ratios of ambient organic aerosol (OA) species provide key constraints for understanding their sources and impacts. Here an improved method for obtaining accurate O:C, H:C, and OM:OC with a widely used aerosol mass spectrometer is developed. These results imply that OA is more oxidized than previously estimated and indicate the need for new chemical mechanisms that simulate ambient oxidation.
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
K. E. Daumit, A. J. Carrasquillo, J. F. Hunter, and J. H. Kroll
Atmos. Chem. Phys., 14, 10773–10784, https://doi.org/10.5194/acp-14-10773-2014, https://doi.org/10.5194/acp-14-10773-2014, 2014
A. Novelli, K. Hens, C. Tatum Ernest, D. Kubistin, E. Regelin, T. Elste, C. Plass-Dülmer, M. Martinez, J. Lelieveld, and H. Harder
Atmos. Meas. Tech., 7, 3413–3430, https://doi.org/10.5194/amt-7-3413-2014, https://doi.org/10.5194/amt-7-3413-2014, 2014
K. Hens, A. Novelli, M. Martinez, J. Auld, R. Axinte, B. Bohn, H. Fischer, P. Keronen, D. Kubistin, A. C. Nölscher, R. Oswald, P. Paasonen, T. Petäjä, E. Regelin, R. Sander, V. Sinha, M. Sipilä, D. Taraborrelli, C. Tatum Ernest, J. Williams, J. Lelieveld, and H. Harder
Atmos. Chem. Phys., 14, 8723–8747, https://doi.org/10.5194/acp-14-8723-2014, https://doi.org/10.5194/acp-14-8723-2014, 2014
H. Fuchs, I.-H. Acir, B. Bohn, T. Brauers, H.-P. Dorn, R. Häseler, A. Hofzumahaus, F. Holland, M. Kaminski, X. Li, K. Lu, A. Lutz, S. Nehr, F. Rohrer, R. Tillmann, R. Wegener, and A. Wahner
Atmos. Chem. Phys., 14, 7895–7908, https://doi.org/10.5194/acp-14-7895-2014, https://doi.org/10.5194/acp-14-7895-2014, 2014
S. Nehr, B. Bohn, H.-P. Dorn, H. Fuchs, R. Häseler, A. Hofzumahaus, X. Li, F. Rohrer, R. Tillmann, and A. Wahner
Atmos. Chem. Phys., 14, 6941–6952, https://doi.org/10.5194/acp-14-6941-2014, https://doi.org/10.5194/acp-14-6941-2014, 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. M. Flores, D. F. Zhao, L. Segev, P. Schlag, A. Kiendler-Scharr, H. Fuchs, Å. K. Watne, N. Bluvshtein, Th. F. Mentel, M. Hallquist, and Y. Rudich
Atmos. Chem. Phys., 14, 5793–5806, https://doi.org/10.5194/acp-14-5793-2014, https://doi.org/10.5194/acp-14-5793-2014, 2014
C. L. Heald, D. A. Ridley, J. H. Kroll, S. R. H. Barrett, K. E. Cady-Pereira, M. J. Alvarado, and C. D. Holmes
Atmos. Chem. Phys., 14, 5513–5527, https://doi.org/10.5194/acp-14-5513-2014, https://doi.org/10.5194/acp-14-5513-2014, 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
K. D. Lu, F. Rohrer, F. Holland, H. Fuchs, T. Brauers, A. Oebel, R. Dlugi, M. Hu, X. Li, S. R. Lou, M. Shao, T. Zhu, A. Wahner, Y. H. Zhang, and A. Hofzumahaus
Atmos. Chem. Phys., 14, 4979–4999, https://doi.org/10.5194/acp-14-4979-2014, https://doi.org/10.5194/acp-14-4979-2014, 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
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
E. S. Cross, J. F. Hunter, A. J. Carrasquillo, J. P. Franklin, S. C. Herndon, J. T. Jayne, D. R. Worsnop, R. C. Miake-Lye, and J. H. Kroll
Atmos. Chem. Phys., 13, 7845–7858, https://doi.org/10.5194/acp-13-7845-2013, https://doi.org/10.5194/acp-13-7845-2013, 2013
Y. J. Rigg, P. A. Alpert, and D. A. Knopf
Atmos. Chem. Phys., 13, 6603–6622, https://doi.org/10.5194/acp-13-6603-2013, https://doi.org/10.5194/acp-13-6603-2013, 2013
S. M. Forrester and D. A. Knopf
Atmos. Chem. Phys., 13, 6507–6522, https://doi.org/10.5194/acp-13-6507-2013, https://doi.org/10.5194/acp-13-6507-2013, 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
H.-P. Dorn, R. L. Apodaca, S. M. Ball, T. Brauers, S. S. Brown, J. N. Crowley, W. P. Dubé, H. Fuchs, R. Häseler, U. Heitmann, R. L. Jones, A. Kiendler-Scharr, I. Labazan, J. M. Langridge, J. Meinen, T. F. Mentel, U. Platt, D. Pöhler, F. Rohrer, A. A. Ruth, E. Schlosser, G. Schuster, A. J. L. Shillings, W. R. Simpson, J. Thieser, R. Tillmann, R. Varma, D. S. Venables, and A. Wahner
Atmos. Meas. Tech., 6, 1111–1140, https://doi.org/10.5194/amt-6-1111-2013, https://doi.org/10.5194/amt-6-1111-2013, 2013
E. U. Emanuelsson, M. Hallquist, K. Kristensen, M. Glasius, B. Bohn, H. Fuchs, B. Kammer, A. Kiendler-Scharr, S. Nehr, F. Rubach, R. Tillmann, A. Wahner, H.-C. Wu, and Th. F. Mentel
Atmos. Chem. Phys., 13, 2837–2855, https://doi.org/10.5194/acp-13-2837-2013, https://doi.org/10.5194/acp-13-2837-2013, 2013
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
Absorption of volatile organic compounds (VOCs) by polymer tubing: implications for indoor air and use as a simple gas-phase volatility separation technique
Response of protonated, adduct, and fragmented ions in Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS)
A flexible device to produce a gas stream with a precisely controlled water vapour mixing ratio and isotope composition based on microdrop dispensing technology
Revision of an open-split-based dual-inlet system for elemental and isotope ratio mass spectrometers with a focus on clumped-isotope measurements
Characterisation of gaseous iodine species detection using the multi-scheme chemical ionisation inlet 2 with bromide and nitrate chemical ionisation methods
Extraction, purification, and clumped isotope analysis of methane (Δ13CDH3 and Δ12CD2H2) from sources and the atmosphere
A novel inlet for enriching concentrations of reactive organic gases in low sampling flows
