Sustainable recovery of phenolic antioxidants from real olive vegetation water with natural hydrophobic eutectic solvents and terpenoids.

Olive oil production leads to the generation of olive mill wastewater (OMWW). Due to the presence of phenolic compounds, they are difficult to process, but they represent a source of high-added value chemicals since they have antioxidant and therapeutic properties. This work has studied the extraction of phenolic compounds from a type of OMWW, olive vegetation water, which presents these compounds in a more diluted dosage than in other studied to date, to revalue this waste stream. A real olive vegetation water from a Spanish olive oil producer was used, and liquid-liquid extraction was applied. Terpenoids and terpene-based hydrophobic eutectic solvents were systematically used to extract phenolic compounds following the concentrations of tyrosol, catechol, caffeic acid, and total phenolic content. By molecular simulation with the COSMO-RS method, 4 terpenoids, and 2 eutectic solvents were selected and compared with 2 conventional solvents. The Solvent/Feed ratio in the extraction of phenolic compounds was studied, showing that the solvents with the highest extraction results were geraniol, eucalyptol, and eutectic solvent menthol + camphor, which outperformed conventional solvents methyl isobutyl ketone and diisopropyl ether. Menthol + camphor gave total phenol extraction yields of 88.73% at a Solvent/Feed ratio in volume of 0.50, surpassing all solvents tested. A solvent reuse and regeneration process was applied by back-extraction of the 4 solvents: FTIR results showed the stability of the solvents while maintaining yields in the solvent reuse process. The phenolic compounds could be concentrated in the alkaline phase to factors up to 49.3 to the initial concentration in olive vegetation water. The alkaline phases were neutralized to obtain a precipitate with a caffeic acid content of up to 26 % wt%, and a tyrosol-rich supernatant with a concentration of up to 6.54 g/L. This work proposes a process using natural solvents to extract phenolic compounds from olive vegetation water.

Enhanced removal of neonicotinoid pesticides present in the Decision 2018/840/EU by new sewage sludge-based carbon materials.

Due to the increasingly strict legislation about the disposal of sewage sludge, it is necessary to find sustainable solutions to manage this waste at low-cost conditions. In addition, priority contaminants are now attracting much attention since they are usually detected in WWTP effluents. In this work, five sludge have been used as precursors for the synthesis of activated carbons subsequently tested in the removal by adsorption of three neonicotinoid pesticides listed in the EU Watch List: acetamiprid (ACT), thiamethoxam (THM), and imidacloprid (IMD). Generally, the activated carbons were prepared by chemical activation using ZnCl2 as an activating agent and then the resulting materials were pyrolyzed at 800 °C for 2 h. The synthesized activated carbons showed different textural properties; thus, the best adsorption results were found for AC-Industrial activated carbon, obtained from an industrial origin sewage sludge, with high equilibrium adsorption capacities (qe = 104.2, 137.0, and 119.9 mg g-1), for ACT, THM, and IMD, respectively. Furthermore, it was elucidated that the use of CO2 in the synthesis generated an opening, followed by widening, of the narrowest microporosity, increasing the specific surface area of the carbon materials. The kinetic and isotherm adsorption experimental data were obtained for each of the pesticide-activated carbon systems; thus, the kinetic curves were well-fitted to the pseudo-second-order kinetic model, as well as, Freundlich and Guggenheim-Anderson-de Boer (GAB) empirical models were used for the fitting of the equilibrium adsorption isotherms, finding that GAB model best fitted the experimental data. Additionally, the regeneration of the activated carbons using methanol as a regenerating agent and the single and simultaneous adsorption of a hospital wastewater effluent, fortified with the three studied pesticides have been explored.

Magnetic Fe3O4/multi-walled carbon nanotubes materials for a highly efficient depletion of diclofenac by catalytic wet peroxideoxidation.

The aim of this work is to synthesize a magnetic magnetite/multi-walled carbon nanotube (Fe3O4/MWCNT) catalyst by a method combining co-precipitation and hydrothermal treatments for the efficient removal of diclofenac (DCF) by catalytic wet peroxide oxidation (CWPO). The support (MWCNTs) shows a moderate-large surface area and good adsorption capacity, leading to the improvement of the magnetite (Fe3O4) dispersion on its surface. The response surface methodology (RSM) was applied in order to find out the effect of the reaction parameters on DCF removal, allowing to establish the optimum operating conditions (T = 60 °C, [H2O2]0 = 2.7 mM, [catalyst] = 1.0 g L-1). The optimum CWPO experiment showed an outstanding catalytic activity at non-modified pH solution (6.7), obtaining a 95% of DCF removal after 3 h reaction time; this high efficiency can be attributed to the synergistic effect of the iron-based catalyst with the high quantity of •OH radicals generated on the surface of the catalyst. In addition, the Fe3O4/MWCNT material exhibited good reusability along three consecutive reaction cycles, finding a pollutant removal close to 95% in each cycle of 3 h reaction time. Additionally, a degradation mechanism pathway was proposed for the removal of DCF by CWPO. The versatility of the material was finally demonstrated in the treatment of different environmentally relevant aqueous matrices (a wastewater treatment plant effluent, surface water, and hospital wastewater), obtaining an effective reduction in the ecotoxicity values.