scholarly journals An IBBCEAS system for atmospheric measurements of glyoxal and methylglyoxal in the presence of high NO<sub>2</sub> concentrations

2019 ◽  
Author(s):  
Jingwei Liu ◽  
Xin Li ◽  
Yiming Yang ◽  
Haichao Wang ◽  
Yusheng Wu ◽  
...  
Keyword(s):  
Cross Sections ◽  
Integration Time ◽  
Absorption Cross ◽  
Measurement Sensitivity ◽  
Atmospheric Measurements ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Spectrally Resolved ◽  
Spectra Fitting

Abstract. A system based on incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) has been developed for simultaneous measurement of nitrogen dioxide (NO2), glyoxal (GLY) and methylglyoxal (MGLY). On this system, the absorption of light around 460 nm is spectrally resolved. The concentration of absorbers is determined from a multi-component fit. At an integration time of 100 s, the measurement sensitivity (2σ) for NO2, GLY, and MGLY can reach 18 ppt, 30 ppt, and 100 ppt, respectively. The measurement uncertainty which mainly originates from path length calibration, sampling loss, and uncertainty of absorption cross sections is estimated to be 8 % for NO2, 8 % for GLY, and 16 % for MGLY. When applying the instrument during field observations, we found significant influence of NO2 on spectra fitting for retrieving GLY and MGLY concentration, which is caused by the fact that NO2 has higher absorption cross section and higher ambient concentration. In order to minimize such an effect, a NO2 photolytic convertor (NPC) which removes sampled NO2 at an efficiency of 76 % was integrated on the IBBCEAS system. Since sampled GLY and MGLY are mostly conserved (≥ 95 %) after passing through the NPC, the quality of the spectra fitting and the measurement accuracy of ambient GLY and MGLY were largely improved.

scholarly journals An IBBCEAS system for atmospheric measurements of glyoxal and methylglyoxal in the presence of high NO<sub>2</sub> concentrations

2019 ◽  
Vol 12 (8) ◽  
pp. 4439-4453 ◽  
Author(s):  
Jingwei Liu ◽  
Xin Li ◽  
Yiming Yang ◽  
Haichao Wang ◽  
Yusheng Wu ◽  
...  
Keyword(s):  
Cross Sections ◽  
Integration Time ◽  
Absorption Cross ◽  
Measurement Sensitivity ◽  
Atmospheric Measurements ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Spectrally Resolved ◽  
Spectra Fitting

Abstract. A system based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) has been developed for simultaneous measurement of nitrogen dioxide (NO2), glyoxal (GLY), and methylglyoxal (MGLY). In this system, the measured light absorption at around 460 nm is spectrally resolved. The concentration of absorbers is determined from a multicomponent fit. At an integration time of 100 s, the measurement sensitivity (2σ) for NO2, GLY, and MGLY is 18, 30, and 100 ppt, respectively. The measurement uncertainty, which mainly originates from path length calibration, sampling loss, and uncertainty of absorption cross sections is estimated to be 8 % for NO2, 8 % for GLY, and 16 % for MGLY. When deploying the instrument during field observations, we found significant influence of NO2 on the spectra fitting for retrieving GLY and MGLY concentrations, which is caused by the fact that NO2 has a higher absorption cross section and higher ambient concentration. In order to minimize such an effect, a NO2 photolytic convertor (NPC), which removes sampled NO2 at an efficiency of 76 %, was integrated on the IBBCEAS system. Since sampled GLY and MGLY are mostly (≥95 %) conserved after passing through the NPC, the quality of the spectra fitting and the measurement accuracy of ambient GLY and MGLY under NO2-rich environments could be improved.

scholarly journals A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

2011 ◽  
Vol 4 (3) ◽  
pp. 425-436 ◽  
Author(s):  
J. Chen ◽  
D. S. Venables
Keyword(s):  
Absorption Spectra ◽  
Cross Sections ◽  
Optical Cavity ◽  
Absorption Cross ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Near Ultraviolet ◽  
Low Concentrations ◽  
Measured Absorption ◽  
Atmospheric Observations

