Cited by 283Adsorption and biosorption for pollutant removalHeavy metals in environmentX-ray Spectroscopy and Fluorescence Analysis

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The Use of XAFS to Distinguish between Inner- and Outer-Sphere Lead Adsorption Complexes on Montmorillonite

Strawn, Daniel G, Sparks, Donald L·1999·Journal of Colloid and Interface Science

DOI 10.1006/jcis.1999.6330

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Abstract

Adsorption mechanisms of Pb on montmorillonite were investigated by conducting equilibrium and X-ray absorption fine structure (XAFS) spectroscopy studies. Data from the batch equilibrium studies indicate that Pb could be adsorbing via two mechanisms, depending on ionic strength. At low ionic strength (I = 0.006 M) Pb adsorption is pH-independent: 97% of the available Pb was removed from solution at pH 4.42 and 100% at pH 8.0. This behavior is consistent with an outer-sphere complexation mechanism. At high ionic strength (I = 0.1 M) Pb adsorption is pH-dependent, suggesting inner-sphere complexation as the adsorption mechanism: 43% of the available Pb was removed from the solution at pH 4.11 and 98.9% at pH 7.83. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy results reveal that in the sample equilibrated at I = 0.006 M, pH 4.48-6.40 the local atomic structure (LAS) surrounding the adsorbed Pb is similar to the LAS surrounding Pb(2+) (aq), confirming that the adsorption mechanism is outer-sphere complexation. In the system equilibrated at I = 0.1 M, pH 6.77 the XANES and EXAFS results show that the LAS surrounding the adsorbed Pb atom is similar to the LAS surrounding reference compounds in which Pb is forming covalent bonds (Pb(4)(OH)(4+)(4) (aq) and a sample of gamma-Al(2)O(3) with Pb adsorbed via inner-sphere complexation). These similarities indicate that Pb is forming inner-sphere complexes on the montmorillonite at this ionic strength and pH. In samples equilibrated at I = 0.006 M, pH 6.77 and I = 0.1 M, pH 6.31 the XAFS results suggest that Pb is forming both inner- and outer-sphere adsorption complexes. This observation could not be distinguished by making macroscopic observations only. Thus, the results of this study reveal important information on Pb sorption behavior on clays and also provides insights into the use of XAFS to determine sorption mechanisms. Copyright 1999 Academic Press.

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Authors: Strawn, D. G., & Sparks, D. L.
Affiliations: University of Delaware (US)
Corresponding author: Strawn, Daniel G
ORCID: Strawn, Daniel G
Sparks, Donald L
Venue: Journal of Colloid and Interface Science
Publisher: Elsevier BV
Published: 1999-08
Volume: 216
Issue: 2
Pages: 257-269
ISSN: 0021-9797 (ISSN-L)
DOI: 10.1006/jcis.1999.6330
OpenAlex: W2151276692
Cited by: 283
References: 51
Citations by year: 2026: 7 · 2025: 4 · 2024: 9 · 2023: 5 · 2022: 10 · 2021: 8 · 2020: 11 · 2019: 11 · 2018: 21 · 2017: 6 · 2016: 16 · 2015: 12 · 2014: 15 · 2013: 7 · 2012: 11
FWCI: 15.50
Type: journal article
Language: en
Open access: closed
Licence: www.elsevier.com/tdm/userlicense/1.0/ (tdm)
www.elsevier.com/legal/tdmrep-license (tdm)
Locations: Journal of Colloid and Interface Science (publishedVersion)
PubMed (publishedVersion)
Funders: University of Delaware
Topics: Physical Sciences › Environmental Science › Water Science and Technology › Adsorption and biosorption for pollutant removal
Physical Sciences › Environmental Science › Pollution › Heavy metals in environment
Physical Sciences › Physics and Astronomy › Radiation › X-ray Spectroscopy and Fluorescence Analysis
Keywords: lead adsorption, montmorillonite, inner-sphere complexation, outer-sphere complexation, adsorption mechanism, ionic strength effects, pH dependence, clay mineral sorption, local atomic structure, X-ray absorption spectroscopy, XANES, EXAFS

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The Use of XAFS to Distinguish between Inner- and Outer-Sphere Lead Adsorption Complexes on Montmorillonite

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