Articles | Volume 4, issue 3
Research article 11 Mar 2011
Research article | 11 Mar 2011
Calibration of atmospheric hydrogen measurements
A. Jordan and B. Steinberg
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Validation and IntercomparisonsImplementation of an incoherent broadband cavity-enhanced absorption spectroscopy technique in an atmospheric simulation chamber for in situ NO3 monitoring: characterization and validation for kinetic studiesA portable, robust, stable, and tunable calibration source for gas-phase nitrous acid (HONO)Characterising water vapour concentration dependence of commercial cavity ring-down spectrometers for continuous onsite atmospheric water vapour isotope measurements in the tropicsOptimisation of a thermal desorption–gas chromatography–mass spectrometry method for the analysis of monoterpenes, sesquiterpenes and diterpenesSIFT-MS optimization for atmospheric trace gas measurements at varying humidityN2O isotopocule measurements using laser spectroscopy: analyzer characterization and intercomparisonAn intercomparison of CH3O2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)Photoacoustic measurement with infrared band-pass filters significantly overestimates NH3 emissions from cattle houses due to volatile organic compound (VOC) interferencesIsotopic characterization of nitrogen oxides (NOx), nitrous acid (HONO), and nitrate (pNO3−) from laboratory biomass burning during FIREXA new laser-based and ultra-portable gas sensor for indoor and outdoor formaldehyde (HCHO) monitoringNegligible influence of livestock contaminants and sampling system on ammonia measurements with cavity ring-down spectroscopyPreparation of primary standard mixtures for atmospheric oxygen measurements with less than 1 µmol mol−1 uncertainty for oxygen molar fractionsThe interference of tetrachloromethane in the measurement of benzene in the air by a gas chromatography–photoionisation detector (GC-PID)Evaluation of cation exchange membrane performance under exposure to high Hg0 and HgBr2 concentrationsGravimetrically prepared carbon dioxide standards in support of atmospheric researchThe importance of cylinder passivation for preparation and long-term stability of multicomponent monoterpene primary reference materialsDynamic–gravimetric preparation of metrologically traceable primary calibration standards for halogenated greenhouse gasesThe water vapour self-continuum absorption in the infrared atmospheric windows: new laser measurements near 3.3 and 2.0 µmInterlaboratory comparison of δ13C and δD measurements of atmospheric CH4 for combined use of data sets from different laboratoriesAbsolute, pressure-dependent validation of a calibration-free, airborne laser hygrometer transfer standard (SEALDH-II) from 5 to 1200 ppmv using a metrological humidity generatorAn intercomparison of HO2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)Abundances of isotopologues and calibration of CO2 greenhouse gas measurementsIntercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2 ∕ 12CO2 measurementDevelopment and evaluation of a suite of isotope reference gases for methane in airMIPAS database: new HNO3 line parameters at 7.6 µm validated with MIPAS satellite measurementsChallenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and offline GC-FIDTwin-cuvette measurement technique for investigation of dry deposition of O3 and PAN to plant leaves under controlled humidity conditionsGas adsorption and desorption effects on cylinders and their importance for long-term gas recordsHOx radical chemistry in oxidation flow reactors with low-pressure mercury lamps systematically examined by modelingACTRIS non-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networksA method for stable carbon isotope ratio and concentration measurements of ambient aromatic hydrocarbonsInstrument intercomparison of glyoxal, methyl glyoxal and NO2 under simulated atmospheric conditionsMeasuring acetic and formic acid by proton-transfer-reaction mass spectrometry: sensitivity, humidity dependence, and quantifying interferencesAccurate measurements of ozone absorption cross-sections in the Hartley bandPressure-dependent calibration of the OH and HO2 channels of a FAGE HOx instrument using the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC)Quantitative infrared absorption cross sections of isoprene for atmospheric measurementsThe AquaVIT-1 intercomparison of atmospheric water vapor measurement techniquesCharacterization and mitigation of water vapor effects in the measurement of ozone by chemiluminescence with nitric oxideResults from the International Halocarbons in Air Comparison Experiment (IHALACE)A smog chamber comparison of a microfluidic derivatisation measurement of gas-phase glyoxal and methylglyoxal with other analytical techniquesHigh-precision analysis of SF6 at ambient levelJena Reference Air Set (JRAS): a multi-point scale anchor for isotope measurements of CO2 in airA combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic airQuantification of biogenic volatile organic compounds with a flame ionization detector using the effective carbon number conceptMeasuring variations of δ18O and δ2H in atmospheric water vapour using two commercial laser-based spectrometers: an instrument characterisation studySimultaneous stable isotope analysis of methane and nitrous oxide on ice core samplesA high volume sampling system for isotope determination of volatile halocarbons and hydrocarbonsAbsolute accuracy and sensitivity analysis of OP-FTIR retrievals of CO2, CH4 and CO over concentrations representative of "clean air" and "polluted plumes"
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Pascal Zapf, Guillaume Siour, Xavier Landsheere, Guillaume Méjean, Daniele Romanini, and Bénédicte Picquet-Varrault
Atmos. Meas. Tech., 13, 6311–6323,Short summary
An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals in the CSA simulation chamber at LISA. The optical cavity allows a high sensitivity for NO3 detection up to 6 ppt for an integration time of 10 s. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (with rate constants up to 10−10 cm3 molecule−1 s−1).
