La reutilización de efluentes depurados en España: retrospectiva, desarrollo del marco normativo, estudio de las tecnologías de regeneración frente a los biorreactores de membrana y sus costes en función del uso

La reutilización de efluentes depurados siempre ha sido una opción en lugares con déficit coyuntural o estructural de recursos hídricos, se haya o no procedido a la regulación y planificación de esta práctica. La necesidad se crea a partir de las demandas de una zona, normalmente riego agrícola, que ven un mejor desarrollo de su actividad por contar con este recurso. España es el país de la UE que más caudal reutiliza, y está dentro de los diez primeros a nivel mundial. La regulación de esta práctica por el RD 1620/2007, ayudó a incorporar la reutilización de efluentes depurados a la planificación hidrológica como parte de los programas de medidas, con objeto de mitigar presiones, como son las extracciones de agua superficial y subterránea, o mejoras medioambientales evitando un vertido. El objeto de este trabajo es conocer la situación de la reutilización de efluentes depurados en España, los diferentes escenarios y planteamientos de esta actividad, el desarrollo del marco normativo y su aplicabilidad, junto a los tratamientos que permiten alcanzar los límites de calidad establecidos en la normativa vigente, en función de los distintos usos. Además, se aporta un análisis de costes de las distintas unidades de tratamiento y tipologías de líneas de regeneración, tanto de las utilizadas después de un tratamiento secundario como de otras opciones de depuración, como son los biorreactores de membrana (MBRs). Para el desarrollo de estos objetivos, en primer lugar, se aborda el conocimiento de la situación de la reutilización en España a través de una base de datos diseñada para cubrir todos los aspectos de esta actividad: datos de la estación depuradora de aguas residuales (EDAR), de la estación regeneradora (ERA), caudales depurados, reutilizados, volúmenes utilizados y ubicación de los distintos usos, tipos de líneas de tratamiento, calidades del agua reutilizada, etc. Las principales fuentes de información son las Confederaciones Hidrográficas (CCHH) a través de las concesiones de uso del agua depurada, las entidades de saneamiento y depuración de las distintas comunidades autónomas (CCAA), ayuntamientos, Planes Hidrológicos de Cuenca (PHC) y visitas a las zonas más emblemáticas. Además, se revisan planes y programas con el fin de realizar una retrospectiva de cómo se ha ido consolidando y desarrollando esta práctica en las distintas zonas de la geografía española. Se han inventariado 322 sistemas de reutilización y 216 tratamientos de regeneración siendo el más extendido la filtración mediante filtro arena seguido de una desinfección mediante hipoclorito, aunque este tratamiento se ha ido sustituyendo por un físico-químico con decantación lamelar, filtro de arena y radiación ultravioleta, tratamiento de regeneración convencional (TRC), y otros tratamientos que pueden incluir membranas, tratamientos de regeneración avanzados (TRA), con dosificación de hipoclorito como desinfección residual, para adaptarse al actual marco normativo. El uso más extendido es el agrícola con el 70% del caudal total reutilizado, estimado en 408 hm3, aunque la capacidad de los tratamientos de regeneración esperada para 2015, tras el Plan Nacional de Reutilización de Aguas (PNRA), es tres veces superior. Respecto al desarrollo normativo, en las zonas donde la reutilización ha sido pionera, las administraciones competentes han ido desarrollando diferentes recomendaciones de calidad y manejo de este tipo de agua. El uso agrícola, y en zonas turísticas, el riego de campos de golf, fueron los dos primeros usos que tuvieron algún tipo de recomendación incluso reglamentación. Esta situación inicial, sin una normativa a nivel estatal ni recomendaciones europeas, creó cierta incertidumbre en el avance de la reutilización tanto a nivel de concesiones como de planificación. En la actualidad sigue sin existir una normativa internacional para la reutilización y regeneración de efluentes depurados. Las recomendaciones de referencia a nivel mundial, y en concreto para el uso agrícola, son las de la OMS (Organización Mundial de la Salud) publicadas 1989, con sus posteriores revisiones y ampliaciones (OMS, 2006). Esta norma combina tratamientos básicos de depuración y unas buenas prácticas basadas en diferentes niveles de protección para evitar problemas sanitarios. Otra normativa que ha sido referencia en el desarrollo del marco normativo en países donde se realiza esta práctica, son las recomendaciones dadas por la Agencia Medioambiente Estadunidense (USEPA, 2012) o las publicadas por el Estado de California (Título 22, 2001). Estas normas establecen unos indicadores y valores máximos dónde el tratamiento de regeneración es el responsable de la calidad final en función del uso. Durante 2015, la ISO trabajaba en un documento para el uso urbano donde se muestra tanto los posibles parámetros que habría que controlar como la manera de actuar para evitar posibles riesgos. Por otro lado, la Comisión Europea (CE) viene impulsando desde el 2014 la reutilización de aguas depuradas dentro del marco de la Estrategia Común de Implantación de la Directiva Marco del Agua, y fundamentalmente a través del grupo de trabajo de “Programas de medidas”. Para el desarrollo de esta iniciativa se está planteando sacar para 2016 una guía de recomendaciones que podría venir a completar el marco normativo de los distintos Estados Miembros (EM). El Real Decreto 1620/2007, donde se establece el marco jurídico de la reutilización de efluentes depurados, tiende más a la filosofía implantada por la USEPA, aunque la UE parece más partidaria de una gestión del riesgo, donde se establecen unos niveles