Articles | Volume 7, issue 8
https://doi.org/10.5194/amt-7-2645-2014
© Author(s) 2014. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/amt-7-2645-2014
© Author(s) 2014. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| 
19 Aug 2014
Research article |
| 19 Aug 2014
Online technique for isotope and mixing ratios of CH4, N2O, Xe and mixing ratios of organic trace gases on a single ice core sample
J. Schmitt
Climate and Environmental Physics, Physics Institute & Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
Climate and Environmental Physics, Physics Institute & Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
Climate and Environmental Physics, Physics Institute & Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
H. Fischer
Climate and Environmental Physics, Physics Institute & Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
Related authors
Lison Soussaintjean, Jochen Schmitt, Joël Savarino, J. Andy Menking, Edward J. Brook, Barbara Seth, Vladimir Lipenkov, Thomas Röckmann, and Hubertus Fischer
EGUsphere, https://doi.org/10.5194/egusphere-2025-3108, https://doi.org/10.5194/egusphere-2025-3108, 2025
This preprint is open for discussion and under review for Biogeosciences (BG).
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Nitrous oxide (N2O) produced in dust-rich Antarctic ice complicates the reconstruction of past atmospheric levels from ice core records. Using isotope analysis, we show that N2O forms from two nitrogen precursors, one being nitrate. For the first time, we demonstrate that the site preference (SP) of N2O reflects the isotopic difference between these precursors, not the production pathway, which challenges the common interpretation of SP.
Michaela Mühl, Jochen Schmitt, Barbara Seth, James E. Lee, Jon S. Edwards, Edward J. Brook, Thomas Blunier, and Hubertus Fischer
Clim. Past, 19, 999–1025, https://doi.org/10.5194/cp-19-999-2023, https://doi.org/10.5194/cp-19-999-2023, 2023
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Our ice core measurements show that methane, ethane, and propane concentrations are significantly elevated above their past atmospheric background for Greenland ice samples containing mineral dust. The underlying co-production process happens during the classical discrete wet extraction of air from the ice sample and affects previous reconstructions of the inter-polar difference of methane as well as methane stable isotope records derived from dust-rich Greenland ice.
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
Short summary
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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.
Loïc Schmidely, Christoph Nehrbass-Ahles, Jochen Schmitt, Juhyeong Han, Lucas Silva, Jinwha Shin, Fortunat Joos, Jérôme Chappellaz, Hubertus Fischer, and Thomas F. Stocker
Clim. Past, 17, 1627–1643, https://doi.org/10.5194/cp-17-1627-2021, https://doi.org/10.5194/cp-17-1627-2021, 2021
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Using ancient gas trapped in polar glaciers, we reconstructed the atmospheric concentrations of methane and nitrous oxide over the penultimate deglaciation to study their response to major climate changes. We show this deglaciation to be characterized by modes of methane and nitrous oxide variability that are also found during the last deglaciation and glacial cycle.
Marcel Haeberli, Daniel Baggenstos, Jochen Schmitt, Markus Grimmer, Adrien Michel, Thomas Kellerhals, and Hubertus Fischer
Clim. Past, 17, 843–867, https://doi.org/10.5194/cp-17-843-2021, https://doi.org/10.5194/cp-17-843-2021, 2021
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Using the temperature-dependent solubility of noble gases in ocean water, we reconstruct global mean ocean temperature (MOT) over the last 700 kyr using noble gas ratios in air enclosed in polar ice cores. Our record shows that glacial MOT was about 3 °C cooler compared to the Holocene. Interglacials before 450 kyr ago were characterized by about 1.5 °C lower MOT than the Holocene. In addition, some interglacials show transient maxima in ocean temperature related to changes in ocean circulation.
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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.
Jinhwa Shin, Christoph Nehrbass-Ahles, Roberto Grilli, Jai Chowdhry Beeman, Frédéric Parrenin, Grégory Teste, Amaelle Landais, Loïc Schmidely, Lucas Silva, Jochen Schmitt, Bernhard Bereiter, Thomas F. Stocker, Hubertus Fischer, and Jérôme Chappellaz
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We reconstruct atmospheric CO2 from the EPICA Dome C ice core during Marine Isotope Stage 6 (185–135 ka) to understand carbon mechanisms under the different boundary conditions of the climate system. The amplitude of CO2 is highly determined by the Northern Hemisphere stadial duration. Carbon dioxide maxima show different lags with respect to the corresponding abrupt CH4 jumps, the latter reflecting rapid warming in the Northern Hemisphere.
