Melting behavior of fluid inclusions in laboratory-grown halite crystals in the systems NaClH 2O, NaClKClH 2O, NaClMgCl 2H 2O, and NaClCaCl 2H 2O

Abstract

The chemical composition of aqueous fluid inclusions in crystals of halite can be accurately determined from observed melting behaviors of ice, hydrohalite, and sylvite. Some fluid inclusion melting behaviors observed in laboratory-grown halite crystals (systems NaClH 2O, NaClKClH 2O, NaClMgCl 2 H 2O, and NaClCaCl 2H 2O) differ from predicted stable equilibrium relations. In the NaClH 2O and NaClKClH 2O systems, observed first melt temperatures are up to 15°C below the equilibrium eutectic temperatures of −21.2° and −22.9°C, respectively. The final melting temperature of ice, in the presence of hydrohalite, and the final melting temperature of hydrohalite are reproducible and match predicted melting temperatures. The limit of detection of sylvite daughter crystals in the NaClKClH 2O system is approximately 5 wt% (≈ 1 molal) KCl. Final melting temperatures of sylvite match published equilibrium data to within 0.3°C. In the NaClKClH 2O system at halite saturation, m KCl can be determined from the final sylvite dissolution temperature or from the final melting temperature of hydrohalite. Fluid inclusions in the NaClMgCl 2H 2O and NaClCaCl 2H 2O systems that form stable salt hydrates (MgCl 2 · 12H 2O and CaCl 2 · 6H 2O) during freezing first melt within 3°C of predicted eutectic temperatures (−37° and −52°C). However, fluid inclusions with MgCl 2 or CaCl 2 may also start melting at temperatures as low as −80°C. Such low first melt temperatures indicate the presence of metastable salt hydrates (presumably MgCl 2 · 8H 2O, MgCl 2 · 6H 2O or CaCl 2 · 4H 2O). The formation of metastable phases during freezing of fluid inclusions can lead to misinterpretation of the chemical composition of fluid inclusions in natural samples. This is especially true for fluid inclusions with first melt temperatures below −37°C which may be erroneously interpreted as being rich in CaCl 2. The final melting of ice in the presence of hydrohalite may vary by more than 15°C in fluid inclusions of different size but identical bulk composition, and occurs at lower temperatures than predicted in fluid inclusions from the NaClMgCl 2H 2O and NaClCaCl 2H 2O systems. However, the final melting temperature of ice in inclusions which fail to nucleate hydrohalite, and the final melting temperature of hydrohalite are reproducible to within ±0.1 ° C and can be used to determine MgCl 2 and CaCl 2 molalities.