Binding mechanism of Cu(II) at the clay–water interface by powder and polarized EXAFS spectroscopy

<div><div><div><p>The interaction between phosphates and soil mineral surfaces, such as Fe- and Al-(oxyhydr)oxides, plays a crucial role in the P immobilization and thus its availability for plants. The reactions of phosphates with Fe-hydroxides and especially goethite have been studied extensively. But a molecular-level picture about the phosphate binding mechanism at the goethite-water interface is still lacking. Therefore, in the current contribution we have explored the molecular binding mechanism for the adsorbed phosphate at the goethite–water interface by performing sorption kinetics experiments for orthophosphate and characterizing the adsorbed species by FT-IR spectroscopy. In parallel, periodic DFT calculations have been performed to explore the interaction mechanism as well as to calculate the IR spectra for monodentate (M) and bidentate (B) orthophosphate complexes at two different goethite surface planes (010 and 100) in the presence of water. In general, our interaction energy results give evidence that the mono-protonated B phosphate complex is more favored to be formed at the goethite–water interface although the M motif could exist as a minor fraction. Moreover, it was found that water plays an important role in controlling the phosphate adsorption process at the goethite surfaces. The interfacial water molecules form H-bonds (HBs) with the phosphate as well as with the goethite surface atoms. Further, some water molecules form covalent bonds with goethite Fe atoms while others dissociate at the surface to protons and hydroxyl groups. The present theoretical assignment of IR spectra introduces a benchmark for characterizing experimental IR data for the adsorbed KH2PO4 species at the goethite–water interface. In particular, IR spectra of the mono-protonated (2O+1Fe) B complex at the 010 goethite surface plane and the M complex at the 100 goethite surface plane were found to be consistent with the experimental data. In order to explore the role of different abundancies of surface planes and binding motifs, IR spectra obtained from weighted averages have been analyzed. Results confirmed the above conclusions drawn from interaction energy calculations.</p></div></div></div>

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Infrared Spectroscopic Characterization of Phosphate Binding at the Goethite-Water InterfaceUntitled Item

10.26434/chemrxiv.7370048.v1 ◽

2018 ◽

Author(s):

Ashour Ahmed ◽

Stella Gypser ◽

Peter Leinweber ◽

Dirk Freese ◽

Oliver Kühn

Keyword(s):

Ir Spectra ◽

Interaction Energy ◽

Phosphate Adsorption ◽

Water Molecules ◽

Hydroxyl Groups ◽

Water Interface ◽

Binding Mechanism ◽

Phosphate Binding ◽

Covalent Bonds ◽

Surface Plane

<div><div><div><p>The interaction between phosphates and soil mineral surfaces, such as Fe- and Al-(oxyhydr)oxides, plays a crucial role in the P immobilization and thus its availability for plants. The reactions of phosphates with Fe-hydroxides and especially goethite have been studied extensively. But a molecular-level picture about the phosphate binding mechanism at the goethite-water interface is still lacking. Therefore, in the current contribution we have explored the molecular binding mechanism for the adsorbed phosphate at the goethite–water interface by performing sorption kinetics experiments for orthophosphate and characterizing the adsorbed species by FT-IR spectroscopy. In parallel, periodic DFT calculations have been performed to explore the interaction mechanism as well as to calculate the IR spectra for monodentate (M) and bidentate (B) orthophosphate complexes at two different goethite surface planes (010 and 100) in the presence of water. In general, our interaction energy results give evidence that the mono-protonated B phosphate complex is more favored to be formed at the goethite–water interface although the M motif could exist as a minor fraction. Moreover, it was found that water plays an important role in controlling the phosphate adsorption process at the goethite surfaces. The interfacial water molecules form H-bonds (HBs) with the phosphate as well as with the goethite surface atoms. Further, some water molecules form covalent bonds with goethite Fe atoms while others dissociate at the surface to protons and hydroxyl groups. The present theoretical assignment of IR spectra introduces a benchmark for characterizing experimental IR data for the adsorbed KH2PO4 species at the goethite–water interface. In particular, IR spectra of the mono-protonated (2O+1Fe) B complex at the 010 goethite surface plane and the M complex at the 100 goethite surface plane were found to be consistent with the experimental data. In order to explore the role of different abundancies of surface planes and binding motifs, IR spectra obtained from weighted averages have been analyzed. Results confirmed the above conclusions drawn from interaction energy calculations.</p></div></div></div>

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Surface loading effects on orthophosphate surface complexation at the goethite/water interface as examined by extended X-ray Absorption Fine Structure (EXAFS) spectroscopy

Journal of Colloid and Interface Science ◽

10.1016/j.jcis.2014.09.057 ◽

2015 ◽

Vol 437 ◽

pp. 297-303 ◽

Cited By ~ 46

Author(s):

Dalton Belchior Abdala ◽

Paul Andrew Northrup ◽

Yuji Arai ◽

Donald Lewis Sparks

Keyword(s):

