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
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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.
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Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
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Sneha Aggarwal, Priyanka Bansal, Yuwei Wang, Spiro Jorga, Gabrielle Macgregor, Urs Rohner, Thomas Bannan, Matthew Salter, Paul Zieger, Claudia Mohr, and Felipe Lopez-Hilfiker
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Atmos. Meas. Tech., 18, 1013–1038, https://doi.org/10.5194/amt-18-1013-2025, https://doi.org/10.5194/amt-18-1013-2025, 2025
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We present a method for the determination of greenhouse gases (CH4, CO2, N2O) using a chromatographic system with a barrier ion discharge detector (BID) and a Carboxen 1010 capillary column. The system omits the need for an electron capture detector (ECD) containing radiogenic components for N2O analysis and a flame ionisation detector (FID) with a methaniser for CO2 samples. This simplification reduces analytical costs, facilitates instrument maintenance and improves measurement robustness.
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Acetylene mole fraction measurements from the Picarro G2203 were characterised. Abnormal sensor behaviour was observed in wet conditions. A dry linear calibration was derived, although this was invalid below 1.2 ppb due to unstable measurements. The instrument was used to measure acetylene as a methane tracer at a landfill site. Fluxes were derived from fourteen downwind transects using both raw and calibrated acetylene mole fraction, with raw measurements resulting in 8 % flux underestimation.
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Atmos. Meas. Tech., 18, 319–325, https://doi.org/10.5194/amt-18-319-2025, https://doi.org/10.5194/amt-18-319-2025, 2025
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Radiocarbon (14C) is an optimal tracer of methane (CH4) emissions, as 14C measurements enable distinguishing between fossil methane and biogenic methane. However, these measurements are particularly challenging, mainly due to technical difficulties in the sampling procedure. We made the sample extraction much simpler and time efficient, providing a new technology that can be used by any research group, with the goal of expanding 14C measurements for an improved understanding of methane sources.
Clément Piel, Daniele Romanini, Morgane Farradèche, Justin Chaillot, Clémence Paul, Nicolas Bienville, Thomas Lauwers, Joana Sauze, Kévin Jaulin, Frédéric Prié, and Amaëlle Landais
Atmos. Meas. Tech., 17, 6647–6658, https://doi.org/10.5194/amt-17-6647-2024, https://doi.org/10.5194/amt-17-6647-2024, 2024
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This paper introduces a new optical gas analyzer based on an optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS) technique enabling high-temporal-resolution and high-precision measurements of oxygen isotopes (δ18O) and dioxygen (O2) concentration of atmospheric O2 (respectively 0.06 ‰ and 0.002 % over 10 min integration). The results underscore the good agreement with isotope ratio mass spectrometry measurements and the ability of the instrument to monitor biological processes.
Alexandra L. Meyer and Lisa R. Welp
Atmos. Meas. Tech., 17, 6193–6212, https://doi.org/10.5194/amt-17-6193-2024, https://doi.org/10.5194/amt-17-6193-2024, 2024
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Water molecules stick to air intake tubing wall surfaces, smoothing measurements of fast isotopic variability in the atmosphere. We tested this stickiness and saw small differences in isotopic signal speed between materials, tubing inner dimensions, and isotopic switch direction, although no consistent temperature effects. Researchers can confidently compare measurements across observation systems using different commonly used tubing materials and plan for optimal inlet designs of new systems.
Matthieu Riva, Veronika Pospisilova, Carla Frege, Sebastien Perrier, Priyanka Bansal, Spiro Jorga, Patrick Sturm, Joel A. Thornton, Urs Rohner, and Felipe Lopez-Hilfiker
Atmos. Meas. Tech., 17, 5887–5901, https://doi.org/10.5194/amt-17-5887-2024, https://doi.org/10.5194/amt-17-5887-2024, 2024
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We present a newly designed reduced-pressure chemical ionization reactor for detection of gas-phase organic and inorganic species. The system operates through the combined use of vacuum ultraviolet ionization and photosensitizers to generate numerous adduct ionization schemes. As a result, it offers the ability to simultaneously measure a wide variety of organic and inorganic species in terms of compound volatility and functionality, while being largely independent of changes in sample humidity.
