Andreani M., Munoz Marguerite, Marcaillou C., Delacour A. (2013). Mu XANES study of iron redox state in serpentine during oceanic serpentinization. Lithos, 178, p. 70-83. ISSN 0024-4937.
Titre du document
Mu XANES study of iron redox state in serpentine during oceanic serpentinization
Andreani M., Munoz Marguerite, Marcaillou C., Delacour A.
Source
Lithos, 2013,
178, p. 70-83 ISSN 0024-4937
Serpentinization of ultramafic rocks at mid-ocean ridges generates significant amounts of H-2, CH4, and supports specific biological communities. The abiotic H-2 production is attributed to the reduction of H2O during serpentinization, which balances oxidation of ferrous iron contained in primary minerals (mainly olivines and pyroxenes) to ferric iron contained in secondary minerals (mainly serpentines and magnetite). Magnetite has thus far been considered as the sole Fe3+-carrier for estimating bulk H-2 production, notably because the valence of iron in serpentine minerals and its relationship with both magnetite abundance and serpentinization degree are usually not determined. We show that the serpentine contribution to the Fe and Fe3+ budget has a significant effect on H-2 production. We performed mu-XANES analysis at the Fe K-edge on thin sections of peridotites with various degrees of serpentinization from ODP Leg 153 (MARK region, 23 degrees N). Fe3+/Fe-Tot in oceanic serpentines is highly variable (from similar to 0.2 to 1) at the thin section scale, and it is related non-linearly to the local degree of serpentinization. A typical value of 0.7 is observed above 60% serpentinization. The highest values of Fe3+/Fe-Tot observed within or close to late veins suggest that the Fe3+/Fe-Tot in serpentine record the local water-rock (W/R) ratio, as previously proposed from thermodynamic modeling. We estimate that the (W/R) ratio increased from similar to 0.6 to 25 during serpentinization at MARK, and locally reached similar to 100 in veins. Mass balance calculations combining all mineral and bulk rock analyses provide the distribution of Fe and Fe3+ as serpentinization progresses. Serpentine dominates the Fe3+ budget of the rock over magnetite during the first 75% of serpentinization, contributing up to 80% of the total Fe3+. At later stages, serpentine contribution to the Fe3+ budget decreases down to similar to 20%, while magnetite formation exponentially increases. Iron transfer from serpentine to magnetite balances the bulk Fe3+ content of the rock that increases almost linearly with the advance of the reaction. Formation of serpentine accounts for the majority of Fe3+ and H-2 production at early stages of serpentinization at a depth >2 km at MARK where the concentration of H-2 can reach more than 100 mM according to the low W/R. H-2 production values and depths can vary from one site to another, depending on the evolution of the temperature, W/R ratio, inlet fluid composition, and favored formation of serpentine vs. magnetite. At MARK, Fe3+ in serpentine represents 15-27% of the total Fe contained in a rock serpentinized to more than 80%, and accounts for 25% of the total H-2 production that is estimated at 325-335 mmol/kg of rock. The absence of magnetite does not necessarily mean a negligible H-2 production, even at low T conditions (<150-200 degrees C) under which the Fe- and Fe3+-richest serpentines have been observed. Serpentine minerals are important Fe3+-carrier in the altered ocean lithosphere, and may affect mantle redox state while dehydrating at depth in subduction zones.
