scholarly journals A thermal dissociation laser-induced fluorescence instrument for in situ detection of NO2, peroxy nitrates, alkyl nitrates, and HNO3

2002 ◽  
Vol 107 (D6) ◽  
pp. ACH 4-1-ACH 4-14 ◽  
Author(s):  
D. A. Day ◽  
P. J. Wooldridge ◽  
M. B. Dillon ◽  
J. A. Thornton ◽  
R. C. Cohen
Keyword(s):  
Thermal Dissociation ◽  
Laser Induced Fluorescence ◽  
Alkyl Nitrates ◽  
Peroxy Nitrates ◽  
In Situ Detection

scholarly journals Day- and Night-time Formation of Organic Nitrates at a Forested Mountain-site in South West Germany

2016 ◽  
Author(s):  
Nicolas Sobanski ◽  
Jim Thieser ◽  
Jan Schuladen ◽  
Carina Sauvage ◽  
Wei Song ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
West Germany ◽  
Organic Nitrates ◽  
Lower Yield ◽  
Night Time ◽  
Alkyl Nitrates ◽  
South West ◽  
Peroxy Nitrates ◽  
Kleiner Feldberg

Abstract. We report in-situ measurement of total peroxy-nitrates (ƩPNs) and total alkyl nitrates (ƩANs) in a forested/urban location at the top of the Kleiner Feldberg mountain in South-West Germany. The data, obtained using Thermal Dissociation Cavity Ring Down Spectroscopy (TD-CRDS) in August-September 2011 (PARADE campaign) and July–August 2015 (NOTOMO campaign), represent the first detailed study of ƩPNs and ƩANs over continental Europe. We find that a significant fraction of NOx (up to 75 %) is sequestered as organics nitrates at this site. Futher, we also show that the night-time production of alkyl nitrates by reaction of NO3 with biogenic hydrocarbons is comparable to that from day-time, OH-initiated oxidation pathways. The ƩANs-to-ozone ratio obtained during PARADE was used to derive an approximate, average yield of organic nitrates at noon time from the OH initiated oxidation of VOCs of 7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs at the site. A much lower yield,

scholarly journals Day and night-time formation of organic nitrates at a forested mountain site in south-west Germany

2017 ◽  
Vol 17 (6) ◽  
pp. 4115-4130 ◽  
Author(s):  
Nicolas Sobanski ◽  
Jim Thieser ◽  
Jan Schuladen ◽  
Carina Sauvage ◽  
Wei Song ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Branching Ratio ◽  
West Germany ◽  
Organic Nitrates ◽  
Night Time ◽  
Alkyl Nitrates ◽  
South West ◽  
Peroxy Nitrates ◽  
Kleiner Feldberg

Abstract. We report in situ measurements of total peroxy nitrates (ΣPNs) and total alkyl nitrates (ΣANs) in a forested–urban location at the top of the Kleiner Feldberg mountain in south-west Germany. The data, obtained using thermal dissociation cavity ring-down spectroscopy (TD-CRDS) in August–September 2011 (PARADE campaign) and July 2015 (NOTOMO campaign), represent the first detailed study of ΣPNs and ΣANs over continental Europe. We find that a significant fraction of NOx (up to 75 %) is sequestered as organics nitrates at this site. Furthermore, we also show that the night-time production of alkyl nitrates by reaction of NO3 with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways. The ΣANs ∕ ozone ratio obtained during PARADE was used to derive an approximate average yield of organic nitrates at noon from the OH initiated oxidation of volatile organic compounds (VOCs) of  ∼  7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs measured during the campaign. A much lower AN yield,  <  2 %, was observed in 2015, which may result from sampling air with different average air mass ages and thus different degrees of breakdown of assumptions used to derive the branching ratio, but it may also reflect a seasonal change in the VOC mixture at the site.

scholarly journals Total Peroxy Nitrates (ΣPNs) in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

2010 ◽  
Vol 3 (3) ◽  
pp. 593-607 ◽  
Author(s):  
P. J. Wooldridge ◽  
A. E. Perring ◽  
T. H. Bertram ◽  
F. M. Flocke ◽  
J. M. Roberts ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Laser Induced Fluorescence ◽  
University Of California ◽  
Individual Species ◽  
Ambient Atmosphere ◽  
Peroxyacetyl Nitrate ◽  
Peroxy Nitrates

Abstract. Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical or the NO2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs) via laser-induced fluorescence (LIF) of the NO2 product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NOx conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.

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.

Prototype for In Situ Detection of Atmospheric NO3and N2O5via Laser-Induced Fluorescence

2003 ◽  
Vol 37 (24) ◽  
pp. 5732-5738 ◽  
Author(s):  
Ezra C. Wood ◽  
Paul J. Wooldridge ◽  
Jens H. Freese ◽  
Tim Albrecht ◽  
Ronald C. Cohen
Keyword(s):  
Laser Induced Fluorescence ◽  
In Situ Detection

scholarly journals Total peroxy nitrates (ΣPNs) in the atmosphere: the thermal dissociation-laser induced fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements

2009 ◽  
Vol 2 (6) ◽  
pp. 3055-3097 ◽  
Author(s):  
P. J. Wooldridge ◽  
A. E. Perring ◽  
T. H. Bertram ◽  
F. M. Flocke ◽  
J. M. Roberts ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Laser Induced Fluorescence ◽  
University Of California ◽  
Individual Species ◽  
Ambient Atmosphere ◽  
Peroxyacetyl Nitrate ◽  
Peroxy Nitrates

Abstract. Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical or the NO2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs) via laser-induced fluorescence (LIF) of the NO2 product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NOx conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.

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 Aircraft‐borne, laser‐induced fluorescence instrument for the in situ detection of hydroxyl and hydroperoxyl radicals

1994 ◽  
Vol 65 (6) ◽  
pp. 1858-1876 ◽  
Author(s):  
P. O. Wennberg ◽  
R. C. Cohen ◽  
N. L. Hazen ◽  
L. B. Lapson ◽  
N. T. Allen ◽  
...  
Keyword(s):  
Laser Induced Fluorescence ◽  
In Situ Detection
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