Lurdes Ciríaco

Cyanuric acid (CYA) is widely used as a chlorine stabilizer in swimming pools, but concentrations above 75 mg L⁻¹ cause overstabilization and loss of disinfection capacity. This study evaluated CYA removal by advanced oxidation processes, including heterogeneous photocatalysis, photo-Fenton, photo-persulfate, and anodic oxidation (AO). AO with boron-doped diamond anodes proved most effective, achieving up to 90% total organic carbon removal in ultrapure water. When applied to real swimming pool samples (118 and 251 mg L⁻¹ CYA), the process achieved significant CYA abatement, demonstrating its potential as a practical strategy to control overstabilization without additional chemicals.

In this study, Sr_0.95Bi_0.05TiO₃ was synthesized via solid state reaction, characterized, and applied as a visible-light-active photocatalyst for the degradation of oxytetracycline, imidacloprid, and their mixture. To evaluate the influence of the aqueous matrix on pollutant degradation, photocatalytic experiments were carried out in both distilled water and a real environmental sample (surface water). The Sr_0.95Bi_0.05TiO₃ perovskite showed high photocatalytic performance under visible light, achieving nearly complete degradation of oxytetracycline after 2 h, and significant removal of imidacloprid in river water (60% after 3 h). Enhanced degradation in surface water was attributed to favorable ionic composition and pH. The perovskite oxide maintained its photocatalytic performance over five consecutive cycles, with no significant loss in photocatalytic activity or structural and morphological stability. Ecotoxicological assessment using Daphnia magna confirmed that the treated water was non-toxic, indicating that no harmful byproducts were formed. Complementary Density Functional Theory calculations were conducted to complement experimental findings, providing insights into the structural, electronic, and optical properties of the photocatalyst, enhancing the understanding of the degradation mechanisms involved. This integrated approach, combining experimental photocatalytic performance evaluation in different matrices, ecotoxicity testing, and theoretical modeling, highlights Sr_0.95Bi_0.05TiO₃ as a promising, stable, and environmentally safe photocatalyst for practical wastewater treatment applications.

The development of recovery processes has become essential in recent years as a strategy to minimize environmental pollution while boosting circular economy and sustainable development. Due to the exponential growth in agricultural production and the increased pollution of waterbodies, the production of fertilizers from recovered phosphorus has become an alternative to phosphate rock-based production. In this work, the effect of different operational parameters in the efficiency of the electrochemical recovery of phosphorus, from organic and inorganic sources, was investigated. Among the studied variables, the most significant was the electrode material utilized in the system. The use of magnesium sacrificial electrodes, as AZ31 alloys, led to phosphorus removal from solution of above 90%, allowing the recovery of both orthophosphates and organic phosphorus (glyphosate) as struvite, brucite, and other amorphous compounds. Since there is a lack in the literature about the use of magnesium electrodes in real wastewater electrochemical treatment, system efficiency was also evaluated using a sanitary landfill leachate, reaching 96% of phosphorus recovery. The specific energy consumption and faradaic efficiency of the phosphorus recovery process were also assessed.

Wastewater reuse has been addressed to promote the sustainable water utilization in textile industry. However, conventional technologies are unable to deliver treated wastewater with the quality required for reuse, mainly due to the presence of dyes and high salinity. In this work, the feasibility of electrooxidation, using a boron-doped diamond anode, to provide treated textile dyeing wastewater (TDW) with the quality required for reuse, and with complete recovery of salts, was evaluated. The influence of the applied current density on the quality of treated TDW and on the consecutive reuse in new dyeing baths was studied. The ecotoxicological evaluation of the process towards Daphnia magna was performed. After 10 h of electrooxidation at 60 and 100 mA cm⁻², discolorized treated TDW, with chemical oxygen demand below 200 (moderate-quality) and 50 mg L⁻¹ (high-quality), respectively, was obtained. Salt content was unchanged in both treatment conditions, enabling the consecutive reuse without any salt addition. For the two reuse cycles performed, both treated samples led to dyed fabrics in compliance with the most restrictive controls, showing that an effective consecutive reuse can be achieved with a moderate-quality water. Besides the water reuse and complete salts saving, electrooxidation accomplished an ecotoxicity reduction up to 18.6-fold, allowing TDW reuse without severe ecotoxicity accumulation.

In this study, Bi-doped SrTiO₃ perovskites (Sr_1−xBi_xTiO₃, x = 0, 0.03, 0.05, 0.07 and 0.1) were synthesized using the solid-state method, characterized, and tested as photocatalysts in the degradation of the azo dye acid orange 7 (AO7) under visible light. The perovskites were successfully synthesized, and XRD data showed a predominant, well-crystallized phase, belonging to the cubic perovskite symmetry. For the doped samples, a minority phase, identified as bismuth titanate, was detected. All doped samples exhibited improved photocatalytic activity under visible light, on the degradation of AO7 (10 mg L⁻¹), when compared with the undoped SrTiO₃, with an increase in relative Abs_{484 nm} decay from 3.7% to ≥67.8% after 1 h, for a powder suspension of 0.2 g L⁻¹. The best photocatalytic activity was exhibited by the Sr_0.95Bi_0.05TiO₃ perovskite. Reusability studies showed no significant loss in photocatalytic activity under visible light. The final solutions showed no toxicity towards D. magna, proving the efficiency of Sr_0.95Bi_0.05TiO₃ as a visible-light-driven photocatalyst to degrade both the AO7 dye as well as its toxic by-products. A degradation mechanism is proposed.

