Treatment of Actual Winery Wastewater by Fenton-like Process: Optimization to Improve Organic Removal, Reduce Inorganic Sludge Production and Enhance Co-Treatment at Municipal Wastewater Treatment Facilities

Despite many wineries being equipped with onsite wastewater treatment, winery wastewater (WWW) co-treatment at municipal wastewater treatment plants (WWTPs) remains a common practice in wine-making regions. The complex and highly variable nature of WWW can result in negative impacts on WWTP operations, highlighting a need for improved co-treatment methods. In this paper, the feasibility of using the Fenton-like process to pre-treat WWW to enhance co-treatment at municipal WWTPs is assessed. First-stage pre-treatment of the WWW, in the form of dilution and settling or aerobic biological treatment, is used prior to the Fenton-like process. A three-factor BBD experimental design is used to identify optimal reaction time and initial H2O2 and Fe3+ concentrations. Chemical oxygen demand (COD) and total organic carbon (TOC) removal rates are not able to accurately reflect the extent of reaction. Additional trials identified solubilization of particulate COD and TOC, as well as samples handling requirements prior to analysis, as factors affecting the apparent COD and TOC removal rates. Inert suspended solids (ISS) generated during the sample handling process are found to be the response variable best suited to quantifying the extent of the Fenton-like reaction. Maximum ISS generation is observed at initial H2O2 and Fe3+ concentrations of 4000 mg/L and 325 mg/L, however, results suggest that optimal concentrations exceed these values. The impact of adding pre-treated WWW, with and without Fenton-like treatment, to municipal WWTPs’ primary clarifiers and aerobic bioreactors is also assessed via bench-scale trials. Challenges associated with co-treating WWW are found to remain despite the pre-treatment alternatives investigated, including negative impacts on simulated primary and secondary effluent quality. The Fenton-like AOP provides limited opportunity to optimize or enhance co-treatment at municipal WWTPs.

Desalination and Detoxification of Textile Wastewater by Novel Photocatalytic Electrolysis Membrane Reactor for Ecosafe Hydroponic Farming

In this study, a novel photoelectrocatalytic membrane (PECM) reactor was tested as an option for the desalination, disinfection, and detoxification of biologically treated textile wastewater (BTTWW), with the aim to reuse it in hydroponic farming. The anionic ion exchange (IEX) process was used before PECM treatment to remove toxic residual dyes. The toxicity evaluation for every effluent was carried out using the Vibrio fischeri, Microtox® test protocol. The disinfection effect of the PECM reactor was studied against E. coli. After PECM treatment, the 78.7% toxicity level of the BTTWW was reduced to 14.6%. However, photocatalytic desalination during treatment was found to be slow (2.5 mg L−1 min−1 at 1 V potential). The reactor demonstrated approximately 52% COD and 63% TOC removal efficiency. The effects of wastewater reuse on hydroponic production were comparatively investigated by following the growth of the lettuce plant. A detrimental effect was observed on the lettuce plant by the reuse of BTTWW, while no negative impact was reported using the PECM treated textile wastewater. In addition, all macro/micronutrient elements in the PECM treated textile wastewater were recovered by hydroponic farming, and the PECM treatment may be an eco-safe wastewater reuse method for crop irrigation.

Comparative Study on UV-AOPs for Efficient Continuous Flow Removal of 4-tert-Butylphenol

In the present study, UV-light-driven advanced oxidation processes (AOPs) have been employed for the degradation of 4-tert-Butylphenol (4-t-BP) in water under continuous flow conditions. The effects of varying space time (10, 20, 40, 60 and 120 min) and oxidant dosage (88.3 mg/L, 176.6 mg/L and 264 mg/L) were examined. 4-t-BP degradation efficiency in the UV-induced AOPs followed the order of UV/H2O2 (264.9 mg/L) ≈ UV/Fe2+/H2O2 > UV/Fe3+/H2O2 > UV/H2O2 (176.6 mg/L) > UV/H2O2 (88.3 mg/L) > UV/Fe-TiO2 > UV/TiO2 > UV, while UV/Fe3+/H2O2 was the most efficient process in terms of Total Organic Carbon (TOC) removal (at the space time of 60 min) among those tested. The combination of UV with 88.3 mg/L H2O2 enhanced pollutant removal from 51.29% to 93.34% after 10 min of irradiation. The presence of H2O2 contributed to the highest 4-t-BP and TOC removal values. Interestingly, the increase in space time from 20 to 60 min resulted in surpassing of the activity of the Fe-TiO2 over commercial TiO2, although it had an almost negligible positive impact on the performance of the UV/H2O2 system as well as H2O2 concentration. The results obtained showed that more than 80% of 4-t-BP could be successfully degraded by both heterogeneous and homogeneous AOPs after 60 min.

