Measurement of heavy isotope enrichment in tropospheric ozone

Krankowsky, D.; Bartecki, F.; Klees, G.; Mauersberger, K.; Schellenbach, K.; Stehr, J. W.

doi:10.1029/95gl01436

Cited by 174 publications

(144 citation statements)

References 21 publications

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“…These findings should improve the photochemical modeling of ⌬ 17 O transfer reactions such as CO 2 ϩ O 1 D exchange (40,41) and NO x conversion to HNO 3 (16,36). We note, however, that most of the ⌬ 17 O values measured in tropospheric O 3 (12,14) fall outside their expected values based on temperature and pressure dependencies of formation (11,30,39,42 …”

Section: Resultsmentioning

confidence: 73%

The role of symmetry in the mass independent isotope effect in ozone

Michalski

Bhattacharya

2009

Proc. Natl. Acad. Sci. U.S.A.

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Understanding the internal distribution of ''anomalous'' isotope enrichments has important implications for validating theoretical postulates on the origin of these enrichments in molecules such as ozone and for understanding the transfer of these enrichments to other compounds in the atmosphere via mass transfer. Here, we present an approach, using the reaction NO 2 ؊ ؉ O3, for assessing the internal distribution of the (7) and non-mass-dependent (NOMAD) (8, 9).The most thoroughly studied MIF system is that of ozone formation. Ozone generated by electric discharge or UV photolysis can produce ⌬ 17 O values of 30-40‰ (‰ ϭ parts per thousand). There have also been numerous studies that have experimentally quantified the pressure and temperature dependence of the isotopic enrichments (10, 11). Most recently, the transfer of the ⌬ 17 O anomaly from ozone to other compounds during oxidation reactions (via atom transfer, e.g., mass balance) has been used to elucidate chemical oxidation pathways in modern atmospheres (16-21). These include ⌬ 17 O observations in atmospheric nitrate, sulfate, CO 2 , and N 2 O. ⌬ 17 O variations in atmospheric nitrate and sulfate are intriguing because they have opened the possibility of using these ⌬ 17 O variations in ice cores as a proxy for paleo-oxidation chemistry (22,23). Modeling such transfer reactions, however, requires knowledge of the internal distribution of the ⌬ 17 O anomaly, i.e., how much is contained in the central versus terminal atoms of ozone, because many atmospheric oxidations are thought to occur through terminal-only transition states.Theories as to the origin of the MIF effect have taken many turns (7,8,24,25), and some theories seem more adept at handling specific experimental cases than others. Most have symmetry as the main, albeit ad hoc, causal mechanism for producing MIF. Recent work by Marcus and coworkers (26-28) is perhaps the most thorough treatment, and they have suggested that nonstatistical RRKM effects arise because of differences in the rovibronic coupling efficiency of the asymmetric molecule when compared with the symmetric isomer. Recent NO 2 spectroscopic data appear to bear the theory out (29), but the uncertainties in that study remain significant, and no mass spectrometer isotope data on the unimolecular decay of NO 2 are available. Because the basis of the ozone MIF theory is symmetry driven, it is implied that the anomalous enrichment must be contained in the terminal atoms of ozone. To be clear, there maybe overall isotopic enrichment (␦ 18 O, ␦ 17 O) distributed throughout the molecule based on isotopologue zero-point energy differences (30), but the 17 O excess (⌬ 17 O) is expected to be only in the terminal position. Others, however, have argued against the symmetry theory (31-33) and have placed anomalous enrichments, even negative ⌬ 17 O values (34), throughout ozone in an attempt to reconcile experimental observations. Precise and accurate measurements of ozone's ⌬ 17 O internal distribution is therefore needed to test the symmet...

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Section: Resultsmentioning

confidence: 73%

The role of symmetry in the mass independent isotope effect in ozone

Michalski

Bhattacharya

2009

Proc. Natl. Acad. Sci. U.S.A.

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“…Field, laboratory, and modeling studies find that in the troposphere 17 O(O 3 ) = 6−54‰ (Johnston and Thiemens, 1997;Krankowsky et al, 1995;Lyons, 2001), 17 O(H 2 O 2 ) = 0.9−2.2‰ (Savarino and Thiemens, 1999;Lyons, 2001), 17 O(OH) ≈ 0‰, and 17 O(O 2 ) = −0.34‰ (Barkan and Luz, 2005 (Morton et al, 1990). Due to potential sampling artifacts from measurements of atmospheric 17 O(O 3 ) (Brenninkmeijer et al, 2003), we assume 17 O(O 3 ) = 35‰ based on calculations by (Lyons, 2001), following Michalski et al (2003).…”

Section: Oxygen Isotopic Composition Of Sulfatementioning

confidence: 99%

The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ17O(SO42–)

2011

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Abstract. We use a global three-dimensional chemical transport model to quantify the influence of anthropogenic emissions on atmospheric sulfate production mechanisms and oxidant concentrations constrained by observations of the oxygen isotopic composition ( ). Additional model simulations are conducted to explore the sensitivity of the oxygen isotopic composition of sulfate to uncertainties in the preindustrial emissions of oxidant precursors.

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“…Nevertheless, this small source has a significant impact on the triple oxygen isotope signature of atmospheric N 2 O, because O( 1 D) is produced mainly by O 3 photolysis and inherits the large oxygen isotope anomaly of stratospheric and tropospheric O 3 . Mass-spectrometric measurements gave bulk D 17 O values of (26 ± 9)% for tropospheric [Johnston and Thiemens, 1997;Krankowsky et al, 1995] and (34 ± 4)% for stratospheric ozone [Mauersberger et al, 2001] As lower limit we adopt the lower limit of the bulk O 3 observations, i.e., 17% and 31% in the troposphere and stratosphere. This translates into flux-weighted average D 17 O sources of (0.26 ± 0.04)% in the stratosphere and (0.10 ± 0.04)% in the troposphere.…”

Section: Reaction Of N 2 + O( 1 D) + Mmentioning

confidence: 99%

Absence of isotope exchange in the reaction of N₂O + O(¹D) and the global Δ¹⁷O budget of nitrous oxide

Kaiser

Röckmann

2005

Geophysical Research Letters

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Measurement of heavy isotope enrichment in tropospheric ozone

Cited by 174 publications

References 21 publications

The role of symmetry in the mass independent isotope effect in ozone

The role of symmetry in the mass independent isotope effect in ozone

The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ<sup>17</sup>O(SO<sub>4</sub><sup>2–</sup>)

Absence of isotope exchange in the reaction of N₂O + O(¹D) and the global Δ¹⁷O budget of nitrous oxide

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Measurement of heavy isotope enrichment in tropospheric ozone

Cited by 174 publications

References 21 publications

The role of symmetry in the mass independent isotope effect in ozone

The role of symmetry in the mass independent isotope effect in ozone

The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ&lt;sup&gt;17&lt;/sup&gt;O(SO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2–&lt;/sup&gt;)

Absence of isotope exchange in the reaction of N2O + O(1D) and the global Δ17O budget of nitrous oxide

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The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ<sup>17</sup>O(SO<sub>4</sub><sup>2–</sup>)

Absence of isotope exchange in the reaction of N₂O + O(¹D) and the global Δ¹⁷O budget of nitrous oxide