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by admin | Jun 15, 2021 | mainpost, vol18 | 0 comments

A.V. Ivanov, F. Corfu, V.S. Kamenetsky, A.E. Marfin, N.V. Vladykin

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207Pb-excess in carbonatitic baddeleyite as the result of Pa scavenging from the melt

A.V. Ivanov1,

1Institute of the Earth’s Crust, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia

F. Corfu2,

2University of Oslo, Department of Geosciences and CEED, Oslo, Norway

V.S. Kamenetsky1,3,

1Institute of the Earth’s Crust, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia
3University of Tasmania, School of Natural Sciences, Hobart, Tasmania, Australia

A.E. Marfin1,4,

1Institute of the Earth’s Crust, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia
4Institute of Experimental Mineralogy, the Russian Academy of Sciences, Chernogolovka, Russia

N.V. Vladykin5

5A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia

Affiliations | Corresponding Author | Cite as | Funding information

A.V. Ivanov
Email: aivanov@crust.irk.ru

1Institute of the Earth’s Crust, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia
2University of Oslo, Department of Geosciences and CEED, Oslo, Norway
3University of Tasmania, School of Natural Sciences, Hobart, Tasmania, Australia
4Institute of Experimental Mineralogy, the Russian Academy of Sciences, Chernogolovka, Russia
5A.P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk, Russia

Ivanov, A.V., Corfu, F., Kamenetsky, V.S., Marfin, A.E., Vladykin, N.V. (2021) 207Pb-excess in carbonatitic baddeleyite as the result of Pa scavenging from the melt. Geochem. Persp. Let. 18, 11–15.

Grant 075-15-2019-1883 from the Ministry of Science and High Education of the Russian Federation.

Geochemical Perspectives Letters v18 | doi: 10.7185/geochemlet.2117
Received 22 January 2021 | Accepted 1 May 2021 | Published 15 June 2021

Copyright © 2021 The Authors

Published by the European Association of Geochemistry
under Creative Commons License CC BY 4.0

Keywords: U-Pb geochronology, baddeleyite, 231Pa-235U disequilibrium, Guli carbonatite, Siberian Traps, Large Igneous Province

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Abstract

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information

For the last two decades, the end of the voluminous phase of eruptions of the Siberian Traps large igneous province has been constrained by a U-Pb date of discordant baddeleyite collected from the Guli carbonatite intrusion with the assumption that the discordance resulted from unsupported 207Pb. In this study we have re-analysed baddeleyite from the same intrusion and found two types of discordance: (1) due to 207Pb-excess, and (2) radiogenic lead loss from high U mineral inclusions. The former implies that baddeleyite is an efficient scavenger of protactinium during crystallisation, leaving the magma depleted in this element. Together with a published high precision U-Pb date of 252.24 ± 0.08 Ma for the Arydzhansky Formation, our new date of 250.33 ± 0.38 Ma for the Guli carbonatite constrains the total duration of the voluminous eruptions of the Siberian Traps LIP at 1.91 ± 0.38 million years. The lower intercept of the (231Pa)/(235U) corrected discordance line yields a date of 129.2 ± 65.0 Ma, which points to the widespread Early Cretaceous rifting in East and Central Asia.

Figures

Figure 1 (a) Scheme of the Siberian Traps LIP (modified after Kogarko and Zartman, 2007). (b) Map of Guli volcanic-intrusive complex (Myshenkova et al., 2020). (c) Generalised stratigraphic relationships between volcanic and intrusive units at the Meimecha-Kotuy region (Ivanov et al., 2018b). High precision U-Pb dates are after Burgess and Bowring (2015) and this study (errors are 2σ analytical). Acronyms: ar – Arydzhansky Fm.; pr – Pravoboyarsky Fm.; kg/on – Kogotoksky Fm.; dl – Delkansky Fm.; mm – Meimechinsky Fm.; m – meimechite intrusions; c – carbonatite-bearing Guli complex; k and l – kimberlite and lamproite intrusions.

Figure 2 Concordia diagrams for Guli baddeleyite. (a) Green (new data), open symbols (Kamo et al., 2003). (b) Data corrected for 231Pa using decay constant of Jerome et al. (2020). The diagrams are plotted and ages calculated using IsoplotR (Vermeesch, 2018). Errors are 2σ analytical.

Figure 3 BSE image of a selected baddeleyite grain. Bdy – baddeleyite, Dol – dolomite, Cal – calcite, Ap – apatite, Nb-Ta-Th-U-oxide – unidentified phase (Table S-3).

Figure 1 Figure 2 Figure 3

View all figures and tables





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Introduction

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


Precise 40Ar/39Ar and U-Pb dating has provided strong evidence for the rapidity of the most voluminous phase of large igneous province (LIP) magmatism. Such events typically last just a few million years or even less than a million years, although low volume eruptions may post-date voluminous magmatic pulses by ten or more million years (e.g., Siberian Traps; Burgess and Bowring, 2015

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

; Ivanov et al., 2018a

Ivanov, A.V., Demonterova, E.I., Savatenkov, V.M., Perepelov, A.B., Ryabov, V.V., Shevko, A.Y. (2018a) Late Triassic (Carnian) lamproites from Noril’sk, polar Siberia: Evidence for melting of the recycled Archean crust and the question of lamproite source for some placer diamond deposits of the Siberian Craton. Lithos 296–299, 67–78.

