Implications of agricultural production, policy and land use changes on water resource assessment

Una gestión más eficiente y equitativa del agua a escala de cuenca no se puede centrar exclusivamente en el recurso hídrico en sí, sino también en otras políticas y disciplinas científicas. Existe un consenso creciente de que, además de la consideración de las cambiantes condiciones climáticas, es necesaria una integración de ámbitos de investigación tales como la agronomía, planificación del territorio y ciencias políticas y económicas a fin de satisfacer de manera sostenible las demandas de agua por parte de la sociedad y del medio natural. La Política Agrícola Común (PAC) es el principal motor de cambio en las tendencias de paisajes rurales y sistemas agrícolas, pero el deterioro del medio ambiente es ahora una de las principales preocupaciones. Uno de los cambios más relevantes se ha producido con la expansión e intensificación del olivar en España, principalmente con nuevas zonas de regadío o la conversión de olivares de secano a sistemas en regadío. Por otra parte, el cambio de las condiciones climáticas podría ejercer un papel importante en las tendencias negativas de las aportaciones a los ríos, pero no queda claro el papel que podrían estar jugando los cambios de uso de suelo y cobertura vegetal sobre las tendencias negativas de caudal observadas. Esta tesis tiene como objetivo mejorar el conocimiento de los efectos de la producción agrícola, política agraria y cambios de uso de suelo y cobertura vegetal sobre las condiciones de calidad del agua, respuesta hidrológica y apropiación del agua por parte de la sociedad. En primer lugar, el estudio determina las tendencias existentes de nitratos y sólidos en suspensión en las aguas superficiales de la cuenca del río Guadalquivir durante el periodo de 1998 a 2009. Desde una perspectiva de política agraria, la investigación trata de evaluar mediante un análisis de datos de panel las principales variables, incluyendo la reforma de la PAC de 2003, que están teniendo una influencia en ambos indicadores de calidad. En segundo lugar, la apropiación del agua y el nivel de contaminación por nitratos debido a la producción del aceite de oliva en España se determinan con una evaluación de la huella hídrica (HH), teniendo en cuenta una variabilidad espacial y temporal a largo de las provincias españolas y entre 1997 y 2008. Por último, la tesis analiza los efectos de los cambios de uso de suelo y cobertura vegetal sobre las tendencias negativas observadas en la zona alta del Turia, cabecera de la cuenca del río Júcar, durante el periodo 1973-2008 mediante una modelización ecohidrológica. En la cuenca del Guadalquivir cerca del 20% de las estaciones de monitoreo muestran tendencias significativas, lineales o cuadráticas, para cada indicador de calidad de agua. La mayoría de las tendencias significativas en nitratos están aumentando, y la mayoría de tendencias cuadráticas muestran un patrón en forma de U. Los modelos de regresión de datos de panel muestran que las variables más importantes que empeoran ambos indicadores de calidad del agua son la intensificación de biomasa y las exportaciones de ambos indicadores de calidad procedentes de aguas arriba. En regiones en las que el abandono agrícola y/o desintensificación han tenido lugar han mejorado las condiciones de calidad del agua. Para los nitratos, el desacoplamiento de las subvenciones a la agricultura y la reducción de la cuantía de las subvenciones a tierras de regadío subyacen en la reducción observada de la concentración de nitratos. Las medidas de modernización de regadíos y el establecimiento de zonas vulnerables a nitratos reducen la concentración en subcuencas que muestran una tendencia creciente de nitratos. Sin embargo, el efecto de las exportaciones de nitratos procedente de aguas arriba, la intensificación de la biomasa y los precios de los cultivos presentan un mayor peso, explicando la tendencia creciente observada de nitratos. Para los sólidos en suspensión, no queda de forma evidente si el proceso de desacoplamiento ha influido negativa o positivamente. Sin embargo, los mayores valores de las ayudas agrarias aún ligadas a la producción, en particular en zonas de regadío, conllevan un aumento de las tasas de erosión. Aunque la cuenca del Guadalquivir ha