Vázquez-Ortega, 2013

Dissertation/Thesis

Coupled Transport, Fractionation and Stabilization of Dissolved Organic Matter and Rare Earth Elements in the Critical Zone

Vázquez-Ortega A. (2013)
Disertation in Soil, Water & Environmental Science. University of Arizona, Tucson, Arizona, 201 pp  

Abstract

It is important to understand the processes that influence the critical zone (CZ) evolution to ensure its sustainability. This thesis reports on laboratory and field experiments designed to measure the behavior of biogenic and lithogenic chemical species and their interaction in the CZ from column to pedon to catchment scales. We postulated that interactions between organic matter and rock-derived metals drive coupled processes of carbon stabilization and chemical weathering and denudation in the Jemez River Basin Critical Zone Observatory (JRB-CZO). First, we observed that secondary mineral coatings (Al and Fe (oxy)hydroxides) on primary silicate surfaces play a major role in sequestering aromatic and "humified" dissolved organic matter (DOM) into sorbate form, significantly retarding their subsurface transport. Further, reinfusion to OM-reacted-porous-media of a different DOM source resulted in exchange reactions consistent with a zonal model of OM adsorption at mineral surfaces. This dissertation also aimed to examine the influence of water and DOM fluxes on the CZ weathering processes. Rare earth elements (REE) were selected because of their coherent trends in reactivity toward organic ligands common to soils. Specifically, trends in REE fractionation were explored for their utility to inform on biogeochemical weathering processes in forested terrain in the JRB-CZO. Mineral weathering mechanisms are expected to differentially influence REE release, fractionation, and transport and the relative importance of such processes should be reflected in REE signatures of bulk soil, pore and surface waters. Our studies showed: (1) REE depletion trends with depth in bulk soils are correlated with topographically-induced variation in water and dissolved organic carbon (DOC) flux (reflected in negative correlations between total water and C fluxes) and solid phase REE concentrations measured at the same depths; (2) REE and DOC concentrations in stream waters were strongly correlated during snowmelt periods of high discharge, consistent with REE complexation and mobilization in association with organic ligands during shallow subsurface flow; (3) preferential sequestration of Eu occurs during formation of secondary Mn(IV)-oxides, explaining patterns of Eu enrichment in bulk soils; and (4) the incremental increase in positive Ce-anomalies with depth in bulk soils are apparently controlled by adsorption/co-precipitation with secondary Fe-(oxy)hydroxide minerals.

Citation

Vázquez-Ortega A. (2013): Coupled Transport, Fractionation and Stabilization of Dissolved Organic Matter and Rare Earth Elements in the Critical Zone. Disertation in Soil, Water & Environmental Science. University of Arizona, Tucson, Arizona, 201 pp.

This Paper/Book acknowledges NSF CZO grant support.