Articles | Volume 5, issue 7
Atmos. Meas. Tech., 5, 1719–1725, 2012
© Author(s) 2012. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Special issue: The CERN CLOUD experiment (ACP/AMT inter-journal SI)
Research article 19 Jul 2012
Research article | 19 Jul 2012
On-line determination of ammonia at low pptv mixing ratios in the CLOUD chamber
F. Bianchi et al.
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and PlatformsNew 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 extractionHigh-precision laser spectrometer for multiple greenhouse gas analysis in 1 mL air from ice core samplesA thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phasesInterference from alkenes in chemiluminescent NOx measurementsApplication of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phaseMeasurements of atmospheric He/N2 as an indicator of fossil fuel extraction and stratospheric circulationAtomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap-GC-AED) for atmospheric trace gas measurementsCalibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)Measurement of ammonia, amines and iodine compounds using protonated water cluster chemical ionization mass spectrometryAn instrument for in situ measurement of total ozone reactivityPortable calibrator for NO based on the photolysis of N2O and a combined NO2∕NO∕O3 source for field calibrations of air pollution monitorsA new instrument for time-resolved measurement of HO2 radicalsInvestigation of adsorption and desorption behavior of small-volume cylinders and its relevance for atmospheric trace gas analysisTowards an understanding of surface effects: testing of various materials in a small volume measurement chamber and its relevance for atmospheric trace gas analysisStability of halocarbons in air samples stored in stainless- steel canistersHigh-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniquesCharacterisation of the transfer of cluster ions through an atmospheric pressure interface time-of-flight mass spectrometer with hexapole ion guidesAddition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixturesMeasurements of delays of gas-phase compounds in a wide variety of tubing materials due to gas–wall interactionsEffects of gas–wall interactions on measurements of semivolatile compounds and small polar moleculesCharacterization of a commercial lower-cost medium-precision non-dispersive infrared sensor for atmospheric CO2 monitoring in urban areasEvaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic speciesCavity-enhanced photoacoustic sensor based on a whispering-gallery-mode diode laserUsing collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH4+ CIMS) to oxygenated volatile organic compoundsA broadband cavity-enhanced spectrometer for atmospheric trace gas measurements and Rayleigh scattering cross sections in the cyan region (470–540 nm)Large-volume air sample system for measuring 34S∕32S isotope ratio of carbonyl sulfideNew and improved infrared absorption cross sections for trichlorofluoromethane (CFC-11)Experiments with CO2-in-air reference gases in high-pressure aluminum cylindersPreflight calibration of the Chinese Environmental Trace Gases Monitoring Instrument (EMI)Production of highly oxygenated organic molecules (HOMs) from trace contaminants during isoprene oxidationPreparation and analysis of zero gases for the measurement of trace VOCs in air monitoringA steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levelsOptical characterisation of three reference Dobsons in the ATMOZ Project – verification of G. M. B. Dobson's original specificationsA new photometric ozone reference in the Huggins bands: the absolute ozone absorption cross section at the 325 nm HeCd laser wavelengthAssessing the degree of plug flow in oxidation flow reactors (OFRs): a study on a potential aerosol mass (PAM) reactorEffects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compoundsSystem for δ13C–CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopyA new method for atmospheric detection of the CH3O2 radicalInfluence of sample temperature and environmental humidity on measurements of benzene in ambient air by transportable GC-PIDThe effects of meteorological parameters and diffusive barrier reuse on the sampling rate of a passive air sampler for gaseous mercuryAn electrospray chemical ionization source for real-time measurement of atmospheric organic and inorganic vaporsCharacterization of interferences to in situ observations of δ13CH4 and C2H6 when using a cavity ring-down spectrometer at industrial sitesThe Caltech Photooxidation Flow Tube reactor: design, fluid dynamics and characterizationImproved methodologies for continuous-flow analysis of stable water isotopes in ice coresStratospheric Air Sub-sampler (SAS) and its application to analysis of Δ17O(CO2) from small air samples collected with an AirCoreSensitive detection of n-alkanes using a mixed ionization mode proton-transfer-reaction mass spectrometerA versatile, refrigerant- and cryogen-free cryofocusing–thermodesorption unit for preconcentration of traces gases in airRadiocarbon analysis of stratospheric CO2 retrieved from AirCore samplingMeasurement of isoprene nitrates by GCMSA new set-up for simultaneous high-precision measurements of CO2, δ13C-CO2 and δ18O-CO2 on small ice core samples