Dandan Li, Dongyu Wang, Lucia Caudillo, Wiebke Scholz, Mingyi Wang, Sophie Tomaz, Guillaume Marie, Mihnea Surdu, Elias Eccli, Xianda Gong, Loic Gonzalez-Carracedo, Manuel Granzin, Joschka Pfeifer, Birte Rörup, Benjamin Schulze, Pekka Rantala, Sébastien Perrier, Armin Hansel, Joachim Curtius, Jasper Kirkby, Neil M. Donahue, Christian George, Imad El-Haddad, and Matthieu Riva
Atmos. Meas. Tech., 17, 5413–5428, https://doi.org/10.5194/amt-17-5413-2024, https://doi.org/10.5194/amt-17-5413-2024, 2024
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Due to the analytical challenges of measuring organic vapors, it remains challenging to identify and quantify organic molecules present in the atmosphere. Here, we explore the performance of the Orbitrap chemical ionization mass spectrometer (CI-Orbitrap) using ammonium ion chemistry. This study shows that ammonium-ion-based chemistry associated with the high mass resolution of the Orbitrap mass analyzer can measure almost all inclusive compounds.
Hideki Nara, Takuya Saito, Taku Umezawa, and Yasunori Tohjima
Atmos. Meas. Tech., 17, 5187–5200, https://doi.org/10.5194/amt-17-5187-2024, https://doi.org/10.5194/amt-17-5187-2024, 2024
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We have developed a high-accuracy dynamic dilution system for generating reference gas mixtures containing carbonyl sulfide (COS). Although COS at ambient levels generally has poor storage stability, our approach involves the dilution of a gas mixture containing micromole-per-mole levels of COS, the stability of which was validated for more than 1 decade. The developed system has excellent dilution performance and will facilitate accurate instrumental calibration for atmospheric COS observation.
Mengdi Song, Shuyu He, Xin Li, Ying Liu, Shengrong Lou, Sihua Lu, Limin Zeng, and Yuanhang Zhang
Atmos. Meas. Tech., 17, 5113–5127, https://doi.org/10.5194/amt-17-5113-2024, https://doi.org/10.5194/amt-17-5113-2024, 2024
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We introduce detailed and improved quantitation and semi-quantitation methods of iodide-adduct time-of-flight chemical ionization mass spectrometry (I-CIMS) to measure toluene oxidation intermediates. We assess the experimental sensitivity of various functional group species and their binding energy with iodide ions in I-CIMS. A novel classification approach was introduced to significantly enhance the accuracy of semi-quantitative methods (improving R2 values from 0.52 to beyond 0.88).
Finja Löher, Esther Borrás, Amalia Muñoz, and Anke Christine Nölscher
Atmos. Meas. Tech., 17, 4553–4579, https://doi.org/10.5194/amt-17-4553-2024, https://doi.org/10.5194/amt-17-4553-2024, 2024
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We constructed and characterized a new indoor Teflon atmospheric simulation chamber. We evaluated wall losses, photolysis rates, and secondary reactions of multifunctional photooxidation products in the chamber. To measure these products on-line, we combined chromatographic and mass spectrometric analyses to obtain both isomeric information and a high temporal resolution. For method validation, we studied the formation yields of the main ring-retaining products of toluene.
Hans Christian Steen-Larsen and Daniele Zannoni
Atmos. Meas. Tech., 17, 4391–4409, https://doi.org/10.5194/amt-17-4391-2024, https://doi.org/10.5194/amt-17-4391-2024, 2024
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The water vapor generation module is completely scalable, allowing autonomous calibrations to use N standards and providing integration times only restricted by sample availability. We document improved reproducibility in 17O-excess liquid measurements. This module makes spectroscopy measurements comparable to mass spectrometry. We document that the vapor generation module can be used to analyze instrument performance and for vapor isotope calibration during field campaign measurements.
Malavika Sivan, Thomas Röckmann, Carina van der Veen, and Maria Elena Popa
Atmos. Meas. Tech., 17, 2687–2705, https://doi.org/10.5194/amt-17-2687-2024, https://doi.org/10.5194/amt-17-2687-2024, 2024
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We have set up a measurement system for methane-clumped isotopologues. We have built an extraction and purification system to extract pure methane for these measurements, for samples of various origins, including atmospheric air, for which we need to process about 1000 L of air for one measurement. We report here the technical setup for extraction and measurements, as well as the calibration, and we give an overview of the samples measured so far.
