Capturing the variable reactivity of goethites in surface complexation modeling by correlating model parameters with specific surface area

Han, Joonkyoung; Katz, Lynn E.

doi:10.1016/j.gca.2018.09.008

Capturing the variable reactivity of goethites in surface complexation modeling by correlating model parameters with specific surface area

Journal Article · Thu Oct 25 00:00:00 EDT 2018 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2018.09.008· OSTI ID:1609496

^[1]; Katz, Lynn E. ^[2]

University of Texas, Austin, TX (United States); DOE/OSTI
University of Texas, Austin, TX (United States)

The development of predictive tools capable of simulating adsorption behavior on goethite (α-FeOOH) surfaces has evolved over the past several decades. Recent research has focused on capturing the variation of surface reactivity and adsorption behavior for different preparations of synthetic goethites. Here in this research, an approach to estimate modeling parameters based on the specific surface area (SSA) of goethites was established and combined with a Charge Distribution – Multi-site Complexation (CD-MUSIC) surface complexation model. It was assumed that differences in crystal face contributions (CFC), inner-Helmholtz capacitances (C₁), and protonation constants of surface oxygens (pK_a’s) among different preparations of goethite contribute to the variation of surface reactivity. Thus, correlations of these modeling parameters with the SSA of a range of goethites were identified by comprehensively combining microscopic, macroscopic, and modeling data reported in literature along with adsorption data collected from macroscopic experiments conducted as part of this study. A CD-MUSIC model shown to be capable of accurately predicting adsorption for several metal ions and oxyanion selenite on a 62.9 m²/g SSA goethite served as the basis for the development of the adsorption modeling approach described in this paper. The predictive capability of the newly developed modeling approach was verified by comparing predictions of protons, SeO₃^2-, and Cd²⁺ adsorption with experimental data from goethites with SSAs ranging between 21.3 and 105 m²/g; in total, 40 adsorption data sets from 13 different goethites were used for model verification. The results from this study indicate that the variation of surface reactivity of goethites can be successfully simulated by changing CFC, C₁, and pK_2,singly (i.e. second protonation constant of singly-coordinated oxygens on the goethite surface) based on the SSA, which implies that self-consistent adsorption parameters can be applied to predict adsorption behavior over a range of goethite preparations.

View Accepted Manuscript (DOE)

Research Organization:: University of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-04ER15496

OSTI ID:: 1609496

Alternate ID(s):: OSTI ID: 1635888

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: C Vol. 244; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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58 GEOSCIENCES
CD-MUSIC model
adsorption
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Capturing the variable reactivity of goethites in surface complexation modeling by correlating model parameters with specific surface area

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