Articles | Volume 13, issue 2
https://doi.org/10.5194/amt-13-1001-2020
© Author(s) 2020. 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-13-1001-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
03 Mar 2020
Research article |
| 03 Mar 2020
| 03 Mar 2020
Portable calibrator for NO based on the photolysis of N2O and a combined NO2∕NO∕O3 source for field calibrations of air pollution monitors
John W. Birks
CORRESPONDING AUTHOR
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Andrew A. Turnipseed
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Peter C. Andersen
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Craig J. Williford
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Stanley Strunk
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Brian Carpenter
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
Christine A. Ennis
2B Technologies, 2100 Central Ave., Boulder, CO 80301, USA
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John W. Birks, Craig J. Williford, Peter C. Andersen, Andrew A. Turnipseed, Stanley Strunk, and Christine A. Ennis
Atmos. Meas. Tech., 11, 4797–4807, https://doi.org/10.5194/amt-11-4797-2018, https://doi.org/10.5194/amt-11-4797-2018, 2018
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A highly portable ozone calibration source based on the photolysis of oxygen is described and evaluated. The ozone mixing ratio produced is independent of both pressure and temperature, and humidity effects are small and correctable. The resulting O3 calibrator has a response time < 20 s, a precision of 0.4 %, and can serve as a U.S. EPA level 4 transfer standard for the calibration of ozone analyzers.
John W. Birks, Peter C. Andersen, Craig J. Williford, Andrew A. Turnipseed, Stanley E. Strunk, Christine A. Ennis, and Erick Mattson
Atmos. Meas. Tech., 11, 2821–2835, https://doi.org/10.5194/amt-11-2821-2018, https://doi.org/10.5194/amt-11-2821-2018, 2018
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A modular long-path folded tubular photometer for making absorbance measurements of air pollutant concentrations is described. The present paper applies this photometer to direct measurements of nitrogen dioxide and, indirectly, to nitric oxide. Excellent agreement for both was observed for measurements along an urban roadside compared with existing standard techniques. Advantages and extension of this technique to other atmospheric pollutants, including particulates, are discussed.
Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Christine A. Ennis, and John W. Birks
Atmos. Meas. Tech., 10, 2253–2269, https://doi.org/10.5194/amt-10-2253-2017, https://doi.org/10.5194/amt-10-2253-2017, 2017
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We investigated a new solid-phase scrubber for use in conventional ozone UV-absorption photometers. A heated graphite scrubber efficiently removed ozone and was less susceptible to interference from water vapor, mercury vapor, and aromatic hydrocarbons compared to conventional metal oxide scrubbers. Reducing interferences from these atmospheric species in conventional ozone photometers could lead to more accurate ozone measurements in compliance monitoring or for indoor air quality.
David D. Parrish and Christine A. Ennis
Atmos. Chem. Phys., 19, 12587–12605, https://doi.org/10.5194/acp-19-12587-2019, https://doi.org/10.5194/acp-19-12587-2019, 2019
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Background ozone transported into cities contributes greatly to urban concentrations. Based on projections of past trends, the largest ozone concentrations on which the 70 ppb National Ambient Air Quality Standard is based will reach that standard by ∼ 2021 in the New York City area but much later (∼ 2050) in the Los Angeles region. The much smaller background contribution in New York City (45.8 ± 1.7 ppb) than in Los Angeles (62.0 ± 2.0 ppb) is the primary reason for this large difference.
John W. Birks, Craig J. Williford, Peter C. Andersen, Andrew A. Turnipseed, Stanley Strunk, and Christine A. Ennis
Atmos. Meas. Tech., 11, 4797–4807, https://doi.org/10.5194/amt-11-4797-2018, https://doi.org/10.5194/amt-11-4797-2018, 2018
Short summary
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A highly portable ozone calibration source based on the photolysis of oxygen is described and evaluated. The ozone mixing ratio produced is independent of both pressure and temperature, and humidity effects are small and correctable. The resulting O3 calibrator has a response time < 20 s, a precision of 0.4 %, and can serve as a U.S. EPA level 4 transfer standard for the calibration of ozone analyzers.
John W. Birks, Peter C. Andersen, Craig J. Williford, Andrew A. Turnipseed, Stanley E. Strunk, Christine A. Ennis, and Erick Mattson
Atmos. Meas. Tech., 11, 2821–2835, https://doi.org/10.5194/amt-11-2821-2018, https://doi.org/10.5194/amt-11-2821-2018, 2018
Short summary
Short summary
A modular long-path folded tubular photometer for making absorbance measurements of air pollutant concentrations is described. The present paper applies this photometer to direct measurements of nitrogen dioxide and, indirectly, to nitric oxide. Excellent agreement for both was observed for measurements along an urban roadside compared with existing standard techniques. Advantages and extension of this technique to other atmospheric pollutants, including particulates, are discussed.