Fortunat Joos, Renato Spahni, Benjamin D. Stocker, Sebastian Lienert, Jurek Müller, Hubertus Fischer, Jochen Schmitt, I. Colin Prentice, Bette Otto-Bliesner, and Zhengyu Liu
Biogeosciences, 17, 3511–3543, https://doi.org/10.5194/bg-17-3511-2020, https://doi.org/10.5194/bg-17-3511-2020, 2020
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Results of the first globally resolved simulations of terrestrial carbon and nitrogen (N) cycling and N2O emissions over the past 21 000 years are compared with reconstructed N2O emissions. Modelled and reconstructed emissions increased strongly during past abrupt warming events. This evidence appears consistent with a dynamic response of biological N fixation to increasing N demand by ecosystems, thereby reducing N limitation of plant productivity and supporting a land sink for atmospheric CO2.
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Biogeosciences, 16, 3997–4021, https://doi.org/10.5194/bg-16-3997-2019, https://doi.org/10.5194/bg-16-3997-2019, 2019
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N2O concentrations were subject to strong variations accompanying glacial–interglacial but also rapid climate changes over the last 21 kyr. The sources of these N2O changes can be identified by measuring the isotopic composition of N2O in ice cores and using the distinct isotopic composition of terrestrial and marine N2O. We show that both marine and terrestrial sources increased from the last glacial to the Holocene but that only terrestrial emissions responded quickly to rapid climate changes.
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Ice core concentration and stable isotope measurements of atmospheric CH4 give valuable insights into the CH4 cycle of the past. New carbon and hydrogen stable isotope CH4 data measured on ice from both Greenland and Antarctica over the Holocene allow us to draw conclusions on the methane emission processes. In particular, our results cast doubt on a hypothesis proposing early human land use to be responsible for the atmospheric methane concentration increase in the second half of the Holocene.
Taku Umezawa, Carl A. M. Brenninkmeijer, Thomas Röckmann, Carina van der Veen, Stanley C. Tyler, Ryo Fujita, Shinji Morimoto, Shuji Aoki, Todd Sowers, Jochen Schmitt, Michael Bock, Jonas Beck, Hubertus Fischer, Sylvia E. Michel, Bruce H. Vaughn, John B. Miller, James W. C. White, Gordon Brailsford, Hinrich Schaefer, Peter Sperlich, Willi A. Brand, Michael Rothe, Thomas Blunier, David Lowry, Rebecca E. Fisher, Euan G. Nisbet, Andrew L. Rice, Peter Bergamaschi, Cordelia Veidt, and Ingeborg Levin
Atmos. Meas. Tech., 11, 1207–1231, https://doi.org/10.5194/amt-11-1207-2018, https://doi.org/10.5194/amt-11-1207-2018, 2018
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Isotope measurements are useful for separating different methane sources. However, the lack of widely accepted standards and calibration methods for stable carbon and hydrogen isotopic ratios of methane in air has caused significant measurement offsets among laboratories. We conducted worldwide interlaboratory comparisons, surveyed the literature and assessed them systematically. This study may be of help in future attempts to harmonize data sets of isotopic composition of atmospheric methane.
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We document our best available data compilation of published ice core records of the greenhouse gases CO2, CH4, and N2O and recent measurements on firn air and atmospheric samples covering the time window from 156 000 years BP to the beginning of the year 2016 CE. A smoothing spline method is applied to translate the discrete and irregularly spaced data points into continuous time series. The radiative forcing for each greenhouse gas is computed using well-established, simple formulations.
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A new high-resolution total air content record over the NGRIP ice core, spanning 0.3–120 kyr is presented. In agreement with Antarctic ice cores, we find a strong local insolation signature but also 3–5 % decreases in total air content as a local response to Dansgaard–Oeschger events, which can only partly be explained by changes in surface pressure and temperature. Accordingly, a dynamic response of firnification to rapid climate changes on the Greenland ice sheet must have occurred.
