UHP metamorphism documented in Ti-chondrodite- and Ti-clinohumite-bearing serpentinized ultramafic rocks from Chinese southwestern Tianshan

The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahighpressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite-harzburgite-dunite association in the mantle (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite+olivine+antigorite+chlorite+magnetite+brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average X_Al=0.204±0.026 of antigorite (X_Al=Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M₄₈T₃₄O₈₅(OH)₆₂, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average X_Al=0.203±0.019 of antigorite in the matrix result in a wellconstrained peak metamorphic temperature of 510-530°C. Peak pressures are less precisely constrained at 37±7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite+antigorite+olivine+chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P-T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25-55 kbar and 600-750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.