Plagioclase and epidote buffering of cation ratios in mid-ocean ridge hydrothermal fluids: Experimental results in and near the supercritical region

Experiments have been performed with Na-Ca-K-Cl fluids of seawater chlorinity and diabase, basalt, and plagioclase bearing mineral mixtures at 350-425 °C and 250-400 bars to help constrain hydrothermal alteration processes at mid-ocean ridges. Dissolved Ca, Na, and pH for all experiments responded systematically to differences in dissolved SiO₂ concentrations and the compositions of plagioclase reactants. Diabase alteration at low fluid/rock mass ratios (0.5 to 1) produces fluids undersaturated with respect to quartz during hydration of primary olivine and orthopyroxene, whereas basalt alteration under similar conditions yields fluids slightly supersaturated with respect to quartz during breakdown of glass to smectite and amphibole. Fluid chemistry in all experiments appears to approach a partial equilibrium state with the albite and anorthite components in plagioclase and approaches a pH consistent with plagioclase alteration to epidote. Trace element data from vent fluids, specifically B and Sr, together with major element chemistry (Ca, Na, SiO₂, pH), provides evidence that the reaction zone for "black-smoker" fluids at mid-ocean ridges is composed of only slightly altered diabase and is characterized by small amounts of epidote, nearly fresh plagioclase and clinopyroxene, and partially to completely hydrated olivine and orthopyroxene. Fluids reacting with this rock may be undersaturated with respect to quartz so pressure estimates based on the quartz geobarometer should be regarded as minimums. Using equilibrium between plagioclase, the dominant reactant, and epidote, the dominant reaction product in experiments, we estimate that temperatures in reaction zones are in excess of 375°C for most vent systems. These temperatures are higher than measured vent temperatures, suggesting that hotspring fluids commonly loose heat during ascent to the seafloor.