K-Ar, δ18O and REE constraints on the genesis of ammonium illite from the Harghita Bãi hydrothermal system, Romania

Abstract

AbstractAmmonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.