Abstract. Accurate absorption spectra of gases in the near–ultraviolet (300 to 400 nm) are essential in atmospheric observations and laboratory studies. This paper describes a novel incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for measuring very weak absorption spectra from 335 to 375 nm. The instrument performance was validated against the 3B1-X1A1 transition of SO2. The measured absorption varied linearly with SO2 column density and the resulting spectrum agrees well with published spectra. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably. In the absorption minimum between the Huggins and Chappuis bands, our absorption spectra fall at the lower range of reported ozone absorption cross-sections. The spectra of the ketones agree with prior spectra at moderate absorptions, but differ significantly at the limits of other instruments' sensitivity. The collision-induced absorption of the O4 dimer at 360.5 nm was also measured and found to have a maximum cross-section of ca. 4.0×10−46 cm5 molecule−2. We demonstrate the application of the instrument to quantifying low concentrations of the short-lived radical, BrO, in the presence of stronger absorptions from Br2 and O3.

scholarly journals A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

2010 ◽  
Vol 3 (5) ◽  
pp. 4571-4602 ◽  
Author(s):  
J. Chen ◽  
D. S. Venables
Keyword(s):  
Absorption Spectra ◽  
Cross Sections ◽  
Optical Cavity ◽  
Absorption Cross ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Near Ultraviolet ◽  
Low Concentrations ◽  
Measured Absorption ◽  
Atmospheric Observations

Abstract. Accurate absorption spectra of gases in the near-ultraviolet (300 to 400 nm) are essential in atmospheric observations and laboratory studies. This paper describes a novel incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for measuring very weak absorption spectra from 335 to 375 nm. The instrument performance was validated against the 3B1−X1A1 transition of SO2. The measured absorption varied linearly with SO2 column density and the resulting spectrum agrees well with published spectra. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably. In the absorption minimum between the Huggins and Chappuis bands, our absorption spectra fall at the lower range of reported ozone absorption cross-sections. The spectra of the ketones agree with prior spectra at moderate absorptions, but differ significantly at the limits of other instruments' sensitivity. The collision-induced absorption of the O4 dimer at 360.5 nm was also measured and found to have a maximum cross-section of ca. 4.0 × 10−46 cm5 molecule−2. We demonstrate the application of the instrument to quantifying low concentrations of the short-lived radical, BrO, in the presence of stronger absorptions from Br2 and O3.

scholarly journals Comparison of nitrous acid detection using open-path incoherent broadband cavity-enhanced absorption spectroscopy and extractive long-path absorption photometry

2021 ◽  
Author(s):  
Sophie Dixneuf ◽  
Albert A. Ruth ◽  
Rolf Häseler ◽  
Theo Brauers ◽  
Franz Rohrer ◽  
...  
Keyword(s):  
Absorption Spectroscopy ◽  
Nitrous Acid ◽  
Hot Spot ◽  
Integration Time ◽  
Mixing Ratios ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Open Path ◽  
Ccd Detector ◽  
No2 Detection

Abstract. An instrument based on 20 m open-path incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) was established at the Jülich SAPHIR chamber in Spring 2011. The setup was optimized for the detection of HONO and NO2 in the near UV region 352–386 nm, utilizing a bright hot-spot Xe-arc lamp and a UV-enhanced CCD detector. A 2σ detection limit of 26 pptv for HONO and 76 pptv for NO2 was achieved for an integration time of 1 min. Methacrolein has also been detected at mixing ratios below 5 ppbv. The IBBCEAS instrument’s performance for HONO and NO2 detection was compared to that of extractive wet techniques, long-path absorption photometry (LOPAP) and chemiluminescence spectrometry (CLS) NOx detection, respectively.

scholarly journals MAX-DOAS formaldehyde slant column measurements during CINDI: intercomparison and analysis improvement

