This research investigates the potential use of pyrite cinder (PC) as an efficient Fenton-like catalyst for the removal of the reactive azo dye Reactive Red 120 (RR120) from aqueous solutions. The characterization of its PC structure and composition confirmed its great potential to act as catalytic iron source in a heterogeneous Fenton system. Dye removal optimization was performed in terms of PC dosage (0.4–8 g/L), H2O2 concentration (2–25 mM), pH value (2–4.6), initial dye concentration (50–200 mg/L), and mixing time. The highest decolorization efficiency (92%) was achieved after a reaction time of 480 min under following conditions: RR120 = 50 mg/L, PC = 4 g/L, H2O2 = 10 mM, and pH = 3. After decolorization, an extensive analysis of the generated effluent was performed regarding metal leaching, mineralization, toxicity, and degradation product formation. The metal leaching indicated the necessity for a pH increase in order to remove the settled metal hydroxides. The mineralization efficiency was satisfactory, reaching 85% and 62% of the COD and TOC removal, respectively. The respirometry measurements and bioluminescence tests indicated the detoxification of the treated solution. The absorption spectra and GC/MS analysis confirmed the changes in the molecular structure in the form of the destruction of the azo bond, with a simpler aromatic and aliphatic intermediates formation. This study provides an effective method for removing azo dye in polluted water by employing waste tailings as alternative Fenton-like catalysts, while also using waste tailings as the secondary resource.
Due to population growth and industrial development consumption of non-renewable energy sources, and consequently pollution, has increased. In order to reduce energy utilisation and preserve the environment, developed and developing countries are increasingly trying to find solutions based on renewable energy sources. Cost-effective wastewater treatment methods using solar energy would significantly ensure effective water source utilisation, thereby contributing towards sustainable development goals. In this paper, special emphasis is given to the use of solar energy as the driving force of the process, as well as the use of highly active magnetic TiO2-based catalysts. Therefore, in this study, we investigated the possibility of photocatalytic degradation of aqueous magenta graphic dye using titanium dioxide as a catalyst and DSD model in order to achieve the best process optimisation. TiO2 was successfully coated with magnetic nanoparticles by one step process and characterized using different techniques (BET, SEM/EDS, FTIR, XRD). Based on DSD statistical method optimal reaction conditions were pH = 6.5; dye concentration 100 mg/L; TiO2–Fe3O4 0.6 g/L, at which the highest degree of magenta dye decolourisation was achieved (85%). Application of solar energy coupled with magnetic TiO2 catalyst which could be recovered and reused makes this approach a promising alternative in green wastewater treatment.
In the framework of wastewater treatment plants, sewage sludge can be directed to biochar production, which when coupled with an external iron source has the potential to be used as a carbon–iron composite material for treating various organic pollutants in advanced oxidation processes. In this research, “green” synthesized nano zero-valent iron (nZVI) supported on sewage sludge-based biochar (BC)–nZVI-BC was used in the Fenton process for the degradation of the recalcitrant organic molecule. In this way, the circular economy principles were supported within wastewater treatment with immediate loop closing; unlike previous papers, where only the water treatment was assessed, the authors proposed a new approach to wastewater treatment, combining solutions for both water and sludge. The following phases were implemented: synthesis and characterization of nano zero-valent iron supported on sewage sludge-based biochar (nZVI-BC); optimization of organic pollutant removal (Reactive Blue 4 as the model pollutant) by nZVI-BC in the Fenton process, using a Definitive Screening Design (DSD) model; reuse of the obtained Fenton sludge, as an additional catalytic material, under previously optimized conditions; and assessment of the exhausted Fenton sludge’s ability to be used as a source of nutrients. nZVI-BC was used in the Fenton treatment for the degradation of Reactive Blue 4—a model substance containing a complex and stable anthraquinone structure. The DSD model proposes a high dye-removal efficiency of 95.02% under the following optimal conditions: [RB4] = 50 mg/L, [nZVI] = 200 mg/L, [H2O2] = 10 mM. pH correction was not performed (pH = 3.2). Afterwards, the remaining Fenton sludge, which was thermally treated (named FStreated), was applied as a heterogeneous catalyst under the same optimal conditions with a near-complete organic molecule degradation (99.56% ± 0.15). It could be clearly noticed that the cumulative amount of released nutrients significantly increased with the number of leaching experiments. The highest cumulative amounts of released K, Ca, Mg, Na, and P were therefore observed at the fifth leaching cycle (6.40, 1.66, 1.12, 0.62, 0.48 and 58.2 mg/g, respectively). According to the nutrient release and toxic metal content, FStreated proved to be viable for agricultural applications; these findings illustrated that the “green” synthesis of nZVI-BC not only provides innovative and efficient Fenton catalysts, but also constitutes a novel approach for the utilization of sewage sludge, supporting overall process sustainability.
The paper reports removal of organic Black (Key) dye from real printing wastewater using nano zero valent iron particles as a catalyst in Fenton-like treatment. The degradation efficiency of Black diazo dye via Fenton-like treatment is reported to be 61% under established optimal process conditions: [Fe2+] = 0.75 mgL-1, pH = 2, [H2O2] = 1 mM, within a reaction time of 75 min. The absorption spectra of Black dye clearly indicate that dye degradation is a slow process with difficult decomposition of aromatic structures, due to the cleavage of diazo bonds by hydroxyl radicals. The physico-chemical characterizations (measurements of pH, electrical conductivity, temperature, turbidity, chemical oxygen demand, biochemical oxygen demand, total organic carbon, anionic surface-active substances and phosphorus content) as well as toxicity study (Vibrio fischeri bacteria) revealed the complex nature of printing effluent. Increased conductivity and biochemical oxygen demand content after Fenton treatment imply the formation of various byproducts and intermediates, formed in a solution during dye degradation. The mineralization percentage of Black dye of 58% is followed with 47% of chemical oxygen demand reduction. Results of toxicity test on Vibrio fischeri bacteria indicate that both untreated and treated printing effluents belong to moderate toxic samples with 58% and 67% of toxicity inhibition, respectively. Among three evaluated kinetic models (the first-order, the second-order, and Behnajady– Modirshahla–Ghanbary), experimental results fitted very well to the Behnajady - Modirshahla - Ghanbary model, indicating high initial rate of Black dye degradation.
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