Experimental study on isotope fractionation effects in visible photolysis of O<sub>3</sub> and in the O + O<sub>3</sub> odd oxygen sink reaction

Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

doi:10.1002/2014jd022944

Cited by 9 publications

(13 citation statements)

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“…The correction depends on the results of Früchtl et al [], where unexplained losses of O 3 might have introduced systematic errors in the determination of

ε_{O_{3} + normalO}

. Estimating the effects of these errors yielded lower limits of

{}^{18}ε_{O_{3} + normalO}

= −18.6‰ and

{}^{17}ε_{O_{3} + normalO}

= −9.3‰ [ Früchtl et al , ]. According to equation , lower values assigned to

ε_{O_{3} + normalO}

would lead to correspondingly higher values for

ε_{O_{3} + h ν}

.…”

Section: Discussionmentioning

confidence: 76%

“…Using the previously determined fractionation values for (R2) of 18 ε O3þO = À11.9(±1.4)‰ and 17 ε O3þO = À5.95(±0.7)‰ [Früchtl et al, 2015], the photolysis-induced fractionations can be calculated from equation (4).…”

Section: Resultsmentioning

confidence: 99%

“…Thus, isotope effects in photolysis and chemical removal cannot be disentangled [ Brenninkmeijer et al ]. Früchtl et al [] combined photolysis experiments of pure O 3 and O 3 mixed in a large excess of CO, which acts as O atom quencher, to separately quantify the fractionation in both removal processes. Photolysis experiments using a broadband light source with a 455 nm long‐pass filter yielded

{}^{18}ε_{O_{3} + h ν}

= −16.1(±1.4)‰ and

{}^{17}ε_{O_{3} + h ν}

= −8.05(±0.7)‰, and

{}^{18}ε_{O_{3} + normalO}

= −11.9(±1.4)‰ and

{}^{17}ε_{O_{3} + normalO}

= −5.95(±0.7)‰.…”

Section: Introductionmentioning

confidence: 99%

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Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications

Früchtl

Janssen

Taraborrelli

et al. 2015

Geophys. Res. Lett.

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The 17O and 18O isotope fractionation associated with photolysis of O3 in the Chappuis band was determined using a broadband light source with cutoff filters at 455, 550, and 620 nm and narrowband light sources at 530, 617, and 660 nm. The isotope effects follow a mass‐dependent fractionation pattern (δ17O/δ18O = 0.53). Contrary to theoretical predictions, fractionations are negative for all wavelength ranges investigated and do not change signs at the absorption cross‐section maximum. Our measurements differ from theoretical calculations by as much as 34‰ in εO3+hν18 = (18J/16J − 1). The wavelength dependence is also weaker than predicted. Photo‐induced fractionation is strongest when using a low‐wavelength cutoff at 620 nm with εO3+hν18 = −26.9(±1.4)‰. With decreasing wavelength, fractionation values diminish to εO3+hν18 = −12.9(±1.3)‰ at 530 nm. Results from an atmospheric model demonstrate that visible light photolysis is the most important tropospheric sink of O3, which thus contributes about one sixth to the ozone enrichment.

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“…The correction depends on the results of Früchtl et al [], where unexplained losses of O 3 might have introduced systematic errors in the determination of

ε_{O_{3} + normalO}

. Estimating the effects of these errors yielded lower limits of

{}^{18}ε_{O_{3} + normalO}

= −18.6‰ and

{}^{17}ε_{O_{3} + normalO}

= −9.3‰ [ Früchtl et al , ]. According to equation , lower values assigned to

ε_{O_{3} + normalO}

would lead to correspondingly higher values for

ε_{O_{3} + h ν}

.…”

Section: Discussionmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

{}^{18}ε_{O_{3} + h ν}

= −16.1(±1.4)‰ and

{}^{17}ε_{O_{3} + h ν}

= −8.05(±0.7)‰, and

{}^{18}ε_{O_{3} + normalO}

= −11.9(±1.4)‰ and

{}^{17}ε_{O_{3} + normalO}

= −5.95(±0.7)‰.…”

Section: Introductionmentioning

confidence: 99%

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Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications

Früchtl

Janssen

Taraborrelli

et al. 2015

Geophys. Res. Lett.

