Dynamic Treatment Response of Olive Mills Wastewater Using Series of Adsorption Steps

Olive mills wastewater (OMW) is a critical environmental problem in the Mediterranean area due to its extremely high levels of COD and phenols. In this study, a group of adsorption experiments were conducted to investigate the dynamic response of the pH, COD, phenols, TSS, TDS, and TS concentrations of pretreated OMW, using different concentrations of activated carbon as adsorbent. The pretreatment included sedimentation and filtration of OMW. The pretreated OMW was then subjected to adsorption. A series of adsorption steps in stirred batch vessels were studied, namely, one stage, two‐stage countercurrent, and three‐stage countercurrent adsorption systems. A combined two‐ two‐stage countercurrent adsorption steps were also studied. Experimental results showed that such treatment protocols were promising. For example, a treatment protocol composed of a three‐stage countercurrent adsorption process using activated carbon of concentration of 24 g/L of OMW was able to reduce the COD from 60 000 mg/L down to 22 300 mg/L, while phenols were reduced from 450 to 15 mg/L.     

Treatability of Dye Solutions Containing Disperse Dyes by Fenton and Fenton‐Solar Light Oxidation Processes

This study attempts to explore the possibility of treating dye solutions containing Disperse Yellow 119 and Disperse Red 167 by Fenton and Fenton under solar‐light oxidation processes. Experiments were conducted to examine the effects of various operating conditions on the performance of the treatment systems. The Fenton results showed that 98.6% spectral absorption coefficient (SAC) and 90.8% chemical oxygen demand (COD) removals were proved at pH 3, 50 mg/L Fe²⁺, and 75 mg/L H₂O₂, 15 min oxidation time for Disperse Yellow 119. After 40 min solar irradiation time during Fenton process the SAC removal was 99.1%. COD reduction of about 98.3% was observed at the same time. It was also obtained as 97.8% SAC and 97.7% COD removal with pH 3, 75 mg/L Fe²⁺, 100 mg/L H₂O₂, and 25 min oxidation time for Disperse Red 167 at this optimum conditions. For Disperse Red 167 during Fenton under solar light process, after 40 min of solar irradiation time the SAC and COD reduction were obtained 99.3 and 98.4%, respectively.     

Color Removal from Synthetic Textile Wastewater by Sono‐Fenton Process

In this study, the oxidative decolorization of C.I. reactive yellow 145 (RY 145) from synthetic textile wastewater including RY 145 and polyvinyl alcohol by Fenton and sono‐Fenton processes which are the combination of Fenton process with ultrasound has been carried out. The effects of some operating parameters which are the initial pH of the solution, the initial concentration of Fe²⁺, H₂O₂, and the dye, temperature, and agitation speed on the color and chemical oxygen demand (COD) removals have been investigated. The optimum conditions have been found as [Fe²⁺] = 20 mg/L, [H₂O₂] = 20 mg/L, pH 3 for Fenton process and [Fe²⁺] = 20 mg/L, [H₂O₂] = 15 mg/L, pH 3 for sono‐Fenton process by indirectly sonication at 35 kHz ultrasonic frequency and 80 W ultrasonic power. The color and COD removal efficiencies have been obtained as 91 and 47% by Fenton process, and 95 and 51% by sono‐Fenton processes, respectively. Kinetic studies have been performed for the decolorization of RY 145 under optimum conditions at room temperature. It has been determined that the decolorization has occurred rapidly by sono‐Fenton process, compared to Fenton process.     

Mineralization of Catechol by Fenton and Photo‐Fenton Processes

Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe²⁺, 7.09 mM H₂O₂, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.     

Response Surface Modeling and Optimization of Microwave‐Activated Persulfate Oxidation of Olive Oil Mill Wastewater

Olive oil mill wastewater (OMW) is environmentally hazardous not only because it contains high recalcitrant and toxic compounds, but also due to its high organic load and turbidity. In this study, oxidation of OMW by microwave (MW)‐activated persulfate is investigated. Box–Behnken design is applied to investigate the effects of operating conditions on operating cost, organic matter, and color removal. Multi response optimization is performed according to minimum operating cost, maximum organic matter and color removal efficiencies. At optimum conditions (persulfate anion dose of 266 g L^?1, oxidation duration of 23.58 min, MW power of 567 W, and initial pH 2), chemical oxygen demand (COD) removal of 63.38%, color removal of 94.85%, and operating cost of 0.0633 Euro/g total organic carbon (TOC) removal are found. The biochemical oxygen demand (BOD₅)/COD ratio is increased from 0.144 to 0.285. Results of Pareto analysis show individual effect of MW power is 92.81% for TOC removal, 15.52% for color removal, 68.99% for operating cost, respectively. According to the results, it is not recommended to use this process as an ultimate treatment unit due to the high amount of oxidizing agent consumed. Instead, it is recommended to be used as a pre‐ or post‐treatment step.     

Treatment of Refractory Organics Contained in Actual Agro‐Industrial Wastewaters by UV/H2O2

In this work, the treatment of actual agro‐industrial wastewaters (IWW) by a UV/H₂O₂ process has been investigated. The aqueous wastes were received from industrial olive oil mills and then treated by laboratory scale physicochemical methods, i. e., coagulation using ferrous and aluminum sulfate, decantation, filtration and adsorption on activated carbon. These wastes are brown colored effluents and have a residual chemical oxygen demand (COD) in the range of 1800 to 3500 mgO₂ L^–1, which cannot be further eliminated with physicochemical processes. The UV/H₂O₂ treatments were carried out under monochromatic irradiation at 254 nm using a thermostated reactor equipped with a mercury vapor lamp located in an axial position. The effects of initial H₂O₂ concentration, initial COD, pH and temperature have been studied in order to determine the optimum conditions for maximum color and COD removals. The experimental results reveal the suitability of the UV/H₂O₂ process for both removal of high levels of COD and effectively decolorizing the solution. In particular, 95% of color removal and 90% of COD removal were obtained under conditions of pH = 5 and 32°C using 2.75 g H₂O₂ g^–1 COD L^–1 during 6 h of UV‐irradiation. The treatment is unaffected by pH over the range 2 to 9. In addition, the COD removal is improved by increasing the temperature, whereas the color removal has not been affected by this parameter. The results show that the hydroxyl radicals generated from the catalytic decomposition of H₂O₂ by UV‐irradiation of the solution could be successfully used to mineralize the organics contained in IWW. The mineralization of the organics seems to occur in three main sequential steps: the first is the rapid decomposition of tannins leading to aromatic compounds, which are confirmed by the decolorization of the IWW; the second step corresponds to the oxidation of aromatics leading to aliphatic intermediates, which occurs by the cleavage of an aromatic ring, and is established by the removal of aromatics, and the final step is the slow oxidation of the aliphatic intermediates, which is measured by the COD removal.