Articles | Volume 12, issue 12
https://doi.org/10.5194/amt-12-6803-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-12-6803-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
20 Dec 2019
Research article |
| 20 Dec 2019
| 20 Dec 2019
High-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniques
Tesfaye A. Berhanu
CORRESPONDING AUTHOR
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
Picarro Inc., 3105 Patrick Henry Drive, Santa Clara, CA, USA
John Hoffnagle
Picarro Inc., 3105 Patrick Henry Drive, Santa Clara, CA, USA
Chris Rella
Picarro Inc., 3105 Patrick Henry Drive, Santa Clara, CA, USA
David Kimhak
Picarro Inc., 3105 Patrick Henry Drive, Santa Clara, CA, USA
Peter Nyfeler
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
Markus Leuenberger
Climate and Environmental Physics, Physics Institute and Oeschger Centre for Climate Change Research, University of Bern, Bern, Switzerland
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In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
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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.
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Greenhouse gases emissions are contributing to global warming and it is essential to better understand where they originate from and how they are transported. In this study we analyze greenhouse gas observations at a Swiss tall tower where measurements are taken more than 200 m above ground and investigate their origin by looking at the condition of the atmosphere at the time of the observations. We find that most pollution at this site is caused from emissions transported from further away.
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Atmos. Chem. Phys., 22, 13243–13268, https://doi.org/10.5194/acp-22-13243-2022, https://doi.org/10.5194/acp-22-13243-2022, 2022
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Stable isotopes in tree-ring cellulose are tools for climatic reconstructions, but interpretation is challenging due to nonclimate trends. We analyzed the tree-age trends in tree-ring isotopes of deciduous larch and evergreen cembran pine. Samples covering the whole Holocene were collected at the tree line in the Alps. For cambial ages over 100 years, we prove the absence of age trends in δD, δ18O, and δ13C for both species. For lower cambial ages, trends differ for each isotope and species.
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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.
Michael Döring and Markus Christian Leuenberger
Clim. Past Discuss., https://doi.org/10.5194/cp-2019-132, https://doi.org/10.5194/cp-2019-132, 2019
Manuscript not accepted for further review
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We analyse Holocen temperatures reconstructed from gas-stable-isotope species measured on ancient air extracted from a Greenland ice core. Also, we compare two state of the art firn-models which are needed for the inversion of the gas-isotope data to paleo-temperature and provide detailed uncertainty estimations for the reconstructed temperature estimates. Finally, we compare our reconstructed temperatures to two recent reconstructions based on the same gas-isotope data as used here.
Friedemann Reum, Christoph Gerbig, Jost V. Lavric, Chris W. Rella, and Mathias Göckede
Atmos. Meas. Tech., 12, 1013–1027, https://doi.org/10.5194/amt-12-1013-2019, https://doi.org/10.5194/amt-12-1013-2019, 2019
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Atmospheric CO2 and CH4 mole fractions are often measured using greenhouse gas analyzers manufactured by Picarro, Inc. We report biases in these measurements that are related to pressure changes in the optical cavity of the analyzers and occur mainly at low water vapor mole fractions. We provide a method to correct the biases, which contributes to keeping the overall accuracy of CO2 and CH4 measurements with Picarro analyzers within the WMO interlaboratory compatibility goals.
Annette Filges, Christoph Gerbig, Chris W. Rella, John Hoffnagle, Herman Smit, Martina Krämer, Nicole Spelten, Christian Rolf, Zoltán Bozóki, Bernhard Buchholz, and Volker Ebert
Atmos. Meas. Tech., 11, 5279–5297, https://doi.org/10.5194/amt-11-5279-2018, https://doi.org/10.5194/amt-11-5279-2018, 2018
Michael Döring and Markus C. Leuenberger
Clim. Past, 14, 763–788, https://doi.org/10.5194/cp-14-763-2018, https://doi.org/10.5194/cp-14-763-2018, 2018
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We present a novel approach for ice-core-based temperature reconstructions, which is based on gas-isotope data measured on enclosed air bubbles in ice cores. The processes of air movement and enclosure are highly temperature dependent due to heat diffusion in and densification of the snow and ice. Our method inverts a model, which describes these processes, to desired temperature histories. This paper examines the performance of our novel approach on different synthetic isotope-data scenarios.
