Sedimentological and paleoclimatological investigation of two sediment cores off Cape Barbas, North-West Africa

Two box cores taken off Cape Barbas (North-West Africa) have been studied using three methods. The analyses of the coarse fraction, of biogenic opal and of planktonic foraminifera revealed : 1. Core GIK12310-4 penetrates Z, Y, X and upper part of W zone, whereas core GIK12379-1 penetrates Z and upper part of Y zone. 2. Holocene sedimentation rates are 2.5 cm/1000 y for core GIK12310-4 and 6.0 cm/1000 y for core GIK12379-1. During the Y zone 5 cm/l000 y were sedimented incore GIK12310-4 and > 10-20 cm/1000 y in core GIK12379-1. 3. Paleoclimatohgical results are: arid climate and relatively warm water temperatures during the Holocene (Z zone) and during X zone; humid climate and relatively cool water temperatures within the Wuerm (Y zone) (with a non-dated more arid interval found in the middle part of the Y zone) and in the upper part of the W zone. 4. Increased contents of benthos and radiolaria in the Y zone indicate upwelling. Upwelling, characterized by high content of biogenic opal and low water temperatures, was found in core GIK12310-4 at 250 to 350 cm in the lower part of the Y zone. The plankton/benthos ratio of foraminifera, the benthos/radiolaria ratio and water temperatures derived from planktonic foraminifera, differ in both cores in the Holocene, and are nearly identical during the Wuerm.

Quantitative component analysis of the coarse fraction of surface sediments from the Persian Gulf

In the Persian Gulf and the Gulf of Oman marl forms the primary sediment cover, particularly on the Iranian side. A detailed quantitative description of the sediment components > 63 µ has been attempted in order to establish the regional distribution of the most important constituents as well as the criteria governing marl sedimentation in general. During the course of the analysis, the sand fraction from about 160 bottom-surface samples was split into 5 phi° fractions and 500 to 800 grains were counted in each individual fraction. The grains were cataloged in up to 40 grain type catagories. The gravel fraction was counted separately and the values calculated as weight percent. Basic for understanding the mode of formation of the marl sediment is the "rule" of independent availability of component groups. It states that the sedimentation of different component groups takes place independently, and that variation in the quantity of one component is independent of the presence or absence of other components. This means, for example, that different grain size spectrums are not necessarily developed through transport sorting. In the Persian Gulf they are more likely the result of differences in the amount of clay-rich fine sediment brought in to the restricted mouth areas of the Iranian rivers. These local increases in clayey sediment dilute the autochthonous, for the most part carbonate, coarse fraction. This also explains the frequent facies changes from carbonate to clayey marl. The main constituent groups of the coarse fraction are faecal pellets and lumps, the non carbonate mineral components, the Pleistocene relict sediment, the benthonic biogene components and the plankton. Faecal pellets and lumps are formed through grain size transformation of fine sediment. Higher percentages of these components can be correlated to large amounts of fine sediment and organic C. No discernable change takes place in carbonate minerals as a result of digestion and faecal pellet formation. The non-carbonate sand components originate from several unrelated sources and can be distinguished by their different grain size spectrum; as well as by other characteristics. The Iranian rivers supply the greatest amounts (well sorted fine sand). Their quantitative variations can be used to trace fine sediment transport directions. Similar mineral maxima in the sediment of the Gulf of Oman mark the path of the Persian Gulf outflow water. Far out from the coast, the basin bottoms in places contain abundant relict minerals (poorly sorted medium sand) and localized areas of reworked salt dome material (medium sand to gravel). Wind transport produces only a minimal "background value" of mineral components (very fine sand). Biogenic and non-biogenic relict sediments can be placed in separate component groups with the help of several petrographic criteria. Part of the relict sediment (well sorted fine sand) is allochthonous and was derived from the terrigenous sediment of river mouths. The main part (coarse, poorly sorted sediment), however, was derived from the late Pleistocene and forms a quasi-autochthonous cover over wide areas which receive little recent sedimentation. Bioturbation results in a mixing of the relict sediment with the overlying younger sediment. Resulting vertical sediment displacement of more than 2.5 m has been observed. This vertical mixing of relict sediment is also partially responsible for the present day grain size anomalies (coarse sediment in deep water) found in the Persian Gulf. The mainly aragonitic components forming the relict sediment show a finely subdivided facies pattern reflecting the paleogeography of carbonate tidal flats dating from the post Pleistocene transgression. Standstill periods are reflected at 110 -125m (shelf break), 64-61 m and 53-41 m (e.g. coare grained quartz and oolite concentrations), and at 25-30m. Comparing these depths to similar occurrences on other shelf regions (e. g. Timor Sea) leads to the conclusion that at this time minimal tectonic activity was taking place in the Persian Gulf. The Pleistocene climate, as evidenced by the absence of Iranian river sediment, was probably drier than the present day Persian Gulf climate. Foremost among the benthonic biogene components are the foraminifera and mollusks. When a ratio is set up between the two, it can be seen that each group is very sensitive to bottom type, i.e., the production of benthonic mollusca increases when a stable (hard) bottom is present whereas the foraminifera favour a soft bottom. In this way, regardless of the grain size, areas with high and low rates of recent sedimentation can be sharply defined. The almost complete absence of mollusks in water deeper than 200 to 300 m gives a rough sedimentologic water depth indicator. The sum of the benthonic foraminifera and mollusca was used as a relative constant reference value for the investigation of many other sediment components. The ratio between arenaceous foraminifera and those with carbonate shells shows a direct relationship to the amount of coarse grained material in the sediment as the frequence of arenaceous foraminifera depends heavily on the availability of sand grains. The nearness of "open" coasts (Iranian river mouths) is directly reflected in the high percentage of plant remains, and indirectly by the increased numbers of ostracods and vertebrates. Plant fragments do not reach their ultimate point of deposition in a free swimming state, but are transported along with the remainder of the terrigenous fine sediment. The echinoderms (mainly echinoids in the West Basin and ophiuroids in the Central Basin) attain their maximum development at the greatest depth reached by the action of the largest waves. This depth varies, depending on the exposure of the slope to the waves, between 12 to 14 and 30 to 35 m. Corals and bryozoans have proved to be good indicators of stable unchanging bottom conditions. Although bryozoans and alcyonarian spiculae are independent of water depth, scleractinians thrive only above 25 to 30 m. The beginning of recent reef growth (restricted by low winter temperatures) was seen only in one single area - on a shoal under 16 m of water. The coarse plankton fraction was studied primarily through the use of a plankton-benthos ratio. The increase in planktonic foraminifera with increasing water depth is here heavily masked by the "Adjacent sea effect" of the Persian Gulf: for the most part the foraminifera have drifted in from the Gulf of Oman. In contrast, the planktonic mollusks are able to colonize the entire Persian Gulf water body. Their amount in the plankton-benthos ratio always increases with water depth and thereby gives a reliable picture of local water depth variations. This holds true to a depth of around 400 m (corresponding to 80-90 % plankton). This water depth effect can be removed by graphical analysis, allowing the percentage of planktonic mollusks per total sample to be used as a reference base for relative sedimentation rate (sedimentation index). These values vary between 1 and > 1000 and thereby agree well with all the other lines of evidence. The "pteropod ooze" facies is then markedly dependent on the sedimentation rate and can theoretically develop at any depth greater than 65 m (proven at 80 m). It should certainly no longer be thought of as "deep sea" sediment. Based on the component distribution diagrams, grain size and carbonate content, the sediments of the Persian Gulf and the Gulf of Oman can be grouped into 5 provisional facies divisions (Chapt.19). Particularly noteworthy among these are first, the fine grained clayey marl facies occupying the 9 narrow outflow areas of rivers, and second, the coarse grained, high-carbonate marl facies rich in relict sediment which covers wide sediment-poor areas of the basin bottoms. Sediment transport is for the most part restricted to grain sizes < 150 µ and in shallow water is largely coast-parallel due to wave action at times supplemented by tidal currents. Below the wave base gravity transport prevails. The only current capable of moving sediment is the Persian Gulf outflow water in the Gulf of Oman.