de tolerancia y unos puntos de control en función de las condiciones socioeconómicas de los distintos Estados, sin entrar a concretar indicadores, valores máximos o tratamientos. Sin embargo, en la normativa estadounidense se indican una serie de tratamientos de regeneración, mientras que, en la española, se hacen recomendaciones a este respecto en una Guía sin validez legal. Por tanto, queda sin regular los procesos para alcanzar estos estándares de calidad, pudiendo ser éstos no apropiados para esta práctica. Es el caso de la desinfección donde el uso de hipoclorito puede generar subproductos indeseables. En la Guía de recomendaciones para la aplicación del RD, publicada por el Ministerio de Agricultura y Medioambiente (MAGRAMA) en 2010, se aclaran cuestiones frecuentes sobre la aplicación del RD, prescripciones técnicas básicas para los sistemas de reutilización, y buenas prácticas en función del uso. Aun así, el RD sigue teniendo deficiencias en su aplicación siendo necesaria una revisión de la misma, como en las frecuencias de muestreo incluso la omisión de algunos parámetros como huevos de nematodos que se ha demostrado ser inexistentes tras un tratamiento de regeneración convencional. En este sentido, existe una tendencia a nivel mundial a reutilizar las aguas con fines de abastecimiento, incluir indicadores de presencia de virus o protozoos, o incluir ciertas tecnologías como las membranas u oxidaciones avanzadas para afrontar temas como los contaminantes emergentes. Otro de los objetivos de este trabajo es el estudio de tipologías de tratamiento en función de los usos establecidos en el RD 1620/2007 y sus costes asociados, siendo base de lo establecido a este respecto en la Guía y PNRA anteriormente indicados. Las tipologías de tratamiento propuestas se dividen en líneas con capacidad de desalar y las que no cuentan con una unidad de desalación de aguas salobres de ósmosis inversa o electrodiálisis reversible. Se realiza esta división al tener actuaciones en zonas costeras donde el agua de mar entra en los colectores, adquiriendo el agua residual un contenido en sales que es limitante en algunos usos. Para desarrollar este objetivo se han estudiado las unidades de tratamiento más implantadas en ERAs españolas en cuanto a fiabilidad para conseguir determinada calidad y coste, tanto de implantación como de explotación. El TRC, tiene un coste de implantación de 28 a 48 €.m-3.d y de explotación de 0,06 a 0,09 €. m-3, mientras que, si se precisara desalar, este coste se multiplica por diez en la implantación y por cinco en la explotación. En caso de los usos que requieren de TRA, como los domiciliarios o algunos industriales, los costes serían de 185 a 398 €.m-3.d en implantación y de 0,14 a 0,20 €.m-3 en explotación. En la selección de tecnologías de regeneración, la capacidad del tratamiento en relación al coste es un indicador fundamental. Este trabajo aporta curvas de tendencia coste-capacidad que sirven de herramienta de selección frente a otros tratamientos de regeneración de reciente implantación como son los MBR, u otros como la desalación de agua de mar o los trasvases entre cuencas dentro de la planificación hidrológica. En España, el aumento de las necesidades de agua de alta calidad en zonas con recursos escasos, aumento de zonas sensibles como puntos de captación para potables, zonas de baño o zonas de producción piscícola, y en ocasiones, el escaso terreno disponible para la implantación de nuevas plantas depuradoras (EDARs), han convertido a los MBRs, en una opción dentro del marco de la reutilización de aguas depuradas. En este trabajo, se estudia esta tecnología frente a los TRC y TRA, aportando igualmente curvas de tendencia coste-capacidad, e identificando cuando esta opción tecnológica puede ser más competitiva frente a los otros tratamientos de regeneración. Un MBR es un tratamiento de depuración de fangos activos donde el decantador secundario es sustituido por un sistema de membranas de UF o MF. La calidad del efluente, por tanto, es la misma que el de una EDAR seguida de un TRA. Los MBRs aseguran una calidad del efluente para todos los usos establecidos en el RD, incluso dan un efluente que permite ser directamente tratado por las unidades de desalación de OI o EDR. La implantación de esta tecnología en España ha tenido un crecimiento exponencial, pasando de 13 instalaciones de menos de 5.000 m3. d-1 en el 2006, a más de 55 instalaciones en operación o construcción a finales del 2014, seis de ellas con capacidades por encima de los 15.000 m3. d-1. Los sistemas de filtración en los MBR son los que marcan la operación y diseño de este tipo de instalaciones. El sistema más implantado en España es de membrana de fibra hueca (MFH), sobre todo para instalaciones de gran capacidad, destacando Zenon que cuenta con el 57% de la capacidad total instalada. La segunda casa comercial con mayor número de plantas es Kubota, con membranas de configuración placa plana (MPP), que cuenta con el 30 % de la capacidad total instalada. Existen otras casas comerciales implantadas en MBR españoles como son Toray, Huber, Koch o Microdym. En este documento se realiza la descripción de los sistemas de filtración de todas estas casas comerciales, aportando información de sus características, parámetros de diseño y operación más relevantes. El estudio de 14 MBRs ha posibilitado realizar otro de los objetivos de este trabajo, la estimación de los costes de explotación e implantación de este tipo de sistemas frente a otras alternativas de tratamiento de regeneración. En este estudio han participado activamente ACA y ESAMUR, entidades públicas de saneamiento y depuración de Cataluña y Murcia respectivamente, que cuentan con una amplia experiencia en la explotación de este tipo de sistemas. Este documento expone los problemas de operación