Articles | Volume 10, issue 11
Research article 22 Nov 2017
Research article | 22 Nov 2017
System for δ13C–CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy
Dane Dickinson et al.
No articles found.
Caroline C. Clason, Will H. Blake, Nick Selmes, Alex Taylor, Pascal Boeckx, Jessica Kitch, Stephanie C. Mills, Giovanni Baccolo, and Geoffrey E. Millward
The Cryosphere, 15, 5151–5168,Short summary
Our paper presents results of sample collection and subsequent geochemical analyses from the glaciated Isfallsglaciären catchment in Arctic Sweden. The data suggest that material found on the surface of glaciers,
cryoconite, is very efficient at accumulating products of nuclear fallout transported in the atmosphere following events such as the Chernobyl disaster. We investigate how this compares with samples in the downstream environment and consider potential environmental implications.
Laura Summerauer, Philipp Baumann, Leonardo Ramirez-Lopez, Matti Barthel, Marijn Bauters, Benjamin Bukombe, Mario Reichenbach, Pascal Boeckx, Elizabeth Kearsley, Kristof Van Oost, Bernard Vanlauwe, Dieudonné Chiragaga, Aimé Bisimwa Heri-Kazi, Pieter Moonen, Andrew Sila, Keith Shepherd, Basile Bazirake Mujinya, Eric Van Ranst, Geert Baert, Sebastian Doetterl, and Johan Six
SOIL, 7, 693–715,Short summary
We present a soil mid-infrared library with over 1800 samples from central Africa in order to facilitate soil analyses of this highly understudied yet critical area. Together with an existing continental library, we demonstrate a regional analysis and geographical extrapolation to predict total carbon and nitrogen. Our results show accurate predictions and highlight the value that the data contribute to existing libraries. Our library is openly available for public use and for expansion.
Heleen Deroo, Masuda Akter, Samuel Bodé, Orly Mendoza, Haichao Li, Pascal Boeckx, and Steven Sleutel
Biogeosciences, 18, 5035–5051,Short summary
We assessed if and how incorporation of exogenous organic carbon (OC) such as straw could affect decomposition of native soil organic carbon (SOC) under different irrigation regimes. Addition of exogenous OC promoted dissolution of native SOC, partly because of increased Fe reduction, leading to more net release of Fe-bound SOC. Yet, there was no proportionate priming of SOC-derived DOC mineralisation. Water-saving irrigation can retard both priming of SOC dissolution and mineralisation.
Sebastian Doetterl, Rodrigue K. Asifiwe, Geert Baert, Fernando Bamba, Marijn Bauters, Pascal Boeckx, Benjamin Bukombe, Georg Cadisch, Matthew Cooper, Landry N. Cizungu, Alison Hoyt, Clovis Kabaseke, Karsten Kalbitz, Laurent Kidinda, Annina Maier, Moritz Mainka, Julia Mayrock, Daniel Muhindo, Basile B. Mujinya, Serge M. Mukotanyi, Leon Nabahungu, Mario Reichenbach, Boris Rewald, Johan Six, Anna Stegmann, Laura Summerauer, Robin Unseld, Bernard Vanlauwe, Kristof Van Oost, Kris Verheyen, Cordula Vogel, Florian Wilken, and Peter Fiener
Earth Syst. Sci. Data, 13, 4133–4153,Short summary
The African Tropics are hotspots of modern-day land use change and are of great relevance for the global carbon cycle. Here, we present data collected as part of the DFG-funded project TropSOC along topographic, land use, and geochemical gradients in the eastern Congo Basin and the Albertine Rift. Our database contains spatial and temporal data on soil, vegetation, environmental properties, and land management collected from 136 pristine tropical forest and cropland plots between 2017 and 2020.
Simon Baumgartner, Marijn Bauters, Matti Barthel, Travis W. Drake, Landry C. Ntaboba, Basile M. Bazirake, Johan Six, Pascal Boeckx, and Kristof Van Oost
SOIL, 7, 83–94,Short summary
We compared stable isotope signatures of soil profiles in different forest ecosystems within the Congo Basin to assess ecosystem-level differences in N cycling, and we examined the local effect of topography on the isotopic signature of soil N. Soil δ15N profiles indicated that the N cycling in in the montane forest is more closed, whereas the lowland forest and Miombo woodland experienced a more open N cycle. Topography only alters soil δ15N values in forests with high erosional forces.
