Innovative biopolyelectrolytes-based technologies for wastewater treatment.

Developing eco-friendly, cost-effective, and efficient methods for treating water pollutants has become paramount in recent years. Biopolyelectrolytes (BPEs), comprising natural polymers like chitosan, alginate, and cellulose, have emerged as versatile tools in this pursuit. This review offers a comprehensive exploration of the diverse roles of BPEs in combating water contamination, spanning coagulation-flocculation, adsorption, and filtration membrane techniques. With ionizable functional groups, BPEs exhibit promise in removing heavy metals, dyes, and various pollutants. Studies showcase the efficacy of chitosan, alginate, and pectin in achieving notable removal rates. BPEs efficiently adsorb heavy metal ions, dyes, and pesticides, leveraging robust adsorption capacity and exceptional mechanical properties. Furthermore, BPEs play a pivotal role in filtration membrane techniques, offering efficient separation systems with high removal rates and low energy consumption. Despite challenges related to production costs and property variability, their environmentally friendly, biodegradable, renewable, and recyclable nature positions BPEs as compelling candidates for sustainable water treatment technologies. This review delves deeper into BPEs' modification and integration with other materials; these natural polymers hold substantial promise in revolutionizing the landscape of water treatment technologies, offering eco-conscious solutions to address the pressing global issue of water pollution.

Sustainable recovery of phenolic antioxidants from real olive vegetation water with natural hydrophobic eutectic solvents and terpenoids.

Olive oil production leads to the generation of olive mill wastewater (OMWW). Due to the presence of phenolic compounds, they are difficult to process, but they represent a source of high-added value chemicals since they have antioxidant and therapeutic properties. This work has studied the extraction of phenolic compounds from a type of OMWW, olive vegetation water, which presents these compounds in a more diluted dosage than in other studied to date, to revalue this waste stream. A real olive vegetation water from a Spanish olive oil producer was used, and liquid-liquid extraction was applied. Terpenoids and terpene-based hydrophobic eutectic solvents were systematically used to extract phenolic compounds following the concentrations of tyrosol, catechol, caffeic acid, and total phenolic content. By molecular simulation with the COSMO-RS method, 4 terpenoids, and 2 eutectic solvents were selected and compared with 2 conventional solvents. The Solvent/Feed ratio in the extraction of phenolic compounds was studied, showing that the solvents with the highest extraction results were geraniol, eucalyptol, and eutectic solvent menthol + camphor, which outperformed conventional solvents methyl isobutyl ketone and diisopropyl ether. Menthol + camphor gave total phenol extraction yields of 88.73% at a Solvent/Feed ratio in volume of 0.50, surpassing all solvents tested. A solvent reuse and regeneration process was applied by back-extraction of the 4 solvents: FTIR results showed the stability of the solvents while maintaining yields in the solvent reuse process. The phenolic compounds could be concentrated in the alkaline phase to factors up to 49.3 to the initial concentration in olive vegetation water. The alkaline phases were neutralized to obtain a precipitate with a caffeic acid content of up to 26 % wt%, and a tyrosol-rich supernatant with a concentration of up to 6.54 g/L. This work proposes a process using natural solvents to extract phenolic compounds from olive vegetation water.

Enhanced removal of neonicotinoid pesticides present in the Decision 2018/840/EU by new sewage sludge-based carbon materials.

Due to the increasingly strict legislation about the disposal of sewage sludge, it is necessary to find sustainable solutions to manage this waste at low-cost conditions. In addition, priority contaminants are now attracting much attention since they are usually detected in WWTP effluents. In this work, five sludge have been used as precursors for the synthesis of activated carbons subsequently tested in the removal by adsorption of three neonicotinoid pesticides listed in the EU Watch List: acetamiprid (ACT), thiamethoxam (THM), and imidacloprid (IMD). Generally, the activated carbons were prepared by chemical activation using ZnCl2 as an activating agent and then the resulting materials were pyrolyzed at 800 °C for 2 h. The synthesized activated carbons showed different textural properties; thus, the best adsorption results were found for AC-Industrial activated carbon, obtained from an industrial origin sewage sludge, with high equilibrium adsorption capacities (qe = 104.2, 137.0, and 119.9 mg g-1), for ACT, THM, and IMD, respectively. Furthermore, it was elucidated that the use of CO2 in the synthesis generated an opening, followed by widening, of the narrowest microporosity, increasing the specific surface area of the carbon materials. The kinetic and isotherm adsorption experimental data were obtained for each of the pesticide-activated carbon systems; thus, the kinetic curves were well-fitted to the pseudo-second-order kinetic model, as well as, Freundlich and Guggenheim-Anderson-de Boer (GAB) empirical models were used for the fitting of the equilibrium adsorption isotherms, finding that GAB model best fitted the experimental data. Additionally, the regeneration of the activated carbons using methanol as a regenerating agent and the single and simultaneous adsorption of a hospital wastewater effluent, fortified with the three studied pesticides have been explored.