Fangbing Li, Dan Dan Huang, Linhui Tian, Bin Yuan, Wen Tan, Liang Zhu, Penglin Ye, Douglas Worsnop, Ka In Hoi, Kai Meng Mok, and Yong Jie Li
Atmos. Meas. Tech., 17, 2415–2427, https://doi.org/10.5194/amt-17-2415-2024, https://doi.org/10.5194/amt-17-2415-2024, 2024
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The responses of protonated, adduct, and fragmented ions of 21 volatile organic compounds (VOCs) were investigated with varying instrument settings and relative humidity (RH) in a Vocus proton-transfer-reaction mass spectrometer (PTR-MS). The protonated ions of most VOCs studied show < 15 % variation in sensitivity, except for some long-chain aldehydes. The relationship between sensitivity and PTR rate constant is complicated by the influences from ion transmission and protonated ion fraction.
Melissa A. Morris, Demetrios Pagonis, Douglas A. Day, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 17, 1545–1559, https://doi.org/10.5194/amt-17-1545-2024, https://doi.org/10.5194/amt-17-1545-2024, 2024
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Polymer absorption of volatile organic compounds (VOCs) is important to characterize for atmospheric sampling setups (as interactions cause sampling delays) and indoor air quality. Here we test different polymer materials and quantify their absorptive capacities through modeling. We found the main polymers in carpets to be highly absorptive, acting as large reservoirs for indoor pollution. We also demonstrated how polymer tubes can be used as a low-cost gas separation technique.
Harald Sodemann, Alena Dekhtyareva, Alvaro Fernandez, Andrew Seidl, and Jenny Maccali
Atmos. Meas. Tech., 16, 5181–5203, https://doi.org/10.5194/amt-16-5181-2023, https://doi.org/10.5194/amt-16-5181-2023, 2023
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We describe a device that allows one to produce a continuous stream of water vapour with a specified level of humidity. As a main innovation, we can mix waters with different water isotope composition. Through a series of tests we show that the performance characteristics of the device are in line with specifications. We present two laboratory applications where the device proves useful, first in characterizing instruments, and second for the analysis of water contained in stalagmites.
Stephan Räss, Peter Nyfeler, Paul Wheeler, Will Price, and Markus Christian Leuenberger
Atmos. Meas. Tech., 16, 4489–4505, https://doi.org/10.5194/amt-16-4489-2023, https://doi.org/10.5194/amt-16-4489-2023, 2023
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Due to technological advances clumped-isotope studies have gained importance in recent years. Typically, these studies are performed with high-resolution isotope ratio mass spectrometers (IRMSs) along with a changeover-valve-based dual-inlet system (DIS). We are taking a different approach, namely performing clumped-isotope measurements with a compact low-resolution IRMS with an open-split-based DIS. Currently, we are working with pure-oxygen gas for which we are providing a proof of concept.
Xu-Cheng He, Jiali Shen, Siddharth Iyer, Paxton Juuti, Jiangyi Zhang, Mrisha Koirala, Mikko M. Kytökari, Douglas R. Worsnop, Matti Rissanen, Markku Kulmala, Norbert M. Maier, Jyri Mikkilä, Mikko Sipilä, and Juha Kangasluoma
Atmos. Meas. Tech., 16, 4461–4487, https://doi.org/10.5194/amt-16-4461-2023, https://doi.org/10.5194/amt-16-4461-2023, 2023
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In this study, the upgraded multi-scheme chemical ionisation inlet 2 is presented. Sulfuric acid, hypoiodous acid, iodine, sulfur dioxide, and hydroperoxyl radicals are calibrated, and the improved ion optics allow us to detect sulfuric acid and iodine-containing molecules at as low as a few parts per quadrillion by volume. Additionally, we confirm the reliable detection of iodic acid using both the nitrate and bromide chemical ionisation methods under atmospherically relevant conditions.
