Stability and mechanical evaluation of bovine pericardium cross-linked with polyurethane prepolymer in aqueous medium

The present study investigates the potential use of non-catalyzed water-soluble blocked polyurethane prepolymer (PUP) as a bifunctional cross-linker for collagenous scaffolds. The effect of concentration (5, 10, 15 and 20%), time (4, 6, 12 and 24 h), medium volume (50, 100, 200 and 300%) and pH (7.4, 8.2, 9 and 10) over stability, microstructure and tensile mechanical behavior of acellular pericardial matrix was studied. The cross-linking index increased up to 81% while the denaturation temperature increased up to 12 °C after PUP crosslinking. PUP-treated scaffold resisted the collagenase degradation (0.167 ± 0.14 mmol/g of liberated amine groups vs. 598 ± 60 mmol/g for non-cross-linked matrix). The collagen fiber network was coated with PUP while viscoelastic properties were altered after cross-linking. The treatment of the pericardial scaffold with PUP allows (i) different densities of cross-linking depending of the process parameters and (ii) tensile properties similar to glutaraldehyde method.

Water option contracts for reducing water supply risks: an application to the Tagus-Segura Transfer

El agua es un recurso cada vez más escaso y valioso. Por ello, los recursos hídricos disponibles deben asignarse de una forma eficiente entre los diferentes usos. El cambio climático aumentará la frecuencia y severidad de los eventos extremos, y podría incrementar la demanda de agua de los cultivos. El empleo de mecanismos flexibles de asignación de agua puede ser imprescindible para hacer frente a este aumento en la variabilidad del balance hídrico y para asegurar que los riesgos de suministro, y no solo los recursos, son compartidos de manera eficiente entre los usuarios. Los mercados de agua permiten la reasignación de los recursos hídricos, favoreciendo su transferencia desde los usos de menor a los de mayor valor. Diferentes tipos de mercados de agua se han establecido en diferentes partes del mundo, ayudando a los participantes a afrontar los problemas de escasez de agua en esas zonas. En España, los intercambios de agua están permitidos desde 1999, aunque la participación de los usuarios en el mercado ha sido limitada. Hay varios aspectos de los mercados de agua en España que deben mejorarse. Esta tesis, además de proponer una serie de cambios en el marco regulatorio, propone la introducción de contratos de opción de agua como una posible mejora. La principal ventaja de este tipo de contratos es la estabilidad legal e institucional que éstos proporcionan tanto a compradores como vendedores. Para apoyar esta propuesta, se han llevado a cabo diferentes análisis que muestran el potencial de los contratos de opción como herramienta de reducción del riesgo asociado a una oferta de agua inestable. La Cuenca del Segura (Sureste de España), la Cuenca del Tajo y el Acueducto Tajo- Segura han sido seleccionados como casos de estudio. Tres análisis distintos aplicados a dicha región se presentan en esta tesis: a) una evaluación de los contratos de opción como mecanismo para reducir los riesgos de disponibilidad de agua sufridos por los regantes en la Cuenca del Segura; b) un marco teórico para analizar las preferencias de los regantes por diferentes mecanismos de gestión del riesgo de disponibilidad de agua, su disposición a pagar por ellos y los precios aproximados de estos instrumentos (seguro de sequía y contratos de opción de agua); y c) una evaluación del papel de los contratos de opción en las decisiones de aprovisionamiento de agua de una comunidad de regantes ante una oferta de agua incierta. Los resultados muestran el potencial de reducción del riesgo de los contratos de opción para regantes en España, pero pueden ser extrapolados a otros sectores o regiones. Las principales conclusiones de esta tesis son: a) la agricultura será uno de los sectores más afectados por el cambio climático. Si los precios del agua aumentan, la rentabilidad de los cultivos puede caer hasta niveles negativos, lo que podría dar lugar al abandono de cultivos de regadío en algunas zonas de España. Las políticas de cambio climático y de agua deben estar estrechamente coordinadas para asegurar un uso de agua eficiente y la rentabilidad de la agricultura; b) aunque los mercados de agua han ayudado a algunos usuarios a afrontar problemas de disponibilidad del recurso en momentos de escasez, hay varios aspectos que deben mejorarse; c) es necesario desarrollar mercados de agua más flexibles y estables para garantizar una asignación