Halogen Cycling in the Solid Earth

Abstract

Each of the halogens constrains a different aspect of volatile cycling in the solid Earth. F is moderately incompatible in the mantle and has a low mobility at Earth's surface, meaning that it is preferentially retained in the mantle and continental crust. In contrast, Cl, Br, and I are strongly incompatible and highly soluble. Chloride is the dominant anion in seawater and many geofluids and a major component of evaporite minerals. Br and I are essential for life and significantly incorporated into organic matter that accumulates in marine sediments. Surficial fluids circulated into continental and oceanic crust incorporate surface-derived halogens into alteration minerals. As a result, subducting slabs and arc lavas are weakly enriched in F and strongly enriched in Cl, Br, and I. Subduction has maintained mantle Cl and Br concentrations at relatively constant levels since Earth's early differentiation, but mantle I/Cl has decreased over time. ▪ Halogen abundances on the early Earth were affected by I partitioning into Earth's core and possible loss of hydrophilic Cl, Br, and I in an early formed ocean. ▪ Halogens are powerful tracers of subduction zone processes on the modern Earth, with Cl, Br, and I having a dominantly subducted origin in Earth's mantle. ▪ The deep subduction cycles of Cl, Br, and I are more similar to that of H2O than they are to F, but the geochemical cycle of each halogen differs in detail. ▪ Halogen abundance ratios and stable isotope ratios vary systematically in Earth's surface reservoirs, meaning that halogens are powerful tracers of geological fluids and melts. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 52 is May 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.