Characterizing the automatic radon flux transfer standard system Autoflux: laboratory calibration and field experiments
Influence of ozone and humidity on PTR-MS and GC-MS VOC measurements with and without a Na2S2O3 ozone scrubber
Laser-induced sublimation extraction for centimeter-resolution multi-species greenhouse gas analysis on ice cores
Ozone reactivity measurement of biogenic volatile organic compound emissions
Comparison of two photolytic calibration methods for nitrous acid
Measurement of enantiomer percentages for five monoterpenes from six conifer species by cartridge-tube-based passive sampling adsorption–thermal desorption (ps-ATD)
Identification, monitoring, and reaction kinetics of reactive trace species using time-resolved mid-infrared quantum cascade laser absorption spectroscopy: development, characterisation, and initial results for the CH2OO Criegee intermediate
Air pollution monitoring: development of ammonia (NH3) dynamic reference gas mixtures at nanomoles per mole levels to improve the lack of traceability of measurements
Formaldehyde and glyoxal measurement deploying a selected ion flow tube mass spectrometer (SIFT-MS)
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides
MULTICHARME: a modified Chernin-type multi-pass cell designed for IR and THz long-path absorption measurements in the CHARME atmospheric simulation chamber
Silicone tube humidity generator
A source for the continuous generation of pure and quantifiable HONO mixtures
Photochemical method for removing methane interference for improved gas analysis
A simulation chamber for absorption spectroscopy in planetary atmospheres
An automated system for trace gas flux measurements from plant foliage and other plant compartments
Simultaneous measurement of δ13C, δ18O and δ17O of atmospheric CO2 – performance assessment of a dual-laser absorption spectrometer
Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers
A method for resolving changes in atmospheric He ∕ N2 as an indicator of fossil fuel extraction and stratospheric circulation
Atomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap–GC–AED) for atmospheric trace gas measurements
New technique for high-precision, simultaneous measurements of CH4, N2O and CO2 concentrations; isotopic and elemental ratios of N2, O2 and Ar; and total air content in ice cores by wet extraction
High-precision laser spectrometer for multiple greenhouse gas analysis in 1 mL air from ice core samples
A thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phases
Interference from alkenes in chemiluminescent NOx measurements
Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)
Measurement of ammonia, amines and iodine compounds using protonated water cluster chemical ionization mass spectrometry
An instrument for in situ measurement of total ozone reactivity
Portable calibrator for NO based on the photolysis of N2O and a combined NO2∕NO∕O3 source for field calibrations of air pollution monitors
A new instrument for time-resolved measurement of HO2 radicals
Investigation of adsorption and desorption behavior of small-volume cylinders and its relevance for atmospheric trace gas analysis
Towards an understanding of surface effects: testing of various materials in a small volume measurement chamber and its relevance for atmospheric trace gas analysis
Stability of halocarbons in air samples stored in stainless- steel canisters
High-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniques
Characterisation of the transfer of cluster ions through an atmospheric pressure interface time-of-flight mass spectrometer with hexapole ion guides
Addition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixtures
Measurements of delays of gas-phase compounds in a wide variety of tubing materials due to gas–wall interactions
Effects of gas–wall interactions on measurements of semivolatile compounds and small polar molecules
Characterization of a commercial lower-cost medium-precision non-dispersive infrared sensor for atmospheric CO2 monitoring in urban areas
Evaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic species
Cavity-enhanced photoacoustic sensor based on a whispering-gallery-mode diode laser
Using collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH4+ CIMS) to oxygenated volatile organic compounds
A broadband cavity-enhanced spectrometer for atmospheric trace gas measurements and Rayleigh scattering cross sections in the cyan region (470–540 nm)
Large-volume air sample system for measuring 34S∕32S isotope ratio of carbonyl sulfide
Melissa A. Morris, Demetrios Pagonis, Douglas A. Day, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 17, 1545–1559, https://doi.org/10.5194/amt-17-1545-2024, https://doi.org/10.5194/amt-17-1545-2024, 2024
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Polymer absorption of volatile organic compounds (VOCs) is important to characterize for atmospheric sampling setups (as interactions cause sampling delays) and indoor air quality. Here we test different polymer materials and quantify their absorptive capacities through modeling. We found the main polymers in carpets to be highly absorptive, acting as large reservoirs for indoor pollution. We also demonstrated how polymer tubes can be used as a low-cost gas separation technique.
