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We investigated hellandite-group mineral phases from the Roman Region, alkali syenite ejecta, by multimethod analyses. They show a complex crystallisation history including co-precipitation of hellandite-(Ce) with brockite, resorption, sub-solidus substitution with mottanaite-(Ce), exsolution of perthite-like ferri-mottanaite-(Ce), overgrowth of an oscillatory-zoned euhedral shell of ferri-mottanaite-(Ce) and late, secondary precipitation of pyrochlore in the cribrose hellandite-(Ce) core. LREE/HREE crossover and a negative Eu anomaly in hellandite-group minerals follows <i>f</i>O₂ increase during magma cooling. The distinction among the hellandite-group minerals is based on the element distribution in the M1, M2, M3, M4 and T sites. Additional information on miscibility relationship among the hellandite <i>sensu strictu</i>, tadzhikite, mottanaite, ferri-mottanaite and ciprianiite endmembers derives from molar fraction calculation. We observed that change in composition of hellandite-group minerals mimic the ligands activity in carbothermal-hydrothermal fluids related to carbonatitic magmatism.