Biofouling and biomineralization of tubular concretions attached to Longquan celadon from Shengbeiyu shipwreck, China (14th Century CE): a multi-analytical case study

Abstract

A comprehensive multi-analytical investigation was conducted on a piece of Longquan celadon excavated from the Shengbeiyu shipwreck site in the East China Sea. This study focused on a representative type of tubular bio-concretions attached to the submerged celadon, believed to have been formed through the construction activities of a marine tubeworm belonging to the benthic phylum of Polychaeta Annelids. The research examined the microstructure, composition and adhesion form of these tubular bio-concretions, aiming to elucidate their developmental and attachment patterns from a biomineralization and biofouling perspective. The tubular bio-concretions were found to have a bimineralic composition, with notably higher content of aragonite than calcite, and display diverse yet highly ordered microstructures. The presence of organic matter within the bio-concretions indicates an organic matrix-controlled crystallization model, commonly observed in the construction of benthic calcareous tubes. Microscopic analyses revealed the primary degradation microstructures and corresponding phases of the glaze to which calcareous tubes attached. These findings closely resembled the corrosion characteristics observed in submerged ceramic glaze without bio-concretion attachments, as documented in earlier studies. OM and SEM observations also indicated that the calcareous tubes intricately intermeshed with the cracked glaze layer of the celadon. Additionally, Raman spectroscopic analysis detected the presence of proteins at the interface, likely residual adhesives secreted by fouling organisms to cement themselves to the settlement substrata, suggesting the occurrence of organic-mediated bio-adhesion mechanisms. These results shed new light on the formation process of bio-concretions and their interaction with attached underwater ceramics. A simplified formation mechanism of this biologically-induced degradation has been discussed.