Paula Alejandra Lamprea Pineda, Marijn Bauters, Hans Verbeeck, Selene Baez, Matti Barthel, Samuel Bodé, and Pascal Boeckx
Biogeosciences, 18, 413–421,Short summary
Tropical forest soils are an important source and sink of greenhouse gases (GHGs) with tropical montane forests having been poorly studied. In this pilot study, we explored soil fluxes of CO2, CH4, and N2O in an Ecuadorian neotropical montane forest, where a net consumption of N2O at higher altitudes was observed. Our results highlight the importance of short-term variations in N2O and provide arguments and insights for future, more detailed studies on GHG fluxes from montane forest soils.
Simon Baumgartner, Matti Barthel, Travis William Drake, Marijn Bauters, Isaac Ahanamungu Makelele, John Kalume Mugula, Laura Summerauer, Nora Gallarotti, Landry Cizungu Ntaboba, Kristof Van Oost, Pascal Boeckx, Sebastian Doetterl, Roland Anton Werner, and Johan Six
Biogeosciences, 17, 6207–6218,Short summary
Soil respiration is an important carbon flux and key process determining the net ecosystem production of terrestrial ecosystems. The Congo Basin lacks studies quantifying carbon fluxes. We measured soil CO2 fluxes from different forest types in the Congo Basin and were able to show that, even though soil CO2 fluxes are similarly high in lowland and montane forests, the drivers were different: soil moisture in montane forests and C availability in the lowland forests.
Hannes P. T. De Deurwaerder, Marco D. Visser, Matteo Detto, Pascal Boeckx, Félicien Meunier, Kathrin Kuehnhammer, Ruth-Kristina Magh, John D. Marshall, Lixin Wang, Liangju Zhao, and Hans Verbeeck
Biogeosciences, 17, 4853–4870,Short summary
The depths at which plants take up water is challenging to observe directly. To do so, scientists have relied on measuring the isotopic composition of xylem water as this provides information on the water’s source. Our work shows that this isotopic composition changes throughout the day, which complicates the interpretation of the water’s source and has been currently overlooked. We build a model to help understand the origin of these composition changes and their consequences for science.
Long Ho, Ruben Jerves-Cobo, Matti Barthel, Johan Six, Samuel Bode, Pascal Boeckx, and Peter Goethals
Revised manuscript not acceptedShort summary
Rivers are being polluted by human activities, especially in urban areas. We studied the greenhouse gas (GHG) emissions from an urban river system. The results showed a clear trend between water quality and GHG emissions in which the more polluted the sites were, the higher were their emissions. When river water quality worsened, its contribution to global warming can go up by 10 times. Urban rivers emitted 4-times more than of the amount of GHGs compared to rivers in natural sites.
Marco Pfeiffer, José Padarian, Rodrigo Osorio, Nelson Bustamante, Guillermo Federico Olmedo, Mario Guevara, Felipe Aburto, Francisco Albornoz, Monica Antilén, Elías Araya, Eduardo Arellano, Maialen Barret, Juan Barrera, Pascal Boeckx, Margarita Briceño, Sally Bunning, Lea Cabrol, Manuel Casanova, Pablo Cornejo, Fabio Corradini, Gustavo Curaqueo, Sebastian Doetterl, Paola Duran, Mauricio Escudey, Angelina Espinoza, Samuel Francke, Juan Pablo Fuentes, Marcel Fuentes, Gonzalo Gajardo, Rafael García, Audrey Gallaud, Mauricio Galleguillos, Andrés Gomez, Marcela Hidalgo, Jorge Ivelic-Sáez, Lwando Mashalaba, Francisco Matus, Francisco Meza, Maria de la Luz Mora, Jorge Mora, Cristina Muñoz, Pablo Norambuena, Carolina Olivera, Carlos Ovalle, Marcelo Panichini, Aníbal Pauchard, Jorge F. Pérez-Quezada, Sergio Radic, José Ramirez, Nicolás Riveras, Germán Ruiz, Osvaldo Salazar, Iván Salgado, Oscar Seguel, Maria Sepúlveda, Carlos Sierra, Yasna Tapia, Francisco Tapia, Balfredo Toledo, José Miguel Torrico, Susana Valle, Ronald Vargas, Michael Wolff, and Erick Zagal
Earth Syst. Sci. Data, 12, 457–468,Short summary
The CHLSOC database is the biggest soil organic carbon (SOC) database that has been compiled for Chile yet, comprising 13 612 data points. This database is the product of the compilation of numerous sources including unpublished and difficult-to-access data, allowing us to fill numerous spatial gaps where no SOC estimates were publicly available before. The values of SOC compiled in CHLSOC have a wide range, reflecting the variety of ecosystems that exists in Chile.
