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In this study, three CuFe-MOFs were successfully synthesized by a solvothermal process by changing the ratio of solvents, salts, or temperature. These MOFs named CuFe(BDC-NH2)R, CuFe(BDC-NH2)S, and CuFe(BDC-NH2)D showed rod-shaped, spindle-like, and diamond-like structures, respectively. The CuFe(BDC-NH2)D and CuFe(BDC-NH2)S were found to exhibit an improved PMS activation for Rhodamine B removal attaining levels around 92%. Their effective removal capability was investigated as a function of the pH, catalyst dosage, and the effect of the application of UV radiation. The best degradation system was photo-assisted activation of PMS when CuFe(BDC-NH2)D and CuFe(BDC-NH2)S were used. Under these conditions, the degradation of a mixture of antibiotic and anti-inflammatory drugs (sulfamethoxazole and antipyrine) was evaluated with the results revealing the total degradation of both drugs after 1 h. A higher antibacterial activity was attained with the system CuFe(BDC-NH2)R/PMS due to the high copper content with respect to the others. Ministerio de Ciencia e Innovación | Ref. PCI2022-132941 Ministerio de Ciencia e Innovación | Ref. PID2020-113667GBI00 Xunta de Galicia | Ref. ED431C 2021-43

The development of novel approaches to the remotion of pharmaceuticals in wastewater is a subject of concern due to their effect on living beings and the environment. Advanced oxidation processes and the use of relevant catalysts are feasible treatment alternatives that require further development. The development of suitable heterogeneous catalysts is a necessity. This work proposes the synthesis of an iron catalyst in a deep eutectic solvent (Fe-DES) composed of choline chloride and citric acid, which was physically and chemically characterized using SEM-EDS and TEM, FTIR, RAMAN, XRD and XPS. The characterisation confirmed the presence of iron in the form of hematite. Fe-DES was shown to be a multipurpose catalyst that can be applied in the removal of sulfamethoxazole as a reagent in the Fenton and electro-Fenton processes and as an activator of peroxymonosulfate (PMS) processes. After testing the catalyst with the aforementioned techniques, the best result was achieved by combining these processes in an electro-PMS, with great efficiency achieved by dual activation of the PMS with the catalyst and electric field, attaining total elimination at natural pH in 90 min. Furthermore, the degradation was confirmed by the detection of short-chain carboxylic acids (oxalic, succinic, and acetic) and reduction in toxicity values. These results confirm the suitability of Fe-DES to degrade high-priority pharmaceutical compounds. Xunta de Galicia y FEDER | Ref. ED431C 2021-43 Ministerio de Ciencia e Innovación | Ref. PCI2022-132941 Ministerio de Ciencia e Innovación | Ref. PDC2021-121394-I00

Analysis of the genotype that predicts the phenotypic characteristics of a cohort of glaucoma and ocular hypertension patients, and the correlation with their personal pharmacological response to beta-blockers (BB) and prostaglandin analogues (PGA). Prospective study that included 139 eyes from 72 patients under BB and/or PGA treatment, and in some cases other types of ocular hypotensive treatments. Five single-nucleotide polymorphisms were genotyped by real-time PCR assays: prostaglandin-F2α receptor (rs3766355, rs3753380); cytochrome-P450 2D6 (rs16947, rs769258); and beta-2-adrenergic receptor (rs1042714). Other studied variables were mean deviation (MD) of visual field, previous ocular interventions, medical treatment, baseline (bIOP), and treated intraocular pressure (tIOP). From a total of 139 eyes, 71 (51.1%) were left eyes. The main diagnosis was primary open angle glaucoma (66.2%). A total of 57 (41%) eyes were under three or more medications (PGA + BB + other) and, additionally, 57 eyes (41%) had had some kind of glaucoma surgery. The mean bIOP and tIOP were 26.55 ± 8.19 and 21.01 ± 5.54 mmHg, respectively. Significant differences in tIOP were found between heterozygous (HT) (21.07 ± 0.607 mmHg) and homozygous (HM) (20.98 ± 0.639 mmHg) rs3766355 with respect to wildtype individuals (16 ± 1.08 mmHg) (p = 0.031). The MD values presented significant differences between wildtype rs3766355 (−2 ± 2.2 dB), HT (−3.87 ± 4 dB), and HM carriers (−9.37 ± 9.51 dB) (p = 0.009). Significant differences were also observed between the MD in wildtype rs3753380 (−6.1 ± 8.67 dB), HT (−9.02 ± 8.63 dB), and HM carriers (−9.51 ± 7.44 dB) (p = 0.017). Patients carrying the variant rs3766355 in HM or HT presented clinically-significantly higher tIOP than wildtype patients. Additionally, some differences in MD were found in rs3766355 and rs3753380 carriers, and the more alleles that were affected, the worse the MD value, meaning greater severity of the glaucoma. Poor response to treatment and more visual field damage may be associated with being a carrier of these mutated alleles.