eficiente de los recursos entre los usuarios de agua; d) los resultados muestran los beneficios derivados del establecimiento de un contrato de opción entre usuarios de agua del Tajo y del Segura para reducir el riesgo de disponibilidad de agua en la cuenca receptora; e) la disposición a pagar de los regantes por un contrato de opción de agua o un seguro de sequía hidrológica, que representa el valor que tienen estos mecanismos para aquellos usuarios de agua que se enfrentan a riesgos relacionados con la disponibilidad del recurso, es consistente con los resultados obtenidos en estudios previos y superior al precio de mercado de estos instrumentos, lo que favorece la viabilidad de estos mecanismos de gestión del riesgo ; y f) los contratos de opción podrían ayudar a optimizar las decisiones de aprovisionamiento de agua bajo incertidumbre, proporcionando más estabilidad y flexibilidad que los mercados temporales de agua. ABSTRACT Water is becoming increasingly scarce and valuable. Thus, existing water resources need to be efficiently allocated among users. Climate change is expected to increase the frequency and severity of extreme events, and it may also increase irrigated crops' water demand. The implementation of flexible allocation mechanisms could be essential to cope with this increased variability of the water balance and ensure that supply risks, and not only water resources, are also efficiently shared and managed. Water markets allow for the reallocation of water resources from low to high value uses. Different water trading mechanisms have been created in different parts of the world and have helped users to alleviate water scarcity problems in those areas. In Spain, water trading is allowed since 1999, although market activity has been limited. There are several issues in the Spanish water market that should be improved. This thesis, besides proposing several changes in the legislative framework, proposes the introduction of water option contracts as a potential improvement. The main advantage for both buyer and seller derived from an option contract is the institutional and legal stability it provides. To support this proposal, different analyses have been carried out that show the potential of option contracts as a risk reduction tool to manage water supply instability. The Segura Basin (Southeast Spain), the Tagus Basin and the Tagus-Segura inter-basin Transfer have been selected as the case study. Three different analyses applied to this region are presented in this thesis: a) an evaluation of option contracts as a mechanisms to reduce water supply availability risks in the Segura Basin; b) a theoretical framework for analyzing farmer’s preferences for different water supply risk management tools and farmers’ willingness to pay for them, together with the assessment of the prices of these mechanisms (drought insurance and water option contracts); and c) an evaluation of the role of option contracts in water procurement decisions under uncertainty. Results show the risk-reduction potential of option contracts for the agricultural sector in Spain, but these results can be extrapolated to other sectors or regions. The main conclusions of the thesis are: a) agriculture would be one of the most affected sectors by climate change. With higher water tariffs, crop’s profitability can drop to negative levels, which may result in the abandoning of the crop in many areas. Climate change and water policies must be closely coordinated to ensure efficient water use and crops’ profitability; b) although Spanish water markets have alleviated water availability problems for some users during water scarcity periods, there are several issues that should be improved; c) more flexible and stable water market mechanisms are needed to allocate water resources and water supply risks among competing users; d) results show the benefits derived from the establishment of an inter-basin option contract between water users in the Tagus and the Segura basins for reducing water supply availability risks in the recipient area; e) irrigators’ willingness to pay for option contracts or drought insurance, that represent the value that this kind of trading mechanisms has for water users facing water supply reliability problems, are consistent with results obtained in previous works and higher than the prices of this risk management tools, which shows the feasibility of these mechanisms; and f) option contracts would help to optimize water procurement decisions under uncertainty, providing more flexibility and stability than the spot market.