Fine Structure ◽

Surface Complexation ◽

Exafs Spectroscopy ◽

Water Interface ◽

Surface Loading ◽

X Ray ◽

Absorption Fine ◽

Loading Effects ◽

X Ray Absorption

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Infrared Spectroscopic Characterization of Phosphate Binding at the Goethite-Water Interface

10.26434/chemrxiv.7370048.v2 ◽

2018 ◽

Author(s):

Ashour Ahmed ◽

Stella Gypser ◽

Peter Leinweber ◽

Dirk Freese ◽

Oliver Kühn

Keyword(s):

Ir Spectra ◽

Interaction Energy ◽

Phosphate Adsorption ◽

Water Molecules ◽

Hydroxyl Groups ◽

Water Interface ◽

Binding Mechanism ◽

Phosphate Binding ◽

Covalent Bonds ◽

Surface Plane

<div><div><div><p>The interaction between phosphates and soil mineral surfaces, such as Fe- and Al-(oxyhydr)oxides, plays a crucial role in the P immobilization and thus its availability for plants. The reactions of phosphates with Fe-hydroxides and especially goethite have been studied extensively. But a molecular-level picture about the phosphate binding mechanism at the goethite-water interface is still lacking. Therefore, in the current contribution we have explored the molecular binding mechanism for the adsorbed phosphate at the goethite–water interface by performing sorption kinetics experiments for orthophosphate and characterizing the adsorbed species by FT-IR spectroscopy. In parallel, periodic DFT calculations have been performed to explore the interaction mechanism as well as to calculate the IR spectra for monodentate (M) and bidentate (B) orthophosphate complexes at two different goethite surface planes (010 and 100) in the presence of water. In general, our interaction energy results give evidence that the mono-protonated B phosphate complex is more favored to be formed at the goethite–water interface although the M motif could exist as a minor fraction. Moreover, it was found that water plays an important role in controlling the phosphate adsorption process at the goethite surfaces. The interfacial water molecules form H-bonds (HBs) with the phosphate as well as with the goethite surface atoms. Further, some water molecules form covalent bonds with goethite Fe atoms while others dissociate at the surface to protons and hydroxyl groups. The present theoretical assignment of IR spectra introduces a benchmark for characterizing experimental IR data for the adsorbed KH2PO4 species at the goethite–water interface. In particular, IR spectra of the mono-protonated (2O+1Fe) B complex at the 010 goethite surface plane and the M complex at the 100 goethite surface plane were found to be consistent with the experimental data. In order to explore the role of different abundancies of surface planes and binding motifs, IR spectra obtained from weighted averages have been analyzed. Results confirmed the above conclusions drawn from interaction energy calculations.</p></div></div></div>

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Sampling and analysis of the air-water interface with SEM and EDS of microlayers

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100157000 ◽

1989 ◽

Vol 47 ◽

pp. 1004-1005

Author(s):

Randall W. Smith ◽

John Dash

Keyword(s):

Heavy Metals ◽

Surface Microlayer ◽

Surface Films ◽

Water Interface ◽

Physical Processes ◽

Infrared Spectroscopic Analysis ◽

Eds Analysis ◽

Air Water Interface ◽

Significant Area ◽

Bulk Chemical

The structure of the air-water interface forms a boundary layer that involves biological ,chemical geological and physical processes in its formation. Freshwater and sea surface microlayers form at the air-water interface and include a diverse assemblage of organic matter, detritus, microorganisms, plankton and heavy metals. The sampling of microlayers and the examination of components is presently a significant area of study because of the input of anthropogenic materials and their accumulation at the air-water interface. The neustonic organisms present in this environment may be sensitive to the toxic components of these inputs. Hardy reports that over 20 different methods have been developed for sampling of microlayers, primarily for bulk chemical analysis. We report here the examination of microlayer films for the documentation of structure and composition.Baier and Gucinski reported the use of Langmuir-Blogett films obtained on germanium prisms for infrared spectroscopic analysis (IR-ATR) of components. The sampling of microlayers has been done by collecting fi1ms on glass plates and teflon drums, We found that microlayers could be collected on 11 mm glass cover slips by pulling a Langmuir-Blogett film from a surface microlayer. Comparative collections were made on methylcel1ulose filter pads. The films could be air-dried or preserved in Lugol's Iodine Several slicks or surface films were sampled in September, 1987 in Chesapeake Bay, Maryland and in August, 1988 in Sequim Bay, Washington, For glass coverslips the films were air-dried, mounted on SEM pegs, ringed with colloidal silver, and sputter coated with Au-Pd, The Langmuir-Blogett film technique maintained the structure of the microlayer intact for examination, SEM observation and EDS analysis were then used to determine organisms and relative concentrations of heavy metals, using a Link AN 10000 EDS system with an ISI SS40 SEM unit. Typical heavy microlayer films are shown in Figure 3.

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