Efflorescences in the geothermal field of SE Melos, Greece, contain significant amounts of hydrated Al sulphate, alunogen, which could represent the Melian alumen exploited in Roman times and commended by Pliny. The efflorescences at subaerial fumaroles are explained as follows: Sulphur crystallizes on oxidation of H2S emanating from depth. Weathering produces sulphuric acid enhancing groundwater alteration of volcanic rocks. The high geothermal gradient and arid climate stimulate efflorescences. Salts are recycled during wet and dry weather leading to Al-enrichment on loss of Fe(II,III) and other cations. δ34S‰ V-CDT values for sulphur in fumarole sublimates, solfatara soils and ‘veins’ range from —0.3 to 6.4‰, mean 3.8‰ (n = 8) while Al, Ca and Mg-sulphates in diverse settings range from —4.1 to 6.8‰ (n = 16). The values for sulphur indicate that the initial H2S had an igneous source and the signature is largely inherited by the sulphates.

This study aims to underpin research into the exploitation of industrial minerals in the Roman period. When searching for early alumen workings, areas with evidence of acid sulphate alteration (white rocks) and sulphurous fumarole activity should be investigated.

Alunogen and meta-alunogen are the dominant phases present in transient sulphate efflorescences that are the latest products of the alteration of ignimbrite country rocks in the long-lived Te Kopia geothermal field. Meta-alunogen pseudomorphs alunogen and both species occur as white, fibrous, tangled masses, as prismatic, parallel growths, and as thin, platy, crystals, 8–15 μm across, that coalesce in an open cellular network. Small (<2 mm diam.) spherical aggregates of radiating, acicular halotrichite (Fe0.51Mg0.49Al2(SO4)4.22H2O), potash alum, mirabilite, melanterite and tschermigite are present locally. The cations needed to form these minerals derive from the host rocks with the exception of sulphur and ammonia that come from H2S and NH3 gases ascending with steam. The particular efflorescence assemblage reflects the prevailing conditions and ionic activities of a local micro-environment. Kaolinite formed by acid sulphate alteration is now being altered by steam to yield alunogen. In turn, alunogen can react with silica, or co-dissociate with silicic acid, to form kaolinite. The alternating dissolution and reprecipitation of kaolinite and alunogen moves aluminium in and through the surficial environment at Te Kopia.