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“…Initial evidence for this comes from laboratory experiments (Bhattacharya and Thiemens, 1988;Chakraborty and Bhattacharya, 2003), and was recently substantiated by measurements where photolytic O 3 removal could be analytically separated from chemical removal (Früchtl et al, 2015a). Wavelengthdependent isotope effects in O 3 photolysis are also suggested by theoretical calculations (Miller et al, 2005;Liang et al, 2006;Ndengué et al, 2014), but the agreement of these calculations with new high-precision measurements is relatively poor (Früchtl et al, 2015b).…”

Section: Introductionmentioning

confidence: 98%

Retrievals of heavy ozone with MIPAS

et al. 2016

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Abstract. A method for retrieval of 18 O-substituted isotopomers of O 3 in the stratosphere with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) is presented. Using a smoothing regularisation constraint, volume mixing ratio profiles are retrieved for the main isotopologue and the symmetric and asymmetric isotopomers of singly substituted O 3 . For the retrieval of the heavy isotopologues, two microwindows in the MIPAS A band (685-970 cm −1 ) and six in the AB band (1020-1170 cm −1 ) are used. As the retrievals are performed as perturbations on the previously retrieved a priori profiles, the vertical resolution of the individual isotopomer profiles is very similar, which is important when calculating the ratio between two isotopomers. The performance of the method is evaluated using 1044 vertical profiles recorded with MIPAS on 1 July 2003.The mean values are separated by latitude bands, along with estimates of their uncertainties. The asymmetric isotopomer shows a mean enrichment of ∼ 8 %, with a vertical profile that increases up to 33 km and decreases at higher altitudes. This decrease with altitude is a robust result that does not depend on retrieval settings, and it has not been reported clearly in previously published datasets. The symmetric isotopomer is considerably less enriched, with mean values around 3 % and with a large spread. In individual retrievals the uncertainty of the enrichment is dominated by the measurement noise (2-4 %), which can be reduced by averaging multiple retrievals; systematic uncertainties linked to the retrieval are generally small at ∼ 0.5 %, but this is likely underestimated because the uncertainties in key spectroscopic parameters are unknown. The variabilities in the retrieval results are largest for the Southern Hemisphere.

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“…In these cases, statistical anti-clumping only occurs when the indistinguishable terminal O atoms are involved (Table 1). In many cases, however, the isotopic composition of O 3 is determined without position information30313233 and in this case the atoms can be treated as effectively indistinguishable and need to be treated according to the formalism developed here.…”

Section: Origin Of the Statistical Negative Clumped Isotope Signaturesmentioning

confidence: 99%

Statistical clumped isotope signatures

Röckmann

Popa

Krol

et al. 2016

Sci Rep

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High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules.

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Experimental study on isotope fractionation effects in visible photolysis of O₃ and in the O + O₃ odd oxygen sink reaction

Cited by 9 publications

References 50 publications

Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications

Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications

Retrievals of heavy ozone with MIPAS

Statistical clumped isotope signatures

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Experimental study on isotope fractionation effects in visible photolysis of O3 and in the O + O3 odd oxygen sink reaction

Cited by 9 publications

References 50 publications

Wavelength-dependent isotope fractionation in visible light O3 photolysis and atmospheric implications

Wavelength-dependent isotope fractionation in visible light O3 photolysis and atmospheric implications

Retrievals of heavy ozone with MIPAS

Statistical clumped isotope signatures

Contact Info

Product

Resources

About

Experimental study on isotope fractionation effects in visible photolysis of O₃ and in the O + O₃ odd oxygen sink reaction

Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications

Wavelength-dependent isotope fractionation in visible light O₃ photolysis and atmospheric implications