The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (Agrostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] 4700 mg kg , [P2O5] 7000 mg kg , pH 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence ( -SXRF), and powder and laterally resolved extended X-ray absorption fine structure ( -EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of -EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra. In the untreated and unvegetated sediment, Zn was distributed as 50% (mole ratio of total Zn) sphalerite, 40% Zn-ferrihydrite, and 10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate ( 30 40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate ( 40–60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite ( 20–40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result 0016-7037/05 $30.00 .00 from heterogeneous precipitation on mineral surface. Copyright © 2005 Elsevier Ltd