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System for δ13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy

Dane Dickinson (UGent) , Samuel Bodé (UGent) and Pascal Boeckx (UGent)
(2017) ATMOSPHERIC MEASUREMENT TECHNIQUES. 10(11). p.4507-4519
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Abstract
A method was devised for analysing small discrete gas samples (50 mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from  <  0.1 to  >  20 000 ppm and δ13C–CO2 values from −100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples h−1, with 13 h−1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C–CO2 levels varying from −27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C–CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.
Keywords
SOIL-RESPIRED CO2, ATMOSPHERIC (CO2)-C-13/(CO2)-C-12 MEASUREMENT, RATIO MASS-SPECTROMETRY, ISOTOPE RATIO, CARBON-DIOXIDE, WATER-VAPOR, AIR, METHANE, CH4, CALIBRATION

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Chicago
Dickinson, Dane, Samuel Bodé, and Pascal Boeckx. 2017. “System for δ13C-CO2 and xCO2 Analysis of Discrete Gas Samples by Cavity Ring-down Spectroscopy.” Atmospheric Measurement Techniques 10 (11): 4507–4519.
APA
Dickinson, D., Bodé, S., & Boeckx, P. (2017). System for δ13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy. ATMOSPHERIC MEASUREMENT TECHNIQUES, 10(11), 4507–4519.
Vancouver
1.
Dickinson D, Bodé S, Boeckx P. System for δ13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy. ATMOSPHERIC MEASUREMENT TECHNIQUES. 2017;10(11):4507–19.
MLA
Dickinson, Dane, Samuel Bodé, and Pascal Boeckx. “System for δ13C-CO2 and xCO2 Analysis of Discrete Gas Samples by Cavity Ring-down Spectroscopy.” ATMOSPHERIC MEASUREMENT TECHNIQUES 10.11 (2017): 4507–4519. Print.
@article{8539518,
  abstract     = {A method was devised for analysing small discrete gas samples (50\unmatched{202f}mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50\unmatched{202f}mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from \,{\textlangle}\,\unmatched{202f}0.1 to \,{\textrangle}\,\unmatched{202f}20\unmatched{202f}000\unmatched{202f}ppm and \ensuremath{\delta}13C--CO2 values from \ensuremath{-}100 up to +30\unmatched{202f}000\unmatched{202f}{\textperthousand} in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples\unmatched{202f}h\ensuremath{-}1, with 13\unmatched{202f}h\ensuremath{-}1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1\unmatched{202f}\%. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109\unmatched{202f}ppm xCO2 and \ensuremath{\delta}13C--CO2 levels varying from \ensuremath{-}27.3 to +21\unmatched{202f}740\unmatched{202f}{\textperthousand}. Repeatability tests demonstrated that method precision for 50\unmatched{202f}mL samples was ca. 0.05\unmatched{202f}\% in xCO2 and 0.15\unmatched{202f}{\textperthousand} in \ensuremath{\delta}13C--CO2 for CO2 compositions from 300 to 2000\unmatched{202f}ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.},
  author       = {Dickinson, Dane and Bod{\'e}, Samuel and Boeckx, Pascal},
  issn         = {1867-1381},
  journal      = {ATMOSPHERIC MEASUREMENT TECHNIQUES},
  keyword      = {SOIL-RESPIRED CO2,ATMOSPHERIC (CO2)-C-13/(CO2)-C-12 MEASUREMENT,RATIO MASS-SPECTROMETRY,ISOTOPE RATIO,CARBON-DIOXIDE,WATER-VAPOR,AIR,METHANE,CH4,CALIBRATION},
  language     = {eng},
  number       = {11},
  pages        = {4507--4519},
  title        = {System for \ensuremath{\delta}13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy},
  url          = {http://dx.doi.org/10.5194/amt-10-4507-2017},
  volume       = {10},
  year         = {2017},
}

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