Trace element concentrations in zircons from ODP Holes 147-894G and 153-923A

The trace element compositions of Hadean zircons have been used in two ways to argue for the existence of Hadean continental crust. One argument is based on low crystallization temperatures of Hadean zircons that have been determined using a novel geothermometer based on the Ti content of zircons in equilibrium with rutile. The second argument is based on using the trace element abundances in zircons to calculate their parental melt compositions, especially the rare earth elements. Here we demonstrate that zircons that grow from a melt formed by basalt differentiation at modern mid-ocean ridges cannot be unambiguously distinguished from Hadean zircons on either of these grounds. Thus, we conclude that the trace element compositions of Hadean zircons are permissive of models that do not include the generation of continental crust in the Hadean.

Analysis and compound of carbon sequestration and serpentinization from the Iberian Margin and the Northern Apennine

Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to < 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to < 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at < 100 °C and carbonate formation at < 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.

Experiments on polar seaweeds

Organisms populating benthic shallow water systems of both polar regions are adapted to a particularly harsh environment. We studied effects of freezing and the combination of high light intensities and low water temperatures on photosynthesis of key macroalgal species from the Arctic intertidal (Fucus distichus) and Antarctic subtidal (Palmaria decipiens). Photosynthetic activity of F. distichus specimens was monitored during the freezing process; there was a marked decrease in quantum yield with decreasing temperatures, and a rapid recovery as soon as temperatures increased again. Thus, under the experimental conditions tested, no indication of photodamage was found. Specimens of Palmaria were exposed to a combination of high light intensities and low water temperatures. A persistent impairment of photosynthetic activity occurred at 0°C at light intensities of 400 µmol photons m-2 s-1. In all treatments, there was a decreasing ratio of phycobiliproteins to chlorophyll a. Overall, the two studies provide baseline data for interpreting physiological responses of two important macroalgal species in an extreme environment, the polar coastal ecosystem.

Organic geochemistry of water and bottom sediments during a seasonal flood in 2006 in the North Dvina River estuary

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 µg/l, respectively, and bottom sediments contained from 26.2 to 329 µg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.

Magnetic properties and geochemistry in DSDP Holes 69-504B an d 69-505B

More than 60 basalt samples from two Deep Sea Drilling Project holes on the Costa Rica Rift were studied for magnetic properties and were found to have no properties significantly different from other DSDP basalts. Opaque mineralogical and thermomagnetic properties of these samples, however, to some extent show differences from normal submarine basalts; a new type of thermomagnetic curve and wide range of chemical compositions were recognized. Oxidized samples possibly containing incipient ilmenite exsolution lamellae were reduced and re-equilibrated during heating. The Curie temperatures of the re-equilibrated titanomagnetites are interpreted to be those of the original crystallized phase before oxidation.