Robert C. Rhew, Malte Julian Deventer, Andrew A. Turnipseed, Carsten Warneke, John Ortega, Steve Shen, Luis Martinez, Abigail Koss, Brian M. Lerner, Jessica B. Gilman, James N. Smith, Alex B. Guenther, and Joost A. de Gouw
Atmos. Chem. Phys., 17, 13417–13438, https://doi.org/10.5194/acp-17-13417-2017, https://doi.org/10.5194/acp-17-13417-2017, 2017
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Alkenes emanate from both natural and anthropogenic sources and can contribute to atmospheric ozone production. This study measured
lightalkene (ethene, propene and butene) fluxes from a ponderosa pine forest using a novel relaxed eddy accumulation method, revealing much larger emissions than previously estimated and accounting for a significant fraction of OH reactivity. Emissions have a diurnal cycle related to sunlight and temperature, and the forest canopy appears to be the source.
Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Christine A. Ennis, and John W. Birks
Atmos. Meas. Tech., 10, 2253–2269, https://doi.org/10.5194/amt-10-2253-2017, https://doi.org/10.5194/amt-10-2253-2017, 2017
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We investigated a new solid-phase scrubber for use in conventional ozone UV-absorption photometers. A heated graphite scrubber efficiently removed ozone and was less susceptible to interference from water vapor, mercury vapor, and aromatic hydrocarbons compared to conventional metal oxide scrubbers. Reducing interferences from these atmospheric species in conventional ozone photometers could lead to more accurate ozone measurements in compliance monitoring or for indoor air quality.
S. P. Burns, P. D. Blanken, A. A. Turnipseed, J. Hu, and R. K. Monson
Biogeosciences, 12, 7349–7377, https://doi.org/10.5194/bg-12-7349-2015, https://doi.org/10.5194/bg-12-7349-2015, 2015
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The effect of warm-season precipitation on
environmental conditions and ecosystem-scale fluxes at a
high-elevation subalpine forest site was investigated. As would be
expected (based on the surface energy balance), precipitation caused
an increase in latent heat flux (evapotranspiration) and a decrease in
sensible heat flux. The evaporative component of evapotranspiration
was, on average, estimated to be around 6% in dry conditions and
between 15-25% in partially wet conditions.
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
Influence of ozone and humidity on PTR-MS and GC-MS VOC measurements with and without a Na2S2O3 ozone scrubber
Laser-induced sublimation extraction for centimeter-resolution multi-species greenhouse gas analysis on ice cores
Ozone reactivity measurement of biogenic volatile organic compound emissions
Comparison of two photolytic calibration methods for nitrous acid
Measurement of enantiomer percentages for five monoterpenes from six conifer species by cartridge-tube-based passive sampling adsorption–thermal desorption (ps-ATD)
Identification, monitoring, and reaction kinetics of reactive trace species using time-resolved mid-infrared quantum cascade laser absorption spectroscopy: development, characterisation, and initial results for the CH2OO Criegee intermediate
Air pollution monitoring: development of ammonia (NH3) dynamic reference gas mixtures at nanomoles per mole levels to improve the lack of traceability of measurements
Formaldehyde and glyoxal measurement deploying a selected ion flow tube mass spectrometer (SIFT-MS)
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides
MULTICHARME: a modified Chernin-type multi-pass cell designed for IR and THz long-path absorption measurements in the CHARME atmospheric simulation chamber
Silicone tube humidity generator
A source for the continuous generation of pure and quantifiable HONO mixtures
Photochemical method for removing methane interference for improved gas analysis
A simulation chamber for absorption spectroscopy in planetary atmospheres
An automated system for trace gas flux measurements from plant foliage and other plant compartments
Simultaneous measurement of δ13C, δ18O and δ17O of atmospheric CO2 – performance assessment of a dual-laser absorption spectrometer
Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers
A method for resolving changes in atmospheric He ∕ N2 as an indicator of fossil fuel extraction and stratospheric circulation
Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase
Atomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap–GC–AED) for atmospheric trace gas measurements
New technique for high-precision, simultaneous measurements of CH4, N2O and CO2 concentrations; isotopic and elemental ratios of N2, O2 and Ar; and total air content in ice cores by wet extraction
High-precision laser spectrometer for multiple greenhouse gas analysis in 1 mL air from ice core samples
A thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phases
Interference from alkenes in chemiluminescent NOx measurements
Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)
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A new instrument for time-resolved measurement of HO2 radicals
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High-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniques
Characterisation of the transfer of cluster ions through an atmospheric pressure interface time-of-flight mass spectrometer with hexapole ion guides
Addition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixtures
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Preparation and analysis of zero gases for the measurement of trace VOCs in air monitoring
A steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levels
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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
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We present a new method to extract the gases from ice cores and measure their greenhouse gas composition. The ice is sublimated continuously with a near-infrared laser, releasing the gases, which are then analyzed on a laser absorption spectrometer. The main advantage over previous efforts is a low effective resolution of 1–2 cm. This capability is crucial for the analysis of highly thinned ice, as expected from ongoing drilling efforts to extend ice core history further back in time.
