Articles | Volume 15, issue 3
https://doi.org/10.5194/amt-15-627-2022
© Author(s) 2022. 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-15-627-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
08 Feb 2022
Research article |
| 08 Feb 2022
| 08 Feb 2022
A source for the continuous generation of pure and quantifiable HONO mixtures
Guillermo Villena
Department of Physical and Theoretical Chemistry, School of Mathematics and Natural Sciences, University of Wuppertal, 42097 Wuppertal, Germany
Jörg Kleffmann
CORRESPONDING AUTHOR
Department of Physical and Theoretical Chemistry, School of Mathematics and Natural Sciences, University of Wuppertal, 42097 Wuppertal, Germany
Related authors
Seán Schmitz, Sherry Towers, Guillermo Villena, Alexandre Caseiro, Robert Wegener, Dieter Klemp, Ines Langer, Fred Meier, and Erika von Schneidemesser
Atmos. Meas. Tech., 14, 7221–7241, https://doi.org/10.5194/amt-14-7221-2021, https://doi.org/10.5194/amt-14-7221-2021, 2021
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The last 2 decades have seen substantial technological advances in the development of low-cost air pollution instruments. This study introduces a seven-step methodology for the field calibration of low-cost sensors with user-friendly guidelines, open-access code, and a discussion of common barriers. Our goal with this work is to push for standardized reporting of methods, make critical data processing steps clear for users, and encourage responsible use in the scientific community and beyond.
Amelia M. H. Bond, Markus M. Frey, Jan Kaiser, Jörg Kleffmann, Anna E. Jones, and Freya A. Squires
Atmos. Chem. Phys., 23, 5533–5550, https://doi.org/10.5194/acp-23-5533-2023, https://doi.org/10.5194/acp-23-5533-2023, 2023
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Atmospheric nitrous acid (HONO) amount fractions measured at Halley Research Station, Antarctica, were found to be low. Vertical fluxes of HONO from the snow were also measured and agree with the estimated HONO production rate from photolysis of snow nitrate. In a simple box model of HONO sources and sinks, there was good agreement between the measured flux and amount fraction. HONO was found to be an important OH radical source at Halley.
Lisa von der Heyden, Walter Wißdorf, Ralf Kurtenbach, and Jörg Kleffmann
Atmos. Meas. Tech., 15, 1983–2000, https://doi.org/10.5194/amt-15-1983-2022, https://doi.org/10.5194/amt-15-1983-2022, 2022
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A relaxed eddy accumulation (REA) system based on the LOPAP technique for the quantification of vertical fluxes of nitrous acid (HONO) was developed and tested in a field campaign. Typical diurnal variations of the HONO fluxes were observed with low, partly negative fluxes during night-time and higher positive fluxes around noon. The highest correlation of the HONO flux was observed with the product of the NO2 photolysis frequency and the NO2 concentration.
Chaoyang Xue, Can Ye, Jörg Kleffmann, Chenglong Zhang, Valéry Catoire, Fengxia Bao, Abdelwahid Mellouki, Likun Xue, Jianmin Chen, Keding Lu, Yong Zhao, Hengde Liu, Zhaoxin Guo, and Yujing Mu
Atmos. Chem. Phys., 22, 3149–3167, https://doi.org/10.5194/acp-22-3149-2022, https://doi.org/10.5194/acp-22-3149-2022, 2022
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Summertime measurements of nitrous acid (HONO) and related parameters were conducted at the foot and the summit of Mt. Tai (1534 m above sea level). We proposed a rapid vertical air mass exchange between the foot and the summit level, which enhances the role of HONO in the oxidizing capacity of the upper boundary layer. Kinetics for aerosol-derived HONO sources were constrained. HONO formation from different paths was quantified and discussed.
Chaoyang Xue, Can Ye, Jörg Kleffmann, Wenjin Zhang, Xiaowei He, Pengfei Liu, Chenglong Zhang, Xiaoxi Zhao, Chengtang Liu, Zhuobiao Ma, Junfeng Liu, Jinhe Wang, Keding Lu, Valéry Catoire, Abdelwahid Mellouki, and Yujing Mu
Atmos. Chem. Phys., 22, 1035–1057, https://doi.org/10.5194/acp-22-1035-2022, https://doi.org/10.5194/acp-22-1035-2022, 2022
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Nitrous acid (HONO) and related parameters were measured at the foot and the summit of Mt. Tai in the summer of 2018. Based on measurements at the foot station, we utilized a box model to explore the roles of different sources in the HONO budget. We also studied radical chemistry in this high-ozone region.
