Chronology of magmatism and mineralization in the Kassandra mining area, Greece: The potentials and limitations of dating hydrothermal illites

Various geochronological methods ( U Pb, Rb Sr, and K Ar) have been applied to constrain the timing of magmatism and polymetallic mineralization in the Kassandra mining district, northern Greece. These data provide the first geochronological evidence that porphyry copper mineralization, proximal copper skarns, and distal high-temperature carbonate-hosted Pb-Zn-Ag-Au replacement ores formed contemporaneously and probably within less than 2 million years. Polymetallic mineralization is temporally related to the emplacement of granodioritic to quartz dioritic porphyries (24-25 Ma) that postdate the largest post-tectonic intrusion of the area, the Stratoni granodiorite (27.9 ± 1.2 Ma). Andesite porphyry dikes, which crosscut the Pb-Zn-Ag-Au ores and associated alterations, represent the last magmatic phase in the area (19.1 ± 0.6 Ma) and did not contribute to metal concentration. The combination of K Ar, Rb Sr, and oxygen isotope studies of hydrothermal illite-rich clays and careful granulometric analysis constrains the reliability of these geochronological methods and emphasizes the importance of characterizing the post-formational history of the sample. We identify various processes which partly disturbed the K Ar and Rb Sr system of some clays, such as retrograde alteration by heated meteoric waters, superimposed supergene illitization, and resetting of both isotopic systems due to a hydrothermal overprint related to the intrusion of the andesite porphyry. Our data, however, suggest that diffusive Ar loss from the finest clay fractions (< 0.6 μm) during cooling of the hydrothermal system probably played the most important role in the disturbance of the K Ar system. Conventional K Ar ages of < 2 μm fractions from high-temperature illites (> 200°C), therefore, do not give reliable formation ages. The loss of Ar may be used to model the cooling history of the hydrothermal system applying the concept of closure temperatures (Dodson, 1973). ⁴⁰K-⁴⁰Ar_rad isochrons of natural, coarser grained (> 0.6 μm) size fractions of illites from single samples, even when slightly contaminated with feldspars, may yield meaningful ages either of the formation or of a reheating event. The Rb Sr dating of hydrothermal clays is sensitive to contamination by adsorbed strontium, which may not be cogenetic with the clay, as well as feldspars, which may not have been homogenized isotopically by the illitization process.