Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

  • B. M. UrannEmail author
  • V. Le Roux
  • K. Hammond
  • H. R. Marschall
  • C.-T. A. Lee
  • B. D. Monteleone
Original Paper


The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.


Fluorine and chlorine content of mantle minerals Halogen partitioning Halogen budget of DMM Peridotite 



This research was supported by Grant NSF EAR-P&G 1524311 and DOEI Award 18563 to VLR. We thank two anonymous reviewers for their insights, which improved the manuscript. We also thank Erik Hauri for providing the Herasil glasses, Henry Dick for providing the MAR sample, and Nobumichi Shimizu for providing the Synthetic Forsterite grains. Urann was supported by the Stanley W. Watson Student Fellowship Fund based at WHOI.

Supplementary material

410_2017_1368_MOESM1_ESM.docx (8.3 mb)
Supplementary material 1 (DOCX 8449 kb)
410_2017_1368_MOESM2_ESM.xlsx (232 kb)
Supplementary material 2 (XLSX 232 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • B. M. Urann
    • 1
    Email author
  • V. Le Roux
    • 1
  • K. Hammond
    • 1
  • H. R. Marschall
    • 1
    • 2
  • C.-T. A. Lee
    • 3
  • B. D. Monteleone
    • 1
  1. 1.Woods Hole Oceanographic InstitutionWoods HoleUSA
  2. 2.Goethe Universität FrankfurtInstitut für GeowissenschaftenFrankfurt am MainGermany
  3. 3.Department of Earth ScienceRice UniversityHoustonUSA

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