Ammonium-Bearing Fluorapophyllite-(K) in the Magnesian Skarns from Aleului Valley, Pietroasa, Romania

An ammonium-bearing fluorapophyllite-(K) occurs as a late hydrothermal product in the outer endoskarn zone from Aleului Valley (N 46°37′04″, E 22°35′22″), located at the contact of the granodiorite laccolith from Pietroasa, of Upper Cretaceous age, with Anisian dolostones. Associated minerals are wollastonite, K feldspar, diopside, fluorapatite, talc, and pectolite. The chemical structural formula is [K0.985Na0.012(NH4)0.076]Σ=1.073(Ca4.009Mn0.001Fe2+0.003Mg0.002Ba0.001)Σ=4.016(Si7.953Al0.047) O20.029[F0.899(OH)0.101]·8.059H2O. The structure was successfully refined as tetragonal, space group P4/mnc, with cell parameters of a = 8.9685(1) Å and c = 15.7885(5) Å. The indices of refraction are ω = 1.534(1) and ε = 1.536(1). The calculated density is Dx = 2.381 g/cm3, in good agreement with the measured density, Dm = 2.379(4) g/cm3. The thermal analysis shows that the mineral completely dehydrates at up to 450 °C (endothermic effects at 330, 371, and 448 °C) and loses ammonium at 634 °C. In the infrared spectra, the multiplicity of the bands assumed to be silicate modes (1ν1 + 3ν3 + 2ν2 + 3ν4) agrees with the reduction in the symmetry of the SiO44− ion from Td to Cδ. Fluorapophyllite-(K) from Aleului Valley is of late hydrothermal origin and crystallized from F-rich fluids originating from the granodiorite intrusion, which mobilized K, Ca, and Si from the pre-existing feldspar.