Fishing effort control regulations influence on stability, safety and operability of small fishing vessels: study of a series of stability related accidents occurred in Spain between 2004 and 2007

Entre los años 2004 y 2007 se hundieron por problemas de estabilidad cinco pesqueros españoles de pequeña eslora, de características parecidas, de relativamente poca edad, que habían sido construidos en un intervalo de pocos años. La mayoría de los tripulantes de esos pesqueros fallecieron o desaparecieron en esos accidentes. Este conjunto de accidentes tuvo bastante repercusión social y mediática. Entre ingenieros navales y marinos del sector de la pesca se relacionó estos accidentes con los condicionantes a los diseños de los pesqueros impuestos por la normativa de control de esfuerzo pesquero. Los accidentes fueron investigados y publicados sus correspondientes informes; en ellos no se exploró esta supuesta relación. Esta tesis pretende investigar la relación entre esos accidentes y los cambios de la normativa de esfuerzo pesquero. En la introducción se expone la normativa de control de esfuerzo pesquero analizada, se presentan datos sobre la estructura de la flota pesquera en España y su accidentalidad, y se detallan los criterios de estabilidad manejados durante el trabajo, explicando su relación con la seguridad de los pesqueros. Seguidamente se realiza un análisis estadístico de la siniestralidad en el sector de la pesca para establecer si el conjunto de accidentes estudiados supone una anomalía, o si por el contrario el conjunto de estos accidentes no es relevante desde el punto de vista estadístico. Se analiza la siniestralidad a partir de diversas bases de datos de buques pesqueros en España y se concluye que el conjunto de accidentes estudiados supone una anomalía estadística, ya que la probabilidad de ocurrencia de los cinco sucesos es muy baja considerando la frecuencia estimada de pérdidas de buques por estabilidad en el subsector de la flota pesquera en el que se encuadran los cinco buques perdidos. A continuación el trabajo se centra en la comparación de los buques accidentados con los buques pesqueros dados de baja para construir aquellos, según exige la normativa de control de esfuerzo pesquero; a estos últimos buques nos referiremos como “predecesores” de los buques accidentados. Se comparan las dimensiones principales de cada buque y de su predecesor, resultando que los buques accidentados comparten características de diseño comunes que son sensiblemente diferentes en los buques predecesores, y enlazando dichas características de diseño con los requisitos de la nueva normativa de control del esfuerzo pesquero bajo la que se construyeron estos barcos. Ello permite establecer una relación entre los accidentes y el mencionado cambio normativo. A continuación se compara el margen con que se cumplían los criterios reglamentarios de estabilidad entre los buques accidentados y los predecesores, encontrándose que en cuatro de los cinco casos los predecesores cumplían los criterios de estabilidad con mayor holgura que los buques accidentados. Los resultados obtenidos en este punto permiten establecer una relación entre el cambio de normativa de esfuerzo pesquero y la estabilidad de los buques. Los cinco buques accidentados cumplían con los criterios reglamentarios de estabilidad en vigor, lo que cuestiona la relación entre esos criterios y la seguridad. Por ello se extiende la comparativa entre pesqueros a dos nuevos campos relacionados con la estabilidad y la seguridad delos buques: • Movimientos a bordo (operatividad del buque), y • Criterios de estabilidad en condiciones meteorológicas adversas El estudio de la operatividad muestra que los buques accidentados tenían, en general, una mayor operatividad que sus predecesores, contrariamente a lo que sucedía con el cumplimiento de los criterios reglamentarios de estabilidad. Por último, se comprueba el desempeño de los diez buques en dos criterios específicos de estabilidad en caso de mal tiempo: el criterio IMO de viento y balance intenso, y un criterio de estabilidad de nueva generación, incluyendo la contribución original del autor de considerar agua en cubierta. Las tendencias observadas en estas dos comparativas son opuestas, lo que permite cuestionar la validez del último criterio sin un control exhaustivo de los parámetros de su formulación, poniendo de manifiesto la necesidad de más investigaciones sobre ese criterio antes de su adopción para uso regulatorio. El conjunto de estos resultados permite obtener una serie de conclusiones en la comparativa entre ambos conjuntos de buques pesqueros. Si bien los resultados de este trabajo no muestran que la aprobación de la nueva normativa de esfuerzo pesquero haya significado una merma general de seguridad en sectores enteros de la flota pesquera, sí se concluye que permitió que algunos diseños de buques pesqueros, posiblemente en busca de la mayor eficiencia compatible con dicha normativa, quedaran con una estabilidad precaria, poniendo de manifiesto que la relación entre seguridad y criterios de estabilidad no es