Photosynthetically active radiation during the experiment, and lipid content of sub- and intertidal specimens of the endemic Antarctic red alga, Palmaria decipiens

In coastal waters, Antarctic rhodophytes are exposed to harsh environmental conditions throughout the year, like low water temperatures ranging from -1.8°C to 2°C and high light during the summer season. Photosynthetic performance under these conditions may be affected by slowed down enzymatic reactions and the increased generation of reactive oxygen species. The consequence might be a chronic photoinhibition of photosynthetic primary reactions related to increased fragmentation of the D1 reaction centre protein in photosystem II. It is hypothesized that changes in lipid composition of biomembranes may represent an adaptive trait to maintain D1 turnover in response to temperature variation. The interactive effects of high light and low temperature were studied on an endemic Antarctic red alga, Palmaria decipiens, sampled from two shore levels, intertidal and subtidal, and exposed to mesocosm experiments using two levels of natural solar radiation and two different temperature regimes (2-5°C and 5-10°C). During the experimental period of 23 days, maximum quantum yield of photosynthesis decreased in all treatments, with the intertidal specimens exposed at 5-10°C being most affected. On the pigment level, a decreasing ratio of phycobiliproteins to chlorophyll a was found in all treatments. A pronounced decrease in D1 protein concentration occurred in subtidal specimens exposed at 2-5°C. Marked changes in lipid composition, i.e. the ratio of saturated to unsaturated fatty acids, indicated an effective response of specimens to temperature change. Results provide new insights into mechanisms of stress adaptation in this key species of shallow Antarctic benthic communities.

Effect of short-term fasting prior to slaughter on welfare and meat quality or rainbow trout (Oncorhynchus mykiss)

