Quantification of Nitryl Chloride at Part Per Trillion Mixing Ratios by Thermal Dissociation Cavity Ring-Down Spectroscopy

2011 ◽  
Vol 83 (7) ◽  
pp. 2761-2766 ◽  
Author(s):  
Robert D. Thaler ◽  
Levi H. Mielke ◽  
Hans D. Osthoff
Keyword(s):  
Thermal Dissociation ◽  
Cavity Ring Down Spectroscopy ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Cavity Ring Down

scholarly journals A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy

2014 ◽  
Vol 7 (6) ◽  
pp. 5953-6019
Author(s):  
T. W. Tokarek ◽  
J. A. Huo ◽  
C. A. Odame-Ankrah ◽  
D. Hammoud ◽  
Y. M. Taha ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Ambient Air ◽  
Calibration Method ◽  
Ionization Mass ◽  
Molecular Formula ◽  
Data Set ◽  
Cavity Ring Down Spectroscopy ◽  
Mixing Ratios ◽  
Advantages And Disadvantages ◽  
Cavity Ring Down

Abstract. The peroxycarboxylic nitric anhydrides (PANs, molecular formula RC(O)O2NO2) can readily be observed by gas chromatography coupled to electron capture detection (PAN-GC). Calibration of a PAN-GC remains a challenge because the response factors (RF's) differ for each of the PANs and because their synthesis in sufficiently high purity is non-trivial, in particular for PANs containing unsaturated side chains. In this manuscript, a PAN-GC and its calibration using diffusion standards, whose output was quantified by blue diode laser thermal dissociation cavity ring-down spectroscopy (TD-CRDS), are described. The PAN-GC peak areas correlated linearly with total peroxy nitrate (ΣPN) mixing ratios measured by TD-CRDS (r > 0.96). Accurate determination of RF's required the concentrations of PAN impurities in the synthetic standards to be subtracted from ΣPN. The PAN-GC and its TD-CRDS calibration method were deployed during ambient air measurement campaigns in Abbotsford, BC, from 20 July to 5 August, 2012, and during the Fort McMurray Oil Sands Strategic Investigation of Local Sources (FOSSILS) campaign at the AMS13 ground site in Fort McKay, AB, from 10 August to 5 September 2013. For the Abbotsford data set, the PAN-GC mixing ratios were compared and agreed with those determined in parallel by thermal dissociation chemical ionization mass spectrometry (TD-CIMS). Advantages and disadvantages of the PAN measurement techniques used in this work and the utility of TD-CRDS as a PAN-GC calibration method are discussed.

scholarly journals A compact, high-purity source of HONO validated by Fourier transform infrared and thermal-dissociation cavity ring-down spectroscopy

2020 ◽  
Vol 13 (8) ◽  
pp. 4159-4167 ◽  
Author(s):  
Nicholas J. Gingerysty ◽  
Hans D. Osthoff
Keyword(s):  
Fourier Transform ◽  
Thermal Dissociation ◽  
Fourier Transform Infrared ◽  
Ambient Air ◽  
Cavity Ring Down Spectroscopy ◽  
Mixing Ratios ◽  
Gas Streams ◽  
Ambient Air Measurements ◽  
By Products ◽  
Cavity Ring Down

Abstract. A well-characterized source of nitrous acid vapour (HONO) is essential for accurate ambient air measurements by instruments requiring external calibration. In this work, a compact HONO source is described in which gas streams containing dilute concentrations of HONO are generated by flowing hydrochloric acid (HCl) vapour emanating from a permeation tube over continuously agitated dry sodium nitrite (NaNO2) heated to 50 ∘C. Mixing ratios of HONO and potential by-products including NO, NO2, and nitrosyl chloride (ClNO) were quantified by Fourier transform infrared (FTIR) and thermal-dissociation cavity ring-down spectroscopy (TD-CRDS). A key parameter is the concentration of HCl, which needs to be kept small (<4 ppmv) to avoid ClNO formation. The source produces gas streams containing HONO in air in >95 % purity relative to other nitrogen oxides. The source output is rapidly tuneable and stabilizes within 90 min. Combined with its small size and portability, this source is highly suitable for calibration of HONO instruments in the field.