Ye Yuan, Ludwig Ries, Hannes Petermeier, Martin Steinbacher, Angel J. Gómez-Peláez, Markus C. Leuenberger, Marcus Schumacher, Thomas Trickl, Cedric Couret, Frank Meinhardt, and Annette Menzel
Atmos. Meas. Tech., 11, 1501–1514, https://doi.org/10.5194/amt-11-1501-2018, https://doi.org/10.5194/amt-11-1501-2018, 2018
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This paper presents a novel statistical method, ADVS, for baseline selection of representative CO2 data at elevated mountain measurement stations. It provides insights on how data processing techniques are critical for measurements and data analyses. Compared with other statistical methods, our method appears to be a good option as a generalized approach with improved comparability, which is important for research on measurement site characteristics and comparisons between stations.
Natasha L. Miles, Douglas K. Martins, Scott J. Richardson, Christopher W. Rella, Caleb Arata, Thomas Lauvaux, Kenneth J. Davis, Zachary R. Barkley, Kathryn McKain, and Colm Sweeney
Atmos. Meas. Tech., 11, 1273–1295, https://doi.org/10.5194/amt-11-1273-2018, https://doi.org/10.5194/amt-11-1273-2018, 2018
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Analyzers measuring methane and methane isotopic ratio were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. The methane isotopic ratio is helpful for differentiating emissions from natural gas activities from other sources (e.g., landfills). We describe the analyzer calibration. The signals observed in the study region were generally small, but the instrumental performance demonstrated here could be used in regions with stronger enhancements.
Malin M. Ziehmer, Kurt Nicolussi, Christian Schlüchter, and Markus Leuenberger
Biogeosciences, 15, 1047–1064, https://doi.org/10.5194/bg-15-1047-2018, https://doi.org/10.5194/bg-15-1047-2018, 2018
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Cellulose content (CC (%)) series from two high-Alpine species, Larix decidua Mill. (European larch, LADE) and Pinus cembra L. (Swiss stone pine, PICE) are investigated in modern wood samples and Holocene wood remains from the Early and mid-Holocene. Trends in modern and Holocene time series as well as climate–cellulose relationships for modern trees in the Alps show high potential for CC (%) to be established as novel supplementary proxy in dendroclimatology.
Tesfaye A. Berhanu, Sönke Szidat, Dominik Brunner, Ece Satar, Rüdiger Schanda, Peter Nyfeler, Michael Battaglia, Martin Steinbacher, Samuel Hammer, and Markus Leuenberger
Atmos. Chem. Phys., 17, 10753–10766, https://doi.org/10.5194/acp-17-10753-2017, https://doi.org/10.5194/acp-17-10753-2017, 2017
Short summary
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Fossil fuel CO2 is the major contributor of anthropogenic CO2 in the atmosphere, and accurate quantification is essential to better understand the carbon cycle. Such accurate quantification can be conducted based on radiocarbon measurements. In this study, we present radiocarbon measurements from a tall tower site in Switzerland. From these measurements, we have observed seasonally varying fossil fuel CO2 contributions and a biospheric CO2 component that varies diurnally and seasonally.
Jennifer E. Johnson and Chris W. Rella
Atmos. Meas. Tech., 10, 3073–3091, https://doi.org/10.5194/amt-10-3073-2017, https://doi.org/10.5194/amt-10-3073-2017, 2017
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Cavity ring-down spectrometers (CRDS) can make accurate measurements of trace gases when the inert gas background is constant but are prone to errors when the background is variable. Here, we report that in one CRDS analyzer (L2120-i, Picarro), these errors result from broadening, narrowing, and shifting of the target absorption lines as well as neighboring lines. New spectral acquisition and analysis strategies are needed to make CRDS measurements robust to variable backgrounds.
Friedemann Reum, Christoph Gerbig, Jost V. Lavric, Chris W. Rella, and Mathias Göckede
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2017-174, https://doi.org/10.5194/amt-2017-174, 2017
Revised manuscript not accepted
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High-accuracy observations of atmospheric CO2 and CH4 levels, which are vital for quantifying sources and sinks of these gases, are often obtained using Picarro greenhouse gas analyzers. These require a correction for the effects of water vapor. We report biases in CO2 and CH4 levels obtained using the traditional water correction for Picarro analyzers related to pressure changes in the optical cavity and mainly affecting measurements at low water vapor mole fractions, and how to correct them.