Melodie Lao, Leigh R. Crilley, Leyla Salehpoor, Teles C. Furlani, Ilann Bourgeois, J. Andrew Neuman, Andrew W. Rollins, Patrick R. Veres, Rebecca A. Washenfelder, Caroline C. Womack, Cora J. Young, and Trevor C. VandenBoer
Atmos. Meas. Tech., 13, 5873–5890,Short summary
Nitrous acid (HONO) is a key intermediate in the generation of oxidants and fate of nitrogen oxides in the atmosphere. High-purity calibration sources that produce stable atmospherically relevant levels under field conditions have not been made to date, reducing measurement accuracy. In this study a simple salt-coated tube humidified with water vapor is demonstrated to produce pure stable low levels of HONO, with modifications allowing the generation of higher amounts.
Shujiro Komiya, Fumiyoshi Kondo, Heiko Moossen, Thomas Seifert, Uwe Schultz, Heike Geilmann, David Walter, and Jost V. Lavric
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMTShort summary
The Amazon basin influences the atmospheric and hydrological cycles on local to global scales. To better understand how, we plan to perform continuous on-site measurements of the stable isotope composition of atmospheric water vapour. For making accurate on-site observations possible, we have investigated the performance of two commercial analysers and determined the best calibration strategy. Well-calibrated, both analysers will allow us to record natural signals in the Amazon rainforest.
Aku Helin, Hannele Hakola, and Heidi Hellén
Atmos. Meas. Tech., 13, 3543–3560,Short summary
A thermal desorption–gas chromatography–mass spectrometry method following sorbent tube sampling was developed for the determination of terpenes in gas-phase samples. The main focus was on the analysis of diterpenes, which have been limited in study in gas-phase samples. The analytical figures of merit were fit for purpose (e.g. quantitation limits <10 pptv and reproducibility <10 % for terpenes). Diterpenes could be detected and identified in emissions from spruce and pine samples.
Ann-Sophie Lehnert, Thomas Behrendt, Alexander Ruecker, Georg Pohnert, and Susan E. Trumbore
Atmos. Meas. Tech., 13, 3507–3520,Short summary
Volatile organic compounds (VOCs) like scents can appear and disappear quickly. For example, when a bug starts on a tree, the tree releases VOCs that warn the trees around him. Thus, one needs instruments measuring their concentration in real time and identify which VOC is measured. In our study, we compared two instruments doing that, PTR-MS and SIFT-MS. Both work similarly, but we found that the PTR-MS can measure lower concentrations, but the SIFT-MS can identify VOCs better.
Stephen J. Harris, Jesper Liisberg, Longlong Xia, Jing Wei, Kerstin Zeyer, Longfei Yu, Matti Barthel, Benjamin Wolf, Bryce F. J. Kelly, Dioni I. Cendón, Thomas Blunier, Johan Six, and Joachim Mohn
Atmos. Meas. Tech., 13, 2797–2831,Short summary
The latest commercial laser spectrometers have the potential to revolutionize N2O isotope analysis. However, to do so, they must be able to produce trustworthy data. Here, we test the performance of widely used laser spectrometers for ambient air applications and identify instrument-specific dependencies on gas matrix and trace gas concentrations. We then provide a calibration workflow to facilitate the operation of these instruments in order to generate reproducible and accurate data.
Lavinia Onel, Alexander Brennan, Michele Gianella, James Hooper, Nicole Ng, Gus Hancock, Lisa Whalley, Paul W. Seakins, Grant A. D. Ritchie, and Dwayne E. Heard
Atmos. Meas. Tech., 13, 2441–2456,
Dezhao Liu, Li Rong, Jesper Kamp, Xianwang Kong, Anders Peter S. Adamsen, Albarune Chowdhury, and Anders Feilberg
Atmos. Meas. Tech., 13, 259–272,
Jiajue Chai, David J. Miller, Eric Scheuer, Jack Dibb, Vanessa Selimovic, Robert Yokelson, Kyle J. Zarzana, Steven S. Brown, Abigail R. Koss, Carsten Warneke, and Meredith Hastings
Atmos. Meas. Tech., 12, 6303–6317,Short summary
Isotopic analysis offers a potential tool to distinguish between sources and interpret transformation pathways of atmospheric species. We applied recently developed techniques in our lab to characterize the isotopic composition of reactive nitrogen species (NOx, HONO, HNO3, pNO3-) in fresh biomass burning emissions. Intercomparison with other techniques confirms the suitability of our methods, allowing for future applications of our techniques in a variety of environments.
Joshua D. Shutter, Norton T. Allen, Thomas F. Hanisco, Glenn M. Wolfe, Jason M. St. Clair, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 6079–6089,Short summary
A new mid-infrared and ultra-portable formaldehyde (HCHO) sensor from Aeris Technologies is characterized and evaluated against well-established laser-induced fluorescence (LIF) instrumentation. The Aeris sensor displays linear behavior (R squared > 0.94) and shows good agreement with LIF instruments. While the compact sensor is not currently a replacement for the most sensitive research-grade instrumentation available, its sub-ppbv precision is sufficient for indoor and outdoor HCHO monitoring.
