The valorization of onion skin wastes (OSW) through the extraction, identification, and quantification of phenolic compounds was studied in this work, using subcritical water in a semicontinuous extractor (2.5 mL/min; 105–180 °C; 5 MPa). The extraction of flavonoids resulted to be fast (<30 min) and temperature sensitive (maximum at 145 °C; total flavonoids, 27.4 ± 0.9 mg/g dry OSW (DOSW)). The experimental results were fitted to the Weibull model. The influence of the solvent properties on the flavonoids quantification was found to be critical. A precipitate was formed once the extracts cooled down. If removed, a significant fraction of the high temperature extracted flavonoids (as much as 71%, at 180 °C) was lost. Such a condition affected especially those compounds that show extremely low solubility in water at room temperature, whereas quercetin glycosylated derivatives were less affected by the polarity change of the medium induced by the temperature change. It was demonstrated that it is necessary to re-dissolve the subcritical water extracts by the addition of ethanol, which led to a medium with a polarity equivalent to that obtained with water at high temperature. At 145 °C, quercetin (15.4 ± 0.4 mg/g DOSW) and quercetin-4′-glucoside (8.4 ± 0.1 mg/g DOSW) accounted for the 90% of the total flavonoids identified. By recovering high added value bioactive compounds from OSW the principles of circular economy were fulfilled, providing a new use for this agricultural waste.

Brewer’s spent grain (BSG) was chemically characterized obtaining 52.1% of carbohydrates, 17.8% protein, 5.9% lipids, 13.5% insoluble lignin and 24.3% of water-soluble extractives. This work has been focused on the study of polyphenol extraction of the extractive fraction by water ultrasound-assisted extraction. Selected extraction conditions were 47 °C and 21.7 mL water/g_dry-BSG. The effect of solvent polarity on polyphenol extraction was studied by using ethanol aqueous mixtures, from 20% to 100% ethanol. The kinetics of polyphenol extraction have been fitted to the power law and the Weibull models yielding mean values of the root mean square deviation lower than 7.5%. Extracts have been characterized in terms of quantification of individual phenolic compounds by HPLC-DAD and protein and sugar soluble fractions (glucose, xylose, and arabinose). Polyphenol profile has been compared with other hydrolytic techniques, such as acid, basic and enzymatic hydrolysis, showing that ultrasound was not as effective as basic hydrolysis to release the phenolic acids esterified to the cell wall. A further centrifuge ultrafiltration concentration step was able to yield a retentate enriched in the protein fraction while individual phenolic compounds where mainly transferred to the permeate.

A systematic kinetic study was conducted in subcritical water medium in the temperature range from 150 to 200 °C for pure glucose, xylose, proline and aspartic acid as well as binary mixtures of sugars + amino acids to understand the reaction kinetics and interactions among biomass components and to discern the influence of Maillard reaction (MR) on the overall reaction kinetics. The main degradation products identified for glucose and xylose were the respective dehydration products, hydroxymethyl furfural and furfural, yielding an increasing solid residue with temperature (15.9 wt% at 200 °C) with an augmented heating value. The degradation of sugars and amino acids in binary systems was faster compared to pure compounds due to MR and the production of dehydration products was delayed when considering total sugar conversion. Higher relative reactivity in MR was observed for xylose over glucose showing also higher antioxidant activity.