Articles | Volume 8, issue 10
https://doi.org/10.5194/amt-8-4475-2015
© Author(s) 2015. 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-8-4475-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| 
23 Oct 2015
Research article |
| 23 Oct 2015
An analytical system for the measurement of stable hydrogen isotopes in ambient volatile organic compounds
T. Meisehen
CORRESPONDING AUTHOR
Institute for Atmospheric and Environmental Research, University of Wuppertal, Wuppertal, Germany
F. Bühler
Institute for Atmospheric and Environmental Research, University of Wuppertal, Wuppertal, Germany
R. Koppmann
Institute for Atmospheric and Environmental Research, University of Wuppertal, Wuppertal, Germany
M. Krebsbach
Institute for Atmospheric and Environmental Research, University of Wuppertal, Wuppertal, Germany
Related authors
No articles found.
Dirk Offermann, Christoph Kalicinsky, Ralf Koppmann, and Johannes Wintel
Atmos. Chem. Phys., 23, 3267–3278, https://doi.org/10.5194/acp-23-3267-2023, https://doi.org/10.5194/acp-23-3267-2023, 2023
Short summary
Short summary
Atmospheric oscillations with periods between 5 and more than 200 years are believed to be self-excited (internal) in the atmosphere, i.e. non-anthropogenic. They are found at all altitudes up to 110 km and at four very different geographical locations (75° N, 70° E; 75° N, 280° E; 50° N, 7° E; 50° S, 7° E). Therefore, they hint at a global-oscillation mode. Their amplitudes are on the order of present-day climate trends, and it is therefore difficult to disentangle them.
M. Dolores Andrés Hernández, Andreas Hilboll, Helmut Ziereis, Eric Förster, Ovid O. Krüger, Katharina Kaiser, Johannes Schneider, Francesca Barnaba, Mihalis Vrekoussis, Jörg Schmidt, Heidi Huntrieser, Anne-Marlene Blechschmidt, Midhun George, Vladyslav Nenakhov, Theresa Harlass, Bruna A. Holanda, Jennifer Wolf, Lisa Eirenschmalz, Marc Krebsbach, Mira L. Pöhlker, Anna B. Kalisz Hedegaard, Linlu Mei, Klaus Pfeilsticker, Yangzhuoran Liu, Ralf Koppmann, Hans Schlager, Birger Bohn, Ulrich Schumann, Andreas Richter, Benjamin Schreiner, Daniel Sauer, Robert Baumann, Mariano Mertens, Patrick Jöckel, Markus Kilian, Greta Stratmann, Christopher Pöhlker, Monica Campanelli, Marco Pandolfi, Michael Sicard, José L. Gómez-Amo, Manuel Pujadas, Katja Bigge, Flora Kluge, Anja Schwarz, Nikos Daskalakis, David Walter, Andreas Zahn, Ulrich Pöschl, Harald Bönisch, Stephan Borrmann, Ulrich Platt, and John P. Burrows
Atmos. Chem. Phys., 22, 5877–5924, https://doi.org/10.5194/acp-22-5877-2022, https://doi.org/10.5194/acp-22-5877-2022, 2022
Short summary
Short summary
EMeRGe provides a unique set of in situ and remote sensing airborne measurements of trace gases and aerosol particles along selected flight routes in the lower troposphere over Europe. The interpretation uses also complementary collocated ground-based and satellite measurements. The collected data help to improve the current understanding of the complex spatial distribution of trace gases and aerosol particles resulting from mixing, transport, and transformation of pollution plumes over Europe.
Dirk Offermann, Christoph Kalicinsky, Ralf Koppmann, and Johannes Wintel
Atmos. Chem. Phys., 21, 1593–1611, https://doi.org/10.5194/acp-21-1593-2021, https://doi.org/10.5194/acp-21-1593-2021, 2021
Short summary
Short summary
Atmospheric oscillations with periods of up to several 100 years exist at altitudes up to 110 km. They are also seen in computer models (GCMs) of the atmospheric. They are often attributed to external influences from the sun, from the oceans, or from atmospheric constituents. This is difficult to verify as the atmosphere cannot be manipulated in an experiment. However, a GCM can be changed arbitrarily. Doing so, we find that long-period oscillations may be excited internally in the atmosphere.
