Case study as an innovative teaching methodology for environmental engineering learning

Este trabajo recoge la experiencia de incorporar el estudio mediante un caso como método docente dentro la asignatura Ingeniería Ambiental (Grado en Ingeniería Química, UAM). Se pretende profundizar en el desarrollo de varias competencias de la asignatura que no se adquieren de manera adecuada con los métodos docentes tradicionales. Dichas competencias incluyen pensamiento crítico, toma y comunicación de decisiones. El caso de estudio está basado en una situación real y resulta más complejo que los problemas resueltos en clase por el profesor. El caso se desarrolla junto a diversas cuestiones que guían a los estudiantes hacia la solución del problema. Los estudiantes resuelven el caso en clase trabajando en pequeños grupos siempre con la ayuda y guía del profesor. Posteriormente, los estudiantes exponen sus principales resultados y conclusiones generando un debate con sus compañeros y con el profesor. La implementación de esta metodología docente ha dado lugar a un aprendizaje más consistente favoreciendo la asimilación de conceptos teóricos complejos, la discusión de ideas y el razonamiento crítico. Además, se ha potenciado la capacidad de transmitir los conocimientos adquiridos por parte de los estudiantesIn this work, the application of a case study has been implemented as a new teaching methodology in the subject of Environmental Engineering (B.Sc. in Chemical Engineering at UAM University). The main goals are focused on improving important competences of the subject which are not correctly acquired by the students with the traditional theoretical lessons. These competences include critical thinking, decisions making and communication skills. The case has been inspired in a real situation and it is more complex than the problems usually solved by the professor in regular classes. The proposed case study has been developed together with questions which will guide the students to solve the problem. The students have solved the case in the classroom working in small groups, always with the support of the professor. Afterwards, the students showed their main results and conclusions generating a debate with their colleagues and the professor. The case study approach has proved to improve the assimilation of complex theoretical concepts, to favor the discussion and the ability to communicate the acquired knowledge as well as to develop critical thinkin

Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation - A review

This study presents a critical review on the application of magnetite-based catalysts to industrial wastewater decontamination by heterogeneous Fenton oxidation. The use of magnetic materials in this field started only around 2008 and continues growing increasingly year by year. The potential of these materials derives from their higher ability for degradation of recalcitrant pollutants compared to the conventional iron-supported catalysts due to the presence of both Fe(II) and Fe(III) species. In addition, their magnetic properties allow their easy, fast and inexpensive separation from the reaction medium. The magnetic materials applied up to now can be classified in three general groups: magnetic natural minerals, in-situ-produced magnetic materials and ferromagnetic nanoparticles. A survey of the catalysts investigated so far is presented paying attention to their nature and competitive features in terms of activity and durabilityThis research has been supported by the Spanish MICINN through the project CTQ2013-4196-R and by the CM through the project S2013/MAE-271

Fast oxidation of the neonicotinoid pesticides listed in the EU Decision 2018/840 from aqueous solutions

Neonicotinoid pesticides family is nowadays identified as the most important type of insecticides in the world. Their consequent widespread occurrence in the environment represents not only a well-known risk for bees but also a significant negative impact in aquatic ecosystems. In this work, the capability of catalytic wet peroxide oxidation (CWPO) (Fe3O4-R400/H2O2) as a low-cost and environmentally-friendly system for the treatment of the neonicotinoid pesticides listed in the EU Watch List (Decision 2018/840) (acetamiprid (ACT), clothianidin (CLT), imidacloprid (IMD), thiacloprid (THC) and thiamethoxam (THM)) has been investigated. Remarkably, complete elimination of the pollutants (1000 g L-1)and the aromatic by-products was reached in 20 min reaction time operating at 25 °C, 1 atm, and pH0 = 5,, with the stoichiometric H2O2 amount (~4 – 5 mg L-1) and 1 g L-1 catalyst load. The reactivity order of the insecticides decreased as follows: THC>IMD>THM>CLT>ACT, being the pseudo-first order rate constant values within the range of 0.26 – 0.61 min-1. Notably, high mineralization yields were obtained (>50%) being the final effluents non-toxic. As example, the oxidation pathway of ACT was proposed. Finally, the catalytic system was tested in real surface waterThis research has been founded by the CTM2016-76454-R project (Spanish MINECO) and by the S2013/MAE-2716 project (CM). M. Munoz thanks the postdoctoral Ramón y Cajal contract (RYC-2016-20648) to the Spanish MINEC