Detlev Helmig, Alex Guenther, Jacques Hueber, Ryan Daly, Wei Wang, Jeong-Hoo Park, Anssi Liikanen, and Arnaud P. Praplan
Atmos. Meas. Tech., 15, 5439–5454, https://doi.org/10.5194/amt-15-5439-2022, https://doi.org/10.5194/amt-15-5439-2022, 2022
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This research demonstrates a new method for determination of the chemical reactivity of volatile organic compounds that are emitted from the leaves and needles of trees. These measurements allow elucidating if and how much of these emissions and their associated reactivity are captured and quantified by currently applicable chemical analysis methods.
Andrew J. Lindsay and Ezra C. Wood
Atmos. Meas. Tech., 15, 5455–5464, https://doi.org/10.5194/amt-15-5455-2022, https://doi.org/10.5194/amt-15-5455-2022, 2022
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Nitrous acid (HONO) is an important source of the main atmospheric oxidant – the hydroxyl radical (OH). Advances in nitrous acid measurement techniques and calibration methods therefore improve our understanding of atmospheric oxidation processes. In this paper, we present two calibration methods based on photo-dissociating water vapor. These calibration methods are useful alternatives to conventional calibrations that involve a reacting hydrogen chloride vapor with sodium nitrite.
Ying Wang, Wentai Luo, Todd N. Rosenstiel, and James F. Pankow
Atmos. Meas. Tech., 15, 4651–4661, https://doi.org/10.5194/amt-15-4651-2022, https://doi.org/10.5194/amt-15-4651-2022, 2022
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A rapid, sensitive, and precise analytical method was developed for measuring the fractional amounts of the (−) and (+) forms of chiral enantiomeric forms of monoterpenes in air containing biogenic plant emissions. The method uses passive air sampling onto adsorption–thermal desorption (ATD) gas sampling cartridge tubes; this is followed by automatable thermal desorption onto a chiral gas chromatography (GC) column, followed by detection with mass spectrometry (MS).
Zara S. Mir, Matthew Jamieson, Nicholas R. Greenall, Paul W. Seakins, Mark A. Blitz, and Daniel Stone
Atmos. Meas. Tech., 15, 2875–2887, https://doi.org/10.5194/amt-15-2875-2022, https://doi.org/10.5194/amt-15-2875-2022, 2022
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In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. This work has significance for the identification and measurement of reactive trace species in complex systems.
Tatiana Macé, Maitane Iturrate-Garcia, Céline Pascale, Bernhard Niederhauser, Sophie Vaslin-Reimann, and Christophe Sutour
Atmos. Meas. Tech., 15, 2703–2718, https://doi.org/10.5194/amt-15-2703-2022, https://doi.org/10.5194/amt-15-2703-2022, 2022
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LNE developed, with the company 2M PROCESS, a gas reference generator to dynamically generate NH3 reference gas mixtures in the air at very low fractions between 1 and 400 nmol/mol. The procedure defined by LNE for calibrating NH3 analyzers used for monitoring air quality guarantees relative expanded uncertainties lower than 2 % for this measurement range. The results of a comparison organized between METAS and LNE allowed the validation of LNE's reference generator and calibration procedure.
Antonia G. Zogka, Manolis N. Romanias, and Frederic Thevenet
Atmos. Meas. Tech., 15, 2001–2019, https://doi.org/10.5194/amt-15-2001-2022, https://doi.org/10.5194/amt-15-2001-2022, 2022
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We emphasize the application of SIFT-MS to detect two important atmospheric pollutants, i.e., formaldehyde (FM) and glyoxal (GL). FM and GL are secondary products formed by volatile organic compound oxidation in indoor and outdoor environments and play a key role in air quality and climate. We show that SIFT-MS is able to monitor these species selectively and in real time, overcoming the limitations of other, classical analytical techniques used to monitor these species in the atmosphere.
Haiyan Li, Thomas Golin Almeida, Yuanyuan Luo, Jian Zhao, Brett B. Palm, Christopher D. Daub, Wei Huang, Claudia Mohr, Jordan E. Krechmer, Theo Kurtén, and Mikael Ehn
Atmos. Meas. Tech., 15, 1811–1827, https://doi.org/10.5194/amt-15-1811-2022, https://doi.org/10.5194/amt-15-1811-2022, 2022
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This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
Jean Decker, Éric Fertein, Jonas Bruckhuisen, Nicolas Houzel, Pierre Kulinski, Bo Fang, Weixiong Zhao, Francis Hindle, Guillaume Dhont, Robin Bocquet, Gaël Mouret, Cécile Coeur, and Arnaud Cuisset
Atmos. Meas. Tech., 15, 1201–1215, https://doi.org/10.5194/amt-15-1201-2022, https://doi.org/10.5194/amt-15-1201-2022, 2022
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We present a multiple pass system developed for the CHamber for Atmospheric Reactivity and Metrology of the Environment. This multi-pass cell allows monitoring of atmospheric species at trace levels by high-resolution spectroscopy with long interaction path lengths in the IR and for the first time in the terahertz range. Interesting prospects are highlighted in this frequency domain, such as a high degree of selectivity or the possibility to monitor in real-time atmospheric processes.
