The carbonate-dominated Mesozoic sequence of the Transdanubian Mountain Range contains Triassic, uranium-enriched phosphorite layers and Cretaceous,REE-enriched nodular phosphorite. Detailed investigation of these deposits may have an economic benefit because of their large U andREEcontents. The dominant minerals in the Triassic phosphorite are carbonate-bearing fluorapatite (CFA) and calcite. According to the electron-probe microanalysis (EPMA) the U is mainly associated with the CFA crystals. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurement shows that CFA contains 137–612 ppm U and 113–261 ppm totalREE + Y. The LA-ICP-MS U-Pb age of the uppermost phosphorite horizon is 237 ± 11 Ma, which conforms with the stratigraphic age of the host limestone.The Cretaceous nodular phosphorite occurs on the base of an Aptian crinoid-bearing limestone mostly in the form of encrustations around bio- and silicic-clasts, but the clasts also contain phosphorite. The main minerals in these crusts are CFA, calcite, quartz, glauconite and Fe-oxide-hydroxides. Based on EPMA theREEenrichment is related to CFA and LA-ICP-MS measurements show that it contains 748–2953 ppm totalREE + Y.The redox-sensitive proxies and the shape of NASC normalizedREEpatterns indicate that both phosphorites formed in anoxic environments. There are significant differences between these deposits such as appearance, rock-forming minerals, and U andREEcontents which indicate differences in their sedimentary environments. The present results suggest that the Triassic phosphorite was formed by inorganic precipitation in a reducing environment close to sea-mounts. The Cretaceous occurrence resulted from a concentric growth mechanism in cold, ascending seawater at the continental margin environment during the anoxic Selli Event (OAE 1a) and/or Paquier Episode (OAE 1b). The critical raw material contents were derived from other sources.
Quartz from the stockwork zone of various Cyprus type volcanogenic massive sulfide deposits (Boccassuolo, Reppia, Campegli, Bargone and Vigonzano) from the unmetamorphosed, Jurassic Northern Apennine ophiolites was studied in order to provide details on the submarine hydrothermal conditions and the characteristics for ore formation. Our detailed SEM-CL investigation of quartz contributed to a robust characterization and interpretation of primary fluid inclusions and microthermometry data. SEM-CL imaging was also useful for reconstructing the consecutive steps of quartz precipitation. The determination of trace element contents according to growth zoning in quartz by LA-ICP-MS constrained the compositional variations of parent fluids during the hydrothermal activity. A continuously cooling fluid regime characterized each studied volcanogenic massive sulfide (VMS) occurrence although the minimum formation temperatures were different (Bargone: 110–270 °C; Boccassuolo: 60–360 °C; Campegli: 110–225 °C; Reppia: 50–205 °C; Vigonzano: 260–330 °C), the range of temperature most probably depends on the original position of sampling in relation to the centers of the hydrothermal systems. Compositional changes are reflected by variations in the methane content (0.13–0.33 mol/kg) and salinity (2.6–9.3 NaCl equiv. wt. %) in the fluid inclusions of quartz and calcite as well as a changeable Al content (11–1526 ppm) in quartz. This study demonstrates that the combined use of SEM-CL imaging and LA-ICP-MS analyses, coupled with fluid inclusion microthermometry, can constrain the different fluid conditions of ore forming and the barren stages of evolving submarine hydrothermal systems.
The middle Anisian extensional tectonics of the Neotethyan realm developed a small, isolated carbonate platform in the middle part of the Balaton Highland (western Hungary), resulted in the deposition of uranium-bearing seamount phosphorite on the top of the drowned platform and produced some epigenetic fluorite veins in the Middle Triassic sequence. The stable C-O isotope data of carbonates are shifted from the typical Triassic carbonate ranges, confirming the epigenetic-hydrothermal origin of veining. Primary fluid inclusions in fluorite indicate that these veins were formed from low temperature (85–169 °C) and high salinity NaCl + CaCl2 + H2O type (apparent total salinity: 15.91–22.46 NaCl wt%) hydrothermal fluids, similar to parent fluids of the Alpine-type Pb-Zn deposits. These findings indicate that the Triassic regional fluid circulation systems in the Alpine platform carbonates also affected the area of the Balaton Highland. This is also in agreement with the previously established palinspatic tectonic reconstructions indicating that the Triassic carbonate and basement units in the Balaton Highland area were a part of the Southern Alpine. Similar fluorite veining in phosphorite deposits is also known in the Southern Alpine areas (e.g., Monte San Giorgi, Italy). Raman spectroscopic analyses detected H2 gas in the vapor phase of the fluid inclusions and a defect-rich fluorite structure in violet to black colored growth zones. This unique phenomenon is assumed to be the result of interaction between the uranium-rich phosphorite and the parent fluids of the epigenetic fluorite veins.
The Jurassic pillow basalt blocks in the Szarvaskő Unit in the SW-Bükk Mountains are incorporated into an accretionary mélange of Cretaceous age which had been displaced from the Dinarides to NE-Hungary during the Alpine-Carpathian collision. The pillow basalt series is a part of an incomplete remnant of an ophiolite-like sequence from which ultramafic units and sheeted dikes are almost completely absent. At the studied Egerbakta quarry, closely packed pillow, pillow fragmented hyaloclastite breccia and peperitic facies of submarine basaltic volcanism were recognized. Peperitic facies was formed by local admixture of unconsolidated siliciclastic sediment into the basaltic lava. Basaltic pillows contains short and thin prehnite-chlorite-carbonate-quartz veins formed during the interaction of seawater with the cooling lava, as well as cross-cutting datolite-prehnite-quartzchlorite-albite bearing veins. Calcite in the short cooling cracks crystallised from upheated seawater at around 160°C temperature and 0.5–0.6 kbar pressure (water depth of about 5–6 km). Datolite precipitations in veins can be classified into at least three different textural-morphological types but all of them contain methane bearing primary fluid inclusion assemblages, with variable methane/water ratios, suggesting an inhomogeneous entrapment from a heterogeneous aqueous-carbonic fluid. End member primary fluid inclusions contain aqueous liquid with methane rich vapour phase and apparently methane only inclusions characterized by liquid phase on room temperature. A combination of results from fluid inclusion microthermometry, Raman spectroscopy (used not only for phase identification but also for determination of salinities) and temperatures calculated from chlorite compositions, show that the precipitation of datolite had taken place from low salinity (0.2–2 NaCl equiv. mass%) aqueous-methane fluids under increasing temperature and pressure (from 160 to 210°C, and from 0.6 to 1.1 kbar) conditions. The elevated pressures and temperatures in comparison to the submarine hydrothermal processes suggest that the datolite bearing mineral parageneses had been formed during the progression of Alpine very low grade metamorphic processes.