unívoca, y la necesidad de que éstos evolucionen y se adapten a los nuevos diseños de buques pesqueros para continuar garantizando su seguridad. También se concluye que la estabilidad es un aspecto transversal del diseño de los buques, por lo que cualquier reforma normativa que afecte al diseño de los pesqueros o su forma de operar debería estar sujeta a evaluación por parte de las autoridades responsables de la seguridad marítima con carácter previo a su aprobación. ABSTRACT Between 2004 and 2007 five small Spanish fishing vessels sank in stability related accidents. These vessels had similar characteristics, had relatively short age, and had been built in a period of a few years. Most crewmembers of these five vessels died or disappeared in those accidents. This set of accidents had significant social and media impact. Among naval architects and seamen of the fishing sector these accidents were related to the design constraints imposed by the fishing control effort regulations. The accidents were investigated and the official reports issued; this alleged relationship was not explored. This thesis aims to investigate the relationship between those accidents and changes in fishing effort control regulations. In the introduction, the fishing effort control regulation is exposed, data of the Spanish fishing fleet structure and its accident rates are presented, and stability criteria dealt with in this work are explained, detailing its relationship with fishing vessel safety. A statistical analysis of the accident rates in the fishing sector in Spain is performed afterwards. The objective is determining whether the set of accidents studied constitute an anomaly or, on the contrary, they are not statistically relevant. Fishing vessels accident rates is analyzed from several fishing vessel databases in Spain. It is concluded that the set of studied accidents is statistically relevant, as the probability of occurrence of the five happenings is extremely low, considering the loss rates in the subsector of the Spanish fishing fleet where the studied vessels are fitted within. From this point the thesis focuses in comparing the vessels lost and the vessels that were decommissioned to build them as required by the fishing effort control regulation; these vessels will be referred to as “predecessors” of the sunk vessels. The main dimensions between each lost vessel and her predecessor are compared, leading to the conclusion that the lost vessels share design characteristics which are sensibly different from the predecessors, and linking these design characteristics with the requirements imposed by the new fishing control effort regulations. This allows establishing a relationship between the accidents and this regulation change. Then the margin in fulfilling the regulatory stability criteria among the vessels is compared, resulting, in four of the five cases, that predecessors meet the stability criteria with greater clearance than the sunk vessels. The results obtained at this point would establish a relationship between the change of fishing effort control regulation and the stability of vessels. The five lost vessels complied with the stability criteria in force, so the relation between these criteria and safety is put in question. Consequently, the comparison among vessels is extended to other fields related to safety and stability: • Motions onboard (operability), and • Specific stability criteria in rough weather The operability study shows that the lost vessels had in general greater operability than their predecessors, just the opposite as when comparing stability criteria. Finally, performance under specific rough weather stability criteria is checked. The criteria studied are the IMO Weather Criterion, and one of the 2nd generation stability criteria under development by IMO considering in this last case the presence of water on deck, which is an original contribution by the author. The observed trends in these two cases are opposite, allowing to put into question the last criterion validity without an exhaustive control of its formulation parameters; indicating that further research might be necessary before using it for regulatory purposes. The analysis of this set of results leads to some conclusions when comparing both groups of fishing vessels. While the results obtained are not conclusive in the sense that the entry into force of a new fishing effort control in 1998 caused a generalized safety reduction in whole sectors of the Spanish fishing fleet, it can be concluded that it opened the door for some vessel designs resulting with precarious stability. This evidences that the relation between safety and stability criteria is not univocal, so stability criteria needs to evolve for adapting to new fishing vessels designs so their safety is still guaranteed. It is also concluded that stability is a transversal aspect to ship design and operability, implying that any legislative reform affecting ship design or operating modes should be subjected to assessing by the authorities responsible for marine safety before being adopted.

