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Continuous Measurements of Dissolved Ne, Ar, Kr, and Xe Ratios with a Field-Deployable Gas Equilibration Mass Spectrometer

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Massachusetts Institute of Technology/Woods Hole Oceanographic Institution Joint Program in Oceanography, Woods Hole, Massachusetts 02543, United States
Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, United States
Department of Chemistry, Wellesley College, Wellesley, Massachusetts 02481, United States
Cite this: Anal. Chem. 2016, 88, 6, 3040–3048
Publication Date (Web):February 8, 2016
https://doi.org/10.1021/acs.analchem.5b03102
Copyright © 2016 American Chemical Society

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    Abstract

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    Noble gases dissolved in natural waters are useful tracers for quantifying physical processes. Here, we describe a field-deployable gas equilibration mass spectrometer (GEMS) that provides continuous, real-time measurements of Ne, Ar, Kr, and Xe mole ratios in natural waters. Gas is equilibrated with a membrane contactor cartridge and measured with a quadrupole mass spectrometer, after in-line purification with reactive metal alloy getters. We use an electron energy of 35 V for Ne to eliminate isobaric interferences, and a higher electron energy for the other gases to improve sensitivity. The precision is 0.7% or better and 1.0% or better for all mole ratios when the instrument is installed in a temperature-controlled environment and a variable-temperature environment, respectively. In the lab, the accuracy is 0.9% or better for all gas ratios using air as the only calibration standard. In the field (and/or at greater levels of disequilbrium), the accuracy is 0.7% or better for Ne/Kr, Ne/Ar, and Ar/Kr, and 2.5% or better for Ne/Xe, Ar/Xe, and Kr/Xe using air as the only calibration standard. The field accuracy improves to 0.6% or better for Ne/Xe, Ar/Xe, and Kr/Xe when the data is calibrated using discrete water samples run on a laboratory-based mass spectrometer. The e-folding response time is 90–410 s. This instrument enables the collection of a large number of continuous, high-precision and accuracy noble gas measurements at substantially reduced cost and labor compared to traditional methods.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.5b03102.

    • Lists of suppliers and parts numbers, photos of the system, a diagram of the getter chambers, descriptions of some alternative configurations of the system, and further details on the calibration of field data (PDF)

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