An Assessment of Anthropogenic Impact in a Nature Reserve: the Santoña Marshes (Northern Spain)

The Santoña Marshes Nature Reserve is one of the most important ecosystems of the Spanish Cantabrian coast due to its ecological value as a wintering area for migratory birds. Since an increase in population and substantial changes in the use of land have been observed in this area during the last century, the aim of this work was to attempt to see if anthropogenic activities are recorded in the accumulating sediments. Two sediment cores (50 cm length) were collected for isotopic dating (210Pb and 137Cs) and geochemical study (heavy metals). The data indicate an increasing trend in sedimentation rates during the last century, probably related to the progressive loss of the estuarine domains and the changes in their original hydrodynamic conditions due to infilling and the construction of dykes. However, no significant anthropogenic inputs of heavy metals have been detected in recent times.La Reserva Natural de las Marismas de Santoña, situada en la costa cantábrica, posee un gran valor ecológico como lugar de invernada de aves migratorias. Dado el importante aumento de la presencia humana en la zona durante el último siglo, este trabajo tiene como objetivo estudiar si estas actividades antrópicas han dejado su huella en los sedimentos acumulados. Para ello se ha abordado la datación isotópica (137Cs y 210Pb) y el estudio geoquímico (metales pesados) de dos sondeos de 50 cm de longitud. Los resultados obtenidos señalan la existencia de un importante incremento en las tasas de sedimentación durante el ultimo siglo, posiblemente relacionado con la pérdida progresiva de la superficie y de las dinámicas estuarinas como consecuencia de los rellenos y de la construcción de diques. Sin embargo, no se han detectado niveles significativos de contaminación en metales pesados en los sedimentos más recientes

Asymmetric 1, 3-dipolar cycloaddition reactions between methacrylonitrile and nitrones catalysed by well-defined M(diphosphane) (M=Rh, Ir) complexes

The cationic half-sandwich aqua-complexes (¿ 5-C5Me5)M(PP*)(H2O)]SbF6]2 M=Rh, Ir; PP* =(R)-Benphos, (R)-Cyphos, (2R, 4R)-Norphos] catalyse the 1, 3-dipolar cycloaddition reaction of nitrones with methacrylonitrile with perfect regioselectivity, low-to-perfect endo-selectivity and low-to-moderate enantioselectivity. The active species involved in the catalytic process, (¿ 5-C5Me5)M(PP*)(methacrylonitrile)]SbF6]2, have been isolated and characterised as mixtures of the (S)- and (R)-at-metal epimers. NMR measurements of these mixtures indicated that the (R M)-isomers epimerise to the corresponding (S M) counterparts. The molecular structure of the rhodium complex (S Rh, R C)-(¿ 5-C5Me5)Rh((R)-Benphos)(methacrylonitrile)]SbF6]2 has been determined by X-ray diffraction methods. Diastereomerically pure (S Rh, R C)-(¿ 5-C5Me5)Rh(PP*)(methacrylonitrile)]SbF6]2 compounds catalyse stoichiometrically the above mentioned dipolar cycloaddition reaction with up to 90% enantiomeric excess, thus indicating the influence of the metal handedness on the catalytic stereochemical outcome. Catalysts can be recycled up to three times without a significant loss of either activity or selectivity

Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays

The transition metal frustrated Lewis pair compounds [(Cym)M(κ3S,P,N-HL1)][SbF6] (Cym = η6-p-MeC6H4iPr; H2L1 = N-(p-tolyl)-N′-(2-diphenylphosphanoethyl)thiourea; M = Ru (5), Os (6)) have been prepared from the corresponding dimer [{(Cym)MCl}2(μ-Cl)2] and H2L1 by successive chloride abstraction with NaSbF6 and AgSbF6 and NH deprotonation with NaHCO3. Complexes 5 and 6 and the previously reported phosphano–guanidino compounds [(Cym)M(κ3P,N,N′-HL2)][SbF6] [H2L2 = N,N′-bis(p-tolyl)-N′′-(2-diphenylphosphanoethyl) guanidine; M = Ru (7), Os (8)] and pyridinyl–guanidino compounds [(Cym)M(κ3N,N′,N′′-HL3)][SbF6] [H2L3 = N,N′-bis(p-tolyl)-N′′-(2-pyridinylmethyl) guanidine; M = Ru (9), Os (10)] heterolytically activate H2 in a reversible manner affording the hydrido complexes [(Cym)MH(H2L)][SbF6] (H2L = H2L1; M = Ru (11), Os (12); H2L = H2L2; M = Ru (13), Os (14); H2L = H2L3; M = Ru (15), Os (16)). DFT calculations carried out on the hydrogenation of complex 7 support an FLP mechanism for the process. Heating 9 and 10 in methanol yields the orthometalated complexes [(Cym)M(κ3N,N′,C-H2L3-H)][SbF6] (M = Ru (17), Os (18)). The phosphano–guanidino complex 7 activates deuterated water in a reversible fashion, resulting in the gradual deuteration of the three cymene methyl protons through sequential C(sp3)–H bond activation. From DFT calculations, a metal–ligand cooperative reversible mechanism that involves the O–H bond activation and the formation of an intermediate methylene cyclohexenyl complex has been proposed. Complexes 5–10 catalyse the hydrogenation of the C[double bond, length as m-dash]C double bond of styrene and a range of acrylates, the C[double bond, length as m-dash]O bond of acetophenone and the C[double bond, length as m-dash]N bond of N-benzylideneaniline and quinoline. The C[double bond, length as m-dash]C double bond of methyl acrylate adds to catalyst 9, affording complex 19 in which a new ligand exhibiting a fac κ3N,N′,C coordination mode has been incorporated

The effect of different short pulse feeding regimes on growth and survival of Atlantic bonito larvae Sarda sarda

One of the most easily manipulated variables in fish larval culture is the photoperiod. Long light photoperiod regimes are commonly used to enhance growth in commercial species. However, for species with a piscivorous larval period, as the Atlantic bonito (Sarda sarda), long time exposure to light could lead to a lower survival through aggressive behavior and cannibalism. One alternative could be modifications of the light and dark cycles during the photophase. These modifications can result in short pulse feeding regimes since bonito larvae fill up their stomach completely during light hours but do not feed in darkness. Little is known about how such intermittent feeding regimes affect growth and survival in fish. In this study, we tried different alternating and continuous light regimes during the culture of bonito larvae to identify the best regime that maximizes growth and survival.Fertilized eggs of Atlantic bonito were obtained from different spontaneous spawning events by a captive broodstock at the Spanish Institute of Oceanography (IEO) in Mazarrón. Bonito larvae 8 days post hatch (dph) were reared in 150 l tanks equipped with a lid that was used to cover and uncover the tanks to manipulate the hours of light and therefore pulse feeding regimes. Bonito larvae were always fed with yolk sac seabream larvae ad libitum. A total of three experiments were conducted. In all, a continuous dark period of 7.5hours was maintained from 24:00 to 7:30. All light regimes had a total of 9 light hours except for one that had 15hours of light (15L:9D). In the first experiment, light regimes provided alternating light and dark conditions of either 1.5, 3 or 4.5hours from 7:30 to 24:00). In the second experiment, the 3hours alternating light regime was compared to two continuous regimes of 15hours of light (15L:9D) and 9hours of light (9L:15D). These two experiments were conducted at the same temperature, 24.7±0.4°C. The third experiment was identical to the second experiment but at colder temperatures, 21.4±0.45°C. All regimes had 3 replicates. 10 larvae were sub-sampled 3 days after the experiments began and were ended after 6 days when all larvae were sampled. Due to slower growth, the third experiment ended after 9 days. The larvae were measured in standard length and individual dry weights were calculated. Larvae were counted in the tanks every 3 days to estimate survivorship. Final larval sizes in the alternating light regimes were larger in the 3hours than those obtained in the 1.5 and 4.5hours (first experiment, Fig. 1a, Tukey test p0.01). The 3hours alternating light regime yielded the largest larval sizes at the end of the experiment compared to the other alternating regimes. Final sizes at the 3hours regime were larger than those obtained under the 9L:15D continuous light regime at both temperatures. The time to satiation and the elapsed time to evacuate food totally from the gut in a similar species is about 3-4hours (Young and Davis, 1990). Our results suggest that a better strategy for bonito larvae growth is to fill their stomach more than once per day followed by a resting period when food is being digested. However, no effect was observed in terms of survival, possibly due to high abundance of larval prey. Changes in the light regime that result in pulse feeding can be a good strategy to increase growth in larval cultures when fitting well the evacuation and satiation rates