El manejo pre-sacrificio es de vital importancia en acuicultura, ya que afecta tanto a las reacciones fisiológicas como a los procesos bioquímicos post mortem, y por tanto al bienestar y a la calidad del producto. El ayuno pre-sacrificio se lleva a cabo de forma habitual en acuicultura, ya que permite el vaciado del aparato digestivo de restos de alimento y heces, reduciendo de esta manera la carga bacteriana en el intestino y la dispersión de enzimas digestivos y potenciales patógenos a la carne. Sin embargo, la duración óptima de este ayuno sin que el pez sufra un estrés innecesario no está clara. Además, se sabe muy poco sobre la mejor hora del día para realizar el sacrificio, lo que a su vez está regido por los ritmos diarios de los parámetros fisiológicos de estrés. Finalmente, se sabe que la temperatura del agua juega un papel muy importante en la fisiología del estrés pero no se ha determinado su efecto en combinación con el ayuno. Además, las actuales recomendaciones en relación a la duración óptima del ayuno previo al sacrificio en peces no suelen considerar la temperatura del agua y se basan únicamente en días y no en grados día (ºC d). Se determinó el efecto del ayuno previo al sacrificio (1, 2 y 3 días, equivalente a 11,1-68,0 grados día) y la hora de sacrificio (08h00, 14h00 y 20h00) en trucha arco iris (Oncorhynchus mykiss) de tamaño comercial en cuatro pruebas usando diferentes temperaturas de agua (Prueba 1: 11,8 ºC; Prueba 2: 19,2 ºC; Prueba 3: 11,1 ºC; y Prueba 4: 22,7 ºC). Se midieron indicadores biométricos, hematológicos, metabólicos y de calidad de la carne. En cada prueba, los valores de los animales ayunados (n=90) se compararon con 90 animales control mantenidos bajo condiciones similares pero nos ayunados. Los resultados sugieren que el ayuno tuvo un efecto significativo sobre los indicadores biométricos. El coeficiente de condición en los animales ayunados fue menor que en los controles después de 2 días de ayuno. El vaciado del aparato digestivo se produjo durante las primeras 24 h de ayuno, encontrándose pequeñas cantidades de alimento después de 48 h. Por otra parte, este vaciado fue más rápido cuando las temperaturas fueron más altas. El peso del hígado de los animales ayunados fue menor y las diferencias entre truchas ayunadas y controles fueron más evidentes a medida que el vaciado del aparato digestivo fue más rápido. El efecto del ayuno hasta 3 días en los indicadores hematológicos no fue significativo. Los niveles de cortisol en plasma resultaron ser altos tanto en truchas ayunadas como en las alimentadas en todas las pruebas realizadas. La concentración media de glucosa varió entre pruebas pero mostró una tendencia a disminuir en animales ayunados a medida que el ayuno progresaba. En cualquier caso, parece que la temperatura del agua jugó un papel muy importante, ya que se encontraron concentraciones más altas durante los días 2 y 3 de ayuno en animales mantenidos a temperaturas más bajas previamente al sacrificio. Los altos niveles de lactato obtenidos en sangre parecen sugerir episodios de intensa actividad muscular pero no se pudo encontrar relación con el ayuno. De la misma manera, el nivel de hematocrito no mostró efecto alguno del ayuno y los leucocitos tendieron a ser más altos cuando los animales estaban menos estresados y cuando su condición corporal fue mayor. Finalmente, la disminución del peso del hígado (índice hepatosomático) en la Prueba 3 no se vio acompañada de una reducción del glucógeno hepático, lo que sugiere que las truchas emplearon una estrategia diferente para mantener constantes los niveles de glucosa durante el periodo de ayuno en esa prueba. En relación a la hora de sacrificio, se obtuvieron niveles más bajos de cortisol a las 20h00, lo que indica que las truchas estaban menos estresadas y que el manejo pre-sacrificio podría resultar menos estresante por la noche. Los niveles de hematocrito fueron también más bajos a las 20h00 pero solo con temperaturas más bajas, sugiriendo que las altas temperaturas incrementan el metabolismo. Ni el ayuno ni la hora de sacrificio tuvieron un efecto significativo sobre la evolución de la calidad de la carne durante los 3 días de almacenamiento. Por el contrario, el tiempo de almacenamiento sí que parece tener un efecto claro sobre los parámetros de calidad del producto final. Los niveles más bajos de pH se alcanzaron a las 24-48 h post mortem, con una lata variabilidad entre duraciones del ayuno (1, 2 y 3 días) en animales sacrificados a las 20h00, aunque no se pudo distinguir ningún patrón común. Por otra parte, la mayor rigidez asociada al rigor mortis se produjo a las 24 h del sacrificio. La capacidad de retención de agua se mostró muy estable durante el período de almacenamiento y parece ser independiente de los cambios en el pH. El parámetro L* de color se incrementó a medida que avanzaba el período de almacenamiento de la carne, mientras que los valores a* y b* no variaron en gran medida. En conclusión, basándose en los resultados hematológicos, el sacrificio a última hora del día parece tener un efecto menos negativo en el bienestar. De manera general, nuestros resultados sugieren que la trucha arco iris puede soportar un período de ayuno previo al sacrificio de hasta 3 días o 68 ºC d sin que su bienestar se vea seriamente comprometido. Es probable que con temperaturas más bajas las truchas pudieran ser ayunadas durante más tiempo sin ningún efecto negativo sobre su bienestar. En cualquier caso, se necesitan más estudios para determinar la relación entre la temperatura del agua y la duración óptima del ayuno en términos de pérdida de peso vivo y la disminución de los niveles de glucosa en sangre y otros indicadores metabólicos. SUMMARY Pre-slaughter handling in fish is important because it affects both physiological reactions and post mortem biochemical processes, and thus welfare and product quality. Pre-slaughter fasting is regularly carried out in aquaculture, as it empties the viscera of food and faeces, thus reducing the intestinal bacteria load and the spread of gut enzymes and potential pathogens to the flesh. However, it is unclear how long rainbow trout can be fasted before suffering unnecessary stress. In addition, very little is known about the best time of the day to slaughter fish, which may in turn be dictated by diurnal rhythms in physiological stress parameters. Water temperature is also known to play a very important role in stress physiology in fish but the combined effect with fasting is unclear. Current recommendations regarding the optimal duration of pre-slaughter fasting do not normally consider water temperature and are only based on days, not degree days (ºC d). The effects of short-term fasting prior to slaughter (1, 2 and 3 days, between 11.1 and 68.0 ºC days) and hour of slaughter (08h00, 14h00 and 20h00) were determined in commercial-sized rainbow trout (Oncorhynchus mykiss) over four trials at different water temperatures (TRIAL 1, 11.8 ºC; TRIAL 2, 19.2 ºC; TRIAL 3, 11.1 ºC; and TRIAL 4, 22.7 ºC). We measured biometric, haematological, metabolic and product quality indicators. In each trial, the values of fasted fish (n=90) were compared with 90 control fish kept under similar conditions but not fasted. Results show that fasting affected biometric indicators. The coefficient of condition in fasted trout was lower than controls 2 days after food deprivation. Gut emptying occurred within the first 24 h after the cessation of feeding, with small traces of digesta after 48 h. Gut emptying was faster at higher water temperatures. Liver weight decreased in food deprived fish and differences between fasted and fed trout were more evident when gut clearance was faster. The overall effect of fasting for up to three days on haematological indicators was small. Plasma cortisol levels were high in both fasted and fed fish in all trials. Plasma glucose response to fasting varied among trials, but it tended to be lower in fasted fish as the days of fasting increased. In any case, it seems that water temperature played a more important role, with higher concentrations at lower temperatures on days 2 and 3 after the cessation of feeding. Plasma lactate levels indicate moments of high muscular activity and were also high, but no variation related to fasting could be found. Haematocrit did not show any significant effect of fasting, but leucocytes tended to be higher when trout were less stressed and when their body condition was higher. Finally, the loss of liver weight was not accompanied by a decrease in liver glycogen (only measured in TRIAL 3), suggesting that a different strategy to maintain plasma glucose levels was used. Regarding the hour of slaughter, lower cortisol levels were found at 20h00, suggesting that trout were less stressed later in the day and that pre-slaughter handling may be less stressful at night. Haematocrit levels were also lower at 20h00 but only at lower temperatures, indicating that higher temperatures increase metabolism. Neither fasting nor the hour of slaughter had a significant effect on the evolution of meat quality during 3 days of storage. In contrast, storage time seemed to have a more important effect on meat quality parameters. The lowest pH was reached 24-48 h post mortem, with a higher variability among fasting durations at 20h00, although no clear pattern could be discerned. Maximum stiffening from rigor mortis occurred after 24 h. The water holding capacity was very stable throughout storage and seemed to be independent of pH changes. Meat lightness (L*) slightly increased during storage and a* and b*-values were relatively stable. In conclusion, based on the haematological results, slaughtering at night may have less of a negative effect on welfare than at other times of the day. Overall, our results suggest that rainbow trout can cope well with fasting up to three days or 68 ºC d prior to slaughter and that their welfare is therefore not seriously compromised. At low water temperatures, trout could probably be fasted for longer periods without negative effects on welfare but more research is needed to determine the relationship between water temperature and days of fasting in terms of loss of live weight and the decrease in plasma glucose and other metabolic indicators.

