The mineralization and early diagenesis of deep-sea coral Madrepora oculata

Abstract

The skeletons of aragonitic corals carry essential information about oceanic environmental changes in the past. However, coral-based geochemical proxies are sensitive to vital effect and post-depositional diagenetic processes, which have not been well understood for deep-sea corals. In this study, we have investigated the mineralization and early diagenetic process of the dendroid stem of a dead deep-sea scleractinian coral sample (Madrepora oculata) collected by Remote Operated Vehicle (ROV) from a seamount in the Caroline Ridge, western Pacific. Despite being only ~270 years old, as dated by the U-series disequilibrium method, this sample already has extensive diagenesis including a visible chalky layer. The outermost chalky layer and the adjacent pristine skeleton of the sample were characterized by multiple mineralogical (SEM, XRD, EBSD, Raman Spectroscopy) and geochemical (ICP-OES, LA-ICP-MS, IR-MS, MC-ICP-MS) techniques. Skeletal stable C and O isotopes display strong linearity, with a trend pointing toward the theoretical isotopic composition of inorganically-precipitated aragonite from local seawater. This observation suggests that the epithecal mineralization of M. oculata is far from equilibrium with seawater and can be quantitatively explained by bio-mineralization models developed for solitary scleractinian corals. We further show that chalking of the outer layer, a common feature in sub-fossilized deep-sea corals, is caused by microbial-driven boring and μm-scale dissolution voids at an average rate of 3.5 μmol/cm2/y (scaled to the skeleton surface) without notable secondary infillings or mineralogical alternations. The higher average δ13C and δ18O of the chalky part than the pristine part might be due to the preferential dissolution of carbonate relatively depleted in 13C and 18O during alteration, and/or reduced isotope fractionation from seawater during coral mineralization of the outer layer. The chalky layer shows significantly higher Mn/Ca and Th/Ca ratios than the pristine part, characterized by Th/Mn ratios similar to that of the dissolved component of local seawater. Our study suggests that the incorporation of external Th into the coral skeleton is most likely associated with organic binding rather than detrital contamination, secondary carbonate mineral formation, adsorption onto surfaces of chalky aragonite or ferromanganese oxides, with important implications for coral U-series geochronology.