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,Short summary
Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Bernhard Bereiter, Béla Tuzson, Philipp Scheidegger, André Kupferschmid, Herbert Looser, Lars Mächler, Daniel Baggenstos, Jochen Schmitt, Hubertus Fischer, and Lukas Emmenegger
Atmos. Meas. Tech., 13, 6391–6406,Short summary
The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
Natalie I. Keehan, Bellamy Brownwood, Andrey Marsavin, Douglas A. Day, and Juliane L. Fry
Atmos. Meas. Tech., 13, 6255–6269,Short summary
This paper describes a new instrument (a thermal-dissociation–cavity ring-down spectrometer, TD-CRDS) for the measurement of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations affecting the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using a TD-CRDS for ambient and laboratory studies.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991,Short summary
We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMTShort summary
We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modelling shows that the method can be used for quantification of a wide range of atmospheric radicals and intermediates.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMT
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMTShort summary
A gas measurement device was developed to measure trace gases (ppt level) in the air based on an atomic emission detector. The instrument combines cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED). The CryoTrap–GC–AED’s instrumental setup, limits of detection and elemental performance are presented and discussed. Two measurement case studies are reported: one in Finnish boreal forest and other based on an aircraft campaign.
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,Short summary
In this study, a calibration device for OH and HO2 instruments is characterized at pressures of 275 to 1000 mbar, allowing instrument pressure sensitivity to be quantified to an accuracy of 22 % (1σ). Computational fluid dynamic simulations supporting the understanding of interactions between generated HOx and the instrument inlet led to enhanced determination of factors affecting instrument sensitivity.
Joschka Pfeifer, Mario Simon, Martin Heinritzi, Felix Piel, Lena Weitz, Dongyu Wang, Manuel Granzin, Tatjana Müller, Steffen Bräkling, Jasper Kirkby, Joachim Curtius, and Andreas Kürten
Atmos. Meas. Tech., 13, 2501–2522,Short summary
Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultrasensitive detection of ammonia at single-digit parts per trillion by volume levels. The instrument is further capable of measuring amines and a suite of iodine compounds at sub-parts per trillion by volume levels.
Roberto Sommariva, Louisa J. Kramer, Leigh R. Crilley, Mohammed S. Alam, and William J. Bloss
Atmos. Meas. Tech., 13, 1655–1670,Short summary
Ozone is a key atmospheric pollutant formed through chemical processing of natural and anthropogenic emissions and removed by reaction with organic compounds emitted by plants. We describe a new instrument – the
Total Ozone Reactivity Systemor TORS – that measures the total loss of ozone in the troposphere. The objective of the TORS instrument is to provide an estimate of the organic compounds emitted by plants which are not measured and thus to improve our understanding of the ozone budget.
John W. Birks, Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Stanley Strunk, Brian Carpenter, and Christine A. Ennis
Atmos. Meas. Tech., 13, 1001–1018,Short summary
We describe a portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide. Combining this with a previous photolytic ozone (O3) source yields a calibrator that produces known mixing ratios of NO, O3, and nitrogen dioxide (NO2); NO2 is produced by the reaction of NO with O3. This portable NO2/NO/O3 calibration source requires no external gas cylinders and can be used as a standard to calibrate O3 and NOx air pollution monitors in the field.
Thomas H. Speak, Mark A. Blitz, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 13, 839–852,Short summary
OH and HO2 radicals are important trace constituents of the atmosphere that are closely coupled via several types of reaction. This paper describes a new laboratory method to simultaneously determine OH kinetics and HO2 yields from chemical processes. The instrument also provides some time resolution on HO2 detection allowing one to separate HO2 produced from the target reaction from HO2 arising from secondary chemistry. Examples of applications are presented.