Seán Schmitz, Sherry Towers, Guillermo Villena, Alexandre Caseiro, Robert Wegener, Dieter Klemp, Ines Langer, Fred Meier, and Erika von Schneidemesser
Atmos. Meas. Tech., 14, 7221–7241, https://doi.org/10.5194/amt-14-7221-2021, https://doi.org/10.5194/amt-14-7221-2021, 2021
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The last 2 decades have seen substantial technological advances in the development of low-cost air pollution instruments. This study introduces a seven-step methodology for the field calibration of low-cost sensors with user-friendly guidelines, open-access code, and a discussion of common barriers. Our goal with this work is to push for standardized reporting of methods, make critical data processing steps clear for users, and encourage responsible use in the scientific community and beyond.
Lisa K. Whalley, Daniel Stone, Rachel Dunmore, Jacqueline Hamilton, James R. Hopkins, James D. Lee, Alastair C. Lewis, Paul Williams, Jörg Kleffmann, Sebastian Laufs, Robert Woodward-Massey, and Dwayne E. Heard
Atmos. Chem. Phys., 18, 2547–2571, https://doi.org/10.5194/acp-18-2547-2018, https://doi.org/10.5194/acp-18-2547-2018, 2018
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This paper presents the first radical observations made in London and subsequent model comparisons. This work highlights that there are uncertainties in the degradation mechanism of complex biogenic and diesel-related VOC species under low-NOx conditions and under high-NOx conditions there is a missing source of RO2 radicals. The impact of these model uncertainties on in situ ozone production as a function of NOx is discussed.
Jutta Metzger, Manuela Nied, Ulrich Corsmeier, Jörg Kleffmann, and Christoph Kottmeier
Hydrol. Earth Syst. Sci., 22, 1135–1155, https://doi.org/10.5194/hess-22-1135-2018, https://doi.org/10.5194/hess-22-1135-2018, 2018
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This paper is motivated by the need for more precise evaporation rates from the Dead Sea (DS) and methods to estimate and forecast evaporation. A new approach to measure lake evaporation with a station located at the shoreline, also transferable to other lakes, is introduced. The first directly measured DS evaporation rates are presented as well as applicable methods for evaporation calculation. These results enable us to further close the DS water budget and to facilitate the water management.
Sebastian Laufs, Mathieu Cazaunau, Patrick Stella, Ralf Kurtenbach, Pierre Cellier, Abdelwahid Mellouki, Benjamin Loubet, and Jörg Kleffmann
Atmos. Chem. Phys., 17, 6907–6923, https://doi.org/10.5194/acp-17-6907-2017, https://doi.org/10.5194/acp-17-6907-2017, 2017
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Sources of nitrous acid (HONO), a major precursor of the OH radical, are still under controversial discussion. Since mainly ground surface sources have been proposed, HONO fluxes were measured above an agricultural field. Positive daytime fluxes were observed which showed strong correlation with the product of the NO2 concentration and J(NO2). These results indicate HONO formation by photosensitized heterogeneous conversion of NO2 on soil surfaces as observed in recent laboratory studies.
Ralf Kurtenbach, Kai Vaupel, Jörg Kleffmann, Ulrich Klenk, Eberhard Schmidt, and Peter Wiesen
Atmos. Chem. Phys., 16, 14285–14295, https://doi.org/10.5194/acp-16-14285-2016, https://doi.org/10.5194/acp-16-14285-2016, 2016
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Emissions from inland shipping were studied at the Rhine. Reliable NOx and PM emission indices are prerequisite for improving emission inventories. The NO2 / NOx emission ratio from the present study points to ship engines without exhaust gas aftertreatment as main emitter. The calculated NOx emissions of all motor ship types were found to be above the threshold values of national German guidelines. Accordingly, the implementation of efficient NOx reduction techniques is strongly recommended.
