Generally all orogenic ultrapotassic rocks are formed after melting of metasomatized sub-continental lithospheric mantle via subducted crustal mica-bearing lithologies. Here we present another possible model, based on the study of the small Stomanovo ultrapotassic monzonite porphyry intrusion in the Central Rhodope Massif, Bulgaria. The monzonite dated at 30.50 ± 0.46 Ma is intruded into the voluminous Oligocene (31.63 ± 0.40 Ma) Bratsigovo–Dospat ignimbrite. The monzonite hosts both normally and reversely zoned clinopyroxene phenocrysts. The normally zoned clinopyroxene is characterized by gradually diminishing core-to-rim Mg no. (89–74), whereas the reversely zoned clinopyroxene has green Fe-rich cores (Mg no. 71–55) mantled by normally zoned clinopyroxene (Mg no. 87–74). Neither the core of the normally zoned clinopyroxene nor the Fe-rich green cores are in equilibrium with the host monzonite. This ultrapotassic monzonite shows more radiogenic Sr isotopes ((87Sr/86Sr)i = 0.71066) and ϵNd(t) = −7.8 to −8.0 that are distinct from the host ignimbrites with (87Sr/86Sr)i = 0.70917–0.70927 and ϵNd(t) = −4.6 to −6.5. The Sr–Nd isotopic data and the presence of copious zircon xenocrysts from the underlying metamorphic basement suggest extensive crustal assimilation. Our observations indicate that the Stomanovo ultrapotassic monzonite formed after extensive lower or middle crustal fractional crystallization from an evolved magma producing cumulates. The process was followed by hybridization with primitive mantle-derived magma and subsequent continuous crustal contamination. We suggest that instead of inheriting their high K2O and large-ion lithophile element enrichments from slab-derived/metasomatic fluids, the Stomanovo ultrapotassic monzonite may owe some of its unusually high alkalinity to the assimilation of potassium-rich phases from the Rhodope Massif basement rocks.

The western Rhodope massif contains a significant number of ‘battery grade’ Mn-oxide deposits which are best developed in the area near Kato Nevrokopi, Drama district, N. Greece. Economic Mn-oxide ore concentrations are confined to fault zones and related karsts in marbles. The mineralisation has formed by weathering of hydrothermal veins that were genetically related to Oligocene magmatism.

At Kato Nevrokopi, progressive and continuous weathering of primary, hydrothermal veins of rhodochrosite, mixed sulphide, quartz and ‘black calcite’ (calcite and todorokite) has resulted in the formation of the assemblage MnO-gel-(amorphous Mn-oxide)-todorokite-azurite-goethite-cerussite in the veins and the assemblage MnO-gel-nsutite-chalcophanite-birnessite-cryptomelane-pyrolusite and malachite and amorphous Fe-oxides in karstic cavities.

The fs2 and fO2 of the hydrothermal fluids increased with time. The breakdown of the hypogene Mn-carbonate was aided by the production of an acidic fluid due to the oxidation of sulphides. Precipitation of the supergene ores was caused by neutralisation of the fluids due to reaction with the host marble and to mixing of relatively reduced fluids with oxygenated surface water in a fluctuation water table regime. Zinc was also mobile during weathering and became concentrated in the intermediate Mn-oxides, effectively stabilising their structures. The mineral paragenesis records the progressive oxidation of the ore and the appearance of less hydrated Mn-oxides, low in alkalis and alkaline earths.