). The Siberian Traps LIP (Fig. 1a) is the most voluminous among Phanerozoic continental LIPs (Ivanov, 2007

Ivanov, A.V. (2007) Evaluation of different models for the origin of the Siberian traps. In: Foulger, G.R., Jurdy, D.M. (Eds.) The origin of melting anomalies: plates, plumes and planetary processes. Special Paper 430, Geological Society of America, Boulder, Colorado, 669–692.

) and is considered as the cause of the most pronounced terrestrial Permian-Triassic mass extinction (Erwin et al., 2002

Erwin, D.H., Bowring, S.A., Yugan, J. (2002) End-permian mass extinctions: A review. In: Koeberl, C., MacLeod, K.G. (Eds.) Catastrophic events and mass extinctions: Impacts and beyond. Special Paper 356, Geological Society of America, Boulder, Colorado, 363–383.

). Thus, the timing and duration of the Siberian Traps LIP are of particular interest for the Earth Sciences.


Figure 1 (a) Scheme of the Siberian Traps LIP (modified after Kogarko and Zartman, 2007

Kogarko, L.N., Zartman, R.E. (2007) A Pb isotope investigation of the Guli massif, Maymecha-Kotuy alkaline-ultramafic complex, Siberian flood basalt province, Polar Siberia. Mineralogy and Petrology 89, 113–132.

). (b) Map of Guli volcanic-intrusive complex (Myshenkova et al., 2020

Myshenkova, M.S., Zaitsev, V.A., Thomson, S., Latyshev, A.V., Zakharov, V.S., Bagdasaryan, T.E., Veselovsky, R.V. (2020) Thermal history of the Guli Pluton (North of the Siberian Platform) according to apatite fission-track dating and computer modeling. Geodynamics & Tectonophysics 11, 75–87.

). (c) Generalised stratigraphic relationships between volcanic and intrusive units at the Meimecha-Kotuy region (Ivanov et al., 2018b

Ivanov, A.V., Mukasa, S.B., Kamenetsky, V.S., Ackerson, M., Demonterova, E.I., Pokrovsky, B.G., Vladykin, N.V., Kolesnichenko, M.V., Litasov, K.D., Zedgenizov, D.A. (2018b) Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism. Chemical Geology 483, 442–462.

). High precision U-Pb dates are after Burgess and Bowring (2015)

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

and this study (errors are 2σ analytical). Acronyms: ar – Arydzhansky Fm.; pr – Pravoboyarsky Fm.; kg/on – Kogotoksky Fm.; dl – Delkansky Fm.; mm – Meimechinsky Fm.; m – meimechite intrusions; c – carbonatite-bearing Guli complex; k and l – kimberlite and lamproite intrusions.
Full size image


Nearly twenty years ago, Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

bracketed the voluminous phase of magmatism of the Siberian Traps LIP between the U-Pb dates of 251.7 ± 0.4 Ma and 250.2 ± 0.3 Ma. These dates were obtained, respectively, from perovskite in melanephelinite in the lowermost, so called Arydzhansky Formation, and baddeleyite from carbonatite, in the uppermost, so called Guli volcanic-intrusive complex (Fig. 1b,c). A stratigraphically consistent U-Pb date of 251.1 ± 0.3 Ma for zircon from trachyrhyodacite in the intermediate Delkansky Formation was also reported (Kamo et al., 2003

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

). The analytical method was at that time state of the art isotope dilution thermal ionisation mass spectrometry (ID-TIMS). A later determination of the age of the Arydzhansky and Delkansky Formations with high precision U-Pb ID-TIMS geochronology by Burgess and Bowring (2015)

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

, gave slightly older perovskite dates of 252.20 ± 0.12 Ma and 252.27 ± 0.11 Ma for the Arydzhansky Formation, and slightly older zircon dates of 251.901 ± 0.061 Ma and 251.483 ± 0.088 Ma for the Delkansky Formation (here errors are 2σ internal analytical for the reason explained below). Subsequent geochronology of the Guli carbonatites by Malich et al. (2015)

Malich, K.N., Khiller, V.V., Badanina, I.Y., Belousova, E.A. (2015) Results of dating of thorianite and baddeleyite from carbonatites of the Guli massif, Russia. Doklady Earth Sciences 464, 1029–1032.

, using chemical microprobe dating of thorianite and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) dating of baddeleyite, obtained dates consistent with Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

. The methods of Malich et al. (2015)

Malich, K.N., Khiller, V.V., Badanina, I.Y., Belousova, E.A. (2015) Results of dating of thorianite and baddeleyite from carbonatites of the Guli massif, Russia. Doklady Earth Sciences 464, 1029–1032.

were, however, unable to yield precisions better than ±1 Ma, at best, which is comparable with the expected total duration of the voluminous phases of LIP magmatism.

The reason to re-assess the Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

data is because the U-Pb results for the dated baddeleyite grains were discordant and the age was calculated from the 206Pb/238U ratio with the assumption that the discordance resulted from unsupported 207Pb. In this study, we provide additional higher precision U-Pb ID-TIMS dating results on baddeleyite of the Guli carbonatite and discuss the relevance of the unsupported 207Pb explanation.

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Geological Setting

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


The Guli complex is the largest alkaline-ultramafic complex on a global scale. It has an exposed area of about 470 km2, but magnetic and gravimetric anomalies suggest an overall extension of 1500 km2 (Egorov, 1991

Egorov, L.S. (1991) Iyolite-carbonatite plutonism. Nedra, Moscow.