Namrata Shanmukh Panji and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 16, 4319–4330, https://doi.org/10.5194/amt-16-4319-2023, https://doi.org/10.5194/amt-16-4319-2023, 2023
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Measuring volatile organic compounds (VOCs) in the atmosphere is crucial for understanding air quality and environmental impact. Since these compounds are present in low concentrations, preconcentration of samples is often necessary for accurate detection. To address this issue, we have developed a novel inlet that uses selective permeation to concentrate organic gases in small sample flows. This device offers a promising approach for accurately detecting low levels of VOCs in the atmosphere.
Claudia Grossi, Daniel Rabago, Scott Chambers, Carlos Sáinz, Roger Curcoll, Peter P. S. Otáhal, Eliška Fialová, Luis Quindos, and Arturo Vargas
Atmos. Meas. Tech., 16, 2655–2672, https://doi.org/10.5194/amt-16-2655-2023, https://doi.org/10.5194/amt-16-2655-2023, 2023
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The automatic and low-maintenance radon flux system Autoflux, completed with environmental soil and atmosphere sensors, has been theoretically and experimentally characterized and calibrated under laboratory conditions to be used as transfer standard for in situ measurements. It will offer for the first time long-term measurements to validate radon flux maps used by the climate and the radiation protection communities for assessing the radon gas emissions in the atmosphere.
Lisa Ernle, Monika Akima Ringsdorf, and Jonathan Williams
Atmos. Meas. Tech., 16, 1179–1194, https://doi.org/10.5194/amt-16-1179-2023, https://doi.org/10.5194/amt-16-1179-2023, 2023
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Atmospheric ozone can induce artefacts in volatile organic compound measurements. Laboratory tests were made using GC-MS and PTR-MS aircraft systems under tropospheric and stratospheric conditions of humidity and ozone, with and without sodium thiosulfate filter scrubbers. Ozone in dry air produces some carbonyls and degrades alkenes. The scrubber lifetime depends on ozone concentration, flow rate and humidity. For the troposphere with scrubber, no significant artefacts were found over 14 d.
Lars Mächler, Daniel Baggenstos, Florian Krauss, Jochen Schmitt, Bernhard Bereiter, Remo Walther, Christoph Reinhard, Béla Tuzson, Lukas Emmenegger, and Hubertus Fischer
Atmos. Meas. Tech., 16, 355–372, https://doi.org/10.5194/amt-16-355-2023, https://doi.org/10.5194/amt-16-355-2023, 2023
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We present a new method to extract the gases from ice cores and measure their greenhouse gas composition. The ice is sublimated continuously with a near-infrared laser, releasing the gases, which are then analyzed on a laser absorption spectrometer. The main advantage over previous efforts is a low effective resolution of 1–2 cm. This capability is crucial for the analysis of highly thinned ice, as expected from ongoing drilling efforts to extend ice core history further back in time.
Detlev Helmig, Alex Guenther, Jacques Hueber, Ryan Daly, Wei Wang, Jeong-Hoo Park, Anssi Liikanen, and Arnaud P. Praplan
Atmos. Meas. Tech., 15, 5439–5454, https://doi.org/10.5194/amt-15-5439-2022, https://doi.org/10.5194/amt-15-5439-2022, 2022
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This research demonstrates a new method for determination of the chemical reactivity of volatile organic compounds that are emitted from the leaves and needles of trees. These measurements allow elucidating if and how much of these emissions and their associated reactivity are captured and quantified by currently applicable chemical analysis methods.
Andrew J. Lindsay and Ezra C. Wood
Atmos. Meas. Tech., 15, 5455–5464, https://doi.org/10.5194/amt-15-5455-2022, https://doi.org/10.5194/amt-15-5455-2022, 2022
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Nitrous acid (HONO) is an important source of the main atmospheric oxidant – the hydroxyl radical (OH). Advances in nitrous acid measurement techniques and calibration methods therefore improve our understanding of atmospheric oxidation processes. In this paper, we present two calibration methods based on photo-dissociating water vapor. These calibration methods are useful alternatives to conventional calibrations that involve a reacting hydrogen chloride vapor with sodium nitrite.