J. D. Lee, L. K. Whalley, D. E. Heard, D. Stone, R. E. Dunmore, J. F. Hamilton, D. E. Young, J. D. Allan, S. Laufs, and J. Kleffmann
Atmos. Chem. Phys., 16, 2747–2764, https://doi.org/10.5194/acp-16-2747-2016, https://doi.org/10.5194/acp-16-2747-2016, 2016
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This paper presents field measurements of HONO and a range of other gas phase and particulate species from an urban background site in London. The measured daytime HONO cannot be reproduced with a simple box model and thus a significant daytime missing source of HONO is present. We show that this missing source could be responsible for 40 % of the OH radical source and 57 % of the OH initiation; hence its potential importance for atmospheric oxidation and ozone production.
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
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Characterizing the automatic radon flux transfer standard system Autoflux: laboratory calibration and field experiments
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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
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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
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Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)
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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.
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
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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
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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.
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
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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
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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.
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
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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
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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.
Merve Polat, Jesper Baldtzer Liisberg, Morten Krogsbøll, Thomas Blunier, and Matthew S. Johnson
Atmos. Meas. Tech., 14, 8041–8067, https://doi.org/10.5194/amt-14-8041-2021, https://doi.org/10.5194/amt-14-8041-2021, 2021
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We have designed a process for removing methane from a gas stream so that nitrous oxide can be measured without interference. These are both key long-lived greenhouse gases frequently studied in relation to ice cores, plants, water treatment and so on. However, many researchers are not aware of the problem of methane interference, and in addition there have not been good methods available for solving the problem. Here we present and evaluate such a method.
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197, https://doi.org/10.5194/amt-14-7187-2021, https://doi.org/10.5194/amt-14-7187-2021, 2021
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A novel simulation chamber, PASSxS (Planetary Atmosphere Simulation System for Spectroscopy), has been developed for absorption measurements with a Fourier transform spectrometer (FTS) and possibly a cavity ring-down (CRD) spectrometer, with a sample temperature ranging from 100 K up to 550 K, while the pressure of the gas can be varied up to 60 bar. These temperature and pressure ranges cover a significant part of the planetary atmospheres in the solar system and possibly extrasolar planets.
Lukas Kohl, Markku Koskinen, Tatu Polvinen, Salla Tenhovirta, Kaisa Rissanen, Marjo Patama, Alessandro Zanetti, and Mari Pihlatie
Atmos. Meas. Tech., 14, 4445–4460, https://doi.org/10.5194/amt-14-4445-2021, https://doi.org/10.5194/amt-14-4445-2021, 2021
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We present ShoTGa-FluMS, a measurement system designed for continuous and automated measurements of trace gas and volatile organic compound (VOC) fluxes from plant shoots. ShoTGa-FluMS uses transparent shoot enclosures equipped with cooling elements, automatically replaces fixated CO2, and removes transpired water from the enclosure, thus solving multiple technical problems that have so far prevented automated plant shoot trace gas flux measurements.
Pharahilda M. Steur, Hubertus A. Scheeren, Dave D. Nelson, J. Barry McManus, and Harro A. J. Meijer
Atmos. Meas. Tech., 14, 4279–4304, https://doi.org/10.5194/amt-14-4279-2021, https://doi.org/10.5194/amt-14-4279-2021, 2021
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For understanding the sources and sinks of atmospheric CO2, measurement of stable isotopes has proven to be highly valuable. We present a new method using laser absorption spectroscopy to simultaneously conduct measurements of three CO2 isotopes, directly on dry-air samples. This new method reduces sample preparation time significantly, compared to the conventional method in which measurements are conducted on pure CO2, and avoids measurement biases introduced by CO2 extraction.
