The iron phosphate mineral vivianite Fe(II)₃(PO₄)₂·8H₂O has emerged as a potential renewable P source. Although the importance of vivianite as a potential P sink in the global P cycle had previously been recognized, a mechanistic understanding of vivianite dissolution at the molecular level, critical to its potential application, is still elusive. The potential of vivianite as a P sink or source in natural or engineered systems is directly dependent on its dissolution kinetics under environmentally relevant conditions. To understand the thermodynamic and kinetic controls on bioavailability, the oxidation and dissolution processes of vivianite must be disentangled. In this study, we conducted controlled batch and flow-through experiments to quantitatively determine the dissolution rates and mechanisms of vivianite under anoxic conditions as a function of pH and temperature. Our results demonstrate that vivianite solubility and dissolution rates strongly decreased with increasing solution pH. Dissolution was nonstoichiometric at alkaline pH (>7). The rapid initial dissolution rate of vivianite is related to the solution saturation state, indicating a thermodynamic rather than a kinetic control. A defect-driven dissolution mechanism is proposed. Dissolution kinetics over pH 5-9 could be described with a rate law with a single rate constant and a reaction order of 0.61 with respect to {H⁺}: Rexp=36.0·e-1.41·pH·[1-e(0.2·ΔG/RT)]4.7 The activation energy of vivianite dissolution proved low (E_a = 20.3 kJ mol^-1), suggesting hydrogen bridge dissociation as the rate-determining step.

Microbial reduction of soluble hexavalent uranium (U(VI)) to sparingly soluble tetravalent uranium (U(IV)) has been explored as an in situ strategy to immobilize U. Organic ligands might pose a potential hindrance to the success of such remediation efforts. In the current study, a set of structurally diverse organic ligands were shown to enhance the dissolution of crystalline uraninite (UO₂) for a wide range of ligand concentrations under anoxic conditions at pH 7.0. Comparisons were made to ligand-induced U mobilization from noncrystalline U(IV). For both U phases, aqueous U concentrations remained low in the absence of organic ligands (500 times more U mobilization). This work shows the potential of numerous organic ligands present in the environment to mobilize both recalcitrant and labile U forms under anoxic conditions to hazardous levels and, in doing so, undermine the stability of immobilized U(IV) sources.

Anthropogenic and biogenic ligands may mobilize uranium (U) from tetravalent U (U(IV)) phases in the subsurface, especially from labile noncrystalline U(IV). The rate and extent of U(IV) mobilization are affected by geochemical processes. Competing metals and humic substances may play a decisive role in U mobilization by anthropogenic and biogenic ligands. A structurally diverse set of anthropogenic and biogenic ligands was selected for assessing the effect of the aforementioned processes on U mobilization from noncrystalline U(IV), including 2,6-pyridinedicarboxylic acid (DPA), citrate, N,N'-di(2-hydroxybenzyl)ethylene-diamine-N,N'-diacetic acid (HBED), and desferrioxamine B (DFOB). All experiments were performed under anoxic conditions at pH 7.0. The effect of competing metals (Ca, Fe(III), and Zn) on ligand-induced U mobilization depended on the particular metal-ligand combination ranging from nearly complete U mobilization inhibition (e.g., Ca-citrate) to no apparent inhibitory effects or acceleration of U mobilization (e.g., Fe(III)-citrate). Humic substances (Suwannee River humic acid and fulvic acid) were tested across a range of concentrations either separately or combined with the aforementioned ligands. Humic substances alone mobilized appreciable U and also enhanced U mobilization in the presence of anthropogenic or biogenic ligands. These findings illustrate the complex influence of competing metals and humic substances on U mobilization by anthropogenic and biogenic ligands in the environment.