Thermal behaviour of bitumen modified by sulphur addition

The most frequent use of bitumen is as binder for pavement applications. The effect of sulphur addition on the properties of the bitumen has been extensively studied several decades ago. Recently, there is a renewed interest in researching the behaviour of sulphur-bitumen combination, because off 1.The future availability of bitumen may be limited and 2. The beneficial consumption of great amounts of sulphur compounds from petroleum refining is advisable. The addition of sulphur to bitumen provokes the beginning of chemical reactions depending on the sulphur content and heating temperature. At heating temperatures T< 140 ºC liquid sulphur reacts with naphthenic-aromatic fraction forming polysulphides. At temperatures above 150 ºC dehydrogenization reactions with emission of hydrogen sulfide take place and naphthenic-aromatic molecules are transformed into asphaltenes. Therefore, the addition of sulphur to bitumen provokes changes in the chemical structure of the bitumen. The objective of this work is to analyze, the thermal behaviour of sulphur-bitumen mixtures of different composition (0-35 %wt sulphur content) prepared at 130 and 140 ºC, by means of differential scanning calorimetry (DSC). Besides, the volatile emissions of the mixtures at high temperature have been estimated from loss weight measurements as a function of stored time

Diseño y síntesis de materiales nanoestructurados basados en aluminatos de estroncio con propiedades fotoluminiscentes