Robert F. Berg, Nicola Chiodo, and Eric Georgin
Atmos. Meas. Tech., 15, 819–832, https://doi.org/10.5194/amt-15-819-2022, https://doi.org/10.5194/amt-15-819-2022, 2022
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We made a humidity generator that adds water vapor to a flowing gas. Its range of humidity is useful for calibrating balloon-borne probes to the Earth's stratosphere. The generator’s novel feature is a saturator that comprises 5 m of silicone tubing immersed in water. The length was enough to ensure that the saturator’s output was independent of the dimensions and permeability of the tube. This simple, low-cost design provides an accuracy that is acceptable for many applications.
Guillermo Villena and Jörg Kleffmann
Atmos. Meas. Tech., 15, 627–637, https://doi.org/10.5194/amt-15-627-2022, https://doi.org/10.5194/amt-15-627-2022, 2022
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A continuous source for the generation of pure HONO mixtures was developed and characterized, which is based on the Henry's law solubility of HONO in acidic aqueous solutions. The source shows a fast time response and an excellent long-term stability and can be easily adjusted to HONO mixing ratios in the range 0.05–500 ppb. A general equation based on Henry's law is developed, whereby the HONO concentration of the source can be absolutely calculated with an accuracy of better than 10 %.
Merve Polat, Jesper Baldtzer Liisberg, Morten Krogsbøll, Thomas Blunier, and Matthew S. Johnson
Atmos. Meas. Tech., 14, 8041–8067, https://doi.org/10.5194/amt-14-8041-2021, https://doi.org/10.5194/amt-14-8041-2021, 2021
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We have designed a process for removing methane from a gas stream so that nitrous oxide can be measured without interference. These are both key long-lived greenhouse gases frequently studied in relation to ice cores, plants, water treatment and so on. However, many researchers are not aware of the problem of methane interference, and in addition there have not been good methods available for solving the problem. Here we present and evaluate such a method.
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197, https://doi.org/10.5194/amt-14-7187-2021, https://doi.org/10.5194/amt-14-7187-2021, 2021
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A novel simulation chamber, PASSxS (Planetary Atmosphere Simulation System for Spectroscopy), has been developed for absorption measurements with a Fourier transform spectrometer (FTS) and possibly a cavity ring-down (CRD) spectrometer, with a sample temperature ranging from 100 K up to 550 K, while the pressure of the gas can be varied up to 60 bar. These temperature and pressure ranges cover a significant part of the planetary atmospheres in the solar system and possibly extrasolar planets.
Lukas Kohl, Markku Koskinen, Tatu Polvinen, Salla Tenhovirta, Kaisa Rissanen, Marjo Patama, Alessandro Zanetti, and Mari Pihlatie
Atmos. Meas. Tech., 14, 4445–4460, https://doi.org/10.5194/amt-14-4445-2021, https://doi.org/10.5194/amt-14-4445-2021, 2021
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We present ShoTGa-FluMS, a measurement system designed for continuous and automated measurements of trace gas and volatile organic compound (VOC) fluxes from plant shoots. ShoTGa-FluMS uses transparent shoot enclosures equipped with cooling elements, automatically replaces fixated CO2, and removes transpired water from the enclosure, thus solving multiple technical problems that have so far prevented automated plant shoot trace gas flux measurements.
Pharahilda M. Steur, Hubertus A. Scheeren, Dave D. Nelson, J. Barry McManus, and Harro A. J. Meijer
Atmos. Meas. Tech., 14, 4279–4304, https://doi.org/10.5194/amt-14-4279-2021, https://doi.org/10.5194/amt-14-4279-2021, 2021
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For understanding the sources and sinks of atmospheric CO2, measurement of stable isotopes has proven to be highly valuable. We present a new method using laser absorption spectroscopy to simultaneously conduct measurements of three CO2 isotopes, directly on dry-air samples. This new method reduces sample preparation time significantly, compared to the conventional method in which measurements are conducted on pure CO2, and avoids measurement biases introduced by CO2 extraction.