Fangbing Li, Dan Dan Huang, Linhui Tian, Bin Yuan, Wen Tan, Liang Zhu, Penglin Ye, Douglas Worsnop, Ka In Hoi, Kai Meng Mok, and Yong Jie Li
EGUsphere, https://doi.org/10.5194/egusphere-2024-16, https://doi.org/10.5194/egusphere-2024-16, 2024
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The response of protonated, adduct, and fragmented ions of 21 volatile organic compounds (VOCs) was investigated with varying instrument setting and relative humidity (RH) in a Vocus proton-transfer-reaction mass spectrometer (PTR-MS). The protonated ions of most VOCs studied show < 15 % variations in sensitivity, except for some long-chain aldehydes. The relationship between sensitivity and PTR rate constant is complicated by the influences from ion transmission and protonated ion fraction.
Harald Sodemann, Alena Dekhtyareva, Alvaro Fernandez, Andrew Seidl, and Jenny Maccali
Atmos. Meas. Tech., 16, 5181–5203, https://doi.org/10.5194/amt-16-5181-2023, https://doi.org/10.5194/amt-16-5181-2023, 2023
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We describe a device that allows one to produce a continuous stream of water vapour with a specified level of humidity. As a main innovation, we can mix waters with different water isotope composition. Through a series of tests we show that the performance characteristics of the device are in line with specifications. We present two laboratory applications where the device proves useful, first in characterizing instruments, and second for the analysis of water contained in stalagmites.
Stephan Räss, Peter Nyfeler, Paul Wheeler, Will Price, and Markus Christian Leuenberger
Atmos. Meas. Tech., 16, 4489–4505, https://doi.org/10.5194/amt-16-4489-2023, https://doi.org/10.5194/amt-16-4489-2023, 2023
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Due to technological advances clumped-isotope studies have gained importance in recent years. Typically, these studies are performed with high-resolution isotope ratio mass spectrometers (IRMSs) along with a changeover-valve-based dual-inlet system (DIS). We are taking a different approach, namely performing clumped-isotope measurements with a compact low-resolution IRMS with an open-split-based DIS. Currently, we are working with pure-oxygen gas for which we are providing a proof of concept.
Xu-Cheng He, Jiali Shen, Siddharth Iyer, Paxton Juuti, Jiangyi Zhang, Mrisha Koirala, Mikko M. Kytökari, Douglas R. Worsnop, Matti Rissanen, Markku Kulmala, Norbert M. Maier, Jyri Mikkilä, Mikko Sipilä, and Juha Kangasluoma
Atmos. Meas. Tech., 16, 4461–4487, https://doi.org/10.5194/amt-16-4461-2023, https://doi.org/10.5194/amt-16-4461-2023, 2023
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In this study, the upgraded multi-scheme chemical ionisation inlet 2 is presented. Sulfuric acid, hypoiodous acid, iodine, sulfur dioxide, and hydroperoxyl radicals are calibrated, and the improved ion optics allow us to detect sulfuric acid and iodine-containing molecules at as low as a few parts per quadrillion by volume. Additionally, we confirm the reliable detection of iodic acid using both the nitrate and bromide chemical ionisation methods under atmospherically relevant conditions.
Malavika Sivan, Thomas Röckmann, Carina van der Veen, and Maria Elena Popa
EGUsphere, https://doi.org/10.5194/egusphere-2023-1906, https://doi.org/10.5194/egusphere-2023-1906, 2023
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We have set up a measurement system for methane clumped isotopologues. We have built an extraction and purification system to extract pure methane for these measurements, for samples of various origins, including atmospheric air, for which we need to process about 1000 L of air for one measurement. We report here the technical setup for extraction and measurements, the calibration, and give an overview of the samples measured so far.
Namrata Shanmukh Panji and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 16, 4319–4330, https://doi.org/10.5194/amt-16-4319-2023, https://doi.org/10.5194/amt-16-4319-2023, 2023
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Measuring volatile organic compounds (VOCs) in the atmosphere is crucial for understanding air quality and environmental impact. Since these compounds are present in low concentrations, preconcentration of samples is often necessary for accurate detection. To address this issue, we have developed a novel inlet that uses selective permeation to concentrate organic gases in small sample flows. This device offers a promising approach for accurately detecting low levels of VOCs in the atmosphere.