). The complex is composed of variable mafic alkaline and ultramafic rocks and carbonatites (Fig. 1b). Carbonatites form two stocks (named plugs in Kamo et al., 2003

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

), a southern and a northern one, each about 4.5 km2 in size (Fig. 1b). The studied sample (GU-70) is from the southern stock. It is composed of calcite, apatite and magnetite, subordinate phlogopite and accessory baddeleyite. Apatite and magnetite form strips of different orientation (Fig. S-1). Baddeleyite is found as well formed crystals of dark brown colour up to 0.5 mm in size.

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Methods

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


Baddeleyite grains and their mineral inclusions were imaged using an Alpha 300r confocal Raman spectrometer and scanning electron microscope (SEM) Hitachi SU-70 supplemented by an energy dispersive X-ray spectrometer of Oxford Instruments for chemical analysis. Apatite grains were analysed for 207Pb/206Pb and 238U/206Pb ratios by LA-ICPMS on an Agilent 7900 quadrupole ICP-MS coupled to a Coherent COMPex Pro 110 utilising an ArF excimer laser operating at the 193 nm wavelength and a pulse width of ∼20 ns. A RESOlution/ Laurin Technic S155 constant geometry ablation cell was used. Calibration of the 207Pb/206Pb ratio was done using analyses of the NIST610 reference glass analysed at the same conditions as the unknowns. Following the procedure of Thompson et al. (2016)

Thompson, J., Meffre, S., Maas, R., Kamenetsky, V., Kamenetsky, M., Goemann, K., Ehrig, K., Danyushevsky, L. (2016) Matrix effects in Pb/U measurements during LA-ICP-MS analysis of the mineral apatite. Journal of Analytical Atomic Spectrometry 31, 1206–1215.

, the OD306 apatite was used as a primary in house geochronology reference material for calibration of Pb/U ratios and to correct for instrument drift. The Durango, McClure Mountain and 401 apatites were employed as secondary geochronology reference materials (Table S-1).

The baddeleyite grains processed for U-Pb dating were dark brown fragments, opaque to marginally translucent. They were first air abraded (Krogh, 1982

Krogh, T.E. (1982) Improved accuracy of U-Pb zircon ages by the creation of more concordant systems using an air abrasion technique. Geochimica et Cosmochimica Acta 46, 637–649.

), then cleaned in warm HNO3 for 20 minutes and rinsed with H2O and acetone. The grains were weighed and transferred to a Krogh-type teflon bomb, with the addition of HF and HNO3 (12∶1) and a 202Pb-205Pb-235U spike. The spike composition has been harmonised with that of the EARTHTIME ET2535 spike (Corfu et al., 2016

Corfu, F., Svensen, H., Mazzini, A. (2016) Comment to paper: Evaluating the temporal link between the Karoo LIP and climatic-biologic events of the Toarcian Stage with high-precision U–Pb geochronology by Bryan Sell, Maria Ovtcharova, Jean Guex, Annachiara Bartolini, Fred Jourdan, Jorge E. Spangenberg, Jean-Claude Vicente, Urs Schaltegger in Earth and Planetary Science Letters 408 (2014) 48–56. Earth and Planetary Science Letters 434, 349–352.

) used by Burgess and Bowring (2015)

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

. Dissolution occurred at 195 °C for 5 days, followed by one night at 195 °C in 3N HCl, and chemical separation in ion exchange resin. The solution with Pb and U was loaded on outgassed Re filaments with silica gel and H3PO4 and measured with a MAT262 mass spectrometer. Blank correction was 2 pg Pb and 0.1 pg U, the remaining common Pb was corrected using a composition calculated with the Stacey and Kramers (1975)

Stacey, J.S., Kramers, J.D. (1975) Approximation of terrestrial lead isotope evolution by a two-stage model. Earth and Planetary Science Letters 26, 207–221.

model for the age of the sample (Table S-2). The ages were calculated using the decay constants of Jaffey et al. (1971)

Jaffey, A.H., Flynn, K.F., Glendenin, L.E., Bentley, W.C., Essling, A.M. (1971) Precision measurement of half-lives and specific activities of 235U and 238U. Physical Review C 4, 1889–1906.

and 238U/235U = 137.88, and were not corrected for 230Th disequilibrium.

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Results and Discussion

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


The results for the Guli baddeleyite are plotted in a concordia diagram together with those obtained previously by Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

(Fig. 2a). Three of the new analyses are clustered together close to previous analyses but the fourth is distinctly younger, indicating Pb loss. The reason for this behaviour is likely due to inclusions of another U-rich mineral as suggested by the higher level of U and initial Pb, and higher Th/U of this analysis (Table S-2). Such a mineral – Ta-Nb-Th-U-oxide was imaged by SEM (Fig. 3, Table S-3). Other common mineral inclusions are apatites (Figs. 3, S-2).


Figure 2 Concordia diagrams for Guli baddeleyite. (a) Green (new data), open symbols (Kamo et al., 2003

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

). (b) Data corrected for 231Pa using decay constant of Jerome et al. (2020)

Jerome, S., Bobin, C., Cassette, P., Dersch, R., Galea, R., Liu, H., Honig, A., Keightley, J., Kossert, K., Liang, J., Marouli, M., Michotte, C., Pomme, S., Rottger, S., Williams, R., Zhang, M. (2020) Half-life determination and comparison of activity standards of 231Pa. Applied Radiation and Isotopes 155, 108837.

