Unveiling the Amphoteric Surface Reactivity of Montebrasite using Spectroscopic and First-Principles Methods

The amblygonite-montebrasite group of minerals is the most abundant lithium-bearing phosphate found in phosphorus-rich lithium pegmatites. The separation of montebrasite from spodumene—the primary lithium ore mineral—commonly by flotation, is necessary for effective downstream lithium extraction. Understanding how water molecules interact with the montebrasite surface is necessary to understand its separation from other minerals by flotation. This study examined the interaction between water and montebrasite using dissolution tests, surface charge analysis, and various spectroscopic techniques (UV, FTIR, XPS, and XANES), all supported by density functional theory calculations. We found evidence of amphoteric properties (hydroxylation of surface Al and Li, and protonation of phosphate group) with acid-base reactions, F/OH ion exchange (-142.61 kcal/mol), non-stoichiometric dissolution (F > Li > Al > P), and dissociative chemisorption (-187.06 kcal/mol) at the mineral–water interface. This surface reactivity could impact solution chemistry and influence collector adsorption on the mineral surface during flotation. Surface dissolution and ion exchange may lead to the release of Li to industrial process water, in addition to F, potentially forming LiF in solution. These findings are important in the froth flotation field because the change in solution pH caused by significant amounts of amphoteric minerals, such as montebrasite, can affect flotation results since flotation performance depends on pH, leading to unstable flotation circuits. However, this issue may be managed by achieving and/or maintaining an equilibrium pH through an appropriate conditioning stage. This work builds important knowledge of montebrasite surface properties and the montebrasite-water interface, essential to understanding many natural phenomena and engineering processes. Accordingly, we discussed the implications for montebrasite froth flotation, mineral alteration, environmental impact, and its potential as a promising functional material for heterogeneous catalysis and Li-ion batteries.

Authors

Institutions

Publication Details

Journal
ChemRxiv
Published
2025-08-25
DOI
https://doi.org/10.26434/chemrxiv-2025-cvj65
Primary Topic
Mineralogy and Gemology Studies
Type
article
Field-Weighted Citation Impact
0.00

Funders

Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Unveiling the Amphoteric Surface Reactivity of Montebrasite using Spectroscopic and First-Principles Methods

Espoir M. Murhula, Charlotte E. Gibson, Lucia Zuin, Gideon Lambiv Dzemua et al.
ChemRxiv
Mineralogy and Gemology Studies
article

Unveiling the Amphoteric Surface Reactivity of Montebrasite using Spectroscopic and First-Principles Methods

Espoir M. Murhula, Charlotte E. Gibson, Lucia Zuin, Gideon Lambiv Dzemua, Wennie Wang, G. Schatte, Suk Gyu Lim
article en

Abstract

The amblygonite-montebrasite group of minerals is the most abundant lithium-bearing phosphate found in phosphorus-rich lithium pegmatites. The separation of montebrasite from spodumene—the primary lithium ore mineral—commonly by flotation, is necessary for effective downstream lithium extraction. Understanding how water molecules interact with the montebrasite surface is necessary to understand its separation from other minerals by flotation. This study examined the interaction between water and montebrasite using dissolution tests, surface charge analysis, and various spectroscopic techniques (UV, FTIR, XPS, and XANES), all supported by density functional theory calculations. We found evidence of amphoteric properties (hydroxylation of surface Al and Li, and protonation of phosphate group) with acid-base reactions, F/OH ion exchange (-142.61 kcal/mol), non-stoichiometric dissolution (F > Li > Al > P), and dissociative chemisorption (-187.06 kcal/mol) at the mineral–water interface. This surface reactivity could impact solution chemistry and influence collector adsorption on the mineral surface during flotation. Surface dissolution and ion exchange may lead to the release of Li to industrial process water, in addition to F, potentially forming LiF in solution. These findings are important in the froth flotation field because the change in solution pH caused by significant amounts of amphoteric minerals, such as montebrasite, can affect flotation results since flotation performance depends on pH, leading to unstable flotation circuits. However, this issue may be managed by achieving and/or maintaining an equilibrium pH through an appropriate conditioning stage. This work builds important knowledge of montebrasite surface properties and the montebrasite-water interface, essential to understanding many natural phenomena and engineering processes. Accordingly, we discussed the implications for montebrasite froth flotation, mineral alteration, environmental impact, and its potential as a promising functional material for heterogeneous catalysis and Li-ion batteries.

ChemRxiv
Queen's University (CA), Government of Northwest Territories (CA), Canadian Light Source (Canada) (CA), The University of Texas at Austin (US)
Canadian Light Source, Department of Mechanical Engineering, University of Texas at Austin, American Chemical Society Petroleum Research Fund, Canadian Institutes of Health Research, Natural Sciences and Engineering Research Council of Canada, Natural Resources Canada
Openalex Percentile: Top 81%
Mineralogy and Gemology Studies
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.