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EGUsphere, https://doi.org/10.5194/egusphere-2025-3108, https://doi.org/10.5194/egusphere-2025-3108, 2025
This preprint is open for discussion and under review for Biogeosciences (BG).
Short summary
Short summary
Nitrous oxide (N2O) produced in dust-rich Antarctic ice complicates the reconstruction of past atmospheric levels from ice core records. Using isotope analysis, we show that N2O forms from two nitrogen precursors, one being nitrate. For the first time, we demonstrate that the site preference (SP) of N2O reflects the isotopic difference between these precursors, not the production pathway, which challenges the common interpretation of SP.
Michaela Mühl, Jochen Schmitt, Barbara Seth, James E. Lee, Jon S. Edwards, Edward J. Brook, Thomas Blunier, and Hubertus Fischer
Clim. Past, 19, 999–1025, https://doi.org/10.5194/cp-19-999-2023, https://doi.org/10.5194/cp-19-999-2023, 2023
Short summary
Short summary
Our ice core measurements show that methane, ethane, and propane concentrations are significantly elevated above their past atmospheric background for Greenland ice samples containing mineral dust. The underlying co-production process happens during the classical discrete wet extraction of air from the ice sample and affects previous reconstructions of the inter-polar difference of methane as well as methane stable isotope records derived from dust-rich Greenland ice.
Lars Mächler, Daniel Baggenstos, Florian Krauss, Jochen Schmitt, Bernhard Bereiter, Remo Walther, Christoph Reinhard, Béla Tuzson, Lukas Emmenegger, and Hubertus Fischer
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Short summary
Short summary
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.
Loïc Schmidely, Christoph Nehrbass-Ahles, Jochen Schmitt, Juhyeong Han, Lucas Silva, Jinwha Shin, Fortunat Joos, Jérôme Chappellaz, Hubertus Fischer, and Thomas F. Stocker
Clim. Past, 17, 1627–1643, https://doi.org/10.5194/cp-17-1627-2021, https://doi.org/10.5194/cp-17-1627-2021, 2021
Short summary
Short summary
Using ancient gas trapped in polar glaciers, we reconstructed the atmospheric concentrations of methane and nitrous oxide over the penultimate deglaciation to study their response to major climate changes. We show this deglaciation to be characterized by modes of methane and nitrous oxide variability that are also found during the last deglaciation and glacial cycle.
Marcel Haeberli, Daniel Baggenstos, Jochen Schmitt, Markus Grimmer, Adrien Michel, Thomas Kellerhals, and Hubertus Fischer
Clim. Past, 17, 843–867, https://doi.org/10.5194/cp-17-843-2021, https://doi.org/10.5194/cp-17-843-2021, 2021
Short summary
Short summary
Using the temperature-dependent solubility of noble gases in ocean water, we reconstruct global mean ocean temperature (MOT) over the last 700 kyr using noble gas ratios in air enclosed in polar ice cores. Our record shows that glacial MOT was about 3 °C cooler compared to the Holocene. Interglacials before 450 kyr ago were characterized by about 1.5 °C lower MOT than the Holocene. In addition, some interglacials show transient maxima in ocean temperature related to changes in ocean circulation.
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
Short summary
Short summary
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.
Jinhwa Shin, Christoph Nehrbass-Ahles, Roberto Grilli, Jai Chowdhry Beeman, Frédéric Parrenin, Grégory Teste, Amaelle Landais, Loïc Schmidely, Lucas Silva, Jochen Schmitt, Bernhard Bereiter, Thomas F. Stocker, Hubertus Fischer, and Jérôme Chappellaz
Clim. Past, 16, 2203–2219, https://doi.org/10.5194/cp-16-2203-2020, https://doi.org/10.5194/cp-16-2203-2020, 2020
Short summary
Short summary
We reconstruct atmospheric CO2 from the EPICA Dome C ice core during Marine Isotope Stage 6 (185–135 ka) to understand carbon mechanisms under the different boundary conditions of the climate system. The amplitude of CO2 is highly determined by the Northern Hemisphere stadial duration. Carbon dioxide maxima show different lags with respect to the corresponding abrupt CH4 jumps, the latter reflecting rapid warming in the Northern Hemisphere.
