Polymer-Supported Heterogeneous Fenton Catalysts for the Environmental Remediation of Wastewater.

Materials based on polymer hydrogels have demonstrated potential as innovative Fenton catalysts for treating water. However, developing these polymer-supported catalysts with robust stability presents a significant challenge. This paper explores the development and application of polymer-supported heterogeneous Fenton catalysts for the environmental remediation of wastewater, emphasizing the enhancement of metal incorporation into catalysts for improved efficiency. The study begins with an introduction to the heterogeneous Fenton process and its relevance to wastewater treatment. It further delves into the specifics of polymer-supported heterogeneous Fenton catalysts, focusing on iron oxide, copper complexes/nanoparticles, and ruthenium as key components. The synthesis methods employed to prepare these catalysts are discussed, highlighting the innovative approaches to achieve substantial metal incorporation. Operational parameters such as catalyst dosage, pollutant concentration, and the effect of pH on the process efficiency are thoroughly examined. The catalytic performance is evaluated, providing insights into the effectiveness of these catalysts in degrading pollutants. Recent developments in the field are reviewed, showcasing advancements in catalyst design and application. The study also addresses the stability and reusability of polymer-supported heterogeneous Fenton catalysts, critical factors for their practical application in environmental remediation. Environmental applications are explored, demonstrating the potential of these catalysts in addressing various pollutants. The Conclusions offers future perspectives, underlining the ongoing challenges and opportunities in the field, and the importance of further research to enhance the efficacy and sustainability of polymer-supported heterogeneous Fenton catalysts for wastewater treatment.

Continuous treatment of diethyl hexyl and dibutyl phthalates by fixed-bed reactor: Comparison of two esterase bionanocomposites.

The removal of Diethyl hexyl phthalate (DEHP) and Dibutyl phthalate (DBP) is of great importance due to their potential adverse effects on the environment and human health. In this study, two bionanocomposites prepared by immobilization of Bacillus subtilis esterase by crosslinking to halloysite and supported in chitosan and alginate beads were studied and proposed as a green approach. The esterase immobilization was confirmed by physical-chemical characterization. Bionanocomposite using chitosan showed the best degradation levels in batch tests attaining complete degradation of DBP and around 90% of DEHP. To determine the operational stability and efficiency of the system, two fixed bed reactors filled with both bionanocomposites were carried out operating in continuous mode. Chitosan based bionanocomposite showed the best performance being able to completely remove DBP and more than 85% of DEHP at the different flowrates. These results proved the potential of these synthesized bionanocomposites to effectively remove Phthalic Acid Esters.

Kinetic and thermodynamic study of laccase cross-linked onto glyoxyl Immobead 150P carrier: Characterization and application for beechwood biografting.

In this study, we cross-linked aminated Thermothelomyces thermophilus laccase onto Immobead 150P epoxy carrier, and achieved an immobilization yield of 99.84 %. The optimum temperature and pH values for the oxidation of ABTS by laccase were determined to be 70 °C and pH 3.0. After 6 h at 50 °C, laccase activity was diminished by about 13 % in the free form and 28 %, in the immobilized form. Km values for both free and cross-linked laccase were 0.051 and 0.567 mM, whereas Vmax values were 2.027 and 0.854 µmol. min-1, respectively. The immobilized laccase was able to preserve its full activity for 6 weeks, retaining approximately 95 % and 78 % of its initial activity after 8 and 20 weeks, respectively. The contact angles were two-fold higher when the laccase enzyme was occupied in the biografting reaction, revealing that the hydrophobic compound bonded stably onto beechwood samples.

Bridging the gap to hydrochar production and its application into frameworks of bioenergy, environmental and biocatalysis areas.

Hydrothermal carbonization (HTC) is a facile, low-cost and eco-friendly thermal conversion process that has recently gained attention with a growing number of publications (lower 50 in 2000 to over 1500 in 2020). Despite being a promising technology, problems such as operational barriers, complex reaction mechanisms and scaling have to be solved to make it a commercial technology. To bridge this current gap, this review elaborates on the chemistry of the conversion of lignocellulosic biomass. Besides, a comprehensive overview of the influence of the HTC operational conditions (pH, temperature, water:biomass ratio, residence time and water recirculation) are discussed to better understand how hydrochar with desired properties can be efficiently produced. Large-scale examples of the application of HTC are also presented. Current applications of hydrochar in the fields of energy, biocatalysis and environment are reviewed. Finally, economic cost and future prospects are analyzed.

