Goethite affects phytolith dissolution through clay particle aggregation and pH regulation

Abstract

Formed in plant tissues as fine silica particles, phytoliths are deposited within plant debris in soils where they can dissolve and feed silicon (Si) fluxes to the biosphere and hydrosphere. Yet, soil phytoliths can be protected from dissolution by entrapment in aggregates, and thus be withdrawn from the global silica cycle. Among clay-sized minerals interacting in stable aggregates, goethite and kaolinite are ubiquitous in soils. We analyzed the impact of goethite-mediated aggregation on the release of aqueous Si from phytoliths entrapped in microaggregates containing organic matter and kaolinite, with quartz and goethite at variable concentrations, simulating a soil sequence with increasing contents of clay and iron oxide, as it can commonly occur in terrestrial ecosystems. The microaggregates stored sizable amount of organic carbon, the release of which decreased with increasing goethite concentration. Aqueous Si was assessed through a kinetic extraction with dilute CaCl2, while pH, aluminum (Al) and germanium (Ge) concentrations were measured in the CaCl2 extracts. Our experimental data showed that phytoliths were the source of aqueous Si. They also showed that the process of phytolith dissolution prevailed over Si adsorption on goethite. As mediated by goethite, aggregation protected phytoliths from dissolution at goethite concentrations above 20 g kg−1. Increasing goethite concentration enhanced aggregation on the one hand, but increased pH from 5.5 to 7.5 on the other. Thus, while aggregation significantly reduced the release of aqueous Si by 1.7- to 3-fold at a given pH, the increase in pH enhanced it. Overall, at common soil solution pH (5–6), aggregation reduced Si release by 2–3 times. Thus, preservation of phytoliths in aggregates can be widespread in well-aerated soils and more effective than Si adsorption on secondary oxides in retaining Si.