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Phosphorus and aluminum zoning in olivine: contrasting behavior of two nominally incompatible trace elements

  • Thomas SheaEmail author
  • Julia E. Hammer
  • Eric Hellebrand
  • Adrien J. Mourey
  • Fidel Costa
  • Emily C. First
  • Kendra J. Lynn
  • Oleg Melnik
Original Paper

Abstract

Phosphorus zoning in olivine is receiving considerable attention for its capacity to preserve key information about rates and mechanisms of crystal growth. Its concentration can vary significantly over sub-micron spatial scales and form intricate, snowflake-like patterns that are generally attributed to fast crystal growth. Ostensibly similar aluminum enrichment patterns have also been observed, suggesting comparable incorporation and partitioning behavior for both elements. We perform 1-atm crystallization experiments on a primitive Kīlauea basalt to examine the formation of P and Al zoning as a function of undercooling − ΔT (− ΔT = Tliquidus − Tcrystallization) during olivine growth. After 24 h spent at Tinitial = 1290 °C (10 °C above olivine stability), charges are rapidly cooled to final temperatures Tfinal = 1220–1270 °C, corresponding to undercoolings − ΔT  = 10–60 °C (with Tliquidus = 1280 °C). Compositional X-ray maps of experimental olivine reveal that only a small undercooling (≤ 25 °C) is required to produce the fine-scale enrichments in P and Al associated with skeletal growth. Concentration profiles indicate that despite qualitatively similar enrichment patterns in olivine, P and Al have contrasting apparent crystal/melt mass distribution coefficients of \(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) = 0.01‒1 and \(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) = 0.002‒0.006. Phosphorus can be enriched by a factor > 40-fold in the same crystal, whereas Al enrichment never exceed factors of 2. Glass in the vicinity of synthetic and natural olivine is usually enriched in Al, but, within analytical uncertainty, not in P. Thus, we find no direct evidence for a compositional boundary layer enriched in P that would suffice to produce P enrichments in natural and synthetic olivine. Numerical models combining growth and diffusion resolve the conditions at which Al-rich boundary layers produce the observed enrichment patterns in olivine. In contrast, the same models fail to reproduce the observed P enrichments, consistent with our observation that P-rich boundary layers are insignificant. If instead, P olivine/melt partitioning is made to depend on growth rate, models adequately reproduce our observations of 40-fold enrichment without boundary layer formation. We surmise that near-partitionless behavior (\(K_{\text{P}}^{{{\text{ol}}/{\text{melt}}}}\) close to 1) of P is related to the olivine lattice being perhaps less stiff in accommodating P during rapid crystallization, and/or to enhanced formation of vacancy defects during fast growth. Our results confirm that P is a robust marker of initial rapid growth, but reveal that the undercooling necessary to induce these enrichments is not particularly large. The near-ubiquitous process of magma mixing under volcanoes, for instance, is likely sufficient to induce low-to-moderate degrees of undercooling required for skeletal growth.

Keywords

Olivine Phosphorus Aluminum Growth kinetics Trace-element partitioning 

Notes

Acknowledgements

This work was funded by National Science Foundation Grant EAR-17225321 to TS and by a National Research Foundation Investigatorship Award (Grant number NRF-NRFI2017-06) to FC. The authors acknowledge Benoît Welsch, Francois Faure, Caroline Bouvet-de-Maisonneuve, and Mike Garcia, for the conversations that stimulated some of the ideas presented in this work. Reviews by Bruce Watson and Youxue Zhang helped improve the clarity of the manuscript. We also thank the editor Gordon Moore for his timely handling of the manuscript. This is SOEST contribution 10796.

Supplementary material

410_2019_1618_MOESM1_ESM.docx (2.4 mb)
Supplementary material 1 (DOCX 2474 kb)
410_2019_1618_MOESM2_ESM.xlsx (31.5 mb)
Supplementary material 2 (XLSX 32276 kb)

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Authors and Affiliations

  1. 1.Department of Earth Sciences, SOESTUniversity of Hawaii at MānoaHonoluluUSA
  2. 2.Department of Earth SciencesUtrecht UniversityUtrechtThe Netherlands
  3. 3.Earth Observatory of Singapore, Nanyang Technological UniversitySingaporeSingapore
  4. 4.Brown University, DEEPSProvidenceUSA
  5. 5.Department of Geological SciencesUniversity of DelawareNewarkUSA
  6. 6.Institute of MechanicsMoscow State UniversityMoscowRussia

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