Environmental application of monolithic carbonaceous aerogels for the removal of emerging pollutants.

In this study, the performance of three commercial available monolithic carbonaceous aerogels (NQ30A, NQ60A and NQ80A) for the removal of different emerging pollutants, detected in water sources, was evaluated. More specifically, the removal of two pharmaceuticals (antipyrine and sulfamethoxazole) and an anti-fungal agent (methyl paraben), widely used in cosmetics, was studied. The NQ60A demonstrated the best adsorption characteristics and effectively adsorbed over 50 mg/g of the antipyrine and around 30 mg/g sulfamethoxazole and methyl paraben. The kinetic study of the adsorption process revealed that pseudo-first order kinetic model described very well the kinetic behaviour of the selected pollutants onto the NQ60A aerogel. After that, the regeneration of the loaded aerogel, with antipyrine alone and in presence of the other two contaminants, was evaluated. The regeneration was accomplished in two ways: (1) by using directly the loaded aerogels as cathode during the electro-Fenton treatment and (2) by its regeneration immersed in the bulk volume of electro-Fenton cell (boron doped diamond as anode and carbon felt as cathode). Both approaches can provide an effective removal of the pollutants inside the aerogel. In addition, the regenerated aerogel proved to maintain its adsorptive properties and can be successfully reused in successive cycles of adsorption-regeneration. On the basis of these promising results, it can be concluded that the proposed strategy based on aerogels adsorption and electro-Fenton regeneration is a suitable alternative for emerging pollutants removal from water streams.

Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation.

The application of the electro-Fenton process for organic compound mineralisation has been widely reported over the past years. However, operational problems related to the use of soluble iron salt as a homogeneous catalyst involve the development of novel catalysts that are able to operate in a wide pH range. For this purpose, polyvinyl alcohol-alginate beads, containing goethite as iron, were synthesised and evaluated as heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride mineralisation. The influence of catalyst dosage and pH solution on ionic liquid degradation was analysed, achieving almost total oxidation after 60 min under optimal conditions (2 g/L catalyst concentration and pH 3). The results showed good catalyst stability and reusability, although its effectiveness decreases slightly after three successive cycles. Furthermore, a plausible mineralisation pathway was proposed based on the oxidation byproducts determined by chromatographic techniques. Finally, the Microtox® test revealed notable detoxification after treatment which demonstrates high catalyst ability for pyridinium-based ionic liquid degradation by the electro-Fenton process.

Towards sustainable removal of methylthioninium chloride by using adsorption-electroradical regeneration.

The current need for effective regeneration processes to be used in valorization of spent adsorbent demands the research of novel alternative techniques such as application of Advances Oxidation Processes. In this sense, the recent application of electroradical (ER) processes turned out to be very promising in terms of the drugs degradation from different environments. Thus, in this study, harnessing of a low cost natural adsorbent, Tunisian bentonite (BE), was evaluated for the removal of a model drug such as methylthioninium chloride (MC), and then its regeneration by ER processes was demonstrated. Initially, the BE was characterized and the adsorption of the MC was studied. This process followed a pseudo-first order kinetic and Langmuir isotherm fitted well to data reaching uptake values around 145-155 mg g-1. After that, BE regeneration by an ER process such as electro-Fenton process was ascertained. Due to the high buffering capacity of the BE, the addition of citric acid (1 mM) was necessary in order to assure the acidic medium to favor the oxidation reaction. By operating under optimized experimental conditions (current intensity 300 mA, pH 3, Fe2+ (1 mM) and citric acid (1 mM)) near complete adsorbent regeneration was achieved after 300 min of treatment and the pseudo-first-order model fitted well the degradation data. Furthermore, the adsorbent was efficiently used in successive cycles of adsorption-regeneration without operational problems that proved the efficiency of this technology. From the obtained results, a side-by-side configuration was designed and simulated, confirming the viability of the design at large scale.

Demonstrating the viability of halolipase production at a mechanically stirred tank biological reactor.

The definition of halophiles as "the coming stars of industrial biotechnology" in a recent review demands new research efforts for their efficient production at bioreactor scale. In this sense, the scarcity of information about halolipases production has furthered the research on the viability of Halomonas sp. LM1C culture in a mechanically stirred bioreactor. The operating conditions have been optimized by means of a Central Composite Face-Centered (CCFC) design. The operation at low aerations (0.25 vvm) and moderate agitation rates (583 rpm) led to activity levels near 8000 U/L, which clearly surpasses the typical values detected for other extremophilic enzymes. The process at optimum conditions has been kinetically characterized and the oxygen volumetric mass transfer coefficient (KLa) has been determined.

