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•The black pigment of sturgeon roe (SRBP) was purified by sequential centrifugation.•Electron paramagnetic resonance allowed to identify SRBP as a eumelanin.•A specific eumelanin marker was detected in SRBP chemical degradation mixture.•This is the first clear-cut demonstration of the occurrence of melanin in a fish roe.•The presence of melanin was detected also in a caviar oil production by-product.
Reported herein is the purification of the pigment of black sturgeon caviar and its unambiguous identification as a typical eumelanin by means of chemical degradation coupled with electron paramagnetic resonance (EPR) evidence. HPLC and LC-MS analysis of oxidative degradation mixtures revealed the formation of pyrrole-2,3,5-tricarboxylic acid (PTCA), a specific marker of eumelanin pigments, in yields compatible with a 6.5% w/w pigment content. EPR spectral features and parameters were in close agreement with those reported for a typical natural eumelanin such as Sepia melanin from squid ink. The identification for the first time of eumelanin in a fish roe is expected to provide a novel molecular basis for the valorization of black caviar and production wastes thereof in food chemistry and diet.