Mineralization kinetics of biosiliceous sediments in hot subseafloors

Temperature affects the timing of the transformation of amorphous silica (opal-A) into crystalline (opal-CT) exponentially. Thus, in hot subseafloor environments opal-A is expected to convert into opal-CT at relatively shallow burial depths, where in situ temperatures do not exceed ∼56 °C, as it has been previously observed at various deep-sea sites and in onshore rock outcrops as well as assessed during lab experiments. The response of biosilica (biogenic opal-A) diagenesis to steep geothermal gradients (∼224–529 °C/km) at extremely high sedimentation rates (∼1 m/kyr) was examined in cores from off-axis boreholes drilled by the International Ocean Discovery Program (IODP) Expedition 385 in the actively spreading, intrusive sill-riddled Guaymas Basin at the Gulf of California (Mexico) rifted margin. At three sites drilled by IODP Expedition 385 (U1545, U1546, and U1547), the conversion from amorphous opal (−A) to crystalline opal (−CT) occurs in relatively deep (up to ∼330 mbsf) and unexpectedly hot (in situ temperatures of ∼74–79 °C) subseafloor conditions. This observation indicates a significantly slower reaction kinetics of biosilica transformation than previously reported. A compilation of empirical data that include biosiliceous basins with a similarly hot subseafloor (Sea of Japan and Bering Sea) yield new kinetic parameters that account for the slower rates of silica transformation. Thus, current kinetic models for the prediction of opal-A to −CT conversion face limitations when burial rates exceed those typical of biogenic sedimentation in open-ocean conditions. At Guaymas Basin Site U1545, where there is no evidence of sill-related metamorphic overprint, the d-spacing of the opal-CT (1 0 1) peak correlates linearly with in situ temperature between ∼75 and 110 °C throughout the opal-CT zone, thus, providing a local silica paleothermometry proxy that can be used to calculate the maximum temperature to which opal-CT sediment has been subjected.