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG There are several disposal and governance difficulties due to rapid bio-waste growth. Therefore, recycling and repurposing them for environmental purposes is garnering increasing attention. Hydrothermal carbonization (HTC) followed by phosphoric acid activation was used in this investigation to synthesize a novel activated hydrochar (AHPP) from pomegranate peels. X-Ray Diffraction, Fourier-transform infrared spectroscopy, Scanning electron microscopy with energy dispersive X-ray spectroscopy, Brunauer, Emmett and Teller (BET) surface area analysis and Barrett- Joyner-Halenda (BJH) pore size distribution, and pH of zero charge were exploited to define the characteristics of AHPP, which was then used to assess the uptake of Basic Red 46 (BR46) dye in the batch mode. Isothermal and kinetic investigations were accomplished with pH = 6, 0.5 g.L−1 of adsorbent, 400 rpm at 298 K upon 60 min. The Freundlich model accurately presented the equilibrium curves with an adsorption capacity of 998.95 mg g−1, while the PSO kinetic model adequately corresponded to the experimental data. Furthermore, thermodynamic data disclosed that the process was spontaneous, endothermic, and linked to a growing disorder at the adsorbent- adsorbate interface. Lastly, the reuse investigation using HCl ascertained that AHPP might be recycled ten times, whereas a probable adsorption mechanism was proffered. Overall, it is possible to conclude that activated hydrochar generated from pomegranate peels as cost-effective waste could be employed as an alternative sorbent in dining substantial effluents retaining BR46 Ministerio de Ciencia e Innovación | Ref. PID2020-113667GBI00

In this study, the removal of persistent emerging and dangerous pollutants (pharmaceuticals and pathogens) in synthetic wastewater was evaluated by the application of heterogeneous Advanced Oxidation Processes. To do that, a Metal-Organic Framework (MOF), Basolite® F-300 was selected as a catalyst and combined with peroxymonosulfate (PMS) as oxidants in order to generate sulphate radicals. Several key parameters such as the PMS and Basolite® F-300 concentration were evaluated and optimized using a Central Composite Experimental Design for response surface methodology for the inactivation of Escherichia coli. The assessment of the degradation of an analgesic and antipyretic pharmaceutical, antipyrine, revealed that is necessary to increase the concentration of PMS and amount of Basolite® F-300, in order to diminish the treatment time. Finally, the PMS-Basolite® F-300 system can be used for at least four cycles without a reduction in its ability to disinfect and degrade persistent emerging and dangerous pollutants such as pharmaceuticals and pathogens. Xunta de Galicia | Ref. ED431C 2021-43 Ministerio de Ciencia e Innovación | Ref. PID2020-113667GBI00

In the current study, a novel-fangled sequential approach, adsorption/electro-Fenton, was developed for the elimination of micropollutants from aqueous matrixes. Therefore, the prompt removal of a pharmaceutical, sulfamethizole, by adsorption on carbonaceous materials is proposed. After that, the concentrated solution was treated by electro-Fenton using novel synthesized perlite-based catalyst. Initially, three different carbonaceous adsorbents (pellets carbonaceous nanogel doped with iron, honeycomb carbonaceous aerogel and orange biochar) were considered. The kinetics and isotherms of the pollutant adsorption were studied. The higher removal level was attained by the pellets with the adsorption process following a pseudo-2nd order model and being well defined by the Langmuir adsorption isotherm. After that, the pollutant was extracted from the pellets, concentrated in aqueous solution and treated by different advanced oxidation processes (anodic oxidation and electro-Fenton process). The results confirmed the higher efficiency of electro-Fenton treatment and its improvement was evaluated using a novel synthesized iron perlite catalyst. For this purpose, the synthesis of iron catalysts supported in perlite was performed by different methods (carbonisation, precipitation and hydrothermal). Among them, the hydrothermal synthesis produced catalysts with high catalytic activity, significant pollutant removal (>95 %), high stability and without iron leaching after several cycles of treatment. Based on these results, the development of a continuous treatment system was successfully carried out attaining high TOC removal values. Moreover, the feasibility of the treatment was also validated in complex water matrixes and toxicity assays demonstrated the viability of the proposed treatment for a global management of this pollutant.