Mingyi Wang, Xu-Cheng He, Henning Finkenzeller, Siddharth Iyer, Dexian Chen, Jiali Shen, Mario Simon, Victoria Hofbauer, Jasper Kirkby, Joachim Curtius, Norbert Maier, Theo Kurtén, Douglas R. Worsnop, Markku Kulmala, Matti Rissanen, Rainer Volkamer, Yee Jun Tham, Neil M. Donahue, and Mikko Sipilä
Atmos. Meas. Tech., 14, 4187–4202, https://doi.org/10.5194/amt-14-4187-2021, https://doi.org/10.5194/amt-14-4187-2021, 2021
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Atmospheric iodine species are often short-lived with low abundance and have thus been challenging to measure. We show that the bromide chemical ionization mass spectrometry, compatible with both the atmospheric pressure and reduced pressure interfaces, can simultaneously detect various gas-phase iodine species. Combining calibration experiments and quantum chemical calculations, we quantify detection sensitivities to HOI, HIO3, I2, and H2SO4, giving detection limits down to < 106 molec. cm-3.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527, https://doi.org/10.5194/amt-14-2515-2021, https://doi.org/10.5194/amt-14-2515-2021, 2021
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The atmospheric helium-to-nitrogen ratio is a promising indicator for circulation changes in the upper atmosphere and fossil fuel burning by humans. We present a very precise analysis method to determine changes in the helium-to-nitrogen ratio of air samples. The method relies on stabilizing the gas flow to a mass spectrometer and continuous removal of reactive gases. These advances enable new insights and monitoring possibilities for anthropogenic and natural processes.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
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We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
Atmos. Meas. Tech., 14, 1817–1831, https://doi.org/10.5194/amt-14-1817-2021, https://doi.org/10.5194/amt-14-1817-2021, 2021
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A gas measurement device was developed to measure trace gases (ppt level) in the air based on an atomic emission detector. It combines a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED). The CryoTrap–GC–AED instrumental setup, limits of detection, and elemental performance are presented and discussed. Two measurement case studies are reported: one in a Finnish boreal forest and the other based on an aircraft campaign.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Bernhard Bereiter, Béla Tuzson, Philipp Scheidegger, André Kupferschmid, Herbert Looser, Lars Mächler, Daniel Baggenstos, Jochen Schmitt, Hubertus Fischer, and Lukas Emmenegger
Atmos. Meas. Tech., 13, 6391–6406, https://doi.org/10.5194/amt-13-6391-2020, https://doi.org/10.5194/amt-13-6391-2020, 2020
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The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
Natalie I. Keehan, Bellamy Brownwood, Andrey Marsavin, Douglas A. Day, and Juliane L. Fry
Atmos. Meas. Tech., 13, 6255–6269, https://doi.org/10.5194/amt-13-6255-2020, https://doi.org/10.5194/amt-13-6255-2020, 2020
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This paper describes a new instrument (a thermal-dissociation–cavity ring-down spectrometer, TD-CRDS) for the measurement of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations affecting the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using a TD-CRDS for ambient and laboratory studies.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991, https://doi.org/10.5194/amt-13-5977-2020, https://doi.org/10.5194/amt-13-5977-2020, 2020
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We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Daniel Marno, Cheryl Ernest, Korbinian Hens, Umar Javed, Thomas Klimach, Monica Martinez, Markus Rudolf, Jos Lelieveld, and Hartwig Harder
Atmos. Meas. Tech., 13, 2711–2731, https://doi.org/10.5194/amt-13-2711-2020, https://doi.org/10.5194/amt-13-2711-2020, 2020
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In this study, a calibration device for OH and HO2 instruments is characterized at pressures of 275 to 1000 mbar, allowing instrument pressure sensitivity to be quantified to an accuracy of 22 % (1σ). Computational fluid dynamic simulations supporting the understanding of interactions between generated HOx and the instrument inlet led to enhanced determination of factors affecting instrument sensitivity.
Joschka Pfeifer, Mario Simon, Martin Heinritzi, Felix Piel, Lena Weitz, Dongyu Wang, Manuel Granzin, Tatjana Müller, Steffen Bräkling, Jasper Kirkby, Joachim Curtius, and Andreas Kürten
Atmos. Meas. Tech., 13, 2501–2522, https://doi.org/10.5194/amt-13-2501-2020, https://doi.org/10.5194/amt-13-2501-2020, 2020
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Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultrasensitive detection of ammonia at single-digit parts per trillion by volume levels. The instrument is further capable of measuring amines and a suite of iodine compounds at sub-parts per trillion by volume levels.
Roberto Sommariva, Louisa J. Kramer, Leigh R. Crilley, Mohammed S. Alam, and William J. Bloss
Atmos. Meas. Tech., 13, 1655–1670, https://doi.org/10.5194/amt-13-1655-2020, https://doi.org/10.5194/amt-13-1655-2020, 2020
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Ozone is a key atmospheric pollutant formed through chemical processing of natural and anthropogenic emissions and removed by reaction with organic compounds emitted by plants. We describe a new instrument – the
Total Ozone Reactivity Systemor TORS – that measures the total loss of ozone in the troposphere. The objective of the TORS instrument is to provide an estimate of the organic compounds emitted by plants which are not measured and thus to improve our understanding of the ozone budget.