2013 ◽  
Vol 6 (1) ◽  
pp. 167-185 ◽  
Author(s):  
G. Pinardi ◽  
M. Van Roozendael ◽  
N. Abuhassan ◽  
C. Adams ◽  
A. Cede ◽  
...  
Keyword(s):  
Cross Sections ◽  
Cross Correlation ◽  
Optical Absorption Spectroscopy ◽  
Integration Time ◽  
Measuring Instruments ◽  
Absorption Cross ◽  
Correlation Effects ◽  
Data Set ◽  
Random Uncertainties ◽  
Ring Effect

Abstract. We present intercomparison results for formaldehyde (HCHO) slant column measurements performed during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI) that took place in Cabauw, the Netherlands, in summer 2009. During two months, nine atmospheric research groups simultaneously operated MAX-DOAS (MultiAXis Differential Optical Absorption Spectroscopy) instruments of various designs to record UV-visible spectra of scattered sunlight at different elevation angles that were analysed using common retrieval settings. The resulting HCHO data set was found to be highly consistent, the mean difference between instruments generally not exceeding 15% or 7.5 × 1015 molec cm−2, for all viewing elevation angles. Furthermore, a sensitivity analysis was performed to investigate the uncertainties in the HCHO slant column retrieval when varying key input parameters such as the molecular absorption cross sections, correction terms for the Ring effect or the width and position of the fitting interval. This study led to the identification of potentially important sources of errors associated with cross-correlation effects involving the Ring effect, O4, HCHO and BrO cross sections and the DOAS closure polynomial. As a result, a set of updated recommendations was formulated for HCHO slant column retrieval in the 336.5–359 nm wavelength range. To conclude, an error budget is proposed which distinguishes between systematic and random uncertainties. The total systematic error is estimated to be of the order of 20% and is dominated by uncertainties in absorption cross sections and related spectral cross-correlation effects. For a typical integration time of one minute, random uncertainties range between 5 and 30%, depending on the noise level of individual instruments.

scholarly journals Quantitative infrared absorption cross sections of isoprene for atmospheric measurements

2014 ◽  
Vol 7 (11) ◽  
pp. 3839-3847 ◽  
Author(s):  
C. S. Brauer ◽  
T. A. Blake ◽  
A. B. Guenther ◽  
S. W. Sharpe ◽  
R. L. Sams ◽  
...  
Keyword(s):  
Cross Sections ◽  
Anthropogenic Sources ◽  
Infrared Detection ◽  
Absorption Cross ◽  
Atmospheric Measurements ◽  
Composite Spectra ◽  
Volatile Organic ◽  
Infrared Studies ◽  
Ftir Spectrometer

Abstract. Isoprene (C5H8, 2-methyl-1,3-butadiene) is a volatile organic compound (VOC) and is one of the primary contributors to annual global VOC emissions. Isoprene is produced primarily by vegetation as well as anthropogenic sources, and its OH- and O3-initiated oxidations are a major source of atmospheric oxygenated organics. Few quantitative infrared studies have been reported for isoprene, limiting the ability to quantify isoprene emissions via remote or in situ infrared detection. We thus report absorption cross sections and integrated band intensities for isoprene in the 600–6500 cm−1 region. The pressure-broadened (1 atmosphere N2) spectra were recorded at 278, 298, and 323 K in a 19.94 cm path-length cell at 0.112 cm−1 resolution, using a Bruker IFS 66v/S Fourier transform infrared (FTIR) spectrometer. Composite spectra are derived from a minimum of seven isoprene sample pressures, each at one of three temperatures, and the number densities are normalized to 296 K and 1 atm.

scholarly journals Implementation of an incoherent broadband cavity-enhanced absorption spectroscopy technique in an atmospheric simulation chamber for in situ NO<sub>3</sub> monitoring: characterization and validation for kinetic studies

2020 ◽  
Vol 13 (11) ◽  
pp. 6311-6323 ◽  
Author(s):  
Axel Fouqueau ◽  
Manuela Cirtog ◽  
Mathieu Cazaunau ◽  
Edouard Pangui ◽  
Pascal Zapf ◽  
...  
Keyword(s):  
Absorption Spectroscopy ◽  
Rate Constants ◽  
Optical Cavity ◽  
In Situ Monitoring ◽  
Effective Length ◽  
Integration Time ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Simulation Chamber