Christoph Kalicinsky, Robert Reisch, Peter Knieling, and Ralf Koppmann
Atmos. Meas. Tech., 13, 467–477, https://doi.org/10.5194/amt-13-467-2020, https://doi.org/10.5194/amt-13-467-2020, 2020
Short summary
Short summary
This study presents an approach to analyse unequally spaced time series of OH* temperatures with respect to time-varying periodic fluctuations. The approach is based on the classical Lomb–Scargle periodogram and, additionally, the idea of a moving window is used. Furthermore, a fast and easy way to analyse the significance of the results is presented. The general performance of the approach is tested with artificially generated time series and results for real observations are presented.
Qiuyu Chen, Martin Kaufmann, Yajun Zhu, Jilin Liu, Ralf Koppmann, and Martin Riese
Atmos. Chem. Phys., 19, 13891–13910, https://doi.org/10.5194/acp-19-13891-2019, https://doi.org/10.5194/acp-19-13891-2019, 2019
Short summary
Short summary
Atomic oxygen is one of the most important trace species in the mesopause region. A common technique to derive it from satellite measurements is to measure airglow emissions involved in the photochemistry of oxygen. In this work, hydroxyl nightglow measured by the GOMOS instrument on Envisat is used to derive a 10-year dataset of atomic oxygen in the middle and upper atmosphere. Annual and semiannual oscillations are observed in the data. The new data are consistent with various other datasets.
Friedhelm Olschewski, Christian Monte, Albert Adibekyan, Max Reiniger, Berndt Gutschwager, Joerg Hollandt, and Ralf Koppmann
Atmos. Meas. Tech., 11, 4757–4762, https://doi.org/10.5194/amt-11-4757-2018, https://doi.org/10.5194/amt-11-4757-2018, 2018
Short summary
Short summary
The Institute for Atmospheric and Environmental Research at the University of Wuppertal designed and manufactured a prototype of the large-area blackbody for in-flight calibration of an infrared interferometer deployed onboard a long-duration balloon for stratospheric research.
Martin Kaufmann, Friedhelm Olschewski, Klaus Mantel, Brian Solheim, Gordon Shepherd, Michael Deiml, Jilin Liu, Rui Song, Qiuyu Chen, Oliver Wroblowski, Daikang Wei, Yajun Zhu, Friedrich Wagner, Florian Loosen, Denis Froehlich, Tom Neubert, Heinz Rongen, Peter Knieling, Panos Toumpas, Jinjun Shan, Geshi Tang, Ralf Koppmann, and Martin Riese
Atmos. Meas. Tech., 11, 3861–3870, https://doi.org/10.5194/amt-11-3861-2018, https://doi.org/10.5194/amt-11-3861-2018, 2018
Short summary
Short summary
The concept and optical layout of a limb sounder using a spatial heterodyne spectrometer is presented. The instrument fits onto a nano-satellite platform, such as a CubeSat. It is designed for the derivation of temperatures in the mesosphere and lower thermosphere. The design parameters of the optics and a radiometric assessment of the instrument as well as the main characterization and calibration steps are discussed.
Christoph Kalicinsky, Peter Knieling, Ralf Koppmann, Dirk Offermann, Wolfgang Steinbrecht, and Johannes Wintel
Atmos. Chem. Phys., 16, 15033–15047, https://doi.org/10.5194/acp-16-15033-2016, https://doi.org/10.5194/acp-16-15033-2016, 2016
Short summary
Short summary
The analysis of temperatures in the mesopause region between 1988 to 2015 shows, besides the known correlation with the 11-year solar activity cycle, a trend reversal in 2008 that can be described by a long-term oscillation. Understanding such long periodic oscillations in the atmosphere is of prime importance for climate modelling and predictions of future trends.