Improved wet peroxide oxidation strategies for the treatment of chlorophenols

Different advanced oxidation strategies have been investigated for the treatment of chlorophenols in aqueous phase with the aim of improving the removal efficiency in terms of mineralization, remanent by-products and kinetics. Those strategies were homogeneous Fenton-like oxidation and CWPO with two different own-prepared FexOy/γ-Al2O3 catalysts. The intensification of the process by increasing the temperature has been also evaluated. CWPO of chlorophenols with those catalysts has proved to be more efficient than homogeneous Fenton-like oxidation due to a lower rate of H2O2 decomposition allowing a higher availability of hydroxyl radicals along the course of reaction. Increasing the temperature clearly improved the oxidation rate and mineralization degree of both homogeneous Fenton-like oxidation and CWPO, achieving almost 90% TOC reduction after 1h at stoichiometric H2O2 dose, 100mgL-1 initial chlorophenol concentration, 1gL-1 Fe3O4/γ-Al2O3 catalyst, pH 3 and 90°C temperature. Both FexOy/γ-Al2O3 catalysts suffered fairly low iron leaching (<5%) and a remarkable stability in a three-cycles test with 2,4,6-TCP. The use of the magnetic catalyst is preferable due to its easy separation and recovery from the liquid phase by a magnet. Its magnetic properties remained unchanged after use in CWPOThis research has been supported by the Spanish MICINN through the projects CTQ2008-03988 and CTQ2010-14807 and by the CM through the project S-2009/AMB-1588. M. Munoz thanks the Spanish Ministry of Education for a FPU research gran

Triclosan breakdown by Fenton-like oxidation

Fenton-like oxidation has proved to be highly efficient for the removal of triclosan, a highly toxic emerging water pollutant. From 10mg/L starting aqueous solutions complete conversion of triclosan was achieved in less than 1h at 25°C and around 20min at 50°C with 1mg/L Fe3+ and H2O2 at the theoretical stoichiometric amount (25mg/L). From the evolution of byproducts a reaction pathway has been proposed according to which oxidation of triclosan gives rise to several aromatic intermediates (mainly, p-hydroquinone of triclosan and 2,4-dichlorophenol) which evolve to short-chain organic acids. These compounds are mineralized except oxalic acid. A dramatic decrease of ecotoxicity was achieved in a relatively short time (more than 95% in 15min at 35°C). The evolution of ecotoxicity is intimately related to the disappearance of triclosan, much more toxic than the aromatic oxidation intermediates. This disappearance was successfully described by a simple pseudo-first order rate equation with an apparent activation energy value close to 27kJ/mol. The apparent rate constant at 25°C was several orders of magnitude higher than the reported in the literature for other chlorophenolic compounds indicating a higher susceptibility of triclosan to OH radical attackThis research has been supported by the Spanish MICINN through the project CTQ2008-03988 and by the CM through the project S-2009/AMB-158

Catalytic hydrodechlorination as polishing step in drinking water treatment for the removal of chlorinated micropollutants

This Accepted Manuscript will be available for reuse under a CC BY-NC-ND license after 24 months of embargo periodThe presence of micropollutants in fresh waters represents an important challenge for drinking water treatment plants (DWTPs). In particular, the chlorinated ones are especially harmful given their high toxicity and strong bioaccumulation potential. The aim of this work is to evaluate the feasibility of catalytic hydrodechlorination (HDC) for the removal of a representative group of chlorinated micropollutants commonly found in the source waters of DWTPs: the antibiotic chloramphenicol (CAP), the anti-inflammatory diclofenac (DCF), the antibacterial agent triclosan (TCL) and the antidepressant sertraline (SRT). The complete degradation of the isolated micropollutants (3 mg L−1) was achieved in 1 h reaction time using a Pd/Al2O3 catalyst load of 0.25 g L−1 and a H2 flow rate of 50 N mL min−1. The experimental data were properly described by a pseudo-first order kinetic equation, obtaining degradation rate constants in the range of 0.32–1.56 L gcat−1 min−1 and activation energy values within 42–52 kJ mol−1. In all cases, the final reaction products were chlorine-free compounds and thus, HDC effluents were non-toxic (&lt;0.1 TU). Remarkably, the catalyst showed a suitable stability upon five consecutive applications. The versatility of the process was demonstrated in the treatment of the micropollutants mixture in different aqueous matrices (mineral, surface and tap waters). Strikingly, the removal rate was not affected by the presence of co-existing substances, being the micropollutants completely removed in 15 min with 1 g L−1 catalyst concentration. Finally, the potential of HDC for the removal of trihalomethanes, by-products formed along the oxidation step by chlorination in DWTPs, was also demonstratedThis research has been supported by the Spanish MINECO thorough the project CTM2016-76454-R and by the CM through the project P2018/EMT-4341. J. Nieto-Sandoval thanks the Spanish MINECO for the FPI predoctoral grant (BES-2017- 081346). M. Munoz thanks the Spanish MINECO for the Ramón y Cajal postdoctoral contract (RYC-2016-20648

