Development of a cavity-enhanced absorption spectrometer for airborne measurements of CH4and CO2

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Abstract

High-resolution CH4 and CO2 measurements were made on board the FAAM BAe-146 UK (Facility for Airborne Atmospheric Measurements, British Aerospace-146) atmospheric research aircraft during a number of field campaigns. The system was based on an infrared spectrometer using the cavity-enhanced absorption spectroscopy technique. Correction functions to convert the mole fractions retrieved from the spectroscopy to dry-air mole fractions were derived using laboratory experiments and over a 3 month period showed good stability. Long-term performance of the system was monitored using WMO (World Meteorological Office) traceable calibration gases. During the first year of operation (29 flights) analysis of the system's in-flight calibrations suggest that its measurements are accurate to 1.28 ppb (1σ repeatability at 1 Hz = 2.48 ppb) for CH4 and 0.17 ppm (1σ repeatability at 1 Hz = 0.66 ppm) for CO2. The system was found to be robust, no major motion or altitude dependency could be detected in the measurements. An inter-comparison between whole-air samples that were analysed post-flight for CH4 and CO2 by cavity ring-down spectroscopy showed a mean difference between the two techniques of -2.4 ppb (1σ = 2.3 ppb) for CH4 and -0.22 ppm (1σ = 0.45 ppm) for CO2. In September 2012, the system was used to sample biomass-burning plumes in Brazil as part of the SAMBBA project (South AMerican Biomass Burning Analysis). From these and simultaneous CO measurements, emission factors for savannah fires were calculated. These were found to be 2.2 ± 0.2 g (kg dry matter) -1 for CH4 and 1710 ± 171 g (kg dry matter) -1 for CO2, which are in excellent agreement with previous estimates in the literature. © Author(s) 2013.

Figures

  • Fig. 1. A diagram of the sample and calibration air flow through the CO2 and CH4 system.
  • Fig. 2. (a) Outboard view of the FAAM core chemistry instrumentation inlet window fitted on starboard side window #14, under the FAAM BAe-146 wing. The lower 3/8′′ OD rearward facing SS tube is the FGGA’s dedicated inlet. The short 1/4′′ OD rearward facing SS tube is the calibrant outboard vent. (b) Inboard view of FAAM core chemistry instrumentation inlet window. The 3-way calibration valve V1 is showed on the lower 3/8′′ OD SS tube. The central 1/4′′ OD tube is the calibrant outboard vent (connected to valve V1 normally open port).
  • Table 1. The in-flight gas standards certified mole fractions used during the BORTAS and MAMM projects. The Max-Planck Institute for Biogeochemistry (Jena) carried out the calibration through the Infrastructure for Measurements of the European Carbon Cycle (EU 13 IMECC) project. A 6 month-mixture stability check showed the standards were stable over this period. The δ13C isotopic ratios, determined using continuous-flow gas chromatography/isotope-ratio mass spectrometry (Fisher et al., 2006), are close enough to the ambient isotopic ratio so as not to cause a significant error in the measured mole fractions.
  • Fig. 3. In-flight high/low span calibration sequence performed during mission B742. The data shown are 1 Hz raw CO2 ppm, acquired with the Los Gatos Research FGGA software.
  • Fig. 4. A schematic of the experimental set-up used to determine how water vapour influences CO2 and CH4 measurements. The humidifier used was a Li-610 dew-point generator (Li-610, Li-Cor Inc., USA).
  • Table 2. a, b and c are the coefficients of the quadratic fit to [X]Wet/[X]Dry versus [H2O]. These values can then be used to determine dry-air mole fractions using Eq. (3).
  • Fig. 5. The FGGA’s response to varying humidity was determined by humidifying air from a cylinder. The dry measurements were determined by passing the humidified air through a dry-ice trap before it was analysed. This test was repeated three times over a threemonth period to test the repeatability of the system. A relationship between the dry-air mole fraction and the measured wet-air mole fraction was determined using a quadratic fit to (a) CH4 wet/CH4 dry versus H2O and (b) CO2 wet/CO2 dry versus H2O. The dashed lines have been determined by applying Eq. (2) to CH4 wet and CO2 wet, this suggests that only correcting for the dilution effect due to H2O is not sufficient to determine dry-air mole fractions.
  • Fig. 6. An estimate of the system’s accuracy can be made by examining the difference between the calibration mole fraction and the scaled FGGA measurement of the target gas mixture. At 1 Hz the mean ±1 standard deviation difference between the two is −0.07± 2.48 ppb for CH4 and −0.06± 0.66 ppb for CO2.

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CITATION STYLE

APA

O’Shea, S. J., Bauguitte, S. J. B., Gallagher, M. W., Lowry, D., & Percival, C. J. (2013). Development of a cavity-enhanced absorption spectrometer for airborne measurements of CH4and CO2. Atmospheric Measurement Techniques, 6(5), 1095–1109. https://doi.org/10.5194/amt-6-1095-2013

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