Jesper Nørlem Kamp, Albarune Chowdhury, Anders Peter S. Adamsen, and Anders Feilberg
Atmos. Meas. Tech., 12, 2837–2850,Short summary
We tested the performance of a cavity ring-down spectroscopy (CRDS) instrument from Picarro for measuring ammonia. Interference tests with 10 volatile organic compounds (VOCs) were conducted to find potential interference of these VOCs. Calibrations show excellent linearity over a large dynamic range of NH3 concentrations. There is negligible interference from humidity and few of the tested VOCs. Overall, the CRDS system performs well with only negligible influence from other compounds.
Nobuyuki Aoki, Shigeyuki Ishidoya, Nobuhiro Matsumoto, Takuro Watanabe, Takuya Shimosaka, and Shohei Murayama
Atmos. Meas. Tech., 12, 2631–2646,Short summary
Observation of atmospheric O2 requires highly precise standard gas mixtures with uncertainty of less than 1 ppm for the O2 mole fraction or 5 per meg for O2 / N2. The uncertainty had not been achieved due unknown uncertainty factors in mass determination of the filled source gases. We first developed the primary standard mixtures with 1 ppm for the O2 mole fraction or 5 per meg by identifying and reducing the unknown uncertainty factors.
Cristina Romero-Trigueros, María Esther González, Marta Doval Miñarro, and Enrique González Ferradás
Atmos. Meas. Tech., 12, 1685–1695,Short summary
Determining benzene in ambient air is mandatory in the European Union. The reference measuring technique is by gas chromatography (GC), and a photometric ionisation detector is recommended. This study shows that the simultaneous presence of benzene and tetrachloromethane causes a significant decrease in GC–photoionisation detector (GC-PID) readings. Given the importance of this behaviour, a possible mechanism was proposed. This study highlights the uncertainty of measuring benzene with a GC-PID.
Matthieu B. Miller, Sarrah M. Dunham-Cheatham, Mae Sexauer Gustin, and Grant C. Edwards
Atmos. Meas. Tech., 12, 1207–1217,Short summary
This study was undertaken to demonstrate that a cation exchange membrane (CEM) material used for sampling reactive mercury (RM) does not possess an inherent tendency to collect gaseous elemental mercury (GEM). Using a custom-built mercury vapor permeation system, we found that the CEM material has a very small GEM uptake of approximately 0.004 %, too small to create a significant artifact. We also found that a representative RM compound was collected by the CEM material with high efficiency.
Bradley D. Hall, Andrew M. Crotwell, Benjamin R. Miller, Michael Schibig, and James W. Elkins
Atmos. Meas. Tech., 12, 517–524,Short summary
We have used a one-step method for gravimetric preparation of CO2-in-air standards in aluminum cylinders. We consider both adsorption to stainless steel surfaces used in the transfer of highly pure CO2 and adsorption of CO2 to cylinder walls. This work compliments ongoing efforts to support atmospheric monitoring of CO2.
Nicholas D. C. Allen, David R. Worton, Paul J. Brewer, Celine Pascale, and Bernhard Niederhauser
Atmos. Meas. Tech., 11, 6429–6438,Short summary
This paper investigates the stability of trace level static terpene primary reference materials (PRMs) and how the choice of passivation affects this process. For the first time, sampling canisters that can be used in the field are tested and demonstrated to be suitable for terpene mixtures. The PRMs were compared against a novel dynamic generator system based on dilution of pure limonene vapour emitted from a permeation tube. The effect of cylinder pressure and decanting are also investigated.
Myriam Guillevic, Martin K. Vollmer, Simon A. Wyss, Daiana Leuenberger, Andreas Ackermann, Céline Pascale, Bernhard Niederhauser, and Stefan Reimann
Atmos. Meas. Tech., 11, 3351–3372,Short summary
We present new primary calibration scales for five halogenated greenhouse gases. The preparation method, newly applied to halocarbons, is dynamic and gravimetric and allows the generation of reference gas mixtures at near-ambient levels (pmol mol−1). Each prepared molar fraction is traceable to the realisation of SI units (International System of Units) and is assigned an uncertainty estimate following international guidelines.
Loic Lechevallier, Semen Vasilchenko, Roberto Grilli, Didier Mondelain, Daniele Romanini, and Alain Campargue
Atmos. Meas. Tech., 11, 2159–2171,Short summary
The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long standing issue in molecular spectroscopy with a direct impact in atmospheric and planetary sciences. Using highly sensitive laser spectrometers, the water self continuum has been determined with unprecedented sensitivity in infrared atmospheric transparency windows.