scholarly journals A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy

2014 ◽  
Vol 7 (10) ◽  
pp. 3263-3283 ◽  
Author(s):  
T. W. Tokarek ◽  
J. A. Huo ◽  
C. A. Odame-Ankrah ◽  
D. Hammoud ◽  
Y. M. Taha ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Ambient Air ◽  
Calibration Method ◽  
Molecular Formula ◽  
Response Factors ◽  
Data Set ◽  
Cavity Ring Down Spectroscopy ◽  
Mixing Ratios ◽  
Advantages And Disadvantages ◽  
Cavity Ring Down

Abstract. The peroxycarboxylic nitric anhydrides (PANs, molecular formula: RC(O)O2NO2) can readily be observed by gas chromatography (PAN-GC) coupled to electron capture detection. Calibration of a PAN-GC remains a challenge, because the response factors differ for each of the PANs, and because their synthesis in sufficiently high purity is non-trivial, in particular for PANs containing unsaturated side chains. In this manuscript, a PAN-GC and its calibration using diffusion standards, whose output was quantified by blue diode laser thermal dissociation cavity ring-down spectroscopy (TD-CRDS), are described. The PAN-GC peak areas correlated linearly with total peroxy nitrate (ΣPN) mixing ratios measured by TD-CRDS (r > 0.96). Accurate determination of response factors required the concentrations of PAN impurities in the synthetic standards to be subtracted from ΣPN. The PAN-GC and its TD-CRDS calibration method were deployed during ambient air measurement campaigns in Abbotsford, BC, from 20 July to 5 August 2012, and during the Fort McMurray Oil Sands Strategic Investigation of Local Sources (FOSSILS) campaign at the AMS13 ground site in Fort McKay, AB, from 10 August to 5 September 2013. The PAN-GC limits of detection for PAN, PPN, and MPAN during FOSSILS were 1, 2, and 3 pptv, respectively. For the Abbotsford data set, the PAN-GC mixing ratios were compared, and agreed with those determined in parallel by thermal dissociation chemical ionization mass spectrometry (TD-CIMS). Advantages and disadvantages of the PAN measurement techniques used in this work and the utility of TD-CRDS as a PAN-GC calibration method are discussed.

scholarly journals A compact, high-purity source of HONO validated by Fourier Transform Infrared and Thermal Dissociation Cavity Ring-down Spectroscopy

2020 ◽  
Author(s):  
Nicholas J. Gingerysty ◽  
Hans D. Osthoff
Keyword(s):  
Fourier Transform ◽  
Thermal Dissociation ◽  
Fourier Transform Infrared ◽  
Ambient Air ◽  
Cavity Ring Down Spectroscopy ◽  
Mixing Ratios ◽  
Gas Streams ◽  
Ambient Air Measurements ◽  
By Products ◽  
Cavity Ring Down

Abstract. A well-characterized source of nitrous acid vapour (HONO) is essential for accurate ambient air measurements by instruments requiring external calibration. In this work, a compact HONO source is described in which gas streams containing dilute concentrations of HONO are generated by flowing hydrochloric acid (HCl) vapour emanating from a permeation tube over continuously agitated dry sodium nitrite (NaNO2) heated to 50 ºC. Mixing ratios of HONO and potential by-products including NO, NO2 and nitrosyl chloride (ClNO) were quantified by Fourier Transform Infrared (FTIR) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). A key parameter is the concentration of HCl, which needs to be kept small ( 97 % purity relative to other nitrogen oxides. The source output is rapidly tuneable and stabilizes within 90 min. Combined with its small size and portability this source is highly suitable for calibration of HONO instruments in the field.

scholarly journals Impact of ozone and inlet design on the detection of isoprene-derived organic nitrates by thermal dissociation cavity ring-down spectroscopy (TD-CRDS)

2021 ◽  
Author(s):  
Patrick Dewald ◽  
Raphael Dörich ◽  
Jan Schuladen ◽  
Jos Lelieveld ◽  
John N. Crowley
Keyword(s):  
Thermal Dissociation ◽  
Volume Ratio ◽  
Reaction Chamber ◽  
Organic Nitrates ◽  
Temperature Dependent ◽  
Alkyl Nitrates ◽  
Cavity Ring Down Spectroscopy ◽  
Viable Solution ◽  
Peroxy Nitrates ◽  
Cavity Ring Down