aumentado la producción agrícola y la eficiencia del uso del agua, el problema de las altas tasas de erosión aún no ha sido mitigado adecuadamente. El estudio de la huella hídrica (HH) revela que en 1 L de aceite de oliva español más del 99,5% de la HH está relacionado con la producción de la aceituna, mientras que menos del 0,5% se debe a otros componentes, es decir, a la botella, tapón y etiqueta. Durante el período estudiado, la HH verde en secano y en regadío representa alrededor del 72% y 12%, respectivamente, del total de la HH. Las HHs azul y gris representan 6% y 10%, respectivamente. La producción de aceitunas se concentra en regiones con una HH menor por unidad de producto. La producción de aceite de oliva ha aumentado su productividad del agua durante 1997-2008, incentivado por los crecientes precios del aceite, como también lo ha hecho la cantidad de exportaciones de agua virtual. De hecho, las mayores zonas productoras presentan una eficiencia alta del uso y de productividad del agua, así como un menor potencial de contaminación por nitratos. Pero en estas zonas se ve a la vez reflejado un aumento de presión sobre los recursos hídricos locales. El aumento de extracciones de agua subterránea relacionadas con las exportaciones de aceite de oliva podría añadir una mayor presión a la ya estresada cuenca del Guadalquivir, mostrando la necesidad de equilibrar las fuerzas del mercado con los recursos locales disponibles. Los cambios de uso de suelo y cobertura vegetal juegan un papel importante en el balance del agua de la cuenca alta del Turia, pero no son el principal motor que sustenta la reducción observada de caudal. El aumento de la temperatura es el principal factor que explica las mayores tasas de evapotranspiración y la reducción de caudales. Sin embargo, los cambios de uso de suelo y el cambio climático han tenido un efecto compensatorio en la respuesta hidrológica. Por un lado, el caudal se ha visto afectado negativamente por el aumento de la temperatura, mientras que los cambios de uso de suelo y cobertura vegetal han compensado positivamente con una reducción de las tasas de evapotranspiración, gracias a los procesos de disminución de la densidad de matorral y de degradación forestal. El estudio proporciona una visión que fortalece la interdisciplinariedad entre la planificación hidrológica y territorial, destacando la necesidad de incluir las implicaciones de los cambios de uso de suelo y cobertura vegetal en futuros planes hidrológicos. Estos hallazgos son valiosos para la gestión de la cuenca del río Turia, y el enfoque empleado es útil para la determinación del peso de los cambios de uso de suelo y cobertura vegetal en la respuesta hidrológica en otras regiones. ABSTRACT Achieving a more efficient and equitable water management at catchment scale does not only rely on the water resource itself, but also on other policies and scientific knowledge. There is a growing consensus that, in addition to consideration of changing climate conditions, integration with research areas such as agronomy, land use planning and economics and political science is required to meet sustainably the societal and environmental water demands. The Common Agricultural Policy (CAP) is a main driver for trends in rural landscapes and agricultural systems, but environmental deterioration is now a principal concern. One of the most relevant changes has occurred with the expansion and intensification of olive orchards in Spain, taking place mainly with new irrigated areas or with the conversion from rainfed to irrigated systems. Moreover, changing climate conditions might exert a major role on water yield trends, but it remains unclear the role that ongoing land use and land cover changes (LULCC) might have on observed river flow trends. This thesis aims to improve the understanding of the effects of agricultural production, policies and LULCC on water quality conditions, hydrological response and human water appropriation. Firstly, the study determines the existing trends for nitrates and suspended solids in the Guadalquivir river basin’s surface waters (south Spain) during the period from 1998 to 2009. From a policy perspective, the research tries to assess with panel data analysis the main drivers, including the 2003 CAP reform, which are having an influence on both water