Ece Satar, Peter Nyfeler, Bernhard Bereiter, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 101–117,Short summary
Good-quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4 and H2O using a commercial and a novel laser spectroscopic analyzer.
Ece Satar, Peter Nyfeler, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 119–130,Short summary
To ensure the best preparation and measurement conditions for trace gases, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. In this article, the previously introduced aluminum measurement chamber is used to investigate materials such as glass, aluminum, copper, brass, steel and three different commercially available coatings. Our measurements focus on temperature and pressure dependencies for the species CO2, CO, CH4 and H2O using a CRDS analyzer.
Tanja J. Schuck, Ann-Katrin Blank, Elisa Rittmeier, Jonathan Williams, Carl A. M. Brenninkmeijer, Andreas Engel, and Andreas Zahn
Atmos. Meas. Tech., 13, 73–84,Short summary
Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless-steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds were depleted. Individual substances were additionally influenced by high mixing ratios of ozone.
Tesfaye A. Berhanu, John Hoffnagle, Chris Rella, David Kimhak, Peter Nyfeler, and Markus Leuenberger
Atmos. Meas. Tech., 12, 6803–6826,Short summary
Accurate measurement of variations in atmospheric O2 can provide useful information about atmospheric, biospheric, and oceanic processes, which is a challenge for existing measurement techniques. Here, we introduce a newly built high-precision, stable CRDS analyzer (Picarro G2207) that can measure O2 mixing ratios with a short-term precision of < 1 ppm and only requires calibration every 12 h. Measurements from tower and mountain sites are also presented.
Markus Leiminger, Stefan Feil, Paul Mutschlechner, Arttu Ylisirniö, Daniel Gunsch, Lukas Fischer, Alfons Jordan, Siegfried Schobesberger, Armin Hansel, and Gerhard Steiner
Atmos. Meas. Tech., 12, 5231–5246,Short summary
We introduce an alternative type of atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) with the main difference of using hexapole instead of quadrupole ion guides. The transfer of cluster ions through the hexapoles was characterised with focus on transmission efficiency, mass range and fragmentation of cluster ions. At the CERN CLOUD experiment we compared the performance of the ioniAPi-TOF with a standard quadrupole APi-TOF under controlled conditions.
Michal Lacko, Nijing Wang, Kristýna Sovová, Pavel Pásztor, and Patrik Španěl
Atmos. Meas. Tech., 12, 4965–4982,Short summary
The soft chemical ionization analytical technique of selected ion flow tube mass spectrometry, SIFT-MS, was enhanced by a fast GC pre-separation unit to identify individual isomers. Experiments were carried out with two GC columns, MXT-1 and MXT-Volatiles, using two reagent ions, H3O+ and NO+, on monoterpene samples (an artificial mixture and coniferous needles). Analyses of product ion ratios allowed for quantification of multiple monoterpenes in partially separated chromatograms.
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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.
Dhruv Mitroo, Yujian Sun, Daniel P. Combest, Purushottam Kumar, and Brent J. Williams
Atmos. Meas. Tech., 11, 1741–1756,Short summary
In light of the widespread use of chemical reactors that simulate daytime atmospheric chemistry, a more critical analysis of the engineering behind new ones is needed. This work seeks to evaluate the geometry and flow dynamics inside a novel reactor, the potential aerosol mass (PAM) reactor, to help researchers tailor its use based upon what chemistry is investigated.
Demetrios Pagonis, Jordan E. Krechmer, Joost de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 10, 4687–4696,Short summary
Laboratory studies were conducted to investigate gas-wall partitioning of atmospheric organic compounds in Teflon tubing and inside an instrument used to monitor concentrations. Rapid partitioning caused time delays in instrument response that vary with tubing length and diameter, flow rate, and compound volatility. Tubing delay times of seconds to hours were described using a model that also included effects of instrument surfaces. The results can enable better design of air sampling systems.
