Thermodynamic analysis of primary and secondary mineral stability in melilite-nephelinite tuff with Australopithecus Afarensis footprints (Laetoli, Tanzania)

The Laetoli area in northern Tanzania is an important palaeo-anthropological site, where the oldest footprints of Australopithecus afarensis reside. Aeolian tuffs are the major rock type at Laetoli and they are divided into Lower and Upper Laetolil Beds that were deposited at an interval of 4.36 and 3.63 million years. The Upper Laetolil Beds contain eight layers of air-fall tuffs known as marker tuffs. The Australopithecus afarensis footprints are observed on the surface of the white tuff, which is a part of the Upper Laetolil marker tuff 7, also known as the “Footprint Tuff.” The interpolated age of the marker tuff 7 is 3.66 million years. Two mineral assemblages are distinguished in the Upper Laetolil marker tuffs. The first assemblage consists of primary tuff minerals and includes clinopyroxene (diopside, augite, aegirine-augite), nepheline, melilite (åkermanite and alumoåkermanite), garnet (andradite and schorlomite), magnetite, and others. The second mineral assemblage consists of secondary minerals, montmorillonite, calcite, and phillipsite. They were formed during replacement of the primary minerals, volcanic glass, and ash cementation. Thermodynamic calculations show that the major primary tuff minerals (melilite and nepheline) are stable at variable sodium activity and pH values. Replacement of melilite and nepheline by montmorillonite is caused by a decrease of sodium activity in slightly alkaline, neutral and acidic conditions (рН < 10). Montmorillonite is not present in the altered nephelinitic tuff of the Sadiman volcano (which is considered as a source of the Laetolil Beds) where kaolinite is the major secondary mineral. This is explained by the difference in H2O fugacity with higher lgfH2O values in Sadiman and lower values in Laetoli. Relationships between primary and secondary tuffs minerals on the lgaHCO3 vs pH plot suggest mineral transformation within the Laetolil Beds in slightly acid and neutral conditions (рН = 5–7) compared with more alkaline conditions at Sadiman (рН > 10).This study was supported by the Ngorongoro Conservation Area Authorities (Tanzania), Russian Foundation for Basic Research (grant 18-05-00835) and The Natural History Museum (London). Scientific research was performed at the Centers for X-ray Diffraction Methods and Geomodel of the Research Park of St Petersburg State University