Claudia Grossi, Daniel Rabago, Scott Chambers, Carlos Sáinz, Roger Curcoll, Peter P. S. Otáhal, Eliška Fialová, Luis Quindos, and Arturo Vargas
Atmos. Meas. Tech., 16, 2655–2672, https://doi.org/10.5194/amt-16-2655-2023, https://doi.org/10.5194/amt-16-2655-2023, 2023
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The automatic and low-maintenance radon flux system Autoflux, completed with environmental soil and atmosphere sensors, has been theoretically and experimentally characterized and calibrated under laboratory conditions to be used as transfer standard for in situ measurements. It will offer for the first time long-term measurements to validate radon flux maps used by the climate and the radiation protection communities for assessing the radon gas emissions in the atmosphere.
Lisa Ernle, Monika Akima Ringsdorf, and Jonathan Williams
Atmos. Meas. Tech., 16, 1179–1194, https://doi.org/10.5194/amt-16-1179-2023, https://doi.org/10.5194/amt-16-1179-2023, 2023
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Atmospheric ozone can induce artefacts in volatile organic compound measurements. Laboratory tests were made using GC-MS and PTR-MS aircraft systems under tropospheric and stratospheric conditions of humidity and ozone, with and without sodium thiosulfate filter scrubbers. Ozone in dry air produces some carbonyls and degrades alkenes. The scrubber lifetime depends on ozone concentration, flow rate and humidity. For the troposphere with scrubber, no significant artefacts were found over 14 d.
Lars Mächler, Daniel Baggenstos, Florian Krauss, Jochen Schmitt, Bernhard Bereiter, Remo Walther, Christoph Reinhard, Béla Tuzson, Lukas Emmenegger, and Hubertus Fischer
Atmos. Meas. Tech., 16, 355–372, https://doi.org/10.5194/amt-16-355-2023, https://doi.org/10.5194/amt-16-355-2023, 2023
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We present a new method to extract the gases from ice cores and measure their greenhouse gas composition. The ice is sublimated continuously with a near-infrared laser, releasing the gases, which are then analyzed on a laser absorption spectrometer. The main advantage over previous efforts is a low effective resolution of 1–2 cm. This capability is crucial for the analysis of highly thinned ice, as expected from ongoing drilling efforts to extend ice core history further back in time.
Detlev Helmig, Alex Guenther, Jacques Hueber, Ryan Daly, Wei Wang, Jeong-Hoo Park, Anssi Liikanen, and Arnaud P. Praplan
Atmos. Meas. Tech., 15, 5439–5454, https://doi.org/10.5194/amt-15-5439-2022, https://doi.org/10.5194/amt-15-5439-2022, 2022
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This research demonstrates a new method for determination of the chemical reactivity of volatile organic compounds that are emitted from the leaves and needles of trees. These measurements allow elucidating if and how much of these emissions and their associated reactivity are captured and quantified by currently applicable chemical analysis methods.
Andrew J. Lindsay and Ezra C. Wood
Atmos. Meas. Tech., 15, 5455–5464, https://doi.org/10.5194/amt-15-5455-2022, https://doi.org/10.5194/amt-15-5455-2022, 2022
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Nitrous acid (HONO) is an important source of the main atmospheric oxidant – the hydroxyl radical (OH). Advances in nitrous acid measurement techniques and calibration methods therefore improve our understanding of atmospheric oxidation processes. In this paper, we present two calibration methods based on photo-dissociating water vapor. These calibration methods are useful alternatives to conventional calibrations that involve a reacting hydrogen chloride vapor with sodium nitrite.
Ying Wang, Wentai Luo, Todd N. Rosenstiel, and James F. Pankow
Atmos. Meas. Tech., 15, 4651–4661, https://doi.org/10.5194/amt-15-4651-2022, https://doi.org/10.5194/amt-15-4651-2022, 2022
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A rapid, sensitive, and precise analytical method was developed for measuring the fractional amounts of the (−) and (+) forms of chiral enantiomeric forms of monoterpenes in air containing biogenic plant emissions. The method uses passive air sampling onto adsorption–thermal desorption (ATD) gas sampling cartridge tubes; this is followed by automatable thermal desorption onto a chiral gas chromatography (GC) column, followed by detection with mass spectrometry (MS).
Zara S. Mir, Matthew Jamieson, Nicholas R. Greenall, Paul W. Seakins, Mark A. Blitz, and Daniel Stone
Atmos. Meas. Tech., 15, 2875–2887, https://doi.org/10.5194/amt-15-2875-2022, https://doi.org/10.5194/amt-15-2875-2022, 2022
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In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. This work has significance for the identification and measurement of reactive trace species in complex systems.
Tatiana Macé, Maitane Iturrate-Garcia, Céline Pascale, Bernhard Niederhauser, Sophie Vaslin-Reimann, and Christophe Sutour
Atmos. Meas. Tech., 15, 2703–2718, https://doi.org/10.5194/amt-15-2703-2022, https://doi.org/10.5194/amt-15-2703-2022, 2022
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LNE developed, with the company 2M PROCESS, a gas reference generator to dynamically generate NH3 reference gas mixtures in the air at very low fractions between 1 and 400 nmol/mol. The procedure defined by LNE for calibrating NH3 analyzers used for monitoring air quality guarantees relative expanded uncertainties lower than 2 % for this measurement range. The results of a comparison organized between METAS and LNE allowed the validation of LNE's reference generator and calibration procedure.