Electro-Fenton process for implementation of acid black liquor waste treatment.

In this work, an eco-friendly solution for the remediation of wastewater generated in the lignin recovery process from eco-industrial paper mill has been proposed in their way towards a more circular economy strategy. Thus, the application of the electro-Fenton process for the degradation of the non-recovered lignin and other organic compounds form a scarcely studied acid black liquor waste (ABLW) was successfully performed. This treatment was able to operate in a range of COD loads (0.5-19.5mgO2·L-1) showing high degradation values of the ABLW determined by the abatement of color, total phenolic content and COD. Then, the optimization of the working conditions for the design of a sustainable treatment system with optimum efficiency was carried out using a response surface methodology. The experiment carried out in the calculated optimal conditions for the electro-Fenton degradation process (current intensity 132.5mA, catalyst dosage of 0.10mM, and temperature 40°C) showed a COD removal of 74.82% and current efficiency 77.79%, close to the theoretical value predicted by the model 73.12% and 77.06%, respectively. In addition, the identification of the final products permitted to confirm the mineralization efficiency.

Optimization of photo-Fenton process for the treatment of prednisolone.

Prednisolone is a widely prescribed synthetic glucocorticoid and stated to be toxic to a number of non-target aquatic organisms. Its extensive consumption generates environmental concern due to its detection in wastewater samples at concentrations ranged from ng/L to µg/L that requests the application of suitable degradation processes. Regarding the actual treatment options, advanced oxidation processes (AOPs) are presented as a viable alternative. In this work, the comparison in terms of pollutant removal and energetic efficiencies, between different AOPs such as Fenton (F), photo-Fenton (UV/F), photolysis (UV), and hydrogen peroxide/photolysis (UV/H2O2), was carried out. Light diode emission (LED) was the selected source to provide the UV radiation. The UV/F process revealed the best performance, reaching high levels of both degradation and mineralization with low energy consumption. Its optimization was conducted and the operational parameters were iron and H2O2 concentrations and the working volume. Using the response surface methodology with the Box-Behnken design, the effect of independent variables and their interactions on the process response were effectively evaluated. Different responses were analyzed taking into account the prednisolone removal (TOC and drug abatements) and the energy consumptions associated. The obtained model showed an improvement of the UV/F process when treating smaller volumes and when adding high concentrations of H2O2 and Fe2+. The validation of this model was successfully carried out, having only 5% of discrepancy between the model and the experimental results. Finally, the performance of the process when having a real wastewater matrix was also tested, achieving complete mineralization and detoxification after 8 h. In addition, prednisolone degradation products were identified. Finally, the obtained low energy permitted to confirm the viability of the process.

Challenges and recent advances in biochar as low-cost biosorbent: From batch assays to continuous-flow systems.

Over the past few years, the increasing amount of pollutants and their diversity demand to develop versatile low-cost adsorption systems. The use of biomass feedstock such as agricultural residues, wood chips, manure or municipal solid wastes as source to produce low-cost biosorbent, and the new advances in their synthesis have encouraged remarkable efforts towards the development of biochar "on demand" in which their characteristics can be improved. This new trend opens the potential of biochar application in the removal of pollutants from wastewater, however, its use in environmental management requires the development of full-scale biosorption in engineered systems. Thus, this paper provides a brief review of recent progress in the research and practical application of biochar with a special emphasis on its potential to reduce the pollutants present in wastewater or to render them harmless. Furthermore, research gaps and uncertainties detected in their scale-up in continuous-flow systems are highlighted.

Removal of polyvinylamine sulfonate anthrapyridone dye by application of heterogeneous electro-Fenton process.

Diversity and rapidly multiplication of the pollutants incite as to improve the conventional treatments wastewater methods. One of the bottlenecks often faced is the presence into wastewater of organic pollutants with complex structures that requests the design of efficient processes. Thus, this work investigates the removal of polyvinylamine sulfonate anthrapyridone (PSA) dye which complex structure makes difficult its degradation by conventional technologies. For that, a heterogeneous oxidative process using pyrite as sustainable catalyst was designed. Initially, the performance of the system BBD-carbon felt as anode and cathode, respectively for the production of H2O2 was determined in comparison with system boron-doped diamond nickel foam. The carbon felt electrode provided the highest oxidant production, and it was selected for the treatment of the polymeric dye. Several oxidative processes were evaluated, and the best degradation levels were obtained by application of electro-Fenton-pyrite process. In addition, it was determined that dye removal followed a kinetic model of pseudo-first-order achieving the highest efficiency by operation at optimum dosage of pyrite 2 g/L and 200 mA of current intensity. Depending on the optimal experimental conditions, these values lead to a nearly complete mineralization (total organic carbon removal of 95%) after 6 h. Furthermore, the reusability of pyrite was evaluated, by removal of PSA in four cycles.

