Sustainable Extraction of Flavonoids from Citrus Waste: A Fast and Simple Approach with UHPLC-PDA ESI-MS Characterization

Citrus fruit processing, mainly for fresh juice production in the food industry, generates significant amounts of residues and by-products enriched with bioactive components. Peels are the primary waste fraction of citrus fruits, along with discarded pulp and seeds. This study aimed to identify the most fast and sustainable extraction process for flavonoids on a laboratory scale by varying the solvent and extraction methodology, and comparing the yields in order to evaluate their influence on total and individual flavonoid content. A chromatographic analysis was also performed using ultrahigh-performance liquid chromatography (UHPLC) with a 10 min run time. Our focus was on selecting the most user-friendly and cost-effective methodology. Ultrasound- and microwave-assisted extraction equipment were used with green solvents (water and ethanol) and compared for their efficiency in recovering flavonoid compounds from a mixture of peel and pulp. For this study, two widely cultivated Mediterranean citrus varieties were selected: ‘Marsh’ seedless grapefruits (Citrus paradisi Macf.) and ‘Comun’ mandarins (C. deliciosa Ten.). Lab-scale extraction results showed that ultrasound-assisted extraction with a simple ultrasonic bath, using an ethanol–water mixture provided the highest total flavonoid recovery and improved the extraction of key flavanones such as hesperidin, narirutin, and naringin. All ethanol–water mixtures tested (1:1, 7:3, and 3:7) yielded higher flavonoid levels in grapefruit (approximately 2500 mg/100 g DW) and mandarin (approximately 1200 mg/100 g DW) wastes compared with water or ethanol alone. This method offers a scalable and green strategy for valorizing citrus residues.