Mingyi Wang, Xu-Cheng He, Henning Finkenzeller, Siddharth Iyer, Dexian Chen, Jiali Shen, Mario Simon, Victoria Hofbauer, Jasper Kirkby, Joachim Curtius, Norbert Maier, Theo Kurtén, Douglas R. Worsnop, Markku Kulmala, Matti Rissanen, Rainer Volkamer, Yee Jun Tham, Neil M. Donahue, and Mikko Sipilä
Atmos. Meas. Tech., 14, 4187–4202, https://doi.org/10.5194/amt-14-4187-2021, https://doi.org/10.5194/amt-14-4187-2021, 2021
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Atmospheric iodine species are often short-lived with low abundance and have thus been challenging to measure. We show that the bromide chemical ionization mass spectrometry, compatible with both the atmospheric pressure and reduced pressure interfaces, can simultaneously detect various gas-phase iodine species. Combining calibration experiments and quantum chemical calculations, we quantify detection sensitivities to HOI, HIO3, I2, and H2SO4, giving detection limits down to < 106 molec. cm-3.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527, https://doi.org/10.5194/amt-14-2515-2021, https://doi.org/10.5194/amt-14-2515-2021, 2021
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The atmospheric helium-to-nitrogen ratio is a promising indicator for circulation changes in the upper atmosphere and fossil fuel burning by humans. We present a very precise analysis method to determine changes in the helium-to-nitrogen ratio of air samples. The method relies on stabilizing the gas flow to a mass spectrometer and continuous removal of reactive gases. These advances enable new insights and monitoring possibilities for anthropogenic and natural processes.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
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We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
Atmos. Meas. Tech., 14, 1817–1831, https://doi.org/10.5194/amt-14-1817-2021, https://doi.org/10.5194/amt-14-1817-2021, 2021
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A gas measurement device was developed to measure trace gases (ppt level) in the air based on an atomic emission detector. It combines a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED). The CryoTrap–GC–AED instrumental setup, limits of detection, and elemental performance are presented and discussed. Two measurement case studies are reported: one in a Finnish boreal forest and the other based on an aircraft campaign.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Bernhard Bereiter, Béla Tuzson, Philipp Scheidegger, André Kupferschmid, Herbert Looser, Lars Mächler, Daniel Baggenstos, Jochen Schmitt, Hubertus Fischer, and Lukas Emmenegger
Atmos. Meas. Tech., 13, 6391–6406, https://doi.org/10.5194/amt-13-6391-2020, https://doi.org/10.5194/amt-13-6391-2020, 2020
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The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
Natalie I. Keehan, Bellamy Brownwood, Andrey Marsavin, Douglas A. Day, and Juliane L. Fry
Atmos. Meas. Tech., 13, 6255–6269, https://doi.org/10.5194/amt-13-6255-2020, https://doi.org/10.5194/amt-13-6255-2020, 2020
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This paper describes a new instrument (a thermal-dissociation–cavity ring-down spectrometer, TD-CRDS) for the measurement of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations affecting the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using a TD-CRDS for ambient and laboratory studies.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991, https://doi.org/10.5194/amt-13-5977-2020, https://doi.org/10.5194/amt-13-5977-2020, 2020
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We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Daniel Marno, Cheryl Ernest, Korbinian Hens, Umar Javed, Thomas Klimach, Monica Martinez, Markus Rudolf, Jos Lelieveld, and Hartwig Harder
Atmos. Meas. Tech., 13, 2711–2731, https://doi.org/10.5194/amt-13-2711-2020, https://doi.org/10.5194/amt-13-2711-2020, 2020
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In this study, a calibration device for OH and HO2 instruments is characterized at pressures of 275 to 1000 mbar, allowing instrument pressure sensitivity to be quantified to an accuracy of 22 % (1σ). Computational fluid dynamic simulations supporting the understanding of interactions between generated HOx and the instrument inlet led to enhanced determination of factors affecting instrument sensitivity.
Joschka Pfeifer, Mario Simon, Martin Heinritzi, Felix Piel, Lena Weitz, Dongyu Wang, Manuel Granzin, Tatjana Müller, Steffen Bräkling, Jasper Kirkby, Joachim Curtius, and Andreas Kürten
Atmos. Meas. Tech., 13, 2501–2522, https://doi.org/10.5194/amt-13-2501-2020, https://doi.org/10.5194/amt-13-2501-2020, 2020
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Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultrasensitive detection of ammonia at single-digit parts per trillion by volume levels. The instrument is further capable of measuring amines and a suite of iodine compounds at sub-parts per trillion by volume levels.
Roberto Sommariva, Louisa J. Kramer, Leigh R. Crilley, Mohammed S. Alam, and William J. Bloss
Atmos. Meas. Tech., 13, 1655–1670, https://doi.org/10.5194/amt-13-1655-2020, https://doi.org/10.5194/amt-13-1655-2020, 2020
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Ozone is a key atmospheric pollutant formed through chemical processing of natural and anthropogenic emissions and removed by reaction with organic compounds emitted by plants. We describe a new instrument – the
Total Ozone Reactivity Systemor TORS – that measures the total loss of ozone in the troposphere. The objective of the TORS instrument is to provide an estimate of the organic compounds emitted by plants which are not measured and thus to improve our understanding of the ozone budget.
Thomas H. Speak, Mark A. Blitz, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 13, 839–852, https://doi.org/10.5194/amt-13-839-2020, https://doi.org/10.5194/amt-13-839-2020, 2020
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OH and HO2 radicals are important trace constituents of the atmosphere that are closely coupled via several types of reaction. This paper describes a new laboratory method to simultaneously determine OH kinetics and HO2 yields from chemical processes. The instrument also provides some time resolution on HO2 detection allowing one to separate HO2 produced from the target reaction from HO2 arising from secondary chemistry. Examples of applications are presented.
