The production of iron oxide during peridotite serpentinization:Influence of pyroxene

Serpentinization produces molecular hydrogen (H2) that can support communities of microorganisms in hydrothermal fields; H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron, and consequently iron oxide (magnetite or hematite) forms. However, the mechanisms that control H2 and iron oxide formation are poorly constrained. In this study, we performed serpentinization experiments at 311 _C and 3.0 kbar on olivine (with <5% pyroxene), orthopyroxene, and peridotite. The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution. Olivine-derived serpentine had a significantly lower FeO content (6.57 _ 1.30 wt.%) than primary olivine (9.86 wt.%), whereas orthopyroxene-derived serpentine had a comparable FeO content (6.26 _ 0.58 wt.%) to that of primary orthopyroxene (6.24 wt.%). In experiments on peridotite, olivine was replaced by serpentine and iron oxide. However, pyroxene transformed solely to serpentine. After 20 days, olivine-derived serpentine had a FeO content of 8.18 _ 1.56 wt.%, which was significantly higher than that of serpentine produced in olivine-only experiments. By contrast, serpentine after orthopyroxene had a slightly higher FeO content (6.53 _ 1.01 wt.%) than primary orthopyroxene. Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral. After 120 days, the FeO content of olivine-derived serpentine decreased significantly (5.71 _ 0.35 wt.%), whereas the FeO content of orthopyroxene-derived serpentine increased (6.85 _ 0.63 wt.%) over the same period. This suggests that iron oxide preferentially formed after olivine serpentinization. Pyroxene in peridotite gained some Fe from olivine during the serpentinization process, which may have led to a decrease in iron oxide production. The correlation between FeO content and SiO2 or Al2O3 content in olivine- and orthopyroxene-derived serpentine indicates that aluminum and silica greatly control the production of iron oxide. Based on our results and data from natural serpentinites reported by other workers, we propose that aluminum may be more influential at the early stages of peridotite serpentinization when the production of iron oxide is very low, whereas silica may have a greater control on iron oxide production during the late stages instead.