quality indicators. Secondly, water appropriation and nitrate pollution level originating from the production of olive oil in Spain is determined with a water footprint (WF) assessment, considering a spatial temporal variability across the Spanish provinces and from 1997 to 2008 years. Finally, the thesis analyzes the effects of the LULCC on the observed negative trends over the period 1973-2008 in the Upper Turia basin, headwaters of the Júcar river demarcation (east Spain), with ecohydrological modeling. In the Guadalquivir river basin about 20% of monitoring stations show significant trends, linear or quadratic, for each water quality indicator. Most significant trends of nitrates are augmenting than decreasing, and most significant quadratic terms of both indicators exhibit U-shaped patterns. The panel data models show that the most important drivers that are worsening nitrates and suspended solids in the basin are biomass intensification and exports of both water quality indicators from upland regions. In regions that agricultural abandonment and/or de-intensification have taken place the water quality conditions have improved. For nitrates, the decoupling of agricultural subsidies and the reduction of the amount of subsidies to irrigated land underlie the observed reduction of nitrates concentration. Measures of irrigation modernization and establishment of vulnerable zones to nitrates ameliorate the concentration of nitrates in subbasins showing an increasing trend. However, the effect of nitrates load from upland areas, intensification of biomass and crop prices present a greater weight leading to the final increasing trend in this subbasins group, where annual crops dominate. For suspended solids, there is no clear evidence that decoupling process have influenced negatively or positively. Nevertheless, greater values of subsidies still linked to production, particularly in irrigated regions, lead to increasing erosion rates. Although agricultural production has augmented in the basin and water efficiency in the agricultural sector has improved, the issue of high erosion rates has not yet been properly faced. The water footprint (WF) assessment reveals that for 1 L Spanish olive oil more than 99.5% of the WF is related to the olive fruit production, whereas less than 0.5% is due to other components i.e. bottle, cap and label. Over the studied period, the green WF in rainfed and irrigated systems represents about 72% and 12%, respectively, of the total WF. Blue and grey WFs represent 6% and 10%, respectively. The olive production is concentrated in regions with the smallest WF per unit of product. The olive oil production has increased its apparent water productivity from 1997 to 2008 incentivized by growing trade prices, but also did the amount of virtual water exports. In fact, the largest producing areas present high water use efficiency per product and apparent water productivity as well as less nitrates pollution potential, but this enhances the pressure on the available water resources. Increasing groundwater abstractions related to olive oil exports may add further pressure to the already stressed Guadalquivir basin. This shows the need to balance the market forces with the available local resources. Concerning the effects of LULCC on the Upper Turia basin’s streamflow, LULCC play a significant role on the water balance, but it is not the main driver underpinning the observed reduction on Turia's streamflow. Increasing mean temperature is the main factor supporting larger evapotranspiration rates and streamflow reduction. In fact, LULCC and climate change have had an offsetting effect on the streamflow generation during the study period. While streamflow has been negatively affected by increasing temperature, ongoing LULCC have positively compensated with reduced evapotranspiration rates, thanks to mainly shrubland clearing and forest degradation processes. The research provides insight for strengthening the interdisciplinarity between hydrological and spatial planning, highlighting the need to include the implications of LULCC in future hydrological plans. These findings are valuable for the management of the Turia river basin, as well as a useful approach for the determination of the weight of LULCC on the hydrological response in other regions.