Dane Dickinson, Samuel Bodé, and Pascal Boeckx
Atmos. Meas. Tech., 10, 4507–4519,Short summary
Cavity ring-down spectroscopy (CRDS) is an increasingly popular technology for isotope analysis of trace gases. However, most commercial CRDS instruments are designed for continuous gas sampling and cannot reliably measure small discrete samples. We present a novel technical adaptation that allows routine analysis of 50 mL syringed samples on an isotopic-CO2 CRDS unit. Our method offers excellent accuracy and precision, fast sample throughput, and is easily implemented in other CRDS instruments.
Lavinia Onel, Alexander Brennan, Paul W. Seakins, Lisa Whalley, and Dwayne E. Heard
Atmos. Meas. Tech., 10, 3985–4000,Short summary
Methyl peroxy (CH3O2) radicals are the most abundant organic peroxy radical species and are critical intermediates in rapid chemical cycling at the heart of tropospheric oxidation. Despite their importance, at present CH3O2 radicals are not specifically measured in the atmosphere by any direct or indirect method. This work presents a new method for the selective and sensitive detection of CH3O2 radicals and its use for the measurement of CH3O2 in the atmospheric simulation chamber HIRAC.
Cristina Romero-Trigueros, Marta Doval Miñarro, Esther González Duperón, and Enrique González Ferradás
Atmos. Meas. Tech., 10, 4013–4022,Short summary
Benzene is a well-known carcinogen which is present in ambient air. Its concentrations have to be continuosly monitored by law. To obtain reliable and comparable measurements, benzene analysers have to be calibrated with standards. These standards are usually prepared without humidity. However, real measurements can be influenced by it. In this work we have found that ambient humidity has an effect on measurements, which depends on both the absolute humidity and the benzene concentration.
David S. McLagan, Carl P. J. Mitchell, Haiyong Huang, Batual Abdul Hussain, Ying Duan Lei, and Frank Wania
Atmos. Meas. Tech., 10, 3651–3660,Short summary
Laboratory experiments indicate that the sampling rate of a passive air sampler for gaseous mercury is (1) not affected by relative humidity, (2) increases slightly with increasing temperature because of the effect of temperature on molecular diffusivity, (3) increases only slightly with wind speed as long as the wind speed is at least 1 m/s, and (4) is not changed when previously deployed diffusive barriers are used.
Yue Zhao, Jeremy K. Chan, Felipe D. Lopez-Hilfiker, Megan A. McKeown, Emma L. D'Ambro, Jay G. Slowik, Jeffrey A. Riffell, and Joel A. Thornton
Atmos. Meas. Tech., 10, 3609–3625,Short summary
We present a novel atmospheric pressure electrospray chemical ionization (ESCI) source that can generate intense and stable currents of several specific reagent ions using a range of salt solutions prepared in methanol. We couple the ESCI source to a high-resolution time-of-flight mass spectrometer (HRToF-MS) and assess instrument performance through calibrations using different gas standards and measurements of organic mixtures formed by ozonolysis of α-pinene.
Sabina Assan, Alexia Baudic, Ali Guemri, Philippe Ciais, Valerie Gros, and Felix R. Vogel
Atmos. Meas. Tech., 10, 2077–2091,Short summary
This study is dedicated to improving measurement methods when using a Cavity Ring Down Spectroscopy instrument to measure methane at sites with elevated ethane concentrations such as Oil and Gas sites. The research was undertaken after measurements of natural gas samples suggested biased δ13CH4 results. Two instruments were extensively tested to characterize the cross sensitivities to ethane and δ13CH4 and propose corrections. Results indicate that it is imperative to account for the biases.
Yuanlong Huang, Matthew M. Coggon, Ran Zhao, Hanna Lignell, Michael U. Bauer, Richard C. Flagan, and John H. Seinfeld
Atmos. Meas. Tech., 10, 839–867,Short summary
We report on the development of a new laminar flow tube reactor for the study of gas-phase atmospheric chemistry and secondary organic aerosol formation. The present paper is devoted to the design and fluid dynamical characterization of the reactor. The results of gas and particle residence time distribution experiments in the reactor, together with an evaluation of the effect of non-isothermal conditions, are reported.