Degradation of imidazolium-based ionic liquids by catalytic wet peroxide oxidation with carbon and magnetic iron catalysts

BACKCGROUND: The ‘green’ image of ionic liquids (ILs) has changed in the last few years since numerous works have evidenced their non-biodegradability, persistence and high ecotoxicity, particularly for the most common imidazolium-based ILs. In this work, the feasibility of catalytic wet peroxide oxidation for the degradation of imidazolium-based ILs of different alkyl chain lengths has been studied under selected operating conditions (1000 mg L−1 IL, stoichiometric H2O2 dose, 2 g L−1 catalyst, pH 3 and 90 °C temperature) using different catalysts such as magnetic iron (Fe3O4) supported on γ-Al2O3 and activated carbon (AC) as well as bare carbon materials (graphite, AC). The catalytic activity and stability and the efficiency of H2O2 consumption have been evaluated. RESULTS: Although both AC-based catalysts led to the conversion of the IL, they yielded a low H2O2 consumption efficiency (24% and 45% with AC and Fe3O4/AC, respectively) due to the fast decomposition of H2O2 and the recombination of radical species into H2O and O2, non-reactive species under the operating conditions. In contrast, graphite and Fe3O4/γ-Al2O3 showed high activity allowing complete conversion and relatively high mineralization degrees of all the ILs tested in 1 h reaction time. Among those catalysts, Fe3O4/γ-Al2O3 exhibited a considerably greater stability upon four successive uses where iron leaching was negligible and the magnetic properties were maintained. CONCLUSIONS: Catalytic wet peroxide oxidation has proved to be an interesting alternative for the treatment of imidazolium-based ILs in water. The application of Fe3O4/γ-Al2O3 is particularly promising due to its high activity, remarkable stability and easy magnetic recoveryThis research has been supported by the Spanish MINECO through the project CTQ2013-4196-R and by the CM through the project S2013/MAE-271

Adsorption of micropollutants onto realistic microplastics: role of microplastic nature, size, age, and NOM fouling

This work aims at evaluating the role of nature, size, age, and natural organic matter (NOM) fouling of realistic microplastics (MPs) on the adsorption of two persistent micropollutants (diclofenac (DCF) and metronidazole (MNZ)). For such goal, four representative polymer types (polystyrene (PS), polyethylene terephthalate (PET), polypropylene (PP) and high-density polyethylene (HDPE)) were tested. MPs were obtained by cryogenic milling of different commercial materials (disposable bottles, containers, and trays), and fully characterized (optical microscopic and SEM images, FTIR, elemental analysis, water contact angle and pHslurry). The micropollutants hydrophobicity determined to a high extent their removal yield from water. Regardless of the MP's nature, the adsorption capacity for DCF was considerably higher than the achieved for MNZ, which can be related to its stronger hydrophobic properties and aromatic character. In fact, aromatic MPs (PS and PET) showed the highest adsorption capacity values with DCF (~100 μg g−1). The MP size also played a key role on its adsorption capacity, which was found to increase with decreasing the particle size (20–1000 μm). MPs aging (simulated by Fenton oxidation) led also to substantial changes on their sorption behavior. Oxidized MPs exhibited acidic surface properties which led to a strong decrease on the adsorption of the hydrophobic micropollutant (DCF) but to an increase with the hydrophilic one (MNZ). NOM fouling (WWTP effluent, river water, humic acid solution) led to a dramatic decrease on the MPs sorption capacity due to sorption sites blocking. Finally, the increase of pH or salinity of the aqueous medium increased the micropollutants desorptionThis research has been supported by the Autonoma University of Madrid and Community of Madrid through the project SI1-PJI-2019-00006, and by the Spanish MINECO through the project PID2019-105079RB-I00. Muñoz and J. Nieto-Sandoval thank the Spanish MINECO for the Ramón y Cajal postdoctoral contract (RYC-2016-20648) and the FPI predoctoral grant (BES-2017-081346), respectively. D. Ortiz thanks the Spanish MIU for the FPU predoctoral grant (FPU19/04816

Degradation of widespread cyanotoxins with high impact in drinking water (microcystins, cylindrospermopsin, anatoxin-a and saxitoxin) by CWPO