Natalie Orlowski, Lutz Breuer, Nicolas Angeli, Pascal Boeckx, Christophe Brumbt, Craig S. Cook, Maren Dubbert, Jens Dyckmans, Barbora Gallagher, Benjamin Gralher, Barbara Herbstritt, Pedro Hervé-Fernández, Christophe Hissler, Paul Koeniger, Arnaud Legout, Chandelle Joan Macdonald, Carlos Oyarzún, Regine Redelstein, Christof Seidler, Rolf Siegwolf, Christine Stumpp, Simon Thomsen, Markus Weiler, Christiane Werner, and Jeffrey J. McDonnell
Hydrol. Earth Syst. Sci., 22, 3619–3637,Short summary
To extract water from soils for isotopic analysis, cryogenic water extraction is the most widely used removal technique. This work presents results from a worldwide laboratory intercomparison test of cryogenic extraction systems. Our results showed large differences in retrieved isotopic signatures among participating laboratories linked to interactions between soil type and properties, system setup, extraction efficiency, extraction system leaks, and each lab’s internal accuracy.
Marijn Bauters, Hans Verbeeck, Miro Demol, Stijn Bruneel, Cys Taveirne, Dries Van der Heyden, Landry Cizungu, and Pascal Boeckx
Biogeosciences, 14, 5313–5321,Short summary
We assessed community-weighted functional canopy traits and indicative δ15N shifts along two new altitudinal transects in the tropical forest biome of both South America and Africa. We found that the functional forest composition and δ15N response along both transects was parallel, with a species shift towards more nitrogen-conservative species at higher elevations.
Lien De Wispelaere, Samuel Bodé, Pedro Hervé-Fernández, Andreas Hemp, Dirk Verschuren, and Pascal Boeckx
Biogeosciences, 14, 73–88,
Louise C. Andresen, Anna-Karin Björsne, Samuel Bodé, Leif Klemedtsson, Pascal Boeckx, and Tobias Rütting
SOIL, 2, 433–442,Short summary
In soil the constant transport of nitrogen (N) containing compounds from soil organic matter and debris out into the soil water, is controlled by soil microbes and enzymes that literally cut down polymers (such as proteins) into single amino acids (AA), hereafter microbes consume AAs and excrete ammonium back to the soil. We developed a method for analysing N turnover and flow of organic N, based on parallel 15N tracing experiments. The numerical model gives robust and simultaneous quantification.
L. C. Andresen, S. Bode, A. Tietema, P. Boeckx, and T. Rütting
SOIL, 1, 341–349,
J. W. van Groenigen, D. Huygens, P. Boeckx, Th. W. Kuyper, I. M. Lubbers, T. Rütting, and P. M. Groffman
SOIL, 1, 235–256,
S. Doetterl, J.-T. Cornelis, J. Six, S. Bodé, S. Opfergelt, P. Boeckx, and K. Van Oost
Biogeosciences, 12, 1357–1371,Short summary
We link the mineralogy of soils affected by erosion and deposition to the distribution of soil carbon fractions, their turnover and microbial activity. We show that the weathering status of soils and their history are controlling the stabilization of carbon with minerals. After burial, aggregated C is preserved more efficiently while non-aggregated C can be released and younger C re-sequestered more easily. Weathering changes the effectiveness of stabilization mechanism limiting this C sink.