John W. Birks, Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Stanley Strunk, Brian Carpenter, and Christine A. Ennis
Atmos. Meas. Tech., 13, 1001–1018, https://doi.org/10.5194/amt-13-1001-2020, https://doi.org/10.5194/amt-13-1001-2020, 2020
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We describe a portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide. Combining this with a previous photolytic ozone (O3) source yields a calibrator that produces known mixing ratios of NO, O3, and nitrogen dioxide (NO2); NO2 is produced by the reaction of NO with O3. This portable
NO2/NO/O3 calibration source requires no external gas cylinders and can be used as a standard to calibrate O3 and NOx air pollution monitors in the field.
Thomas H. Speak, Mark A. Blitz, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 13, 839–852, https://doi.org/10.5194/amt-13-839-2020, https://doi.org/10.5194/amt-13-839-2020, 2020
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OH and HO2 radicals are important trace constituents of the atmosphere that are closely coupled via several types of reaction. This paper describes a new laboratory method to simultaneously determine OH kinetics and HO2 yields from chemical processes. The instrument also provides some time resolution on HO2 detection allowing one to separate HO2 produced from the target reaction from HO2 arising from secondary chemistry. Examples of applications are presented.
Ece Satar, Peter Nyfeler, Bernhard Bereiter, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 101–117, https://doi.org/10.5194/amt-13-101-2020, https://doi.org/10.5194/amt-13-101-2020, 2020
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Good-quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4 and H2O using a commercial and a novel laser spectroscopic analyzer.
Ece Satar, Peter Nyfeler, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 119–130, https://doi.org/10.5194/amt-13-119-2020, https://doi.org/10.5194/amt-13-119-2020, 2020
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To ensure the best preparation and measurement conditions for trace gases, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. In this article, the previously introduced aluminum measurement chamber is used to investigate materials such as glass, aluminum, copper, brass, steel and three different commercially available coatings. Our measurements focus on temperature and pressure dependencies for the species CO2, CO, CH4 and H2O using a CRDS analyzer.
Tanja J. Schuck, Ann-Katrin Blank, Elisa Rittmeier, Jonathan Williams, Carl A. M. Brenninkmeijer, Andreas Engel, and Andreas Zahn
Atmos. Meas. Tech., 13, 73–84, https://doi.org/10.5194/amt-13-73-2020, https://doi.org/10.5194/amt-13-73-2020, 2020
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Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless-steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds were depleted. Individual substances were additionally influenced by high mixing ratios of ozone.
Tesfaye A. Berhanu, John Hoffnagle, Chris Rella, David Kimhak, Peter Nyfeler, and Markus Leuenberger
Atmos. Meas. Tech., 12, 6803–6826, https://doi.org/10.5194/amt-12-6803-2019, https://doi.org/10.5194/amt-12-6803-2019, 2019
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Accurate measurement of variations in atmospheric O2 can provide useful information about atmospheric, biospheric, and oceanic processes, which is a challenge for existing measurement techniques. Here, we introduce a newly built high-precision, stable CRDS analyzer (Picarro G2207) that can measure O2 mixing ratios with a short-term precision of < 1 ppm and only requires calibration every 12 h. Measurements from tower and mountain sites are also presented.
Markus Leiminger, Stefan Feil, Paul Mutschlechner, Arttu Ylisirniö, Daniel Gunsch, Lukas Fischer, Alfons Jordan, Siegfried Schobesberger, Armin Hansel, and Gerhard Steiner
Atmos. Meas. Tech., 12, 5231–5246, https://doi.org/10.5194/amt-12-5231-2019, https://doi.org/10.5194/amt-12-5231-2019, 2019
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We introduce an alternative type of atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) with the main difference of using hexapole instead of quadrupole ion guides. The transfer of cluster ions through the hexapoles was characterised with focus on transmission efficiency, mass range and fragmentation of cluster ions. At the CERN CLOUD experiment we compared the performance of the ioniAPi-TOF with a standard quadrupole APi-TOF under controlled conditions.
