Calcium Sulfate Nanoparticles in Surface Sediments of Lingding Bay of the Pearl River Estuary, China: Implications for the Nonclassical Crystallization Pathway of Gypsum in the Natural Estuary Environment

The mechanism of the nonclassical crystallization pathway of calcium sulfate dihydrate (gypsum) with calcium sulfate hemihydrate (bassanite) as a precursor has been considered in many studies. However, studies on the crystallization of gypsum in natural environments have rarely been reported, especially with regard to natural estuaries, which are one of the most important precipitation environments for calcium sulfate. Here, surface sediments (0–5 cm) of Lingding Bay of the Pearl River Estuary in China were sampled and analyzed. X-ray powder diffraction (XRD) analysis showed that calcium sulfate in the surface sediments mainly existed in the form of gypsum. In high-resolution transmission electron microscopy (HR-TEM) analysis, calcium sulfate nanoparticles were observed in the surface sediments. These particles mainly included spherical calcium sulfate nanoparticles (diameter ranging from 10–50 nm) and bassanite nanorod clusters (sizes ranging from 30 nm × 150 nm to 100 nm × 650 nm), and their main elements included O, S and Ca, with small amounts of N, Si, Na and Mg. The bassanite nanorods self-assembled into aggregates primarily co-oriented along the c axis (i.e., [001] direction). In epitaxial growth into larger bassanite nanorods (100 nm × 650 nm), the crystal form of gypsum could be observed. Based on the observations and analyses, we proposed that the crystallization of gypsum in surface sediments of the natural estuary environment could occur through the nonclassical crystallization pathway. In this pathway, bassanite nanoparticles and nanorods appear as precursors (nanoscale precursors), grow via self-assembly, and are finally transformed into gypsum. This work provided evidence supporting and enhancing the understanding of the crystallization pathway of calcium sulfate phases in the natural estuary environment. Furthermore, the interactions between calcium sulfate nanoparticles and the natural estuary environment were examined.