La construcción del espacio litoral : el caso de la costa de Cartagena

El litoral ha constituido a lo largo de la historia una importante fuente de recursos económicos además de un punto estratégico para la defensa del territorio. El comercio, la pesca o la industria de la sal han propiciado la formación de poblaciones y ciudades al borde del mar. La costa funcionó como un ámbito defensivo, peligroso e insalubre durante siglos donde el mar modulaba el frente costero sin grandes interacciones con un entorno prácticamente deshabitado. A mediados del siglo XIX, las innovaciones técnicas y la pacificación definitiva del Mediterráneo permiten poner en valor sus características naturales y de oportunidad. Sin perder del todo su valor defensivo, el litoral resurge como recurso productivo y como lugar de ocio y disfrute de la población. El valor estratégico de la costa quedará también reflejado en el marco normativo. El derecho civil moderno recuperará el concepto de Dominio público Marítimo Terrestre a través de la Ley de Aguas de 1866 que regulará también los usos y las limitaciones en la propiedad privada litoral. Desde ese momento, las transformaciones económicas, sociales, jurídicas y ambientales van a provocar un cambio significativo en la relación entre la sociedad y la costa que dará paso a la construcción del espacio litoral que hemos heredado. Desde la triple perspectiva del litoral como sistema físico ambiental, sistema económico, productivo y cultural, y sistema administrativo y legal, el principal objetivo de la tesis será reconstruir el proceso de transformación del litoral consecuencia de la evolución en la forma de producción del espacio, de área defensiva a recurso productivo, y desde mediados del siglo XIX hasta principios del siglo XXI. Sin embargo, la construcción del litoral no ha sido homogénea ni constante a lo largo del tiempo. Ha estado sujeta a los distintos vaivenes económicos y sociales pero también a los cambios en el modelo territorial definido por el marco legal vigente, así como a los reajustes del propio sistema físico. Como instrumento sociopolítico, el marco legal regula las presiones del sistema económico sobre el medio, apostando por una visión frente a otra, y posibilitando el grado de transformación final. Así, el conocimiento sobre el territorio en el que se interviene y la definición del modelo de litoral por parte de los poderes públicos irán configurando el espacio físico, económico y social desarrollado en la costa. Para la reconstrucción del proceso de construcción del litoral, la tesis define cuatro fases diferentes y aplica las hipótesis y la metodología a la costa de Cartagena. Se presenta gráficamente la evolución en los tres sistemas en cada una de las fases, y se recompone el relato histórico a través de los hitos más relevantes para el proceso. En cada una de las fases, el nuevo modelo intentará dar respuesta a todo aquello que no funcionó o se quedó a medias en el periodo anterior. Las crisis económicas provocan la ralentización de la actividad productiva y, consecuentemente, de las transformaciones en el territorio. Servirán para establecer, en principio, un cambio de paradigma en la lectura y gestión del litoral que acabará traduciéndose en un nuevo texto legislativo en materia de costas (1969, 1988 y 2013). La reforma de la normativa responde a una nueva forma de entender, ordenar, gestionar e intervenir en el territorio, donde se modulan las pautas pero también la intensidad en la intervención. Pero nace condicionada por el litoral heredado: los derechos generados durante la vigencia del marco legal anterior; el modelo económico y sus presiones y expectativas sobre el litoral; y el medio físico en el que se acumulan los procesos de degradación no resueltos y los nuevos riesgos. Así, las conclusiones de la tesis ponen de manifiesto la necesidad de una visión compleja e integral sobre el litoral, en la que el urbanismo y la ordenación del territorio serán fundamentales para afrontar los nuevos retos en su construcción a futuro. ABSTRACT The littoral has been throughout history an important source of economic resources and a strategic point for the defense of territory. Trade, fishing or salt industry have led to the formation of towns and cities on the edge of the sea. The coast served as a defensive, dangerous and unhealthy place where the sea modulated for centuries the waterfront without major interactions with a virtually uninhabited environment. In the mid-nineteenth century, technical innovations and the final pacification of the Mediterranean allowed to value its natural features and opportunities. Without entirely losing its defensive value, the coast emerges as a productive resource and as a place of leisure and enjoyment of people. The strategic value of the coast will also be reflected in the legal framework. The concept of maritime-terrestrial public domain will be recovered by the modern civil law and the law of waters of 1866 governs the uses and limitations of private ownership of the coast. Since then, the economic, social, legal and environmental changes will to cause a significant change in the relationship between society and the coast that will give way to the construction of littoral space inherited. From the triple perspective of the littoral as a physical environmental system, an economic, productive and cultural system, and an administrative and legal system, the main objective of the thesis is to rebuild its process of transformation, as a result of the evolution in the way that space is produced, from defensive zone to productive resource, and from the middle of the nineteenth century until the beginning of the twenty-first century. However, the construction of the coast has not been uniform nor constant over time. It has been subject to different economic and social fluctuations and also to changes in the territorial model defined by the legal framework in force, as well as to readjustments of the physical system itself. As socio-political instrument, the legal framework regulates the pressure of the economic system on the environment, it bets on a vision over another and facilitates the final degree of transformation. Thus, the knowledge on the territory that is being intervened and the definition of the model of shoreline by public authorities will configure the physical, economic and social space developed on the coast. For the reconstruction of the littoral building process, the thesis defines four different phases and applies the hypothesis and methodology to the coast of Cartagena. It introduces graphically the evolution of the three systems in each of the phases and it recomposes the historical account through of the most important milestones for the process. In each phase, the new model will attempt to answer everything that did not work or was half in the previous period. Economic crises cause a slowdown in productive activity and, consequently, in the changes of territory. They serve to establish, in principle, a paradigm shift for reading and managing the littoral, eventually resulting in new legal texts on coasts matter (1969, 1988 and 2013). The reform of legislation responds to a new way for understanding, arranging, managing and intervening on the territory, where the guidelines and also the intervention intensity are modulated. But it is born conditioned by the inherited coast: the rights generated under previous legal framework; the economic model and its pressures and expectations on the littoral; and the physical environment which accumulates degradation processes unresolved and new risks. Thus, the thesis conclusions highlight the need for a complex and comprehensive view on the littoral, where urban planning and land-use planning will be key to meet the future challenges in its construction.