Durante la última década, se han llevado acabo numeroso estudios sobre la síntesis de materiales fotoluminiscentes sub-micrónicos, en gran medida, al amplio número de aplicaciones que demandan este tipo de materiales. En concreto dentro de los materiales fosforescentes o también denominados materiales con una prolongada persistencia de la luminiscencia, los estudios se han enfocado en la matriz de SrAl2O4 dopada con Europio (Eu2+) y Disprosio (Dy3+) dado que tiene mayor estabilidad y persistencia de la fosforescencia con respecto a otras matrices. Estos materiales se emplean mayoritariamente en pinturas luminiscentes, tintas, señalización de seguridad pública, cerámicas, relojes, textiles y juguetes fosforescentes. Dado al amplio campo de aplicación de los SrAl2O4:Eu, Dy, se han investigado múltiples rutas de síntesis como la ruta sol-gel, la síntesis hidrotermal, la síntesis por combustión, la síntesis láser y la síntesis en estado sólido con el fin de desarrollar un método eficiente y que sea fácilmente escalable. Sin embargo, en la actualidad el método que se emplea para el procesamiento a nivel industrial de los materiales basados en aluminato de estroncio es la síntesis por estado sólido, que requiere de temperaturas de entre 1300 a 1900oC y largos tiempos de procesamiento. Además el material obtenido tiene un tamaño de partícula de 20 a 100 μm; siendo este tamaño restrictivo para el empleo de este tipo de material en determinadas aplicaciones. Por tanto, el objetivo de este trabajo es el desarrollo de nuevas estrategias que solventen las actuales limitaciones. Dentro de este marco se plantean una serie de objetivos específicos: Estudio de los parámetros que gobiernan los procesos de reducción del tamaño de partícula mediante molienda y su relación en la respuesta fotoluminiscente. Estudio de la síntesis por combustión de SrAl2O4:Eu, Dy, evaluando el efecto de la temperatura y la cantidad de combustible (urea) en el proceso para la obtención de partículas cristalinas minimizando la presencia de fases secundarias. Desarrollo de nuevas rutas de síntesis de SrAl2O4:Eu, Dy empleando el método de sales fundidas. Determinación de los mecanismos de reacción en presencia de la sal fundida en función de los parámetros de proceso que comprende la relación de sales y reactivos, la naturaleza de la alúmina y su tamaño, la temperatura y atmósfera de tratamiento. Mejora de la eficiencia de los procesos de síntesis para obtener productos con propiedades finales óptimas en procesos factibles industrialmente para su transferencia tecnológica. Es este trabajo han sido evaluados los efectos de diferentes procesos de molienda para la reducción del tamaño de partícula del material de SrAl2O4:Eu, Dy comercial. En el proceso de molienda en medio húmedo por atrición se observa la alteración de la estructura cristalina del material debido a la reacción de hidrólisis generada incluso empleando como medio líquido etanol absoluto. Con el fin de solventar las desventajas de la molienda en medio húmedo se llevo a cabo un estudio de la molturación en seco del material. La molturación en seco de alta energía reduce significativamente el tamaño medio de partícula. Sin embargo, procesos de molienda superiores a una duración de 10 minutos ocasionan un aumento del estado de aglomeración de las partículas y disminuyen drásticamente la respuesta fotoluminiscente del material. Por tanto, se lleva a cabo un proceso de molienda en seco de baja energía. Mediante este método se consigue reducir el tamaño medio de partícula, d50=2.8 μm, y se mejora la homogeneidad de la distribución del tamaño de partícula evitando la amorfización del material. A partir de los resultados obtenidos mediante difracción de rayos X y microscopia electrónica de barrido se infiere que la disminución de la intensidad de la fotoluminiscencia después de la molienda en seco de alta energía con respecto al material inicial se debe principalmente a la reducción del tamaño de cristalito. Se observan menores variaciones en la intensidad de la fotoluminiscencia cuando se emplea un método de molienda de baja de energía ya que en estos procesos se preserva el dominio cristalino y se reduce la amorfización significativamente. Estos resultados corroboran que la intensidad de la fotoluminiscencia y la persistencia de la luminiscencia de los materiales de SrAl2O4:Eu2+, Dy3+ dependen extrínsecamente de la morfología de las partículas, del tamaño de partícula, el tamaño de grano, los defectos superficiales e intrínsecamente del tamaño de cristalito. Siendo las características intrínsecas las que dominan con respecto a las extrínsecas y por tanto tienen mayor relevancia en la respuesta fotoluminiscente. Mediante síntesis por combustión se obtuvieron láminas nanoestructuradas de SrAl2O4:Eu, Dy de ≤1 μm de espesor. La cantidad de combustible, urea, en la reacción influye significativamente en la formación de determinadas fases cristalinas. Para la síntesis del material de SrAl2O4:Eu, Dy es necesario incluir un contenido de urea mayor que el estequiométrico (siendo m=1 la relación estequiométrica). La incorporación de un exceso de urea (m>1) requiere de la presencia de un agente oxidante interno, HNO3, para que la reacción tenga lugar. El empleo de un mayor contenido de urea como combustible permite una quelación efectiva de los cationes en el sistema y la creación de las condiciones reductoras para obtener un material de mayor cristalinidad y con mejores propiedades fotoluminiscentes. El material de SrAl2O4:Eu, Dy sintetizado a una temperatura de ignición de 600oC tiene un tamaño medio 5-25 μm con un espesor de ≤1 μm. Mediante procesos de molturación en seco de baja energía es posible disminuir el tamaño medio de partícula ≈2 μm y homogenizar la distribución del tamaño de partícula pero hay un deterioro asociado de la respuesta luminiscente. Sin embargo, se puede mejorar la respuesta fotoluminiscente empleando un tratamiento térmico posterior a 900oC N2-H2 durante 1 hora que no supone un aumento del tamaño de partícula pero si permite aumentar el tamaño de cristalito y la reducción del Eu3+ a Eu2+. Con respecto a la respuesta fotoluminiscente, se obtiene valores de la intensidad de la fotoluminiscencia entre un 35%-21% con respecto a la intensidad de un material comercial de referencia. Además la intensidad inicial del decaimiento de la fosforescencia es un 20% de la intensidad del material de referencia. Por tanto, teniendo en cuenta estos resultados, es necesario explorar otros métodos de síntesis para la obtención de los materiales bajo estudio. Por esta razón, en este trabajo se desarrollo una ruta de síntesis novedosa para sintetizar SrAl2O4:Eu, Dy mediante el método de sales fundidas para la obtención de materiales de gran cristalinidad con tamaños de cristalito del orden nanométrico. Se empleo como sal fundente la mezcla eutéctica de NaCl y KCl, denominada (NaCl-KCl)e. La principal ventaja de la incorporación de la mezcla es el incremento la reactividad del sistema, reduciendo la temperatura de formación del SrAl2O4 y la duración del tratamiento térmico en comparación con la síntesis en estado sólido. La formación del SrAl2O4 es favorecida ya que se aumenta la difusión de los cationes de Sr2+ en el medio líquido. Se emplearon diferentes tipos de Al2O3 para evaluar el papel del tamaño de partícula y su naturaleza en la reacción asistida por sales fundidas y por tanto en la morfología y propiedades del producto final. Se obtuvieron partículas de morfología pseudo-esférica de tamaño ≤0.5 μm al emplear como alúmina precursora partículas sub-micrónicas ( 0.5 μm Al2O3, 0.1 μm Al2 O3 y γ-Al2O3). El mecanismo de reacción que tiene lugar se asocia a procesos de disolución-precipitación que dominan al emplear partículas de alúmina pequeñas y reactivas. Mientras al emplear una alúmina de 6 μm Al2O3 prevalecen los procesos de crecimiento cristalino siguiendo un patrón o plantilla debido a la menor reactividad del sistema. La nucleación y crecimiento de nanocristales de SrAl2O4:Eu, Dy se genera sobre la superficie de la alúmina que actúa como soporte. De esta forma se desarrolla una estructura del tipo coraza-núcleo («core-shell» en inglés) donde la superficie externa está formada por los cristales fosforescentes de SrAl2O4 y el núcleo está formado por alúmina. Las partículas obtenidas tienen una respuesta fotoluminiscente diferente en función de la morfología final obtenida. La optimización de la relación Al2O3/SrO del material de SrAl2O4:Eu, Dy sintetizado a partir de la alúmina de 6 μm permite reducir las fases secundarias y la concentración de dopantes manteniendo la respuesta fotoluminiscente. Comparativamente con un material comercial de SrAl2O4:Eu, Dy de referencia, se han alcanzado valores de la intensidad de la emisión de hasta el 90% y de la intensidad inicial de las curvas de decaimiento de la luminiscencia de un 60% para el material sintetizado por sales fundidas que tiene un tamaño medio ≤ 10μm. Por otra parte, es necesario tener en cuenta que el SrAl2O4 tiene dos polimorfos, la fase monoclínica que es estable a temperaturas inferiores a 650oC y la fase hexagonal, fase de alta temperatura, estable a temperaturas superiores de 650oC. Se ha determinado que fase monoclínica presenta propiedades luminiscentes, sin embargo existen discordancias a cerca de las propiedades luminiscentes de la fase hexagonal. Mediante la síntesis por sales fundidas es posible estabilizar la fase hexagonal empleando como alúmina precursora γ-Al2O3 y un exceso de Al2O3 (Al2O3/SrO:2). La estabilización de la fase hexagonal a temperatura ambiente se produce cuando el tamaño de los cristales de SrAl2O4 es ≤20 nm. Además se observó que la fase hexagonal presenta respuesta fotoluminiscente. El diseño de materiales de SrAl2O4:Eu,Dy nanoestructurados permite