Michal Lacko, Nijing Wang, Kristýna Sovová, Pavel Pásztor, and Patrik Španěl
Atmos. Meas. Tech., 12, 4965–4982, https://doi.org/10.5194/amt-12-4965-2019, https://doi.org/10.5194/amt-12-4965-2019, 2019
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The soft chemical ionization analytical technique of selected ion flow tube mass spectrometry, SIFT-MS, was enhanced by a fast GC pre-separation unit to identify individual isomers. Experiments were carried out with two GC columns, MXT-1 and MXT-Volatiles, using two reagent ions, H3O+ and NO+, on monoterpene samples (an artificial mixture and coniferous needles). Analyses of product ion ratios allowed for quantification of multiple monoterpenes in partially separated chromatograms.
Benjamin L. Deming, Demetrios Pagonis, Xiaoxi Liu, Douglas A. Day, Ranajit Talukdar, Jordan E. Krechmer, Joost A. de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 12, 3453–3461, https://doi.org/10.5194/amt-12-3453-2019, https://doi.org/10.5194/amt-12-3453-2019, 2019
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Losses or measurement delays of gas-phase compounds sampled through tubing are important to atmospheric science. Here we characterize 14 tubing materials by measuring the effects on step changes in organic compound concentration. We find that polymeric tubings exhibit absorptive partitioning behaviour while glass and metal tubings show adsorptive partitioning. Adsorptive materials impart complex humidity, concentration, and VOC–VOC interaction dependencies that absorptive tubings do not.
Cited articles
Acker, K., Möller, D., Wieprecht, W., Meixner, F. X., Bohn, B., Gilge,
S., Plass-Dülmer, C., and Berresheim, H.: Strong Daytime Production of
OH from HNO2 at a Rural Mountain Site, Geophys. Res. Lett., 33,
L02809, https://doi.org/10.1029/2005GL024643, 2006.
Alduchov, O. A. and Eskridge, R. E.: Improved Magnus Form Approximation of
Saturation Vapor Pressure, J. Appl. Meteorol., 35, 601–609, https://doi.org/10.1175/1520-0450(1996)035<0601:IMFAOS>2.0.CO;2, 1996.
Bates, R. G.: Determination of pH, Theory and Practice, John Wiley &
Sons, New York, ISBN 0-471-05647-2, 1973.
Becker, K. H., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: Solubility of
Nitrous Acid (HONO) in Sulfuric Acid Solutions, J. Phys. Chem., 100,
14984–14990, https://doi.org/10.1021/jp961140r, 1996.
Braman, R. S. and de la Cantera, M. A.: Sublimation Source for Nitrous Acid
and Other Nitrogen Compounds in Air, Anal. Chem., 58, 1533–1537, https://doi.org/10.1021/ac00298a059, 1986.
Brust, A. S., Becker, K. H., Kleffmann, J., and Wiesen, P.: UV Absorption
Cross Sections of Nitrous Acid, Atmos. Environ., 34, 13–19, https://doi.org/10.1016/S1352-2310(99)00322-2, 2000.
da Silva, G., Kennedy, E. M., and Dlugogorski, B. Z.: Ab Initio Procedure
for Aqueous-Phase pKa Calculation: The Acidity of Nitrous Acid, J. Phys. Chem. A, 110, 11371–11376, doi:10/1021/jp0639243, 2006.
Febo, A., Perrino, C., Gherardi, M., and Sparapani, R.: Evaluation of a
High-Purity and High-Stability Continuous Generation System for Nitrous
Acid, Environ. Sci. Technol., 29, 2390–2395, https://doi.org/10.1021/es00009a035,
1995.
Gingerysty, N. J. and Osthoff, H. D.: A compact, high-purity source of HONO validated by Fourier transform infrared and thermal-dissociation cavity ring-down spectroscopy, Atmos. Meas. Tech., 13, 4159–4167, https://doi.org/10.5194/amt-13-4159-2020, 2020.
Gu, R., Zheng, P., Chen, T., Dong, C., Wang, Y., Liu, Y., Liu, Y., Luo, Y.,
Han, G., Wang, X., Zhou, X., Wang, T., Wang, W., and Xue, L.: Atmospheric
Nitrous Acid (HONO) at a Rural Coastal Site in North China: Seasonal
Variations and Effects of Biomass Burning, Atmos. Environ., 229, 117429,
https://doi.org/10.1016/j.atmosenv.2020.117429, 2020.
Heland, J., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: A New Instrument
to Measure Gaseous Nitrous Acid (HONO) in the Atmosphere, Environ. Sci.
Technol., 35, 3207–3212, https://doi.org/10.1021/es000303t, 2001.