Degradação de atrazina por processo foto-Fenton monitorado por injeção seqüencial e cromatografia a líquido de alta eficiência

Processos de fotodegradação de compostos orgânicos tóxicos têm sido bastante estudados. Este trabalho trata da aplicação do processo foto-Fenton para a degradação de atrazina em água (composto modelo). O efeito das concentrações dos seguintes compostos foi avaliado: peróxido de hidrogênio (2 a 6 mmol L-1) e ferrioxalato de potássio (0,2 a 1 mmol L-1). Os experimentos foram realizados em um reator com lâmpada UV - 8W (254nm). O processo de fotodegradação foi monitorado por medidas de espectrofotometria de absorção molecular automatizada por injeção seqüencial (SIA) para determinação de peróxido de hidrogênio e por cromatografia a líquido de alta eficiência (CLAE) para determinação de atrazina e metabólitos. Os experimentos demonstram que o processo de foto-Fenton é viável para o tratamento de atrazina em água.

Mass fluxes and organic carbon fluxes at four stations off Cape Blanc, NW Africa (Mauritania)

Vertical carbon fluxes between the surface and 2500 m depth were estimated from in situ profiles of particle size distributions and abundances me/asured off Cape Blanc (Mauritania) related to deep ocean sediment traps. Vertical mass fluxes off Cape Blanc were significantly higher than recent global estimates in the open ocean. The aggregates off Cape Blanc contained high amounts of ballast material due to the presence of coccoliths and fine-grained dust from the Sahara desert, leading to a dominance of small and fast-settling aggregates. The largest changes in vertical fluxes were observed in the surface waters (<250 m), and, thus, showing this site to be the most important zone for aggregate formation and degradation. The degradation length scale (L), i.e. the fractional degradation of aggregates per meter settled, was estimated from vertical fluxes derived from the particle size distribution through the water column. This was compared with fractional remineralization rate of aggregates per meter settled derived from direct ship-board measurements of sinking velocity and small-scale O2 fluxes to aggregates measured by micro-sensors. Microbial respiration by attached bacteria alone could not explain the degradation of organic matter in the upper ocean. Instead, flux feeding from zooplankton organisms was indicated as the dominant degradation process of aggregated carbon in the surface ocean. Below the surface ocean, microbes became more important for the degradation as zooplankton was rare at these depths.