Fortunat Joos, Renato Spahni, Benjamin D. Stocker, Sebastian Lienert, Jurek Müller, Hubertus Fischer, Jochen Schmitt, I. Colin Prentice, Bette Otto-Bliesner, and Zhengyu Liu
Biogeosciences, 17, 3511–3543, https://doi.org/10.5194/bg-17-3511-2020, https://doi.org/10.5194/bg-17-3511-2020, 2020
Short summary
Short summary
Results of the first globally resolved simulations of terrestrial carbon and nitrogen (N) cycling and N2O emissions over the past 21 000 years are compared with reconstructed N2O emissions. Modelled and reconstructed emissions increased strongly during past abrupt warming events. This evidence appears consistent with a dynamic response of biological N fixation to increasing N demand by ecosystems, thereby reducing N limitation of plant productivity and supporting a land sink for atmospheric CO2.
Hubertus Fischer, Jochen Schmitt, Michael Bock, Barbara Seth, Fortunat Joos, Renato Spahni, Sebastian Lienert, Gianna Battaglia, Benjamin D. Stocker, Adrian Schilt, and Edward J. Brook
Biogeosciences, 16, 3997–4021, https://doi.org/10.5194/bg-16-3997-2019, https://doi.org/10.5194/bg-16-3997-2019, 2019
Short summary
Short summary
N2O concentrations were subject to strong variations accompanying glacial–interglacial but also rapid climate changes over the last 21 kyr. The sources of these N2O changes can be identified by measuring the isotopic composition of N2O in ice cores and using the distinct isotopic composition of terrestrial and marine N2O. We show that both marine and terrestrial sources increased from the last glacial to the Holocene but that only terrestrial emissions responded quickly to rapid climate changes.
Jonas Beck, Michael Bock, Jochen Schmitt, Barbara Seth, Thomas Blunier, and Hubertus Fischer
Biogeosciences, 15, 7155–7175, https://doi.org/10.5194/bg-15-7155-2018, https://doi.org/10.5194/bg-15-7155-2018, 2018
Short summary
Short summary
Ice core concentration and stable isotope measurements of atmospheric CH4 give valuable insights into the CH4 cycle of the past. New carbon and hydrogen stable isotope CH4 data measured on ice from both Greenland and Antarctica over the Holocene allow us to draw conclusions on the methane emission processes. In particular, our results cast doubt on a hypothesis proposing early human land use to be responsible for the atmospheric methane concentration increase in the second half of the Holocene.
Taku Umezawa, Carl A. M. Brenninkmeijer, Thomas Röckmann, Carina van der Veen, Stanley C. Tyler, Ryo Fujita, Shinji Morimoto, Shuji Aoki, Todd Sowers, Jochen Schmitt, Michael Bock, Jonas Beck, Hubertus Fischer, Sylvia E. Michel, Bruce H. Vaughn, John B. Miller, James W. C. White, Gordon Brailsford, Hinrich Schaefer, Peter Sperlich, Willi A. Brand, Michael Rothe, Thomas Blunier, David Lowry, Rebecca E. Fisher, Euan G. Nisbet, Andrew L. Rice, Peter Bergamaschi, Cordelia Veidt, and Ingeborg Levin
Atmos. Meas. Tech., 11, 1207–1231, https://doi.org/10.5194/amt-11-1207-2018, https://doi.org/10.5194/amt-11-1207-2018, 2018
Short summary
Short summary
Isotope measurements are useful for separating different methane sources. However, the lack of widely accepted standards and calibration methods for stable carbon and hydrogen isotopic ratios of methane in air has caused significant measurement offsets among laboratories. We conducted worldwide interlaboratory comparisons, surveyed the literature and assessed them systematically. This study may be of help in future attempts to harmonize data sets of isotopic composition of atmospheric methane.
Peter Köhler, Christoph Nehrbass-Ahles, Jochen Schmitt, Thomas F. Stocker, and Hubertus Fischer
Earth Syst. Sci. Data, 9, 363–387, https://doi.org/10.5194/essd-9-363-2017, https://doi.org/10.5194/essd-9-363-2017, 2017
Short summary
Short summary
We document our best available data compilation of published ice core records of the greenhouse gases CO2, CH4, and N2O and recent measurements on firn air and atmospheric samples covering the time window from 156 000 years BP to the beginning of the year 2016 CE. A smoothing spline method is applied to translate the discrete and irregularly spaced data points into continuous time series. The radiative forcing for each greenhouse gas is computed using well-established, simple formulations.