Kathrin M. Keller, Sebastian Lienert, Anil Bozbiyik, Thomas F. Stocker, Olga V. Churakova (Sidorova), David C. Frank, Stefan Klesse, Charles D. Koven, Markus Leuenberger, William J. Riley, Matthias Saurer, Rolf Siegwolf, Rosemarie B. Weigt, and Fortunat Joos
Biogeosciences, 14, 2641–2673, https://doi.org/10.5194/bg-14-2641-2017, https://doi.org/10.5194/bg-14-2641-2017, 2017
Michael F. Schibig, Emmanuel Mahieu, Stephan Henne, Bernard Lejeune, and Markus C. Leuenberger
Atmos. Chem. Phys., 16, 9935–9949, https://doi.org/10.5194/acp-16-9935-2016, https://doi.org/10.5194/acp-16-9935-2016, 2016
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Two CO2 time series measured at the High Alpine Research Station Jungfraujoch, Switzerland (3580 m a.s.l.), in the period from 2005 to 2013 were compared. One data set was measured in situ whereas the other data set was measured in the column above Jungfraujoch. The trends of the column integrated and the in situ data set are in good agreement, the amplitude of the in situ data set is ca. two times the amplitude of the column integrated data set, because it is closer to the sources and sinks.
Tesfaye Ayalneh Berhanu, Ece Satar, Rudiger Schanda, Peter Nyfeler, Hanspeter Moret, Dominik Brunner, Brian Oney, and Markus Leuenberger
Atmos. Meas. Tech., 9, 2603–2614, https://doi.org/10.5194/amt-9-2603-2016, https://doi.org/10.5194/amt-9-2603-2016, 2016
Short summary
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In this manuscript, we have presented Co, CO2 and CH4 measurement data from an old radio tower tower (217.5 m) at Beromunster, Switzerland. From about 2 years of continuous CO, CO2 and CH4 measurement at five different heights, we have determined a long-term reproducibility of 2.79 ppb, 0.05 ppm and 0.29 ppb for CO, CO2 and CH4, respectively, compliant with the GAW requirements. We have also observed seasonal and diurnal variation of these species.
Ece Satar, Tesfaye A. Berhanu, Dominik Brunner, Stephan Henne, and Markus Leuenberger
Biogeosciences, 13, 2623–2635, https://doi.org/10.5194/bg-13-2623-2016, https://doi.org/10.5194/bg-13-2623-2016, 2016
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Beromünster tall tower is the flagship of the densely placed Swiss greenhouse gas observation network (CarboCount CH). In this research article we report the first 2 years of the continuous greenhouse gas measurements using cavity ring down spectroscopy analyzer from this tall tower. We have adopted a purely observation based, multi-species and multi-level approach to characterize the site with respect to sources and sinks of natural and anthropogenic origin at diurnal to annual timescales.
Lucie Bazin, Amaelle Landais, Emilie Capron, Valérie Masson-Delmotte, Catherine Ritz, Ghislain Picard, Jean Jouzel, Marie Dumont, Markus Leuenberger, and Frédéric Prié
Clim. Past, 12, 729–748, https://doi.org/10.5194/cp-12-729-2016, https://doi.org/10.5194/cp-12-729-2016, 2016
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We present new measurements of δO2⁄N2 and δ18Oatm performed on well-conserved ice from EDC covering MIS5 and between 380 and 800 ka. The combination of the observation of a 100 ka periodicity in the new δO2⁄N2 record with a MIS5 multi-site multi-proxy study has revealed a potential influence of local climatic parameters on δO2⁄N2. Moreover, we propose that the varying delay between d18Oatm and precession for the last 800 ka is affected by the occurrence of ice sheet discharge events.
Stephan Henne, Dominik Brunner, Brian Oney, Markus Leuenberger, Werner Eugster, Ines Bamberger, Frank Meinhardt, Martin Steinbacher, and Lukas Emmenegger
Atmos. Chem. Phys., 16, 3683–3710, https://doi.org/10.5194/acp-16-3683-2016, https://doi.org/10.5194/acp-16-3683-2016, 2016
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Greenhouse gas emissions can be assessed by "top-down" methods that combine atmospheric observations, a transport model and a mathematical optimisation framework. Here, we apply such a top-down method to the methane emissions of Switzerland, utilising observations from the recently installed CarboCount-CH network. Our Swiss total emissions largely agree with those of the national "bottom-up" inventory, whereas regional differences suggest lower than reported emissions from manure handling.
