Articles | Volume 7, issue 7
https://doi.org/10.5194/amt-7-1999-2014
© 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-7-1999-2014
© Author(s) 2014. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| 
04 Jul 2014
Research article |
| 04 Jul 2014
Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
J. Schmitt
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
R. Schneider
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
H. Fischer
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
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Anders Svensson, Dorthe Dahl-Jensen, Jørgen Peder Steffensen, Thomas Blunier, Sune O. Rasmussen, Bo M. Vinther, Paul Vallelonga, Emilie Capron, Vasileios Gkinis, Eliza Cook, Helle Astrid Kjær, Raimund Muscheler, Sepp Kipfstuhl, Frank Wilhelms, Thomas F. Stocker, Hubertus Fischer, Florian Adolphi, Tobias Erhardt, Michael Sigl, Amaelle Landais, Frédéric Parrenin, Christo Buizert, Joseph R. McConnell, Mirko Severi, Robert Mulvaney, and Matthias Bigler
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We identify signatures of large bipolar volcanic eruptions in Greenland and Antarctic ice cores during the last glacial period, which allows for a precise temporal alignment of the ice cores. Thereby the exact timing of unexplained, abrupt climatic changes occurring during the last glacial period can be determined in a global context. The study thus provides a step towards a full understanding of elements of the climate system that may also play an important role in the future.
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.
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
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Johannes Sutter, Hubertus Fischer, Klaus Grosfeld, Nanna B. Karlsson, Thomas Kleiner, Brice Van Liefferinge, and Olaf Eisen
The Cryosphere, 13, 2023–2041, https://doi.org/10.5194/tc-13-2023-2019, https://doi.org/10.5194/tc-13-2023-2019, 2019
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40 000 to a 100 000 year periodicity. Our findings also suggest that ice as old as 1.5 Myr still exists at the bottom of the East Antarctic Ice Sheet despite the major climate reorganisations in the past.
Tobias Erhardt, Emilie Capron, Sune Olander Rasmussen, Simon Schüpbach, Matthias Bigler, Florian Adolphi, and Hubertus Fischer
Clim. Past, 15, 811–825, https://doi.org/10.5194/cp-15-811-2019, https://doi.org/10.5194/cp-15-811-2019, 2019
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The cause of the rapid warming events documented in proxy records across the Northern Hemisphere during the last glacial has been a long-standing puzzle in paleo-climate research. Here, we use high-resolution ice-core data from to cores in Greenland to investigate the progression during the onset of these events on multi-annual timescales to test their plausible triggers. We show that atmospheric circulation changes preceded the warming in Greenland and the collapse of the sea ice by a decade.
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
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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.
Florian Adolphi, Christopher Bronk Ramsey, Tobias Erhardt, R. Lawrence Edwards, Hai Cheng, Chris S. M. Turney, Alan Cooper, Anders Svensson, Sune O. Rasmussen, Hubertus Fischer, and Raimund Muscheler
Clim. Past, 14, 1755–1781, https://doi.org/10.5194/cp-14-1755-2018, https://doi.org/10.5194/cp-14-1755-2018, 2018
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The last glacial period was characterized by a number of rapid climate changes seen, for example, as abrupt warmings in Greenland and changes in monsoon rainfall intensity. However, due to chronological uncertainties it is challenging to know how tightly coupled these changes were. Here we exploit cosmogenic signals caused by changes in the Sun and Earth magnetic fields to link different climate archives and improve our understanding of the dynamics of abrupt climate change.