Olivier Eicher, Matthias Baumgartner, Adrian Schilt, Jochen Schmitt, Jakob Schwander, Thomas F. Stocker, and Hubertus Fischer
Clim. Past, 12, 1979–1993, https://doi.org/10.5194/cp-12-1979-2016, https://doi.org/10.5194/cp-12-1979-2016, 2016
Short summary
Short summary
A new high-resolution total air content record over the NGRIP ice core, spanning 0.3–120 kyr is presented. In agreement with Antarctic ice cores, we find a strong local insolation signature but also 3–5 % decreases in total air content as a local response to Dansgaard–Oeschger events, which can only partly be explained by changes in surface pressure and temperature. Accordingly, a dynamic response of firnification to rapid climate changes on the Greenland ice sheet must have occurred.
G. Gfeller, H. Fischer, M. Bigler, S. Schüpbach, D. Leuenberger, and O. Mini
The Cryosphere, 8, 1855–1870, https://doi.org/10.5194/tc-8-1855-2014, https://doi.org/10.5194/tc-8-1855-2014, 2014
M. Bock, J. Schmitt, J. Beck, R. Schneider, and H. Fischer
Atmos. Meas. Tech., 7, 1999–2012, https://doi.org/10.5194/amt-7-1999-2014, https://doi.org/10.5194/amt-7-1999-2014, 2014
N. Merz, A. Born, C. C. Raible, H. Fischer, and T. F. Stocker
Clim. Past, 10, 1221–1238, https://doi.org/10.5194/cp-10-1221-2014, https://doi.org/10.5194/cp-10-1221-2014, 2014
R. Schneider, J. Schmitt, P. Köhler, F. Joos, and H. Fischer
Clim. Past, 9, 2507–2523, https://doi.org/10.5194/cp-9-2507-2013, https://doi.org/10.5194/cp-9-2507-2013, 2013
J. Schmitt, B. Seth, M. Bock, C. van der Veen, L. Möller, C. J. Sapart, M. Prokopiou, T. Sowers, T. Röckmann, and H. Fischer
Atmos. Meas. Tech., 6, 1425–1445, https://doi.org/10.5194/amt-6-1425-2013, https://doi.org/10.5194/amt-6-1425-2013, 2013
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Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)
Getachew Agmuas Adnew, Gerbrand Koren, Neha Mehendale, Sergey Gromov, Maarten Krol, and Thomas Röckmann
Atmos. Meas. Tech., 18, 2701–2719, https://doi.org/10.5194/amt-18-2701-2025, https://doi.org/10.5194/amt-18-2701-2025, 2025
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This study presents high-precision measurements of ∆′17O(CO2). Key findings include the extension of the N2O–∆′17O correlation to the upper troposphere and the identification of significant differences in the N2O–∆′17O slope in StratoClim samples. Additionally, the ∆′17O measurements are used to estimate global stratospheric production and surface removal of ∆′17O, providing an independent estimate of global vegetation CO2 exchange.
Laura Wüst, Patrick Dewald, Gunther N. T. E. Türk, Jos Lelieveld, and John N. Crowley
Atmos. Meas. Tech., 18, 1943–1959, https://doi.org/10.5194/amt-18-1943-2025, https://doi.org/10.5194/amt-18-1943-2025, 2025
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Detection of NO2 via cavity ring-down spectroscopy (CRDS) after thermal dissociation (TD) of alkyl and peroxy nitrates can be used to detect total atmospheric organic nitrates originating from the interaction between biogenic emissions of volatile organic compounds and nitrogen oxides of anthropogenic origin. Here we present an improved TD-CRDS technique that avoids systematic bias resulting from secondary chemistry in the heated inlets and that can be deployed in regions with strong biogenic emissions.
