Thermodynamic assessment of raw material use in passenger vehicles

Conseguir una economía mundial libre de carbono es de vital importancia para evitar el aumento de las temperaturas del planeta y sus fatales consecuencias para la humanidad. Para lograr ese objetivo se están llevando a cabo grandes avances en el desarrollo tanto de energías renovables como de vehículos más limpios. En el caso de los vehículos esos avances se están centrando principalmente en mejorar la eficiencia de los motores combustión, reducir la emisión tanto de gases de efecto invernadero como de otros perjudiciales para la salud y en el desarrollo de vehículos libres de emisiones directas, como los vehículos eléctricos.Estos avances hacía la obtención de automóviles más limpios está provocando un cambio en la actual flota de vehículos y se espera que en las próximas décadas habrá una renovación total de la misma. La nueva generación de vehículos reducirá en gran parte su dependencia con relación a los combustibles fósiles, sin embargo a cambio demandará una gran cantidad de recursos naturales, tan valiosos e incluso más escasos en ocasiones que el petróleo. Algunos de estos recursos serán: Co, Ni, Mn o Li para fabricar baterías; Ga, Ge, Y para hacer sistemas de iluminación tipo LEDs; Nd, Dy, Pr para construir imanes permanentes de motores eléctricos; Pt, Pd, Zr para hacer catalizadores que reduzcan la contaminación; Au, Ag, Sn, Ta, Yb para fabricar unidades electrónica; Ce, Tb, Se, La para hacer sensores o Nb, Mo, Cr, Ti, V, Sc, W para hacer aleaciones de acero de alta resistencia. Lamentablemente, estos recursos son finitos y algunos de ellos incluso ya son considerados como críticos por la Comisión Europea y otras institucionesinternacionales.Una de las soluciones para mejorar la sostenibilidad en la fabricación de vehículos desde el puntode vista de los materiales que se emplean es el reciclaje. Sin embargo hay dos grandes problemas en torno al mismo. Por un lado los ratios de reciclaje no están avanzando tan rápidamente como la demanda de materiales y por otro lado las políticas de reciclaje no incentivan la recuperación de metales escasos. En la actualidad, los objetivos de reciclaje de vehículos se fijan en alcanzar un porcentaje de reciclabilidad sobre la masa total del vehículo. Para conseguir esas cuotas de reciclaje se llevan a cabo convencionalmente procesos mecánicos de separación de materiales.Estos procesos son de baja intensidad energética y a la vez muy eficaces para recuperar los metales que se emplean en mayores cantidades (acero, aluminio o cobre) pero resultan ineficaces para recuperar metales empleados en pequeñas proporciones (metales críticos o escasos). Como consecuencia, los metales críticos terminan subciclados en los procesos de fabricación de aleaciones de acero o aluminio y en el peor de los casos dispersos en un vertedero.Esta tesis se desarrolla con el objetivo principal de mejorar la eficiencia en el uso de los recursos necesarios para la fabricación de automóviles. Para conseguir dicho propósito se presenta una metodología que mide la eficiencia en el uso de los recursos e identifica posibles restricciones de suministro de metales.La metodología desarrollada se basa en la aplicación de la segunda ley termodinámica y el concepto de rareza termodinámica. Este enfoque cuantifica el valor real físico de todos los metales empleados y destaca en especial la aportación de aquellos cuya contribución al peso total del vehículo es pequeña, pero cuya escasez y por tanto su valor para el planeta es elevada. Este método evalúa la calidad de los materiales en función de su abundancia en la naturaleza y la energía útil (exergía) requerida tanto para extraerlos como para procesarlos y ponerlos a disposición de las industrias.Además del enfoque termodinámico, en esta Tesis se analizan las posibles restricciones de metales que puedan surgir en las próximas décadas. Para ello se aplica un modelo que considera la disponibilidad geológica de materiales (reservas y recursos), la capacidad de producción anual de los metales, la demanda anual estimada de cada metal, la demanda acumulada hasta 2050, la evolución de las cuotas de reciclaje y el impacto de la demanda de materiales de otros sectores.Los métodos desarrollados se aplican a diferentes tipos de vehículos (ICEV1, PHEV2 y BEV3) y han permitido alcanzar entre otros los siguientes resultados principales: (1) Desde el punto de vista del valor mineral de los recursos empleados, un vehículo eléctrico demanda 2.2 veces más recursos que un vehículo de combustión; (2) Hay 31componentes críticos en un vehículo convencional desde la perspectiva de los materiales que emplean; (3) Se han definido recomendaciones de ecodiseño para esos componentes basadas en reducir la demanda de metales escasos y mejorar tanto su reciclabilidad como su reusabilidad; (4) En los actuales procesos de reciclaje de vehículos un 27 % del valor mineral de los metales no se recicla funcionalmente; (5) Se han propuesto recomendaciones para la reducción de dichas pérdidas; (6) Se ha definido un ranking de los metales más estratégicos para el sector de la fabricación de vehículos siendo los 10 más estratégicos los siguientes: Ni, Li, Tb, Co, Dy, Sb, Nd, Pt, Au y Ag.Las contribuciones de esta Tesis son de gran valor para mejorar la sostenibilidad del sector de la fabricación de vehículos desde la perspectiva de los materiales que se emplean y están principalmente dirigidas a los siguientes grupos de interés: (1) Los diseñadores de vehículos, porque les ayudará a identificar propuestas de ecodiseño desde la perspectiva de los materiales; (2) Los responsables de desarrollar políticas en torno a la eficiencia en el uso de los recursos, ya que