Taku Umezawa, Carl A. M. Brenninkmeijer, Thomas Röckmann, Carina van der Veen, Stanley C. Tyler, Ryo Fujita, Shinji Morimoto, Shuji Aoki, Todd Sowers, Jochen Schmitt, Michael Bock, Jonas Beck, Hubertus Fischer, Sylvia E. Michel, Bruce H. Vaughn, John B. Miller, James W. C. White, Gordon Brailsford, Hinrich Schaefer, Peter Sperlich, Willi A. Brand, Michael Rothe, Thomas Blunier, David Lowry, Rebecca E. Fisher, Euan G. Nisbet, Andrew L. Rice, Peter Bergamaschi, Cordelia Veidt, and Ingeborg Levin
Atmos. Meas. Tech., 11, 1207–1231,Short summary
Isotope measurements are useful for separating different methane sources. However, the lack of widely accepted standards and calibration methods for stable carbon and hydrogen isotopic ratios of methane in air has caused significant measurement offsets among laboratories. We conducted worldwide interlaboratory comparisons, surveyed the literature and assessed them systematically. This study may be of help in future attempts to harmonize data sets of isotopic composition of atmospheric methane.
Bernhard Buchholz and Volker Ebert
Atmos. Meas. Tech., 11, 459–471,Short summary
This paper describes the absolute validation of the novel, calibration-free SEALDH-II hygrometer at a traceable humidity generator. During 23 days of permanent operation, 15 H2O mole fractions levels (5–1200 ppmv) at 6 gas pressures (65–950 hPa) were validated. With this validation, SEALDH-II is the first metrologically validated humidity transfer standard which links several scientific airborne and laboratory measurement campaigns to the international metrological water vapor scale.
Lavinia Onel, Alexander Brennan, Michele Gianella, Grace Ronnie, Ana Lawry Aguila, Gus Hancock, Lisa Whalley, Paul W. Seakins, Grant A. D. Ritchie, and Dwayne E. Heard
Atmos. Meas. Tech., 10, 4877–4894,Short summary
Hydroperoxy (HO2) radicals are key intermediates participating in a rapid chemical cycling at the centre of the tropospheric oxidation. Fluorescence assay by gas expansion (FAGE) technique is the most commonly used for the HO2 measurements in the atmosphere. However, FAGE is an indirect technique, requiring calibration. This work finds a good agreement between the indirect FAGE method and the direct cavity ring-down spectroscopy method and hence validates FAGE and the FAGE calibration method.
Pieter P. Tans, Andrew M. Crotwell, and Kirk W. Thoning
Atmos. Meas. Tech., 10, 2669–2685,Short summary
We describe a new CO2 calibration system for the Central Calibration Laboratory of the World Meteorological Organization Global Atmosphere Watch program. The system uses two laser spectroscopic instruments to measure the three major CO2 isotopologues individually. We account for isotopic differences between standards in the calibration hierarchy when assigning CO2 mole fraction, eliminating bias due to variations in the isotopic composition.
Jiaping Pang, Xuefa Wen, Xiaomin Sun, and Kuan Huang
Atmos. Meas. Tech., 9, 3879–3891,
Peter Sperlich, Nelly A. M. Uitslag, Jürgen M. Richter, Michael Rothe, Heike Geilmann, Carina van der Veen, Thomas Röckmann, Thomas Blunier, and Willi A. Brand
Atmos. Meas. Tech., 9, 3717–3737,Short summary
Isotope measurements in atmospheric CH4 are performed since more than 3 decades. However, standard gases to harmonize global measurements are not available to this day. We designed two methods to calibrate a suite of 8 CH4 gases with a wide range in isotopic composition to the VPDB and VSMOW scales with high precision and accuracy. Synthetic air mixtures with ~2 ppm of calibrated CH4 can be provided to the community by the ISOLAB of the Max Planck Institute for Biogeochemistry in Jena, Germany.
Agnès Perrin, Jean-Marie Flaud, Marco Ridolfi, Jean Vander Auwera, and Massimo Carlotti
Atmos. Meas. Tech., 9, 2067–2076,Short summary
Improved line positions and intensities have been generated for the 7.6 µm spectral region of nitric acid, relying on a recent laboratory reinvestigation and comparisons of HNO3 volume mixing ratios retrieved from Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) radiances in the 11 and 7.6 µm regions. The much improved consistency of line intensities in both regions will make it possible to use them simultaneously to retrieve atmospheric HNO3.
Véronique Perraud, Simone Meinardi, Donald R. Blake, and Barbara J. Finlayson-Pitts
Atmos. Meas. Tech., 9, 1325–1340,Short summary
Gas phase organosulfur compounds in air serve as precursors of particles which impact human health, visibility, and climate. We compare here two different approaches to measuring these compounds, one an online mass spectrometry technique and the other canister sampling followed by offline analysis by gas chromatography. We show that each approach has its own advantages and limitations in measuring these compounds in complex mixtures, including some artifacts due to reactions on surfaces.
Shang Sun, Alexander Moravek, Lisa von der Heyden, Andreas Held, Matthias Sörgel, and Jürgen Kesselmeier
Atmos. Meas. Tech., 9, 599–617,Short summary
We present a dynamic twin-cuvette system for quantifying the trace gas exchange fluxes between plants and the atmosphere under controlled temperature, light, and humidity conditions. We found out that at a relative humidity of 40 %, the deposition velocity ratio of O3 and PAN was determined to be 0.45. At that humidity, the O3-deposition to the plant leaves was found to be only controlled by leaf stomata. For PAN, an additional resistance inhibited the uptake of PAN by the leaves.