Masa Kageyama, Pascale Braconnot, Sandy P. Harrison, Alan M. Haywood, Johann H. Jungclaus, Bette L. Otto-Bliesner, Jean-Yves Peterschmitt, Ayako Abe-Ouchi, Samuel Albani, Patrick J. Bartlein, Chris Brierley, Michel Crucifix, Aisling Dolan, Laura Fernandez-Donado, Hubertus Fischer, Peter O. Hopcroft, Ruza F. Ivanovic, Fabrice Lambert, Daniel J. Lunt, Natalie M. Mahowald, W. Richard Peltier, Steven J. Phipps, Didier M. Roche, Gavin A. Schmidt, Lev Tarasov, Paul J. Valdes, Qiong Zhang, and Tianjun Zhou
Geosci. Model Dev., 11, 1033–1057, https://doi.org/10.5194/gmd-11-1033-2018, https://doi.org/10.5194/gmd-11-1033-2018, 2018
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The Paleoclimate Modelling Intercomparison Project (PMIP) takes advantage of the existence of past climate states radically different from the recent past to test climate models used for climate projections and to better understand these climates. This paper describes the PMIP contribution to CMIP6 (Coupled Model Intercomparison Project, 6th phase) and possible analyses based on PMIP results, as well as on other CMIP6 projects.
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.
Pascal Bohleber, Tobias Erhardt, Nicole Spaulding, Helene Hoffmann, Hubertus Fischer, and Paul Mayewski
Clim. Past, 14, 21–37, https://doi.org/10.5194/cp-14-21-2018, https://doi.org/10.5194/cp-14-21-2018, 2018
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The Colle Gnifetti (CG) glacier is the only drilling site in the European Alps offering ice core records back to some 1000 years. We aim to fully exploit these unique long-term records by establishing a reliable long-term age scale and an improved ice core proxy interpretation for reconstructing temperature. Our findings reveal a site-specific temperature-related signal in the trends of the mineral dust proxy Ca2+ that may supplement other proxy evidence over the last millennium.
Bette L. Otto-Bliesner, Pascale Braconnot, Sandy P. Harrison, Daniel J. Lunt, Ayako Abe-Ouchi, Samuel Albani, Patrick J. Bartlein, Emilie Capron, Anders E. Carlson, Andrea Dutton, Hubertus Fischer, Heiko Goelzer, Aline Govin, Alan Haywood, Fortunat Joos, Allegra N. LeGrande, William H. Lipscomb, Gerrit Lohmann, Natalie Mahowald, Christoph Nehrbass-Ahles, Francesco S. R. Pausata, Jean-Yves Peterschmitt, Steven J. Phipps, Hans Renssen, and Qiong Zhang
Geosci. Model Dev., 10, 3979–4003, https://doi.org/10.5194/gmd-10-3979-2017, https://doi.org/10.5194/gmd-10-3979-2017, 2017
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The PMIP4 and CMIP6 mid-Holocene and Last Interglacial simulations provide an opportunity to examine the impact of two different changes in insolation forcing on climate at times when other forcings were relatively similar to present. This will allow exploration of the role of feedbacks relevant to future projections. Evaluating these simulations using paleoenvironmental data will provide direct out-of-sample tests of the reliability of state-of-the-art models to simulate climate changes.
Frédéric Parrenin, Marie G. P. Cavitte, Donald D. Blankenship, Jérôme Chappellaz, Hubertus Fischer, Olivier Gagliardini, Valérie Masson-Delmotte, Olivier Passalacqua, Catherine Ritz, Jason Roberts, Martin J. Siegert, and Duncan A. Young
The Cryosphere, 11, 2427–2437, https://doi.org/10.5194/tc-11-2427-2017, https://doi.org/10.5194/tc-11-2427-2017, 2017
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The oldest dated deep ice core drilled in Antarctica has been retrieved at EPICA Dome C (EDC), reaching ~ 800 000 years. Obtaining an older palaeoclimatic record from Antarctica is one of the greatest challenges of the ice core community. Here, we estimate the age of basal ice in the Dome C area. We find that old ice (> 1.5 Myr) likely exists in two regions a few tens of kilometres away from EDC:
Little Dome C Patchand
North Patch.
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
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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.
Michel Legrand, Joseph McConnell, Hubertus Fischer, Eric W. Wolff, Susanne Preunkert, Monica Arienzo, Nathan Chellman, Daiana Leuenberger, Olivia Maselli, Philip Place, Michael Sigl, Simon Schüpbach, and Mike Flannigan
Clim. Past, 12, 2033–2059, https://doi.org/10.5194/cp-12-2033-2016, https://doi.org/10.5194/cp-12-2033-2016, 2016
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Here, we review previous attempts made to reconstruct past forest fire using chemical signals recorded in Greenland ice. We showed that the Greenland ice records of ammonium, found to be a good fire proxy, consistently indicate changing fire activity in Canada in response to past climatic conditions that occurred since the last 15 000 years, including the Little Ice Age and the last large climatic transition.