The electro-oxidation of recalcitrant compounds, phthalic acid, tyrosol, and catechin was studied in simulated and real winery wastewater samples using a boron-doped diamond (BDD) anode. In the simulated samples, catechin, although presenting a higher removal rate than that of phthalic acid and tyrosol, attained lower combustion efficiency, indicating that this compound is readily converted into other products rather than being completely oxidized. On the other hand, phthalic acid was easily mineralized. Regarding the electro-oxidation assays performed with the spiked winery wastewater, recalcitrant compounds and overall organic load removal rates increased with applied current density (j), but the removal efficiency of recalcitrant compounds decreased with the increase in j, and the specific energy consumption was significantly raised. The increase in treatment time showed to be a feasible solution for the WW treatment at lower j. After 14 h treatment at 300 A m⁻², phthalic acid, tyrosol, and catechin removals above 99.9% were achieved, with a chemical oxygen demand removal of 98.3%. Moreover, the biodegradability index was increased to 0.99, and toxicity towards Daphnia magna was reduced 1.3-fold, showing that the electro-oxidation process using a BDD anode is a feasible solution for the treatment of winery wastewaters, including phthalic acid, tyrosol, and catechin degradation.

Perovskites of the (La,Ba)(Fe,Ti)O₃ family were prepared, characterized, and utilized as heterogeneous photocatalysts, activated by natural sunlight, for environmental remediation of Acid Orange 7 (AO7) aqueous solutions. Catalysts were prepared by the ceramic (CM) and the complex polymerization (CP) methods and characterized by XRD, SEM, EDS, and band gap energy. It was found that catalytic properties depend on the synthesis method and annealing conditions. In the photocatalytic assays with sunlight, different AO7 initial concentrations and perovskite amounts were tested. During photocatalytic assays, AO7 and degradation products concentrations were followed by HPLC. Only photocatalysis with BaFeO₃-CM and BaTiO₃-CP presented AO7 removals higher than that observed for photolysis. However, photolysis leads to the formation of almost exclusively amino-naphthol and sulfanilic acid, whereas some of the perovskites utilized form less-toxic compounds as degradation products, such as carboxylic acids (CA). Partial substitution of Ba by La in BaTiO₃-CM does not produce any change in the photocatalytic properties, but the replacement of Ti by Fe in the La_0.1Ba_0.9TiO₃ leads to reduced AO7 removal rate, but with the formation of CAs. The best AO7 removal (92%) was obtained with BaFeO₃-CM (750 mg L⁻¹), after 4 h of photocatalytic degradation with solar radiation.

This study focuses on preventing scale formation in hard waters by controlled electrode-position of Ca²⁺ and Mg²⁺ on a stainless-steel cathode at constant applied current intensity. The influence of the anode material, BDD or Ti/Pt/PbO₂, cathode active area, stirring speed, and applied anodic current intensity on the inorganic carbon (IC), Ca^2+, and Mg²⁺ removal was investigated. Assays were performed with model hard water solutions, simulating Bounouara (Algeria) water. The scaling inhibiting properties of the treated water were followed by measuring IC, calcium, and magnesium concentrations and chronoamperometric characterization of the treated solutions. The influence of the Ca/Mg molar ratio on the inorganic carbon removal by electrolysis was also evaluated, utilizing model solutions with different compositions. It was found that an increase in stirring speed or cathode geometric area favors IC and Ca²⁺ and Mg²⁺ removal rates. The applied current intensity was varied from 0.025 to 0.5 A, and the best results were obtained for 0.1 A, either in IC and Ca²⁺ and Mg²⁺ removals or by the accelerated scaling tests. However, energy costs increase with applied current. The deposit formed over the cathode does not seem to influence posterior deposition rate, and after eight consecutive assays, the solid deposition rate was kept constant. Ca/Mg ratio influences IC removal rate that increases with it. The results showed that hard-water scaling phenomena can be prevented by solid electrodeposition on the cathode at applied constant current.

Complex wastewater matrices present a major environmental concern. Besides the biodegradable organics, they may contain a great variety of toxic chemicals, heavy metals, and other xenobiotics. The electrochemically activated persulfate process, an efficient way to generate sulfate radicals, has been widely applied to the degradation of such complex effluents with very good results. This review presents the fundamentals of the electro-persulfate processes, highlighting the advantages and limitations, followed by an exhaustive evaluation on the application of this process for the treatment of complex industrial effluents. An overview of the main relevant experimental parameters/details and their influence on the organic load removal is presented and discussed, having in mind the application of these technologies at an industrial scale. Finally, the future perspectives for the application of the electro-persulfate processes in the treatment of complex wastewater matrices is outlined.

A short review on the treatment of effluents from food processing industries by electrochemical oxidation (EO) was performed. Olive mill wastewater (OMW) and boron-doped diamond (BDD) are the most reported effluent and anode material, respectively. The addition of NaCl or Na₂SO₄ as supporting electrolytes is common in these studies, and their influence on the EO performance depends, among other things, on the anode material, since the electrolyte oxidation mechanism is different when active and non-active anode materials are utilized. A case-study on the application of a pilot plant, working in batch mode with recirculation, equipped with a BDD anode, to treat 4 L of OMW, slaughterhouse (SW) and winery (WW) wastewaters, with initial chemical oxygen demands (COD) of 20.5, 3.6 and 0.26 g L⁻¹, respectively, is presented and discussed. In 16 h assays, 94% COD removal was achieved for OMW, and for SW and WW the Portuguese COD legal discharge limit of 150 mg L⁻¹ was accomplished. Process efficiency decreased for lower organic load. NaCl addition increased COD removal in SW and WW, but presented an adverse effect for OMW COD removal, when compared to Na₂SO₄ addition. Nevertheless, lower specific energy consumptions were attained in chloride medium (48 Wh (g COD)⁻¹).