Current management of diabetic macular edema (DME) predominantly involves treatment with short-acting intravitreal injections of anti-vascular endothelial growth factors (anti-VEGFs) and/or corticosteroids; however, short-acting therapies (lasting between 1 and 6 months) require frequent injections to maintain efficacy, meaning a considerable treatment burden for diabetic patients with multiple comorbidities. Continuous injections needed in some cases are an economic burden for patients/healthcare system, so real-life clinical practice tends to adopt a reactive approach, ie, watch and wait for worsening symptoms, which consequently increases the risk of undertreatment and edema recurrence. On March 7th 2019, a group of experts in retinal medicine and surgery held a roundtable meeting in Madrid, Spain to discuss how to (1) optimize clinical outcomes through earlier use of fluocinolone acetonide (FAc) implant (ILUVIEN®) in patients with persistent or recurrent DME despite therapy; and, (2) to provide guidance to assist physicians in deciding which patients should be treated with ILUVIEN. In this regard, a 36-month follow-up consensus protocol is presented. In conclusion, patients that achieve a complete or partial anatomical, and preferably functional, response following one or two intravitreal dexametha-sone implants, but with recurrence of edema after 3–4 months, are deemed by the authors most likely to benefit from ILUVIEN, and the switch to FAc implant should not be delayed more than 12 months after the initiation of at least the first dexamethasone implant.

Currently, the interest in eco-friendly treatments for the removal of pollutants has increased and more sustainable treatment solutions are required. In this study, the homogeneous and heterogeneous activation of peroxymonosulfate (PMS) was carried out for the degradation of an industrial dye. Initially, the homogeneous PMS activation by different transition metals (Co, Cu, Ni, Fe) was ascertained. Cobalt resulted in the best performance attaining removal levels around 100% in only 30 min. Then, the influence of operational parameters such as pH and pollutant concentration were evaluated. The results displayed a high efficiency in the degradation and mineralisation operating close to neutral pH. The mechanism of the reaction was also studied and the obtained results demonstrated that sulfate radical is the primary reactive specie involved in the pollutant degradation. The optimisation of the degradation process was then carried out by a response surface methodology and several variables (PMS and Co concentration and temperature) were evaluated. The optimisation was performed in order to maximise the degradation and minimise the consumption of catalyst resulting in values of Co concentration 0.0125 mM, temperature 40 °C and PMS concentration 0.895 mM. Finally, heterogeneous activation by Co-catalyst immobilisation using alginate beads (Co-AB) and amberlite (Co-A) was performed. The results showed the superiority of Co-AB maintaining a high removal level after four treatment cycles with low Co leaching.

In this study, magnetic iron particles doped with TiO2 were synthetized to be used as a photo electro Fenton catalyst, being easily eliminated from the treated solution. Thus, the synergistic and scarcely reported combination of photocatalyst with electro Fenton process was evaluated for the degradation of an emerging pollutant: the ionic liquid 1-butyl-2, 3-dimethyl imidazolium chloride. To increase the radiation leverage, a cyclic two-cell configuration reactor was set, so the photolysis is applied directly and without obstacles in one cell and the electrolysis in another. The effect of the catalyst synthesis method and the ratio Fe/TiO2 were evaluated. With the most active bifunctional catalyst, a deep study of the two-cell reactor was done in terms of recirculation flow, applied intensity and catalyst dosage. Under the best conditions (respectively, 480 mL min−1, 70 mA and 1 g L−1), complete pollutant removal (in 10 min) and high mineralization (100% in 2 h) was achieved. Encouragingly, the results were almost equal when degrading the model pollutant on a real wastewater matrix. The reusability of the catalyst was also confirmed after three trials without almost no detriment on the performance.

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG 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. Xunta de Galicia | Ref. ED431C 2021-43 Agencia Estatal de Investigación | Ref. PCI2022-132941

Glaucoma; Retinògrafs; Telemedicina Glaucoma; Retinógrafos; Telemedicina Glaucoma; Retinographs; Telemedicine Purpose: To evaluate interobserver and intertest agreement between optical coherence tomography (OCT) and retinography in the detection of glaucoma through a telemedicine program. Methods: A stratified sample of 4113 individuals was randomly selected, and those who accepted underwent examination including visual acuity, intraocular pressure (IOP), non-mydriatic retinography, and imaging using a portable OCT device. Participants’ data and images were uploaded and assessed by 16 ophthalmologists on a deferred basis. Two independent evaluations were performed for all participants. Agreement between methods was assessed using the kappa coefficient and the prevalence-adjusted bias-adjusted kappa (PABAK). We analyzed potential factors possibly influencing the level of agreement. Results: The final sample comprised 1006 participants. Of all suspected glaucoma cases (n = 201), 20.4% were identified in retinographs only, 11.9% in OCT images only, 46.3% in both, and 21.4% were diagnosed based on other data. Overall interobserver agreement outcomes were moderate to good with a kappa coefficient of 0.37 and a PABAK index of 0.58. Higher values were obtained by experienced evaluators (kappa = 0.61; PABAK = 0.82). Kappa and PABAK values between OCT and photographs were 0.52 and 0.82 for the first evaluation. Conclusion: In a telemedicine screening setting, interobserver agreement on diagnosis was moderate but improved with greater evaluator expertise. The study has been funded by the Fondo de InvestigacionesSanitarias of the Spanish Ministry of Health (PI15/00412).

