The exsolution of magmatic hydrosaline chloride liquids

Hydrosaline liquid represents the most Cl-enriched volatile phase that occurs in magmas, and the exsolution of this phase has important consequences for processes of hydrothermal mineralization and for volcanic emission of Cl to the atmosphere. To understand the exsolution of hydrosaline liquids in felsic to mafic magmas, the volatile abundances and (Cl/H2O) ratios of more than 1000 silicate melt inclusions (MI) have been compared with predicted and experimentally determined solubilities of Cl and H2O and associated (Cl/H2O) ratios of silicate melts that were saturated in hydrosaline chloride liquid with or without aqueous vapor in hydrothermal experiments. This approach identifies the minimum volatile contents and the values of (Cl/H2O) at which a hydrosaline chloride liquid exsolves from any CO2- or SO2-poor silicate melt. Chlorine solubility is a strong function of melt composition, so it follows that Cl solubility in magmas varies with melt evolution. Computations show that the (Cl/H2O) ratio of residual melt in evolving silicate magmas either remains constant or increases to a small extent with fractional crystallization. Consequently, the initial (Cl/H2O) in melt that is established early during partial melting has important consequences for the exsolution of vapor, vapor plus hydrosaline liquid, or hydrosaline liquid later during the final stages of melt ascent, emplacement, and crystallization or eruption. It is demonstrated that the melt (Cl/H2O) controls the type of volatile phase that exsolves, whereas the volatile abundances in melt control the relative timing of volatile phase exsolution (i.e., the time of earliest volatile exsolution relative to the rate of magma ascent and crystallization history). Comparing melt inclusion compositions with experimentally determined (Cl/H2O) ratios and corresponding volatile solubilities of hydrosaline liquid-saturated silicate melts suggests that some fractions of the eruptive, calc-alkaline dacitic magmas of the Bonnin and Izu arcs should have saturated in and exsolved hydrosaline liquid at pressures of 2000 bars. Application of these same melt inclusion data to the predicted volatile solubilities of Cu-, Au-, and Mo-mineralized, calc-alkaline porphyritic magmas suggests that the chemical evolution of dioritic magmas to more-evolved quartz monzonite compositions involves a dramatic reduction in Cl solubility that increases the probability of hydrosaline liquid exsolution. The prediction that quartz monzonite magmas should exsolve a hydrosaline chloride liquid, that is potentially mineralizing, is consistent with the general observation of metal-enriched, hypersaline fluid inclusions in the more felsic plutons of numerous porphyry copper systems. Moreover, comparing the volatile contents of melt inclusions from the potassic, alkaline magmas of Mt. Somma-Vesuvius with the predicted (Cl/H2O) ratios of hydrosaline liquid-saturated melts having compositions similar to those of the volatile-rich, alkaline magmas associated with the orthomagmatic gold–tellurium deposits of Cripple Creek, Colorado, suggests that hydrosaline chloride liquid should have exsolved at Cripple Creek as the magmas evolved to phonolite compositions. This prediction is consistent with the well-documented role of Cl-enriched, mineralizing hydrothermal fluids at this major gold-mining district.