modular la morfología del material y por tanto la intensidad de la de la fotoluminiscencia y la persistencia de la luminiscencia. La disminución de los materiales precursores, la temperatura y el tiempo de tratamiento significa la reducción de los costes económicos del material. De ahí la viabilidad de los materiales de SrAl2O4:Eu,Dy obtenidos mediante los procesos de síntesis propuestos en esta memoria de tesis para su posterior escalado industrial. ABSTRACT The synthesis of sub-micron photoluminescent particles has been widely studied during the past decade because of the promising industrial applications of these materials. A large number of matrices has been developed, being SrAl2O4 host doped with europium (Eu2+) and dysprosium (Dy3+) the most extensively studied, because of its better stability and long-lasting luminescence. These functional inorganic materials have a wide field of application in persistent luminous paints, inks and ceramics. Large attention has been paid to the development of an efficient method of preparation of SrAl2O4 powders, including solgel method, hydrothermal synthesis, laser synthesis, combustion synthesis and solid state reaction. Many of these techniques are not compatible with large-scale production and with the principles of sustainability. Moreover, industrial processing of highly crystalline powders usually requires high synthesis temperatures, typically between 1300 a 1900oC, with long processing times, especially for solid state reaction. As a result, the average particle size is typically within the 20-100 μm range. This large particle size is limiting for current applications that demand sub-micron particles. Therefore, the objective of this work is to develop new approaches to overcome these limitations. Within this frame, it is necessary to undertake the following purposes: To study the parameters that govern the particle size reduction by milling and their relation with the photoluminescence properties. To obtain SrAl2O4:Eu, Dy by combustion synthesis, assessing the effect of the temperature and the amount of fuel (urea) to synthesize highly crystalline particles minimizing the presence of secondary phases. To develop new synthesis methods to obtain SrAl2O4:Eu, Dy powders. The molten salt synthesis has been proposed. As the method is a novel route, the reaction mechanism should be determine as a function of the salt mixture, the ratio of the salt, the kind of Al2O3 and their particle size and the temperature and the atmosphere of the thermal treatment. To improve the efficiency of the synthesis process to obtain SrAl2O4:Eu, Dy powders with optimal final properties and easily scalable. On the basis of decreasing the particle size by using commercial product SrAl2O4:Eu2+, Dy3+ as raw material, the effects of different milling methods have been evaluated. Wet milling can significantly alter the structure of the material through hydrolysis reaction even in ethanol media. For overcoming the drawbacks of wet milling, a dry milling-based processes are studied. High energy dry milling process allows a great reduction of the particle size, however milling times above 10 min produce agglomeration and accelerates the decrease of the photoluminescence feature. To solve these issues the low energy dry milling process proposed effectively reduces the particle size to d50=2.8 μm, and improves the homogeneity avoiding the amorphization in comparison with previous methods. The X-ray diffraction and scanning electron microscope characterization allow to infer that the large variations in PL (Photoluminescence) values by high energy milling process are a consequence mainly of the crystallite size reduction. The lesser variation in PL values by low energy milling proces is related to the coherent crystalline domain preservation and the unnoticeable amorphization. These results corroborate that the photoluminescence intensity and the persistent luminescence of the SrAl2O4:Eu2+, Dy3+ powders depend extrinsically on the morphology of the particles such as particle size, grain size, surface damage and intrinsically on the crystallinity (crystallite size); being the intrinsically effects the ones that have a significant influence on the photoluminescent response. By combustion method, nanostructured SrAl2O4:Eu2+, Dy3+ sheets with a thickness ≤1 μm have been obtained. The amount of fuel (urea) in the reaction has an important influence on the phase composition; urea contents larger than the stoichiometric one require the presence of an oxidant agent such as HNO3 to complete the reaction. A higher amount of urea (excess of urea: denoted m>1, being m=1 the stoichiometric composition) including an oxidizing agent produces SrAl2O4:Eu2+,Dy3+ particles with persistent luminescence due to the effective chelation of the cations and the creation of suitable atmospheric conditions to reduce the Eu3+ to Eu2+. Therefore, optimizing the synthesis parameters in combustion synthesis by using a higher amount of urea and an internal oxidizing agent allows to complete the reaction. The amount of secondary phases can be significantly reduced and the photoluminescence response can be enhanced. This situation is attributed to a higher energy that improves the crystallinity of the powders. The powders obtained have a particle size c.a. 5-25 μm with a thickness ≤1 μm and require relatively low ignition temperatures (600oC). It is possible to reduce the particle size by a low energy dry milling but this process implies the decrease of the photoluminescent response. However, a post-thermal treatment in a reducing atmosphere allows the improvement of the properties due to the increment of crystallinity and the reduction of Eu3+ to Eu2+. Compared with the powder resulted from solid state method (commercial reference: average particle size, 20 μm and heterogeneous particle size distribution) the emission intensity of the powder prepared by combustion method achieve the values between 35% to 21% of the reference powder intensity. Moreover, the initial intensity of the decay curve is 20% of the intensity of the reference powder. Taking in account these results, it is necessary to explore other methods to synthesize the powders For that reason, an original synthetic route has been developed in this study: the molten salt assisted process to obtain highly crystalline SrAl2O4 powders with nanometric sized crystallites. The molten salt was composed of a mixture of NaCl and KCl using a 0.5:0.5 molar ratio (eutectic mixture hereafter abbreviated as (NaCl-KCl)e). The main advantages of salt addition is the increase of the reaction rate, the significant reduction of the synthesis temperature and the duration of the thermal treatment in comparison with classic solid state method. The SrAl2O4 formation is promoted due to the high mobility of the Sr2+ cations in the liquid medium. Different kinds of Al2O3 have been employed to evaluate the role of the size and the nature of this precursor on the kinetics of reaction, on the morphology and the final properties of the product. The SrAl2O4:Eu2+, Dy3+ powders have pseudo-spherical morphology and particle size ≤0.5 μm when a sub-micron Al2O3 ( 0.5 μm Al2O3, 0.1 μm Al2O3 and γ-Al2O3) has been used. This can be attributed to a higher reactivity in the system and the dominance of dissolution-precipitation mechanism. However, the use of larger alumina (6 μm Al2O3) modifies the reaction pathway leading to a different reaction evolution. More specifically, the growth of SrAl2O4 sub-micron particles on the surface of hexagonal platelets of 6μm Al2O3 is promoted. The particles retain the shape of the original Al2O3 and this formation process can be attributed to a «core-shell» mechanism. The particles obtained exhibit different photoluminescent response as a function of the final morphology of the powder. Therefore, through this study, it has been elucidated the reaction mechanisms of SrAl2O4 formation assisted by (NaCl-KCl)e that are governed by the diffusion of SrCO3 and the reactivity of the alumina particles. Optimizing the Al2O3/SrO ratio of the SrAl2O4:Eu, Dy powders synthesized with 6 μm Al2O3 as a precursor, the secondary phases and the concentration of dopant needed can be reduced keeping the photoluminescent response of the synthesized powder. Compared with the commercial reference powder, up to 90% of the emission intensity of the reference powder has been achieved for the powder prepared by molten salt method using 6μm Al2O3 as alumina precursor. Concerning the initial intensity of the decay curve, 60% of the initial intensity of the reference powder has been obtained. Additionally, it is necessary to take into account that SrAl2O4 has two polymorphs: monoclinic symmetry that is stable at temperatures below 650oC and hexagonal symmetry that is stable above this temperature. Monoclinic phase shows luminescent properties. However, there is no clear agreement on the emission of the hexagonal structure. By molten salt, it is possible to stabilize the hexagonal phase of SrAl2O4 employing an excess of Al2O3 (Al2O3/SrO: 2) and γ-Al2O3 as a precursor. The existence of nanometric crystalline domains with lower size (≤20 nm) allows the stabilization of the hexagonal phase. Moreover, it has been evidenced that the hexagonal polymorph exhibits photoluminescent response. To sum up, the design of nanostructured SrAl2O4:Eu2+, Dy3+ materials allows to obtain different morphologies and as consequence different photoluminescent responses. The reduction of temperature, duration of the thermal treatment and the precursors materials needed imply the decrease of the economic cost of the material. Therefore, the viability, suitability and scalability of the synthesis strategy developed in this work to process SrAl2O4:Eu2+, Dy3+ are demonstrated.

