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Wastewaters from the olive oil industry are a regional environmental problem. Their phenolic content provides inherent toxicity, which reduces the treatment potential of conventional biological systems. In this study, Sulfate Radical based Advanced Oxidation Processes (SRbAOPs) are compared with advanced oxidation processes (namely Fenton’s peroxidation) as a depuration alternative. Synthetic olive mill wastewaters were submitted to homogeneous and heterogeneous SRbAOPs using iron sulfate and solid catalysts (red mud and Fe-Ce-O) as the source of iron (II). The homogenous process was optimized by testing different pH values, as well as iron and persulfate loads. At the best conditions (pH 5, 300 mg/L of iron and 600 mg/L of persulfate), it was possible to achieve 39%, 63% and 37% COD, phenolic compounds and TOC removal, respectively. The catalytic potential of a waste (red mud) and a laboratory material (Fe-Ce-O) was tested using heterogenous SRbAOPs. The best performance was achieved by Fe-Ce-O, with an optimal load of 1600 mg/L. At these conditions, 27%, 55% and 5% COD, phenolic compounds and TOC removal were obtained, respectively. Toxicity tests on A. fischeri and L. sativum showed no improvements in toxicity from the treated solutions when compared with the original one. Thus, SRbAOPs use a suitable technology for synthetic OMW.

The main drawback of Fenton′s process is the formation of ferric sludge. In this work, ion exchange (IE) appears as a complement to the Fenton process, allowing, on the one hand, to remove the iron excess present in the sludge, as well as reduce the COD of the real olive oil industry extraction wastewater (OOIEW) from the Fenton process. The Fenton process uses iron (II) sulfate as catalyst, therefore concentrations of iron up to 2 g L−1 could be present in the treated OOIEW. The iron and COD adsorption equilibrium behavior has been modelized by Langmuir, Freundlich and Temkin isotherms. Moreover, the resin efficiency was tested in a continuous fixed-bed column. It was concluded that the resin maintains iron adsorption capacity over at least three reuse cycles. Overall Fenton’s process followed by ion exchange seems to be a promising approach for the treatment of cumbersome industrial wastewaters.

Wastewater from the olive oil industry is an environmental problem which is growing in the Mediterranean region. Presence of phenolic compounds and high organic matter load are characteristics of this effluent that make it difficult to treat. In this study, the applicability of sulfate radical based advanced oxidation processes (SRbAOPs), using peroxymonosulfate (PMS) as oxidant, was evaluated in the treatment of synthetic olive mill wastewater (OMW). Different procedures for PMS activation were studied such as activation by Fe(II), radiation (visible and UV-A) and ultrasounds. The operation conditions were optimized by testing pH values, Fe(II) and PMS loads. At optimal conditions ([PMS] = 1600 mg/L, [Fe2+] = 700 mg/L and pH = 5) 60 ± 2% COD removal was achieved. This process shows to be selective since complete degradation of 3,4,5-trimetoxybenzoic acid was obtained after 3 min of reaction. The addition of light, PMS/LED/Fe(II) and PMS/UV-A/Fe(II), did not increase the efficiency of organic matter removal, with 56 ± 2% and 58 ± 1% of COD removal, respectively, comparatively to PMS/Fe(II) (60 ± 2%). PMS activated by ultrasounds led to 52 ± 3% and 23 ± 2% removal of phenolic compounds and COD, respectively, after 60 min. Toxicity tests using Lepidium sativum showed that treatment with PMS/UV-A led to a treated sample with mild inhibition of plant growth.