D. Xue, P. Boeckx, and Z. Wang
Biogeosciences, 11, 5957–5967,
R. M. Rees, J. Augustin, G. Alberti, B. C. Ball, P. Boeckx, A. Cantarel, S. Castaldi, N. Chirinda, B. Chojnicki, M. Giebels, H. Gordon, B. Grosz, L. Horvath, R. Juszczak, Å. Kasimir Klemedtsson, L. Klemedtsson, S. Medinets, A. Machon, F. Mapanda, J. Nyamangara, J. E. Olesen, D. S. Reay, L. Sanchez, A. Sanz Cobena, K. A. Smith, A. Sowerby, M. Sommer, J. F. Soussana, M. Stenberg, C. F. E. Topp, O. van Cleemput, A. Vallejo, C. A. Watson, and M. Wuta
Biogeosciences, 10, 2671–2682,
N. Gharahi Ghehi, C. Werner, K. Hufkens, R. Kiese, E. Van Ranst, D. Nsabimana, G. Wallin, L. Klemedtsson, K. Butterbach-Bahl, and P. Boeckx
Revised manuscript not accepted
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and PlatformsA simulation chamber for absorption spectroscopy in planetary atmospheresAn automated system for trace gas flux measurements from plant foliage and other plant compartmentsSimultaneous measurement of δ13C, δ18O and δ17O of atmospheric CO2 – performance assessment of a dual-laser absorption spectrometerMeasurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometersPhotochemical method for removing methane interference for improved gas analysisA method for resolving changes in atmospheric He ∕ N2 as an indicator of fossil fuel extraction and stratospheric circulationApplication of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phaseAtomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap–GC–AED) for atmospheric trace gas measurementsNew 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 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 compoundsA 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 spectrometer
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197,Short summary
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,Short summary
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,Short summary
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,Short summary
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.
Merve Polat, Jesper Baldtzer Liisberg, Morten Krogsbøll, Thomas Blunier, and Matthew S. Johnson
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMTShort summary
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, and 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.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527,Short summary
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,Short 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 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,Short summary
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,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.
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.
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).
Albanito, F., McAllister, J. L., Cescatti, A., Smith, P., and Robinson, D.: Dual-chamber measurements of δ13C of soil-respired CO2 partitioned using a field-based three end-member model, Soil Biol. Biochem., 47, 106–115, 2012.
Bai, M., Köstler, M., Kunstmann, J., Wilske, B., Gattinger, A., Frede, H.-G., and Breuer, L.: Biodegradability screening of soil amendments through coupling of wavelength-scanned cavity ring-down spectroscopy to multiple dynamic chambers, Rapid Commun. Mass Sp., 25, 3683–3689, 2011.
Berryman, E. M., Marshall, J. D., Rahn, T., Cook, S. P., and Litvak, M.: Adaptation of continuous-flow cavity ring-down spectroscopy for batch analysis of δ13C of CO2 and comparison with isotope ratio mass spectrometry, Rapid Commun. Mass Sp., 25, 2355–2360, 2011.
Brewer, P. J., Brown, R. J., Miller, M. N., Miñarro, M. D., Murugan, A., Milton, M. J., and Rhoderick, G. C.: Preparation and Validation of Fully Synthetic Standard Gas Mixtures with Atmospheric Isotopic Composition for Global CO2 and CH4 Monitoring, Anal. Chem., 86, 1887–1893, 2014.
Christiansen, J. R., Outhwaite, J., and Smukler, S. M.: Comparison of CO2, CH4 and N2O soil-atmosphere exchange measured in static chambers with cavity ring-down spectroscopy and gas chromatography, Agr. Forest. Meteorol., 211–212, 48–57, 2015.
Crosson, E. R.: A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor, Appl. Phys. B, 92, 403–408, 2008.