M. C. Leuenberger, M. F. Schibig, and P. Nyfeler
Atmos. Meas. Tech., 8, 5289–5299,Short summary
Adsorption/desorption effects of trace gases in gas cylinders were investigated. Our measurements indicate a rather strong effect on steel cylinders for CO2 that becomes easily visible through enhanced concentrations for low (<20 bars) gas pressure. Much smaller effects are observed for CO and CH4. Significantly smaller effects are measured for all gas species investigated on aluminium cylinders. Careful selection of gas cylinders for high-precision calibration purposes is recommended.
Z. Peng, D. A. Day, H. Stark, R. Li, J. Lee-Taylor, B. B. Palm, W. H. Brune, and J. L. Jimenez
Atmos. Meas. Tech., 8, 4863–4890,
C. C. Hoerger, A. Claude, C. Plass-Duelmer, S. Reimann, E. Eckart, R. Steinbrecher, J. Aalto, J. Arduini, N. Bonnaire, J. N. Cape, A. Colomb, R. Connolly, J. Diskova, P. Dumitrean, C. Ehlers, V. Gros, H. Hakola, M. Hill, J. R. Hopkins, J. Jäger, R. Junek, M. K. Kajos, D. Klemp, M. Leuchner, A. C. Lewis, N. Locoge, M. Maione, D. Martin, K. Michl, E. Nemitz, S. O'Doherty, P. Pérez Ballesta, T. M. Ruuskanen, S. Sauvage, N. Schmidbauer, T. G. Spain, E. Straube, M. Vana, M. K. Vollmer, R. Wegener, and A. Wenger
Atmos. Meas. Tech., 8, 2715–2736,Short summary
The performance of 20 European laboratories involved in long-term non-methane hydrocarbon (NMHC) measurements was assessed with respect to ACTRIS and GAW data quality objectives. The participants were asked to measure both a 30-component NMHC mixture in nitrogen and whole air. The NMHCs were analysed either by GC-FID or GC-MS. Most systems performed well for the NMHC in nitrogen, whereas in air more scatter was observed. Reasons for this are explained in the paper.
A. Kornilova, S. Moukhtar, M. Saccon, L. Huang, W. Zhang, and J. Rudolph
Atmos. Meas. Tech., 8, 2301–2313,Short summary
A technique for compound specific analysis of stable carbon isotope ratios and concentration of ambient volatile organic compounds (VOC) is presented. It is based on selective VOC sampling onto adsorbent filled cartridges. Examples of measurements conducted demonstrate that the ability to make accurate measurements in air with low VOC mixing ratios is important to avoid bias from an overrepresentation of samples that are strongly impacted by recent emissions.
R. Thalman, M. T. Baeza-Romero, S. M. Ball, E. Borrás, M. J. S. Daniels, I. C. A. Goodall, S. B. Henry, T. Karl, F. N. Keutsch, S. Kim, J. Mak, P. S. Monks, A. Muñoz, J. Orlando, S. Peppe, A. R. Rickard, M. Ródenas, P. Sánchez, R. Seco, L. Su, G. Tyndall, M. Vázquez, T. Vera, E. Waxman, and R. Volkamer
Atmos. Meas. Tech., 8, 1835–1862,Short summary
Measurements of α-dicarbonyl compounds, like glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO), are informative about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation in the atmosphere. We have compared nine instruments and seven techniques to measure α-dicarbonyl, using simulation chamber facilities in the US and Europe. We assess our understanding of calibration, precision, accuracy and detection limits, as well as possible sampling biases.