Robby Rynek, Thomas Mayer, and Helko Borsdorf
EGUsphere, https://doi.org/10.5194/egusphere-2025-1387, https://doi.org/10.5194/egusphere-2025-1387, 2025
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A novel, reusable ozone filter design for the monitoring of biogenic volatile organic compounds using sorbent tubes and multi-tube samplers was evaluated. The ozone filters proved high efficiency in retaining high recovery rates across different environmental relevant levels of relative humidity and ozone concentrations, while safeguarding the sorbent material, both in laboratory and field experiments. The filter design has the advantage of not requiring additional equipment or regular checks.
Sneha Aggarwal, Priyanka Bansal, Yuwei Wang, Spiro Jorga, Gabrielle Macgregor, Urs Rohner, Thomas Bannan, Matthew Salter, Paul Zieger, Claudia Mohr, and Felipe Lopez-Hilfiker
EGUsphere, https://doi.org/10.5194/egusphere-2025-696, https://doi.org/10.5194/egusphere-2025-696, 2025
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Chemical ionization mass spectrometers used for trace gas analysis can be operated at various conditions, complicating quantitative comparisons. We evaluate sensitivity dependence on relatively few key instrument parameters and show that when these are held constant, consistent performance is achieved. We show that the maximum sensitivity of a given flow tube reactor across various reagent ion chemistries is a constant, which aids in the quantification of compounds lacking analytical standards.
Michael F. Link, Megan S. Claflin, Christina E. Cecelski, Ayomide A. Akande, Delaney Kilgour, Paul A. Heine, Matthew Coggon, Chelsea E. Stockwell, Andrew Jensen, Jie Yu, Han N. Huynh, Jenna C. Ditto, Carsten Warneke, William Dresser, Keighan Gemmell, Spiro Jorga, Rileigh L. Robertson, Joost de Gouw, Timothy Bertram, Jonathan P. D. Abbatt, Nadine Borduas-Dedekind, and Dustin Poppendieck
Atmos. Meas. Tech., 18, 1013–1038, https://doi.org/10.5194/amt-18-1013-2025, https://doi.org/10.5194/amt-18-1013-2025, 2025
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Proton-transfer-reaction mass spectrometry (PTR-MS) is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. An analytical challenge for PTR-MS measurements is the formation of unintended measurement interferences, product ion distributions (PIDs), that may appear in the data as VOCs of interest. We developed a method for quantifying PID formation and use interlaboratory comparison data to put quantitative constraints on PID formation.
John W. Halfacre, Lewis Marden, Marvin D. Shaw, Lucy J. Carpenter, Emily Matthews, Thomas J. Bannan, Hugh Coe, Scott C. Herndon, Joseph R. Roscioli, Christoph Dyroff, Tara I. Yacovitch, Patrick R. Veres, Michael A. Robinson, Steven S. Brown, and Pete M. Edwards
EGUsphere, https://doi.org/10.5194/egusphere-2025-831, https://doi.org/10.5194/egusphere-2025-831, 2025
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Nitryl chloride (ClNO2) is a reservoir of chlorine atoms and nitrogen oxides, both of which play important roles in atmospheric chemistry. However, all ambient ClNO2 observations so far have been made by a single technique, mass spectrometry, which needs complex calibrations. Here, we present a laser-based method that detects ClNO2 (TD-TILDAS) without the need for complicated calibrations. The results show excellent agreement between these two methods from both laboratory and ambient samples.
Michał Bucha, Dominika Lewicka-Szczebak, and Piotr Wójtowicz
Atmos. Meas. Tech., 18, 897–908, https://doi.org/10.5194/amt-18-897-2025, https://doi.org/10.5194/amt-18-897-2025, 2025
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We present a method for the determination of greenhouse gases (CH4, CO2, N2O) using a chromatographic system with a barrier ion discharge detector (BID) and a Carboxen 1010 capillary column. The system omits the need for an electron capture detector (ECD) containing radiogenic components for N2O analysis and a flame ionisation detector (FID) with a methaniser for CO2 samples. This simplification reduces analytical costs, facilitates instrument maintenance and improves measurement robustness.
