249:
Mass-independent fractionation of sulfur can be observed in ancient sediments, where it preserves a signal of the prevailing environmental conditions. The creation and transfer of the mass-independent signature into minerals would be unlikely in an atmosphere containing abundant oxygen, constraining
192:
of the two formation channels available (e.g., OO + O vs O + OO for formation of OOO.) These mass-dependent zero-point energy effects cancel one another out and do not affect the enrichment in heavy isotopes observed in ozone. The mass-independent enrichment in ozone is still not fully understood,
342:
The disappearance of distinctive non-mass-dependent (NMD) sulphur isotope fractionations in sedimentary rocks deposited after about 2.4–2.3 Gyr ago16 (Fig. 2). Almost all fractionations among isotopes of a given element scale to differences in their masses; NMD fractionations deviate from this
105:. Both ratios vary by the same amount in the inclusions, although the mass difference between O and O is almost twice as large as the difference between O and O. Originally this was interpreted as evidence of incomplete mixing of O-rich material (created and distributed by a large star in a
664:
Koren, G.; Schneider, L.; Velde, I. R.; Schaik, E.; Gromov, S. S.; Adnew, G. A.; Mrozek
Martino, D. J.; Hofmann, M. E. G.; Liang, M.-C.; Mahata, S.; Bergamaschi, P.; Laan-Luijkx, I. T.; Krol, M. C.; Röckmann, T.; Peters, W. (16 August 2019).
261:. Prior to this time, the MIS record implies that sulfate-reducing bacteria did not play a significant role in the global sulfur cycle, and that the MIS signal is due primarily to changes in volcanic activity.
121:, shows that the most O-rich inclusions are close to the bulk composition of the solar system. This implies that Earth, the Moon, Mars, and asteroids all formed from O- and O-enriched material.
343:
typical behaviour. The remarkable NMD signals are tied to photochemical reactions at short wavelengths involving gaseous sulphur compounds released from volcanoes into the atmosphere.
406:
Thiemens, M. H.; Heidenreich, J. E. (1983). "The Mass-Independent
Fractionation of Oxygen: A Novel Isotope Effect and Its Possible Cosmochemical Implications".
62:. Observation of mass-independently fractionated materials can therefore be used to trace these types of reactions in nature and in laboratory experiments.
206:
300:
Timothy W. Lyons; Christopher T. Reinhard; Noah J. Planavsky (February 19, 2014). "The rise of oxygen in Earth's early ocean and atmosphere".
90:
144:
air samples measured by Konrad
Mauersberger. These enrichments were eventually traced to the three-body ozone formation reaction.
824:
Halevy, I.; Johnston, D.; Schrag, D. (2010). "Explaining the structure of the
Archean mass-independent sulfur isotope record".
355:
Clayton, R. N.; Grossman, L.; Mayeda, T. K. (1973). "A Component of
Primitive Nuclear Composition in Carbonaceous Meteorites".
38:, where the amount of separation does not scale in proportion with the difference in the masses of the isotopes. Most isotopic
270:
47:
188:
properties. The mass-dependent isotope effect occurs in asymmetric species, and arises from the difference in
168:
and others suggest that the enrichments are the result of a combination of mass-dependent and mass-independent
217:
The mass-independent distribution of isotopes in stratospheric ozone can be transferred to carbon dioxide (CO
251:
891:
169:
886:
275:
202:
181:
136:. Large, 1:1 enrichments of O/O and O/O in ozone were discovered in laboratory synthesis experiments by
43:
19:
773:
Farquhar, J.; Bao, H.; Thiemens, M. (2000). "Atmospheric
Influence of Earth's Earliest Sulfur Cycle".
580:"Kinetic origin of the ozone isotope effect: a critical analysis of enrichments and rate coefficients"
833:
782:
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682:
630:
591:
536:
501:
466:
415:
364:
309:
280:
118:
492:
Morton, J.; Barnes, J.; Schueler, B.; Mauersberger, K. (1990). "Laboratory
Studies of Heavy Ozone".
70:
The most notable examples of mass-independent fractionation in nature are found in the isotopes of
579:
54:
or bond strengths. Mass-independent fractionation processes are less common, occurring mainly in
857:
806:
560:
439:
388:
333:
226:
185:
75:
71:
730:"Leaf-scale quantification of the effect of photosynthetic gas exchange on ΔO of atmospheric CO
881:
849:
798:
710:
646:
552:
431:
380:
325:
189:
122:
94:
79:
527:
Gao, Y.; Marcus, R. (2001). "Strange and unconventional isotope effects in ozone formation".
841:
790:
753:
700:
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638:
599:
544:
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474:
423:
372:
317:
126:
31:
27:
50:) are caused by the effects of the mass of an isotope on atomic or molecular velocities,
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234:
165:
83:
59:
55:
875:
173:
137:
39:
861:
810:
443:
392:
667:"Global 3-D Simulations of the Triple Oxygen Isotope Signature ΔO in Atmospheric CO
337:
237:. This effect of terrestrial vegetation on the isotopic signature of atmospheric CO
141:
110:
98:
564:
427:
794:
619:"Isotopic exchange between carbon dioxide and ozone via O(D) in the stratosphere"
376:
728:
Adnew, G. A.; Pons, T. L.; Koren, G.; Peters, W.; Röckmann, T. (31 July 2020).
114:
87:
618:
129:
in the Solar nebula has been proposed to explain this isotope fractionation.
845:
758:
729:
548:
513:
478:
106:
51:
853:
802:
714:
650:
556:
435:
384:
329:
101:, show a pattern of low O/O and O/O relative to samples from the Earth and
457:
Mauersberger, K (1987). "Ozone isotope measurements in the stratosphere".