Antonia G. Zogka, Manolis N. Romanias, and Frederic Thevenet
Atmos. Meas. Tech., 15, 2001–2019, https://doi.org/10.5194/amt-15-2001-2022, https://doi.org/10.5194/amt-15-2001-2022, 2022
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We emphasize the application of SIFT-MS to detect two important atmospheric pollutants, i.e., formaldehyde (FM) and glyoxal (GL). FM and GL are secondary products formed by volatile organic compound oxidation in indoor and outdoor environments and play a key role in air quality and climate. We show that SIFT-MS is able to monitor these species selectively and in real time, overcoming the limitations of other, classical analytical techniques used to monitor these species in the atmosphere.
Haiyan Li, Thomas Golin Almeida, Yuanyuan Luo, Jian Zhao, Brett B. Palm, Christopher D. Daub, Wei Huang, Claudia Mohr, Jordan E. Krechmer, Theo Kurtén, and Mikael Ehn
Atmos. Meas. Tech., 15, 1811–1827, https://doi.org/10.5194/amt-15-1811-2022, https://doi.org/10.5194/amt-15-1811-2022, 2022
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This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
Jean Decker, Éric Fertein, Jonas Bruckhuisen, Nicolas Houzel, Pierre Kulinski, Bo Fang, Weixiong Zhao, Francis Hindle, Guillaume Dhont, Robin Bocquet, Gaël Mouret, Cécile Coeur, and Arnaud Cuisset
Atmos. Meas. Tech., 15, 1201–1215, https://doi.org/10.5194/amt-15-1201-2022, https://doi.org/10.5194/amt-15-1201-2022, 2022
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We present a multiple pass system developed for the CHamber for Atmospheric Reactivity and Metrology of the Environment. This multi-pass cell allows monitoring of atmospheric species at trace levels by high-resolution spectroscopy with long interaction path lengths in the IR and for the first time in the terahertz range. Interesting prospects are highlighted in this frequency domain, such as a high degree of selectivity or the possibility to monitor in real-time atmospheric processes.
Robert F. Berg, Nicola Chiodo, and Eric Georgin
Atmos. Meas. Tech., 15, 819–832, https://doi.org/10.5194/amt-15-819-2022, https://doi.org/10.5194/amt-15-819-2022, 2022
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We made a humidity generator that adds water vapor to a flowing gas. Its range of humidity is useful for calibrating balloon-borne probes to the Earth's stratosphere. The generator’s novel feature is a saturator that comprises 5 m of silicone tubing immersed in water. The length was enough to ensure that the saturator’s output was independent of the dimensions and permeability of the tube. This simple, low-cost design provides an accuracy that is acceptable for many applications.
Guillermo Villena and Jörg Kleffmann
Atmos. Meas. Tech., 15, 627–637, https://doi.org/10.5194/amt-15-627-2022, https://doi.org/10.5194/amt-15-627-2022, 2022
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A continuous source for the generation of pure HONO mixtures was developed and characterized, which is based on the Henry's law solubility of HONO in acidic aqueous solutions. The source shows a fast time response and an excellent long-term stability and can be easily adjusted to HONO mixing ratios in the range 0.05–500 ppb. A general equation based on Henry's law is developed, whereby the HONO concentration of the source can be absolutely calculated with an accuracy of better than 10 %.
Merve Polat, Jesper Baldtzer Liisberg, Morten Krogsbøll, Thomas Blunier, and Matthew S. Johnson
Atmos. Meas. Tech., 14, 8041–8067, https://doi.org/10.5194/amt-14-8041-2021, https://doi.org/10.5194/amt-14-8041-2021, 2021
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We have designed a process for removing methane from a gas stream so that nitrous oxide can be measured without interference. These are both key long-lived greenhouse gases frequently studied in relation to ice cores, plants, water treatment and so on. However, many researchers are not aware of the problem of methane interference, and in addition there have not been good methods available for solving the problem. Here we present and evaluate such a method.
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197, https://doi.org/10.5194/amt-14-7187-2021, https://doi.org/10.5194/amt-14-7187-2021, 2021
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A novel simulation chamber, PASSxS (Planetary Atmosphere Simulation System for Spectroscopy), has been developed for absorption measurements with a Fourier transform spectrometer (FTS) and possibly a cavity ring-down (CRD) spectrometer, with a sample temperature ranging from 100 K up to 550 K, while the pressure of the gas can be varied up to 60 bar. These temperature and pressure ranges cover a significant part of the planetary atmospheres in the solar system and possibly extrasolar planets.
Lukas Kohl, Markku Koskinen, Tatu Polvinen, Salla Tenhovirta, Kaisa Rissanen, Marjo Patama, Alessandro Zanetti, and Mari Pihlatie
Atmos. Meas. Tech., 14, 4445–4460, https://doi.org/10.5194/amt-14-4445-2021, https://doi.org/10.5194/amt-14-4445-2021, 2021
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We present ShoTGa-FluMS, a measurement system designed for continuous and automated measurements of trace gas and volatile organic compound (VOC) fluxes from plant shoots. ShoTGa-FluMS uses transparent shoot enclosures equipped with cooling elements, automatically replaces fixated CO2, and removes transpired water from the enclosure, thus solving multiple technical problems that have so far prevented automated plant shoot trace gas flux measurements.