M. Baasandorj, D. B. Millet, L. Hu, D. Mitroo, and B. J. Williams
Atmos. Meas. Tech., 8, 1303–1321,
J. Viallon, S. Lee, P. Moussay, K. Tworek, M. Petersen, and R. I. Wielgosz
Atmos. Meas. Tech., 8, 1245–1257,
F. A. F. Winiberg, S. C. Smith, I. Bejan, C. A. Brumby, T. Ingham, T. L. Malkin, S. C. Orr, D. E. Heard, and P. W. Seakins
Atmos. Meas. Tech., 8, 523–540,
C. S. Brauer, T. A. Blake, A. B. Guenther, S. W. Sharpe, R. L. Sams, and T. J. Johnson
Atmos. Meas. Tech., 7, 3839–3847,
D. W. Fahey, R.-S. Gao, O. Möhler, H. Saathoff, C. Schiller, V. Ebert, M. Krämer, T. Peter, N. Amarouche, L. M. Avallone, R. Bauer, Z. Bozóki, L. E. Christensen, S. M. Davis, G. Durry, C. Dyroff, R. L. Herman, S. Hunsmann, S. M. Khaykin, P. Mackrodt, J. Meyer, J. B. Smith, N. Spelten, R. F. Troy, H. Vömel, S. Wagner, and F. G. Wienhold
Atmos. Meas. Tech., 7, 3177–3213,
P. Boylan, D. Helmig, and J.-H. Park
Atmos. Meas. Tech., 7, 1231–1244,
B. D. Hall, A. Engel, J. Mühle, J. W. Elkins, F. Artuso, E. Atlas, M. Aydin, D. Blake, E.-G. Brunke, S. Chiavarini, P. J. Fraser, J. Happell, P. B. Krummel, I. Levin, M. Loewenstein, M. Maione, S. A. Montzka, S. O'Doherty, S. Reimann, G. Rhoderick, E. S. Saltzman, H. E. Scheel, L. P. Steele, M. K. Vollmer, R. F. Weiss, D. Worthy, and Y. Yokouchi
Atmos. Meas. Tech., 7, 469–490,
X. Pang, A. C. Lewis, A. R. Rickard, M. T. Baeza-Romero, T. J. Adams, S. M. Ball, M. J. S. Daniels, I. C. A. Goodall, P. S. Monks, S. Peppe, M. Ródenas García, P. Sánchez, and A. Muñoz
Atmos. Meas. Tech., 7, 373–389,
J. S. Lim, D. M. Moon, J. S. Kim, W.-T. Yun, and J. Lee
Atmos. Meas. Tech., 6, 2293–2299,
M. Wendeberg, J. M. Richter, M. Rothe, and W. A. Brand
Atmos. Meas. Tech., 6, 817–822,
P. Sperlich, M. Guillevic, C. Buizert, T. M. Jenk, C. J. Sapart, H. Schaefer, T. J. Popp, and T. Blunier
Atmos. Meas. Tech., 5, 2227–2236,
C. L. Faiola, M. H. Erickson, V. L. Fricaud, B. T. Jobson, and T. M. VanReken
Atmos. Meas. Tech., 5, 1911–1923,
F. Aemisegger, P. Sturm, P. Graf, H. Sodemann, S. Pfahl, A. Knohl, and H. Wernli
Atmos. Meas. Tech., 5, 1491–1511,
C. J. Sapart, C. van der Veen, I. Vigano, M. Brass,, R. S. W. van de Wal, M. Bock, H. Fischer, T. Sowers, C. Buizert, P. Sperlich, T. Blunier, M. Behrens, J. Schmitt, B. Seth, and T. Röckmann
Atmos. Meas. Tech., 4, 2607–2618,
E. Bahlmann, I. Weinberg, R. Seifert, C. Tubbesing, and W. Michaelis
Atmos. Meas. Tech., 4, 2073–2086,
T. E. L. Smith, M. J. Wooster, M. Tattaris, and D. W. T. Griffith
Atmos. Meas. Tech., 4, 97–116,
Aalto, T., Lallo, M., Hatakka, J., and Laurila, T.: Atmospheric hydrogen variations and traffic emissions at an urban site in Finland, Atmos. Chem. Phys., 9, 7387–7396, https://doi.org/10.5194/acp-9-7387-2009, 2009.
Aluminum Association: International Alloy Designations and Chemical Composition Limits for Wrought Aluminum and Wrought Aluminum Alloys, http://www.aluminum.org/Content/NavigationMenu/TheIndustry/IndustryStandards/Teal_Sheet_Final_031009_PRINTED.pdf, last access: 7 October, 2010.
Bever, M. B.: Encyclopedia of material science and engineering, Pergamon Press, Oxford, UK, 1986.
Beyer, B., Cyrener, E., Grahl, F., Holze, J., Molle, W., and Paul, M.: Tabellenbuch Aluminiumwerkstoffe, 2, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, Germany, 1986.
Bonasoni, P., Calzolari, F., Colombo, T., Corazza, E., Santaguida, R., and Tesi, G.: Continuous CO and H2 measurements at Mt. Cimone (Italy): Preliminary results, Atmos. Environ., 31(7), 959–967, 1997.
Bond, S. W., Vollmer, M. K., Steinbacher, M., Henne, S., and Reimann, S.: Atmospheric molecular hydrogen (H2): observations at the high-altitude site Jungfraujoch, Switzerland, Tellus B, 63(1), 64–76, https://doi.org/10.1111/j.1600-0889.2010.00509.x, 2011.
Brown, R. J. C. and Milton, M. J. T.: Developments in accurate and traceable chemical measurements, Chem. Soc. Rev., 36, 904–913, 2007.
Ehhalt, D. H. and Rohrer, F.: The tropospheric cycle of H2: a critical review, Tellus B, 61(3), 500–535, https://doi.org/10.1111/j.1600-0889.2009.00416.x, 2009.
Francey, R. J., Steele, L. P., Langenfelds, R. L., Lucarelli, M. P., Allison, C. E., Beardsmore, D. J., Coram, S. A., Derek, N., de Silva, F. A., Etheridge, D. M., Fraser, P. J., Henry, R. J., Turner, B., Welch, E. D., Spencer, D. A., and Cooper, L. N.: Global Atmospheric Sampling Laboratory (GASLAB): supporting and extending the Cape Grim trace gas program, in: Baseline Atmospheric Program Australia 1993, Bureau of Meteorology and CSIRO Division of Atmospheric Research, Melbourne, 23–25, 1996.
