Positionally dependent 15N fractionation factors in the UV photolysis of N2O determined by high resolution FTIR spectroscopy

Turatti, F.; Griffith, David; Wilson, Stephen R.; Esler, M. B.; Rahn, T.; Zhang, H.; Blake, Geoffrey A.

doi:10.1029/2000gl011371

Cited by 49 publications

(62 citation statements)

References 28 publications

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“…The data from this study are in good agreement with the single wavelength results for 185 nm (Kaiser et al, 2003c), 193 nm and 207.6 nm (Turatti et al, 2000); whereas this study is not in agreement with the 193 nm and 211.5 nm experiments by Turatti et al (2000) as well as the 213 nm experiment by Zhang et al (2000). The disagreement for ε( 14 N 15 NO) at λ>205 nm with the existing data is a matter of concern.…”

Section: Comparison With Previous Experimentscontrasting

confidence: 52%

“…range from 185 to 213 nm (Kaiser et al, 2002b(Kaiser et al, , 2003cRahn et al, 1998;Röckmann et al, 2000Röckmann et al, , 2001Toyoda et al, 2001a;Turatti et al, 2000;Umemoto, 1999;Zhang et al, 2000), broadband photolysis experiments (Kaiser et al, 2003c;Röckmann et al, 2001) as well as spectroscopic data from 173 nm to 197 nm (Selwyn and Johnston, 1981). For the low temperatures the only existing wavelength resolved experimental data are those from Selwyn and Johnston (1981) from 173 nm to 197 nm; however a temperature dependence study based on broadband photolysis exists (Kaiser et al, 2002b).…”

Section: Comparison With Other Datamentioning

confidence: 99%

“…amplifier -data transfer to PC via serial port Software Data collection software written using Matlab Data collection and experimental control software written using Matlab Gas handling system 6 mm stainless steel and copper tubing with Swagelok and UltraTorr fittings and Whitey shutoff valves 3 pressure gauges (0-13 hPa, 0-130 hPa, 0-1300 hPa) Edwards 600 AB Barocell capacitance manometer, 0.15% accuracy Vacuum rotary vane pump backing Varian VD-70 turbopump Röckmann et al, 2000Röckmann et al, , 2001Toyoda et al, 2001a;Turatti et al, 2000;Umemoto, 1999;Zhang et al, 2000) have been carried out to investigate the isotopic composition of N 2 O in the atmosphere and to determine the effect of stratospheric photolysis on the isotopic composition. Also, new theoretical models of the absorption cross section and the resulting isotopic fractionation constants have been presented (Blake et al, 2003;Johnson et al, 2001;Morgan et al, 2004;Nanbu and Johnson, 2004).…”

Section: Introductionmentioning

confidence: 99%

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Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: 14N14NO, 15N14NO, 14N15NO and 15N15NO

et al. 2004

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Abstract. The isotopically substituted nitrous oxide species 14N14NO, 15N14NO, 14N15NO and 15N15NO were investigated by ultra-violet (UV) absorption spectroscopy. High precision cross sections were obtained for the wavelength range 181 to 218nm at temperatures of 233 and 283K. These data are used to calculate photolytic isotopic fractionation constants as a function of wavelength. The fractionation constants were used in a three-dimensional chemical transport model in order to simulate the actual fractionation of N2O in the stratosphere, and the results were found to be in good agreement with field studies.

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Section: Comparison With Previous Experimentscontrasting

confidence: 52%

Section: Comparison With Other Datamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: 14N14NO, 15N14NO, 14N15NO and 15N15NO

et al. 2004

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“…N 2 O isotope fractionation by photolysis at various wavelengths has been the subject of at least eight recent experimental studies (Johnston et al, 1995;Rahn et al, 1998;Röckmann et al, 2000Röckmann et al, , 2001Toyoda et al, 2001a;Turatti et al, 2000;Umemoto, 1999;Zhang et al, 2000). In line with theoretical calculations Yung and Miller, 1997), the measured fractionation constants exhibit a dependence on the wavelength of photolysis radiation.…”

Section: Introductionmentioning

confidence: 84%

“…In retrospect, this was also in agreement with pioneering vacuum ultraviolet (VUV) spectroscopy of 15 N substituted N 2 O species (Selwyn and Johnston, 1981), although they seem to have been overlooked at that time. The further prediction of position-dependent enrichments of 15 N in the N 2 O molecule led to the development of new spectrometric techniques (Brenninkmeijer and Röckmann, 1999;Toyoda and Yoshida, 1999;Turatti et al, 2000). Subsequent tests of this theory found it to be in qualitative agreement with new experimental data, but the measured enrichment constants were always higher than predicted (Rahn et al, 1998;Röckmann et al, 2000Röckmann et al, , 2001Toyoda et al, 2001a;Turatti et al, 2000;Umemoto, 1999;Zhang et al, 2000).…”