Adil Shah, Olivier Laurent, Pramod Kumar, Grégoire Broquet, Loïc Loigerot, Timothé Depelchin, Mathis Lozano, Camille Yver Kwok, Carole Philippon, Clément Romand, Elisa Allegrini, Matthieu Trombetti, and Philippe Ciais
EGUsphere, https://doi.org/10.5194/egusphere-2024-4089, https://doi.org/10.5194/egusphere-2024-4089, 2025
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Acetylene mole fraction measurements from the Picarro G2203 were characterised. Abnormal sensor behaviour was observed in wet conditions. A dry linear calibration was derived, although this was invalid below 1.2 ppb due to unstable measurements. The instrument was used to measure acetylene as a methane tracer at a landfill site. Fluxes were derived from fourteen downwind transects using both raw and calibrated acetylene mole fraction, with raw measurements resulting in 8 % flux underestimation.
Giulia Zazzeri, Lukas Wacker, Negar Haghipour, Philip Gautschi, Thomas Laemmel, Sönke Szidat, and Heather Graven
Atmos. Meas. Tech., 18, 319–325, https://doi.org/10.5194/amt-18-319-2025, https://doi.org/10.5194/amt-18-319-2025, 2025
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Radiocarbon (14C) is an optimal tracer of methane (CH4) emissions, as 14C measurements enable distinguishing between fossil methane and biogenic methane. However, these measurements are particularly challenging, mainly due to technical difficulties in the sampling procedure. We made the sample extraction much simpler and time efficient, providing a new technology that can be used by any research group, with the goal of expanding 14C measurements for an improved understanding of methane sources.
Clément Piel, Daniele Romanini, Morgane Farradèche, Justin Chaillot, Clémence Paul, Nicolas Bienville, Thomas Lauwers, Joana Sauze, Kévin Jaulin, Frédéric Prié, and Amaëlle Landais
Atmos. Meas. Tech., 17, 6647–6658, https://doi.org/10.5194/amt-17-6647-2024, https://doi.org/10.5194/amt-17-6647-2024, 2024
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This paper introduces a new optical gas analyzer based on an optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) technique enabling high-temporal-resolution and high-precision measurements of oxygen isotopes (δ18O) and dioxygen (O2) concentration of atmospheric O2 (respectively 0.06 ‰ and 0.002 % over 10 min integration). The results underscore the good agreement with isotope ratio mass spectrometry measurements and the ability of the instrument to monitor biological processes.
Alexandra L. Meyer and Lisa R. Welp
Atmos. Meas. Tech., 17, 6193–6212, https://doi.org/10.5194/amt-17-6193-2024, https://doi.org/10.5194/amt-17-6193-2024, 2024
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Water molecules stick to air intake tubing wall surfaces, smoothing measurements of fast isotopic variability in the atmosphere. We tested this stickiness and saw small differences in isotopic signal speed between materials, tubing inner dimensions, and isotopic switch direction, although no consistent temperature effects. Researchers can confidently compare measurements across observation systems using different commonly used tubing materials and plan for optimal inlet designs of new systems.
Matthieu Riva, Veronika Pospisilova, Carla Frege, Sebastien Perrier, Priyanka Bansal, Spiro Jorga, Patrick Sturm, Joel A. Thornton, Urs Rohner, and Felipe Lopez-Hilfiker
Atmos. Meas. Tech., 17, 5887–5901, https://doi.org/10.5194/amt-17-5887-2024, https://doi.org/10.5194/amt-17-5887-2024, 2024
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We present a newly designed reduced-pressure chemical ionization reactor for detection of gas-phase organic and inorganic species. The system operates through the combined use of vacuum ultraviolet ionization and photosensitizers to generate numerous adduct ionization schemes. As a result, it offers the ability to simultaneously measure a wide variety of organic and inorganic species in terms of compound volatility and functionality, while being largely independent of changes in sample humidity.