encontrados y sus posibles soluciones, tanto en la explotación como en los futuros diseños de este tipo de plantas. El trabajo concluye que los MBRs son una opción más para la reutilización de efluentes depurados, siendo ventajosos en costes, tanto de implantación como de explotación, respecto a EDARs seguidas de TRA en capacidades por encima de los 10.000 m3.d-1. ABSTRACT The reuse of treated effluent has always been an option in places where a situational or structural water deficit exists, whether regulatory and/or planning efforts are completed or not. The need arises from the demand of a sector, commonly agricultural irrigation, which benefits of this new resource. Within the EU, Spain is ahead in the annual volume of reclaimed water, and is among the top ten countries at a global scale. The regulation of this practice through the Royal Decree 1620/2007 has helped to incorporate the water reuse to the hydrological plans as a part of the programme of measures to mitigate pressures such as surface or ground water extraction, or environmental improvements preventing discharges. The object of this study is to gain an overview of the state of the water reuse in Spain, the different scenarios and approaches to this activity, the development of the legal framework and its enforceability, together with the treatments that achieve the quality levels according to the current law, broken down by applications. Additionally, a cost analysis of technologies and regeneration treatment lines for water reclamation is performed, whereas the regeneration treatment is located after a wastewater treatment or other options such as membrane bioreactors (MBR). To develop the abovementioned objectives, the state of water reuse in Spain is studied by means of a database designed to encompass all aspects of the activity: data from the wastewater treatment plants (WWTP), from the water reclamation plants (WRP), the use of reclaimed water, treated water and reclaimed water annual volumes and qualities, facilities and applications, geographic references, technologies, regeneration treatment lines, etc. The main data providers are the River Basin authorities, through the concession or authorization for water reuse, (sanitary and wastewater treatment managers from the territorial governments, local governments, Hydrological Plans of the River Basins and field visits to the main water reuse systems. Additionally, a review of different plans and programmes on wastewater treatment or water reuse is done, aiming to put the development and consolidation process of this activity in the different regions of Spain in perspective. An inventory of 322 reuse systems and 216 regeneration treatments has been gathered on the database, where the most extended regeneration treatment line was sand filtration followed by hypochlorite disinfection, even though recently it is being replaced by physical–chemical treatment with a lamella settling system, depth sand filtration, and a disinfection with ultraviolet radiation and hypochlorite as residual disinfectant, named conventional regeneration treatment (CRT), and another treatment that may include a membrane process, named advanced regeneration treatment (ART), to adapt to legal requirements. Agricultural use is the most extended, accumulating 70% of the reclaimed demand, estimated at 408 hm3, even though the expected total capacity of WRPs for 2015, after the implementation of the National Water Reuse Plan (NWRP) is three times higher. According to the development of the water reuse legal framework, there were pioneer areas where competent authorities developed different quality and use recommendations for this new resource. Agricultural use and golf course irrigation in touristic areas were the first two uses with recommendations and even legislation. The initial lack of common legislation for water reuse at a national or European level created some doubts which affected the implementation of water reuse, both from a planning and a licensing point of view. Currently there is still a lack of common international legislation regarding water reuse, technologies and applications. Regarding agricultural use, the model recommendations at a global scale are those set by the World Health Organization published in 1989, and subsequent reviews and extensions about risk prevention (WHO, 2006). These documents combine wastewater treatments with basic regeneration treatments reinforced by good practices based on different levels of protection to avoid deleterious health effects. Another relevant legal reference for this practices has been the Environmental Protection Agency of the US (USEPA, 2012), or those published by the State of California (Title 22, 2001). These establish indicator targets and maximum thresholds where regeneration treatment lines are responsible for the final quality according to the different uses. During 2015, the ISO has worked on a document aimed at urban use, where the possible parameters to be monitored together with risk prevention have been studied. On the other hand, the European Commission has been promoting the reuse of treated effluents within the Common Implementation Strategy of the Water Framework Directive, mainly through the work of the Programme of Measures Working Group. Within this context, the publication of a recommendation guide during 2016 is intended, as a useful tool to fill in the legal gaps of different Member States on the matter. The Royal Decree 1620/2007, where the water reuse regulation is set, resembles the principles of the USEPA more closely, even though the EU shows a tendency to prioritize risk assessment by establishing tolerance levels and thresholds according to socioeconomic conditions of the different countries, without going into details of indicators, maximum thresholds or treatments. In