M. C. Leuenberger, M. F. Schibig, and P. Nyfeler
Atmos. Meas. Tech., 8, 5289–5299, https://doi.org/10.5194/amt-8-5289-2015, https://doi.org/10.5194/amt-8-5289-2015, 2015
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Adsorption/desorption effects of trace gases in gas cylinders were investigated. Our measurements indicate a rather strong effect on steel cylinders for CO2 that becomes easily visible through enhanced concentrations for low (<20 bars) gas pressure. Much smaller effects are observed for CO and CH4. Significantly smaller effects are measured for all gas species investigated on aluminium cylinders. Careful selection of gas cylinders for high-precision calibration purposes is recommended.
T. Kobashi, T. Ikeda-Fukazawa, M. Suwa, J. Schwander, T. Kameda, J. Lundin, A. Hori, H. Motoyama, M. Döring, and M. Leuenberger
Atmos. Chem. Phys., 15, 13895–13914, https://doi.org/10.5194/acp-15-13895-2015, https://doi.org/10.5194/acp-15-13895-2015, 2015
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We find that argon/nitrogen ratios of trapped air in the GISP2 ice core on “gas ages” are significantly negatively correlated with accumulation rate changes over the past 6000 years. Lines of evidence indicate that changes in overloading pressure at bubble closeoff depths induced the gas fractionation in closed bubbles. Further understanding of the fractionation processes may lead to a new proxy for the past temperature and accumulation rate.
C. W. Rella, J. Hoffnagle, Y. He, and S. Tajima
Atmos. Meas. Tech., 8, 4539–4559, https://doi.org/10.5194/amt-8-4539-2015, https://doi.org/10.5194/amt-8-4539-2015, 2015
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We describe an innovative instrument based on cavity ring-down spectroscopy that analyzes the stable isotopes of methane in the ambient atmosphere. This instrument was used to study atmospheric emissions from oil and gas extraction activities in the Uintah Basin in Utah. These measurements suggest that 85 ± 7% of the total emissions in the basin are from natural gas production. The easy field deployment of this instrument can enable similar regional attribution studies across the world.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
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In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
B. Oney, S. Henne, N. Gruber, M. Leuenberger, I. Bamberger, W. Eugster, and D. Brunner
Atmos. Chem. Phys., 15, 11147–11164, https://doi.org/10.5194/acp-15-11147-2015, https://doi.org/10.5194/acp-15-11147-2015, 2015
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We present a detailed analysis of a new greenhouse gas measurement network
in the Swiss Plateau, situated between the Jura mountains and the Alps. We
find the network's measurements to be information rich and suitable
for studying surface carbon fluxes of the study region. However, we are
limited by the high-resolution (2km) atmospheric transport model's ability
to simulate meteorology at the individual measurement stations, especially
at those situated in rough terrain.
C. Yver Kwok, O. Laurent, A. Guemri, C. Philippon, B. Wastine, C. W. Rella, C. Vuillemin, F. Truong, M. Delmotte, V. Kazan, M. Darding, B. Lebègue, C. Kaiser, I. Xueref-Rémy, and M. Ramonet
Atmos. Meas. Tech., 8, 3867–3892, https://doi.org/10.5194/amt-8-3867-2015, https://doi.org/10.5194/amt-8-3867-2015, 2015
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We present the results of tests of CRDS instruments in the laboratory (47 instruments) and in the field (15 instruments). We demonstrate that, thanks to rigorous testing, newer models generally perform better than older models, especially in terms of reproducibility between instruments. In the field, we see the importance of individual diagnostics during the installation phase, and we show the value of calibration and target gases that assess the quality of the data.
C. E. Yver Kwok, D. Müller, C. Caldow, B. Lebègue, J. G. Mønster, C. W. Rella, C. Scheutz, M. Schmidt, M. Ramonet, T. Warneke, G. Broquet, and P. Ciais
Atmos. Meas. Tech., 8, 2853–2867, https://doi.org/10.5194/amt-8-2853-2015, https://doi.org/10.5194/amt-8-2853-2015, 2015
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This study presents two methods for estimating methane emissions from a waste water treatment plant (WWTP) along with results from a measurement campaign at a WWTP in Valence, France. We show that the tracer release method is suitable to quantify facility emissions, while the chamber measurements, provide insights into individual processes. We confirm that the open basins are not a major source of CH4 on the WWTP but that the pretreatment and sludge treatment are the main emitters.
