Abstract
Initial excess protactinium (231Pa) is a frequently suspected source of discordance in baddeleyite (ZrO2) geochronology, which limits accurate U/Pb dating, but such excesses have never been directly demonstrated. In this study, Pa incorporation in late Holocene baddeleyite from Somma-Vesuvius (Campanian Volcanic Province, central Italy) and Laacher See (East Eifel Volcanic Field, western Germany) was quantified by U-Th-Pa measurements using a large-geometry ion microprobe. Bad-deleyite crystals isolated from subvolcanic syenites have average U concentrations of ~200 ppm and are largely stoichiometric with minor abundances of Nb, Hf, Ti, and Fe up to a few weight percent. Measured (231Pa)/(235U) activity ratios are significantly above the secular equilibrium value of unity and range from 3.4(8) to 14.9(2.6) in Vesuvius baddeleyite and from 3.6(9) to 8.9(1.4) in Laacher See baddeleyite (values within parentheses represent uncertainties in the last significant figures reported as 1σ throughout the text). Crystallization ages of 5.12(56) ka (Vesuvius; MSWD = 0.96, n = 12) and 15.6(2.0) ka (Laacher See; MSWD = 0.91, n = 10) were obtained from (230Th)/(238U) disequilibria for the same crystals, which are close to the respective eruption ages. Applying a corresponding age correction indicates average initial (231Pa)/(235U)0 of 8.8(1.0) (Vesuvius) and 7.9(5) (Laacher See). For reasonable melt activities, model baddeleyite-melt distribution coefficients of DPa/DU = 5.8(2) and 4.1(2) are obtained for Vesuvius and Laacher See, respectively. Speciation-dependent (Pa4+ vs. Pa5+) partitioning coefficients (D values) from crystal lattice strain models for tetra- and pentavalent proxy ions significantly exceed DPa/DU inferred from direct analysis of 231Pa for Pa5+. This is consistent with predominantly reduced Pa4+ in the melt, for which D values similar to U4+ are expected. Contrary to common assumptions, baddeleyite-crystallizing melts from Vesuvius and Laacher See appear to be dominated by Pa4+ rather than Pa5+. An initial disequilibrium correction for baddeleyite geochronology using DPa/DU = 5 ± 1 is recommended for oxidized phonolitic melt compositions.
Acknowledgments
We are grateful to I. Fin and A. Thum (Heidelberg University) for the preparation of epoxy mounts and thin sections. The donation of samples by I. Punzo (Gruppo Mineralogico Geologico Napoletano) is much appreciated. A. Varychev and J. Schmitt (Heidelberg University) are thanked for the assistance with scanning electron microscopy and Raman spectroscopy, respectively. R. Avanzinelli (University of Florence) is thanked for providing helpful information about the U-Pa systematics of Somma-Vesuvius. Journal reviewers M. Ibañez-Mejia and M. Rioux are thanked for their comprehensive and insightful comments; manuscript handling by associate editor C. Hetherington is appreciated.
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Articles in the same Issue
- MSA Centennial Review Paper
- The incompressibility of atoms at high pressures
- Phase transitions in Ɛ-FeOOH at high pressure and ambient temperature
- Thermal state of the upper mantle and the origin of the Cambrian-Ordovician ophiolite pulse: Constraints from ultramafic dikes of the Hayachine-Miyamori ophiolite
- Quadrivalent praseodymium in planetary materials
- Quantitative microscale Fe redox imaging by multiple energy X-ray fluorescence mapping at the Fe K pre-edge peak
- Quantification of excess 231Pa in late Quaternary igneous baddeleyite
- Magma oxygen fugacity of mafic-ultramafic intrusions in convergent margin settings: Insights for the role of magma oxidation states on magmatic Ni-Cu sulfide mineralization
- Investigation of the crystal structure of a low water content hydrous olivine to 29.9 GPa: A high-pressure single-crystal X-ray diffraction study
- Ferric-ferrous iron ratios of experimental majoritic garnet and clinopyroxene as a function of oxygen fugacity
- The origin of Ti-oxide minerals below and within the eastern Athabasca Basin, Canada
- Partition behavior of platinum-group elements during the segregation of arsenide melts from sulfide magma
- Vapor-bubble growth in olivine-hosted melt inclusions
- New Mineral Names
Articles in the same Issue
- MSA Centennial Review Paper
- The incompressibility of atoms at high pressures
- Phase transitions in Ɛ-FeOOH at high pressure and ambient temperature
- Thermal state of the upper mantle and the origin of the Cambrian-Ordovician ophiolite pulse: Constraints from ultramafic dikes of the Hayachine-Miyamori ophiolite
- Quadrivalent praseodymium in planetary materials
- Quantitative microscale Fe redox imaging by multiple energy X-ray fluorescence mapping at the Fe K pre-edge peak
- Quantification of excess 231Pa in late Quaternary igneous baddeleyite
- Magma oxygen fugacity of mafic-ultramafic intrusions in convergent margin settings: Insights for the role of magma oxidation states on magmatic Ni-Cu sulfide mineralization
- Investigation of the crystal structure of a low water content hydrous olivine to 29.9 GPa: A high-pressure single-crystal X-ray diffraction study
- Ferric-ferrous iron ratios of experimental majoritic garnet and clinopyroxene as a function of oxygen fugacity
- The origin of Ti-oxide minerals below and within the eastern Athabasca Basin, Canada
- Partition behavior of platinum-group elements during the segregation of arsenide melts from sulfide magma
- Vapor-bubble growth in olivine-hosted melt inclusions
- New Mineral Names