Ece Satar, Peter Nyfeler, Bernhard Bereiter, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 101–117, https://doi.org/10.5194/amt-13-101-2020, https://doi.org/10.5194/amt-13-101-2020, 2020
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Good-quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4 and H2O using a commercial and a novel laser spectroscopic analyzer.
Ece Satar, Peter Nyfeler, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 119–130, https://doi.org/10.5194/amt-13-119-2020, https://doi.org/10.5194/amt-13-119-2020, 2020
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To ensure the best preparation and measurement conditions for trace gases, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. In this article, the previously introduced aluminum measurement chamber is used to investigate materials such as glass, aluminum, copper, brass, steel and three different commercially available coatings. Our measurements focus on temperature and pressure dependencies for the species CO2, CO, CH4 and H2O using a CRDS analyzer.
Tanja J. Schuck, Ann-Katrin Blank, Elisa Rittmeier, Jonathan Williams, Carl A. M. Brenninkmeijer, Andreas Engel, and Andreas Zahn
Atmos. Meas. Tech., 13, 73–84, https://doi.org/10.5194/amt-13-73-2020, https://doi.org/10.5194/amt-13-73-2020, 2020
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Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless-steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds were depleted. Individual substances were additionally influenced by high mixing ratios of ozone.
Tesfaye A. Berhanu, John Hoffnagle, Chris Rella, David Kimhak, Peter Nyfeler, and Markus Leuenberger
Atmos. Meas. Tech., 12, 6803–6826, https://doi.org/10.5194/amt-12-6803-2019, https://doi.org/10.5194/amt-12-6803-2019, 2019
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Accurate measurement of variations in atmospheric O2 can provide useful information about atmospheric, biospheric, and oceanic processes, which is a challenge for existing measurement techniques. Here, we introduce a newly built high-precision, stable CRDS analyzer (Picarro G2207) that can measure O2 mixing ratios with a short-term precision of < 1 ppm and only requires calibration every 12 h. Measurements from tower and mountain sites are also presented.
Markus Leiminger, Stefan Feil, Paul Mutschlechner, Arttu Ylisirniö, Daniel Gunsch, Lukas Fischer, Alfons Jordan, Siegfried Schobesberger, Armin Hansel, and Gerhard Steiner
Atmos. Meas. Tech., 12, 5231–5246, https://doi.org/10.5194/amt-12-5231-2019, https://doi.org/10.5194/amt-12-5231-2019, 2019
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We introduce an alternative type of atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) with the main difference of using hexapole instead of quadrupole ion guides. The transfer of cluster ions through the hexapoles was characterised with focus on transmission efficiency, mass range and fragmentation of cluster ions. At the CERN CLOUD experiment we compared the performance of the ioniAPi-TOF with a standard quadrupole APi-TOF under controlled conditions.
Michal Lacko, Nijing Wang, Kristýna Sovová, Pavel Pásztor, and Patrik Španěl
Atmos. Meas. Tech., 12, 4965–4982, https://doi.org/10.5194/amt-12-4965-2019, https://doi.org/10.5194/amt-12-4965-2019, 2019
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The soft chemical ionization analytical technique of selected ion flow tube mass spectrometry, SIFT-MS, was enhanced by a fast GC pre-separation unit to identify individual isomers. Experiments were carried out with two GC columns, MXT-1 and MXT-Volatiles, using two reagent ions, H3O+ and NO+, on monoterpene samples (an artificial mixture and coniferous needles). Analyses of product ion ratios allowed for quantification of multiple monoterpenes in partially separated chromatograms.
Benjamin L. Deming, Demetrios Pagonis, Xiaoxi Liu, Douglas A. Day, Ranajit Talukdar, Jordan E. Krechmer, Joost A. de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 12, 3453–3461, https://doi.org/10.5194/amt-12-3453-2019, https://doi.org/10.5194/amt-12-3453-2019, 2019
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Losses or measurement delays of gas-phase compounds sampled through tubing are important to atmospheric science. Here we characterize 14 tubing materials by measuring the effects on step changes in organic compound concentration. We find that polymeric tubings exhibit absorptive partitioning behaviour while glass and metal tubings show adsorptive partitioning. Adsorptive materials impart complex humidity, concentration, and VOC–VOC interaction dependencies that absorptive tubings do not.
Xiaoxi Liu, Benjamin Deming, Demetrios Pagonis, Douglas A. Day, Brett B. Palm, Ranajit Talukdar, James M. Roberts, Patrick R. Veres, Jordan E. Krechmer, Joel A. Thornton, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 12, 3137–3149, https://doi.org/10.5194/amt-12-3137-2019, https://doi.org/10.5194/amt-12-3137-2019, 2019
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Delays or losses of gases in sampling tubing and instrumental surfaces due to surface interactions can lead to inaccurate quantification. By sampling with several chemical ionization mass spectrometers and six tubing materials, we quantify delays of semivolatile organic compounds and small polar gases. Delay times generally increase with decreasing volatility or increasing polarity and also depend on materials. The method and results will inform inlet material selection and instrumental design.