Jurkat, T., Voigt, C., Arnold, F., Schlager, H., Kleffmann, J., Aufmhoff,
H., Schäuble, D., Schaefer, M., and Schumann, U.: Measurements of HONO,
NO, NOy and SO2 in aircraft exhaust plumes at cruise, Geophys.
Res. Lett., 38, L10807, https://doi.org/10.1029/2011GL046884, 2011.
Kirchner, J. J. and Hopkins, P. B.: Nitrous Acid Cross-Links Duplex DNA
Fragments through Deoxyguanosine Residues at the Sequence 5'-CG, J. Am. Chem. Soc., 113, 4681–4682, https://doi.org/10.1021/ja00012a047, 1991.
Kleffmann, J.: Daytime Sources of Nitrous Acid (HONO) in the Atmospheric
Boundary Layer, Chem. Phys. Chem., 8, 1137–1144, https://doi.org/10.1002/cphc.200700016, 2007.
Kleffmann, J. and Wiesen, P.: Technical Note: Quantification of interferences of wet chemical HONO LOPAP measurements under simulated polar conditions, Atmos. Chem. Phys., 8, 6813–6822, https://doi.org/10.5194/acp-8-6813-2008, 2008.
Kleffmann, J., Heland, J., Kurtenbach, R., Lörzer, J., and Wiesen, P.: A
New Instrument (LOPAP) for the Detection of Nitrous Acid (HONO), Environ.
Sci. Pollut. Res., 9 (special issue 4), 48–54, 2002.
Kleffmann, J., Benter, T., and Wiesen, P.: Heterogeneous Reaction of Nitric
Acid with Nitric Oxide on Glass Surfaces under Simulated Atmospheric
Conditions, J. Phys. Chem. A, 108, 5793–5799, https://doi.org/10.1021/jp040184u,
2004.
Kleffmann, J., Gavriloaiei, T., Hofzumahaus, A., Holland, F., Koppmann, R.,
Rupp, L., Schlosser, E., Siese, M., and Wahner, A.: Daytime Formation of
Nitrous Acid: A Major Source of OH Radicals in a Forest, Geophys. Res.
Lett., 32, L05818, https://doi.org/10.1029/2005GL022524, 2005.
Lao, M., Crilley, L. R., Salehpoor, L., Furlani, T. C., Bourgeois, I., Neuman, J. A., Rollins, A. W., Veres, P. R., Washenfelder, R. A., Womack, C. C., Young, C. J., and VandenBoer, T. C.: A portable, robust, stable, and tunable calibration source for gas-phase nitrous acid (HONO), Atmos. Meas. Tech., 13, 5873–5890, https://doi.org/10.5194/amt-13-5873-2020, 2020.
Ma, J., Liu, Y., Han, C., Ma, Q., Liu, C., and He, H.: Review of
heterogeneous photochemical reactions of NOy on aerosol – A possible
daytime source of nitrous acid (HONO) in the atmosphere, J. Environ. Sci.,
25, 326–334, https://doi.org/10.1016/S1001-0742(12)60093-X, 2013.
Michoud, V., Colomb, A., Borbon, A., Miet, K., Beekmann, M., Camredon, M., Aumont, B., Perrier, S., Zapf, P., Siour, G., Ait-Helal, W., Afif, C., Kukui, A., Furger, M., Dupont, J. C., Haeffelin, M., and Doussin, J. F.: Study of the unknown HONO daytime source at a European suburban site during the MEGAPOLI summer and winter field campaigns, Atmos. Chem. Phys., 14, 2805–2822, https://doi.org/10.5194/acp-14-2805-2014, 2014.
Park, J.-Y. and Lee, Y.-N.: Solubility and Decomposition Kinetics of
Nitrous Acid in Aqueous Solution, J. Phys. Chem., 92, 6294–6302, https://doi.org/10.1021/j100333a025, 1988.
Pitts Jr., J. N., Grosjean, D., Van Cauwenberghe, K., Schmid, J. P., and
Fitz, D. R.: Photooxidation of Aliphatic Amines under Simulated Atmospheric
Conditions: Formation of Nitrosamines, Nitramines, Amides, and Photochemical
Oxidant, Environ. Sci. Technol., 12, 946–953, https://doi.org/10.1021/es60144a009,
1978.