demuestra la debilidad de las políticas actuales basadas en el peso de los materiales y ofrece como alternativa un método que evalúa tanto la cantidad como la calidad de los materiales; (3)Los ejecutivos de las empresas, porque les presenta la dependencia y vulnerabilidad de la tecnología sobre ciertos materiales y les ayudará a planificar con antelación líneas de I+D+ibasadas en la eficiencia en el uso de los recursos.Decarbonizing world economies is necessary to avoid the continuous increase of global temperature and its negative consequences for humanity. To get this ambitious target new advances in the fields of power generation with renewables and mobility with cleaner vehicles are being made. In the case of vehicles, these advances are being mainly focused on improving the performance of combustion engines, to reduce greenhouse and polluting emissions and the development of free direct emission vehicles like the electric ones. Advances towards cleaner vehicles are encouraging the continuous renovation of vehicle fleet so it is expected that in the following decades a complete renovation will take place. This new generation of vehicles will significantly reduce its fossil dependency. But in contrast, it will demand a huge quantity of other kinds of natural resources being some of them even scarcer than oil. Some of these resources will be necessary to manufacture the following components: batteries (Co, Ni, Mn or Li); LEDs for lighting (Ga, Ge, Y); permanent magnets for motors (Nd, Dy, Pr); catalytic converters (Pt, Pd, Zr); electronic units (Au, Ag, Sn, Ta, Yb), different kinds of sensors (Ce, Tb, Se, La), infotainment screens (In); automotive high performance steel or aluminum alloys (Nb, Mo, Cr, Ti, V, Sc, W) or injectors (Tb). Unfortunately these resources are finite and some of them are very scarce being even considered as critical for the European Commission and other institutions from several perspectives such as vulnerability, economic importance, supply, or ecological risks. One of the solutions to improve resource efficiency in vehicles is to recycle these valuable metals. Nevertheless, there are two main problems around the recycling situation. On one hand, recycling rates are not growing up as faster as metal demand. On the other hand, current recycling policies define targets based on mass weight approaches, and even if they are ambitious, they fail in enhancing the recycling of minor but critical metals. The legislation compliance is achieved by means of applying mechanical separation techniques. These processes are effective to recycle those metals with the highest contribution in the vehicle weight (steel, aluminum and copper) but they are not effective for the recovery of minor metals like those that are scarce and/or critical. Consequently, minor metals end downcycled during steel or aluminum smelting or in the worst case they finish dispersed in landfills. This Thesis is presented with the main aim to improve the resource efficiency in the vehicle manufacturing sector. To accomplish with this aim, a novel method for measuring the resource efficiency and to identify possible shortages in the supply of metals is presented. The resource efficiency is analyzed through the second law of Thermodynamics through the concept of thermodynamic rarity. This method takes into account the quality of mineral commodities as a function of their relative abundance in Nature and the energy intensity required to extract and process them. The application of the thermodynamic approach allows not only to recognize the physical value of materials with a low weight contribution but also to identify those components that use them. As it has been mentioned before this Thesis also assesses possible metal shortages. This activity is made by means of an own method which combines geological data (reserves and resources), annual capacity production, annual expected demand, cumulative expected demand to 2050, recycling rates evolutions and future resource demand of other technologies. The methodology is applied to different types of vehicles (ICEV , PHEV and BEV ) and it has been useful to achieve the following main results: (1) From a thermodynamic point of view an electric vehicle demands 2.2 times more quality resources than a combustion one; (2) 31 critical components were identified in a conventional vehicle from the perspective of the materials used to manufacture them; (3) Eco-design recommendations for these components have been defined. These recommendations are based on: reducing the demand of scarce metals and to increase both the recyclability and the reusability; (4) In current End of Life Vehicle (ELV) processes 27 % of the mineral capital (measured in rarity terms) is not functionally recycled; (5) Recommendations to reduce these losses have been proposed; (6) A strategic metal ranking for the automobile sector has been produced, being the top 10 most strategic metals the following: Ni, Li, Tb, Co, Dy, Sb, Nd, Pt, Au and Ag. The contributions of this Thesis are valuable to improve the sustainability of the vehicle manufacturing sector from the raw materials point of view. These contributions are mainly valuable for the following stakeholders: (1) Designers because it helps them to apply eco-design proposals from a raw materials point of view; (2) Policy makers because it evidences the weakness of mass based approach recycling policies and it proposes an alternative method that takes into considerations not only quantity but also quality; (3) Company’s executives because it confronts them with the metal dependency and vulnerability of technology and it helps them to plan with enough time R+D+i lines based on resource efficiency.<br /