Crosson, E. R., Ricci, K. N., Richman, B. A., Chilese, F. C., Owano, T. G., Provencal, R. A., Todd, M. W., Glasser, J., Kachanov, A. A., Paldus, B. A., Spence, T. G., and Zare, R. N.: Stable isotope ratios using cavity ring-down spectroscopy: Determination of 13C/12C for carbon dioxide in human breath, Anal. Chem., 74, 2003–2007, 2002.
Dahnke, H., Kleine, D., Urban, W., Hering, P., and Mürtz, M.: Isotopic ratio measurement of methane in ambient air using mid-infrared cavity leak-out spectroscopy, Appl. Phys. B, 72, 121–125, 2001.
Dickinson, D., Bodé, S., and Boeckx, P.: Measuring 13C-enriched CO2 in air with a cavity ring-down spectroscopy gas analyser: Evaluation and calibration, Rapid Commun. Mass Sp., 31, 1892–1902, https://doi.org/10.1002/rcm.7969, 2017.
Friedrichs, G., Bock, J., Temps, F., Fietzek, P., Körtzinger, A., and Wallace, D. W. R.: Toward continuous monitoring of seawater 13CO2/12CO2 isotope ratio and pCO2: Performance of cavity ringdown spectroscopy and gas matrix effects, Limnol. Oceanogr.-Meth., 8, 539–551, 2010.
Gkinis, V., Popp, T. J., Blunier, T., Bigler, M., Schüpbach, S., Kettner, E., and Johnsen, S. J.: Water isotopic ratios from a continuously melted ice core sample, Atmos. Meas. Tech., 4, 2531–2542, https://doi.org/10.5194/amt-4-2531-2011, 2011.
Gupta, P., Noone, D., Galewsky, J., Sweeney, C., and Vaughn, B. H.: Demonstration of high-precision continuous measurements of water vapor isotopologues in laboratory and remote field deployments using wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology, Rapid Commun. Mass Sp., 23, 2534–2542, 2009.
Hancock, G. and Orr-Ewing, A. J.: Applications of Cavity Ring-Down Spectroscopy in Atmospheric Chemistry, in: Cavity Ring-Down Spectroscopy, John Wiley & Sons Ltd., 181–211, 2010.
Hoffnagle, J.: Understanding the G2131-i isotopic carbon dioxide data log, Picarro Inc., Santa Clara, California, USA, 2015.
Hope, D., Dawson, J. J. C., Cresser, M. S., and Billett, M. F.: A method for measuring free CO2 in upland streamwater using headspace analysis, J. Hydrol., 166, 1–14, 1995.
Jassal, R. S., Webster, C., Black, T. A., Hawthorne, I., and Johnson, M. S.: Simultaneous Measurements of Soil CO2 and CH4 Fluxes Using Laser Absorption Spectroscopy, Agric. Environ. Lett., 1, 150014, https://doi.org/10.2134/ael2015.12.0014, 2016.
Joos, O., Saurer, M., Heim, A., Hagedorn, F., Schmidt, M. W. I., and Siegwolf, R. T. W.: Can we use the CO2 concentrations determined by continuous-flow isotope ratio mass spectrometry from small samples for the Keeling plot approach?, Rapid Commun. Mass Sp., 22, 4029–4034, 2008.
Kerstel, E. R. T., Iannone, R. Q., Chenevier, M., Kassi, S., Jost, H. J., and Romanini, D.: A water isotope (2H, 17O, and 18O) spectrometer based on optical feedback cavity-enhanced absorption for in situ airborne applications, Appl. Phys. B, 85, 397–406, 2006.
Leffler, A. J. and Welker, J. M.: Long-term increases in snow pack elevate leaf N and photosynthesis in Salix arctica: responses to a snow fence experiment in the High Arctic of NW Greenland, Environ. Res. Lett., 8, 025023, https://doi.org/10.1088/1748-9326/8/2/025023, 2013.
Loose, B., Stute, M., Alexander, P., and Smethie, W. M.: Design and deployment of a portable membrane equilibrator for sampling aqueous dissolved gases, Water Resour. Res., 45, W00D34, https://doi.org/10.1029/2008WR006969, 2009.
McAlexander, W. I., Fellers, R., Owano, T. G., and Baer, D. S.: Carbon isotope analysis of discrete CO2 samples ranging from 300 ppmv to 100 % using cavity enhanced laser absorption, European Geophysical Union General Assembly, Vienna, Austria, 2010.