First results on ongrowing of hatchery reared Atlantic bluefin tuna, Thunnus thynnus, kept in sea cages

Bluefin tuna (ABFT) fingerlings born in captivity were raised during 15 months in sea cages. ABFT were fed with raw fish, and they grew during this period from 4 gr to 8 kg. Mortality rate was great, mainly during the first three months. This is the first experience of ongrowing ABFT born in captivity.EU (SELFDOTT), Caladeros del Mediterráneo, S.A. Instituto Español de Oceanografí

Разработка казуального игрового приложения для развития аналитического мышления

В настоящее время рынок мобильных игр активно развивается. На мобильные игры приходится 33% всех загрузок приложений. Игры — это непрерывный процесс обучения пользователей. Люди не перестают обучаться через какое-то время, они постоянно развиваются и движутся вперёд. Объектом исследования являются платформа Unity, в которой разработано игровое приложение, среда разработки Microsoft Visual Studio, для написания скриптов на языке программирования С#, методы генерации случайных событий, среда моделирования Blender, для создания 3D объектов и Adobe Photoshop для реализации графического интерфейса пользователя. Цель работы – разработать казуальное игровое приложения для развития аналитического мышления.Currently, the mobile games market is actively developing. Mobile games account for 33% of all app downloads. Games are a continuous learning process for users. People do not stop learning after a while, they are constantly developing and moving forward. The object of research is the Unity platform, in which a game application has been developed, the Microsoft Visual Studio development environment for writing scripts in the C # programming language, methods for generating random events, the Blender modeling environment for creating 3D objects and Adobe Photoshop for implementing a graphical user interface. The purpose of the work is to develop a casual game application for the development of analytical thinking

Reproducción del atún rojo Thunnus thynnus en jaulas flotantes obtención de puestas masivas mediante implantes hormonales

In the frame of the SELFDOTT project (From capture based to SELF-sustained aquaculture and Domestication Of bluefin tuna, Thunnus thynnus) captive-reared Atlantic bluefin tuna (Thunnus thynnus) (n=15, estimated body weight=90 Kg) maintained for 3 years in captivity in El Gorguel (Cartagena, Spain) were administered a gonadotrophin releasing hormone agonist (GnRHa) implant underwater, during the natural spawning period for this species in the Mediterranean Sea (June). Beginning 48-72 h later, massive spawnings occurred everyday for 17 days, with a daily maximum fecundity of 34 million eggs. Egg collection was accomplished by placing a special curtain around the perimeter of the cage and at 6 m allowed the floating eggs to be maintained within the cage and be collected at night and sunrise with 500 ìm mesh size nets from the surface of the water.Proyecto SELFDOTT. UE

Implementation of an innovative teaching project in a Chemical Process Design course at the University of Cantabria, Spain