Hannah Sonderfeld, Iain R. White, Iain C. A. Goodall, James R. Hopkins, Alastair C. Lewis, Ralf Koppmann, and Paul S. Monks
Atmos. Chem. Phys., 16, 6303–6318, https://doi.org/10.5194/acp-16-6303-2016, https://doi.org/10.5194/acp-16-6303-2016, 2016
Short summary
Short summary
Unknown sinks of OH and oxidation processes in the atmosphere have been attributed to what has been termed "missing" OH reactivity. Often overlooked are the differences in timescales over which the diverse measurement techniques operate. The effect of the sampling time and thus the contribution of unmeasured VOC variability on OH reactivity is investigated.
B. Bonn, E. Bourtsoukidis, T. S. Sun, H. Bingemer, L. Rondo, U. Javed, J. Li, R. Axinte, X. Li, T. Brauers, H. Sonderfeld, R. Koppmann, A. Sogachev, S. Jacobi, and D. V. Spracklen
Atmos. Chem. Phys., 14, 10823–10843, https://doi.org/10.5194/acp-14-10823-2014, https://doi.org/10.5194/acp-14-10823-2014, 2014
J. Wintel, E. Hösen, R. Koppmann, M. Krebsbach, A. Hofzumahaus, and F. Rohrer
Atmos. Chem. Phys., 13, 11059–11071, https://doi.org/10.5194/acp-13-11059-2013, https://doi.org/10.5194/acp-13-11059-2013, 2013
F. Olschewski, A. Ebersoldt, F. Friedl-Vallon, B. Gutschwager, J. Hollandt, A. Kleinert, C. Monte, C. Piesch, P. Preusse, C. Rolf, P. Steffens, and R. Koppmann
Atmos. Meas. Tech., 6, 3067–3082, https://doi.org/10.5194/amt-6-3067-2013, https://doi.org/10.5194/amt-6-3067-2013, 2013
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
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)
Evaluation of a reduced pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species
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
Ammonium CI-Orbitrap: a tool for characterizing the reactivity of oxygenated organic molecules
Characterizing the automatic radon flux transfer standard system Autoflux: laboratory calibration and field experiments
Water vapor stable isotope memory effects of common tubing materials
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
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Matthieu Riva, Veronika Pospisilova, Carla Frege, Sebastien Perrier, Priyanka Bansal, Spiro Jorga, Patrick Sturm, Joel Thornton, Urs Rohner, and Felipe Lopez-Hilfiker
EGUsphere, https://doi.org/10.5194/egusphere-2024-945, https://doi.org/10.5194/egusphere-2024-945, 2024
Short summary
Short summary
We present a newly designed reduced-pressure chemical ionization reactor for the detection of gas phase organic and inorganic species. The system operates through the combined use of VUV 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 the sample humidity.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
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. Discuss., https://doi.org/10.5194/amt-2023-149, https://doi.org/10.5194/amt-2023-149, 2023
Revised manuscript accepted for AMT
Short summary
Short summary
Due to various analytical challenges in measuring organic vapors, it remains challenging to identify and quantify organic molecules present in the atmosphere, Here, we explore the performance of the chemical ionization Orbitrap mass spectrometer (CI-Orbitrap) using ammonium ion chemistry. This study shows that ammonium ion-based chemistry associated with the high mass resolving power of the Orbitrap mass analyzer can measure almost all-inclusive compounds.
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
Short summary
Short summary
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.
Alexandra L. Meyer and Lisa R. Welp
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2023-56, https://doi.org/10.5194/amt-2023-56, 2023
Revised manuscript accepted for AMT
Short summary
Short summary
Water molecules stick to air intake tubing wall surfaces and exchange with ambient vapor. This can slow signal change measurements. We tested whether material type affects this stickiness. Less stickiness would lead to an instrument seeing signal changes faster. We unexpectedly saw no difference in signal speed between material types. Water vapor stable isotope users can more confidently use plastic tubing and compare measurements across observation systems that used different tubing materials.