. The diagrams are plotted and ages calculated using IsoplotR (Vermeesch, 2018

Vermeesch, P. (2018) IsoplotR: A free and open toolbox for geochronology. Geoscience Frontiers 9, 1479–1493.

). Errors are 2σ analytical.
Full size image



Figure 3 BSE image of a selected baddeleyite grain. Bdy – baddeleyite, Dol – dolomite, Cal – calcite, Ap – apatite, Nb-Ta-Th-U-oxide – unidentified phase (Table S-3).
Full size image


A discordia line can be drawn through the new, more precise data (Fig. 2a). It yields an upper intercept with concordia of 279.3 ± 11.0 Ma. However, this cannot reflect the true age of Guli carbonatite. It is too old relative to the date of thorianite (250.1 ± 2.9 Ma; Malich et al., 2015

Malich, K.N., Khiller, V.V., Badanina, I.Y., Belousova, E.A. (2015) Results of dating of thorianite and baddeleyite from carbonatites of the Guli massif, Russia. Doklady Earth Sciences 464, 1029–1032.

) and to the host volcanic rocks (Fig. 1c).

All U-Pb data points are located to the right of concordia. This cannot be due to an incorrect correction of common lead because the ratio of radiogenic to common Pb is very high and, in addition, the initial 207Pb/206Pb in apatite, the most probable source of common lead in baddeleyite, is equal within uncertainty to that obtained with the Stacey and Kramers (1975)

Stacey, J.S., Kramers, J.D. (1975) Approximation of terrestrial lead isotope evolution by a two-stage model. Earth and Planetary Science Letters 26, 207–221.

model (Fig. S-3). Thus, discordance of baddeleyite is real.

To explain such discordant baddeleyite data, Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

assumed unsupported 207Pb, which accumulated from an excess of 231Pa inherited by baddeleyite during its crystallisation from carbonatite magma. The 231Pa-235U disequilibrium required for the explanation of the discordant Guli baddeleyite data can be calculated as follows: the upper (231Pa)/(235U) value is constrained by the reasoning that the analyses should not be reversely discordant and the positive discordance cannot be such as to make the upper intercept of the discordia line older than the age of the Delkansky Formation (Fig. 1c). Using these constraints for the new, more precise data, (231Pa)/(235U) falls in the range between ∼39.6 and 35.6. Assuming no loss of radiogenic lead for the two oldest grains and (231Pa)/(235U) = 38.8 (the value with the lowest MSWD) we obtain a concordia age of 250.33 ± 0.38 Ma (Fig. 2b). (Note: this age stays practically the same for a wide range of (231Pa)/(235U) values). Considering that the Nd isotope composition of Guli carbonatites (ɛNdT = +4.9; Kogarko and Zartman, 2007

Kogarko, L.N., Zartman, R.E. (2007) A Pb isotope investigation of the Guli massif, Maymecha-Kotuy alkaline-ultramafic complex, Siberian flood basalt province, Polar Siberia. Mineralogy and Petrology 89, 113–132.

) agrees only with that of meimechites (+4.5 to + 5.7; Ivanov et al., 2018b

Ivanov, A.V., Mukasa, S.B., Kamenetsky, V.S., Ackerson, M., Demonterova, E.I., Pokrovsky, B.G., Vladykin, N.V., Kolesnichenko, M.V., Litasov, K.D., Zedgenizov, D.A. (2018b) Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism. Chemical Geology 483, 442–462.

), the age for the Guli baddeleyite may characterise the timing of emplacement of voluminous meimechite lavas.

Drawing a discordia line through the (231Pa)/(235U) corrected data yields the lower intercept age of 129.2 ± 65.0 Ma. This fits well with the timing of the Early Cretaceous large scale rifting event that occurred in the vast region of Central and East Asia (Wang et al., 2011

Wang, T., Zheng, Y.D., Zhang, J.J., Zeng, L.S., Donskaya, T., Guo, L., Li, J.B. (2011) Pattern and kinematic polarity of Late Mesozoic extension in continental NE Asia: Perspectives from metamorphic core complexes. Tectonics 30, TC6007.

).

The 231Pa-235U disequilibrium required for the explanation of the discordant Guli baddeleyite data by unsupported 207Pb is not the largest among values suggested in other studies. For example, a study of Kovdor carbonatite-bearing massif suggests that (231Pa)/(235U) up to 100 can explain the discordance of baddeleyite data from this massif by unsupported 207Pb (Amelin and Zaitsev, 2002

Amelin, Y., Zaitsev, A.N. (2002) Precise geochronology of phoscorites and carbonatites: The critical role of U-series disequilibrium in age interpretations. Geochimica et Cosmochimica Acta 66, 2399–2419.

). To our knowledge, only one study exists which analysed (231Pa)/(235U) directly in very young baddeleyite (Sun et al., 2020

Sun, Y., Schmitt, A.K., Pappalardo, L., Russo, M. (2020) Quantification of excess 231Pa in late Quaternary igneous baddeleyite. American Mineralogist 105, 1830–1840.

