The behaviour of zirconium, hafnium and rare earth elements during the crystallisation of halite and other salt minerals

Halite crystals from Messinian and Tortonian evaporites from Sicily and Spain and current precipitated halite crystals and the relative parent brines (active evaporation systems) were investigated in order to evaluate the Zr, Hf and Rare Earth Element (REE) behaviour. Halite crystallisation from evaporating brines fractionates Zr, Hf and REE through a two-step process. During the first step, dissolved complexes of studied elements are scavenged onto the surfaces of crystallising halite. During the second step, elements are co-precipitated into the crystal lattice as it grows. The first step mechanism is determined by the dissolved REE speciation. In saltworks where carbonate-REE complexes occur, surface complexation of REE onto halite crystals does not occur. On the contrary, surface REE-complexes onto halite crystals are forming in the Dead Sea water where aqueous REE speciation is dominated by chloride-complexes. Under the latter conditions, halite crystallises with cubic and cubic-octahedral composite habitus. Octahedral planes involve the formation of strong coulombic interactions, mainly with [Hf(H2O)3(OH)5]− rather than with [Zr(H2O)4(OH)4]0 complexes. As a consequence, newly formed halite in the Dead Sea shows strong subchondritic Zr/Hf ratios. Based on these indications, analyses carried out on salt minerals from Messinian and Tortonian evaporites in Sicily and Spain show that their overall REE content can be considered a discriminating parameter between authigenic minerals and diagenetic modified materials. However, features of shale-normalised REE patterns are driven by the mineralogical composition of evaporites rather than their authigenic or secondary nature. On the contrary, the Zr/Hf signature of salt minerals is influenced by their origin. Indeed, subchondritic Zr/Hf values are found in primary salt minerals, whereas larger Zr/Hf values are recognised in those diagenetically modified. Calculated distribution coefficients of Zr, Hf and REE are employed for modelling the REE distribution in halite equilibrated with the deep-sea brines from Typo, Medee and Thetis basins (Eastern Mediterranean). The obtained indications allow us to discriminate brines formed by dissolution of evaporites relative to those representing relics of fossil evaporated seawater.