contrast, in the US law, regeneration treatments are indicated, while in the Spanish legislation, the only recommendations to this respect are compiled in a non-compulsory guide. Therefore, there is no regulation on the different treatment lines used to achieve the required quality standards, giving room for inappropriate practices in this respect. This is the case of disinfection, where the use of hypochlorite may produce harmful byproducts. In the recommendation Guide for the application of the Royal Decree (RD), published by the Ministry of Agriculture and Environment (MAGRAMA) in 2010, clarifications of typical issues that may arise from the application of the RD are given, as well as basic technical parameters to consider in reuse setups, or good practices according to final use. Even so, the RD still presents difficulties in its application and requires a review on issues such as the sampling frequency of current quality parameters or even the omission of nematode eggs indicator, which have been shown to be absent after CRT. In this regard, there is a global tendency to employ water reuse for drinking water, including indicators for the presence of viruses and protozoans, or to include certain technologies such as membranes or advanced oxidation processes to tackle problems like emerging pollutants. Another of the objectives of this study is to provide different regeneration treatment lines to meet the quality requirements established in the RD 1620/2007 broken down by applications, and to estimate establishment and operational costs. This proposal has been based on what is established in the above mentioned Guide and NWRP. The proposed treatment typologies are divided in treatment trains with desalination, like reverse osmosis or reversible electrodialisis, and those that lack this treatment for brackish water. This separation is done due to coastal facilities, where sea water may permeate the collecting pipes, rising salt contents in the wastewater, hence limiting certain uses. To develop this objective a study of the most common treatment units set up in Spanish WRPs is conducted in terms of treatment train reliability to obtain an acceptable relationship between the required quality and the capital and operational costs. The CRT has an establishment cost of 28 to 48 €.m-3.d and an operation cost of 0.06 to 0.09 €.m-3, while, if desalination was required, these costs would increase tenfold for implementation and fivefold for operation. In the cases of uses that require ART, such as residential or certain industrial uses, the costs would be of 185 to 398 €.m-3.d for implementation and of 0.14 to 0.20 €.m-3 for operation. When selecting regeneration treatment lines, the relation between treatment capacity and cost is a paramount indicator. This project provides cost-capacity models for regeneration treatment trains. These may serve as a tool when selecting between different options to fulfill water demands with MBR facilities, or others such as sea water desalination plants or inter-basin water transfer into a water planning framework. In Spain, the requirement for high quality water in areas with low resource availability, the increasing number of sensitive zones, such as drinking water extraction, recreational bathing areas, fish protected areas and the lack of available land to set up new WWTPs, have turned MBRs into a suitable option for water reuse. In this work this technology is analyzed in contrast to CRT and ART, providing cost-capacity models, and identifying when and where this treatment option may outcompete other regeneration treatments. An MBR is an activated sludge treatment where the secondary settling is substituted by a membrane system of UF or MF. The quality of the effluent is, therefore, comparable to that of a WWTP followed by an ART. MBRs ensure a sufficient quality level for the requirements of the different uses established in the RD, even producing an effluent that can be directly treated in OI or EDR processes. The implementation of this technology in Spain has grown exponentially, growing from 13 facilities with less than 5000 m3.d-1 in 2006 to above 55 facilities operating by the end of 2014, 6 of them with capacities over 15000 m3.d-1. The membrane filtration systems for MBR are the ones that set the pace of operation and design of this type of facilities. The most widespread system in Spain is the hollow fiber membrane configuration, especially on high flow capacities, being Zenon commercial technology, which mounts up to 57% of the total installed capacity, the main contributor. The next commercial technology according to plant number is Kubota, which uses flat sheet membrane configuration, which mounts up to 30% of the total installed capacity. Other commercial technologies exist within the Spanish MBR context, such as Toray, Huber, Koch or Microdym. In this document an analysis of all of these membrane filtration systems is done, providing information about their characteristics and relevant design and operation parameters. The study of 14 full scale running MBRs has enabled to pursue another of the objectives of this work: the estimation of the implementation and operation costs of this type of systems in contrast to other regeneration alternatives. Active participation of ACA and ESAMUR, public wastewater treatment and reuse entities of Cataluña and Murcia respectively, has helped attaining this objective. A number of typical operative problems and their possible solutions are discussed, both for operation and plant design purposes. The conclusion of this study is that MBRs are another option to consider for water reuse, being advantageous in terms of both implementation and operational costs, when compared with WWTPs followed by ART, when considering flow capacities above 10000 m3.d-1.

