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The agricultural processing industry usually generates a remarkable amount of by-products rich in bioactive compounds, which can be exploited for agri-food or nutraceutical applications. Pistachio’s hard shell is one of the major by-products from pistachio industrial processing. The aim of this work was the evaluation of pistachio shells as a potential source of natural antioxidants. We evaluated different extraction procedures by measuring total phenolic content, total flavonoid content and antioxidative activity (DPPH•, TEAC and ORAC). The microwave-assisted ethanol extract turned out to be the most promising and was fractionated by XAD-16 column chromatography, affording six fractions analyzed through HPLC/ESI-MS/MS and 1H-NMR to identify the main antioxidative constituents. Fractions Fr4–Fr6 demonstrated the highest antioxidant activity. Gallic acid and a monogalloylglusose isomer are the main phenolic constituents of Fr4. Both simple and complex phenolics, such as flavonoids and hydrolysable tannins, were identified in fractions Fr5 and Fr6; pentagalloylglucose and kaempferol, well-known for their antioxidant activity, are the most abundant constituents. The results highlighted that the proposed methodology can be an effective way to recover bioactive phenolic compounds from pistachio hard shell, making this by-product a promising source of compounds with potential applications in food and healthcare sectors.

Valorization of Agri-Food Waste from Pistachio Hard Shells: Extraction of Polyphenols as Natural Antioxidants