# Impact of High Energy Milling and Mineral Additives on a Carbonate–Quartz–Apatite System for Ecological Applications

## TL;DR

This study explores how high-energy milling affects the structure of minerals in Estonian phosphorites, offering an eco-friendly alternative to traditional acid methods.

## Contribution

The study introduces high-energy milling as an ecological method to enhance the reactivity and solubility of phosphorite minerals.

## Key findings

- High-energy milling leads to anionic isomorphism and formation of carbonate-apatites and hydroxyl-fluorapatite.
- Solid-phase synthesis of calcium orthophosphate and dicalcium diphosphate occurs after milling.
- Milling increases chemical reactivity and solubility of the mineral samples by about three times.

## Abstract

In this study, high-energy milled (HEM) samples of natural phosphorites from Estonian deposits were investigated. The activation was performed via planetary mill with Cr-Ni grinders with a diameter of 20 mm. This method is an ecological alternative, since it eliminates the disadvantages of conventional acid methods, namely the release of gaseous and solid technogenic products. The aim of the study is to determine the changes in the structure to follow the solid-state transitions and the isomorphic substitutions in the anionic sub-lattice in the structure of the main mineral apatite in the samples from Estonia, under the influence of HEM activation. It is also interesting to investigate the influence of HEM on structural-phase transformations on the structure of impurity minerals-free calcite/dolomite, pyrite, quartz, as well as to assess their influence on the thermal behavior of the main mineral apatite. The effect of HEM is monitored by using a complex of analytical methods, such as chemical analysis, powder X-ray diffraction (PXRD), wavelength-dispersive X-ray fluorescence (WD-XRF) analysis, and Fourier-transformed infrared (FTIR) analysis. The obtained results prove the correlation in the behavior of the studied samples with regard to their quartz content and bonded or non-bonded carbonate ions. After HEM activation of the raw samples, the following is established: (i) anionic isomorphism with formation of A and A-B type carbonate-apatites and hydroxyl-fluorapatite; (ii) solid-phase synthesis of calcium orthophosphate-CaHPO4 (monetite) and dicalcium diphosphate-β-Ca2P2O7; (iii) enhanced chemical reactivity by approximately three times by increasing the solubility via HEM activation. The dry milling method used is a suitable approach for solving technological projects to improve the composition and structure of soils, increasing soil fertility by introducing soluble forms of calcium phosphates. It provides a variety of application purposes depending on the composition, impurities, and processing as a soil improver, natural mineral fertilizer, or activator.