The MPI-Mainz UV/VIS Spectral Atlas of Gaseous Molecules of  Atmospheric Interest

Keller-Rudek, Hannelore; Moortgat, G. K.; Sander, R.; Sörensen, Rüdiger

doi:10.5194/essd-5-365-2013

Cited by 398 publications

(354 citation statements)

References 12 publications

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“…Thus, following the rationale that radiation is primarily absorbed by the OQC-CQC chromophore, we assume a cross section equal to the average of those measured for three molecules with the same chromophore (methacrolein, 28 acrolein 29 and (E)-2-hexenal 30,31 ). 32 w Cross sections for these compounds differ by an average of 14% over our experimental wavelength range. From these values, we estimate a bulk photolysis quantum yield of 1.0 AE 0.4 over the range 300-400 nm.…”

Section: Methodsmentioning

confidence: 99%

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Wolfe

Crounse

Parrish

et al. 2012

Phys. Chem. Chem. Phys.

106

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The C 5 -hydroperoxyenals (C 5 -HPALDs) are a newly-recognized class of multi-functional hydrocarbons produced during the hydroxyl radical (OH)-initiated oxidation of isoprene. Recent theoretical calculations suggest that fast photolysis of these compounds may be an important OH source in high-isoprene, low-NO regions. We report experimental constraints for key parameters of photolysis, OH reaction and ozone reaction of these compounds as derived from a closelyrelated, custom-synthesized C 6 -HPALD. The photolysis quantum yield is 1.0 AE 0.4 over the range 300-400 nm, assuming an absorption cross section equal to the average of those measured for several analogous enals. The yield of OH from photolysis was determined as 1.0 AE 0.8. The OH reaction rate constant is (5.1 AE 1.8) Â 10 À11 cm 3 molecule À1 s À1 at 296 K. The ozone reaction rate constant is (1.2 AE 0.2) Â 10 À18 cm 3 molecule À1 s À1 at 296 K. These results are consistent with previous first-principles estimates, though the nature and fate of secondary oxidation products remains uncertain. Incorporation of C 5 -HPALD chemistry with the above parameters in a 0-D box model, along with experimentally-constrained rates for C 5 -HPALD production from isomerization of first-generation isoprene hydroxyperoxy radicals, is found to enhance modeled OH concentrations by 5-16% relative to the traditional isoprene oxidation mechanism for the chemical regimes of recent observational studies in rural and remote regions. This enhancement in OH will increase if C 5 -HPALD photo-oxidation products also photolyze to yield additional OH or if the C 5 -HPALD production rate is faster than has been observed.

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Section: Methodsmentioning

confidence: 99%

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Wolfe

Crounse

Parrish

et al. 2012

Phys. Chem. Chem. Phys.

106

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“…It is noted that the UV-absorption spectrum of CH 3 O 2 is relatively broad and hence may prevent a selective detection due to the difficulty in discriminating from the potential presence of other species also absorbing around 250 nm, such as Cl 2 and CH 3 CHO used in concentrations as high as 10 16 molecule cm −3 , while [CH 3 O 2 ] was ∼ 10 13 molecule cm −3 (Dagaut and Kurylo, 1990;Roehl et al, 1996). As the absorption cross sections of Cl 2 and CH 3 CHO at 250 nm lay in the range 10 −21 -10 −22 cm 2 molecule −1 (Keller-Rudek et al, 2013), the unaccounted for absorption of these species may have led to an overestimation of σ 250 nm (CH 3 O 2 ).…”

Section: Comparison Between the Fage Sensitivities For Ch 3 O 2 Obtaimentioning

confidence: 99%

A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical

et al. 2017

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Abstract.A new method for measurement of the methyl peroxy (CH 3 O 2 ) radical has been developed using the conversion of CH 3 O 2 into CH 3 O by excess NO with subsequent detection of CH 3 O by fluorescence assay by gas expansion (FAGE) with laser excitation at ca. 298 nm. The method can also directly detect CH 3 O, when no nitric oxide is added. Laboratory calibrations were performed to characterise the FAGE instrument sensitivity using the conventional radical source employed in OH calibration with conversion of a known concentration of OH into CH 3 O 2 via reaction with CH 4 in the presence of O 2 . Detection limits of 3.8 × 10 8 and 3.0 × 10 8 molecule cm −3 were determined for CH 3 O 2 and CH 3 O respectively for a signal-to-noise ratio of 2 and 5 min averaging time. Averaging over 1 h reduces the detection limit for CH 3 O 2 to 1.1 × 10 8 molecule cm −3 , which is comparable to atmospheric concentrations. The kinetics of the second-order decay of CH 3 O 2 via its self-reaction were observed in HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) at 295 K and 1 bar and used as an alternative method of calibration to obtain a calibration constant with overlapping error limits at the 1σ level with the result of the conventional method of calibration. The overall uncertainties of the two methods of calibrations are similar -15 % for the kinetic method and 17 % for the conventional method -and are discussed in detail. The capability to quantitatively measure CH 3 O in chamber experiments is demonstrated via observation in HIRAC of CH 3 O formed as a product of the CH 3 O 2 self-reaction.

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“…However, absorption of alkenes 330 and aromatics occurs in the UV range (< 300 nm) (Keller-Rudek et al, 2013), well below the wavelengths used in GANDALF.…”

Section: Interferences By Other Species 295mentioning

confidence: 99%

Laser induced fluorescence based detection of atmospheric nitrogen dioxide and comparison of different techniques during the PARADE 2011 field campaign

Javed¹,

Kubistin²,

Martínez³

et al. 2018

Preprint

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Abstract. GANDALF (Gas Analyzer for Nitrogen Dioxide Applying Laser-induced Fluorescence), a new instrument for the detection of nitrogen dioxide based on the laser-induced fluorescence (LIF) technique, is presented in this paper. GANDALF is designed for ground based and air-borne deployment with a robust calibration system. In the current setup, it uses a multi-mode diode laser (447 -450 nm) and performs in situ, continuous, and autonomous measurements with a laser pulse repetition rate of 5 MHz. The performance of GANDALF was tested during the field experiment at a forested location with urban influence where 20 NO x levels were between 0.12 and 22 parts per billion by volume (ppb v ). Based on the field results, the limit of detection is estimated at 5 -10 parts per trillion by volume (ppt v ) in 60 s at a signal to noise ratio (SNR) of 2. The overall accuracy and precision of the instrument are better than 5 % (1 σ) and 0.5 % + 3 ppt v (1 σ min -1 ), respectively. A comparison of nitrogen dioxide measurements based on several techniques during the field campaign is presented to explore methodic differences. 25

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The MPI-Mainz UV/VIS Spectral Atlas of Gaseous Molecules of Atmospheric Interest

Cited by 398 publications

References 12 publications

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical

Laser induced fluorescence based detection of atmospheric nitrogen dioxide and comparison of different techniques during the PARADE 2011 field campaign

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The MPI-Mainz UV/VIS Spectral Atlas of Gaseous Molecules of Atmospheric Interest

Cited by 398 publications

References 12 publications

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)

A new method for atmospheric detection of the CH&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; radical

Laser induced fluorescence based detection of atmospheric nitrogen dioxide and comparison of different techniques during the PARADE 2011 field campaign

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A new method for atmospheric detection of the CH<sub>3</sub>O<sub>2</sub> radical