695:
321:
97:. The inclusions, thought to be among the oldest solid materials in the
256:
113:. However, recent measurement of the oxygen-isotope composition of the
86:, and Lawrence Grossman in 1973, in the oxygen isotopic composition of
35:
642:
603:
133:
241:
was simulated with a global model and confirmed experimentally.
102:
209:, resulting in a mass-independent distribution of isotopes.
132:
Mass-independent fractionation also has been observed in
617:Yung, Y. L.; DeMore, W. B.; Pinto, J. P. (1991).
140:and John Heidenreich in 1983, and later found in
213:Mass-independent carbon dioxide fractionation
197:* having a shorter lifetime than asymmetric O
8:
675:Journal of Geophysical Research: Atmospheres
221:). This anomalous isotopic composition in CO
205:distribution of energy throughout all the
193:but may be due to isotopically symmetric O
757:
704:
694:
66:Mass-independent fractionation in nature
292:
78:. The first example was discovered by
245:Mass-independent sulfur fractionation
7:
584:Physical Chemistry Chemical Physics
14:
117:, using samples collected by the
91:calcium–aluminium-rich inclusions
24:Non-mass-dependent fractionation
494:Journal of Geophysical Research
1:
428:10.1126/science.219.4588.1073
795:10.1126/science.289.5480.756
623:Geophysical Research Letters
459:Geophysical Research Letters
377:10.1126/science.182.4111.485
164:Theoretical calculations by
908:
48:equilibrium fractionations
271:Equilibrium fractionation
227:gross primary production
225:can be used to quantify
184:related to some unusual
60:spin-forbidden reactions
846:10.1126/science.1190298
759:10.5194/bg-17-3903-2020
549:10.1126/science.1058528
514:10.1029/JD095iD01p00901
479:10.1029/gl014i001p00080
259: million years ago
252:Great Oxygenation Event
201:*, thus not allowing a
170:kinetic isotope effects
578:Janssen, Carl (2001).
233:by vegetation through
44:kinetic fractionations
34:that acts to separate
276:Kinetic fractionation
26:(NMD), refers to any
20:isotope fractionation
696:10.1029/2019JD030387
281:Isotope geochemistry
172:(KIE) involving the
838:2010Sci...329..204H
787:2000Sci...289..756F
750:2020BGeo...17.3903A
687:2019JGRD..124.8808K
635:1991GeoRL..18...13Y
596:2001PCCP....3.4718J
541:2001Sci...293..259G
506:1990JGR....95..901M
471:1987GeoRL..14...80M
420:1983Sci...219.1073T
414:(4588): 1073–1075.
369:1973Sci...182..485C
322:10.1038/nature13068
314:2014Natur.506..307L
254:to some time after
42:(including typical
229:, the uptake of CO
207:degrees of freedom
119:Genesis spacecraft
832:(5988): 204–207.
781:(5480): 756–758.
744:(14): 3903–3922.
681:(15): 8808–8836.
643:10.1029/90GL02478
535:(5528): 259–263.
363:(4111): 485–488.
308:(7488): 307–315.
190:zero-point energy
123:Photodissociation
95:Allende meteorite
80:Robert N. Clayton
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17:Mass-independent
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84:Toshiko Mayeda
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40:fractionations
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174:excited state
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142:stratospheric
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138:Mark Thiemens
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56:photochemical
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52:diffusivities
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18:
887:Geochemistry
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629:(1): 13–16.
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590:(21): 4718.
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465:(1): 80–83.
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182:intermediate
163:
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111:Solar nebula
99:Solar System
69:
23:
16:
15:
500:(D1): 901.
203:statistical
109:) into the
876:Categories
287:References
115:Solar wind
88:refractory
156:* + M → O
107:supernova
882:Isotopes
862:45825809
854:20508089
811:12287304
803:10926533
715:31598450
651:11538378
557:11387441
444:26466899
436:17811750
393:22386977
385:17832468
330:24553238
265:See also
186:symmetry
36:isotopes
28:chemical
834:Bibcode
826:Science
783:Bibcode
775:Science
746:Bibcode
706:6774299
683:Bibcode
631:Bibcode
592:Bibcode
537:Bibcode
529:Science
502:Bibcode
467:Bibcode
416:Bibcode
408:Science
365:Bibcode
357:Science
338:4443958
310:Bibcode
93:in the
860:
852:
809:
801:
713:
703:
649:
565:867229
563:
555:
442:
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391:
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336:
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302:Nature
76:sulfur
72:oxygen
858:S2CID
807:S2CID
561:S2CID
440:S2CID
389:S2CID
334:S2CID
257:2,450
148:O + O
134:ozone
850:PMID
799:PMID
711:PMID
647:PMID
553:PMID
432:PMID
381:PMID
326:PMID
250:the
160:+ M*
103:Moon
74:and
58:and
46:and
22:or
842:doi
830:329
791:doi
779:289
754:doi
701:PMC
691:doi
679:124
639:doi
600:doi
545:doi
533:293
510:doi
475:doi
424:doi
412:219
373:doi
361:182
318:doi
306:506
152:→ O
125:of
30:or
878::
856:.
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840:.
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805:.
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789:.
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752:.
742:17
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180:*
82:,
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762:.
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748::
734:"
732:2
717:.
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685::
671:"
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588:3
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375::
367::
320::
312::
239:2
231:2
223:2
219:2
199:3
195:3
178:3
176:O
158:3
154:3
150:2
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