Insights into the generation of hydroxyl radicals from H2O2 decomposition by the combination of Fe2+ and chloranilic acid

In this work, the degradation of chloranilic acid (CAA) by chemical oxidation with H2O2 alone and in the presence of ferrous iron Fe2+ catalyst was investigated in order to improve our understanding on the novel metal-independent approach. The interesting and efficient metal-independent hydroxyl radicals (OH) production by using halogenated quinones and H2O2 has been currently demonstrated. The results clearly confirmed the formation of OH radicals from the reaction of CAA with H2O2. CAA was slowly decayed by chemical oxidation with H2O2 and followed a pseudo-first kinetics. H2O2 doses ≥ 1000 mM were required to achieve complete CAA decay from 1 mM CAA. However, low total organic carbon (TOC) removal was measured with the accumulation of carboxylic acids. The addition of Fe2+ enhanced the kinetics of CAA degradation and reduced the required dose of H2O2. High TOC removal was obtained, almost complete release of chloride ions, without accumulation of carboxylic acids. The decolorization of methylene blue (MB) aqueous solutions was performed using H2O2, H2O2/CAA, H2O2/Fe2+, and H2O2/CAA/Fe2+. H2O2/CAA/Fe2+ was the most effective method in decolorizing MB solutions due to the accelerated Fe2+ regeneration. Coupling Fenton reagent with CAA seems to be promising alternative to physical activation in water and soil treatment.

Microbial Electrochemical Fluidized Bed Reactor: A Promising Solution for Removing Pollutants From Pharmaceutical Industrial Wastewater

The capacity of electroactive bacteria to exchange electrons with electroconductive materials has been explored during the last two decades as part of a new field called electromicrobiology. Such microbial metabolism has been validated to enhance the bioremediation of wastewater pollutants. In contrast with standard materials like rods, plates, or felts made of graphite, we have explored the use of an alternative strategy using a fluid-like electrode as part of a microbial electrochemical fluidized bed reactor (ME-FBR). After verifying the low adsorption capacity of the pharmaceutical pollutants on the fluid-bed electrode [7.92 ± 0.05% carbamazepine (CBZ) and 9.42 ± 0.09% sulfamethoxazole (SMX)], our system showed a remarkable capacity to outperform classical solutions for removing pollutants (more than 80%) from the pharmaceutical industry like CBZ and SMX. Moreover, the ME-FBR performance revealed the impact of selecting an anode potential by efficiently removing both pollutants at + 200 mV. The high TOC removal efficiency also demonstrated that electrostimulation of electroactive bacteria in ME-FBR could overcome the expected microbial inhibition due to the presence of CBZ and SMX. Cyclic voltammograms revealed the successful electron transfer between microbial biofilm and the fluid-like electrode bed throughout the polarization tests. Finally, Vibrio fischeri-based ecotoxicity showed a 70% reduction after treating wastewater with a fluid-like anode (+ 400 mV), revealing the promising performance of this bioelectrochemical approach.

COD, TOC determination using UV spectrophotometry and its application to monitor the potassium hydrogen phthalate degradation by H2O2-HCO3– oxidation system

In this study, the COD and TOC in H2O2-HCO3– oxidation system containing potassium hydrogen phthalate were determined by UV spectrophotometry (260-310 nm). The pH and H2O2 concentrations were investigated as factors influencing the absorbance measurements. The obtained standard curves were Abs = (3.10±0.04)x103xCOD - (0.015±0.003) (R2=0.9996) with LOD of 5.1 mg O2/l and LOQ of 13.6 mg O2/l, and Abs = (0.008±0.0001)xTOC - (0.015±0.003) (R2=0.9996) with LOD of 1.6 mg/l and LOQ of 5.4 mg/l. The method was applied to monitor the degradation of potassium hydrogen phthalate by the H2O2-HCO3– oxidation system. The results revealed that the COD and TOC removal efficiencies reached ~85% after 90 minutes of UVC irradiation. The UV spectra and HPLC chromatographs showed that no aromatic compounds were obtained in the degradation products.