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
Short summary
Short summary
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
Short summary
Short summary
We present a new method to extract the gases from ice cores and measure their greenhouse gas composition. The ice is sublimated continuously with a near-infrared laser, releasing the gases, which are then analyzed on a laser absorption spectrometer. The main advantage over previous efforts is a low effective resolution of 1–2 cm. This capability is crucial for the analysis of highly thinned ice, as expected from ongoing drilling efforts to extend ice core history further back in time.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
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.
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
Short summary
Short summary
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
Short summary
Short summary
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.
Cited articles
Archbold, M. E., Redeker, K. R., Davis, S., Elliot, T., and Kalin, R. M.: A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations, Rapid Commun. Mass Sp., 19, 337–342, https://doi.org/10.1002/rcm.1791, 2005.
Bi, X., Sheng, G., Liu, X., Li, C., and Fu, J.: Molecular and carbon and hydrogen isotopic composition of n-alkanes in plant leaf waxes, Org. Geochem., 36, 1405–1417, https://doi.org/10.1016/j.orggeochem.2005.06.001, 2005.
Brand, W. A.: Mass spectrometer hardware for analyzing stable isotope ratios, in: Handbook of Stable Isotope Analytical Techniques, edited by: Groot, P. A. D., Elsevier, Amsterdam, chap. 38, 835–856, https://doi.org/10.1016/B978-044451114-0/50040-5, 2004.
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.
Brenninkmeijer, C. A. M., Janssen, C., Kaiser, J., Röckmann, T., Rhee, T. S., and Assonov, S. S.: Isotope effects in the chemistry of atmospheric trace compounds, Chem. Rev., 103, 5125–5162, https://doi.org/10.1021/cr020644k, 2003.
Burgoyne, T. W. and Hayes, J. M.: Quantitative production of H2 by pyrolysis of gas chromatographic effluents, Anal. Chem., 70, 5136–5141, https://doi.org/10.1021/ac980248v, 1998.
De Biévre, P., Gallet, M., Holden, N. E., and Barnes, I. L.: Isotopic abundances and atomic weights of the elements, J. Phys. Chem. Ref. Data, 13, 809–891, https://doi.org/10.1063/1.555720, 1984.
De Bortoli, M., Knöppel, H., Pecchio, E., Schauenburg, H., and Vissers, H.: Comparison of tenax and carbotrap for VOC sampling in indoor air, Indoor Air, 2, 216–224, https://doi.org/10.1111/j.1600-0668.1992.00004.x, 1992.
Duan, Y., Wu, B., Xu, L., He, J., and Sun, T.: Characterisation of n-alkanes and their hydrogen isotopic composition in sediments from Lake Qinghai, China, Org. Geochem., 42, 720–726, https://doi.org/10.1016/j.orggeochem.2011.06.009, 2011.
Gensch, I., Kiendler-Scharr, A., and Rudolph, J.: Isotope ratio studies of atmospheric organic compounds: principles, methods, applications and potential, Int. J. Mass Spectrom., 365–366, 206–221, https://doi.org/10.1016/j.ijms.2014.02.004, 2014.
Goldstein, A. H. and Shaw, S. L.: Isotopes of volatile organic compounds: an emerging approach for studying atmospheric budgets and chemistry, Chem. Rev., 103, 5025–5048, https://doi.org/10.1021/cr0206566, 2003.
Greule, M., Huber, S. G., and Keppler, F.: Stable hydrogen-isotope analysis of methyl chloride emitted from heated halophytic plants, Atmos. Environ., 62, 584–592, https://doi.org/10.1016/j.atmosenv.2012.09.007, 2012
Helmig, D. and Vierling, L.: Water adsorption capacity of the solid adsorbents Tenax TA, Tenax GR, Carbotrap, Carbotrap C, Carbosieve SIII, and Carboxen 569 and water management techniques for the atmospheric sampling of volatile organic trace gases, Anal. Chem., 67, 4380–4386, https://doi.org/10.1021/ac00119a029, 1995.