Stability Analysis of a Run-of-River Diversion Hydropower Plant With Surge Tank And Spillway in the Head Pond

Run-of-river hydropower plants usually lack significant storage capacity; therefore, the more adequate control strategy would consist of keeping a constant water level at the intake pond in order to harness the maximum amount of energy from the river flow or to reduce the surface flooded in the head pond. In this paper, a standard PI control system of a run-of-river diversion hydropower plant with surge tank and a spillway in the head pond that evacuates part of the river flow plant is studied. A stability analysis based on the Routh-Hurwitz criterion is carried out and a practical criterion for tuning the gains of the PI controller is proposed. Conclusions about the head pond and surge tank areas are drawn from the stability analysis. Finally, this criterion is applied to a real hydropower plant in design state; the importance of considering the spillway dimensions and turbine characteristic curves for adequate tuning of the controller gains is highlighted

Use of spacecraft data to derive regions on Mars where liquid water would be stable

Combining Viking pressure and temperature data with Mars Orbital Laser Altimeter topography data, we have computed the fraction of the martian year during which pressure and temperature allow for liquid water to be stable on the martian surface. We find that liquid water would be stable within the Hellas and Argyre basin and over the northern lowlands equatorward of about 40°. The location with the maximum period of stable conditions for liquid water is in the southeastern portion of Utopia Planitia, where 34% of the year liquid water would be stable if it were present. Locations of stability appear to correlate with the distribution of valley networks.

Altered ubiquitination and stability of aquaporin-1 in hypertonic stress

Aquaporin-1 (AQP1) water channel protein expression is increased by hypertonic stress. The contribution of changes in protein stability to hypertonic induction of AQP1 have not been described. Incubation of BALB/c fibroblasts spontaneously expressing AQP1 with proteasome inhibitors increased AQP1 expression, suggesting basal proteasome-dependent degradation of the protein. Degradation by the proteasome is thought to be triggered by polyubiquitination of a target protein. To determine whether AQP1 is ubiquitinated, immunoprecipitation with anti-AQP1 antibodies was performed, and the resultant samples were probed by protein immunoblot for the presence of ubiquitin. Immunoblots demonstrated ubiquitination of AQP1 under control conditions that increased after treatment with proteasome inhibitors (MG132, lactacystin). Exposure of cells to hypertonic medium for as little as 4 h decreased ubiquitination of AQP1, an effect that persisted through 24 h in hypertonic medium. Using metabolic labeling with [35S]methionine, the half-life of AQP1 protein under isotonic conditions was found to be <4 h. AQP1 protein half-life was markedly increased by exposure of cells to hypertonic medium. These observations provide evidence that aquaporins are a target for ubiquitination and proteasome-dependent degradation. Additionally, these studies demonstrate that reduced protein ubiquitination and increased protein stability lead to increased levels of AQP1 expression during hypertonic stress.

Influence of Water Content and Temperature on Molecular Mobility and Intracellular Glasses in Seeds and Pollen1

Although the occurrence of intracellular glasses in seeds and pollen has been established, physical properties such as rotational correlation times and viscosity have not been studied extensively. Using electron paramagnetic resonance spectroscopy, we examined changes in the molecular mobility of the hydrophilic nitroxide spin probe 3-carboxy-proxyl during melting of intracellular glasses in axes of pea (Pisum sativum L.) seeds and cattail (Typha latifolia L.) pollen. The rotational correlation time of the spin probe in intracellular glasses of both organisms was approximately 10−3 s. Using the distance between the outer extrema of the electron paramagnetic resonance spectrum (2Azz) as a measure of molecular mobility, we found a sharp increase in mobility at a definite temperature during heating. This temperature increased with decreasing water content of the samples. Differential scanning calorimetry data on these samples indicated that this sharp increase corresponded to melting of the glassy matrix. Molecular mobility was found to be inversely correlated with storage stability. With decreasing water content, the molecular mobility reached a minimum, and increased again at very low water content. Minimum mobility and maximum storage stability occurred at a similar water content. This correlation suggests that storage stability might be at least partially controlled by molecular mobility. At low temperatures, when storage longevity cannot be determined on a realistic time scale, 2Azz measurements can provide an estimate of the optimum storage conditions.

