Fe-Cu-loaded γ-Al2O3 as an efficient heterogeneous Fenton catalyst for the advanced treatment of petrochemical wastewater

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Fe-Cu-loaded γ-Al2O3 as an efficient heterogeneous Fenton catalyst for the advanced treatment of petrochemical wastewater

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Ozonation has gradually become a routine process for advanced wastewater treatment. During the technology innovation on the advanced treatment of wastewater by ozonation, researchers have to assess the performance of abundant new technologies, new reactors, and new materials. However, they are usually puzzled by the rational selection of model pollutants to assess the capability of such new technologies to eliminate the chemical oxygen demand (COD) and total organic carbon (TOC) of practical wastewater. It is unclear how well the various model pollutants reported in the literature could represent the COD/TOC removal of actual wastewater. The rational selection and evaluation of model pollutants for advanced treatment of industrial wastewater is of great significance in establishing the technological standard system for advanced treatment of wastewater via ozonation. Herein, the aqueous solutions (including unbuffered solutions and bicarbonate-buffered solutions) of 19 model pollutants and four practical secondary effluents from industrial parks were investigated through ozonation under identical conditions. The similarity in COD/TOC removal of the above wastewater/solutions were evaluated using mainly clustering analysis. The results showed that the dissimilarity among the model pollutants was greater than that among the actual wastewaters, thus enabling the rational selection of several model pollutants to assess the performance of advanced treatment of wastewater using ozonation by different technologies. The errors of predicting the COD removal of secondary sedimentation tank effluent by ozonation in 60 min using the unbuffered aqueous solutions of ketoprofen (KTP), dichlorophenoxyacetic acid (2,4-D), and sulfamethazine (SMT) were less than 9%, and those using the bicarbonate-buffered solutions of phenacetin (PNT), SMT, and sucralose were less than 5%. The evolution of pH by using the bicarbonate-buffered solutions was more similar to that in practical wastewater than by using unbuffered aqueous solutions. In the similarity evaluation of COD/TOC removal between the bicarbonate-buffered solutions and the practical wastewaters, the results were almost the same whether considering different input ozone concentration conditions. Therefore, the protocol proposed in this study based on similarity evaluation to assess the performance treating actual wastewater could be extended to different ozone concentration conditions with certain universality.

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As waste discharge into numerous river systems escalates, the pollution of water bodies typically rises. Given the limited capacity of rivers to withstand pollution and their constrained self-cleaning capabilities, treated pollutants from waste discharge must be released into the river. Despite numerous models and algorithms proposed for managing river water quality to meet standards, literature, to our awareness, lacks the utilization of a comprehensive multi-criteria group decision-making approach for water quality management, particularly in river systems. Therefore, this research introduces a new, comprehensive multi-criteria group decision-making for the management of water quality in the Haraz River basin, located in Iran. To do so, the water quality of the basin, a one-dimensional water quality model, QUAL2Kw, was employed to simulate and calibrate the water quality along the river. The simulation results revealed that the downstream water quality violates the water quality standards. To mitigate this issue, various scenarios for waste load allocation (WLA) were evaluated, including no wastewater treatment, primary wastewater treatment, advanced secondary wastewater treatment utilizing the activated sludge (AS) method, and advanced wastewater treatment via the membrane bioreactor (MBR) method. Utilizing the Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS) and Fuzzy TOPSIS group decision-making model, it was determined that the optimal solution was the implementation of secondary wastewater treatment utilizing the activated sludge method for the 11 PS of pollution, while still adhering to Iranian water quality standard. In addition, the findings of the present study indicate that the implementation of primary wastewater treatment, advanced secondary wastewater treatment utilizing AS, and advanced wastewater treatment through MBR within the study area led to a significant enhancement in water quality. This enhancement ranged from 35 to 105% across various scenarios when compared to conditions where no actions were taken to the treatment of water.

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This study focused on the feasibility of using Fe3O4/graphene oxide (FGO) nanocomposites as heterogeneous catalysts for the advanced treatment of real industrial wastewater. FGO nanocomposites with different graphene oxide (GO) ratios were synthesized by coprecipitating iron salts onto GO sheets in basic solution. The characterization of the resulting material structures and functionalities was performed using a range of analytical techniques. A low GO loading afforded a good Fe3O4 nanoparticle dispersibility and resulted in a higher Brunauer-Emmett-Teller surface area and pore volume. The FGO nanocomposites and pure Fe3O4 were used to treat papermaking wastewater in a heterogeneous photo-Fenton process. The results suggested that the nanocomposite designated FGO1 (GO loading of 25 mg) exhibits a higher photocatalytic efficiency than other FGO nanocomposites and pure Fe3O4. A maximum chemical oxygen demand degradation efficiency of 89.6% was achieved in 80 min with 1.5 g L-1 FGO1 at pH 3. The degradation of different pollutants present in wastewater was evaluated with the aid of gas chromatography-mass spectrometry and 3D excitation-emission-matrix analysis. Inductively coupled plasma atomic emission spectroscopy and magnetic measurements confirmed that the FGO1 nanocomposites possess a low iron leachability and a high reusability. Thus, a comprehensive advanced treatment of real industrial wastewater using a magnetic FGO catalyst is demonstrated.

