Surface complexation model for strontium sorption to amorphous silica and goethite

Susan A Carroll,Peggy A O'Day,Louise J Criscenti,Sarah K Roberts

doi:10.1186/1467-4866-9-2

Abstract

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface complexation database to estimate alkaline earth sorption in the environment.

Highlights

Ion sorption to mineral and amorphous solids has long been recognized as a process that controls the composition of trace elements in water
Databases tend to adopt surface complexation models that account for surface charge if only one solid is available for uptake [2] and non-electrostatic models that ignore surface charge if multiple solids are available for uptake [3,4,5]
We showed that rapid quenching of sorption samples for data collection at low temperature does not appear to introduce any new features into extended X-ray absorption fine structure (EXAFS) spectra when compared with room temperature spectra

Summary

Introduction

Ion sorption to mineral and amorphous solids has long been recognized as a process that controls the composition of trace elements in water. Efforts to describe sorption in complex geological settings has evolved from a purely empirical approach in which distribution coefficients (Kd) are a measure of the total amount of specific ion between the solid and aqueous phases for a complex solution and solid matrix specific to a contaminated site This approach provides a direct measure of the ability of the solid matrix to sequester the contaminant from a specific solution, its empirical nature does not allow it to be applied outside of the specific parameters of the contaminated site. Another approach measures thermodynamic surface complexation constants which describe sorption as a series of specific reactions between dissolved ions and surface sites. Databases tend to adopt surface complexation models that account for surface charge if only one solid is available for uptake [2] and non-electrostatic models that ignore surface charge if multiple solids are available for uptake [3,4,5]

Methods

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Discussion

Conclusion