Robustness of mathematical models for biological systems

The robustness of mathematical models for biological systems is studied by sensitivity analysis and stochastic simulations. Using a neural network model with three genes as the test problem, we study robustness properties of synthesis and degradation processes. For single parameter robustness, sensitivity analysis techniques are applied for studying parameter variations and stochastic simulations are used for investigating the impact of external noise. Results of sensitivity analysis are consistent with those obtained by stochastic simulations. Stochastic models with external noise can be used for studying the robustness not only to external noise but also to parameter variations. For external noise we also use stochastic models to study the robustness of the function of each gene and that of the system.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

Novel organo-modifier for thermally-stable polymer-layered silicate nanocomposites

A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes.

Chemical characterization of soil organic matter in an oligotrophic, subtropical, freshwater wetland system: Sources, diagenesis and preservation

Freshwater wetland soils of the Everglades were studied in order to assess present environmental conditions and paleo-environmental changes using organic geochemistry techniques. Organic matter in dominant vegetation, peat and marl soils was characterized by geochemical means. Samples were selected along nutrient and hydrology gradients with the objective to determine the historical sources of organic matter as well as the extent of its preservation. Effective molecular proxies were developed to differentiate the relative input of organic matter from different biological sources to wetland soils. Thus historical vegetation shifts and hydroperiods were reconstructed using those proxies. The data show good correlations with historical water management practices starting at the turn of the century and during the mid 1900's. Overall, significant shortening of hydroperiods during this period was observed. The soil organic matter (SOM) preservation was assessed through elemental analysis and molecular characterizations of bulk 13C stable isotopes, solid state 13C NMR spectroscopy, UV-Vis spectroscopy, and tetramethyl ammonium hydroxide (TMAH) thermochemolysis-GC/MS. The relationship of the environmental conditions and degradation status of the soil organic matter (SOM) among the sites suggested that both high nutrient levels and long hydroperiod favor organic matter degradation in the soils. This is probably the result of an increase in the microbial activity in the soils which have higher nutrient levels, while longer hydroperiods may enhance physical/chemical degradation processes. The most significant transformations of biomass litter in this environment are controlled by very early physical/chemical processes and once the OM is incorporated into surface soils, the diagenetic change, even over extended periods of time is comparatively minimal, and SOM is relatively well preserved regardless of hydroperiod or nutrient levels. SOM accumulated in peat soils is more prone to continued degradation than the SOM in the marl soils. The latter is presumably stabilized early on through direct air exposure (oxidation) and thus, it is more refractory to further diagenetic transformations such as humification and aromatization reactions.

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt–titanate nanotubes

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na+ -> Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti4+ ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na+ ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Corrosion protection of PVD and paint coatings for selective solar absorber surfaces

The selective solar absorber surface is a fundamental part of a solar thermal collector, as it is responsible for the solar radiation absorption and for reduction of radiation heat losses. The surface’s optical properties, the solar absorption (á) and the emittance (å), have great impact on the solar thermal collector efficiency. In this work, two coatings types were studied: coatings obtained by physical vapor deposition (PVDs) and coatings obtained by projection with different paints (PCs) on aluminum substrates. The most common industrial high performing solar selective absorbers are nowadays produced by vacuum deposition methods, showing some disadvantages, such as lower durability, lower resistance to corrosion, adhesion and scratch, higher cost and complex production techniques. Currently, spectrally selective paints are a potential alternative for absorbing surfaces in low temperature applications, with attractive features such as ease of processing, durability and commercial availability with low cost. Solar absorber surfaces were submitted to accelerated ageing tests, specified in ISO 22975-3. This standard is applicable to the evaluation of the long term behavior and service life of selective solar absorbers for solar collectors working under typical domestic hot water system conditions. The studied coatings have, in the case of PVDs solar absorptions between 0.93 and 0.96 and emittance between 0.07 and 0.10, and in the case of PCs, solar absorptions between 0.91 and 0.93 and emittance between 0.40 and 0.60. In addition to evaluating long term behavior based on artificial ageing tests, it is also important to know the degradation mechanism of different coatings that are currently in the market. Electrochemical impedance spectroscopy (EIS) allows for the assessment of mechanistic information concerning the degradation processes, providing quantitative data as output, which can easily relate to the kinetic parameters of the system. EIS measures were carried out on Gamry FAS2 Femostat coupled with a PCL4 Controller. Two electrolytes were used, 0.5 M NaCl and 0.5 M Na2SO4, and the surfaces were tested at different immersion times up to 4 weeks. The following types of specimens have been tested: Aluminium with/without surface treatment, 3 selective paint coatings (one with a poly(urethane) binder and two with silicone binders) and 2 PVD coatings. Based on the behaviour of the specimens throughout the 4 weeks of immersion, it is possible to conclude that the coating showing the best protective properties corresponds to the selective paint coating with a polyurethane resin followed by the other paint coatings, whereas both the PVD coatings do not confer any protection to the substrate, having a deleterious effect as compared to the untreated aluminium reference.

