Treatment of Winery Wastewater by Combined Almond Skin Coagulant and Sulfate Radicals: Assessment of HSO5- Activators.

The large production of wine and almonds leads to the generation of sub-products, such as winery wastewater (WW) and almond skin. WW is characterized by its high content of recalcitrant organic matter (biodegradability index < 0.30). Therefore, the aim of this work was to (1) apply the coagulation-flocculation-decantation (CFD) process with an organic coagulant based on almond skin extract (ASE), (2) treat the organic recalcitrant matter through sulfate radical advanced oxidation processes (SR-AOPs) and (3) evaluate the efficiency of combined CFD with UV-A, UV-C and ultrasound (US) reactors. The CFD process was applied with variation in the ASE concentration vs. pH, with results showing a chemical oxygen demand (COD) removal of 61.2% (0.5 g/L ASE, pH = 3.0). After CFD, the germination index (GI) of cucumber and corn seeds was ≥80%; thus, the sludge can be recycled as fertilizer. The SR-AOP initial conditions were achieved by the application of a Box-Behnken response surface methodology, which described the relationship between three independent variables (peroxymonosulfate (PMS) concentration, cobalt (Co2+) concentration and UV-A radiation intensity). Afterwards, the SR-AOPs were optimized by varying the pH, temperature, catalyst type and reagent addition manner. With the application of CFD as a pre-treatment followed by SR-AOP under optimal conditions (pH = 6.0, [PMS] = 5.88 mM, [Co2+] = 5 mM, T = 343 K, reaction time 240 min), the COD removal increased to 85.9, 82.6 and 80.2%, respectively, for UV-A, UV-C and US reactors. All treated wastewater met the Portuguese legislation for discharge in a municipal sewage network (COD ≤ 1000 mg O2/L). As a final remark, the combination of CFD with SR-AOPs is a sustainable, safe and clean strategy for WW treatment and subproduct valorization.