Biogenic dissolution of a soil cerium-phosphate mineral

The productivity of many terrestrial ecosystems is controlled or limited by phosphorus bioavailability. Within these ecosystems, nearly all of the bioavailable phosphate is ultimately derived via the weathering of apatite [Ca-5(PO4)(3) (OH,F,Cl)]. Highly insoluble lanthanide phosphate minerals form during apatite weathering and are important secondary phosphorus repositories in soils. Prior studies indicate that these phases can be dissolved via biologically mediated pathways. However, mechanistic understanding of biotically- and abiotically-mediated dissolution mechanisms is lacking. We tested the impact of biogenic substances ubiquitous in soils, namely oxalate, ascorbate, citrate, and humic acids, as well as the commercial chelating agent EDTA, on the dissolution of rhabdophane [CePO4 center dot H2O], a representative of a large class of soil phosphate minerals. We show that these compounds can facilitate the dissolution of rhabdophane at 3 < pH < 8 and result in the non-stoichiometric release of Ce3+ ((aq)) and PO4(aq)3-.Release of Ce-(aq)(3+) and PO4(aq)3- is a function of ligand type and pH, except for EDTA, whose impact is not pH dependent. With the exception of oxalate reacted at pH 3, the effectiveness of EDTA surpasses that of any other ligand in releasing Ce3+ from the CePO4 center dot H2O surface. Speciation calculations are consistent with miner:3 dissolution through formation of aqueous Ce3+-EDTA complexes. Mineral dissolution in the presence of oxalate at low pH likely involves concomitant proton and ligand attack of the mineral surface. In these experiments, a fast release of Ce-(aq)(3+) is followed by a sharp decrease in solution Ce-(aq)(3+) concentration, consistent with precipitation of a Ce phase. In the presence of ligands other than EDTA and oxalate, no accumulation of Ce3+ occurred in solution due to the precipitation of CeO2(s) on the rhabdophane surface. CeO2 may be responsible for the observed oxidation of ascorbate, as it has been reported for catechol (Cervini-Silva and Banfield, 2003). Our results indicate that rhabdophane dissolution is controlled either by strong ligand complexation of Ce-(aq)(3+) or by sequestration of Ce4+ ions as CeO2 effectively increasing the mineral solubility. This work shows that interactions between organics, CePO4 center dot H2O, and CeO2(s) imply potentially important linkages among the cerium, phosphorus, and organic carbon cycles in soil.