Dandan Li, Dongyu Wang, Lucia Caudillo, Wiebke Scholz, Mingyi Wang, Sophie Tomaz, Guillaume Marie, Mihnea Surdu, Elias Eccli, Xianda Gong, Loic Gonzalez-Carracedo, Manuel Granzin, Joschka Pfeifer, Birte Rörup, Benjamin Schulze, Pekka Rantala, Sébastien Perrier, Armin Hansel, Joachim Curtius, Jasper Kirkby, Neil M. Donahue, Christian George, Imad El-Haddad, and Matthieu Riva
Atmos. Meas. Tech., 17, 5413–5428, https://doi.org/10.5194/amt-17-5413-2024, https://doi.org/10.5194/amt-17-5413-2024, 2024
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Due to the analytical challenges of measuring organic vapors, it remains challenging to identify and quantify organic molecules present in the atmosphere. Here, we explore the performance of the Orbitrap chemical ionization mass spectrometer (CI-Orbitrap) using ammonium ion chemistry. This study shows that ammonium-ion-based chemistry associated with the high mass resolution of the Orbitrap mass analyzer can measure almost all inclusive compounds.
Hideki Nara, Takuya Saito, Taku Umezawa, and Yasunori Tohjima
Atmos. Meas. Tech., 17, 5187–5200, https://doi.org/10.5194/amt-17-5187-2024, https://doi.org/10.5194/amt-17-5187-2024, 2024
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We have developed a high-accuracy dynamic dilution system for generating reference gas mixtures containing carbonyl sulfide (COS). Although COS at ambient levels generally has poor storage stability, our approach involves the dilution of a gas mixture containing micromole-per-mole levels of COS, the stability of which was validated for more than 1 decade. The developed system has excellent dilution performance and will facilitate accurate instrumental calibration for atmospheric COS observation.
Mengdi Song, Shuyu He, Xin Li, Ying Liu, Shengrong Lou, Sihua Lu, Limin Zeng, and Yuanhang Zhang
Atmos. Meas. Tech., 17, 5113–5127, https://doi.org/10.5194/amt-17-5113-2024, https://doi.org/10.5194/amt-17-5113-2024, 2024
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We introduce detailed and improved quantitation and semi-quantitation methods of iodide-adduct time-of-flight chemical ionization mass spectrometry (I-CIMS) to measure toluene oxidation intermediates. We assess the experimental sensitivity of various functional group species and their binding energy with iodide ions in I-CIMS. A novel classification approach was introduced to significantly enhance the accuracy of semi-quantitative methods (improving R2 values from 0.52 to beyond 0.88).
Finja Löher, Esther Borrás, Amalia Muñoz, and Anke Christine Nölscher
Atmos. Meas. Tech., 17, 4553–4579, https://doi.org/10.5194/amt-17-4553-2024, https://doi.org/10.5194/amt-17-4553-2024, 2024
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We constructed and characterized a new indoor Teflon atmospheric simulation chamber. We evaluated wall losses, photolysis rates, and secondary reactions of multifunctional photooxidation products in the chamber. To measure these products on-line, we combined chromatographic and mass spectrometric analyses to obtain both isomeric information and a high temporal resolution. For method validation, we studied the formation yields of the main ring-retaining products of toluene.
Hans Christian Steen-Larsen and Daniele Zannoni
Atmos. Meas. Tech., 17, 4391–4409, https://doi.org/10.5194/amt-17-4391-2024, https://doi.org/10.5194/amt-17-4391-2024, 2024
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The water vapor generation module is completely scalable, allowing autonomous calibrations to use N standards and providing integration times only restricted by sample availability. We document improved reproducibility in 17O-excess liquid measurements. This module makes spectroscopy measurements comparable to mass spectrometry. We document that the vapor generation module can be used to analyze instrument performance and for vapor isotope calibration during field campaign measurements.
Malavika Sivan, Thomas Röckmann, Carina van der Veen, and Maria Elena Popa
Atmos. Meas. Tech., 17, 2687–2705, https://doi.org/10.5194/amt-17-2687-2024, https://doi.org/10.5194/amt-17-2687-2024, 2024
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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, as well as the calibration, and we give an overview of the samples measured so far.
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
Atmos. Meas. Tech., 17, 2415–2427, https://doi.org/10.5194/amt-17-2415-2024, https://doi.org/10.5194/amt-17-2415-2024, 2024
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The responses of protonated, adduct, and fragmented ions of 21 volatile organic compounds (VOCs) were investigated with varying instrument settings and relative humidity (RH) in a Vocus proton-transfer-reaction mass spectrometer (PTR-MS). The protonated ions of most VOCs studied show < 15 % variation 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.
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.
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.
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.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
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We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
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.
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