Inhibition of advanced glycation endproduct formation by acetaldehyde: Role in the cardioprotective effect of ethanol

Epidemiological studies suggest that there is a beneficial effect of moderate ethanol consumption on the incidence of cardiovascular disease. Ethanol is metabolized to acetaldehyde, a two-carbon carbonyl compound that can react with nucleophiles to form covalent addition products. We have identified a biochemical modification produced by the reaction of acetaldehyde with protein-bound Amadori products. Amadori products typically arise from the nonenzymatic addition of reducing sugars (such as glucose) to protein amino groups and are the precursors to irreversibly bound, crosslinking moieties called advanced glycation endproducts, or AGEs. AGEs accumulate over time on plasma lipoproteins and vascular wall components and play an important role in the development of diabetes- and age-related cardiovascular disease. The attachment of acetaldehyde to a model Amadori product produces a chemically stabilized complex that cannot rearrange and progress to AGE formation. We tested the role of this reaction in preventing AGE formation in vivo by administering ethanol to diabetic rats, which normally exhibit increased AGE formation and high circulating levels of the hemoglobin Amadori product, HbA1c, and the hemoglobin AGE product, Hb-AGE. In this model study, diabetic rats fed an ethanol diet for 4 weeks showed a 52% decrease in Hb-AGE when compared with diabetic controls (P < 0.001). Circulating levels of HbA1c were unaffected by ethanol, pointing to the specificity of the acetaldehyde reaction for the post-Amadori, advanced glycation process. These data suggest a possible mechanism for the so-called “French paradox,” (the cardioprotection conferred by moderate ethanol ingestion) and may offer new strategies for inhibiting advanced glycation.