This Accepted Manuscript will be available for reuse under a CC BY-NC-ND license after 24 months of embargo periodThe occurrence of harmful cyanobacterial blooms has unabated increased over the last few decades, posing a significant risk for public health. In this work, we investigate the feasibility of catalytic wet peroxide oxidation (CWPO) promoted by modified natural magnetite (Fe3O4-R400/H2O2), as an inexpensive, simple-operation and environmentally-friendly process for the removal of the cyanotoxins that show the major impact on drinking water: microcystins (MC-LR and MC-RR), cylindrospermopsin (CYN), anatoxin-a (ATX) and saxitoxin (STX). The performance of the system was evaluated under ambient conditions and circumneutral pH (pH0 = 5) using relevant cyanotoxin concentrations (100–500 μg L−1). The nature of the cyanotoxins determined their reactivity towards CWPO, which decreased in the following order: MC-RR &gt; CYN &gt; MC-LR ≫ ATX &gt; STX. In this sense, microcystins and CYN were completely removed in short reaction times (1–1.5 h) with a low catalyst concentration (0.2 g L−1) and the stoichiometric amount of H2O2 (2–2.6 mg L−1), while only 60–80% conversion was achieved with ATX and STX in 5 h. In these cases, an intensification of the operating conditions (1 g L−1 catalyst and up to 30 mg H2O2 L−1) was required to remove both toxins in 1 h. The impact of the main components of freshwaters i.e. natural organic matter (NOM) and several inorganic ions (HCO3−, HPO42-, SO42-) on the performance of the process was also investigated. Although the former led to a partial inhibition of the reaction due to HO· scavenging and catalyst coating, the latter did not show any remarkably effect, and the versatility of the process was finally confirmed in a real surface water. To further demonstrate the effectiveness of the catalytic system, the toxicity of both the initial cyanotoxins and the resulting CWPO effluents was measured with the brine shrimp Artemia salina. Remarkably, all CWPO effluents were non-toxic at the end of the treatment.This research has been supported by the Spanish MINECO through the project CTM-2016-76454-R and by the CM through the project P2018/EMT-4341. M. Munoz thanks the Spanish MINECO for the Ramón y Cajal postdoctoral contract (RYC-2016-20648). J. Nieto-Sandoval thanks the Spanish MINECO for the FPI predoctoral grant (BES-2017-081346

Insights on the removal of the azole pesticides included in the EU Watch List by Catalytic Wet Peroxide Oxidation

The aim of this work is to evaluate the feasibility of the Catalytic Wet Peroxide Oxidation (CWPO) process using the inexpensive and environmentally friendly Fe3O4-R400 catalyst for the removal from water of a representative group of azole pesticides recently listed in the European Union (EU) Watch Lists (penconazole (PEN), prochloraz (PCZ), tebuconazole (TEB), tetraconazole (TET), metconazole (MET)). The complete removal of these pollutants (1000 μg L−1) was achieved in <1 h reaction time under ambient conditions using a catalyst concentration of 0.5 g L−1 and the stoichiometric dose of H2O2 (3 – 5 mg L−1) at a slightly acidic pH (pH0 = 5.0). To further demonstrate the effectiveness of the process, the ecotoxicity abatement was also considered. The initial toxicity of the pesticides and the CWPO effluents were evaluated with the brine shrimp Artemia salina and the bacterium Vibrio fischeri. Remarkably, the effluents were non-toxic for V. fischeri and a decrease of more than 80% in mortality was achieved for A. salina. Furthermore, the versatility of the system was proved in real water matrices (surface water and WWTP effluent), although a slight decrease on the oxidation rate was found due to the occurrence of organic matter and inorganic salts. The reactivity of the azole pesticides was finally compared with the achieved for other groups of pollutants included in the EU Watch Lists (pharmaceuticals, hormones, and neonicotinoid pesticides). Clearly, azole compounds showed the least reactivity to oxidation, suggesting that they can be used as general indicators of the overall efficiency of the proposed catalytic system for the removal of EU Watch Lists micropollutantsThis research has been supported by the Spanish AEI through the project PID2019-105079RB-100 and by the CM, Spain through the project P2018/EMT-4341. M. Munoz, N. Lopez-Arago and J. Nieto-Sandoval thanks the Spanish AEI for the Ramón y Cajal postdoctoral contract (RYC-2016-20648), the FPI predoctoral, Spain grant (PRE2020-09452) and the FPI postdoctoral, Spain grant (BES-2017-081346), respectivel