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 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 Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada

2006 ◽  
Vol 6 (3) ◽  
pp. 4415-4464 ◽  
Author(s):  
J. G. Murphy ◽  
D. A. Day ◽  
P. A. Cleary ◽  
P. J. Wooldridge ◽  
R. C. Cohen
Keyword(s):  
Nitrogen Oxides ◽  
Sierra Nevada ◽  
Thermal Dissociation ◽  
Ozone Production ◽  
Organic Nitrates ◽  
Research Station ◽  
Small Contribution ◽  
Free Troposphere ◽  
Alkyl Nitrates ◽  
Peroxy Nitrates

Abstract. Observations of speciated nitrogen oxides, namely NO2, total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), and HNO3 by thermal dissociation laser induced fluorescence (TD-LIF), and supporting chemical and meteorological measurements at Big Hill (1860 m), a high elevation site in California's Sierra Nevada Mountains, are described. From May through October, terrain-driven winds in the region routinely bring air from Sacramento, 100 km southwest of the site, upslope over oak and pine forests to Big Hill during the day, while at night, the site often samples clean, dry air characteristic of the free troposphere. Winter differs mainly in that the meteorology does not favour the buildup of Sacramento's pollution over the Sierra Nevada range, and the urban-influenced air that is seen has been less affected by biogenic VOC emissions, resulting in longer lifetime for NO2 and a predominance of the inorganic forms of nitrogen oxides. Summertime observations at Big Hill can be compared with those from Granite Bay, a Sacramento suburb, and from the University of California's Blodgett Forest Research Station to examine the evolution of nitrogen oxides and ozone within the urban plume. Nitrogen oxide radicals (NO and NO2), which dominate total nitrogen oxides (NOy) at Granite Bay, are rapidly converted into HNO3, ΣPNs, and ΣANs, such that these compounds contribute 29, 30, and 21% respectively to the NOy budget in the plume at Big Hill. Nevertheless, the decreasing concentrations of NO2 as the plume is advected to Big Hill lead to decreases in the production rate of HNO3 and ozone. The data also demonstrate the role that temperature plays in sequestering NO2 into peroxy nitrates, effectively decreasing the rate of ozone production. The important contribution of ΣANs to NOy in the region suggests that they should be considered with regards to export of NOy from the boundary layer. Nocturnal observations of airmasses characteristic of the free troposphere showed lower NOy concentrations, which were dominated by HNO3 with a relatively small contribution from the organic nitrates.

scholarly journals Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada

2006 ◽  
Vol 6 (12) ◽  
pp. 5321-5338 ◽  
Author(s):  
J. G. Murphy ◽  
D. A. Day ◽  
P. A. Cleary ◽  
P. J. Wooldridge ◽  
R. C. Cohen
Keyword(s):  
Nitrogen Oxides ◽  
Sierra Nevada ◽  
Thermal Dissociation ◽  
Ozone Production ◽  
Organic Nitrates ◽  
Research Station ◽  
Small Contribution ◽  
Free Troposphere ◽  
Alkyl Nitrates ◽  
Peroxy Nitrates

Abstract. Observations of speciated nitrogen oxides, namely NO2, total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), and HNO3 by thermal dissociation laser induced fluorescence (TD-LIF), and supporting chemical and meteorological measurements at Big Hill (1860 m), a high elevation site in California's Sierra Nevada Mountains, are described. From May through October, terrain-driven winds in the region routinely bring air from Sacramento, 100 km southwest of the site, upslope over oak and pine forests to Big Hill during the day, while at night, the site often samples clean, dry air characteristic of the free troposphere. Winter differs mainly in that the meteorology does not favour the buildup of Sacramento's pollution over the Sierra Nevada range, and the urban-influenced air that is seen has been less affected by biogenic VOC emissions, resulting in longer lifetime for NO2 and a predominance of the inorganic forms of nitrogen oxides. Summertime observations at Big Hill can be compared with those from Granite Bay, a Sacramento suburb, and from the University of California's Blodgett Forest Research Station to examine the evolution of nitrogen oxides and ozone within the urban plume. Nitrogen oxide radicals (NO and NO2), which dominate total nitrogen oxides (NOy) at Granite Bay, are rapidly converted into HNO3, ΣPNs, and ΣANs, such that these compounds contribute 29, 30, and 21% respectively to the NOy budget in the plume at Big Hill. Nevertheless, the decreasing concentrations of NO2 as the plume is advected to Big Hill lead to decreases in the production rate of HNO3 and ozone. The data also demonstrate the role that temperature plays in sequestering NO2 into peroxy nitrates, effectively decreasing the rate of ozone production. The important contribution of ΣANs to NOy in the region suggests that they should be considered with regards to export of NOy from the boundary layer. Nocturnal observations of airmasses characteristic of the free troposphere showed lower NOy concentrations, which were dominated by HNO3 with a relatively small contribution from the organic nitrates.