A comparative study among catalytic wet air oxidation, Fenton, and Photo-Fenton technologies for the on-site treatment of hospital wastewater.

The feasibility of catalytic wet air oxidation, intensified homogeneous Fenton and heterogeneous Photo-Fenton systems for the treatment of real hospital wastewater has been investigated. Wastewater samples were collected from a hospital sewer, during a weekly monitoring program, and fully characterized. Up to seventy-nine pharmaceuticals, including mostly parent compounds and some of their transformation products, were analyzed. Catalytic wet air oxidation allowed the complete removal of several pharmaceutical groups, but it did not allow to eliminate analgesics/anti-inflammatories and antibiotics, whose average removal was around 85%. Intensified Fenton oxidation was the most efficient process for all the drugs removal with an almost complete reduction of the initial pharmaceutical load (99.8%). The heterogeneous Photo-Fenton system reached a 94.5% reduction of the initial pharmaceutical load. The environmental risk of the treated samples by the hazard quotient (HQ) method was also evaluated. Fenton oxidation was the most effective system with a final ∑HQ of 5.4. Catalytic wet air oxidation and Photo-Fenton systems achieved total ∑HQ values of 895 and 88, respectively. This fact was related to the presence of refractory antibiotics in the treated catalytic wet air oxidation samples. On the opposite, the Photo-Fenton system provided the elimination of most pharmaceutical pollutants that pose a high environmental risk such as antibiotics. Simplified cost estimation was finally performed as a preliminary approach of the economy of the three oxidation processes for the hospital wastewater treatment.

Boosting the catalytic activity of natural magnetite for wet peroxide oxidation.

This work explores the modification of naturally occurring magnetite by controlled oxidation (200-400 °C, air atmosphere) and reduction (300-600 °C, H2 atmosphere) treatments with the aim of boosting its activity in CWPO. The resulting materials were fully characterized by XRD, XPS, TGA, TPR, SEM, and magnetization measurements, allowing to confirm the development of core-shell type structures. The magnetite core of the solid remained unchanged upon the treatment whereas the Fe(II)/Fe(III) ratio of the shell was modified (e.g. 0.42, 0.11 and 0.63 values were calculated for pristine Fe3O4, Fe3O4-O400, and Fe3O4-R400, respectively). The performance of the catalysts was tested in the CWPO of sulfamethoxazole (SMX) (5 mg L-1) under ambient conditions and circumneutral pH (pH0 = 5), using the stoichiometric dose of H2O2 (25 mg L-1) and a catalyst load of 1 g L-1. The key role of the ferrous species on the mineral shell was evidenced. Whereas the oxidation of magnetite led to significantly slower degradation rates of the pollutant, its reduction gave rise to a dramatic increase, achieving the complete removal of SMX in 1.5 h reaction time with the optimum catalyst (Fe3O4-R400) compared to the 3.5 h required with the pristine mineral. A reaction mechanism was proposed for SMX degradation, and a kinetic equation based on the Eley-Rideal model was accordingly developed. This model successfully fitted the experimental results. The stability of Fe3O4-R400 was evaluated upon five sequential runs. Finally, the versatility of the catalytic system was proved in real environmentally relevant water matrices.

Magnetic Fe3O4/multi-walled carbon nanotubes materials for a highly efficient depletion of diclofenac by catalytic wet peroxideoxidation.