). In that study, baddeleyite from Holocene syenite in the Vesuvius and Laacher See volcanoes requires (231Pa)/(235U) between 3 and 15. The most pronounced (231Pa)/(235U) suggested disequilibrium reaches 1,100 in zircon of Oligocene pegmatite in Pakistan’s Himalaya (Anczkiewicz et al., 2001

Anczkiewicz, R., Oberli, F., Burg, J.P., Villa, I.M., Gunther, D., Meier, M. (2001) Timing of normal faulting along the Indus Suture in Pakistan Himalaya and a case of major 231Pa/235U initial disequilibrium in zircon. Earth and Planetary Science Letters 191, 101–114.

).

The largest negative 231Pa-235U disequilibrium for igneous suites was recorded in the Oldoinyo Lengai volcano with (231Pa)/(235U) of ∼0.2 in carbonatite melts (Peate and Hawkesworth, 2005

Peate, D.W., Hawkesworth, C.J. (2005) U series disequilibria: Insights into mantle melting and the timescales of magma differentiation. Reviews in Geophysics 43, RG1003.

). In order to explain the positive and negative disequilibrium (231Pa)/(235U) values in baddeleyite and carbonatite melt, respectively, we need to accept that protactinium, compared to uranium, goes preferentially to baddeleyite, which is a typical early crystallising phase of carbonatites. No baddeleyite has ever been found in Oldoinyo Lengai natrocarbonatites, suggesting it could accumulate at the base of the magma chamber leaving the erupting carbonatite with low (231Pa)/(235U). Accumulation of baddeleyite agrees with the very low Zr concentrations in Oldoinyo Lengai natrocarbonatites (<32 μg/g) relative to associated silicate alkaline melts (>317 μg/g) (Simonetti et al., 1997

Simonetti, A., Bell, K., Shrady, C. (1997) Trace- and rare-earth-element geochemistry of the June 1993 natrocarbonatite lavas, Oldoinyo Lengai (Tanzania): Implications for the origin of carbonatite magmas. Journal of Volcanology and Geothermal Research 75, 89–106.

; Jung et al., 2019

Jung, S.G., Choi, S.H., Ji, K.H., Ryu, J.-S., Lee, D.-C. (2019) Geochemistry of volcanic rocks from Oldoinyo Lengai, Tanzania: Implications for mantle source lithology. Lithos 350, 105223.

).

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Conclusions

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


Our new data concur with the idea that discordance of carbonatitic baddeleyite results from the presence of unsupported 207Pb and agree with a previously published date for the Guli carbonatite by Kamo et al. (2003)

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

. A (231Pa)/(235U) of 39.6–35.6 is required to explain the discordant baddeleyite data. The high 207Pb excess in baddeleyite implies that much protactinium is scavenged by crystallising baddeleyite, leaving the magma depleted in this element, as shown in carbonatitic magma such as at Oldoinyo Lengai. The total duration of the voluminous phase of the Siberian Traps LIP magmatism can be estimated from the period between the mean of two dates reported by Burgess and Bowring (2015)

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

of 252.24 ± 0.08 Ma for the Arydzhansky formation and the preferred date of 250.33 ± 0.38 Ma for Guli carbonatite (errors are analytical because the two data sets are obtained with mutually homogenised isotopic tracers). This duration amounts to 1.91 ± 0.38 million years.

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Acknowledgements

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


This is the contribution to the grant 075-15-2019-1883. We thank Axel Schmitt and anonymous reviewer for useful suggestions and Horst Marschall for editorial handling.

Editor: Horst R. Marschall

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References

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information

Amelin, Y., Zaitsev, A.N. (2002) Precise geochronology of phoscorites and carbonatites: The critical role of U-series disequilibrium in age interpretations. Geochimica et Cosmochimica Acta 66, 2399–2419.
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For example, a study of Kovdor carbonatite-bearing massif suggests that (231Pa)/(235U) up to 100 can explain the discordance of baddeleyite data from this massif by unsupported 207Pb (Amelin and Zaitsev, 2002).
View in article


Anczkiewicz, R., Oberli, F., Burg, J.P., Villa, I.M., Gunther, D., Meier, M. (2001) Timing of normal faulting along the Indus Suture in Pakistan Himalaya and a case of major 231Pa/235U initial disequilibrium in zircon. Earth and Planetary Science Letters 191, 101–114.
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The most pronounced (231Pa)/(235U) suggested disequilibrium reaches 1,100 in zircon of Oligocene pegmatite in Pakistan’s Himalaya (Anczkiewicz et al., 2001).
View in article


Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.
Show in context

Such events typically last just a few million years or even less than a million years, although low volume eruptions may post-date voluminous magmatic pulses by ten or more million years (e.g., Siberian Traps; Burgess and Bowring, 2015; Ivanov et al., 2018a).
View in article
High precision U-Pb dates are after Burgess and Bowring (2015) and this study (errors are 2σ analytical).
View in article
A later determination of the age of the Arydzhansky and Delkansky Formations with high precision U-Pb ID-TIMS geochronology by Burgess and Bowring (2015), gave slightly older perovskite dates of 252.20 ± 0.12 Ma and 252.27 ± 0.11 Ma for the Arydzhansky Formation, and slightly older zircon dates of 251.901 ± 0.061 Ma and 251.483 ± 0.088 Ma for the Delkansky Formation (here errors are 2σ internal analytical for the reason explained below).
View in article
The spike composition has been harmonised with that of the EARTHTIME ET2535 spike (Corfu et al., 2016) used by Burgess and Bowring (2015).
View in article
The total duration of the voluminous phase of the Siberian Traps LIP magmatism can be estimated from the period between the mean of two dates reported by Burgess and Bowring (2015) of 252.24 ± 0.08 Ma for the Arydzhansky formation and the preferred date of 250.33 ± 0.38 Ma for Guli carbonatite (errors are analytical because the two data sets are obtained with mutually homogenised isotopic tracers).
View in article