Bette L. Otto-Bliesner, Pascale Braconnot, Sandy P. Harrison, Daniel J. Lunt, Ayako Abe-Ouchi, Samuel Albani, Patrick J. Bartlein, Emilie Capron, Anders E. Carlson, Andrea Dutton, Hubertus Fischer, Heiko Goelzer, Aline Govin, Alan Haywood, Fortunat Joos, Allegra N. Legrande, William H. Lipscomb, Gerrit Lohmann, Natalie Mahowald, Christoph Nehrbass-Ahles, Jean-Yves Peterschmidt, Francesco S.-R. Pausata, Steven Phipps, and Hans Renssen
Clim. Past Discuss., https://doi.org/10.5194/cp-2016-106, https://doi.org/10.5194/cp-2016-106, 2016
Preprint retracted
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
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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.
Amaelle Landais, Valérie Masson-Delmotte, Emilie Capron, Petra M. Langebroek, Pepijn Bakker, Emma J. Stone, Niklaus Merz, Christoph C. Raible, Hubertus Fischer, Anaïs Orsi, Frédéric Prié, Bo Vinther, and Dorthe Dahl-Jensen
Clim. Past, 12, 1933–1948, https://doi.org/10.5194/cp-12-1933-2016, https://doi.org/10.5194/cp-12-1933-2016, 2016
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The last lnterglacial (LIG; 116 000 to 129 000 years before present) surface temperature at the upstream Greenland NEEM deposition site is estimated to be warmer by +7 to +11 °C compared to the preindustrial period. We show that under such warm temperatures, melting of snow probably led to a significant surface melting. There is a paradox between the extent of the Greenland ice sheet during the LIG and the strong warming during this period that models cannot solve.
Thomas Röckmann, Simon Eyer, Carina van der Veen, Maria E. Popa, Béla Tuzson, Guillaume Monteil, Sander Houweling, Eliza Harris, Dominik Brunner, Hubertus Fischer, Giulia Zazzeri, David Lowry, Euan G. Nisbet, Willi A. Brand, Jaroslav M. Necki, Lukas Emmenegger, and Joachim Mohn
Atmos. Chem. Phys., 16, 10469–10487, https://doi.org/10.5194/acp-16-10469-2016, https://doi.org/10.5194/acp-16-10469-2016, 2016
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A dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months, yielding a combined dataset with more than 2500 measurements of both δ13C and δD.
S. Eyer, B. Tuzson, M. E. Popa, C. van der Veen, T. Röckmann, M. Rothe, W. A. Brand, R. Fisher, D. Lowry, E. G. Nisbet, M. S. Brennwald, E. Harris, C. Zellweger, L. Emmenegger, H. Fischer, and J. Mohn
Atmos. Meas. Tech., 9, 263–280, https://doi.org/10.5194/amt-9-263-2016, https://doi.org/10.5194/amt-9-263-2016, 2016
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We present a newly developed field-deployable, autonomous platform simultaneously measuring the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy.
The instrument consists of a compact quantum cascade laser absorption spectrometer (QCLAS) coupled to a preconcentration unit, called TRace gas EXtractor (TREX).
The performance of this new in situ technique was investigated during a 2-week measurement campaign and compared to other techniques.
G. van der Wel, H. Fischer, H. Oerter, H. Meyer, and H. A. J. Meijer
The Cryosphere, 9, 1601–1616, https://doi.org/10.5194/tc-9-1601-2015, https://doi.org/10.5194/tc-9-1601-2015, 2015
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The diffusion of the stable water isotope signal during firnification of snow is a temperature-dependent process. Therefore, past local temperatures can be derived from the differential diffusion length. In this paper we develop a new method for determining this quantity and compare it with the existing method. Both methods are applied to a large number of synthetic data sets to assess the precision and accuracy of the reconstruction and to a section of the Antarctic EDML ice core record.