A meanfield approach to the thermodynamics of a protein-solvent system with application to the oligomerization of the tumor suppressor p53

The thermodynamic stability and oligomerization status of the tumor suppressor p53 tetramerization domain have been studied experimentally and theoretically. A series of hydrophilic mutations at Met-340 and Leu-344 of human p53 were designed to disrupt the hydrophobic dimer–dimer interface of the tetrameric oligomerization domain of p53 (residues 325–355). Meanfield calculations of the free energy of the solvated mutants as a function of interdimer distance were compared with experimental data on the thermal stability and oligomeric state (tetramer, dimer, or equilibrium mixture of both) of each mutant. The calculations predicted a decreasing stability and oligomeric state for the following amino acids at residue 340: Met (tetramer) > Ser Asp, His, Gln, > Glu, Lys (dimer), whereas the experimental results showed the following order: Met (tetramer) > Ser > Gln > His, Lys > Asp, Glu (dimers). For residue 344, the calculated trend was Leu (tetramer) > Ala > Arg, Gln, Lys (dimer), and the experimental trend was Leu (tetramer) > Ala, Arg, Gln, Lys (dimer). The discrepancy for the lysine side chain at residue 340 is attributed to the dual nature of lysine, both hydrophobic and charged. The incorrect prediction of stability of the mutant with Asp at residue 340 is attributed to the fact that within the meanfield approach, we use the wild-type backbone configuration for all mutants, but low melting temperatures suggest a softening of the α-helices at the dimer–dimer interface. Overall, this initial application of meanfield theory toward a protein-solvent system is encouraging for the application of the theoretical model to more complex systems.

Critical behavior of the specific heat in glass formers

We show numeric evidence that, at low enough temperatures, the potential energy density of a glass-forming liquid fluctuates over length scales much larger than the interaction range. We focus on the behavior of translationally invariant quantities. The growing correlation length is unveiled by studying the finite-size effects. In the thermodynamic limit, the specific heat and the relaxation time diverge as a power law. Both features point towards the existence of a critical point in the metastable supercooled liquid phase.

Gas production during the pyrolysis and gasification of biological and physico-chemical sludges from oil refinery

Pyrolysis and gasification of two different sludges coming from a Spanish refinery have been performed at different experimental conditions. A physico-chemical (PC) and a biological (BIO) sludge have been studied. Runs at different heating rates (approx. 4 and 10 K/s) and with different contact time between gases and decomposed sludge have been performed. In general, the ratio H2/CO is higher in pyrolytic runs. The highest ratio is obtained in the pyrolysis at low heating rate and parallel flow, using both sludges. The maximum emission of CO, i.e. the worst combustion conditions, is given in the runs where contact time is minimized and at high heating rates.

Micro/Mesoporous Activated Carbons Derived from Polyaniline: Promising Candidates for CO2 Adsorption

A series of activated carbons were prepared by carbonization of polyaniline at different temperatures, using KOH or K2CO3 as activating agent. Pure microporous or micro/mesoporous activated carbons were obtained depending on the preparation conditions. Carbonization temperature has been proven to be a key parameter to define the textural properties of the carbon when using KOH. Low carbonization temperatures (400–650 °C) yield materials with a highly developed micro- and mesoporous structure, whereas high temperatures (800 °C) yield microporous carbons. Some of the materials prepared using KOH exhibit a BET surface area superior to 4000 m2/g, with total pore volume exceeding 2.5 cm3/g, which are among the largest found for activated carbons. On the other hand, microporous materials are obtained when using K2CO3, independently of carbonization temperature. Some of the materials were tested for CO2 capture due to their high microporosity and N content. The adsorption capacity for CO2 at atmospheric pressure and 0 °C achieves a value of ∼7.6 mmol CO2/g, which is among the largest reported in the literature. This study provides guidelines for the design of activated carbons with a proper N/C ratio for CO2 capture at atmospheric pressure.