Hybrid magnetic graphitic nanocomposites for catalytic wet peroxide oxidation applications

Hybrid magnetic graphitic nanocomposites (MGNC) prepared by inclusion of magnetite nanoparticles (obtained by coprecipitation) into an organic-organic self-assembly system, followed by calcination, revealed high activity for the catalytic wet peroxide oxidation (CWPO) of 4-nitrophenol solutions (5 g L-l), with pollutant removais up to 1245 mg g-' h-l being obtained when considering the mass ratio [pollutant]/[catalyst] =10. The stability of the MGNC catalyst against metal leaching was ascribed to the confinement effect of the carbon based material. These observations, together with the magnetically recoverable characteristics of MGNC, open new prospects for the wide use of this catalyst in highly efficient CWPO applications.

Oxidation of mixed-valence CoIII/FeII complexes reversed at high pH: A kinetico-mechanistic study of water oxidation

The outer-sphere oxidation of Fell in the mixed-valence complex trans-[(LCoNCFeII)-Co-14S-N-III(CN)(6)](-), being L-14S an N3S2 macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N-5 macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S2O82- and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(double dagger) and DeltaV(double dagger). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[(LCoNCFeIII)-Co-14S-N-III(CN)(6)], as well as the analogous N-5 systems trans-[(LCoNCFeIII)-Co-14-N-III(CN)(6)], trans-[(LCoNCFeIII)-Co-15-N-III-(CN)(6)], and cis-[(LCoNCFeIII)-Co-n-N-III(CN)(6)], Oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [(LCoNCFeIII)-Co-n-N-III(CN)(5)] + OH- - [(LCoNCFeII)-Co-n-N-III(CN)(5)](-) + 1/2H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH- adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(double dagger) and DeltaV(double dagger) (-76 to -113 J K-1 mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O2- to Fe-III.

Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

The integrated chemical-biological degradation combining advanced oxidation by UV/H2O2 followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H2O2/L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required. (c) 2006 Elsevier B.V. All rights reserved.

Phagocyte oxidation of phospholipids: comparison of hydroperoxide, chlorohydrin and epoxyisoprostane formation by LC-MS

Phagocytic cells produce a variety of oxidants as part of the immune defence, which react readily both with proteins and lipids, and could contribute to the oxidation of low density lipoprotein in atherosclerosis. We have investigated the oxidation of phospholipid vesicles by isolated human polymorphonuclear and mononuclear leukocytes, to provide a model of lipid oxidation in the absence of competing protein. PMA-stimulated cells were incubated with phospholipid vesicles contammg dipalmitoyl phosphatidylcholine (DPPC), palmitoyl-arachidonoyl phosphatidylcholine (PAPC), and stearoyl-oleoyl phosphatidylcholine (SOPC), before extraction of the lipids for analysis by HPLC coupled to electrospray mass spectrometry. In this system, oxidized phosphatidylcholines elute earlier than the native lipids owing to their decreased hydrophobicity, and can be identified according to their molecular mass. The formation of monohydroperoxides of P APC was observed routinely, together with low levels of hydroxides, but no chlorohydrin derivatives of P APC or SOPC were detected. However, the major oxidized product occurred at 828 m/z, and was identified as I-palmitoyl-2-(5,6-epoxyisoprostane E2)-sn-glycero-3-phosphocholine. These results show that phagocytes triggered by PMA cause oxidative damage to lipids predominantly by free radical mechanisms, and that electrophilic addition involving HOCl is not a major mechanism of attack. The contribution of myeloperoxidase and metal ions to the oxidation process is currently being investigated, and preliminary data suggest that myeloperoxidase-derived oxidants are responsible for the epoxyisoprostane phospholipid formation. The identification of an epoxyisoprostane phospholipid as the major product following phagocyte-induced phospholipid oxidation is novel and has implications for phagocyte involvement in atherogenesis.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Modelagem da degradação de fenol em efluentes aquosos através do processo de foto-fenton

Advanced Oxidation Processes (AOP) are techniques involving the formation of hydroxyl radical (HO•) with high organic matter oxidation rate. These processes application in industry have been increasing due to their capacity of degrading recalcitrant substances that cannot be completely removed by traditional processes of effluent treatment. In the present work, phenol degrading by photo-Fenton process based on addition of H2O2, Fe2+ and luminous radiation was studied. An experimental design was developed to analyze the effect of phenol, H2O2 and Fe2+ concentration on the fraction of total organic carbon (TOC) degraded. The experiments were performed in a batch photochemical parabolic reactor with 1.5 L of capacity. Samples of the reactional medium were collected at different reaction times and analyzed in a TOC measurement instrument from Shimadzu (TOC-VWP). The results showed a negative effect of phenol concentration and a positive effect of the two other variables in the TOC degraded fraction. A statistical analysis of the experimental design showed that the hydrogen peroxide concentration was the most influent variable in the TOC degraded fraction at 45 minutes and generated a model with R² = 0.82, which predicted the experimental data with low precision. The Visual Basic for Application (VBA) tool was used to generate a neural networks model and a photochemical database. The aforementioned model presented R² = 0.96 and precisely predicted the response data used for testing. The results found indicate the possible application of the developed tool for industry, mainly for its simplicity, low cost and easy access to the program.