scholarly journals A thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phases

2020 ◽  
Vol 13 (11) ◽  
pp. 6255-6269
Author(s):  
Natalie I. Keehan ◽  
Bellamy Brownwood ◽  
Andrey Marsavin ◽  
Douglas A. Day ◽  
Juliane L. Fry
Keyword(s):  
Thermal Dissociation ◽  
Organic Nitrates ◽  
Alkyl Nitrates ◽  
Aerosol Mass Spectrometer ◽  
Particle Measurements ◽  
Aerosol Mass ◽  
Oxidant Concentration ◽  
Peroxy Nitrates ◽  
Concentration Chamber ◽  
Cavity Ring Down

Abstract. A thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) was developed to measure NO2, peroxy nitrates (PNs), alkyl nitrates (ANs), and HNO3 in the gas and particle phase, built using a commercial Los Gatos Research NO2 analyzer. The detection limit of the TD-CRDS is 0.66 ppb for ANs, PNs, and HNO3 and 0.48 ppb for NO2. For all four classes of NOy, the time resolution for separate gas and particle measurements is 8 min, and for total gas + particle measurements it is 3 min. The accuracy of the TD-CRDS was tested by comparison of NO2 measurements with a chemiluminescent NOx monitor and aerosol-phase ANs with an aerosol mass spectrometer (AMS). N2O5 causes significant interference in the PN and AN channel under high oxidant concentration chamber conditions, and ozone pyrolysis causes a negative interference in the HNO3 channel. Both interferences can be quantified and corrected for but must be considered when using TD techniques for measurements of organic nitrates. This instrument has been successfully deployed for chamber measurements at widely varying concentrations, as well as ambient measurements of NOy.

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

2021 ◽  
Vol 14 (8) ◽  
pp. 5501-5519
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 ◽  
Reactive Material ◽  
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, for example, 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). The use of a TDI consisting of a non-reactive material suppresses the conversion of isoprene-derived ANs at 473 K, thus allowing selective detection of PNs. The potential for interference by the thermolysis of nitric acid (HNO3), nitrous acid (HONO) and O3 is assessed.

scholarly journals Thermal dissociation cavity-enhanced absorption spectrometer for measuring NO<sub>2</sub>, RO<sub>2</sub>NO<sub>2</sub>, and RONO<sub>2</sub> in the atmosphere

2021 ◽  
Vol 14 (6) ◽  
pp. 4033-4051
Author(s):  
Chunmeng Li ◽  
Haichao Wang ◽  
Xiaorui Chen ◽  
Tianyu Zhai ◽  
Shiyi Chen ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Lookup Table ◽  
Organic Nitrates ◽  
Peroxy Radicals ◽  
Alkyl Nitrates ◽  
Mixing Ratios ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Peroxy Nitrates ◽  
Field Deployment

Abstract. We developed thermal dissociation cavity-enhanced absorption spectroscopy (TD-CEAS) for the in situ measurement of NO2, total peroxy nitrates (PNs, RO2NO2), and total alkyl nitrates (ANs, RONO2) in the atmosphere. PNs and ANs were thermally converted to NO2 at the corresponding pyrolytic temperatures and detected by CEAS at 435–455 nm. The instrument sampled sequentially from three channels at ambient temperature, 453 and 653 K, with a cycle of 3 min, to measure NO2, NO2+ PNs, and NO2+ PNs + ANs. The absorptions between the three channels were used to derive the mixing ratios of PNs and ANs by spectral fitting. The detection limit (LOD, 1σ) for retrieving NO2 was 97 parts per trillion by volume (pptv) in 6 s. The measurement uncertainty of NO2 was 9 %, while the uncertainties of PN and AN detection were larger than those of NO2 due to chemical interferences that occurred in the heated channels, such as the reaction of NO (or NO2) with the peroxy radicals produced by the thermal dissociation of organic nitrates. Based on laboratory experiments and numerical simulations, we created a lookup table method to correct these interferences in PN and AN channels under various ambient organic nitrates, NO, and NO2. Finally, we present the first field deployment and compare it with other instruments during a field campaign in China. The advantages and limitations of this instrument are outlined.

In-situ U-Pb dating of Ries Crater lacustrine carbonates (Miocene, South-West Germany): Implications for continental carbonate chronostratigraphy

2021 ◽  
Vol 568 ◽  
pp. 117011
Author(s):  
Damaris Montano ◽  
Marta Gasparrini ◽  
Axel Gerdes ◽  
Giovanna Della Porta ◽  
Richard Albert
Keyword(s):  
West Germany ◽  
South West ◽  
Lacustrine Carbonates

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.

Sign in / Sign up

Export Citation Format

Share Document