M. S. Studer, R. T. W. Siegwolf, M. Leuenberger, and S. Abiven
Biogeosciences, 12, 1865–1879, https://doi.org/10.5194/bg-12-1865-2015, https://doi.org/10.5194/bg-12-1865-2015, 2015
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We present a new technique to label organic matter (OM) at its place of formation by the application of 13C, 18O and 2H through the gaseous phase. The label diffused into leaves was incorporated into assimilates and was detected in plant tissues. This technique can be applied in soil sciences, e.g. to trace the decomposition pathways of soil OM inputs, or in plant physiology and palaeoclimatic reconstruction, e.g. to further investigate the origin of the 18O and 2H signal in tree ring cellulose.
M. F. Schibig, M. Steinbacher, B. Buchmann, I. T. van der Laan-Luijkx, S. van der Laan, S. Ranjan, and M. C. Leuenberger
Atmos. Meas. Tech., 8, 57–68, https://doi.org/10.5194/amt-8-57-2015, https://doi.org/10.5194/amt-8-57-2015, 2015
M. C. Leuenberger, M. F. Schibig, and P. Nyfeler
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acpd-14-19293-2014, https://doi.org/10.5194/acpd-14-19293-2014, 2014
Revised manuscript not accepted
S. Affolter, D. Fleitmann, and M. Leuenberger
Clim. Past, 10, 1291–1304, https://doi.org/10.5194/cp-10-1291-2014, https://doi.org/10.5194/cp-10-1291-2014, 2014
I. Mariani, A. Eichler, T. M. Jenk, S. Brönnimann, R. Auchmann, M. C. Leuenberger, and M. Schwikowski
Clim. Past, 10, 1093–1108, https://doi.org/10.5194/cp-10-1093-2014, https://doi.org/10.5194/cp-10-1093-2014, 2014
P. Kindler, M. Guillevic, M. Baumgartner, J. Schwander, A. Landais, and M. Leuenberger
Clim. Past, 10, 887–902, https://doi.org/10.5194/cp-10-887-2014, https://doi.org/10.5194/cp-10-887-2014, 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
Z. Kern, B. Kohán, and M. Leuenberger
Atmos. Chem. Phys., 14, 1897–1907, https://doi.org/10.5194/acp-14-1897-2014, https://doi.org/10.5194/acp-14-1897-2014, 2014
C. E. Yver-Kwok, D. Müller, C. Caldow, B. Lebegue, J. G. Mønster, C. W. Rella, C. Scheutz, M. Schmidt, M. Ramonet, T. Warneke, G. Broquet, and P. Ciais
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amtd-6-9181-2013, https://doi.org/10.5194/amtd-6-9181-2013, 2013
Revised manuscript not accepted
J.-L. Wang, G. Jacobson, C. W. Rella, C.-Y. Chang, I. Liu, W.-T. Liu, C. Chew, C.-F. Ou-Yang, W.-C. Liao, and C.-C. Chang
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amtd-6-7633-2013, https://doi.org/10.5194/amtd-6-7633-2013, 2013
Revised manuscript not accepted
L. Bazin, A. Landais, B. Lemieux-Dudon, H. Toyé Mahamadou Kele, D. Veres, F. Parrenin, P. Martinerie, C. Ritz, E. Capron, V. Lipenkov, M.-F. Loutre, D. Raynaud, B. Vinther, A. Svensson, S. O. Rasmussen, M. Severi, T. Blunier, M. Leuenberger, H. Fischer, V. Masson-Delmotte, J. Chappellaz, and E. Wolff
Clim. Past, 9, 1715–1731, https://doi.org/10.5194/cp-9-1715-2013, https://doi.org/10.5194/cp-9-1715-2013, 2013
I. T. van der Laan-Luijkx, S. van der Laan, C. Uglietti, M. F. Schibig, R. E. M. Neubert, H. A. J. Meijer, W. A. Brand, A. Jordan, J. M. Richter, M. Rothe, and M. C. Leuenberger
Atmos. Meas. Tech., 6, 1805–1815, https://doi.org/10.5194/amt-6-1805-2013, https://doi.org/10.5194/amt-6-1805-2013, 2013
M. Guillevic, L. Bazin, A. Landais, P. Kindler, A. Orsi, V. Masson-Delmotte, T. Blunier, S. L. Buchardt, E. Capron, M. Leuenberger, P. Martinerie, F. Prié, and B. M. Vinther
Clim. Past, 9, 1029–1051, https://doi.org/10.5194/cp-9-1029-2013, https://doi.org/10.5194/cp-9-1029-2013, 2013
E. Capron, A. Landais, D. Buiron, A. Cauquoin, J. Chappellaz, M. Debret, J. Jouzel, M. Leuenberger, P. Martinerie, V. Masson-Delmotte, R. Mulvaney, F. Parrenin, and F. Prié
Clim. Past, 9, 983–999, https://doi.org/10.5194/cp-9-983-2013, https://doi.org/10.5194/cp-9-983-2013, 2013
