Halogens in Terrestrial and Cosmic Geochemical Systems: Abundances, Geochemical Behaviors, and Analytical Methods

  • Jacob J. HanleyEmail author
  • Kenneth T. Koga
Part of the Springer Geochemistry book series (SPRIGEO)


The aims of this review chapter are to (i) summarize the distribution of halogens in different fluid (surficial, formation and crystalline shield waters, metamorphic, magmatic-hydrothermal-geothermal) and solid (oceanic and continental crust, mantle and core) domains of the Earth, and various extra-terrestrial materials and bodies (meteorites, planets and moons, and the Sun); (ii) briefly discuss characteristic fractionation processes; and direct the reader to other chapters in this volume; (iii) provide an estimate of the total halogen abundance for the Earth and in its dominant reservoirs contributing to the Earth’s halogen endowment; and (iv) discuss some missing observations that could further improve our understanding of halogen abundances and geochemical systematics. Determination of the distribution of the non-radioactive halogen elements (fluorine, F; chlorine, Cl; bromine, Br; and iodine, I) in, and the geochemical processes controlling their mass transfer between, solid and fluid repositories on Earth and in extraterrestrial environments has seen increasing attention in recent years. In part, this has been enabled by the development of dedicated analytical methodologies (e.g., in situ beam methods, secondary ion mass-spectrometer [SIMS], laser ablation-inductively coupled mass-spectrometer [LA-ICPMS], combined noble gas-halogen methods) that can provide a low detection level, accurate and precise determinations of halogen concentrations, and their isotope systematics in complex matrices (e.g., fluid inclusions, glasses, and minerals). However, a key motivation for this method development stems from an increased awareness of the value in halogen characterization for studying specific processes in Earth’s hydrosphere, crust, mantle, and core (e.g., crustal and mantle metasomatism; ore metal transfer; magmatic differentiation and volatile exsolution; fluid reservoir contamination and fluid mixing; mineral-melt-fluid partitioning; and basinal fluid evolution) in which the chemical and isotopic properties of the halogens provide significant advantages over other element groups. These properties include their (i) differential (i.e., temperature- and melt composition-dependent) incompatibility during fluid-melt and mineral-melt partitioning; (ii) collectively highly mobile and volatile nature but with only a few processes capable of fractionating the halogens from one another or leading to significant halogen mass transfer from one repository to another (e.g., the formation of evaporites, fluid phase separation [immiscibility, boiling], crystallization and degassing of magmas, subduction devolatilization and metamorphism); and (iii) strong systematic covariance of Cl and Br, but commonly differential behaviors of F and I (in response to organic processes) in most fluids in the hydrosphere, sediments, crustal rocks in general, the mantle, and mantle-derived lavas. Mass balance calculations show that F is dominantly hosted by mantle and crust, while Cl and Br show nearly identical distribution patterns in which a total of the seawater, formation waters, and evaporites comprise more than half of the Earth’s halogen budget. Experimentally determined metal-silicate partition coefficients suggest that a significant quantity of I is potentially hosted by the Earth’s core.


Glossary of acronyms


Bulk silicate earth


Continental crust


Continuous flow


Depleted mantle


Electron microprobe analyzer


Epithermal neutron activation analysis


Gas chromatography


Ion chromatography


Inductively coupled mass spectrometry


International mineralogical association


Instrumental neutron activation analysis


Isotope ratio mass spectrometry


Laser ablation inductively coupled plasma isotope dilution mass spectrometry


Laser ablation inductively coupled mass spectrometry


Lower continental crust


Mid-ocean ridge basalt


Instrumental neutron activation


Noble gas mass spectrometry


Photon activation analysis


Prompt gamma-ray analysis


Proton induced X-ray emission


Radiochemical neutron activation analysis


Radiochemical photon activation analysis


Ion-selective electrode


Secondary ion mass spectrometry


Standard temperature and pressure


Thermal ionization mass spectrometry




Total reflection X-ray fluorescence analysis


Upper continental crust


Ultra high pressure/Ultra high temperature


X-ray fluorescence


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© Springer International Publishing AG 2018

Authors and Affiliations

  1. 1.Mineral Exploration Laboratory, Department of GeologySaint Mary’s UniversityHalifaxCanada
  2. 2.Laboratoire Magmas et VolcansUniversité Clermont AuvergneAUBIERE CedexFrance

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