Abstract. We present measurements of isoprene-derived organic nitrates (ISOP-NITs) generated in the reaction of isoprene with the nitrate radical (NO3) in a 1 m3 Teflon reaction chamber. Detection of ISOP-NITs is achieved via their thermal dissociation to nitrogen dioxide (NO2), which is monitored by cavity ring-down spectroscopy (TD-CRDS). Using thermal dissociation inlets (TDIs) made of quartz, the temperature-dependent dissociation profiles (thermograms) of ISOP-NITs measured in the presence of ozone (O3) are broad (350 to 700 K), which contrasts the narrower profiles previously observed for e.g. isopropyl nitrate (iPN) or peroxy acetyl nitrate (PAN) under the same conditions. The shape of the thermograms varied with the TDI’s surface to volume ratio and with material of the inlet walls, providing clear evidence that ozone and quartz surfaces catalyse the dissociation of unsaturated organic nitrates leading to formation of NO2 at temperatures well below 475 K, impeding the separate detection of alkyl nitrates (ANs) and peroxy nitrates (PNs). We present a simple, viable solution to this problem and discuss the potential for interference by the thermolysis of nitric acid (HNO3), nitrous acid (HONO) and O3.

scholarly journals A five-channel cavity ring-down spectrometer for the detection of NO<sub>2</sub>, NO<sub>3</sub>, N<sub>2</sub>O<sub>5</sub>, total peroxy nitrates and total alkyl nitrates

2016 ◽  
Vol 9 (10) ◽  
pp. 5103-5118 ◽  
Author(s):  
Nicolas Sobanski ◽  
Jan Schuladen ◽  
Gerhard Schuster ◽  
Jos Lelieveld ◽  
John N. Crowley
Keyword(s):  
Thermal Decomposition ◽  
Thermal Dissociation ◽  
Organic Radical ◽  
Alkyl Nitrates ◽  
Mixing Ratios ◽  
Instrument Construction ◽  
Peroxy Nitrates ◽  
Field Deployment ◽  
And Performance ◽  
Cavity Ring Down

Abstract. We report the characteristics and performance of a newly developed five-channel cavity ring-down spectrometer to detect NO3, N2O5, NO2, total peroxy nitrates (ΣPNs) and total alkyl nitrates (ΣANs). NO3 and NO2 are detected directly at 662 and 405 nm, respectively. N2O5 is measured as NO3 after thermal decomposition at 383 K. PNs and ANs are detected as NO2 after thermal decomposition at 448 and 648 K. We describe details of the instrument construction and operation as well as the results of extensive laboratory experiments that quantify the chemical and optical interferences that lead to biases in the measured mixing ratios, in particular involving the reactions of organic radical fragments following thermal dissociation of PNs and ANs. Finally, we present data obtained during the first field deployment of the instrument in July 2015.

scholarly journals Carbon Dioxide and Methane in the China Sea Shelf Boundary Layer Observed by Cavity Ring-Down Spectroscopy

2017 ◽  
Vol 34 (10) ◽  
pp. 2233-2244 ◽  
Author(s):  
Kun-Peng Zang ◽  
Ling-Xi Zhou ◽  
Ju-Ying Wang
Keyword(s):  
Carbon Dioxide ◽  
Boundary Layer ◽  
Measurement Data ◽  
Cavity Ring Down Spectroscopy ◽  
Trade Winds ◽  
Air Masses ◽  
China Sea ◽  
Mixing Ratios ◽  
First Time ◽  
Cavity Ring Down

AbstractHigh-accuracy continuous ship-based cavity ring-down spectroscopy was used to simultaneously measure the mixing ratios of the carbon dioxide and methane in the China Sea shelf boundary layer for the first time, from 22 March to 2 April 2013. The mixing ratios of CO2 and CH4 ranged from 397.40 to 432.40 µmol mol−1 and from 1812.8 to 2068.7 nmol mol−1, respectively. Measurement data showed latitudinal distributions, with a slight fluctuation between 35.52° and 22.00°N but a sharp decline from 22.00° to 20.50°N. This distribution was not only the result of airmass transport from the Asian continent and Pacific Ocean induced by winter monsoon and trade winds but also by air–sea exchange and atmospheric chemical processes. Moreover, mixing ratios of CO2 and CH4 showed a temporal and spatial correlation that was possibly due to the effects of multisource air masses and their mixed status.

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