Grant, A., Witham, C. S., Simmonds, P. G., Manning, A. J., and O'Doherty, S.: A 15 year record of high-frequency, in situ measurements of hydrogen at Mace Head, Ireland, Atmos. Chem. Phys., 10, 1203–1214, https://doi.org/10.5194/acp-10-1203-2010, 2010a.
Grant, A., Stanley, K. F., Henshaw, S. J., Shallcross, D. E., and O'Doherty, S.: High-frequency urban measurements of molecular hydrogen and carbon monoxide in the United Kingdom, Atmos. Chem. Phys., 10, 4715–4724, https://doi.org/10.5194/acp-10-4715-2010, 2010b.
Hammer, S. and Levin, I.: Seasonal variation of the molecular hydrogen uptake by soils inferred from continuous atmospheric observations in Heidelberg, southwest Germany, Tellus B, 61(3), 556–565, https://doi.org/10.1111/j.1600-0889.2009.00417.x, 2009.
Hammer, S., Vogel, F., Kaul, M., and Levin, I.: The H2/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany, Tellus B, 61(3), 547–555, https://doi.org/10.1111/j.1600-0889.2009.00418.x, 2009.
IMECC – Infrastructure for Measurements of the European Carbon Cycle: Sausage Flask Intercomparison, http://imecc.ipsl.jussieu.fr/web_na3/index.php?p=ts_lsce_all&rub=r12&smenu=smenuInfo1, last access: 18 February, 2011.
Jordan, A.: Calibration of atmospheric hydrogen, in: Proceedings of the 14th WMO/IAEA meeting of experts on carbon dioxide, other greenhouse gases and related tracers measurement techniques, edited by: Laurila, T., WMO Technical Document No. 1487, World Meteorological Organisation, Geneva, CH, 21–25, 2009.
Kehiaian, H. V.: Virial coefficients of selected gases, in: CRC Handbook of Chemistry and Physics, 77, edited by: Lide, D. R., CRC Press, Boca Raton, USA, 6.27–6.46, 1997.
Khalil, M. A. K. and Rasmussen, R. A.: Global increase of atmospheric molecular-hydrogen, Nature, 347(6295), 743–745, 1990.
Lallo, M., Aalto, T., Hatakka, J., and Laurila, T.: Hydrogen soil deposition at an urban site in Finland, Atmos. Chem. Phys., 9, 8559–8571, https://doi.org/10.5194/acp-9-8559-2009, 2009.
Langenfelds, R. L., Francey, R. J., Pak, B. C., Steele, L. P., Lloyd, J., Trudinger, C. M., and Allison, C. E.: Interannual growth rate variations of atmospheric CO2 and its delta 13C, H2, CH4, and CO between 1992 and 1999 linked to biomass burning, Global Biogeochem. Cy., 16(3), 1048, https://doi.org/10.1029/2001GB001466, 2002.
Masarie, K. A., Langenfelds, R. L., Allison, C. E., Conway, T. J., Dlugokencky, E. J., Francey, R. J., Novelli, P. C., Steele, L. P., Tans, P. P., Vaughn, B., and White, J. W. C.: NOAA/CSIRO Flask Air Intercomparison Experiment: A strategy for directly assessing consistency among atmospheric measurements made by independent laboratories, J. Geophys. Res., 106(D17), 20445–20464, 2001.
Monson, L., Moon, S. I., and Extrand, C. W.: Gas Permeation Resistance of Various Grades of Perfluoroalkoxy-Polytetrafluoroethylene Copolymers, J. Appl. Polym. Sci., 111(1), 141–147, https://doi.org/10.1002/app.28858, 2009.
Necki, J. M., Heliasz, M., Rosiek, J., Pycia, M., Rozanski, K., Sliwka, L., and Bartyzel, J.: Detection of atmospheric hydrogen using ECD detector doped with N2O, Chem. Anal.-Warsaw, 54(4), 705–716, 2009.
NOAA, NASA, USAF: U.S. Standard Atmosphere 1976, U.S. Government Printing Office, Washington, DC, USA, 1976.
NOAA-ESRL-GMD Standard Reference Gases: Products and Services, http://www.esrl.noaa.gov/gmd/ccl/services.html, last access: 7 October, 2010.
Novelli, P. C., Lang, P. M., Masarie, K. A., Hurst, D. F., Myers, R., and Elkins, J. W.: Molecular hydrogen in the troposphere: Global distribution and budget, J. Geophys. Res., 104(D23), 30427–30444, 1999.
Novelli, P. C., Crotwell, A. M., and Hall, B. D.: Application of gas chromatography with a pulsed discharge helium ionization detector for measurements of molecular hydrogen in the atmosphere, Environ. Sci. Technol., 43(7), 2431–2436, https://doi.org/10.1021/es803180g, 2009.
Ostermann, F.: Anwendungstechnologie Aluminium, Springer, Berlin, Germany, 1998.
Paglia, G., Buckley, C. E., Udovic, T. J., Rohl, A. L., Jones, F., Maitland, C. F., and Connolly, J.: Boehmite-derived γ-alumina system, 2. Consideration of hydrogen and surface effects: consideration of hydrogen and surface effects, Chem. Mater., 16, 1914–1923, 2004.