Modelagem da degradação de fenol em efluentes aquosos através do processo de foto-fenton

Advanced Oxidation Processes (AOP) are techniques involving the formation of hydroxyl radical (HO•) with high organic matter oxidation rate. These processes application in industry have been increasing due to their capacity of degrading recalcitrant substances that cannot be completely removed by traditional processes of effluent treatment. In the present work, phenol degrading by photo-Fenton process based on addition of H2O2, Fe2+ and luminous radiation was studied. An experimental design was developed to analyze the effect of phenol, H2O2 and Fe2+ concentration on the fraction of total organic carbon (TOC) degraded. The experiments were performed in a batch photochemical parabolic reactor with 1.5 L of capacity. Samples of the reactional medium were collected at different reaction times and analyzed in a TOC measurement instrument from Shimadzu (TOC-VWP). The results showed a negative effect of phenol concentration and a positive effect of the two other variables in the TOC degraded fraction. A statistical analysis of the experimental design showed that the hydrogen peroxide concentration was the most influent variable in the TOC degraded fraction at 45 minutes and generated a model with R² = 0.82, which predicted the experimental data with low precision. The Visual Basic for Application (VBA) tool was used to generate a neural networks model and a photochemical database. The aforementioned model presented R² = 0.96 and precisely predicted the response data used for testing. The results found indicate the possible application of the developed tool for industry, mainly for its simplicity, low cost and easy access to the program.

Degradação de paracetamol empregando tecnologia oxidativa avançada baseada em fotocatálise heterogênea usando irradiação artificial e solar

In this work, the oxidation and mineralization of paracetamol, based in an advanced oxidative process promoted by heterogeneous photocatalysis, was evaluated. The action of two photocatalysts (titanium dioxide, and a composite based on the association between titanium dioxide and zinc phthalocyanine dye) was studied. First of all, experiments in laboratory scale were performed using as radiation font a 400 W high pressure mercury lamp. The mineralization of paracetamol, promoted by both photocatalysts, was evaluated working with 4L of solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. To find the best experimental conditions, the influence of hydrogen peroxide concentration and pH was evaluated for the reactions. The best results for the reactions in laboratory scale was obtained using 33,00 mg L-1 of hydrogen peroxide in natural pH (6,80). Under these conditions, 100% oxidation was reached in just 40 minutes of reaction using TiO2 P25, while the mineralization was 78%. Using the composite, the mineralization was 63% in 2 hours of reaction and a oxidation of almost 100% was reached after 60 minutes. A CPC reactor (compound parabolic concentrator) was employed in the expanded work scale, using the sun as irradiation source. In this case the experiments were performed using 50 L of aqueous solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. The assays were done at pH 3,00 and natural pH (6,80). The used concentration of hydrogen peroxide was 33,00 mg L-1, adopted after laboratory scale studies. The reaction at pH 3,00 shows to be more advantageous, since under natural pH (6,80), the use of deionized water was necessary to prepare the solutions, probably because the deleterious action of carbonate ions, known hydroxyl radical scavengers. Using solar irradiation, the reaction mediated by the composite was more efficient when compared with the assays under laboratory scale since the composite presents the advantage of promoting a better use of visible radiation. Under these conditions, the mineralization increased from 40% to 56% under pH 3,00. At natural pH the oxidation occurred more slowly and the mineralization decreased from 56% to 50%. Thus, the use of pH 3,00 will be more interesting in real scale applications, even if it is necessary the pH correction before the discard of the treated effluent to the environment.

Thermal degradation studies on Edible Oil during Deep Fat Frying Process

Deep fat frying process is one of the widely followed cooking practices throughout the world. Cooking oils serve as a medium for frying food for transferring heat and makes fried food tasty and palatable. Frying process is a most complex process involving numerous physicochemical changes which are complicated to understand. Frying leads to thermal degradation of oil through thermo-oxidation, hydrolysis, and polymerization. Hydrolysis results in formation of free fatty acids whereas oxidation process produces hydroperoxides and small molecular carbonyl compounds. This whole process leads to the formation of polar compounds and degradation of antioxidants that further degrades frying oil. Eventually, through mass transfer process these degradation products accumulate into fried food and reduce the nutritional quality of both oil and food. Thus, the frying process is of research interest calls for detailed systematic study which is chosen for the present study. The primary objective of this study is to understand the mechanism of degradation and characterization ofdegraded products which helps in arriving at the limits for frying oil utilization in terms of number of frying cycles. The mechanistic studies and the knowledge on the degraded products help to understand the way to retard the deterioration of oil for stability and enhancement of frying cycles. The study also explores the formation of the predominant polar compounds and their structural elucidation through mass spectrometry. Oxidation of oil is another important factor that ignites the degradation phenomena. One of the best ways to increase thermal stability of any oil is addition of potent antioxidants. But, most of the natural and synthetic antioxidants are unstable and ineffective at frying temperatures. Therefore, it is necessary to screen alternative antioxidants for their activity in the refined oils which are devoid of any added antioxidants. In this context, this study discussed the efficacy of several natural and synthetic antioxidants to retard the formation of polar compounds and thermooxidation during prolonged frying conditions. Similarly, the advantage of blending of two different oils to improve the thermal stability was explored. The present study brings out the total picture on the type of degradation products formed during frying and the ways of retarding the determination to improve upon the stability of the oil and enhancement of frying cycles.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Processos Oxidativos Avançados para Remediação de Águas Contaminadas por Pesticidas

