Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates

Planetary and Space Sciences Research Institute, The Open University, Walton Hall, Milton Keynes MK7 6AA, United Kingdom.
Proceedings of the National Academy of Sciences (Impact Factor: 9.67). 09/2002; 99(17):10988-93. DOI: 10.1073/pnas.172378499
Source: PubMed

ABSTRACT Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (delta17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 +/- 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by -0.241 +/- 0.042 per thousand. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 +/- 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation.

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Available from: Andre Brack, Sep 27, 2015
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    • "This line Fig. 4. Three-isotope plot (d 18 O vs. d 17 O) relative to Standard Mean Ocean Water (SMOW) of analyzed Ca-carbonate. TFL refers to the Terrestrial Fractionation Line (Miller et al., 2002). "
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    ABSTRACT: We present petrologic and Secondary Ion Mass Spectrometry (SIMS) oxygen isotope analyses of Ca-carbonate within a group of paired Antarctic CM2 chondrites. The carbonates can be grouped into two isotopically and morphologically distinct populations. Type 1 grains (small matrix grains) possess average δ18O of 33.7±2.3‰ (1σ) and average Δ17O of −0.81‰±0.90‰ (1σ). Type 2 grains (calcite aggregates) possess distinct oxygen isotopic compositions, average δ18O of 19.4‰±1.5‰ (1σ) and average Δ17O of −1.98±0.9‰ (1σ). These differences are interpreted to indicate that the two populations of calcite formed under different conditions at different times. The carbonates have textural features that suggest an extraterrestrial origin. The data presented here fall within error of a previously measured array for carbonates from CM falls (Benedix et al., 2003). The presence of two generations of carbonate suggests carbonate formation in two discrete events on the parent body of these meteorites. The oxygen isotopic data presented here deviate from prior bulk carbonate measurements undertaken for these meteorites. Most likely, this deviation is because bulk carbonate analyses included vein carbonate which formed during terrestrial weathering.
    Geochimica et Cosmochimica Acta 01/2012; 77. DOI:10.1016/j.gca.2011.10.003 · 4.33 Impact Factor
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    • "Much less is known about the prospects for mass-independent isotope effects involving condensed phases (cf. Miller et al. 2002). "
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    ABSTRACT: In this chapter we compare and contrast chemical and photochemical pathways for mass-independent fractionation (MIF) of oxygen isotopes in the solar nebula. We begin by assessing the galactic evolution model for oxygen isotope variation in the Solar System in order to compare the predictions of a leading nucleosynthetic model with those of the chemical models. There are two fundamentally different classes of possible chemical mechanisms for mass-independent oxygen isotope fractionation in the early Solar System. One is symmetry-induced intramolecular vibrational disequilibrium of vibrationally excited reactant oxygen-bearing molecules. The other is isotope selective photodissociation of CO coupled with self-shielding and formation of H 2 O. Symmetry-induced fractionation is an experimentally verifi ed process with solid theoretical foundations. It is observed to occur in Earth's atmosphere. It could have resulted in preservation of oxygen MIF effects only if mediated by dust grain surfaces. CO self-shielding is an attractive hypothesis for the origin of mass-independent oxygen isotope fractionation in the early Solar System because it appeals to a process that apparently occurs in the interstellar medium, but it lacks experimental verifi cation. Three astrophysical settings for CO self-shielding are proposed as sites for generating Δ 17 O variability in the early Solar System. One is the inner annulus of the protostellar disk at relatively high temperature. Another is the surface of the disk high above the midplane where light from the central star grazes the 188 Young et al. gas and dust of the disk, resulting in a zone of active CO predissociation and self-shielding. Interstellar light illuminating the disk at high incident angles causes a similar horizon of CO photodestruction. Variations in 16 O could also have been inherited from self-shielding by CO in the molecular cloud that gave rise to the protosun. The overall consequence of CO self-shielding is conversion of CO gas to 16 O-poor H 2 O. A key difference between galactic evolution, chemically-induced MIF effects, and CO self-shielding is the predicted relative oxygen isotopic compositions of primeval dust and the Sun. Therefore, the oxygen isotopic composition of the Sun will be a crucial arbiter that may permit us to narrow the list of possible origins for oxygen MIF in the early Solar System.
    Reviews in Mineralogy and Geochemistry 01/2008; 68(1):187-218. DOI:10.2138/rmg.2008.68.9 · 4.76 Impact Factor
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    • "Other factors may be oxygen isotope exchange reactions between CO and CaO [67] or between CO 2 and CaO [68]. In case of a non-quantitative reaction of the carbonates, a recently reported mass-independent oxygen isotope fractionation during the thermal decomposition of carbonates [69] "
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    ABSTRACT: Oxygen is a globally important element, in inorganic compounds it is involved in key structural compounds of the earth, and it is providing functional groups for most organic compounds. Oxygen isotope ratio analyses on these compounds provide information on the oxygen sources and (formation) reactions in which the compound was involved. Therefore generally applicable analytical methods for the delta18O determination are highly desirable. After a description of online high temperature "carbon reduction" methods for the conversion of oxygen in the compounds mentioned into CO and discussion of problems involved, especially in analysis of inorganic substances like carbonates and silicates, selected examples for the application of these carbon reduction methods will be presented. The well-known correlation of delta18O values of cellulose (in tree rings) to that of (leaf) water is used since the 1970's as climate indicator. The observed enrichment in 18O in cellulose by about 27% in comparison to leaf water is attributed to an oxygen equilibrium isotope effect between carbonyl groups and water. But not all carbohydrates show this "general"18O enrichment relative to water. By means of a recently published model a non-statistical oxygen isotope distribution in carbohydrates is postulated. Oxygen isotope discrimination has been recognized long ago as an important principle of authenticity evaluation in food and beverages. Though many basic mechanisms of isotope discrimination in nature are known, the corresponding application of data is often based only on empirical observations in this field. The fact that oxygen in natural organic plant material is derived from three sources (CO2, H2O, O2) with distinct differences in and that their incorporation by different reactions implies oxygen isotope effects of different sizes, is therefore of special importance, and it is attempted by means of individual isotopic increments of functional groups to predict global delta18O values of natural and nature-identical compounds. Vice versa delta18O values can also give hints on the elucidation of biosynthetic pathways.
    Isotopes in Environmental and Health Studies 07/2003; 39(2):85-104. DOI:10.1080/1025601031000108642 · 0.96 Impact Factor
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