Midwood, A. J. and Millard, P.: Challenges in measuring the δ13C of the soil surface CO2 efflux, Rapid Commun. Mass Sp., 25, 232–242, 2011.
Midwood, A. J., Thornton, B., and Millard, P.: Measuring the 13C content of soil-respired CO2 using a novel open chamber system, Rapid Commun. Mass Sp., 22, 2073–2081, 2008.
Munksgaard, N. C., Davies, K., Wurster, C. M., Bass, A. M., and Bird, M. I.: Field-based cavity ring-down spectrometry of δ13C in soil-respired CO2, Isotopes Environ. Health Stud., 49, 232–242, 2013.
Mürtz, M. and Hering, P.: Cavity Ring-Down Spectroscopy for Medical Applications, in: Cavity Ring-Down Spectroscopy, John Wiley & Sons Ltd., 213–235, 2010.
Nara, H., Tanimoto, H., Tohjima, Y., Mukai, H., Nojiri, Y., Katsumata, K., and Rella, C. W.: Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy, Atmos. Meas. Tech., 5, 2689–2701, https://doi.org/10.5194/amt-5-2689-2012, 2012.
Pang, J., Wen, X., Sun, X., and Huang, K.: Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2∕12CO2 measurement, Atmos. Meas. Tech., 9, 3879–3891, https://doi.org/10.5194/amt-9-3879-2016, 2016.
Picarro: WS-CRDS for Isotopes – Cost of Measurement Comparison with IRMS for Liquid Water, Picarro Inc., Sunnyvale, California, USA, 2009.
Picarro: Picarro G2131-i δ13C High-Precision Isotopic CO2 CRDS Analyzer, Picarro Inc., Santa Clara, California, USA, 2011.
Picarro: Picarro A0314 Small Sample Isotope Module 2, Picarro Inc., Santa Clara, California, USA, 2013.
Picarro: G2131-i Analyser for Isotopic CO2 User's Guide, Picarro Inc., Santa Clara, California, USA, 2012.
Picarro: Picarro G2201-i CRDS Analyzer for Isotopic Carbon in CO2 and CH4, Picarro Inc., Santa Clara, California, USA, 2015.
R Core Team: R: A Language Environment for Statistical Computing, R Foundation for Statistical Computing, Vienna, Austria, 2015.
Ramlow, M. and Cotrufo, M. F.: Woody biochar's greenhouse gas mitigation potential across fertilized and unfertilized agricultural soils and soil moisture regimes, GCB Bioenergy, https://doi.org/10.1111/gcbb.12474, online first, 2017.
Rella, C.: Accurate stable carbon isotope ratio measurements in humid gas streams using the Picarro δ13CO2 G2101-i gas analyzer, Picarro Inc., Sunnyvale, California, USA, 2010a.
Rella, C.: Accurate stable carbon isotope ratio measurements with rapidly varying carbon dioxide concentrations using the Picarro δ13CO2 G2101-i gas analyzer, Picarro Inc., Sunnyvale, California, USA, 2010b.
Rella, C.: Reduced drift, high accuracy stable carbon isotope ratio measurements using a reference gas with the Picarro δ13CO2 G2101-i gas analyzer, Picarro Inc., Sunnyvale, California, USA, 2010c.
Rella, C. W., Chen, H., Andrews, A. E., Filges, A., Gerbig, C., Hatakka, J., Karion, A., Miles, N. L., Richardson, S. J., Steinbacher, M., Sweeney, C., Wastine, B., and Zellweger, C.: High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air, Atmos. Meas. Tech., 6, 837–860, https://doi.org/10.5194/amt-6-837-2013, 2013.
Sigrist, M. W., Bartlome, R., Marinov, D., Rey, J. M., Vogler, D. E., and Wächter, H.: Trace gas monitoring with infrared laser-based detection schemes, Appl. Phys. B, 90, 289–300, 2008.