Abstract. An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals at the parts per trillion level in the CSA simulation chamber (at LISA). The technique couples an incoherent broadband light source centered at 662 nm with a high-finesse optical cavity made of two highly reflecting mirrors. The optical cavity which has an effective length of 82 cm allows for up to 3 km of effective absorption and a high sensitivity for NO3 detection (up to 6 ppt for an integration time of 10 s). This technique also allows for NO2 monitoring (up to 9 ppb for an integration time of 10 s). Here, we present the experimental setup as well as tests for its characterization and validation. The validation tests include an intercomparison with another independent technique (Fourier-transform infrared, FTIR) and the absolute rate determination for the reaction trans-2-butene + NO3, which is already well documented in the literature. The value of (4.13 ± 0.45) × 10−13 cm3 molecule−1 s−1 has been found, which is in good agreement with previous determinations. From these experiments, optimal operation conditions are proposed. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (VOCs; with rate constants up to 10−10 cm3 molecule−1 s−1).

scholarly journals Fast response cavity enhanced ozone monitor

2013 ◽  
Vol 6 (2) ◽  
pp. 487-494 ◽  
Author(s):  
A. L. Gomez ◽  
E. P. Rosen
Keyword(s):  
Radiative Forcing ◽  
Dynamic Range ◽  
Optical Cavity ◽  
Fast Response ◽  
Integration Time ◽  
New Device ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Rapid Monitoring ◽  
Measurement Cell

Abstract. Ozone is an important atmospheric gas due to its role in air quality and radiative forcing. A new method for sensitive, rapid monitoring of ambient ozone has been developed using a compact platform and relatively inexpensive components. Based on incoherent broadband cavity enhanced absorption spectroscopy (IBB-CEAS), the device utilizes an optical cavity of just 14.5 cm and 99.3% reflective mirrors. Performance of the instrument has been validated against direct absorption measurements in a single-pass measurement cell. Currently, the IBB-CEAS ozone instrument can achieve ∼1 ppb sensitivities at 0.1 s integration time with a dynamic range over four orders of magnitude, accessing relevant ozone concentrations in both the stratosphere and troposphere. This new device offers improved sensitivity and time response for mapping ozone aboard airborne platforms.

scholarly journals Development of a cavity-enhanced absorption spectrometer for airborne measurements of CH<sub>4</sub> and CO<sub>2</sub>

2013 ◽  
Vol 6 (5) ◽  
pp. 1095-1109 ◽  
Author(s):  
S. J. O'Shea ◽  
S. J.-B. Bauguitte ◽  
M. W. Gallagher ◽  
D. Lowry ◽  
C. J. Percival
Keyword(s):  
Biomass Burning ◽  
Dry Matter ◽  
First Year ◽  
Atmospheric Measurements ◽  
Airborne Measurements ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Research Aircraft ◽  
Infrared Spectrometer ◽  
Term Performance

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.

scholarly journals Fast response cavity enhanced ozone monitor

2012 ◽  
Vol 5 (5) ◽  
pp. 7223-7241
Author(s):  
A. L. Gomez ◽  
E. P. Rosen
Keyword(s):  
Radiative Forcing ◽  
Dynamic Range ◽  
Optical Cavity ◽  
Fast Response ◽  
Integration Time ◽  
New Device ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Rapid Monitoring ◽  
Measurement Cell

Abstract. Ozone is an important atmospheric gas due to its role in air quality and radiative forcing. A new method for sensitive, rapid monitoring of ambient ozone has been developed using a compact platform and relatively inexpensive components. Based on Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBB-CEAS), the device utilizes an optical cavity of just 14.5 cm and moderately high reflectivity mirrors (R = 99.3%). Performance of the instrument has been validated against direct absorption measurements in a single-pass measurement cell. Currently, the IBB-CEAS ozone instrument can achieve 1 ppb sensitivities at 0.1 s integration time with a dynamic range over four orders of magnitude, accessing relevant ozone concentrations in both the stratosphere and troposphere. This new device offers improved sensitivity and time response for mapping ozone aboard airborne platforms.

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