Ying Wang, Wentai Luo, Todd N. Rosenstiel, and James F. Pankow
Atmos. Meas. Tech., 15, 4651–4661, https://doi.org/10.5194/amt-15-4651-2022, https://doi.org/10.5194/amt-15-4651-2022, 2022
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A rapid, sensitive, and precise analytical method was developed for measuring the fractional amounts of the (−) and (+) forms of chiral enantiomeric forms of monoterpenes in air containing biogenic plant emissions. The method uses passive air sampling onto adsorption–thermal desorption (ATD) gas sampling cartridge tubes; this is followed by automatable thermal desorption onto a chiral gas chromatography (GC) column, followed by detection with mass spectrometry (MS).
Zara S. Mir, Matthew Jamieson, Nicholas R. Greenall, Paul W. Seakins, Mark A. Blitz, and Daniel Stone
Atmos. Meas. Tech., 15, 2875–2887, https://doi.org/10.5194/amt-15-2875-2022, https://doi.org/10.5194/amt-15-2875-2022, 2022
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In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. This work has significance for the identification and measurement of reactive trace species in complex systems.
Tatiana Macé, Maitane Iturrate-Garcia, Céline Pascale, Bernhard Niederhauser, Sophie Vaslin-Reimann, and Christophe Sutour
Atmos. Meas. Tech., 15, 2703–2718, https://doi.org/10.5194/amt-15-2703-2022, https://doi.org/10.5194/amt-15-2703-2022, 2022
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LNE developed, with the company 2M PROCESS, a gas reference generator to dynamically generate NH3 reference gas mixtures in the air at very low fractions between 1 and 400 nmol/mol. The procedure defined by LNE for calibrating NH3 analyzers used for monitoring air quality guarantees relative expanded uncertainties lower than 2 % for this measurement range. The results of a comparison organized between METAS and LNE allowed the validation of LNE's reference generator and calibration procedure.
Antonia G. Zogka, Manolis N. Romanias, and Frederic Thevenet
Atmos. Meas. Tech., 15, 2001–2019, https://doi.org/10.5194/amt-15-2001-2022, https://doi.org/10.5194/amt-15-2001-2022, 2022
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We emphasize the application of SIFT-MS to detect two important atmospheric pollutants, i.e., formaldehyde (FM) and glyoxal (GL). FM and GL are secondary products formed by volatile organic compound oxidation in indoor and outdoor environments and play a key role in air quality and climate. We show that SIFT-MS is able to monitor these species selectively and in real time, overcoming the limitations of other, classical analytical techniques used to monitor these species in the atmosphere.
Haiyan Li, Thomas Golin Almeida, Yuanyuan Luo, Jian Zhao, Brett B. Palm, Christopher D. Daub, Wei Huang, Claudia Mohr, Jordan E. Krechmer, Theo Kurtén, and Mikael Ehn
Atmos. Meas. Tech., 15, 1811–1827, https://doi.org/10.5194/amt-15-1811-2022, https://doi.org/10.5194/amt-15-1811-2022, 2022
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This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
Jean Decker, Éric Fertein, Jonas Bruckhuisen, Nicolas Houzel, Pierre Kulinski, Bo Fang, Weixiong Zhao, Francis Hindle, Guillaume Dhont, Robin Bocquet, Gaël Mouret, Cécile Coeur, and Arnaud Cuisset
Atmos. Meas. Tech., 15, 1201–1215, https://doi.org/10.5194/amt-15-1201-2022, https://doi.org/10.5194/amt-15-1201-2022, 2022
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We present a multiple pass system developed for the CHamber for Atmospheric Reactivity and Metrology of the Environment. This multi-pass cell allows monitoring of atmospheric species at trace levels by high-resolution spectroscopy with long interaction path lengths in the IR and for the first time in the terahertz range. Interesting prospects are highlighted in this frequency domain, such as a high degree of selectivity or the possibility to monitor in real-time atmospheric processes.
Robert F. Berg, Nicola Chiodo, and Eric Georgin
Atmos. Meas. Tech., 15, 819–832, https://doi.org/10.5194/amt-15-819-2022, https://doi.org/10.5194/amt-15-819-2022, 2022
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We made a humidity generator that adds water vapor to a flowing gas. Its range of humidity is useful for calibrating balloon-borne probes to the Earth's stratosphere. The generator’s novel feature is a saturator that comprises 5 m of silicone tubing immersed in water. The length was enough to ensure that the saturator’s output was independent of the dimensions and permeability of the tube. This simple, low-cost design provides an accuracy that is acceptable for many applications.
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.
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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,...