Hembeck, L.: Aufbau und Charakterisierung eines dynamischen Gasmischsystems zur Kalibrierung eines Gaschromatograph-Isotopenverhältnis-Massenspektrometers (GC-IRMS), Bachelor Thesis, University of Wuppertal, Wuppertal, Germany, 49 pp., 2008.
Iannone, R., Anderson, R., Vogel, A., Rudolph, J., Eby, P., and Whiticar, M.: Laboratory studies of the hydrogen Kinetic Isotope Effects (KIES) of the reaction of non-methane hydrocarbons with the OH radical in the gas phase, J. Atmos. Chem., 47, 191–208, https://doi.org/10.1023/B:JOCH.0000021035.49613.f7, 2004.
Iannone, R., Anderson, R., Vogel, A., Eby, P., Whiticar, M., and Rudolph, J.: The hydrogen kinetic isotope effects of the reactions of n-alkanes with chlorine atoms in the gas phase, J. Atmos. Chem., 50, 121–138, https://doi.org/10.1007/s10874-005-2365-1, 2005.
Iannone, R., Koppmann, R., and Rudolph, J.: A technique for atmospheric measurements of stable carbon isotope ratios of isoprene, methacrolein, and methyl vinyl ketone, J. Atmos. Chem., 58, 181–202, https://doi.org/10.1007/s10874-007-9087-5, 2007.
Kikuchi, N. and Kawashima, H.: Hydrogen isotope analysis of benzene and toluene emitted from vehicles, Atmos. Environ., 72, 151–158, https://doi.org/10.1016/j.atmosenv.2013.02.029, 2013.
Kornexl, B. E., Gehre, M., Höfling, R., and Werner, R. A.: On-line δ18O measurement of organic and inorganic substances, Rapid Commun. Mass Sp., 13, 1685–1693, https://doi.org/10.1002/(SICI)1097-0231(19990830)13:16<1685::AID-RCM699>3.0.CO;2-9, 1999.
Liu, J., Geng, A., and Xiong, Y.: The application of stable carbon and hydrogen isotopic compositions of individual n-alkanes to Paleozoic oil/source rock correlation enigmas in the Huanghua depression, China, J. Petrol. Sci. Eng., 54, 70–78, https://doi.org/10.1016/j.petrol.2006.07.003, 2006.
Redeker, K. R., Davis, S., and Kalin, R. M.: Isotope values of atmospheric halocarbons and hydrocarbons from Irish urban, rural, and marine locations, J. Geophys. Res.-Atmos., 112, D16307, https://doi.org/10.1029/2006JD007784, 2007.
Rice, A. L. and Quay, P.: Isotopic composition of formaldehyde in urban air, Environ. Sci. Technol., 43, 8752–8758, https://doi.org/10.1021/es9010916, 2009.
Rudolph, J.: Gas chromatography-isotope ratio mass spectrometry, in: Volatile Organic Compounds in the Atmosphere, edited by: Koppmann, R., chap. 10, Blackwell Publishing Ltd, Oxford, UK, 388–466, ISBN:978-1-4051-3115-5, 2007.
Rudolph, J., Müller, K., and Koppmann, R.: Sampling of organic volatiles in the atmosphere at moderate and low pollution levels, Anal. Chim. Acta, 236, 197–211, https://doi.org/10.1016/S0003-2670(00)83313-9, 1990.
Rudolph, J., Lowe, D. C., Martin, R. J., and Clarkson, T. S.: A novel method for compound specific determination of δ13C in volatile organic compounds at ppt levels in ambient air, Geophys. Res. Lett., 24, 659–662, https://doi.org/10.1029/97GL00537, 1997.
Rudolph, J., Czuba, E., Norman, A., Huang, L., and Ernst, D.: Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere, Atmos. Environ., 36, 1173–1181, https://doi.org/10.1016/S1352-2310(01)00537-4, 2002.