Este trabalho teve como objectivo inicial o estudo de processos oxidativos avançados de forma a remediar e tratar águas contaminadas por pesticidas. No entanto, ao longo do trabalho experimental, constatou-se que os produtos resultantes da degradação de pesticidas são muitas vezes mais tóxicos do que os compostos que lhes deram origem e que, por isso, degradar um composto nem sempre é o melhor para o ambiente. Assim, neste trabalho, procurou-se estudar o processo de degradação com o objectivo de minimizar o impacto ambiental dos pesticidas na água e no ambiente em geral. A parte experimental deste trabalho foi dividida em duas etapas, sendo que, em ambas, a voltametria de onda quadrada e a espectrofotometria de UV/Vis foram os métodos de análise utilizados, para acompanhar o processo de fotodegradação. Na primeira etapa estudou-se a relação entre a estrutura química dos pesticidas MCPA, MCPP, 2.4-D e Dicloroprop e a sua fotodegradação. Soluções aquosas dos pesticidas enunciados foram submetidas a irradiação UV/vis, com incrementos variáveis de tempo de irradiação. Os resultados obtidos, nesta etapa, permitiram constatar diferenças na percentagem de degradação dos diferentes pesticidas. Dos pesticidas estudados verificou-se uma maior fotodegradação para o MCPA e MCPP seguido do Dicloroprop e finalmente o 2.4-D que se degradou menos. Os dados obtidos sugerem que a fotodegradação destes pesticidas está intimamente ligada com a estrutura das moléculas. A presença de um maior número de grupos cloro ligados ao anel aromático nos pesticidas 2,4-D e Dicloroprop faz com que estes sejam mais estáveis e por isso se degradam menos que o MCPA e o MCPP. Por outro lado, o facto de o 2,4-D apresentar um potencial de oxidação mais elevado do que o Dicloroprop, faz com que este seja mais difícil de degradar, o que justifica a diferença entre os dois. Desta forma, foi possível concluir que a estrutura dos pesticidas condiciona o processo de degradação, como esperado. Na segunda etapa, estudou-se a estabilização dos pesticidas MCPA e MCPP após encapsulação, com 2-hidroxipropil-β-ciclodextrina (HP-β-CD), em água desionizada e em água do rio. Para tal, submeteram-se as soluções aquosas dos pesticidas com e sem ciclodextrina, a irradiação UV/vis, também com incrementos variáveis de tempo. No caso do MCPA verificou-se que, tanto para água desionizada como para água do rio, que este herbicida encapsulado se degrada bastante menos do que o MCPA livre. O encapsulamento permitiu reduzir quase para metade a taxa de fotodegradação. Assim, confirmou-se que a HP-β-CD permite estabilizar este pesticida, tornando-o mais resistente à fotodegradação. Desta forma, originam-se menos produtos de degradação, os quais podem ser mais tóxicos, e reduz-se de o impacto ambiental deste herbicida. Verificou-se também que o MCPA livre se degrada mais em água do rio do que em água desionizada, provavelmente devido à matéria orgânica presente nesta água, que promove o processo de degradação. No que respeita ao MCPP também se constatou que este herbicida se degrada menos encapsulado do que livre, em água desionizada e em água do rio. Neste caso, conseguiu-se reduzir pouco a taxa de fotodegradação, mas, ainda assim se verifica uma estabilização deste pesticida através do encapsulamento. No entanto, tornou-se mais evidente a estabilização do MCPP após encapsulação em água do rio, já que apresenta uma taxa de fotodegradação menor. Este facto demonstra que a HP-β-CD permite estabilizar também este pesticida, tornando-o mais resistente à fotodegradação, e reduzindo seu impacto ambiental.

Non chemical natural organic matter removal with a contact TiO2 process

Dissertação de Mestrado, Tecnologia dos Alimentos, Instituto Superior de Engenharia, Universidade do Algarve, 2014