Serpentinization Changes Nd, but not Hf Isotopes of Abyssal Peridotites

Abstract:

Serpentinization of the oceanic lithosphere is a known sink for fluid mobile elements (B, Cl, Li, Sr, etc.), while high field strength elements (HFSE: e.g., Hf, Zr, Ti, Nb) are thought to be unaffected by it. In contrast, the fate of REE during serpentinization is equivocal. Correlations between REE and HFSE concentrations in abyssal peridotites suggest control by magmatic processes (Niu, 2004, J. Pet), while some LREE enrichments in serpentinized peridotites compared to their clinopyroxene (cpx) and Nd, Sr isotope data (Delacour et al., 2008, Chem. Geol.) imply seawater-derived REE addition to the mantle protolith (Paulick et al., 2006, Chem. Geol). To further constrain peridotite-seawater interaction during serpentinization we compare bulk rock and cpx Hf and Nd isotope data in partially (up to ~70%) serpentinized abyssal peridotites (9-16°E South West Indian Ridge). We also present a new method that improves yields in Hf, Nd and Pb separations from depleted (<0.03 ppm Hf) ultramafic rocks, which includes coprecipitation of metals with Al-Fe hydroxides and ether-HCl liquid-liquid exchange for Fe removal. Nd isotopes in the bulk peridotite are up to 7ε_Nd units less radiogenic than their cpx (i.e., the magmatic value) while Hf isotopes remain equal to cpx within 1 ε_Hf. Melt-rock reaction by the local lavas cannot generate this decoupling. The largest Nd isotopic difference between cpx and bulk is seen in the most LREE-depleted samples, while refertilized samples show little change. Leaching experiments show that 30-60% of REE are mobilized from the rock, but >90% of Hf, Zr, Ti are retained in the residue. LA-ICPMS data shows that serpentine after olivine typically has higher LREE/HREE ratios than cpx, pronounced negative Ce anomalies, high U, Sr concentrations and low HFSE, unlike the coexisting cpx. These data are consistent with some seawater-derived LREE addition to peridotite during serpentinization, localized in the serpentine and other secondary phases, while cpx retains the magmatic value. This process will lower the Sm/Nd relative to Lu/Hf ratio in the peridotite and can lead to decoupled radiogenic Hf and unradiogenic Nd isotopes upon recycling and aging. Our data further testifies to the fidelity of Hf isotopes in tracing mantle processes, even in serpentinized rocks.