Tyler R. Jones, James W. C. White, Eric J. Steig, Bruce H. Vaughn, Valerie Morris, Vasileios Gkinis, Bradley R. Markle, and Spruce W. Schoenemann
Atmos. Meas. Tech., 10, 617–632,Short summary
New measurement systems have been developed that continuously melt ice core samples, in contrast to other methods that analyze a single sample at a time. These newer systems are capable of reducing analysis time by many years and improving data set resolution. In this study, we introduce improved methodologies that optimize the speed, accuracy, and precision of a water isotope continuous-flow system. The presented system will be used for Antarctic and Greenland ice core projects.
Dorota Janina Mrozek, Carina van der Veen, Magdalena E. G. Hofmann, Huilin Chen, Rigel Kivi, Pauli Heikkinen, and Thomas Röckmann
Atmos. Meas. Tech., 9, 5607–5620,Short summary
Stratospheric Air Sub-sampler (SAS) is a device to collect and to store the stratospheric profile of air collected with an AirCore (Karion et al., 2010) in numerous sub-samples. The sub-samples (each of 25 mL at ambient temperature and pressure) can be later introduced to the continuous flow systems to measure for example the isotopic composition of CO2. The performance of the coupled system is demonstrated for a set of air samples from an AirCore flight in November 2014 near Sodankylä, Finland.
Omar Amador-Muñoz, Pawel K. Misztal, Robin Weber, David R. Worton, Haofei Zhang, Greg Drozd, and Allen H. Goldstein
Atmos. Meas. Tech., 9, 5315–5329,Short summary
Proton transfer reaction mass spectrometry (PTR-MS) was used to detect n-alkanes that generally have a lower proton affinity than water and therefore proton transfer (PT) by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+) in the reaction chamber (drift tube).
Florian Obersteiner, Harald Bönisch, Timo Keber, Simon O'Doherty, and Andreas Engel
Atmos. Meas. Tech., 9, 5265–5279,Short summary
The analysis of trace gases in ambient air requires a preconcentration technique, in many cases to make the species of interest detectable and quantifiable. In this paper, such a preconcentration set-up is presented. Target species are trapped on adsorptive material cooled by a Stirling cooler which allows for a very low adsorption temperature but only requires electrical power. A simple and lightweight mechanical design guarantees very good suitability for remote-site field operation.
Dipayan Paul, Huilin Chen, Henk A. Been, Rigel Kivi, and Harro A. J. Meijer
Atmos. Meas. Tech., 9, 4997–5006,Short summary
Here we describe the determination of C-14 concentration in stratospheric CO2 samples collected using the AirCore sampling method. Two stratospheric AirCore profiles, collected in Sodankylä, were used for this study. The stratospheric profile was divided into six sections. CO2 from each section was extracted and converted to graphite for the determination of C-14 using AMS. Through this study, we show that the AirCore is a viable and valuable sampling method for stratospheric C-14 measurements.
Graham P. Mills, Glyn D. Hiatt-Gipson, Sean P. Bew, and Claire E. Reeves
Atmos. Meas. Tech., 9, 4533–4545,Short summary
The paper describes the development of an instrument to measure isoprene-derived nitrates in the atmosphere, compounds that are crucial to understanding the impact of biogenic hydrocarbons on ozone production. The instrument is suitable for deployment in field studies.
Theo Manuel Jenk, Mauro Rubino, David Etheridge, Viorela Gabriela Ciobanu, and Thomas Blunier
Atmos. Meas. Tech., 9, 3687–3706,Short summary
Atmospheric CO2 and δ13C-CO2 records from polar ice cores provide important constraints on the natural carbon cycle variability. Still, data exist only from a limited number of sampling sites and time periods due to demanding analytical challenges. Additional analytical state-of-the-art resources are desirable. This study describes such a new facility. Its analytical performance and new approaches for dealing with procedural blank contribution and analytical outliers are discussed in detail.
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