Expression of a barley cystatin gene in maize enhances resistance against phytophagous mites by altering their cysteine-proteases

Phytocystatins are inhibitors of cysteine-proteases from plants putatively involved in plant defence based on their capability of inhibit heterologous enzymes. We have previously characterised the whole cystatin gene family members from barley (HvCPI-1 to HvCPI-13). The aim of this study was to assess the effects of barley cystatins on two phytophagous spider mites, Tetranychus urticae and Brevipalpus chilensis. The determination of proteolytic activity profile in both mite species showed the presence of the cysteine-proteases, putative targets of cystatins, among other enzymatic activities. All barley cystatins, except HvCPI-1 and HvCPI-7, inhibited in vitro mite cathepsin L- and/or cathepsin B-like activities, HvCPI-6 being the strongest inhibitor for both mite species. Transgenic maize plants expressing HvCPI-6 protein were generated and the functional integrity of the cystatin transgene was confirmed by in vitro inhibitory effect observed against T. urticae and B. chilensis protein extracts. Feeding experiments impaired on transgenic lines performed with T. urticae impaired mite development and reproductive performance. Besides, a significant reduction of cathepsin L-like and/or cathepsin B-like activities was observed when the spider mite fed on maize plants expressing HvCPI-6 cystatin. These findings reveal the potential of barley cystatins as acaricide proteins to protect plants against two important mite pests

Infecciones virales encubiertas en Ceratitis capitata Wiedemann (Diptera: Tephritidae) detección, distribución y coste biológico