The aim of this study was to develop a comprehensive strategy for the degradation of a pharmaceutical compound, i.e., diclofenac (DCF), in which the solubility is strongly related to the solution pH. Therefore, in this study, alternative treatments according to DCF concentration ranges were developed. Working at the concentration of 7.5 mg/L and pH below 4, the considered treatments by sonolysis, anodic oxidation and electro-Fenton resulted in a good performance with high abatement levels. At high concentrations (140 mg/L), it was necessary to operate at near neutral pH, and the three proposed treatments (sonolysis, anodic oxidation and electro-Fenton using iron-alginate spheres as the heterogeneous catalyst) were performed. Heterogeneous electro-Fenton (HEF) resulted in the best option for the pollutant removal, and three new chitosan-based heterogeneous catalysts were synthesized and evaluated. The operational conditions (intensity and dosage of catalyst) were optimized resulting in an intensity of 300 mA and catalyst dose of 20 g/L. Operating at these conditions, high levels of DCF degradation and mineralization were achieved. Several treatment cycles, using the same catalyst, were successfully carried out, and the catalysts demonstrated good stability and the potential to operate in a continuous way. Finally, the evolution of carboxylic acids and intermediate generation were analysed leading to the proposal of a plausible DCF degradation pathway for HEF.

In the present study, the degradation of ionic liquid 1-butyl-1-methylpyrrolidinium chloride has been carried out through sulfate radicals. These radicals were generated by different methods of activation of the commercial peroxymonosulfate (PMS) formulation, Oxone®. Among them, the electro-assisted activation in presence of iron provided the best results in terms of pollutant removal and mineralization. However, radical scavenging takes place at high concentration of catalyst (Fe 2+ ) in solution, that provokes the reduction of the removal rate. In order to control the iron self-regulation in the process, iron-based minerals such as pyrite, goethite and magnetite were studied as catalyst. This process was evaluated in detail and the key factors as catalyst concentration, oxidant dosage and applied current were analyzed. It was confirmed that the removal reaction in the heterogeneous system followed pseudo-first order kinetic model. Pyrite catalyst achieved the best results and its application was optimized. The activation of PMS (10 mM) by pyrite (1 mM) under electric field (150 mA) showed a very high pollutant degradation efficiency (over 80% TOC decay in 300 min) with a low electrical energy consumption per log-unit of pollutant concentration decrease (5.45 kWh m −3 order −1 ). In addition, the use of solid catalyst eased its separation from the reaction medium and its reuse at least 5 cycles, achieving in all cases a degradation efficiency near 100% in 300 min. This fact justifies the developed process as a promising treatment for a novel class of neoteric contaminants such as ionic liquids.

The release of antibiotics in aquatic ecosystems from the effluents of wastewater treatment plants (WTPs) is of great concern due to possible chronic toxic effects as well as contribution to antibiotic resistance spread. In the present work, the degradation of the antibiotic chloramphenicol (CAP) by ultraviolet (UV)/peracetic acid (PAA) (an advanced oxidation process that has been poorly investigated so far) and UV/H2O2 processes as well as its transformation products were studied under different light sources. UV-C/PAA process was found to be effective in the degradation of CAP (half life time (t1/2) = 20 min, initial CAP concentration 25 mg/L), but not effective when solar radiation was used as light source. It is worthy to note that the presence of H2O2 in the commercial PAA solution significantly affected the removal efficiency of CAP by UV-C/PAA process. When H2O2 was quenched by catalase addition, t1/2 increased to 99 min, meaning that PAA can still produce hydroxyl radicals but at a lower rate compared to H2O2. Moreover, process efficiency further decreased in the presence of both solar simulated and natural solar irradiation, being CAP removal also the result of thermal decomposition. The transformation products detected during CAP degradation by UV-C/PAA were different respect to those produced during UV-C/H2O2 process. In particular, after 120 min most of the compounds detected presented a molecular weight >300 m/z., meaning that UV-C/PAA process needs more time to degrade the transformation products.