Pharahilda M. Steur, Hubertus A. Scheeren, Dave D. Nelson, J. Barry McManus, and Harro A. J. Meijer
Atmos. Meas. Tech., 14, 4279–4304, https://doi.org/10.5194/amt-14-4279-2021, https://doi.org/10.5194/amt-14-4279-2021, 2021
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For understanding the sources and sinks of atmospheric CO2, measurement of stable isotopes has proven to be highly valuable. We present a new method using laser absorption spectroscopy to simultaneously conduct measurements of three CO2 isotopes, directly on dry-air samples. This new method reduces sample preparation time significantly, compared to the conventional method in which measurements are conducted on pure CO2, and avoids measurement biases introduced by CO2 extraction.
Mingyi Wang, Xu-Cheng He, Henning Finkenzeller, Siddharth Iyer, Dexian Chen, Jiali Shen, Mario Simon, Victoria Hofbauer, Jasper Kirkby, Joachim Curtius, Norbert Maier, Theo Kurtén, Douglas R. Worsnop, Markku Kulmala, Matti Rissanen, Rainer Volkamer, Yee Jun Tham, Neil M. Donahue, and Mikko Sipilä
Atmos. Meas. Tech., 14, 4187–4202, https://doi.org/10.5194/amt-14-4187-2021, https://doi.org/10.5194/amt-14-4187-2021, 2021
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Atmospheric iodine species are often short-lived with low abundance and have thus been challenging to measure. We show that the bromide chemical ionization mass spectrometry, compatible with both the atmospheric pressure and reduced pressure interfaces, can simultaneously detect various gas-phase iodine species. Combining calibration experiments and quantum chemical calculations, we quantify detection sensitivities to HOI, HIO3, I2, and H2SO4, giving detection limits down to < 106 molec. cm-3.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527, https://doi.org/10.5194/amt-14-2515-2021, https://doi.org/10.5194/amt-14-2515-2021, 2021
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The atmospheric helium-to-nitrogen ratio is a promising indicator for circulation changes in the upper atmosphere and fossil fuel burning by humans. We present a very precise analysis method to determine changes in the helium-to-nitrogen ratio of air samples. The method relies on stabilizing the gas flow to a mass spectrometer and continuous removal of reactive gases. These advances enable new insights and monitoring possibilities for anthropogenic and natural processes.
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
Atmos. Meas. Tech., 14, 1817–1831, https://doi.org/10.5194/amt-14-1817-2021, https://doi.org/10.5194/amt-14-1817-2021, 2021
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A gas measurement device was developed to measure trace gases (ppt level) in the air based on an atomic emission detector. It combines a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED). The CryoTrap–GC–AED instrumental setup, limits of detection, and elemental performance are presented and discussed. Two measurement case studies are reported: one in a Finnish boreal forest and the other based on an aircraft campaign.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Bernhard Bereiter, Béla Tuzson, Philipp Scheidegger, André Kupferschmid, Herbert Looser, Lars Mächler, Daniel Baggenstos, Jochen Schmitt, Hubertus Fischer, and Lukas Emmenegger
Atmos. Meas. Tech., 13, 6391–6406, https://doi.org/10.5194/amt-13-6391-2020, https://doi.org/10.5194/amt-13-6391-2020, 2020
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The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
Natalie I. Keehan, Bellamy Brownwood, Andrey Marsavin, Douglas A. Day, and Juliane L. Fry
Atmos. Meas. Tech., 13, 6255–6269, https://doi.org/10.5194/amt-13-6255-2020, https://doi.org/10.5194/amt-13-6255-2020, 2020
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This paper describes a new instrument (a thermal-dissociation–cavity ring-down spectrometer, TD-CRDS) for the measurement of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations affecting the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using a TD-CRDS for ambient and laboratory studies.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991, https://doi.org/10.5194/amt-13-5977-2020, https://doi.org/10.5194/amt-13-5977-2020, 2020
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We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Daniel Marno, Cheryl Ernest, Korbinian Hens, Umar Javed, Thomas Klimach, Monica Martinez, Markus Rudolf, Jos Lelieveld, and Hartwig Harder
Atmos. Meas. Tech., 13, 2711–2731, https://doi.org/10.5194/amt-13-2711-2020, https://doi.org/10.5194/amt-13-2711-2020, 2020
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In this study, a calibration device for OH and HO2 instruments is characterized at pressures of 275 to 1000 mbar, allowing instrument pressure sensitivity to be quantified to an accuracy of 22 % (1σ). Computational fluid dynamic simulations supporting the understanding of interactions between generated HOx and the instrument inlet led to enhanced determination of factors affecting instrument sensitivity.
Joschka Pfeifer, Mario Simon, Martin Heinritzi, Felix Piel, Lena Weitz, Dongyu Wang, Manuel Granzin, Tatjana Müller, Steffen Bräkling, Jasper Kirkby, Joachim Curtius, and Andreas Kürten
Atmos. Meas. Tech., 13, 2501–2522, https://doi.org/10.5194/amt-13-2501-2020, https://doi.org/10.5194/amt-13-2501-2020, 2020
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Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultrasensitive detection of ammonia at single-digit parts per trillion by volume levels. The instrument is further capable of measuring amines and a suite of iodine compounds at sub-parts per trillion by volume levels.
