An experimental assessment of the chalcophile behavior of F, Cl, Br and I: Implications for the fate of halogens during planetary accretion and the formation of magmatic ore deposits

Abstract

The elemental and isotopic abundances of halogens (F, Cl, Br, I) are used to constrain planetary volatile loss and volatile delivery processes, but their behavior during magmatic differentiation in general, and sulfide liquid segregation in particular, is currently not well constrained. To test whether sulfide liquid segregation could affect halogen behavior during magmatic processes, we performed high-pressure experiments to systematically quantify the sulfide liquid – silicate melt partition coefficients (Dsulliq-silmelt values, defined as the ratio between the wt.% concentration of the halogen in the sulfide liquid and silicate melt, respectively) of F, Cl, Br and I at a pressure of 1 GPa and temperatures of 1683–1883 K.Results show that dry-polishing target surfaces is crucial for obtaining representative halogen concentrations of sulfide liquids. The results also show that no appreciable amounts of F partition into sulfide liquids, whereas Cl, Br and I behave increasingly chalcophile with increasing atomic radius (i.e., DFsulliq-silmelt <DClsulliq-silmelt <DBrsulliq-silmelt < DIsulliq-silmelt), presumably as a result of an increasingly covalent nature of Fe-halogen bonds with increasing radius. This results in I behaving chalcophile (DIsulliq-silmelt > 1) in several experiments. In contrast to previous observations, DCl/Brsulliq-silmelt was found to be <1. The DCl,Br,Isulliq-silmelt predominantly vary with sulfide liquid melt composition, showing an increase with increasing O in the sulfide liquid, which itself is correlated with more oxidizing conditions (i.e., higher fO2) or silicate melt FeO contents. The DCl,Br,Isulliq-silmelt values remain constant and/or potentially decrease again at the highest O concentrations of the sulfide liquids in this study (∼2.5 wt.% O).Results indicate that the magnitude of halogen depletions in the terrestrial, martian and lunar mantle are not strongly affected by segregation of sulfide liquids during their accretion, given the expected low modal abundance of sulfide liquids and/or relatively low DCl,Br,Isulliq-silmelt values. Core formation remains the most important process in establishing iodine depletion in the terrestrial mantle, whereas volatility-related loss seems most likely for F, Cl, Br and I, in case of the martian mantle. However, segregation of sulfide liquids during accretion could have resulted in a relative increase of the offset between the mantle depletions of the lighter and heavier halogens. The experimental results confirm the previously proposed feasibility of sulfide liquids as reservoirs for halogens in magmatic sulfide ore environments. As proposed by Mungall and Brenan (2003), fractional crystallization of these sulfide liquids in the absence of a silicate melt can lead to the formation of halide melts or fluids, consistent with the association between halide minerals and magmatic sulfide ores in some localities.