Aged Biogenic Carbonates from Crustacean Waste: Structural and Functional Evaluation of Calibrated Fine Powders and Their Conversion into Phosphate Minerals

甲壳类动物废弃物中的老化生物成因碳酸盐:校准细粉的结构和功能评价及其向磷酸盐矿物的转化

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Abstract

Seafood-derived carbonate waste, primarily calcium carbonate (CaCO(3)), has attracted growing interest for sustainable reuse, yet the unique potential of aged biogenic sources remains underexplored. Blue crab (Callinectes sapidus) shells are particularly distinctive: they consist of Mg-calcite with an intrinsic 3D-porous structure and naturally embedded astaxanthin, a potent antioxidant not found in other calcite- or aragonite-based residues. While organic degradation over time is often assumed to compromise functionality, this study demonstrates that five-years-aged crustacean shell waste retains both its crystallinity and bioactive carotenoids after calibrated ball milling. Across four powder batches produced under distinct milling conditions by varying frequencies and durations, dynamic light scattering confirmed only subtle particle size variation, while Raman spectroscopy, XRD, FT-IR, and SEM-EDX confirmed structural and chemical integrity and highlighted the subtle amorphization induced by slightly different milling parameters, which, in turn, driven to slightly different conversion efficiency into phosphate mineral. Strikingly, all powders underwent rapid transformation into dicalcium phosphate dihydrate (brushite) enriched with carotenoids upon reaction with phosphoric acid. This work reveals, for the first time, that years-aged biogenic Mg-calcite waste not only preserves its naturally embedded carotenoids but also offers a direct route to functional phosphate composites, establishing its untapped value in environmental and biomedical applications.

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