Park, S. Y., Kim, J. S., Lee, J. B., Esler, M. B. Davis, R. S., and Wielgosz, R. I.: A redetermination of the argon content of air for buoyancy corrections in mass standard comparisons, Metrologia, 41(6), 387–395, 2004.
Prather, M. J.: An environmental experiment with H2?, Science, 302(5645), 581–582, 2003.
Schmidt, U.: Molecular-hydrogen in atmosphere, Tellus, 26(1–2), 78–90, 1974.
Schmidt, U. and Seiler, W.: A new method for recording molecular hydrogen in atmospheric air, J. Geophys. Res., 75(9), 1713–1716, 1970.
Simmonds, P. G., Derwent, R. G., O'Doherty, S., Ryall, D. B., Steele, L. P., Langenfelds, R. L., Salameh, P., Wang, H. J., Dimmer, C. H., and Hudson, L. E.: Continuous high-frequency observations of hydrogen at the Mace Head baseline atmospheric monitoring station over the 1994–1998 period, J. Geophys. Res., 105(10), 12105–12121, 2000.
Simmonds, P. G., Derwent, R. G., Manning, A. J., Grant, A., O'Doherty, S., and Spain, T. G.: Estimation of hydrogen deposition velocities from 1995–2008 at Mace Head, Ireland using a simple box model and concurrent ozone depositions, Tellus B, 63(1), 40–51, https://doi.org/10.1111/j.1600-0889.2010.00518.x, 2011.
Steinbacher, M., Fischer, A., Vollmer, M. K., Buchmann, B., Reimann, S., and Hueglin, C.: Perennial observations of molecular hydrogen (H2) at a suburban site in Switzerland, Atmos. Environ., 41(10), 2111–2124, https://doi.org/10.1016/j.atmosenv.2006.10.075, 2007.
Tohjima, Y., Machida, T., Watai, T., Akama, I., Amari, T., and Moriwaki, Y.: Preparation of gravimetric standards for measurements of atmospheric oxygen and reevaluation of atmospheric oxygen concentration, J. Geophys. Res., 110(D11), D11302, https://doi.org/10.1029/2004JD005595, 2005.
Vollmer, M. K., Juergens, N., Steinbacher, M., Reimann, S., Weilenmann, M., and Buchmann, B.: Road vehicle emissions of molecular hydrogen (H2) from a tunnel study, Atmos. Environ., 41(37), 8355–8369, https://doi.org/10.1016/j.atmosenv.2007.06.037, 2007.
Wang, Z. G., Chen, T. L., and Xu, J. P.: Gas transport properties of a series of cardo polyarylethers, J. Appl. Polym. Sci., 83(4), 791–801, 2002.
Wieser, M. E. and Berglund, M.: Atomic weights of the elements. Review 2007 (IUPAC Technical Report), Pure Appl. Chem., 81(11), 2131–2156, https://doi.org/10.1351/PAC-REP-09-08-03, 2009.
WMO: WMO Global Atmosphere Watch (GAW) Strategic Plan (2008–2015), GAW Report No. 172 (WMO TD NO. 1384), ftp://ftp.wmo.int/Documents/PublicWeb/arep/gaw/gaw172-26sept07.pdf,, last access: 18 February 2011, World Meteorological Organization, Geneva, Switzerland, 104 pp., 2007.
Xiao, X., Prinn, R. G., Simmonds, P. G., Steele, L. P., Novelli, P. C., Huang, J., Langenfelds, R. L., O'Doherty, S., Krummel, P. B., Fraser, P. J., Porter, L. W., Weiss, R. F., Salameh, P., and Wang, R. H. J.: Optimal estimation of the soil uptake rate of molecular hydrogen from the Advanced Global Atmospheric Gases Experiment and other measurements, J. Geophys. Res., 112(D7), D07303, https://doi.org/10.1029/2006JD007241, 2007.
Yver, C., Schmidt, M., Bousquet, P., Zahorowski, W., and Ramonet, M.: Estimation of the molecular hydrogen soil uptake and traffic emissions at a suburban site near Paris through hydrogen, carbon monoxide, and radon-222 semicontinuous measurements, J. Geophys. Res., 114, D18304, https://doi.org/10.1029/2009JD012122, 2009.
Yver, C., Pison, I., Fortems-Cheiney, A., Schmidt, M., Bousquet, P., Ramonet, M., Jordan, A., Søvde, A., Engel, A., Fisher, R., Lowry, D., Nisbet, E., Levin, I., Hammer, S., Necki, J., Bartyzel, J., Reimann, S., Vollmer, M. K., Steinbacher, M., Aalto, T., Maione, M., Arduini, I., O'Doherty, S., Grant, A., Sturges, W., Lunder, C. R., Privalov, V., and Paramonova, N.: A new estimation of the recent tropospheric molecular hydrogen budget using atmospheric observations and variational inversion, Atmos. Chem. Phys. Discuss., 10, 28963–29005, https://doi.org/10.5194/acpd-10-28963-2010, 2010.