Snell, H. S. K., Robinson, D., and Midwood, A. J.: Minimising methodological biases to improve the accuracy of partitioning soil respiration using natural abundance 13C, Rapid Commun. Mass Sp., 28, 2341–2351, 2014.
Sowers, T., Bernard, S., Aballain, O., Chappellaz, J., Barnola, J. M., and Marik, T.: Records of the δ13C of atmospheric CH4 over the last 2 centuries as recorded in Antarctic snow and ice, Global Biogeochem. Cy., 19, GB2002, https://doi.org/10.1029/2004GB002408, 2005.
Stowasser, C., Buizert, C., Gkinis, V., Chappellaz, J., Schüpbach, S., Bigler, M., Faïn, X., Sperlich, P., Baumgartner, M., Schilt, A., and Blunier, T.: Continuous measurements of methane mixing ratios from ice cores, Atmos. Meas. Tech., 5, 999–1013, https://doi.org/10.5194/amt-5-999-2012, 2012.
Stowasser, C., Farinas, A. D., Ware, J., Wistisen, D. W., Rella, C., Wahl, E., Crosson, E., and Blunier, T.: A low-volume cavity ring-down spectrometer for sample-limited applications, Appl. Phys. B, 116, 255–270, 2014.
Sumner, A. L., Hanft, E., Dindal, A., and McKernan, J.: Isotopic Carbon Dioxide Analyzers For Carbon Sequestration Monitoring Picarro Cavity Ring-Down Spectroscopy Analyzer For Isotopic CO2 – Model G1101-i, Battelle Memorial Institute, Environmental Technology Verification Report 600F11053, 2011.
Vogel, F. R., Huang, L., Ernst, D., Giroux, L., Racki, S., and Worthy, D. E. J.: Evaluation of a cavity ring-down spectrometer for in situ observations of 13CO2, Atmos. Meas. Tech., 6, 301–308, https://doi.org/10.5194/amt-6-301-2013, 2013.
Wahl, E. H., Fidric, B., Rella, C. W., Koulikov, S., Kharlamov, B., Tan, S., Kachanov, A. A., Richman, B. A., Crosson, E. R., Paldus, B. A., Kalaskar, S., and Bowling, D. R.: Applications of cavity ring-down spectroscopy to high precision isotope ratio measurement of 13C ∕12C in carbon dioxide, Isotopes Environ. Health Stud., 42, 21–35, 2006.
Wang, C., Miller, G. P., and Winstead, C. B.: Cavity Ringdown Laser Absorption Spectroscopy, in: Encyclopedia of Analytical Chemistry, John Wiley & Sons Ltd., 2008.
Wang, J.-L., Jacobson, G., Rella, C. W., Chang, C.-Y., Liu, I., Liu, W.-T., Chew, C., Ou-Yang, C.-F., Liao, W.-C., and Chang, C.-C.: Flask sample measurements for CO2, CH4 and CO using cavity ring-down spectrometry, Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amtd-6-7633-2013, 2013.
Wen, X.-F., Meng, Y., Zhang, X.-Y., Sun, X.-M., and Lee, X.: Evaluating calibration strategies for isotope ratio infrared spectroscopy for atmospheric 13CO2 ∕ 12CO2 measurement, Atmos. Meas. Tech., 6, 1491–1501, https://doi.org/10.5194/amt-6-1491-2013, 2013.
Werner, R. A. and Brand, W. A.: Referencing strategies and techniques in stable isotope ratio analysis, Rapid Commun. Mass Sp., 15, 501–519, 2001.
Zeeman, M. J., Werner, R. A., Eugster, W., Siegwolf, R. T. W., Wehrle, G., Mohn, J., and Buchmann, N.: Optimization of automated gas sample collection and isotope ratio mass spectrometric analysis of δ13C of CO2 in air, Rapid Commun. Mass Sp., 22, 3883–3892, 2008.
Zhu, C., Byrd, R. H., Lu, P., and Nocedal, J.: Algorithm 778: L-BFGS-B: Fortran subroutines for large-scale bound-constrained optimization, ACM T. Math. Software, 23, 550–560, 1997.
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.
Cavity ring-down spectroscopy (CRDS) is an increasingly popular technology for isotope analysis...