The aim of this work is to synthesize a magnetic magnetite/multi-walled carbon nanotube (Fe3O4/MWCNT) catalyst by a method combining co-precipitation and hydrothermal treatments for the efficient removal of diclofenac (DCF) by catalytic wet peroxide oxidation (CWPO). The support (MWCNTs) shows a moderate-large surface area and good adsorption capacity, leading to the improvement of the magnetite (Fe3O4) dispersion on its surface. The response surface methodology (RSM) was applied in order to find out the effect of the reaction parameters on DCF removal, allowing to establish the optimum operating conditions (T = 60 °C, [H2O2]0 = 2.7 mM, [catalyst] = 1.0 g L-1). The optimum CWPO experiment showed an outstanding catalytic activity at non-modified pH solution (6.7), obtaining a 95% of DCF removal after 3 h reaction time; this high efficiency can be attributed to the synergistic effect of the iron-based catalyst with the high quantity of •OH radicals generated on the surface of the catalyst. In addition, the Fe3O4/MWCNT material exhibited good reusability along three consecutive reaction cycles, finding a pollutant removal close to 95% in each cycle of 3 h reaction time. Additionally, a degradation mechanism pathway was proposed for the removal of DCF by CWPO. The versatility of the material was finally demonstrated in the treatment of different environmentally relevant aqueous matrices (a wastewater treatment plant effluent, surface water, and hospital wastewater), obtaining an effective reduction in the ecotoxicity values.

Adsorption and removal of phenoxy acetic herbicides from water by using commercial activated carbons: experimental and computational studies.

In this study, commercial activated carbons (GAB and CBP) were successfully used for the removal of two phenoxy acetic class-herbicides, 4-chloro-2-methyl phenoxy acetic acid and 2.4-dichlorophenoxy acetic acid (MCPA and 2.4-D) from aqueous solution. The adsorbent materials were characterized, and their equilibrium adsorption capacity was evaluated. The results suggest that the microporous properties of GAB activated carbon enhanced the adsorption capacity, in comparison to CBP carbon. Thus, the increasing in the ionic strength favored the adsorption removal of both pesticides, indicating that electrostatic interactions between the pollutant and the adsorbate surface are governing the adsorption mechanism, but increasing pH values decreased adsorption capacity. Experimental data for equilibrium was analyzed by two models: Langmuir and Freundlich. Finally, computational simulation studies were used to explore both the geometry and energy of the pesticides adsorption.

Application of CWPO to the treatment of pharmaceutical emerging pollutants in different water matrices with a ferromagnetic catalyst.

CWPO has proved to be effective for the treatment of representative pharmaceuticals (sulfamethoxazole, atenolol, metronidazole, diltiazem, trimethoprim and ranitidine) in different water matrices (ultrapure water, surface water, WWTP effluent and hospital wastewater). Complete removal of the pollutants and the aromatic intermediates was achieved using the stoichiometric dose of H2O2, a catalyst (Fe3O4/γ-Al2O3) load of 2gL-1, pH 3 and temperature of 50-75°C. Accordingly, the ecotoxicity was reduced to negligible values. The degradation was faster when the pharmaceuticals were together, being the reaction time for the elimination of the most refractory species (metronidazole) shortened from 4h to 1h. The mineralization of the drugs was fairly different, being the most reactive species those containing several aromatic rings (XTOC∼80%) and the most refractory that bearing an imidazolium ring (XTOC∼35%). The water matrix affected the kinetics of the process but in all cases complete conversion of the drugs was reached within 1h. The presence of dissolved organic matter (surface water) seemed to promote drugs degradation while the occurrence of inorganic ions (real WTTP and hospital effluents) partially inhibited it due to scavenging effects. Remarkably, the process was successfully operated at the typical concentrations of main micropollutant sources (µgL-1).

Removal of caffeine from pharmaceutical wastewater by adsorption: influence of NOM, textural and chemical properties of the adsorbent.

This work involves the study of the influence of textural and chemical adsorbent properties on natural organic matter (NOM) removal and the simultaneous adsorption of caffeine and NOM in pharmaceutical wastewater. The performance of a microporous activated carbon, Calgon F400, a synthesized mesoporous carbon from peach stones and a commercial sepiolite in the removal of NOM of a WWTP effluent, and the competitive adsorption of caffeine/NOM were evaluated. It was evidenced that the microporous structure of the adsorbents significantly conditioned the removal of NOM, finding that F400 activated carbon (microporous volume of 0.46 cm(3) g(-1)) led to a NOM removal of 45%. The presence of NOM in the aqueous medium led to worse adsorption parameters, including adsorption capacity at breakthrough time, mass transfer zone length and fractional bed utilization. Additionally, an overshooting in the Total Organic Carbon concentration (TOC/TOC0 = 1.05) was observed in the sepiolite adsorption fixed-bed experiment, due to the displacement of the background NOM. The tested adsorbents were efficient in the removal of caffeine from a pharmaceutical wastewater, finding a competitive effect between the target compound and the background NOM for the active sites.