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Article Type:
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A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide

Brett F. Thornton Department of Applied Environmental Science, Department of Geological Sciences, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Axel Horst Department of Applied Environmental Science, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Daniel Carrizo Department of Applied Environmental Science, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Henry Holmstrand Department of Applied Environmental Science, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Per Andersson Laboratory for Isotope Geology, Swedish Museum of Natural History, Stockholm, Sweden

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Patrick M. Crill Department of Geological Sciences, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Örjan Gustafsson Department of Applied Environmental Science, and Bolin Centre for Climate Research, Stockholm University, Stockholm, Sweden

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Print Publication:
01 Sep 2013
DOI:
https://doi.org/10.1175/JTECH-D-12-00228.1
Page(s):
2095–2107
Restricted access

Abstract

A system was developed for collecting from the ambient atmosphere the methyl halides CH3Cl and CH3Br in quantities sufficient for chlorine and bromine isotope analysis. The construction and operation of the novel cryogenic collection system (cryosampler) and sample purification system developed for this task are described. This study demonstrates the capability of the cryosampler by quantifying the CH3Cl and CH3Br collected from atmospheric samples and the nonfractionating bromine isotope fingerprint of CH3Br from synthetic air samples of controlled composition. An optimized cryosampler operation time of 4 h at a flow rate of 15 L min−1 is applied to yield the nearly 40 ng required for subsequent δ81Br-CH3Br analyses. The sample purification system is designed around a packed column gas chromatography–quadropole–mass spectrometry (GCqMS) system with three additional cryotraps and backflushing capacity. The system's suitability was tested by observing both the mass recovery and the lack of Δ81Br isotope fractionation induced during sample purification under varying flow rates and loading scenarios. To demonstrate that the entire system samples and dependably delivers CH3Br to the isotope analysis system without inducing isotope fractionation, diluted synthetic air mixtures prepared from standard gases were processed through the entire system, yielding a Δ81Br-CH3Br of +0.03‰ ± 0.10‰ relative to their starting composition. Finally, the combined cryosampler–purification and analysis system was applied to demonstrate the first-ever δ81Br-CH3Br in the ambient atmosphere with two samples collected in the autumn of 2011, yielding −0.08‰ ± 0.43‰ and +1.75‰ ± 0.13‰ versus standard mean ocean bromide for samples collected at a suburban Stockholm, Sweden, site.

Supplemental information related to this paper is available at the Journals Online website: http://dx.doi.org/10.1175/JTECH-D-12-00228.s1.

Current affiliation: Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain.

Corresponding author address: Brett F. Thornton, Dept. of Geological Sciences, Stockholm University, Svante Arrhenius väg 8, SE-106 91 Stockholm, Sweden. E-mail: brett.thornton@geo.su.se

Abstract

A system was developed for collecting from the ambient atmosphere the methyl halides CH3Cl and CH3Br in quantities sufficient for chlorine and bromine isotope analysis. The construction and operation of the novel cryogenic collection system (cryosampler) and sample purification system developed for this task are described. This study demonstrates the capability of the cryosampler by quantifying the CH3Cl and CH3Br collected from atmospheric samples and the nonfractionating bromine isotope fingerprint of CH3Br from synthetic air samples of controlled composition. An optimized cryosampler operation time of 4 h at a flow rate of 15 L min−1 is applied to yield the nearly 40 ng required for subsequent δ81Br-CH3Br analyses. The sample purification system is designed around a packed column gas chromatography–quadropole–mass spectrometry (GCqMS) system with three additional cryotraps and backflushing capacity. The system's suitability was tested by observing both the mass recovery and the lack of Δ81Br isotope fractionation induced during sample purification under varying flow rates and loading scenarios. To demonstrate that the entire system samples and dependably delivers CH3Br to the isotope analysis system without inducing isotope fractionation, diluted synthetic air mixtures prepared from standard gases were processed through the entire system, yielding a Δ81Br-CH3Br of +0.03‰ ± 0.10‰ relative to their starting composition. Finally, the combined cryosampler–purification and analysis system was applied to demonstrate the first-ever δ81Br-CH3Br in the ambient atmosphere with two samples collected in the autumn of 2011, yielding −0.08‰ ± 0.43‰ and +1.75‰ ± 0.13‰ versus standard mean ocean bromide for samples collected at a suburban Stockholm, Sweden, site.

Supplemental information related to this paper is available at the Journals Online website: http://dx.doi.org/10.1175/JTECH-D-12-00228.s1.

Current affiliation: Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain.

Corresponding author address: Brett F. Thornton, Dept. of Geological Sciences, Stockholm University, Svante Arrhenius väg 8, SE-106 91 Stockholm, Sweden. E-mail: brett.thornton@geo.su.se

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