Natural occurrence of nanocrystalline Al-hydroxysulfates: Insights on formation, Al solubility control and As retention

Wanner, Christoph; Pöthig, Rosemarie; Carrero, Sergio; Fernandez-Martinez, Alejandro; Jäger, Christian; Furrer, Gerhard (2018). Natural occurrence of nanocrystalline Al-hydroxysulfates: Insights on formation, Al solubility control and As retention. Geochimica et cosmochimica acta, 238, pp. 252-269. Elsevier Science 10.1016/j.gca.2018.06.031

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Nanocrystalline basaluminite [Al4OH10(SO4)(H2O)3–5] and aggregation of the e-Keggin polyoxocation [Al12(AlO4)(OH)24(H2O)12]7+, referred to as Al13, have both been described to form in acid mine drainage environments. Although the chemical composition is quite similar, their crystalline varieties significantly differ, demonstrating that various types of Al-hydroxysulfates can form under similar conditions and that their respective formation is not fully understood yet. Here, we report the occurrence of nanocrystalline precipitates that form naturally in a small alpine catchment in Switzerland where an acidic mountainous stream (pH 4) is neutralized successively after mixing with several neutral tributaries. The stepwise
neutralization in conjunction with the large amount of precipitates provide an ideal setting for obtaining new insights into (i) the structure of naturally forming Al-hydroxysulfates, (ii) their formation mechanism, (iii) their role in controlling the solubility of Al, and (iv) their ability to lower the mobility of As. Synchrotron-based high-energy X-ray diffraction and subsequent pair distribution function analyses demonstrate that these precipitates are structurally identical to basaluminite samples obtained from acid mine drainage sites. In contrast, only minor amounts of tetrahedrally coordinated Al, as present in Al13, were identified by nuclear magnetic resonance spectroscopy. The precipitates are further characterized by elevated As concentrations up to 600 lg/g, whereas other heavy metals are at background concentrations only. Given the low As concentrations in the stream from which precipitation occurs (<0.03 mg/L), high As concentrations confirm that basaluminite serves as a highly efficient As sink, which is attributed to its high anion-exchange capacity. Chemical analysis of streamwater samples in combination with geochemical modeling show that precipitation occurs instantaneously upon mixing with neutral streams. Moreover, our data reveal that the precipitation of basaluminite exerts a strong solubility control on dissolved Al concentrations as manifested by the quasi-constant basaluminite ion activity product observed during neutralization from pH 5 to pH 5.9. We hypothesize that in our field system, high fluoride and sulfate concentrations on the order of 100 and 1–2 mg/L, respectively, as well as low water temperatures (<8 °C) favor the formation of basaluminite instead of Al13-bearing sulfate precipitates.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Institute of Geological Sciences
08 Faculty of Science > Institute of Geological Sciences > Rock-Water Interaction

UniBE Contributor:

Wanner, Christoph


500 Science > 550 Earth sciences & geology




Elsevier Science




Christoph Wanner

Date Deposited:

07 Aug 2018 10:07

Last Modified:

02 Oct 2020 02:30

Publisher DOI:





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