La mosca mediterránea de la fruta, Ceratitis capitata Wiedemann (Diptera: Tephritidae), es una plaga agrícola capaz de atacar una gran variedad de frutas. Una de las principales estrategias para su gestión es la técnica del insecto estéril (TIE) que consiste en la cría masiva y posterior liberación en campo de machos estériles. La presencia de virus en C. capitata amenaza la cría masiva y la posterior aplicación de la TIE. Recientemente, ciertos virus se han relacionado con infecciones encubiertas en C. capitata

Evaluation of juvenoid insect growth regulators and a new non-steroidal ecdysone agonist on the American grasshopper, Schistocerca americana (Drury), and the desert locust, Schistocerca gregaria (Forskal) (Orthoptera: Acrididae).

Three aromatic juvenoids (fenoxycarb, JH-286 and a new pyrazole analog) were evaluated for morphogenetic, chromotropic, morphometric and prothoracicotropic activities on the American grasshopper, Schistocerca americana (Drury), and their activities compared with those of commercial methoprene and synthetic JH-III. Fenoxycarb, the most active insect growth regulator examined, was found to induce a significant mortality in developing nymphs and caused severe morphogenetic damage during ecdysis to the adult. Juvenoid treatment were also observed to promote some overaged nymphs and to induce chromotropic changes in both the cuticle and hemolymph pigmentation. Except for a reduced larvicidal action, similar levels of activity were obtained when fenoxycarb was tested on the desert locust, Schistocerca gregaria (Forskal). The chromoproteins responsible for the green coloration characteristic of the hemolymph of S. americana and S. gregaria were isolated and characterized. Hemolymph from last instar nymphs and adults of S. americana was characterized by the presence of yellow lipophorin (Lp), a green chromoprotein (G-P), and two cyanoproteins (Cp-I and Cp-II). Treatment with fenoxycarb enhanced the concentration of the two cyanoproteins in nymphs and adults, and induced the appearance of a third cyanoprotein (Cp-F) in nymphs. Hemolymph from last instar nymphs of S. gregaria was characterized by the presence of yellow lipophorin (Lp) and two blue cyanoproteins (HCp and LCp), whereas only Lp and LCp were present in adults. Treatment with fenoxycarb increased the concentration of both cyanoproteins in nymphs, but only of LCp in adults. The non-steroidal ecdysone-agonist 2RH-5849 (1,2-dibenzoyl-1-tert-buthyl-hydrazine) was found to be an effective neuropoison when injected on S. americana. Treated grasshoppers became immediately hyperactive, followed by loss of coordination, paralysis and eventually death. We discovered that this insect growth regulator also induced bilateral autotomy of the methatoracic legs. However, no evidence of ecdysonergic or morphogenetic activities were found. Synergism studies with neurotoxins of known mode of action suggested that RH-5849 has a mechanism of action similar to that of 4-amino pyridine, which blocks potassium channels

Topology Analysis of Wireless Power Transfer Systems Manufactured Via Inkjet Printing Technology

The potential of inkjet printing technology (IjP) for the fabrication of coils for biomedical applications in inductively coupled power transfer systems is studied in terms of needed compensations, bifurcation phenomena, and power transfer efficiency. The effect of using coils manufactured with IjP in the secondary side has been analyzed by studying the effect of the increase in internal resistance. The present study makes it possible to select the best topology depending on the load impedance, the coupling coefficient, and coil design. In terms of the compensations needed at the primary side, IjP does not significantly affect the behavior of the system; however, the series-series topology is preferable since the compensating capacitance is independent from the internal resistance. In terms of bifurcation, amore restricted condition is obtained for parallel compensated secondary circuits. There is a decrease on the power transfer efficiency due to the increase of the internal resistance introduced by IjP. However, it is important to select the best topology according to the application since the decrease could be from 63% to only 6%. It is concluded that IjP is a promising fabrication technique for coils for biomedical applications