Emmanuel Arzoumanian, Felix R. Vogel, Ana Bastos, Bakhram Gaynullin, Olivier Laurent, Michel Ramonet, and Philippe Ciais
Atmos. Meas. Tech., 12, 2665–2677, https://doi.org/10.5194/amt-12-2665-2019, https://doi.org/10.5194/amt-12-2665-2019, 2019
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We tested commercial lower-cost CO2 sensors in laboratory and field studies to see if they can measure atmospheric CO2 mole fractions with less than 1 ppm bias (with monthly calibration), to allow continuous urban CO2 monitoring.
We find that the sensors' CO2 readings are influenced by temperature, atmospheric pressure and water vapour content, but this can be corrected for by adding sensors (T, p, RH) and carefully calibrating each sensor against a high-precision instrument.
Matthieu Riva, Pekka Rantala, Jordan E. Krechmer, Otso Peräkylä, Yanjun Zhang, Liine Heikkinen, Olga Garmash, Chao Yan, Markku Kulmala, Douglas Worsnop, and Mikael Ehn
Atmos. Meas. Tech., 12, 2403–2421, https://doi.org/10.5194/amt-12-2403-2019, https://doi.org/10.5194/amt-12-2403-2019, 2019
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The impact of aerosol particles on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated species, formed from the oxidation of volatile organic compounds (VOCs) to aerosol formation. Taking advantage of recent mass spectrometric developments, we have evaluated and compared the capability of multiple state-of-the-art mass spectrometers to detect a wide variety of oxygenated VOCs.
Yufeng Pan, Lei Dong, Hongpeng Wu, Weiguang Ma, Lei Zhang, Wangbao Yin, Liantuan Xiao, Suotang Jia, and Frank K. Tittel
Atmos. Meas. Tech., 12, 1905–1911, https://doi.org/10.5194/amt-12-1905-2019, https://doi.org/10.5194/amt-12-1905-2019, 2019
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Photoacoustic spectroscopy has one important advantage: its sensitivity is proportional to the excitation light power and thus the performance of PAS-based sensors can benefit from a high excitation light power. We developed a cavity-enhanced photoacoustic sensor in which a photoacoustic cell was placed into a high-finesse optical cavity. A signal gain factor of 166 was observed. For C2H2 detection, a 1σ detection limit of 0.45 ppmV was obtained at atmospheric pressure with a 1 s averaging time.
Alexander Zaytsev, Martin Breitenlechner, Abigail R. Koss, Christopher Y. Lim, James C. Rowe, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 1861–1870, https://doi.org/10.5194/amt-12-1861-2019, https://doi.org/10.5194/amt-12-1861-2019, 2019
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We present the development of a chemical ionization mass spectrometer which can be operated with either ammonium (NH4+) or hydronium (H3O+) as the reagent ion. We describe a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of detected ammonium–organic ions and hence constrain the sensitivity of the instrument to a wide range of organic compounds that cannot be calibrated directly.
Nick Jordan, Connie Z. Ye, Satyaki Ghosh, Rebecca A. Washenfelder, Steven S. Brown, and Hans D. Osthoff
Atmos. Meas. Tech., 12, 1277–1293, https://doi.org/10.5194/amt-12-1277-2019, https://doi.org/10.5194/amt-12-1277-2019, 2019
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A new spectrometer to measure abundances of the atmospheric trace gases nitrogen dioxide and iodine is described. The spectrometer uses a light-emitting diode between 470 and 540 nm and two highly reflective mirrors to yield an effective absorption path of 6.3 km. We remeasured scattering cross sections of common atmospheric gases in the cyan region and present sample NO2 measurements that agreed with those made with a laser-based instrument.
Kazuki Kamezaki, Shohei Hattori, Enno Bahlmann, and Naohiro Yoshida
Atmos. Meas. Tech., 12, 1141–1154, https://doi.org/10.5194/amt-12-1141-2019, https://doi.org/10.5194/amt-12-1141-2019, 2019
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Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. We present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. The system presented herein is useful for application of sulfur isotopic compositions for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.
Jeremy J. Harrison
Atmos. Meas. Tech., 11, 5827–5836, https://doi.org/10.5194/amt-11-5827-2018, https://doi.org/10.5194/amt-11-5827-2018, 2018
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CFC-11 is a stratospheric-ozone-depleting molecule which is banned under the Montreal Protocol but still present in the atmosphere due to its long lifetime. Using infrared limb sounders on satellite platforms to monitor its concentration crucially requires accurate laboratory spectroscopic data. This paper describes a new high-resolution infrared absorption cross-section dataset for remote-sensing purposes; this improves upon the one currently available in the HITRAN and GEISA databases.
Michael F. Schibig, Duane Kitzis, and Pieter P. Tans
Atmos. Meas. Tech., 11, 5565–5586, https://doi.org/10.5194/amt-11-5565-2018, https://doi.org/10.5194/amt-11-5565-2018, 2018
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For long-term monitoring of CO2 in the atmosphere it is crucial that standard reference gas mixtures stored in high-pressure aluminum cylinders, used to calibrate global measurements, remain stable over their whole time of use. This study finds a reproducible small enrichment as a cylinder is emptied at a low-flow rate, as well as somewhat larger and variable effects when a cylinder is emptied using a high-flow rate.
