Limestone Processing Sludge: From Waste to Sustainable Resource

The limestone quarrying and processing industry generates huge amounts of waste, with limestone sludge being one of the most prevalent and challenging by-products. This study aims to evaluate the potential of limestone sludge as a sustainable secondary raw material for the mechanochemical synthesis of bioceramics, specifically hydroxyapatite (HA), for high-added-value applications in bone tissue engineering. High-energy milling is innovatively used as the processing route: dry sludge (functioning as the calcium source), a phosphate source, and water were milled with the aim of producing calcium phosphates (in particular, hydroxyapatite) via mechanosynthesis. The industrial sludge was thoroughly analyzed for chemical composition, heavy metals, and mineral phases to ensure suitability for biomedical applications. The mixture of reagents was tailored to comply with Ca/P = 1.67 molar ratio. Milling was carried out at room temperature; the milling velocity was 600 rpm, and milling time ranged from 5 to 650 min. Characterization by XRD, Raman spectroscopy, and SEM confirmed the progressive transformation of calcite into hydroxyapatite through a metastable DCPD intermediate, following logarithmic reaction kinetics. The resulting powders are fine, homogeneous, and phase-pure, demonstrating that mechanosynthesis provides a low-cost and environmentally friendly pathway to convert limestone waste into functional bioceramic materials. This suggests that Moleanos sludge is a viable and sustainable source to produce tailored calcium phosphates and confirms mechanosynthesis as a cost-effective and reliable technology to activate the low-kinetics chemical reactions in the CaCO3-H3PO4–H2O system. This work highlights a novel circular economy approach for the valorization of industrial limestone sludge, turning a difficult waste stream into a high-value, sustainable resource.