Atomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap-GC-AED) for atmospheric trace gas measurements

Abstract. A gas detection system has been developed, characterized and deployed for pressurized gas phase sample analyses and near real-time online measurements. It consists of a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED III). Here the CryoTrap–GC–AED instrumental setup is presented and the performance for iodine (1635 ± 135 counts I-atom-1 pptv-1), sulfur (409 ± 57 counts S-atom-1 pptv-1), carbon (636 ± 69 counts C-atom-1 pptv-1), bromine (9.1 ± 1.8 counts Br-atom-1 pptv-1) and nitrogen (28 ± 2 counts N-atom-1 pptv-1) emission lines is reported and discussed. The limits of detection (LODs) are in the low pptv range (0.5–9.7 pptv) and the signal is linear to at least 4 orders of magnitude, which makes it a suitable method for diverse volatile organic compound (VOC) measurements in the atmosphere, even in remote, unpolluted regions. The new system was utilized in a field study in a boreal forest at Hyytiälä, Finland in late summer 2016 which made monoterpene measurements possible among the other VOCs. Furthermore, pressurized global whole-air sample measurement collected onboard the Lufthansa Airbus A340-600 IAGOS-CARIBIC aircraft in the upper troposphere and lower stratosphere region was carried out with the new setup, providing the observational data of many VOCs, including the long-lived organosulfur compound carbonyl sulfide.

[1]  J. D. de Gouw,et al.  Evaluation of a New Reagent-Ion Source and Focusing Ion-Molecule Reactor for Use in Proton-Transfer-Reaction Mass Spectrometry. , 2018, Analytical chemistry.

[2]  J. Lelieveld,et al.  Direct measurement of NO 3 radical reactivity in a boreal forest , 2018 .

[3]  J. Lelieveld,et al.  An aircraft gas chromatograph–mass spectrometer System for Organic Fast Identification Analysis (SOFIA): design, performance and a case study of Asian monsoon pollution outflow , 2017 .

[4]  I. Mammarella,et al.  Canopy uptake dominates nighttime carbonyl sulfide fluxes in a boreal forest , 2017 .

[5]  C. Timmreck,et al.  Stratospheric aerosol—Observations, processes, and impact on climate , 2016 .

[6]  L. Oman,et al.  Measuring and modeling the lifetime of nitrous oxide including its variability , 2015, Journal of geophysical research. Atmospheres : JGR.

[7]  G. Berthet,et al.  Carbonyl Sulphide (OCS) Variability with Latitude in the Atmosphere , 2015 .

[8]  Mike D. Flannigan,et al.  An introduction to Canada’s boreal zone: ecosystem processes, health, sustainability, and environmental issues , 2013 .

[9]  J. Lelieveld,et al.  The role of carbonyl sulphide as a source of stratospheric sulphate aerosol and its impact on climate , 2011 .

[10]  F. Slemr,et al.  Analysis of non-methane hydrocarbons in air samples collected aboard the CARIBIC passenger aircraft , 2009 .

[11]  Franz Slemr,et al.  Greenhouse gas analysis of air samples collected onboard the CARIBIC passenger aircraft , 2009 .

[12]  Christopher A. Cantrell,et al.  Technical Note: Review of methods for linear least-squares fitting of data and application to atmospheric chemistry problems , 2008 .

[13]  P. Bernath,et al.  Global distributions of carbonyl sulfide in the upper troposphere and stratosphere , 2008 .

[14]  Paul J. Crutzen,et al.  Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system , 2007 .

[15]  C. Sweeney,et al.  On the global distribution, seasonality, and budget of atmospheric carbonyl sulfide (COS) and some similarities to CO2 , 2007 .

[16]  J. Kesselmeier,et al.  Global uptake of carbonyl sulfide (COS) by terrestrial vegetation: Estimates corrected by deposition velocities normalized to the uptake of carbon dioxide (CO 2 ) , 2005 .

[17]  Kevin E. Trenberth,et al.  The Mass of the Atmosphere: A Constraint on Global Analyses , 2005 .

[18]  P. Hari,et al.  Temperature and light dependence of the VOC emissions of Scots pine , 2004 .

[19]  J. Baltrus,et al.  Rapid determination of total sulfur in fuels using gas chromatography with atomic emission detection. , 2002, Journal of chromatographic science.

[20]  Jonathan Williams,et al.  HO cycle in 1997 and 1998 over the southern Indian Ocean derived from CO, radon, and hydrocarbon measurements made at Amsterdam Island , 2001 .

[21]  Kenneth J. Davis,et al.  Tethered balloon measurements of biogenic VOCs in the atmospheric boundary layer , 1999 .

[22]  David D. Parrish,et al.  Spatial and temporal variability of nonmethane hydrocarbon mixing ratios and their relation to photochemical lifetime , 1998 .

[23]  E. Kjellström A Three-Dimensional Global Model Study of Carbonyl Sulfide in the Troposphere and the Lower Stratosphere , 1997 .

[24]  H. Swan,et al.  Analysis of atmospheric sulfur gases by capillary gas chromatography with atomic emission detection , 1994 .

[25]  David W. Fahey,et al.  An estimate of the flux of stratospheric reactive nitrogen and ozone into the troposphere , 1994 .

[26]  Malcolm K. W. Ko,et al.  Interrelationships between mixing ratios of long‐lived stratospheric constituents , 1992 .

[27]  James J. Sullivan,et al.  Evaluation of a microwave cavity, discharge tube, and gas flow system for combined gas chromatography-atomic emission detection , 1990 .

[28]  Paul J. Crutzen,et al.  The possible importance of CSO for the sulfate layer of the stratosphere , 1976 .

[29]  C. Junge Residence time and variability of tropospheric trace gases , 1974 .

[30]  A. Mccormack,et al.  Sensitive Selective Gas Chromatography Detector Based on Emission Spectrometry of Organic Compounds. , 1965 .

[31]  Eero Nikinmaa,et al.  Station for Measuring Ecosystem-Atmosphere Relations: SMEAR , 2013 .

[32]  T. Risby,et al.  Microwave Induced Electrical Discharge Detectors for Gas Chromatography , 1983 .

[33]  C.I.M. Beenaker Evaluation of a microwave-induced plasma in helium at atmospheric pressure as an element-selective detector for gas chromatography , 1977 .