Min Jie Zhao, Fu Qi Si, Hai Jin Zhou, Shi Mei Wang, Yu Jiang, and Wen Qing Liu
Atmos. Meas. Tech., 11, 5403–5419, https://doi.org/10.5194/amt-11-5403-2018, https://doi.org/10.5194/amt-11-5403-2018, 2018
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EMI is a nadir-viewing wide-field imaging spectrometer aiming to quantify the global distribution of tropospheric and stratospheric trace gases. The spectral range is 240–710 nm, with the spectral resolution 0.3–0.5 nm. The preflight accuracy of wavelength calibration is less than 0.05 nm; the accuracy of radiance calibration is less than 5 %. The obtained calibration key data are used for the L1b processor. In-orbit wavelength/radiometric calibration is used to monitor performance changes.
Anne-Kathrin Bernhammer, Lukas Fischer, Bernhard Mentler, Martin Heinritzi, Mario Simon, and Armin Hansel
Atmos. Meas. Tech., 11, 4763–4773, https://doi.org/10.5194/amt-11-4763-2018, https://doi.org/10.5194/amt-11-4763-2018, 2018
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During new particle formation (NPF) studies from pure isoprene oxidation in the CLOUD chamber at CERN we observed unexpected ion signals. We identified two origins of these signals: first secondary association reactions of protonated isoprene with isoprene within the PTR3 reaction chamber and, second, polymerization of isoprene inside the gas bottle.
In order to study NPF from pure isoprene oxidation we had to install a cryogenic trap in the isoprene inlet line to remove polymerized isoprene.
Jennifer Englert, Anja Claude, Alessia Demichelis, Stefan Persijn, Annarita Baldan, Jianrong Li, Christian Plass-Duelmer, Katja Michl, Erasmus Tensing, Rina Wortman, Yousra Ghorafi, Maricarmen Lecuna, Guido Sassi, Maria Paola Sassi, and Dagmar Kubistin
Atmos. Meas. Tech., 11, 3197–3203, https://doi.org/10.5194/amt-11-3197-2018, https://doi.org/10.5194/amt-11-3197-2018, 2018
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For volatile organic compound (VOC) observations, zero gases free of VOC traces are essential for the characterisation of the measurement devices and procedures, for instrument operation as well as for calibrations. Three gas purifiers were tested for their removal efficiency of VOCs following a standardised procedure. Results show that not all purification methods removed VOCs from the zero gas and that a gas purifier needs to be tested before its intended application in the field.
Xuan Zhang, John Ortega, Yuanlong Huang, Stephen Shertz, Geoffrey S. Tyndall, and John J. Orlando
Atmos. Meas. Tech., 11, 2537–2551, https://doi.org/10.5194/amt-11-2537-2018, https://doi.org/10.5194/amt-11-2537-2018, 2018
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We present the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady state continuous
flow mode for simulating atmospheric daytime and nighttime chemistry over chemical regimes not accessible in traditional static chamber
experiments. We focus on establishing an
intermediate NOregime characterized by a constant steady-state NO level ranging from tens of ppt to a few ppb in the chamber.
Ulf Köhler, Saulius Nevas, Glen McConville, Robert Evans, Marek Smid, Martin Stanek, Alberto Redondas, and Fritz Schönenborn
Atmos. Meas. Tech., 11, 1989–1999, https://doi.org/10.5194/amt-11-1989-2018, https://doi.org/10.5194/amt-11-1989-2018, 2018
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Laboratory investigations of optical characteristics of three standard Dobsons provide real wavelength settings and slit functions. These parameters were compared with the original values given in the manuals. The differences between real and nominal values are not too large, but their application will in any case improve the quality of the total ozone column measurements in the global
network. This improvement was the main objective of the ATMOZ project funding these activities.
Christof Janssen, Hadj Elandaloussi, and Julian Gröbner
Atmos. Meas. Tech., 11, 1707–1723, https://doi.org/10.5194/amt-11-1707-2018, https://doi.org/10.5194/amt-11-1707-2018, 2018
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Monitoring ozone layer recovery at a rate of few percent per decade requires dedicated instrumentation and spectroscopic data of the highest quality. Highly accurate absorption cross sections of ozone are rare, especially in the important UV region between 300 and 340 nm. Our measurement provides the first reference point with permil level of accuracy in this range. Interestingly, our value is lower than currently used data. This might resolve an inconsistency between UV and IR measurements.
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Short summary
We describe a portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide. Combining this with a previous photolytic ozone (O3) source yields a calibrator that produces known mixing ratios of NO, O3, and nitrogen dioxide (NO2); NO2 is produced by the reaction of NO with O3. This portable
NO2/NO/O3 calibration source requires no external gas cylinders and can be used as a standard to calibrate O3 and NOx air pollution monitors in the field.
We describe a portable calibration source of nitric oxide (NO) based on the photolysis of...