Corfu, F., Svensen, H., Mazzini, A. (2016) Comment to paper: Evaluating the temporal link between the Karoo LIP and climatic-biologic events of the Toarcian Stage with high-precision U–Pb geochronology by Bryan Sell, Maria Ovtcharova, Jean Guex, Annachiara Bartolini, Fred Jourdan, Jorge E. Spangenberg, Jean-Claude Vicente, Urs Schaltegger in Earth and Planetary Science Letters 408 (2014) 48–56. Earth and Planetary Science Letters 434, 349–352.
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The spike composition has been harmonised with that of the EARTHTIME ET2535 spike (Corfu et al., 2016) used by Burgess and Bowring (2015).
View in article


Egorov, L.S. (1991) Iyolite-carbonatite plutonism. Nedra, Moscow.
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It has an exposed area of about 470 km2, but magnetic and gravimetric anomalies suggest an overall extension of 1500 km2 (Egorov, 1991).
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Erwin, D.H., Bowring, S.A., Yugan, J. (2002) End-permian mass extinctions: A review. In: Koeberl, C., MacLeod, K.G. (Eds.) Catastrophic events and mass extinctions: Impacts and beyond. Special Paper 356, Geological Society of America, Boulder, Colorado, 363–383.
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The Siberian Traps LIP (Fig. 1a) is the most voluminous among Phanerozoic continental LIPs (Ivanov, 2007) and is considered as the cause of the most pronounced terrestrial Permian-Triassic mass extinction (Erwin et al., 2002).
View in article


Ivanov, A.V. (2007) Evaluation of different models for the origin of the Siberian traps. In: Foulger, G.R., Jurdy, D.M. (Eds.) The origin of melting anomalies: plates, plumes and planetary processes. Special Paper 430, Geological Society of America, Boulder, Colorado, 669–692.
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The Siberian Traps LIP (Fig. 1a) is the most voluminous among Phanerozoic continental LIPs (Ivanov, 2007) and is considered as the cause of the most pronounced terrestrial Permian-Triassic mass extinction (Erwin et al., 2002).
View in article


Ivanov, A.V., Demonterova, E.I., Savatenkov, V.M., Perepelov, A.B., Ryabov, V.V., Shevko, A.Y. (2018a) Late Triassic (Carnian) lamproites from Noril’sk, polar Siberia: Evidence for melting of the recycled Archean crust and the question of lamproite source for some placer diamond deposits of the Siberian Craton. Lithos 296–299, 67–78.
Show in context

Such events typically last just a few million years or even less than a million years, although low volume eruptions may post-date voluminous magmatic pulses by ten or more million years (e.g., Siberian Traps; Burgess and Bowring, 2015; Ivanov et al., 2018a).
View in article


Ivanov, A.V., Mukasa, S.B., Kamenetsky, V.S., Ackerson, M., Demonterova, E.I., Pokrovsky, B.G., Vladykin, N.V., Kolesnichenko, M.V., Litasov, K.D., Zedgenizov, D.A. (2018b) Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism. Chemical Geology 483, 442–462.
Show in context

(c) Generalised stratigraphic relationships between volcanic and intrusive units at the Meimecha-Kotuy region (Ivanov et al., 2018b).
View in article
Considering that the Nd isotope composition of Guli carbonatites (ɛNdT = +4.9; Kogarko and Zartman, 2007) agrees only with that of meimechites (+4.5 to + 5.7; Ivanov et al., 2018b), the age for the Guli baddeleyite may characterise the timing of emplacement of voluminous meimechite lavas.
View in article


Jaffey, A.H., Flynn, K.F., Glendenin, L.E., Bentley, W.C., Essling, A.M. (1971) Precision measurement of half-lives and specific activities of 235U and 238U. Physical Review C 4, 1889–1906.
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The ages were calculated using the decay constants of Jaffey et al. (1971) and 238U/235U = 137.88, and were not corrected for 230Th disequilibrium.
View in article


Jerome, S., Bobin, C., Cassette, P., Dersch, R., Galea, R., Liu, H., Honig, A., Keightley, J., Kossert, K., Liang, J., Marouli, M., Michotte, C., Pomme, S., Rottger, S., Williams, R., Zhang, M. (2020) Half-life determination and comparison of activity standards of 231Pa. Applied Radiation and Isotopes 155, 108837.
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(b) Data corrected for 231Pa using decay constant of Jerome et al. (2020).
View in article


Jung, S.G., Choi, S.H., Ji, K.H., Ryu, J.-S., Lee, D.-C. (2019) Geochemistry of volcanic rocks from Oldoinyo Lengai, Tanzania: Implications for mantle source lithology. Lithos 350, 105223.
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Accumulation of baddeleyite agrees with the very low Zr concentrations in Oldoinyo Lengai natrocarbonatites (<32 μg/g) relative to associated silicate alkaline melts (>317 μg/g) (Simonetti et al., 1997; Jung et al., 2019).
View in article


Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.
Show in context

Nearly twenty years ago, Kamo et al. (2003) bracketed the voluminous phase of magmatism of the Siberian Traps LIP between the U-Pb dates of 251.7 ± 0.4 Ma and 250.2 ± 0.3 Ma.
View in article
A stratigraphically consistent U-Pb date of 251.1 ± 0.3 Ma for zircon from trachyrhyodacite in the intermediate Delkansky Formation was also reported (Kamo et al., 2003).
View in article
Subsequent geochronology of the Guli carbonatites by Malich et al. (2015), using chemical microprobe dating of thorianite and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) dating of baddeleyite, obtained dates consistent with Kamo et al. (2003).
View in article
The reason to re-assess the Kamo et al. (2003) data is because the U-Pb results for the dated baddeleyite grains were discordant and the age was calculated from the 206Pb/238U ratio with the assumption that the discordance resulted from unsupported 207Pb.
View in article
Carbonatites form two stocks (named plugs in Kamo et al., 2003), a southern and a northern one, each about 4.5 km2 in size (Fig. 1b).
View in article
The results for the Guli baddeleyite are plotted in a concordia diagram together with those obtained previously by Kamo et al. (2003) (Fig. 2a).
View in article
(a) Green (new data), open symbols (Kamo et al., 2003).
View in article
To explain such discordant baddeleyite data, Kamo et al. (2003) assumed unsupported 207Pb, which accumulated from an excess of 231Pa inherited by baddeleyite during its crystallisation from carbonatite magma.
View in article
Our new data concur with the idea that discordance of carbonatitic baddeleyite results from the presence of unsupported 207Pb and agree with a previously published date for the Guli carbonatite by Kamo et al. (2003).
View in article


Kogarko, L.N., Zartman, R.E. (2007) A Pb isotope investigation of the Guli massif, Maymecha-Kotuy alkaline-ultramafic complex, Siberian flood basalt province, Polar Siberia. Mineralogy and Petrology 89, 113–132.
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(a) Scheme of the Siberian Traps LIP (modified after Kogarko and Zartman, 2007).
View in article
Considering that the Nd isotope composition of Guli carbonatites (ɛNdT = +4.9; Kogarko and Zartman, 2007) agrees only with that of meimechites (+4.5 to + 5.7; Ivanov et al., 2018b), the age for the Guli baddeleyite may characterise the timing of emplacement of voluminous meimechite lavas.
View in article


Krogh, T.E. (1982) Improved accuracy of U-Pb zircon ages by the creation of more concordant systems using an air abrasion technique. Geochimica et Cosmochimica Acta 46, 637–649.
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They were first air abraded (Krogh, 1982), then cleaned in warm HNO3 for 20 minutes and rinsed with H2O and acetone.
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Malich, K.N., Khiller, V.V., Badanina, I.Y., Belousova, E.A. (2015) Results of dating of thorianite and baddeleyite from carbonatites of the Guli massif, Russia. Doklady Earth Sciences 464, 1029–1032.
Show in context

Subsequent geochronology of the Guli carbonatites by Malich et al. (2015), using chemical microprobe dating of thorianite and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) dating of baddeleyite, obtained dates consistent with Kamo et al. (2003).
View in article
The methods of Malich et al. (2015) were, however, unable to yield precisions better than ±1 Ma, at best, which is comparable with the expected total duration of the voluminous phases of LIP magmatism.
View in article
It is too old relative to the date of thorianite (250.1 ± 2.9 Ma; Malich et al., 2015) and to the host volcanic rocks (Fig. 1c).
View in article


Myshenkova, M.S., Zaitsev, V.A., Thomson, S., Latyshev, A.V., Zakharov, V.S., Bagdasaryan, T.E., Veselovsky, R.V. (2020) Thermal history of the Guli Pluton (North of the Siberian Platform) according to apatite fission-track dating and computer modeling. Geodynamics & Tectonophysics 11, 75–87.
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(b) Map of Guli volcanic-intrusive complex (Myshenkova et al., 2020).
View in article


Peate, D.W., Hawkesworth, C.J. (2005) U series disequilibria: Insights into mantle melting and the timescales of magma differentiation. Reviews in Geophysics 43, RG1003.
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The largest negative 231Pa-235U disequilibrium for igneous suites was recorded in the Oldoinyo Lengai volcano with (231Pa)/(235U) of ∼0.2 in carbonatite melts (Peate and Hawkesworth, 2005).
View in article


Simonetti, A., Bell, K., Shrady, C. (1997) Trace- and rare-earth-element geochemistry of the June 1993 natrocarbonatite lavas, Oldoinyo Lengai (Tanzania): Implications for the origin of carbonatite magmas. Journal of Volcanology and Geothermal Research 75, 89–106.
Show in context

Accumulation of baddeleyite agrees with the very low Zr concentrations in Oldoinyo Lengai natrocarbonatites (<32 μg/g) relative to associated silicate alkaline melts (>317 μg/g) (Simonetti et al., 1997; Jung et al., 2019).
View in article


Stacey, J.S., Kramers, J.D. (1975) Approximation of terrestrial lead isotope evolution by a two-stage model. Earth and Planetary Science Letters 26, 207–221.
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Blank correction was 2 pg Pb and 0.1 pg U, the remaining common Pb was corrected using a composition calculated with the Stacey and Kramers (1975) model for the age of the sample (Table S-2).
View in article
This cannot be due to an incorrect correction of common lead because the ratio of radiogenic to common Pb is very high and, in addition, the initial 207Pb/206Pb in apatite, the most probable source of common lead in baddeleyite, is equal within uncertainty to that obtained with the Stacey and Kramers (1975) model (Fig. S-3).
View in article