Transgenic expression of trypsin inhibitor CMe from barley in indica and japonica rice, confers resistance to the rice weevil Sitophilus oryzae

Indica and japonica rice (Oryza sativa L.) plants were transformed by particle bombardment with the Itr1 gene encoding the barley trypsin inhibitor BTI-CMe, under the control of its own promoter that confers endosperm specificity, and the maize ubiquitin promoter. From 38 independent transgenic lines of indica (breeding line IR58) and 15 of the japonica (cv Senia) selected, 22 and 11, respectively, expressed the barley inhibitor at detectable levels. The transgene was correctly translated as indicated by western blot analysis with a level of expression in R3 seeds up to 0.31% (IR58) and 0.43% (Senia) of the total extracted protein. The functional integrity of BTI-CMe was confirmed by trypsin activity assays in liquid media and by activity staining gels, performed with seed extracts. The significant reduction of the survival rate of the rice weevil (Sitophilus oryzae, Coleoptera: Curculionidae) reared on homozygous transgenic indica and japonica rice seeds expressing the BTI-CMe, compared to non-transformed controls, and the decrease in the trypsin-like activity of insect crude midgut extracts, confirmed the utility of this proteinase inhibitor gene for the control of important storage pests

Editorial: plant-pest interactions volume II: hemiptera

2 p.Peer reviewe

Effects of Pesticides Used on Citrus Grown in Spain on the Mortality of Ceratitis capitata (Diptera: Tephritidae) Vienna-8 Strain Sterile Males

Vienna-8 sterile males are currently released in Spain to reduce wild populations of the medfly. Because pesticides are required to maintain populations of some citrus key pests below economic thresholds, there is a need to evaluate the effects of pesticides commonly used in citrus on Vienna-8 males. Males were exposed to differently aged residues of eight pesticides. Abamectin, etofenprox, etoxazole, petroleum spray oil, pymetrozine, and pyriproxyfen resulted harmless to Vienna-8 males. However, fresh residues of chlorpyrifos and spinosad caused high mortalities and had residual effects until 21 and 28 d after treatment, respectively. Following the same method, the lethal effects of chlorpyrifos and spinosad on Ceratitis capitata (Wiedemann) wild-type (wt) males were determined. Surprisingly, these pesticides resulted more toxic for wt than for Vienna-8 males. To determine whether these results could be attributed to intrinsic characteristics of the pesticides or to behavioral differences among Vienna-8 and wt males, a topical application trial was conducted. Vienna-8 males were twice as susceptible to chlorpyrifos as wt males, whereas their susceptibility to spinosad was slightly lower. These results in intrinsic toxicity did not directly explain the differences observed in the extended-laboratory tests with these pesticides. We hypothesize that the lower flight activity of Vienna-8 males relative to wt conspecifies can explain the lower risk observed for Vienna-8 males in the residual tests. Our results should be taken into account when planning area-wide Sterile Insect Technique programs against C. capitata especially in those areas where treatments with chlorpyrifos are approved

Adaptation of Spodoptera exigua (Lepidoptera: Noctuidae) to barley trypsin inhibitor BTI-CMe expressed in transgenic tobacco

Nicotiana tabacum plants were transformed with the cDNA of barley trypsin inhibitor BTI-CMe under the control of the 35S CaMV promoter. Although the transgene was expressed and the protein was active in the homozygous lines selected, growth of Spodoptera exigua (Lepidoptera: Noctuidae) larvae reared on transgenic plants was not affected. The protease activity in larval midgut extracts after 2 days feeding on transformed tobacco leaves from the highest expressing plant showed a reduction of 25% in the trypsin-like activity compared to that from insects fed on non-transformed controls. The susceptibility of digestive serine-proteases to inhibition by BTI-CMe was confirmed by activity staining gels. This decrease was compensated with a significant induction of leucine aminopeptidase-like and carboxipeptidase A-like activities, whilechymotrypsin-, elastase-, and carboxipeptidase B-like proteases were not affected