H. Chen, A. Karion, C. W. Rella, J. Winderlich, C. Gerbig, A. Filges, T. Newberger, C. Sweeney, and P. P. Tans
Atmos. Meas. Tech., 6, 1031–1040, https://doi.org/10.5194/amt-6-1031-2013, https://doi.org/10.5194/amt-6-1031-2013, 2013
C. W. Rella, H. Chen, A. E. Andrews, A. Filges, C. Gerbig, J. Hatakka, A. Karion, N. L. Miles, S. J. Richardson, M. Steinbacher, C. Sweeney, B. Wastine, and C. Zellweger
Atmos. Meas. Tech., 6, 837–860, https://doi.org/10.5194/amt-6-837-2013, https://doi.org/10.5194/amt-6-837-2013, 2013
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
Product ion distributions using H3O+ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability
Simultaneous measurement of greenhouse gases (CH4, CO2 and N2O) using a simplified gas chromatography system
A new portable sampler of atmospheric methane for radiocarbon measurements
Influence of ambient NO and NO2 on the quantification of total peroxy nitrates (∑PNs) and total alkyl nitrates (∑ANs) by thermal dissociation cavity ring-down spectroscopy (TD-CRDS)
High-precision oxygen isotope (δ18O) measurements of atmospheric dioxygen using optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS)
Triple oxygen isotope composition of CO2 in the upper troposphere and stratosphere
Water vapor stable isotope memory effects of common tubing materials
Evaluation of a reduced-pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species
Ammonium CI-Orbitrap: a tool for characterizing the reactivity of oxygenated organic molecules
A high-accuracy dynamic dilution method for generating reference gas mixtures of carbonyl sulfide at sub-nanomole-per-mole levels for long-term atmospheric observation
Optimizing the iodide-adduct chemical ionization mass spectrometry (CIMS) quantitative method for toluene oxidation intermediates: experimental insights into functional-group differences
Characterization of a new Teflon chamber and on-line analysis of isomeric multifunctional photooxidation products
A versatile water vapor generation module for vapor isotope calibration and liquid isotope measurements
Extraction, purification, and clumped isotope analysis of methane (Δ13CDH3 and Δ12CD2H2) from sources and the atmosphere
Response of protonated, adduct, and fragmented ions in Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS)
Absorption of volatile organic compounds (VOCs) by polymer tubing: implications for indoor air and use as a simple gas-phase volatility separation technique
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
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
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.
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.
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.
Laura Wüst, Patrick Dewald, Gunther N. T. E. Türk, Jos Lelieveld, and John N. Crowley
EGUsphere, https://doi.org/10.5194/egusphere-2024-3694, https://doi.org/10.5194/egusphere-2024-3694, 2024
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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 which avoids systematic bias resulting from secondary chemistry in the heated inlets and which can be deployed in regions with strong biogenic emissions.
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.
Getachew Agmuas Adnew, Gerbrand Koren, Neha Mehendale, Sergey Gromov, Maarten Krol, and Thomas Röckmann
EGUsphere, https://doi.org/10.5194/egusphere-2024-3231, https://doi.org/10.5194/egusphere-2024-3231, 2024
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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.
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.
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.
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Short summary
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.
Accurate measurement of variations in atmospheric O2 can provide useful information about...