  • Preprint Article
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Fe-Cu-Loaded γ-Al2O3 as an Efficient Heterogeneous Fenton Catalyst for the Advanced Treatment of Petrochemical Wastewater
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Fe-Cu-Loaded γ-Al2O3 as an Efficient Heterogeneous Fenton Catalyst for the Advanced Treatment of Petrochemical Wastewater

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Wastewater treatment plants can become a source of valuable resources, such as clean water, energy, fuels and nutrients and thus contribute to the sustainable development goals and a transition to a circular economy. This can be achieved by adopting advanced wastewater and sludge treatment techniques. However, these have to be evaluated on their sustainability to avoid any unintentional consequences. Therefore, this paper presents a life cycle sustainability assessment of advanced wastewater and sludge treatment techniques by integrating the environmental, economic and social aspects. The options considered for advanced wastewater treatment are: i) granular activated carbon; ii) nanofiltration; iii) solar photo-Fenton; and iv) ozonation. The technologies for advanced sludge treatment are: i) agricultural application of anaerobically digested sludge; ii) agricultural application of composted sludge; iii) incineration; iv) pyrolysis; and v) wet air oxidation. The results for the advanced wastewater treatment techniques demonstrate that nanofiltration is the most sustainable option if all the sustainability aspects are considered equally important. If, however, a higher preference is given to the economic aspect, ozonation and granular activated carbon would both be comparable to nanofiltration; if the social aspect is considered more important, only activated carbon would be comparable to nanofiltration. Among the sludge treatment methods, agricultural application of sludge is the most sustainable technique for mean-to-high resource recovery. If the recovery rate is lower, this option is comparable with incineration and pyrolysis with high recovery of their respective products. This work helps to identify the most sustainable techniques that could be combined with conventional wastewater treatments for promoting wastewater reuse and resource recovery across a wide range of operating parameters and products outputs. The findings also support the notion that more sustainable wastewater treatment could be achieved by a circular use of water, energy and nutrients contained in urban wastewaters.

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Anthropogenic micropollutants and transformation products (TPs) negatively affect aquatic ecosystems and water resources. Wastewater treatment plants (WWTP) represent major point sources for (micro)pollutants and TPs in urban water cycles. The aim of the current study was to assess the removal of micropollutants and toxicity during conventional and advanced wastewater treatment. Using wild-type and transgenic Caenorhabditis elegans, the endpoint reproduction, growth, and cytochrome P450 (CYP) 35A3 induction (via cyp-35A3::GFP) were assessed. Samples were collected at four WWTPs and a receiving surface water. One WWTP included the advanced treatments: ozonation followed by granular activated carbon (GAC) or biological filtration (BF), respectively. Relevant micropollutants and WWTP parameters (n = 111) were included. Significant reproductive toxicity was detected for one WWTP effluent (31-83% reduced brood size). Three of four effluents significantly promoted the growth of C. elegans larvae (49-55% increased lengths). This effect was also observed for the GAC (34-41%) and BF (30%) post-treatments. Markedly, significant cyp-35A3::GFP induction was detected for one effluent before and after ozonation, being more pronounced for the ozonated samples (5- and 7.4-fold above controls). While the advanced treatments decreased the concentrations of most micropollutants, the observed effects may be attributed to effects of residual target compounds and/or compounds not included in the target chemical analysis. This highlights the need for an integrated assessment of (advanced) wastewater treatment covering both biological and chemical parameters.

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Ozonation applied for advanced (waste)water treatment has a great potential to form polar transformation products (TPs) with often unknown toxicity. The antiviral drug acyclovir is transformed during biological wastewater treatment into carboxy-acyclovir. Ozone further transforms carboxy-acyclovir into N-(4-carbamoyl-2-imino-5-oxoimidazolidin)formamido-n-methoxy-acid (COFA). Both TPs have been detected in environmental samples and finished drinking water. Here, carboxy-acyclovir and COFA were produced at bench scale using treated wastewater and sewage sludge and were tested for aquatic toxicity in parallel with acyclovir. Carboxy-acyclovir was found to significantly reduce the level of reproduction of Daphnia magna (by 40% at 102 mg L–1), and COFA inhibited the growth of green algae (ErC10 of 14.1 mg L–1); no toxicity was observed for acyclovir up to 100 mg L–1. The predicted genotoxicity was not increased compared to that of the parent compound. In summary, the results highlight the importance of assessi...

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Emerging Technologies and Recent Advances in the Advanced Treatment of Petrochemical Wastewater: A Comprehensive Review
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The petrochemical industry, one of the fastest‐growing sectors, is projected to continue expanding in the coming years. As environmental regulations tighten and demand for cleaner production increases, the petrochemical industry is compelled to adopt environmentally sustainable technologies and advanced wastewater treatment solutions. Petrochemical wastewater contains a range of pollutants, including petroleum hydrocarbons, emulsified oils, phenols, ammonia, sulfides, and other organic compounds. These contaminants often occur in complex physicochemical forms at discharge, posing significant environmental risks. Conventional biological and physicochemical treatments frequently fail to meet stringent discharge standards because of limited resilience to load fluctuations, restricted biodegradability, and secondary sludge generation. Advanced treatment has therefore become essential for petrochemical wastewater management. Among available options, adsorption, membrane separations, and advanced oxidation processes stand out for their performance. Adsorption excels at removing heavy metals and recalcitrant organics owing to diverse sorbent chemistries and operational simplicity. Membrane technologies achieve molecular‐level selectivity with high water recovery potential. Catalytic ozonation effectively mineralizes refractory pollutants and enhances subsequent biodegradability. Current research highlights innovations in graphene‐based adsorbents, ceramic nanofiltration membranes, and multifunctional catalysts that improve treatment efficiency, stability, and reusability. This review synthesizes recent advances in the deep treatment of petrochemical wastewater, outlines research priorities for evaluating the effectiveness of these technologies in oil‐based wastewater management, and provides reference for research and application in this field.

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