Sun, Y., Schmitt, A.K., Pappalardo, L., Russo, M. (2020) Quantification of excess 231Pa in late Quaternary igneous baddeleyite. American Mineralogist 105, 1830–1840.
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To our knowledge, only one study exists which analysed (231Pa)/(235U) directly in very young baddeleyite (Sun et al., 2020).
View in article


Thompson, J., Meffre, S., Maas, R., Kamenetsky, V., Kamenetsky, M., Goemann, K., Ehrig, K., Danyushevsky, L. (2016) Matrix effects in Pb/U measurements during LA-ICP-MS analysis of the mineral apatite. Journal of Analytical Atomic Spectrometry 31, 1206–1215.
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Following the procedure of Thompson et al. (2016), the OD306 apatite was used as a primary in house geochronology reference material for calibration of Pb/U ratios and to correct for instrument drift.
View in article


Vermeesch, P. (2018) IsoplotR: A free and open toolbox for geochronology. Geoscience Frontiers 9, 1479–1493.
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The diagrams are plotted and ages calculated using IsoplotR (Vermeesch, 2018).
View in article


Wang, T., Zheng, Y.D., Zhang, J.J., Zeng, L.S., Donskaya, T., Guo, L., Li, J.B. (2011) Pattern and kinematic polarity of Late Mesozoic extension in continental NE Asia: Perspectives from metamorphic core complexes. Tectonics 30, TC6007.
Show in context

This fits well with the timing of the Early Cretaceous large scale rifting event that occurred in the vast region of Central and East Asia (Wang et al., 2011).
View in article



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Supplementary Information

Abstract | Introduction | Geological Setting | Methods | Results and Discussion | Conclusions | Acknowledgements | References | Supplementary Information


The Supplementary Information includes:
  • Supplementary Tables S-1 to S-3
  • Supplementary Figures S-1 to S-3
  • Supplementary Information References


Download Table S-1 (Excel).

Download the Supplementary Information (PDF).
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Figures



Figure 1 (a) Scheme of the Siberian Traps LIP (modified after Kogarko and Zartman, 2007

Kogarko, L.N., Zartman, R.E. (2007) A Pb isotope investigation of the Guli massif, Maymecha-Kotuy alkaline-ultramafic complex, Siberian flood basalt province, Polar Siberia. Mineralogy and Petrology 89, 113–132.

). (b) Map of Guli volcanic-intrusive complex (Myshenkova et al., 2020

Myshenkova, M.S., Zaitsev, V.A., Thomson, S., Latyshev, A.V., Zakharov, V.S., Bagdasaryan, T.E., Veselovsky, R.V. (2020) Thermal history of the Guli Pluton (North of the Siberian Platform) according to apatite fission-track dating and computer modeling. Geodynamics & Tectonophysics 11, 75–87.

). (c) Generalised stratigraphic relationships between volcanic and intrusive units at the Meimecha-Kotuy region (Ivanov et al., 2018b

Ivanov, A.V., Mukasa, S.B., Kamenetsky, V.S., Ackerson, M., Demonterova, E.I., Pokrovsky, B.G., Vladykin, N.V., Kolesnichenko, M.V., Litasov, K.D., Zedgenizov, D.A. (2018b) Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism. Chemical Geology 483, 442–462.

). High precision U-Pb dates are after Burgess and Bowring (2015)

Burgess, S.D., Bowring, S.A. (2015) High-precision geochronology confirms voluminous magmatism before, during, and after Earth’s most severe extinction. Science Advances 1, e1500470.

and this study (errors are 2σ analytical). Acronyms: ar – Arydzhansky Fm.; pr – Pravoboyarsky Fm.; kg/on – Kogotoksky Fm.; dl – Delkansky Fm.; mm – Meimechinsky Fm.; m – meimechite intrusions; c – carbonatite-bearing Guli complex; k and l – kimberlite and lamproite intrusions.
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Figure 2 Concordia diagrams for Guli baddeleyite. (a) Green (new data), open symbols (Kamo et al., 2003

Kamo, S.L., Czamanske, G.K., Amelin, Y., Fedorenko, V.A., Davis, D.W., Trofimov, V.R. (2003) Rapid eruption of Siberian flood-volcanic rocks and evidence for coincidence with the Permian-Triassic boundary and mass extinction at 251 Ma. Earth and Planetary Science Letters 214, 75–91.

). (b) Data corrected for 231Pa using decay constant of Jerome et al. (2020)

Jerome, S., Bobin, C., Cassette, P., Dersch, R., Galea, R., Liu, H., Honig, A., Keightley, J., Kossert, K., Liang, J., Marouli, M., Michotte, C., Pomme, S., Rottger, S., Williams, R., Zhang, M. (2020) Half-life determination and comparison of activity standards of 231Pa. Applied Radiation and Isotopes 155, 108837.

. The diagrams are plotted and ages calculated using IsoplotR (Vermeesch, 2018

Vermeesch, P. (2018) IsoplotR: A free and open toolbox for geochronology. Geoscience Frontiers 9, 1479–1493.

). Errors are 2σ analytical.
Back to article


Figure 3 BSE image of a selected baddeleyite grain. Bdy – baddeleyite, Dol – dolomite, Cal – calcite, Ap – apatite, Nb-Ta-Th-U-oxide – unidentified phase (Table S-3).
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