M.J. Trindade

FIRING TESTS ON CLAY-RICH RAW MATERIALS FROM THE ALGARVE BASIN (SOUTHERN PORTUGAL): STUDY OF MINERAL TRANSFORMATIONS WITH TEMPERATURE

In cases where the provenance of raw materials used in the manufacture of local archeological ceramics is of interest, a detailed study of thermal transformations of minerals may be useful. The purpose of this study was to measure mineralogical transformations of different types of clays obtained during experimental firing runs, carried out at different temperatures, with the main goal of establishing Algarve reference groups based on the composition of raw material and high-temperature mineralogy, which may be compared with ceramics in studies of provenance. Eleven samples of clay-rich raw materials from the Algarve Basin (southern Portugal) were fired to temperatures ranging from 300 to 1100°C in increments of 100°C under oxidizing conditions. These were chosen to have variable chemical and mineralogical compositions, representing the main compositional range of the clay deposits from the region. Mineralogical and geochemical characterizations of the original clays were carried out by X-ray diffraction (XRD) and X-ray fluorescence (XRF), respectively. Mineral transformations on the fired products were also studied by XRD.Three groups of clays were distinguished according to the type of neoformed high-temperature minerals: (1) non-calcareous clays; (2) clays containing calcite as the only carbonate; and (3) clays with dolomite or dolomite + calcite. Firing of non-calcareous clays produced mullite at 1100–1200°C. Gehlenite and wollastonite formed by firing calcite-rich clays above 900°C, accompanied by anorthite or larnite in samples with small or large calcite contents, respectively. Firing of dolomite-rich clays at temperatures >900°C yielded a member of the gehlenite-åkermanite group and diopside. Anorthite, enstatite, periclase, forsterite, and monticellite may also form in the firing products.

Geochemistry and Mineralogy of Clays from the Algarve Basin, Portugal: A Multivariate Approach to Palaeoenvironmental Investigations

Lower Cretaceous and Triassic-Hettangian clays from the Algarve Basin (South Portugal) were deposited in distinct environments during basin subsidence due to Pangea break up. The mineralogy, geochemistry and granulometry of 45 samples of both clay groups were studied, using X-ray diffraction, instrumental neutron activation analysis, X-ray fluorescence and laser diffractometry by attenuation of X-rays. Multivariate statistical techniques (principal component analysis and K-means clustering), after scandium normalization of chemical contents, were used to study simultaneously all data, enabling to distinguish the different clay types by establishing the best discriminatory parameters: high contents (in decreased order) of kaolinite, quartz, Chemical Index of Alteration (CIA), Ti, goethite, Hf, Si, > 63 μm fraction and Zr, characterize the group of clays from Cretaceous; while high contents of hematite, Mg, mobile elements (K, Cs and P), illite, Ca, phyllosilicates in general, Mn and dolomite, are associated to Triassic-Hettangian clays. This approach revealed useful to facilitate the integration of all data, as was possible to confront the geochemistry with the mineralogy, enabling the best palaeoenvironmental interpretations. In fact, the clay mineral assemblage is significantly influenced by the domi- nant weathering process and provides information on changes in aridity/humidity patterns.