Rudolph, J., Anderson, R., Czapiewski, K., Czuba, E., Ernst, D., Gillespie, T., Huang, L., Rigby, C., and Thompson, A.: The stable carbon isotope ratio of biogenic emissions of isoprene and the potential use of stable isotope ratio measurements to study photochemical processing of isoprene in the atmosphere, J. Atmos. Chem., 44, 39–55, https://doi.org/10.1023/A:1022116304550, 2003.
Saito, T., Tsunogai, U., Kawamura, K., Nakatsuka, T., and Yoshida, N.: Stable carbon isotopic compositions of light hydrocarbons over the western North Pacific and implication for their photochemical ages, J. Geophys. Res.-Atmos., 107, ACH 2–1–ACH 2–9, https://doi.org/10.1029/2000JD000127, 2002.
Saito, T., Kawamura, K., Tsunogai, U., Chen, T.-Y., Matsueda, H., Nakatsuka, T., Gamo, T., Uematsu, M., and Huebert, B. J.: Photochemical histories of nonmethane hydrocarbons inferred from their stable carbon isotope ratio measurements over east Asia, J. Geophys. Res.-Atmos., 114, D11303, https://doi.org/10.1029/2008JD011388, 2009.
Sessions, A. L., Burgoyne, T. W., and Hayes, J. M.: Determination of the H3 factor in hydrogen isotope ratio monitoring mass spectrometry, Anal. Chem., 73, 200–207, https://doi.org/10.1021/ac000488m, 2001a.
Sessions, A. L., Burgoyne, T. W., and Hayes, J. M.: Correction of H3+ contributions in hydrogen isotope ratio monitoring mass spectrometry, Anal. Chem., 73, 192–199, https://doi.org/10.1021/ac000489e, 2001b.
Thompson, A. E.: Stable Carbon Isotope Ratios of Nonmethane Hydrocarbons and Halocarbons in the Atmosphere, PhD thesis, York University Toronto, Toronto, Ontario, 299 pp., 2003.
Tsunogai, U., Yoshida, N., and Gamo, T.: Carbon isotopic compositions of C2-C5 hydrocarbons and methyl chloride in urban, coastal, and maritime atmospheres over the western North Pacific, J. Geophys. Res.-Atmos., 104, 16033–16039, https://doi.org/10.1029/1999JD900217, 1999.
von Eckstaedt, C. V., Grice, K., Ioppolo-Armanios, M., Chidlow, G., and Jones, M.: δD and δ13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry, J. Chromatogr. A, 1218, 6511–6517, https://doi.org/10.1016/j.chroma.2011.06.098, 2011a.
von Eckstaedt, C. V., Grice, K., Ioppolo-Armanios, M., and Jones, M.: δ13C and δD of volatile organic compounds in an alumina industry stack emission, Atmos. Environ., 45, 5477–5483, https://doi.org/10.1016/j.atmosenv.2011.06.064, 2011b.
Wintel, J., Hösen, E., Koppmann, R., Krebsbach, M., Hofzumahaus, A., and Rohrer, F.: Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere, Atmos. Chem. Phys., 13, 11059–11071, https://doi.org/10.5194/acp-13-11059-2013, 2013.
Xiong, Y., Geng, A., Pan, C., Liu, D., and Peng, P.: Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks, Appl. Geochem., 20, 455–464, https://doi.org/10.1016/j.apgeochem.2004.09.014, 2005.
Yamamoto, S. and Kawamura, K.: Compound-specific stable carbon and hydrogen isotopic compositions of n-alkanes in urban atmospheric aerosols from Tokyo, Geochem. J., 44, 419–430, 2010.
Yeh, H.-W. and Epstein, S.: Hydrogen and carbon isotopes of petroleum and related organic matter, Geochim. Cosmochim. Ac., 45, 753–762, https://doi.org/10.1016/0016-7037(81)90046-6, 1981.