In the present study, natural phyllosilicate clays, Illite and Montmorillonite, were stablished as efficient adsorbents for the removal of the ionic liquid 1-butyl, 2,3-dimethyl imidazolium chloride, achieving, respectively, 14 and 25 mg/g of adsorption. In addition, the regeneration of both adsorbents was hereby firstly performed by Fenton-based processes, using the catalytic action of the iron naturally present in clays. Two different reactor configurations, with regard to the ratio of adsorbent to liquid phase, were tested: fluidized and fixed bed reactors. The desorption equilibrium was the main limiting factor for the effective regeneration of the Illite clay by electro-Fenton process in the fluidized bed reactor. On the other hand, the fixed bed reactor, based on electrokinetic-Fenton phenomenon, proved to be suitable for the regeneration of the Montmorillonite clay and it would be an appropriate solution for the implementation of adsorbent regeneration by Fenton-based technology at large adsorbent/solution ratios. Both reactor configurations were suitable for the adsorbents regeneration, and 80% of ionic liquid degradation has been accomplished. Additionally, the adsorption capability of both clays was confirmed after the regeneration process, achieving almost the same initial uptake.

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 (0.5–19.5 mg O2·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 132.5 mA, catalyst dosage of 0.10 mM, 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.

Personal care products are known as endocrine-disrupting compounds and their degradation is a matter of concern to avoid their release into the environment. For this reason, the main objective of this study is to develop an effective advanced oxidation process able to degrade a paraben as methyl paraben (MePa). Initially, the efficiency of two electrodes, Graphite felt (GF) and Ruthenium (Ru), was compared on the degradation of MePa by anodic oxidation (AO) and electro-Fenton (EF). Near complete degradation was obtained after 1 h when Graphite felt (GF) was used as cathode in EF, showing the superiority of this treatment over AO. To improve this process, heterogeneous EF through inclusion of iron into the cathode was carried out. To do that, four iron-carbonaceous cathodes were prepared based on GF (raw or activated with H 2 SO 4 , named AGF-1) showing a significant iron content (25–30%) and attaining high degradation values (95–100%) in all of them. From preliminary experiments was determined that by the use of AGF-1 as cathode the electrode performance improved, reducing significantly the treatment time required and the total amount of MePa contained in the solution had disappeared after 30 min with a TOC reduction of 98.68% after 120 min. The profiles of MePa exhibit an exponential decay throughout time being satisfactorily described by pseudo-first order reaction kinetic showing a maximum degradation rate of around 0.143 min −1 at optimal conditions (100 mA and pH 3). In addition, the selected cathode showed high structural and catalytic stability after several reuses. Finally, key steps of a plausible degradation pathway were tailored in accordance with identified and quantified intermediate products of the degradation process.

Despite the proven efficiency of heterogeneous photocatalysis using immobilized catalysts, this process lacks integration with the industry due to limitations on mass and photon transfer. The current study aimed to go up against this scenario by applying for the first time a Kenics® static mixer as catalyst support for heterogeneous photocatalysis in tubular reactors. Stainless steel Kenics® static mixers coated with TiO2 or Fe2O3 photocatalyst were assembled in a borosilicate tube coupled to a compound parabolic collector (CPC) and applied to the degradation of the antibiotic oxytetracycline (OTC) in aqueous solution. The use of the Kenics® static mixer provided intense mixing even under laminar flow, and, beyond that, the use of sunlight and a CPC ensured that the entire photocatalyst surface area was receiving front side illumination. Fe2O3 catalyst showed superiority over TiO2 for OTC degradation, exhibiting a pseudo-first-order kinetic constant 79% higher. However, while no TiO2 leaching occurred, up to around 0.7 mg L−1 of total dissolved iron were leachated. Thus, both homogeneous and heterogeneous photo-Fenton reactions may have contributed to the higher OTC degradation by Fe2O3 photocatalysis. The effect of various parameters on the photocatalytic efficiency was assessed: (i) photocatalyst deposition technique, (ii) photocatalyst dosage, (iii) H2O2 concentration, and (iv) number of static mixing elements. Spray coating technique showed superiority over dip coating. OTC degradation was improved by using 50 mL of TiO2 suspension together with 77 mg L−1 of H2O2, and 75 mL of Fe2O3 suspension together with 154 mg L−1 of H2O2. The increase of the number of Kenics® static mixing elements from two to six did not improve the OTC degradation rate. Furthermore, the reusability of both catalysts was proved.

