Spatial and temporal association of As and Fe species on aquatic plant roots

The formation of an Fe(III) precipitate (plaque) on the surface of aquatic plant roots may provide a means of attenuation and external exclusion of metals. Presently, the mechanisms of metal(loid) sequestration at the root surface are unresolved. Accordingly, we investigated the mechanisms of Fe and As attenuation and association on the roots of two common aquatic plant species, Phalaris arundinacea (reed canarygrass) and Typha latifolia (cattail) using X-ray absorption spectroscopy and X-ray fluorescence microtomography. Iron plaque of both P. arundinacea and T. latifolia consist predominantly of hydrated iron oxides (ferrihydrite) with lesser amounts of goethite and minor levels of siderite. Typha latifolia, however, differs from P. arundinacea by having a significant contribution from lepidocrocite as well as a greater proportion of crystalline minerals. Coexistence of goethite and lepidocrocite suggests the presence of chemically diverse microenvironments at the root surface. Arsenic exists as a combination of two sorbed As species, being comprised predominantly of arsenate- (approximately 82%) with lesser amounts (approximately 18%) of As(III)-iron (hydr)oxide complexes. Furthermore, both spatial and temporal correlations between As and Fe on the root surfaces were observed. While the iron (hydr)oxide deposits form a continuous surficial rind around the root, As exists in isolated regions on the exterior and interior of the root. Root surface-associated As generally corresponds to regions of enhanced Fe levels and may therefore occur as a direct consequence of Fe phase heterogeneity and preferential As sorption reactions.