The formation of opal in marine reptile bones and wood

Abstract

The age of precious opal and the mechanisms that result in formation as opposed to the ubiquitous common opal are poorly understood. Until now, there has been no research on the replacement of biominerals in vertebrate bones by opal. As the microtexture, mineralogy and chemistry of bones are well-known, they provide a unique opportunity to study the mechanism of precious opal deposition. In this article chemical and textural features of Andamooka opalised plesiosaur bones were compared with those in non-opalised ichthyosaur bones from Moon Plain and a recent dolphin bone. Opalised wood samples from Nevada and White Cliffs were also studied to compare with bone opalisation and different depositional environments (sedimentary vs volcanogenic). The cellular form of a continuous irregular framework of silica was retained in the wood samples. The mineralogy of the wood samples reflects their depositional environment, where opal-CT and opal-C is dominant in volcanic deposits (Nevada) and opal-A in sedimentary deposits (White Cliffs). Comparison of the Nevada wood to Post-Archean average shale (PAAS) shows that it is rich in most trace elements with the exception of Y and U. The high amount of trace elements is a reflection of its volcanic origin. In contrast, the opalised wood from White Cliffs is depleted in most trace elements with the exception of Co. Cracks were observed in both the opalised wood and bone samples which allowed the void space required to form precious opal. The opalised wood from White Cliffs and the opalised plesiosaur bones from Andamooka are chemically very similar and reflect similar compositions for the opalising fluids. The Haversian system was preserved in the non-opalised ichthyosaur bone but not in the opalised bones. The ichthyosaur bone is comprised mostly of carbonate-hydroxylapatite but in the opalised bones the major mineral is quartz. Modern dolphin bone consists of bioapatite with water and organic material: its trace element composition is broadly similar to the ichthyosaur bone from Moon Plain but is richer in Sr, Zn and Co. When normalized to PAAS, the ichthyosaur bone is depleted in all trace elements with the exception of Sr, which is likely a product of the carbonate-rich mineralogy. Like the ichthyosaur bones, the opalised bones are also depleted in trace elements, with the exception of Co and Zn. There is no evidence of remnant bioapatite in the opalised bone, a finding consistent with the chemical analyses that show only trace amounts of Ca and no P. The level of microstructural preservation in the opalised bone suggests that opalisation is not a closely coupled dissolution-reprecipitation reaction and that there was a fluid filled space between the reaction fronts which allowed the opal silica spheres to form and settle within a comparatively small space (100 µm). An alternative interpretation is that the fibrous quartz filled the osteon canals before opalisation and that the bioapatite was then dissolved away leaving a hollow cast that filled slowly with opal.