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Mass independent isotope effects [Physical Sciences] (2013)

Thiemens, M. H.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

Electronic ISSN: 1091-6490

Topics: Biology , Medicine , Natural Sciences in General

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Marine sulfur cycle constraints on S MIF [Earth, Atmospheric, and Planetary Sciences] (2013)

Halevy, I.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Mass-independent fractionation of sulfur isotopes (S MIF) in Archean and Paleoproterozoic rocks provides strong evidence for an anoxic atmosphere before ∼2,400 Ma. However, the origin of this isotopic anomaly remains unclear, as does the identity of the molecules that carried it from the atmosphere to Earth’s surface. Irrespective of the...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

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Role of polysulfide in Neoarchean pyrite formation [Earth, Atmospheric, and Planetary Sciences] (2013)

Farquhar, J., Cliff, J., Zerkle, A. L., Kamyshny, A., Poulton, S. W., Claire, M., Adams, D., Harms, B.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: It is generally thought that the sulfate reduction metabolism is ancient and would have been established well before the Neoarchean. It is puzzling, therefore, that the sulfur isotope record of the Neoarchean is characterized by a signal of atmospheric mass-independent chemistry rather than a strong overprint by sulfate reducers. Here,...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

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Oxygen isotope anomaly of sulfate aerosol and ENSO [Earth, Atmospheric, and Planetary Sciences] (2013)

Shaheen, R., Abauanza, M., Jackson, T. L., McCabe, J., Savarino, J., Thiemens, M. H.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth’s system are intricately linked to planetary scale processes, and precise characterization...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

Electronic ISSN: 1091-6490

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17O-excess at Vostok indicates stratospheric input [Earth, Atmospheric, and Planetary Sciences] (2013)

Winkler, R., Landais, A., Risi, C., Baroni, M., Ekaykin, A., Jouzel, J., Petit, J. R., Prie, F., Minster, B., Falourd, S.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Combined measurements of water isotopologues of a snow pit at Vostok over the past 60 y reveal a unique signature that cannot be explained only by climatic features as usually done. Comparisons of the data using a general circulation model and a simpler isotopic distillation model reveal a stratospheric signature...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

Electronic ISSN: 1091-6490

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Mass-independent fractionation concepts [Physical Sciences] (2013)

Marcus, R. A.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Key experimental and theoretical features of mass-independent fractionation (MIF) of isotopes, also known as the η-effect, are summarized, including its difference from the exit channel zero-point energy difference effect. The latter exactly cancels in the MIF. One key experimental result is that the MIF for O3 formation is a low-pressure...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

Electronic ISSN: 1091-6490

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Sulfur MIF in photoexcitation of SO2 [Chemistry] (2013)

Whitehill, A. R., Xie, C., Hu, X., Xie, D., Guo, H., Ono, S.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen (16O,17O,18O) and sulfur (32S, 33S, 34S, 36S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

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Nitrate isotopologues in a tropical MBL [Earth, Atmospheric, and Planetary Sciences] (2013)

Savarino, J., Morin, S., Erbland, J., Grannec, F., Patey, M. D., Vicars, W., Alexander, B., Achterberg, E. P.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

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MIF via SO2 photoexcitation [Earth, Atmospheric, and Planetary Sciences] (2013)

Hattori, S., Schmidt, J. A., Johnson, M. S., Danielache, S. O., Yamada, A., Ueno, Y., Yoshida, N.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

Electronic ISSN: 1091-6490

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Mass-independent fractionation in ozone formation [Earth, Atmospheric, and Planetary Sciences] (2013)

Ivanov, M. V., Babikov, D.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Theoretical treatment of ozone forming reaction is developed within the framework of mixed quantum/classical dynamics. Formation and stabilization steps of the energy transfer mechanism are both studied, which allows simultaneous capture of the delta zero-point energy effect and η-effect and identification of the molecular level origin of mass-independent isotope fractionation....

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

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S-isotopic fractionation in VUV photolysis of H2S [Earth, Atmospheric, and Planetary Sciences] (2013)

Chakraborty, S., Jackson, T. L., Ahmed, M., Thiemens, M. H.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV)...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

Print ISSN: 0027-8424

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Nuclear volume isotope effects in crystals [Earth, Atmospheric, and Planetary Sciences] (2013)

Schauble, E. A.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: Mass-independent isotope fractionations driven by differences in volumes and shapes of nuclei (the field shift effect) are known in several elements and are likely to be found in more. All-electron relativistic electronic structure calculations can predict this effect but at present are computationally intensive and limited to modeling small gas...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

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CO2 UV spectrum from first principles [Earth, Atmospheric, and Planetary Sciences] (2013)

Schmidt, J. A., Johnson, M. S., Schinke, R.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ∼167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ∼0.5 nm without scaling the...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

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Oxygen isotopic composition of stratospheric CO2 [Earth, Atmospheric, and Planetary Sciences] (2013)

Wiegel, A. A., Cole, A. S., Hoag, K. J., Atlas, E. L., Schauffler, S. M., Boering, K. A.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

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Duration of sulfate-17 depletion at 635 Ma [Earth, Atmospheric, and Planetary Sciences] (2013)

Killingsworth, B. A., Hayles, J. A., Zhou, C., Bao, H.

National Academy of Sciences

In: PNAS - Proceedings of the National Academy of Sciences

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Publication Date: 2013-10-30

Description: The ∼635 Ma Marinoan glaciation is marked by dramatic Earth system perturbations. Deposition of nonmass-dependently 17O-depleted sulfate (SO42−) in worldwide postglacial sediments is, thus far, unique to this glaciation. It is proposed that an extremely high-pCO2 atmosphere can result in highly 17O-depleted atmospheric O2, or the Marinoan Oxygen-17 Depletion (MOSD)...

Keywords: Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

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