Section: Introductionmentioning

confidence: 94%

Wavelength dependence of isotope fractionation in N2O photolysis

et al. 2003

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Abstract. In previous reports on isotopic fractionation in the ultraviolet photolysis of nitrous oxide (N 2 O) only enrichments of heavy isotopes in the remaining N 2 O fraction have been found. However, most direct photolysis experiments have been performed at wavelengths far from the absorption maximum at 182 nm. Here we present high-precision measurements of the 15 N and 18 O fractionation constants (ε) in photolysis at 185 nm. Small, but statistically robust depletions of heavy isotopes for the terminal atoms in the linear N 2 O molecule are found. This means that the absorption cross sections σ ( 15 N 14 N 16 O) and σ ( 14 N 2 18 O) are larger than σ ( 14 N 2 16 O) at this specific wavelength. In contrast, the central N atom becomes enriched in 15 N. The corresponding fractionation constants (±1 standard deviation) areTo our knowledge, this is the first documented case of such a heavy isotope depletion in the photolysis of N 2 O which supports theoretical models and pioneering vacuum ultraviolet spectroscopic measurements of 15 N substituted N 2 O species that predict fluctuations of ε around zero in this spectral region (Selwyn and Johnston, 1981). Such a variability in isotopic fractionation could have consequences for atmospheric models of N 2 O isotopes since actinic flux varies also strongly over narrow wavelength regions between 175 and 200 nm due to the Schumann-Runge bands of oxygen. However, the spacing between maxima and minima of the fractionation constants and of the actinic flux differ by two orders of magnitude in the wavelength domain. The wavelength dependence of fractionation constants in N 2 O photolysis can thus be approximated by a linear fit with negligible consequences on the actual value of the spectrally averaged fractionation constant. In order to establish this linear fit,Correspondence to: J. Kaiser (kaiser@princeton.edu) additional measurements at wavelengths other than 185 nm were made using broadband light sources, namely D 2 , Hg/Xe and Sb lamps. The latter lamp was used in conjunction with various interference filters to shift the peak photolysis rate to longer wavelengths. From these experiments and existing data in the literature, a comprehensive picture of the wavelength dependence of N 2 O photolysis near room-temperature is created.

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Clumped isotope perturbation in tropospheric nitrous oxide from stratospheric photolysis

Schmidt

Johnson

2015

Geophysical Research Letters

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Nitrous oxide (N2O) is potent greenhouse gas and source of ozone depleting NO to the stratosphere. Recent advances in mass spectrometry allow accurate measurement of multiply substituted (“clumped”) N2O isotopocules, providing new constraints on the N2O source budget. However, this requires a quantification of the “clumped” N2O fractionation from stratospheric photolysis (main sink). We use time‐dependent quantum dynamics and a 1‐D atmospheric model to determine the effect of stratospheric photolysis on the abundances of multisubstituted N2O isotopocules in the atmosphere. The ultraviolet absorption cross sections of 557 (i.e., 15N15N17O), 458, 548, 457, and 547 are presented for the first time and used to derive altitude‐dependent photolysis rates and fractionation constants. We find that photolysis alters the N2O isotopic composition with multisubstituted mass 47 isotopocules being less abundant than expected from stochastics (Δ47 = −1.7‰ in the troposphere and down to −12‰ in the upper stratosphere).

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Positionally dependent ¹⁵N fractionation factors in the UV photolysis of N₂O determined by high resolution FTIR spectroscopy

Cited by 49 publications

References 28 publications

Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: <sup>14</sup>N<sup>14</sup>NO, <sup>15</sup>N<sup>14</sup>NO, <sup>14</sup>N<sup>15</sup>NO and <sup>15</sup>N<sup>15</sup>NO

Ultra-violet absorption cross sections of isotopically substituted nitrous oxide species: <sup>14</sup>N<sup>14</sup>NO, <sup>15</sup>N<sup>14</sup>NO, <sup>14</sup>N<sup>15</sup>NO and <sup>15</sup>N<sup>15</sup>NO

Wavelength dependence of isotope fractionation in N<sub>2</sub>O photolysis

Clumped isotope perturbation in tropospheric nitrous oxide from stratospheric photolysis

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Positionally dependent 15N fractionation factors in the UV photolysis of N2O determined by high resolution FTIR spectroscopy

Cited by 49 publications

References 28 publications

Wavelength dependence of isotope fractionation in N&lt;sub&gt;2&lt;/sub&gt;O photolysis

Clumped isotope perturbation in tropospheric nitrous oxide from stratospheric photolysis

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Positionally dependent ¹⁵N fractionation factors in the UV photolysis of N₂O determined by high resolution FTIR spectroscopy

Wavelength dependence of isotope fractionation in N<sub>2</sub>O photolysis