Aluminum coprecipitates with Fe (hydr)oxides: Does isomorphous substitution of Al³⁺ for Fe³⁺ in goethite occur?

• Published in: Geochimica et cosmochimica acta Vol. 75; no. 16; pp. 4667 - 4683
• Main Authors: Bazilevskaya, Ekaterina, Archibald, Douglas D, Aryanpour, Masoud, Kubicki, James D, Martínez, Carmen Enid
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 15-08-2011
• Subjects: aluminum; coprecipitation; ferrihydrite; gibbsite; goethite; hematite; hydrolysis; infrared spectroscopy; iron; oxides; X-ray diffraction
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/j.gca.2011.05.041

Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe–Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with ⩽20mol% Al, and of ferrihydrite and gibbsite in initial suspensions with ⩾25mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with ⩽25mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with ⩾30mol% Al (at pH ∼2.25 for Fe³⁺ and at pH ∼4 for Al³⁺), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlikely at ⩾8mol% Al substitution.