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Desorption mechanisms of phosphate from ferrihydrite and goethite surfaces

Krumina, Lelde LU ; Kenney, Janice P L; Loring, John S. and Persson, Per LU (2016) In Chemical Geology 427. p.54-64
Abstract

The fate of phosphate in the environment is governed by reactions at particle surfaces. These adsorption and desorption reactions display biphasic kinetics involving an initial rapid reaction followed by a substantially slower one extending over long time periods. In this study we have investigated the molecular mechanisms of desorption kinetics of phosphate from ferrihydrite and goethite nanoparticles in the absence of competing ligands. Desorption was studied by means of in-situ infrared (IR) spectroscopy over a wide pH range and a time period of 24 h. The spectroscopic data sets were subjected to multivariate curve resolution alternating least squares (MCR-ALS), which enabled the resolution of surface species characterized by unique... (More)

The fate of phosphate in the environment is governed by reactions at particle surfaces. These adsorption and desorption reactions display biphasic kinetics involving an initial rapid reaction followed by a substantially slower one extending over long time periods. In this study we have investigated the molecular mechanisms of desorption kinetics of phosphate from ferrihydrite and goethite nanoparticles in the absence of competing ligands. Desorption was studied by means of in-situ infrared (IR) spectroscopy over a wide pH range and a time period of 24 h. The spectroscopic data sets were subjected to multivariate curve resolution alternating least squares (MCR-ALS), which enabled the resolution of surface species characterized by unique IR spectra together with their corresponding kinetic profiles. The desorption results showed the typical biphasic behavior and that increasing positive surface charge of ferrihydrite and goethite slowed down desorption of the negatively charged phosphate ions. Moreover, diprotonated phosphate desorbed faster than monoprotonated phosphate at a given pH. At circumneutral pH values desorption from ferrihydrite was substantially faster as compared to goethite, and this could be ascribed to electrostatic effects and differences in charging between ferrihydrite and goethite. The collective desorption results were explained by a model, consisting of a series monodentate phosphate surface complexes in different protonation states, in conjunction with a description that accounts for the electrostatic effects on desorption kinetics at charged mineral-water interfaces. The fast and slow desorption followed directly from this model and indicated that biphasic kinetics can be caused by a single phosphate surface complex as a result of decreasing surface coverage along with the lateral repulsive interactions between adsorbed phosphate groups. Hence, in contrast to previous models our study has shown that biphasic desorption kinetics do not have to involve several different structural complexes related to either weak and strong sites or a distribution of phosphate between external surfaces and mineral pores.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Desorption, Electrostatic interactions, Ferrihydrite, Goethite, Infrared spectroscopy, MCR-ALS, Phosphate
in
Chemical Geology
volume
427
pages
11 pages
publisher
Elsevier
external identifiers
  • Scopus:84958998993
  • WOS:000371765500005
ISSN
0009-2541
DOI
10.1016/j.chemgeo.2016.02.016
language
English
LU publication?
yes
id
2af0897b-fc12-4bf0-a691-bafff9ceb0e1
date added to LUP
2016-05-10 08:06:57
date last changed
2016-07-27 10:57:44
@misc{2af0897b-fc12-4bf0-a691-bafff9ceb0e1,
  abstract     = {<p>The fate of phosphate in the environment is governed by reactions at particle surfaces. These adsorption and desorption reactions display biphasic kinetics involving an initial rapid reaction followed by a substantially slower one extending over long time periods. In this study we have investigated the molecular mechanisms of desorption kinetics of phosphate from ferrihydrite and goethite nanoparticles in the absence of competing ligands. Desorption was studied by means of in-situ infrared (IR) spectroscopy over a wide pH range and a time period of 24 h. The spectroscopic data sets were subjected to multivariate curve resolution alternating least squares (MCR-ALS), which enabled the resolution of surface species characterized by unique IR spectra together with their corresponding kinetic profiles. The desorption results showed the typical biphasic behavior and that increasing positive surface charge of ferrihydrite and goethite slowed down desorption of the negatively charged phosphate ions. Moreover, diprotonated phosphate desorbed faster than monoprotonated phosphate at a given pH. At circumneutral pH values desorption from ferrihydrite was substantially faster as compared to goethite, and this could be ascribed to electrostatic effects and differences in charging between ferrihydrite and goethite. The collective desorption results were explained by a model, consisting of a series monodentate phosphate surface complexes in different protonation states, in conjunction with a description that accounts for the electrostatic effects on desorption kinetics at charged mineral-water interfaces. The fast and slow desorption followed directly from this model and indicated that biphasic kinetics can be caused by a single phosphate surface complex as a result of decreasing surface coverage along with the lateral repulsive interactions between adsorbed phosphate groups. Hence, in contrast to previous models our study has shown that biphasic desorption kinetics do not have to involve several different structural complexes related to either weak and strong sites or a distribution of phosphate between external surfaces and mineral pores.</p>},
  author       = {Krumina, Lelde and Kenney, Janice P L and Loring, John S. and Persson, Per},
  issn         = {0009-2541},
  keyword      = {Desorption,Electrostatic interactions,Ferrihydrite,Goethite,Infrared spectroscopy,MCR-ALS,Phosphate},
  language     = {eng},
  month        = {06},
  pages        = {54--64},
  publisher    = {ARRAY(0x861fd68)},
  series       = {Chemical Geology},
  title        = {Desorption mechanisms of phosphate from ferrihydrite and goethite surfaces},
  url          = {http://dx.doi.org/10.1016/j.chemgeo.2016.02.016},
  volume       = {427},
  year         = {2016},
}