Roberto Sommariva, Louisa J. Kramer, Leigh R. Crilley, Mohammed S. Alam, and William J. Bloss
Atmos. Meas. Tech., 13, 1655–1670, https://doi.org/10.5194/amt-13-1655-2020, https://doi.org/10.5194/amt-13-1655-2020, 2020
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Ozone is a key atmospheric pollutant formed through chemical processing of natural and anthropogenic emissions and removed by reaction with organic compounds emitted by plants. We describe a new instrument – the
Total Ozone Reactivity Systemor TORS – that measures the total loss of ozone in the troposphere. The objective of the TORS instrument is to provide an estimate of the organic compounds emitted by plants which are not measured and thus to improve our understanding of the ozone budget.
John W. Birks, Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Stanley Strunk, Brian Carpenter, and Christine A. Ennis
Atmos. Meas. Tech., 13, 1001–1018, https://doi.org/10.5194/amt-13-1001-2020, https://doi.org/10.5194/amt-13-1001-2020, 2020
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We describe a portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide. Combining this with a previous photolytic ozone (O3) source yields a calibrator that produces known mixing ratios of NO, O3, and nitrogen dioxide (NO2); NO2 is produced by the reaction of NO with O3. This portable
NO2/NO/O3 calibration source requires no external gas cylinders and can be used as a standard to calibrate O3 and NOx air pollution monitors in the field.
Thomas H. Speak, Mark A. Blitz, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 13, 839–852, https://doi.org/10.5194/amt-13-839-2020, https://doi.org/10.5194/amt-13-839-2020, 2020
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OH and HO2 radicals are important trace constituents of the atmosphere that are closely coupled via several types of reaction. This paper describes a new laboratory method to simultaneously determine OH kinetics and HO2 yields from chemical processes. The instrument also provides some time resolution on HO2 detection allowing one to separate HO2 produced from the target reaction from HO2 arising from secondary chemistry. Examples of applications are presented.
Ece Satar, Peter Nyfeler, Bernhard Bereiter, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 101–117, https://doi.org/10.5194/amt-13-101-2020, https://doi.org/10.5194/amt-13-101-2020, 2020
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Good-quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4 and H2O using a commercial and a novel laser spectroscopic analyzer.
Ece Satar, Peter Nyfeler, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 119–130, https://doi.org/10.5194/amt-13-119-2020, https://doi.org/10.5194/amt-13-119-2020, 2020
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To ensure the best preparation and measurement conditions for trace gases, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. In this article, the previously introduced aluminum measurement chamber is used to investigate materials such as glass, aluminum, copper, brass, steel and three different commercially available coatings. Our measurements focus on temperature and pressure dependencies for the species CO2, CO, CH4 and H2O using a CRDS analyzer.
Tanja J. Schuck, Ann-Katrin Blank, Elisa Rittmeier, Jonathan Williams, Carl A. M. Brenninkmeijer, Andreas Engel, and Andreas Zahn
Atmos. Meas. Tech., 13, 73–84, https://doi.org/10.5194/amt-13-73-2020, https://doi.org/10.5194/amt-13-73-2020, 2020
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Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless-steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds were depleted. Individual substances were additionally influenced by high mixing ratios of ozone.
Tesfaye A. Berhanu, John Hoffnagle, Chris Rella, David Kimhak, Peter Nyfeler, and Markus Leuenberger
Atmos. Meas. Tech., 12, 6803–6826, https://doi.org/10.5194/amt-12-6803-2019, https://doi.org/10.5194/amt-12-6803-2019, 2019
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Accurate measurement of variations in atmospheric O2 can provide useful information about atmospheric, biospheric, and oceanic processes, which is a challenge for existing measurement techniques. Here, we introduce a newly built high-precision, stable CRDS analyzer (Picarro G2207) that can measure O2 mixing ratios with a short-term precision of < 1 ppm and only requires calibration every 12 h. Measurements from tower and mountain sites are also presented.
Markus Leiminger, Stefan Feil, Paul Mutschlechner, Arttu Ylisirniö, Daniel Gunsch, Lukas Fischer, Alfons Jordan, Siegfried Schobesberger, Armin Hansel, and Gerhard Steiner
Atmos. Meas. Tech., 12, 5231–5246, https://doi.org/10.5194/amt-12-5231-2019, https://doi.org/10.5194/amt-12-5231-2019, 2019
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We introduce an alternative type of atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) with the main difference of using hexapole instead of quadrupole ion guides. The transfer of cluster ions through the hexapoles was characterised with focus on transmission efficiency, mass range and fragmentation of cluster ions. At the CERN CLOUD experiment we compared the performance of the ioniAPi-TOF with a standard quadrupole APi-TOF under controlled conditions.
Michal Lacko, Nijing Wang, Kristýna Sovová, Pavel Pásztor, and Patrik Španěl
Atmos. Meas. Tech., 12, 4965–4982, https://doi.org/10.5194/amt-12-4965-2019, https://doi.org/10.5194/amt-12-4965-2019, 2019
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The soft chemical ionization analytical technique of selected ion flow tube mass spectrometry, SIFT-MS, was enhanced by a fast GC pre-separation unit to identify individual isomers. Experiments were carried out with two GC columns, MXT-1 and MXT-Volatiles, using two reagent ions, H3O+ and NO+, on monoterpene samples (an artificial mixture and coniferous needles). Analyses of product ion ratios allowed for quantification of multiple monoterpenes in partially separated chromatograms.
