Early diagenesis of carbonate biocrystals : isomineralogical changes in aragonite coral skeletons

Early diagenetic changes occurring in aragonite coral skeletons were characterized at the micro- and ultra-structural scales in living and fossil scleractinian colonies, the latter of Pleistocene age. The skeleton of scleractinian corals, like all biomineralized structures, is a composite material formed by the intimate association of inorganic aragonite crystallites and organic matrices. In addition to its organo-mineral duality, the scleractinian skeleton is formed by the three-dimensional arrangement of two clearly distinct basic structural features, the centers of calcification and the fibers. The latter are typically characterized by a transverse micron-scale zonation revealing their incremental growth process. The size, geometry and three-dimensional arrangement of calcification centers and fibers are taxon-specific. The earliest diagenetic modifications of these skeletons have been clearly recognized in the older parts of living colonies. The first steps of diagenesis therefore take place only a few years after the skeleton had been secreted by the living polyps, and in the same environmental conditions. Comparisons with the uppermost living parts of the coral colonies clearly show that these first diagenetic changes are driven by the biological ultrastructural characteristics of these skeletons and are conditioned by the presence of organic envelopes interbedded with and surrounding aragonite crystallites. These first diagenetic processes induce the development of thin fringes of fibrous aragonite cements growing syntaxially on the aragonitic coral fibers, an alteration of the incremental zonation of coral fibers and also preferential diagenetic changes in the calcification centers, including dissolution of their minute internal crystals. Diagenetic patterns observed in Pleistocene coral colonies typically involve the same processes already recognized in the older skeletal parts of living colonies, suggesting that diagenesis occurs through continuous processes instead of clearly differentiated stages. Selective dissolution affects calcification centers and some growth increments of coral fibers. Alteration of the initial transverse zonation of coral fibers also occur through the development of micro-inclusions clearly seen in ultra-thin sections. Although usually thicker than those observed in the ancient skeletal parts of living colonies, syntaxial aragonite cements commonly occur in these fossil skeletons. These cements are often associated with gradual textural modifications of the underlying coral fibers, in particular the loss of the transverse micron-scale zonation. This suggests that the coral skeleton forming the substratum of diagenetic cements is progressively recrystallized in secondary aragonite. This recrystallization of coral aragonite begins at the external margin of the skeleton, just below the diagenetic cements and gradually moves towards the internal skeletal parts. Recrystallization takes place through concomitant fine-scale dissolution-precipitation processes and occurs with textural changes but no mineralogical change. The process of recrystallization is likely initiated by a biological degradation of organic skeletal matrices and can be also driven by thermodynamical constraints involving the lowering of surface free energies resulting from changes in crystal size. Alteration of skeletal organic matrix, textural changes in coral biocrystals through recrystallization and precipitation of secondary diagenetic aragonite may bias the original geochemical characteristics of coral skeletons. Although more work is needed to establish the influence of these early diagenetic processes on the geochemical signatures, it is already well known that the breakdown of organic skeletal envelopes and early recrystallization of shallow-water carbonates alter the stable isotopic composition. The widespread use of coral skeletons as environmental and climatic proxies makes strongly necessary a better understanding of these early diagenetic mechanisms and a precise characterization of the fine-scale diagenetic patterns of specimens for the optimization of geochemical interpretations. In particular, it cannot be assumed that an entire aragonitic composition can guarantee that there is no or slight diagenetic alteration.