Influence of Synthesis Approach on Controlled Microstructures and Photocatalytic Properties of Ag/AgBr-Activated Carbon Composites on Visible Light Degradation of Tetracycline

The influence of the synthesis approach (thermal polyol and deposition–precipitation) regarding the dispersion of Ag/AgBr nanoparticles dispersed on activated carbon prepared from chemical impregnated pinecone (TP-AABR-ACK, and DP-AABR-ACK) was studied, to increase their photocatalytic efficiency on the degradation of tetracycline (TC). The physicochemical characterization evidenced the significance of the ACK catalyst promoter in enhancing controlled microstructures (morphologies and particle size distributions), synergistic interface interaction between AABR NPs and the carbonaceous support, and efficient photogenerated charge carriers separation within TP-AABR-ACK, and DP-AABR-ACK composites. The results revealed 92% removal of TC within 180 min under the LED visible light irradiation, which was achieved using TP-AABR-ACK when compared to DP-AABR-ACK composite and other catalysts in this study. Such superior results achieved with TP-AABR-ACK composite were attributed to controlled morphologies, reduced particle size and agglomeration, improved absorptivity, and superior cooperative effect between the AABR and ACK catalyst promoter as evidenced from SEM, EDX, TEM, UV-DRS, and electrochemical characterizations, respectively. Furthermore, enhanced TOC removal and abundance of reactive superoxide anion generation were achieved with the TP-AABR-ACK composite in this study.

Ozonation of Amoxicillin and Ciprofloxacin in Model Hospital Wastewater to Increase Biotreatability

Amoxicillin (AMX) and Ciprofloxacin (CIP) are antibiotics commonly used in human medicine with high environmental toxicity and poor biodegradability. They have been found in various hospital effluents and groundwater, and their environmental impact is still not fully understood. In this work, we investigated the possibility of treating model wastewaters containing the antibiotics AMX and CIP using ozonation, with the addition of H2O2 under various conditions, including different pH values, H2O2, and ozone dosages. The quantification of and treatment efficacy for antibiotic removal were determined via solid phase extraction followed by chromatographic separation by liquid chromatography coupled with tandem triple quadrupole mass spectrometry (LC/MS/MS). This analytical system is quite efficient for the detection of all major antibiotic classes, even if they are present at very low concentrations. The efficiency of ozonation was determined by measuring the TOC (Total Organic Carbon) changes after ozonation of the model wastewater and by measuring the concentration of the two antibiotics. In a sequential activated sludge process of ozone-treated model wastewater, almost complete TOC removal and an overwhelming decrease in antibiotic concentrations (up to 99%) were observed. Ozonation resulted in complete removal of AMX and CIP in less than 30 and 120 min, respectively. The results of this work indicate that ozonation could be a suitable pretreatment method to reduce the toxicity of contaminants (AMX and CIP) and improve the biodegradability of hospital wastewater.

Electrocatalytic Degradation of Levofloxacin, a Typical Antibiotic in Hospital Wastewater

Presently, in the context of the novel coronavirus pneumonia epidemic, several antibiotics are overused in hospitals, causing heavy pressure on the hospital’s wastewater treatment process. Therefore, developing stable, safe, and efficient hospital wastewater treatment equipment is crucial. Herein, a bench-scale electrooxidation equipment for hospital wastewater was used to evaluate the removal effect of the main antibiotic levofloxacin (LVX) in hospital wastewater using response surface methodology (RSM). During the degradation process, the influence of the following five factors on total organic carbon (TOC) removal was discussed and the best reaction condition was obtained: current density, initial pH, flow rate, chloride ion concentration, and reaction time of 39.6 A/m2, 6.5, 50 mL/min, 4‰, and 120 min, respectively. The TOC removal could reach 41% after a reaction time of 120 min, which was consistent with the result predicted by the response surface (40.48%). Moreover, the morphology and properties of the electrode were analyzed. The degradation pathway of LVX was analyzed using high-performance liquid chromatography–mass spectrometry (LC–MS). Subsequently, the bench-scale electrooxidation equipment was changed into onboard-scale electrooxidation equipment, and the onboard-scale equipment was promoted to several hospitals in Dalian.

Persulfate Process Activated by Homogeneous and Heterogeneous Catalysts for Synthetic Olive Mill Wastewater Treatment

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.