Nowadays, the majority of the remediation studies have been carried out using artificially spiked soils with individual target pollutants. One of the bottlenecks is the application of developed technologies to the removal of pollutants in real aged contaminated soils, which is much more difficult than in spiked ones. Thus, in this study, the performance of a combined technology as flushing using different oxidants coupled with the electrokinetic technique was performed and its feasibility was evaluated to remediate a real industrial polluted soil with low permeability in which is not possible the conventional flushing system. Initially, the characterization of this soil showed a wide distribution of hydrocarbons with a total petroleum hydrocarbons content of 29,666 mg·kg − 1 . Based on the hydrocarbons distribution, the source of the pollutants was identified as a spillage of motor oil and diesel. Moreover, the aging of the pollution was evaluated (around 16 years) resulting in a historically polluted soil. Initially, an ex-situ oxidative treatment was considered. This treatment demonstrated the feasibility of the different oxidants on the removal of the hydrocarbons, achieving removal values higher than 65% in all the experiments. Furthermore, a critical parameter in the treatment, as pH, was also evaluated resulting in an acidic environment for KMnO 4 and Na 2 S 2 O 8 and basic environment for NaOCl. Later, the simulated bench scale in situ removal of the contaminants was considered, but the delivery of the oxidants into the polluted soil is hard, and for this reason, the coupling of flushing and electrokinetics was carried out. Working at the optimal conditions determined before, the treatment with the selected oxidants was performed. The total petroleum hydrocarbons (TPH) removal (40–60%), the profile of hydrocarbons and metals in the different sections of the soil after the treatments proved the efficiency of the system. The viability of the selected hybrid technique in the removal of TPH from historically polluted soils was demonstrated.

Heterogeneous electro-Fenton process using a natural pyrite as solid catalyst was used to degrade vanillic acid (VA), one of the major phenolic components of olive mill wastewaters. This heterogeneous process has advantages over classical electro-Fenton process such as large working pH range, recovering and recycling of the catalyst and thus cost reduction. Experiments were performed in an undivided electrochemical cell equipped with a Pt anode and a carbon felt cathode. The effect of operating parameters such as pyrite dosage, applied current and initial pH on VA degradation has been investigated. The VA decay kinetics and the mineralization of the aqueous solutions were monitored by HPLC analysis and TOC measurements, respectively. Results showed that VA was completely removed by the reaction with hydroxyl radicals generated from electrochemically assisted Fenton's reaction. The decay kinetics of VA oxidation was found to follow pseudo-first order reaction and the rate constant for oxidation of VA was determined to be (5.27 ± 0.03) × 10 9 mol − 1 L s − 1 . A mineralization rate of 89.2% was reached with a pyrite dosage of 1 g L − 1 . HPLC and GC–MS analyses permitted to identify a large number of aromatic/cyclic and aliphatic reaction intermediate products. Based on these intermediates products as well as the release of inorganic ions and TOC removal determination a detailed reaction pathway was proposed for the mineralization of VA by OH generated during heterogeneous electro-Fenton process.

The presence of emerging contaminants like ionic liquids in the environment is prompting the search of new methods to remove them from environments. To our knowledge, there are only few studies reported in the literature regarding to the application of electro-Fenton to solve this problem. Nonetheless, during the last years it has demonstrated great effectiveness on the elimination of wide diversity of pollutants. For this reason, this study is focus on the degradation of a commonly used imidazolium ionic liquid 1-Butyl-3-methylimidazolium triflate ([C4mim][CF3SO3]) by electro-Fenton technology. Initial trials were performed using different supporting electrolytes, including NaNO3, Na2SO4 or NaCl. Voltammetric studies were carried out in order to elucidate the behavior of the studied pollutant at the anode surface in each tested electrolyte. Comparative experiments pointed out to NaNO3 (0.025 M) as the one yielding higher mineralization and degradation rates. Thus, [C4mim][CF3SO3], was completely degraded after 120 min with 87% of TOC reduction after 240 min. Moreover, these results can be improved by the increase of the NaNO3 concentration (0.075 M) and complete degradation and TOC reduction was attained at shorter treatment time. The ionic analysis ascertained these results, showing faster elimination under the use of NaNO3. Differential Pulse Voltammetry on this media revealed a strong interaction between the fluoride anion and the iron present in the medium and the formation of a complex between them. Finally, HPLC and GC/MS analysis permitted to follow the main intermediates formed along the treatment, thus proposing a plausible degradation pathway of [C4mim][CF3SO3].

In this work, a comparative study using anodic oxidation, Fenton and electro-Fenton treatments was performed in order to determine the synergic effect for the removal of thiamethoxan. The results determined that electro-Fenton process showed high efficiency in comparison with Fenton or anodic oxidation. After that, this hybrid process was optimized and the influence of iron catalyst concentration and applied current intensity on the degradation and mineralization were evaluated. Degradation profiles were monitored by high performance liquid chromatography (HPLC) being satisfactorily described by pseudo-first order kinetic model. At the optimal experimental conditions (300mA and 0.2mM Fe(+2)), the complete degradation of thiamethoxam was achieved after 10min. On the other hand, mineralization of thiamethoxam was monitored by total organic carbon (TOC) decay reaching more than 92% of TOC removal after 8h. Furthermore, a plausible mineralization pathway for the thiamethoxam degradation was proposed based on the identification of by-products such as aromatic intermediates, carboxylic acids and inorganic ions released throughout electro-Fenton process.