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.

Aplicação de peroxidase para degradação de deoxinivalenol

Deoxinivalenol (DON), uma das principais micotoxinas encontradas em matrizes alimentares, é um composto químico que possui em sua estrutura um anel epóxido que lhe confere alto grau de toxicidade. A aplicação de enzimas em processos de degradação de DON vem se destacando, pela estabilidade durante o processo reacional e baixo custo de produção. O objetivo desse trabalho foi estudar o potencial de peroxidase proveniente de farelo de arroz (FA) e farelo de soja (FS) para degradar DON. As condições de obtenção da PO a partir de FA foram definidas por planejamento experimental DCCR 23 , sendo extraída de 5 g de farelo com 50 mL de tampão fosfato 0,04 mol L-1 pH 5, agitados orbitalmente durante 60 min a 100 rpm, e para a PO obtida de FS as condições diferenciaram somente quanto a solução extratora, tampão fosfato 0,01 mol L-1 pH 4,7. A técnica que apresentou melhores índices de purificação para a enzima foi a partição trifásica apresentando fator de purificação e recuperação de 5,6 e 50 % para a obtida de FA e 13,61 e 50 % para FS. A PO de FA apresentou maior atividade em tampão fosfato 5 mmol L-1 pH 5,5 para as formas bruta e pura, diferindo na temperatura de reação de 25 °C e 10 °C, KM de 0,15 e 0,06 mmol L-1 e Vmáx de 769 e 667 U mg-1 , respectivamente. A PO de FS as condições foram: tampão fosfato 5 mmol L-1 pH 5, reação a 35 e 30 °C durante 10 e 5 min, KM de 0,17 e 0,05 mmol L-1 e Vmáx de 196 e 182 U mg-1 , respectivamente. A PO de FA demonstrou maior estabilidade em pH 5 enquanto que a de FS em pH 6, ambas enzimas apresentaram maior estabilidade térmica a 0 °C, as massas moleculares encontradas por eletroforese foram 41 e 34 kDa, respectivamente. Ao final das etapas de obtenção, purificação e caracterização obteve-se uma atividade específica de 116 e 794 U.mg-1 , e 4363 e 17453 U g-1 , respectivamente para PO de FA e FS. A determinação de DON e De-DON foi realizada por HPLC-DAD e LC-ESI-MS/MS para avaliação dos ensaios de degradação. A enzima comercial HRP, mostrou maior potencial de redução sobre DON (55% após 1 h de reação), no entanto em 3 h de reação, a concentração inicial da micotoxina DON foi verificada, o que evidencia que a redução pode ocorrer por adsorção ou por formação de um composto de degradação que apresente a mesma massa molecular. O emprego da enzima PO obtida de FA e FS na degradação necessita de uma avaliação cinética micotoxicologica para definição das condições de redução significativa dos níveis de DON.