Chemical zoning is commonly seen in inorganic minerals,
and it
holds implications for magmatic processes, hydrothermal evolution,
or metal mineralization. However, few studies are available on oscillatory
zoning in biominerals, which carries the most direct and unique information
on the biomineralization mechanism. This study investigates spatial
and temporal resolution of trace element distributions in pearls that
were cultivated in the Hyriopsis cumingii mantle (non-nucleated pearls and nucleated Akoya pearls) or visceral
mass (nucleated Edison pearls) for 1–5 years. Using synchrotron
radiation micro-X-ray fluorescence imaging, we find a variety of trace
elements such as Sc, Cr, Mn, Cu, Zn, Ge, and Ba. The types of trace
elements are slightly different for individuals. For the first time,
submillimeter-scale Mn zoning is identified ubiquitously, concentric
with the pearl, and exhibits increased concentrations toward the pearl
margin. In non-nucleated pearls and nucleated Akoya pearls, the Mn
zones are superposed with a spatially damped pattern with a decrease
in the interzones. In contrast, no damped trends are observed in the
Mn zones in nucleated Edison pearls. This difference may be due to
different cultivation sites within mollusks that have different requirements
for Mn during pearl growth. We suggest a growth model of dissipative
structure for the Mn zoning in pearls, which depends upon the coupling
between the interface kinetics and the diffusion of chemical species
in the environment. The trace elements (including Mn) substitute Ca
in aragonite isomorphically, based on Raman imaging. The scanning
electron microscopy images show a periodic structure of aragonite
platelets and organic matter of pearls. Locally in the Mn zones, there
are minor defects on platelets, which may arise from the enrichment
of trace elements. This study would develop a new research field for
chemical zoning in minerals and introduce a new angle in understanding
trace element incorporation in biominerals and the biomineralization
processes.