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The minerals contained in all of the food we consume are essential for our organ systems. However, certain essential minerals, such as calcium, phosphorus, magnesium, manganese, and fluoride, largely affect bone health.
Calcium and Phosphorus
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Rapid Mix Preparation of Bioinspired Nanoscale Hydroxyapatite for Biomedical Applications
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Internalization of Fluoride in Hydroxyapatite Nanoparticles.

Daniel S Mosiman1, Andre Sutrisno2, Riqiang Fu3

  • 1Safe Global Water Institute, Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign (UIUC), Urbana, Illinois 61801, United States.

Environmental Science & Technology
|February 3, 2021
PubMed
Summary

This study investigates how hydroxyapatite (HAP) removes fluoride from water. Previous research focused on surface adsorption, but this paper shows that fluoride also integrates into the HAP crystal lattice. Using nuclear magnetic resonance and electron microscopy, the researchers confirmed that all removed fluoride is apatitic. A model was developed to quantify how much fluoride internalizes versus adsorbs. Experimental results showed high uptake levels after 864 hours. The findings suggest HAP's fluoride removal capacity extends beyond surface interactions. This work provides a new tool to understand and optimize HAP-based water treatment systems.

Keywords:
Hydroxyapatite fluoride removalFluoride internalizationWater treatment nanoparticlesFluoride adsorption mechanisms

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Area of Science:

  • Environmental chemistry
  • Materials science
  • Water treatment technologies

Background:

Prior research has shown hydroxyapatite (HAP) can remove fluoride from water, but most studies focus on surface adsorption mechanisms. No prior work had resolved whether fluoride integrates into the HAP crystal lattice. This gap motivated investigation into internalization versus adsorption. Established methods track surface interactions, but lattice incorporation remains poorly quantified. The need for a model to distinguish these processes is clear. This paper introduces a new approach to quantify internalized fluoride in HAP. Understanding lattice uptake is essential for optimizing HAP in water treatment. The study addresses a fundamental question about fluoride removal mechanisms.

Purpose Of The Study:

The aim of this work is to determine whether fluoride integrates into the HAP crystal lattice during water treatment. This paper tests the hypothesis that fluoride is not only adsorbed but also assimilated into the apatite structure. The researchers propose to use nuclear magnetic resonance and electron microscopy to distinguish adsorption from internalization. The study seeks to quantify the extent of lattice incorporation. A fixed-bed filter system was used to simulate real-world conditions. The goal is to develop a model that explains how much fluoride internalizes versus adsorbs. This work addresses a key uncertainty in HAP's fluoride removal capacity. The findings may improve HAP-based water treatment systems.

Main Methods:

Pellets of HAP nanoparticles were packed into a fixed-bed media filter to treat fluoride solutions. The system operated at pH 8 with 30 mg-F/L solutions for 864 hours. Solid-state 19F and 13C magic-angle spinning nuclear magnetic resonance spectroscopy was used to analyze fluoride integration. Transmission electron microscopy examined particle morphology and crystal structure. The data informed a model to estimate adsorption and internalization capacities. Low- and high-estimate median adsorption capacities were calculated. The model tracks discrepancies between total uptake and adsorption values. This approach distinguishes surface adsorption from lattice internalization.

Main Results:

The study found that all removed fluoride was apatitic, indicating lattice incorporation. Experimental uptake reached 15.97 ± 0.03 mg-F/g-HAP after 864 hours. Median adsorption capacities were 2.40 and 6.90 mg-F/g-HAP for low and high estimates. Discrepancies between uptake and adsorption suggest significant internalization. The model quantifies how much fluoride satisfies conservation of mass. Transmission electron microscopy confirmed nanoparticle morphology and crystal habit. Nuclear magnetic resonance data supported lattice integration. These results demonstrate that fluoride internalizes into HAP under environmental conditions.

Conclusions:

The authors propose that fluoride internalizes into the HAP lattice during water treatment. This finding suggests HAP's fluoride removal capacity extends beyond surface adsorption. The model provides a tool to quantify internalization in any HAP nanoparticle system. Experimental results confirm that lattice integration occurs under environmentally relevant conditions. The study supports a paradigm shift in understanding HAP's fluoride removal mechanism. The model accounts for discrepancies between uptake and adsorption measurements. These conclusions align with the authors' stated goals of quantifying internalization. The findings may inform future water treatment applications using HAP.

The authors propose that hydroxyapatite removes fluoride through both surface adsorption and lattice internalization. Experimental uptake reached 15.97 mg-F/g-HAP after 864 hours.

Solid-state 19F and 13C magic-angle spinning nuclear magnetic resonance spectroscopy was used to confirm lattice incorporation of fluoride.

Transmission electron microscopy showed nanoparticle morphology and crystal habit, which informed the model to quantify adsorption and internalization.

The model estimates adsorption and internalization capacities, showing discrepancies between uptake and adsorption values.

The experiment used a pH 8 solution containing 30 mg-F/L, simulating environmentally relevant conditions.

The authors propose that lattice integration increases HAP's fluoride removal capacity beyond surface adsorption alone.