J.-L. Tison, M. de Angelis, G. Littot, E. Wolff, H. Fischer, M. Hansson, M. Bigler, R. Udisti, A. Wegner, J. Jouzel, B. Stenni, S. Johnsen, V. Masson-Delmotte, A. Landais, V. Lipenkov, L. Loulergue, J.-M. Barnola, J.-R. Petit, B. Delmonte, G. Dreyfus, D. Dahl-Jensen, G. Durand, B. Bereiter, A. Schilt, R. Spahni, K. Pol, R. Lorrain, R. Souchez, and D. Samyn
The Cryosphere, 9, 1633–1648, https://doi.org/10.5194/tc-9-1633-2015, https://doi.org/10.5194/tc-9-1633-2015, 2015
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The oldest paleoclimatic information is buried within the lowermost layers of deep ice cores. It is therefore essential to judge how deep these records remain unaltered. We study the bottom 60 meters of the EPICA Dome C ice core from central Antarctica to show that the paleoclimatic signal is only affected at the small scale (decimeters) in terms of some of the global ice properties. However our data suggest that the time scale has been considerably distorted by mechanical stretching.
J. Schmitt, B. Seth, M. Bock, and H. Fischer
Atmos. Meas. Tech., 7, 2645–2665, https://doi.org/10.5194/amt-7-2645-2014, https://doi.org/10.5194/amt-7-2645-2014, 2014
M. Baumgartner, P. Kindler, O. Eicher, G. Floch, A. Schilt, J. Schwander, R. Spahni, E. Capron, J. Chappellaz, M. Leuenberger, H. Fischer, and T. F. Stocker
Clim. Past, 10, 903–920, https://doi.org/10.5194/cp-10-903-2014, https://doi.org/10.5194/cp-10-903-2014, 2014
S. Schüpbach, U. Federer, P. R. Kaufmann, S. Albani, C. Barbante, T. F. Stocker, and H. Fischer
Clim. Past, 9, 2789–2807, https://doi.org/10.5194/cp-9-2789-2013, https://doi.org/10.5194/cp-9-2789-2013, 2013
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
H. Fischer, J. Severinghaus, E. Brook, E. Wolff, M. Albert, O. Alemany, R. Arthern, C. Bentley, D. Blankenship, J. Chappellaz, T. Creyts, D. Dahl-Jensen, M. Dinn, M. Frezzotti, S. Fujita, H. Gallee, R. Hindmarsh, D. Hudspeth, G. Jugie, K. Kawamura, V. Lipenkov, H. Miller, R. Mulvaney, F. Parrenin, F. Pattyn, C. Ritz, J. Schwander, D. Steinhage, T. van Ommen, and F. Wilhelms
Clim. Past, 9, 2489–2505, https://doi.org/10.5194/cp-9-2489-2013, https://doi.org/10.5194/cp-9-2489-2013, 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
S. Zürcher, R. Spahni, F. Joos, M. Steinacher, and H. Fischer
Biogeosciences, 10, 1963–1981, https://doi.org/10.5194/bg-10-1963-2013, https://doi.org/10.5194/bg-10-1963-2013, 2013
B. Bereiter, T. F. Stocker, and H. Fischer
Atmos. Meas. Tech., 6, 251–262, https://doi.org/10.5194/amt-6-251-2013, https://doi.org/10.5194/amt-6-251-2013, 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
Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase
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)
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.
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.
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.
Cited articles
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Bergamaschi, P., Bräunlich, M., Marik, T., and Brenninkmeijer, C. A. M.: Measurements of the carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: Seasonal cycles and synoptic-scale variations, J. Geophys. Res., 105, 14531–14546, https://doi.org/10.1029/1999JD901176, 2000.
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Brass, M. and Röckmann, T.: Continuous-flow isotope ratio mass spectrometry method for carbon and hydrogen isotope measurements on atmospheric methane, Atmos. Meas. Tech., 3, 1707–1721, https://doi.org/10.5194/amt-3-1707-2010, 2010.
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