The removal of radiocontrast agent diatrizoic acid (DIA) from water was performed using photo-Fenton (PF) process. First, the effect of H2O2 dosage on mineralization efficiency was determined using ultraviolet (UV) irradiation. The system reached a maximum mineralization degree of 60 % total organic carbon (TOC) removal at 4 h with 20 mM initial H2O2 concentration while further concentration values led to a decrease in TOC abatement efficiency. Then, the effect of different concentrations of Fenton's reagents was studied for homogeneous Fenton process. Obtained results revealed that 0.25 mM Fe(3+) and 20 mM H2O2 were the best conditions, achieving 80 % TOC removal efficiency at 4 h treatment. Furthermore, heterogeneous PF treatment was developed using iron-activated carbon as catalyst. It was demonstrated that this catalyst is a promising option, reaching 67 % of TOC removal within 4 h treatment without formation of iron leachate in the medium. In addition, two strategies of enhancement for process efficiency are proposed: coupling of PF with electro-Fenton (EF) process in two ways: photoelectro-Fenton (PEF) or PF followed by EF (PF-EF) treatments, achieving in both cases the complete mineralization of DIA solution within only 2 h. Finally, the Microtox tests revealed the formation of more toxic compounds than the initial DIA during PF process, while, it was possible to reach total mineralization by both proposed alternatives (PEF or PF-EF) and thus to remove the toxicity of DIA solution.

One of the bottlenecks often faced in environmental processes is focused on the design of efficient technologies. Thus, the hunt of suitable alternatives is a must to be tackled in order to improve the conventional methods. In this study the applicability of nickel foam as cathode in electro-Fenton's treatment of Poly R-478, a recalcitrant dye, was demonstrated. Linear sweep voltammetry and initial studies show the ability of nickel foam to increase the H2O2 generation during the electro-Fenton treatment, enhancing the removal yields achieved in comparison with other carbonaceous materials. Furthermore, complete mineralization of the pollutant was reached when using Boron Doped Diamond (BDD) as anode. A heterogeneous electro-Fenton process using iron loaded polyacrylamide hydrogels enhance the efficiency of the process with respect to homogeneous electro-Fenton and anodic oxidation technologies. Furthermore, the evaluation of the generated hydroxyl radicals confirms the obtained results. Finally, the reusability of the designed process was evaluated by decolorization of Poly R-478 in successive batches. SEM study of the nickel foam along the successive experiments confirms that no structure changes were detected. Summing up, nickel foam seems to be a suitable cathode material for the electro-Fenton treatment of recalcitrant compounds in continuous mode.

In the last decades, a wide range of organic pollutants has been identified as emerging pollutants in the aquatic environment. However, limited work has been done examining the ability of microorganisms to degrade emerging pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and pesticides. In this work, a novel PAH and pesticide degrading bacterium was isolated from polluted marine sediment. After morphological and genetic characterization, the novel strain showed the highest similarity to Bacillus thuringiensis . The ability of the isolated bacterium to degrade the target pollutants was evaluated in shake flasks and bioreactor assays, reaching high levels of degradation for the model pollutants studied, phenanthrene and imidacloprid. Furthermore, the plausible degradation pathways of both pollutants were established. Based on the reported results, it can be concluded that B. thuringiensis has an enormous potential to mineralize a wide spectrum of emerging pollutants, such as PAHs and pesticides.

The treatment of winery wastewater is necessary since it constitutes an environmental problem due to its high organic content and chemical oxygen demand and its low pH. However, these characteristics hinder the use of conventional technologies commonly utilized for the treatment of effluents. Therefore, new technologies for the management of this type of wastewater are required. In this sense, the photo electro Fenton process (PEF) was proposed as a good alternative because of the synergetic effect among Fenton, electrolysis and photolysis processes. In this study, the development of a new double chamber cubic reactor for the treatment of winery wastewater using PEF was performed. Surface response methodology was applied based on Box–Behnken design to define the best operational conditions. The selected key variables were voltage, distance between electrodes and the organic load of the effluent. Among the parameters optimized, distance between electrodes and voltage were identified as significant in the model. Under the optimized conditions the treatment of real winery wastewater was efficiently carried out. Finally, it can be concluded that the configuration of this reactor is suitable for the remediation of this type of effluents.

