Transport of chloride and deuterated water in peat: The role of anion exclusion, diffusion, and anion adsorption in a dual porosity organic media
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Date
2019-08
Authors
McCarter, Colin
Rezanezhad, Fereidoun
Gharedaghloo, Behrad
Price, Jonathan S.
Van Cappellen, P.
Journal Title
Journal ISSN
Volume Title
Publisher
Elsevier
Abstract
The dual-porosity structure of peat and the extremely high organic matter content give rise to a complex medium that typically generates prolonged tailing and early 50% concentration breakthrough in the breakthrough curves (BTCs) of chloride (Cl−) and other anions. Untangling whether these observations are due to rate-limited (physical) diffusion into inactive pores, (chemical) adsorption or anion exclusion remains a critical question in peat hydrogeochemistry. This study aimed to elucidate whether Cl− is truly conservative in peat, as usually assumed, and whether the prolonged tailing and early 50% concentration breakthrough of Cl− observed is due to diffusion, adsorption, anion exclusion or a combination of all three. The mobile-immobile (MiM) dual-porosity model was fit to BTCs of Cl− and deuterated water measured on undisturbed cores of the same peat soils, and equilibrium Cl− adsorption batch experiments were conducted. Adsorption of Cl− to undecomposed and decomposed peat samples in batch experiments followed Freundlich isotherms but did not exhibit any trends with the degree of peat decomposition and sorption became negligible below aqueous Cl− concentrations of ~310 mg L−1. The dispersivity determined by fitting the Cl− BTCs whether assuming adsorption or no adsorption were significantly different than determined by the deuterated water (p < .0001). However, no statistical differences in dispersivity (p = .27) or immobile water content (p = .97) was observed between deuterated water and Cl− when accounting for anion exclusion. A higher degree of decomposition significantly increased anion exclusion (p < .0001) but did not influence the diffusion of either tracer into the immobile porosity. Contrary to previous assumptions, Cl− is not truly conservative in peat due to anion exclusion, and adsorption at higher aqueous concentrations, but the overall effect of anion exclusion on transport is likely minimal.
Description
The final publication is available at Elsevier via https://doi.org/10.1016/j.jconhyd.2019.103497. © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license
http://creativecommons.org/licenses/by-nc-nd/4.0/
Keywords
conservative tracer, breakthrough curve, equilibrium adsorption, pore structure, solute transport