Reed, C., Brumby, C. A., Crilley, L. R., Kramer, L. J., Bloss, W. J., Seakins, P. W., Lee, J. D., and Carpenter, L. J.: HONO measurement by differential photolysis, Atmos. Meas. Tech., 9, 2483–2495, https://doi.org/10.5194/amt-9-2483-2016, 2016.
Ren, X., Gao, H., Zhou, X., Crounse, J. D., Wennberg, P. O., Browne, E. C., LaFranchi, B. W., Cohen, R. C., McKay, M., Goldstein, A. H., and Mao, J.: Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007, Atmos. Chem. Phys., 10, 6283–6294, https://doi.org/10.5194/acp-10-6283-2010, 2010.
Riordan, E., Minogue, N., Healy, D., O'Driscoll, P., and Sodeau, J. R.:
Spectroscopic and Optimization Modeling Study of Nitrous Acid in Aqueous
Solution, J. Phys. Chem. A, 109, 779–786, https://doi.org/10.1021/jp040269v, 2005.
Ródenas, M., Muñoz, A., Alacreu, F., Brauers, T., Dorn, H.-P.,
Kleffmann, J., and Bloss, W. J.: Assessment of HONO Measurements: The FIONA
Campaign at EUPHORE, in: Disposal of
Dangerous Chemicals in Urban Areas and Mega Cities. Role of Oxides and Acids
of Nitrogen in Atmospheric Chemistry, edited by: Barnes, I. and Rudziński, K., NATO Science for Peace and Security Series C: Environmental Security, Springer, Dordrecht, 45–58, https://doi.org/10.1007/978-94-007-5034-0_4, 2013.
Seel, F. and Winkler, R.: Das Gleichgewicht salpetrige
Säure–Stickoxydkation im System Schwefelsäure–Wasser, Z. Phys.
Chem., 25, 217–232, https://doi.org/10.1524/zpch.1960.25.3_4.217, 1960.
Stemmler, K., Ammann, M., Donders, C., Kleffmann, J., and George, C.:
Photosensitized Reduction of Nitrogen Dioxide on Humic Acid as a Source of
Nitrous Acid, Nature, 440, 195–198, https://doi.org/10.1038/nature04603, 2006.
Taira, M. and Kanda, Y.: Continuous Generation System for Low-Concentration
Gaseous Nitrous Acid, Anal. Chem., 62, 630–633, https://doi.org/10.1021/ac00205a018,
1990.
Večeřa Z. and Dasgupta, P. K.: Measurement of Ambient Nitrous Acid
and a Reliable Calibration Source for Gaseous Nitrous Acid, Environ. Sci.
Technol., 25, 255–260, https://doi.org/10.1021/es00014a006, 1991.
Večeřa, Z. and Dasgupta, P. K.: Indoor Nitrous Acid Levels.
Production of Nitrous Acid from Open-Flame Sources, Int. J. Environ. Anal.
Chem., 56, 311–316, https://doi.org/10.1080/03067319408034109, 1994.
Villena, G., Bejan, I., Kurtenbach, R., Wiesen, P., and Kleffmann, J.: Development of a new Long Path Absorption Photometer (LOPAP) instrument for the sensitive detection of NO2 in the atmosphere, Atmos. Meas. Tech., 4, 1663–1676, https://doi.org/10.5194/amt-4-1663-2011, 2011.
Villena, G., Bejan, I., Kurtenbach, R., Wiesen, P., and Kleffmann, J.: Interferences of commercial NO2 instruments in the urban atmosphere and in a smog chamber, Atmos. Meas. Tech., 5, 149–159, https://doi.org/10.5194/amt-5-149-2012, 2012.
Wayne, L. G. and Yost, D. M.: Kinetics of the Rapid Gas Phase Reaction
between NO, NO2, and H2O, J. Chem. Phys., 19, 41–47, https://doi.org/10.1063/1.1747986, 1951.
Zhou, X., Zhang, N., TerAvest, M., Tang, D., Hou, J., Bertman, S.,
Alaghmand, M., Shepson, P. B., Caroll, M. A., Griffith, S., Dusanter, S.,
and Stevens, P. S.: Nitric Acid Photolysis on Forest Canopy Surface as a
Source for Tropospheric Nitrous Acid, Nat. Geosci., 4, 440–443, https://doi.org/10.1038/NGEO1164, 2011.
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 %.
A continuous source for the generation of pure HONO mixtures was developed and characterized,...