In the last years, the presence of pesticides in aquatic environments has increased mainly as a result of the intensification of agricultural activities. Among the different techniques that can be used to remove these contaminants, the adsorption process can disclose as an appropriate treatment. In this work, chestnut shells were evaluated as a low-cost biosorbent for the pesticides pirimicarb, imidacloprid, acetamiprid and thiamethoxam, widely used in agricultural activities. Furthermore, economic acid pretreatments were evaluated in order to increase the removal efficiency. The highest removal was obtained when chestnut shells were pretreated with citric acid, increasing a 15% of adsorption capacity in comparison to raw chestnut shells. Scanning electron microscopy images, energy disperse spectroscopy analysis, Fourier transform infrared spectroscopy and Boehm method were performed in order to characterize the biosorbent. The new biosorbent was analysed in deep by kinetic and isotherm studies. The values of the correlation coefficients and standard error of estimate indicated that the Freundlich isotherm and pseudo-second-order model fitted well to the experimental data. In addition, the biosorbent showed a good behaviour working in continuous mode. The reported results open a new alternative for the restoration of polluted aquatic environments through the application of this new low-cost biosorbent developed.

PURPOSE: To characterize early optic nerve head (ONH) structural change in rat experimental glaucoma (EG). METHODS: Unilateral intraocular pressure (IOP) elevation was induced in Brown Norway rats by hypertonic saline injection into the episcleral veins and animals were sacrificed 4 weeks later by perfusion fixation. Optic nerve cross-sections were graded from 1 (normal) to 5 (extensive injury) by 5 masked observers. ONHs with peripapillary retina and sclera were embedded, serial sectioned, 3-D reconstructed, delineated, and quantified. Overall and animal-specific EG versus Control eye ONH parameter differences were assessed globally and regionally by linear mixed effect models with significance criteria adjusted for multiple comparisons. RESULTS: Expansions of the optic nerve and surrounding anterior scleral canal opening achieved statistical significance overall (p < 0.0022), and in 7 of 8 EG eyes (p < 0.005). In at least 5 EG eyes, significant expansions (p < 0.005) in Bruch's membrane opening (BMO) (range 3-10%), the anterior and posterior scleral canal openings (8-21% and 5-21%, respectively), and the optic nerve at the anterior and posterior scleral canal openings (11-30% and 8-41%, respectively) were detected. Optic nerve expansion was greatest within the superior and inferior quadrants. Optic nerve expansion at the posterior scleral canal opening was significantly correlated to optic nerve damage (R = 0.768, p = 0.042). CONCLUSION: In the rat ONH, the optic nerve and surrounding BMO and neurovascular scleral canal expand early in their response to chronic experimental IOP elevation. These findings provide phenotypic landmarks and imaging targets for detecting the development of experimental glaucomatous optic neuropathy in the rat eye. Supported in part by NIH grants R01EY011610 (CFB), R01EY10145 (JCM) and R01EY16866 (ECJ)) from the National Eye Institute, National Institutes of Health, Bethesda, Maryland; The Legacy Good Samaritan Foundation, Portland, Oregon; the Sears Trust for Biomedical Research, Mexico, Missouri; the Alcon Research Institute, Fort Worth, Texas; and an unrestricted grant from Research to Prevent Blindness.

The requirement of feasible adsorption-regeneration systems in the treatment of emerging pollutants such as pharmaceuticals is a social demand. In this work, the treatment of a mixture with sulfamethoxazole (SMX) and methyl paraben (MP) was performed by the preparation of biochar derived from the lime fiber waste at different conditions (320–500 °C and residence time 5–30 min). Based on the adsorption efficiency (maximum uptake of MP 54.25 mg/g and SMX 64.04 mg/g) and energy expenditure, the biochar obtained at 320 °C with a residence time of 30 min was selected as the best material. Subsequently, a deep study of this biochar adsorption process demonstrated that pseudo-second order model fitted well the adsorption kinetics of both pollutants and the Freundlich isotherm model describes the binary system equilibrium. After that, the regeneration of the adsorbent was carried out by advanced oxidation processes. Initially, Fenton process was considered and the regeneration of the adsorbent was performed in homogeneous and heterogeneous systems. The necessity of continuous addition of H2O2 led to the evaluation of other alternatives (electro-oxidation-H2O2 or electro-Fenton). The optimisation of the conditions was performed in liquid phase and operational parameters such as cathode electrode (carbon black modified electrodes), H2O2 production, intensity, pH and degradation kinetics were studied. Among them, the electro-Fenton process demonstrated to be quite successful in the removal of the pollutants and it was applied in successive cycles of adsorption-regeneration.