Benjamin L. Deming, Demetrios Pagonis, Xiaoxi Liu, Douglas A. Day, Ranajit Talukdar, Jordan E. Krechmer, Joost A. de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 12, 3453–3461, https://doi.org/10.5194/amt-12-3453-2019, https://doi.org/10.5194/amt-12-3453-2019, 2019
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Losses or measurement delays of gas-phase compounds sampled through tubing are important to atmospheric science. Here we characterize 14 tubing materials by measuring the effects on step changes in organic compound concentration. We find that polymeric tubings exhibit absorptive partitioning behaviour while glass and metal tubings show adsorptive partitioning. Adsorptive materials impart complex humidity, concentration, and VOC–VOC interaction dependencies that absorptive tubings do not.
Xiaoxi Liu, Benjamin Deming, Demetrios Pagonis, Douglas A. Day, Brett B. Palm, Ranajit Talukdar, James M. Roberts, Patrick R. Veres, Jordan E. Krechmer, Joel A. Thornton, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 12, 3137–3149, https://doi.org/10.5194/amt-12-3137-2019, https://doi.org/10.5194/amt-12-3137-2019, 2019
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Delays or losses of gases in sampling tubing and instrumental surfaces due to surface interactions can lead to inaccurate quantification. By sampling with several chemical ionization mass spectrometers and six tubing materials, we quantify delays of semivolatile organic compounds and small polar gases. Delay times generally increase with decreasing volatility or increasing polarity and also depend on materials. The method and results will inform inlet material selection and instrumental design.
Emmanuel Arzoumanian, Felix R. Vogel, Ana Bastos, Bakhram Gaynullin, Olivier Laurent, Michel Ramonet, and Philippe Ciais
Atmos. Meas. Tech., 12, 2665–2677, https://doi.org/10.5194/amt-12-2665-2019, https://doi.org/10.5194/amt-12-2665-2019, 2019
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We tested commercial lower-cost CO2 sensors in laboratory and field studies to see if they can measure atmospheric CO2 mole fractions with less than 1 ppm bias (with monthly calibration), to allow continuous urban CO2 monitoring.
We find that the sensors' CO2 readings are influenced by temperature, atmospheric pressure and water vapour content, but this can be corrected for by adding sensors (T, p, RH) and carefully calibrating each sensor against a high-precision instrument.
Matthieu Riva, Pekka Rantala, Jordan E. Krechmer, Otso Peräkylä, Yanjun Zhang, Liine Heikkinen, Olga Garmash, Chao Yan, Markku Kulmala, Douglas Worsnop, and Mikael Ehn
Atmos. Meas. Tech., 12, 2403–2421, https://doi.org/10.5194/amt-12-2403-2019, https://doi.org/10.5194/amt-12-2403-2019, 2019
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The impact of aerosol particles on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated species, formed from the oxidation of volatile organic compounds (VOCs) to aerosol formation. Taking advantage of recent mass spectrometric developments, we have evaluated and compared the capability of multiple state-of-the-art mass spectrometers to detect a wide variety of oxygenated VOCs.
Yufeng Pan, Lei Dong, Hongpeng Wu, Weiguang Ma, Lei Zhang, Wangbao Yin, Liantuan Xiao, Suotang Jia, and Frank K. Tittel
Atmos. Meas. Tech., 12, 1905–1911, https://doi.org/10.5194/amt-12-1905-2019, https://doi.org/10.5194/amt-12-1905-2019, 2019
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Photoacoustic spectroscopy has one important advantage: its sensitivity is proportional to the excitation light power and thus the performance of PAS-based sensors can benefit from a high excitation light power. We developed a cavity-enhanced photoacoustic sensor in which a photoacoustic cell was placed into a high-finesse optical cavity. A signal gain factor of 166 was observed. For C2H2 detection, a 1σ detection limit of 0.45 ppmV was obtained at atmospheric pressure with a 1 s averaging time.
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
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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.
Nick Jordan, Connie Z. Ye, Satyaki Ghosh, Rebecca A. Washenfelder, Steven S. Brown, and Hans D. Osthoff
Atmos. Meas. Tech., 12, 1277–1293, https://doi.org/10.5194/amt-12-1277-2019, https://doi.org/10.5194/amt-12-1277-2019, 2019
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A new spectrometer to measure abundances of the atmospheric trace gases nitrogen dioxide and iodine is described. The spectrometer uses a light-emitting diode between 470 and 540 nm and two highly reflective mirrors to yield an effective absorption path of 6.3 km. We remeasured scattering cross sections of common atmospheric gases in the cyan region and present sample NO2 measurements that agreed with those made with a laser-based instrument.
Kazuki Kamezaki, Shohei Hattori, Enno Bahlmann, and Naohiro Yoshida
Atmos. Meas. Tech., 12, 1141–1154, https://doi.org/10.5194/amt-12-1141-2019, https://doi.org/10.5194/amt-12-1141-2019, 2019
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Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. We present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. The system presented herein is useful for application of sulfur isotopic compositions for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.
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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.
We have developed an online method for speciated measurements of organic peroxy radicals and...
