The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids

We present an inventory of B, Cl and Li concentrations in (a) key minerals from a set of ultramafic samples featuring the main evolutionary stages encountered by the subducted oceanic mantle, and in (b) fluid inclusions produced during high-pressure breakdown of antigorite serpentinite. Samples correspond to (i) nonsubducted serpentinites (Northern Apennine and Alpine ophiolites), (ii) high-pressure olivine-bearing antigorite serpentinites (Western Alps and Betic Cordillera), (iii) high-pressure olivine-orthopyroxene rocks recording the subduction breakdown of antigorite serpentinites (Betic Cordillera). Two main dehydration episodes are recorded by the sample suite: partial serpentinite dewatering during formation of metamorphic olivine. followed by full breakdown of antigorite serpentine to olivine + orthopyroxene + fluid. Ion probe and laser ablation ICP-MS (LA ICP-MS) analyses of Cl, B and Li in the rock-forming minerals indicate that the hydrous mantle is an important carrier of light elements. The estimated bulk-rock B and Cl concentrations progressively decrease from oceanic serpentinites (46.7 ppm B and 729 ppm Cl) to antigorite serpentinites (20 ppm B and 221 ppm Cl) to olivine-orthopyroxene rocks (9.4 ppm B and 45 ppm Cl). This suggests release of oceanic Cl and B in subduction fluids, apparently without inputs from external sources. Lithium is less abundant in oceanic serpentinites (1.3 ppm) and the initial concentrations are still preserved in high-pressure antigorite serpentinites. Higher Li contents in olivine, Ti-clinohumite of the olivine-orthopyroxene rocks (4.9 ppm bulk rock Li), as well as in the coexisting fluid inclusions, suggest that their budget may not be uniquely related to recycling of oceanic Li, but may require input from external sources. Laser ablation ICP-MS analyses of fluid inclusions in the olivine-orthopyroxene rocks enabled an estimate of the Li and B concentrations in the antigorite breakdown fluid. The inclusion compositions were quantified using a range of salinity ovalues (0.4-2 wt.% NaClequiv) as internal standards, yielding maximum average D-fluid/rock(B) similar to 5 and D-fluid/rock(Li) similar to 3.5. We also performed model calculations to estimate the B and Cl loss during the two dehydration episodes of serpentinite subduction. The first event is characterized by high fluid/rock partition coefficients for Cl (similar to 100) and B (similar to 60) and by formation of a fluid with salinity of 4-8 wt.% NaClequiv. The antigorite breakdown produces less saline fluids (0.4-2 wt.% NaClequip) and is characterized by lower partition coefficients for Cl (25-60) and B (12-30). Our calculations indicate that the salinity of the subduction fluids decreases with increasing depths. D-fluid/rock(B)/(fluid/rock) D-Cl < 1 (similar to 0.5) indicates that Cl preferentially partitions into the evolved fluids relative to B and that the B/Cl of fluids progressively increases with increasing depths and temperatures. Despite light element release in fluids, appreciable B, Cl and Li are still retained in chlorite, olivine and Ti-clinohumite beyond the antigorite stability field. This permits a bulk storage of about 10 ppm B, 45 ppm Cl and 5 ppm Li, i.e., concentrations much higher than in mantle reservoirs. Chlorite is the Cl repository and its stability controls the Cl and H2O budget beyond the antigorite stability; B and Li are bound in olivine and clinohumite. The subducted oceanic mantle thus retains light elements beyond the depths of arc magma sources, potentially introducing anomalies in the upper mantle. (C) 2004 Elsevier B.V. All rights reserved.