Role of aromatic residues in stabilization of the [Fe4S4] cluster in high-potential iron proteins (HiPIPs): physical characterization and stability studies of Tyr-19 mutants of Chromatium vinosum HiPIP.

The functional role of residue Tyr-19 of Chromatium vinosum HiPIP has been evaluated by site-directed mutagenesis experiments. The stability of the [Fe4S4] cluster prosthetic center is sensitive to side-chain replacements. Polar residues result in significant instability, while nonpolar residues (especially with aromatic side chains) maintain cluster stability. Two-dimensional NMR data of native and mutant HiPIPs are consistent with a model where Tyr-19 serves to preserve the structural rigidity of the polypeptide backbone, thereby maintaining a hydrophobic barrier for exclusion of water from the cluster cavity. Solvent accessibility results in more facile oxidation of the cluster by atmospheric oxygen, with subsequent rapid hydrolysis of the [Fe4S4]3+ core.

Synthetic Boron-Doped Diamond Electrodes for Electrochemical Water Treatment

Boron-doped diamond electrodes have emerged as anodic material due to their high physical, chemical and electrochemical stability. These characteristics make it particularly interesting for electrochemical wastewater treatments and especially due to its high overpotential for the Oxygen Evolution Reaction. Diamond electrodes present the maximum efficiency in pollutant removal in water, just limited by diffusion-controlled electrochemical kinetics. Results are presented for the elimination of benzoic acid and for the electrochemical treatment of synthetic tannery wastewater. The results indicate that diamond electrodes exhibit the best performance for the removal of total phenols, COD, TOC, and colour.

Steam reforming of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction conditions

Recently, the steam reforming of biofuels has been presented as a potential hydrogen source for fuel cells. Because this scenario represents an interesting opportunity for Colombia (South America), which produces large amounts of bioethanol, the steam reforming of ethanol was studied over a bimetallic RhPt/La2O3 catalyst under bulk mass transfer conditions. The effect of temperature and the initial concentrations of ethanol and water were evaluated at space velocities above 55,000 h−1 to determine the conditions that maximize the H2/CO ratio and reduce CH4 production while maintaining 100% conversion of ethanol. These requirements were accomplished when 21 mol% H2O and 3 mol% C2H5OH (steam/ethanol molar ratio = 7) were reacted at 600 °C. The catalyst stability was assessed under these reaction conditions during 120 h on stream, obtaining ethanol conversions above 99% during the entire test. The effect of both H2 and air flows as catalyst regeneration treatments were evaluated after 44 and 67 h on stream, respectively. The results showed that H2 treatment accelerated catalyst deactivation, and air regeneration increased both the catalyst stability and the H2 selectivity while decreasing CH4 generation. Fresh and spent catalyst samples were characterized by TEM/EDX, XPS, TPR, and TGA. Although the Rh and Pt in the fresh catalyst were completely reduced, the spent samples showed a partial oxidation of Rh and small amounts of carbonaceous residue. A possible Rh–Pt–Rh2O3 structure was proposed as the active site on the catalyst, which was regenerated by air treatment.

Sol–gel copper chromium delafossite thin films as stable oxide photocathodes for water splitting

Significant effort is being devoted to the study of photoactive electrode materials for artificial photosynthesis devices. In this context, photocathodes promoting water reduction, based on earth-abundant elements and possessing stability under illumination, should be developed. Here, the photoelectrochemical behavior of CuCrO2 sol–gel thin film electrodes prepared on conducting glass is presented. The material, whose direct band gap is 3.15 eV, apparently presents a remarkable stability in both alkaline and acidic media. In 0.1 M HClO4 the material is significantly photoactive, with IPCE values at 350 nm and 0.36 V vs. RHE of over 6% for proton reduction and 23% for oxygen reduction. This response was obtained in the absence of charge extraction layers or co-catalysts, suggesting substantial room for optimization. The photocurrent onset potential is equal to 1.06 V vs. RHE in both alkaline and acidic media, which guarantees the combination of the material with different photoanodes such as Fe2O3 or WO3, potentially yielding bias-free water splitting devices.