Unravelling the suitability of biological induction for halophilic lipase production by Halomonas sp. LM1C cultures.

In this study, the viability of using biological induction as an alternative to the conventional chemical induction in lipase production by a novel halophilic microorganism, Halomonas sp. LM1C, has been demonstrated. Thus, a 9-times increase of lipase activity (3000U/L) was recorded when Staphylococcus equorum sp. AMC7 was present in the medium, which is competitive with the results obtained when Triton X-100 was added as chemical inducer. The GC-MS data allowed concluding the true nature of the biological inducer effect, as the existence of high percentages of isomeric forms of pentadecanoic acid were detected. The suitability of the proposed strategy was validated by operating at bench scale bioreactor, and the influence of bioreactor configuration on the biomass and lipolytic activity levels was studied. All the data were fitted to logistic and Luedeking & Piret models to characterize the bioprocess kinetics, concluding the growth-associated character of the produced lipolytic enzymes.

Application of electro-Fenton technology to remediation of polluted effluents by self-sustaining process.

The applicability of electro-Fenton technology to remediation of wastewater contaminated by several organic pollutants such as dyes and polycyclic aromatic hydrocarbons has been evaluated using iron-enriched zeolite as heterogeneous catalyst. The electro-Fenton technology is an advanced oxidation process that is efficient for the degradation of organic pollutants, but it suffers from the high operating costs due to the need for power investment. For this reason, in this study microbial fuel cells (MFCs) were designed in order to supply electricity to electro-Fenton processes and to achieve high treatment efficiency at low cost. Initially, the effect of key parameters on the MFC power generation was evaluated. Afterwards, the degradation of Reactive Black 5 dye and phenanthrene was evaluated in an electro-Fenton reactor, containing iron-enriched zeolite as catalyst, using the electricity supplied by the MFC. Near complete dye decolourization and 78% of phenanthrene degradation were reached after 90 min and 30 h, respectively. Furthermore, preliminary reusability tests of the developed catalyst showed high degradation levels for successive cycles. The results permit concluding that the integrated system is adequate to achieve high treatment efficiency with low electrical consumption.

Bacterial-fungal interactions enhance power generation in microbial fuel cells and drive dye decolourisation by an ex situ and in situ electro-Fenton process.

In this work, the potential for sustainable energy production from wastes has been exploited using a combination fungus-bacterium in microbial fuel cell (MFC) and electro-Fenton technology. The fungus Trametes versicolor was grown with Shewanella oneidensis so that the bacterium would use the networks of the fungus to transport the electrons to the anode. This system generated stable electricity that was enhanced when the electro-Fenton reactions occurred in the cathode chamber. This configuration reached a stable voltage of approximately 1000 mV. Thus, the dual benefits of the in situ-designed MFC electro-Fenton, the simultaneous dye decolourisation and the electricity generation, were demonstrated. Moreover, the generated power was effectively used to drive an ex situ electro-Fenton process in batch and continuous mode. This newly developed MFC fungus-bacterium with an in situ electro-Fenton system can ensure a high power output and a continuous degradation of organic pollutants.

Studies of laccase from Trametes versicolor in aqueous solutions of several methylimidazolium ionic liquids.

Stability and kinetic behavior of laccase from Trametes versicolor in the presence of several ionic liquids from the methylimidazolium family have been investigated. In general laccase stability diminished as the size of the alkylic substitute in the methylimidazolium ring increased. Higher concentrations of ionic liquids caused more destabilization than lower ones. Thus, low concentrations of [C(2)mim(+)][EtSO(4)(-)] allowed maintaining enzymatic stability. [C(4)mim(+)][Cl(-)] appeared to have a stabilizing effect on laccase, as little activity decay was observed within three weeks. Kinetic studies indicated that both [C(2)mim(+)][EtSO(4)(-)] and [C(4)mim(+)][Cl(-)] inhibited laccase activity, although 10-fold more [C(2)mim(+)][EtSO(4)(-)] than [C(4)mim(+)][Cl(-)] was required to cause the same degree of inhibition. A kinetic model was developed to represent the experimental data.