This paper shows the planning, the teaching activities and the evaluation of the learning and teaching process implemented in the Chemical Process Design course at the University of Cantabria, Spain. Educational methods to address the knowledge, skills and attitudes that students who complete the course are expected to acquire are proposed and discussed. Undergraduate and graduate engineers' perceptions of the methodology used are evaluated by means of a questionnaire. Results of the teaching activities and the strengths and weaknesses of the proposed case study are discussed in relation to the course characteristics. The findings of the empirical evaluation shows that the excessive time students had to dedicate to the case study project and dealing with limited information are the most negative aspects obtained, whereas an increase in the students' self-confidence and the practical application of the methodology are the most positive aspects. Finally, improvements are discussed in order to extend the application of the methodology to other courses offered as part of the chemical engineering degree.This work was partially supported with the financial help of the University of Cantabria, 1st and 2nd Teaching Innovation Programs 2011-2012, 2013-2014, Projects Innodesign 1 and 2

Development, validation and application of a GC-MS method for the simultaneous detection and quantification of neutral lipid species in Trypanosoma cruzi

The development and validation of an analytical method for the simultaneous analysis of five neutral lipids in Trypanosoma cruzi epimastigotes by GC-MS is presented in this study. The validated method meets all validation parameters for all components and the chromatographic conditions have been optimized during its development. This analytical method has demonstrated good selectivity, accuracy, within-day precision, recovery and linearity in each of the established ranges. In addition, detection and quantification limits for squalene, cholesterol, ergosterol and lanosterol have been improved and it is worth highlighting the fact that this is the first time that squalene-2,3-epoxide validation data have been reported. The new validated method has been applied to epimastigotes treated with compounds with in vitro anti- T.cruzi activity. This new methodology is straightforward and constitutes a tool for screening possible sterol biosynthesis pathway inhibitors in Trypanosoma cruzi, one of the most studied targets in Chagas disease treatment. Therefore, it is an interesting and useful contribution to medicinal chemistry research

Tris(diphenylthiophosphinoyl)methanide as tripod ligand in rhodium(III), iridium(III) and ruthenium(II) complexes. Crystal structures of [(η5-C5Me5)Ir{η3-(SPPh2)3C-S,S′,S″}]BF4 and [(η6-MeC6H4Pri)Ru{η3-(SPPh2)3C-S,S′,S″}]BPh4

Reaction of the complex [{(η5-C5Me5)RhCl2}2], in CH2Cl2 solution, with AgBF4 (1:2 molar ratio) and (SPPh2)3CH leads to the cationic compound [(η5-C5Me5)RhCl{η2-(SPPh2)2CH(SPPh2)-S,S′}]BF4 (1) which is deprotonated by thallium(I) pyrazolate affording [(η5-C5Me5)Rh{η3-(SPPh2)3C−S,S′,S″}]BF4 (2a). The iridium dimer [(η5-C5Me5)IrCl2}2] reacts with silver salts and (SPPh2)3CH, in CH2Cl2 or Me2CO, under analogous conditions, affording mixtures of [(η5-C5Me5)IrCl{η2-(SPPh2)2)-S,S′}]+ and [(η5-C5Me5)Ir{η3-(SPPh2)3C-S,S′,S″}]A [A=BF4− (3a), PF6− (3b). Addition of Et3N to the mixture gives pure complexes 3. The ruthenium complexes [{η6j6-arene)RuCl2}2] (arene = C6Me6, p-MeC6H4Pri) react with (SPPh2)3CH, in the presence of AgA (A = PF6− or BF4−) or Na BPh4, in CH2Cl2 or Me2CO, yielding only the deprotonated complexes [(η6-arene)Ru{η3-(SPPH2)3C−S,S′,S″}]A [arene = C6Me6, A = BF4; arene = p-MeC6H4Pri, A - BPh4 (4a), PF6 (4b)]. The crystal structures of 3a and 4a were established by X-ray crystallography. Compound 3a crystallizes in the orthorhombic space group Pna21, with lattice parameters a-41.477(6), b = 10.6778(11), c = 20.162(3) Å and Z=8. Complex 4a crystallizes in a monoclinic lattice, space group P21/n, with a = 20.810(4), b = 12.555(3), c = 23.008(4) Å, β = 95.82(2)° and Z = 4. Both cationic complexes exhibit analogous pseudo-octahedml molecular structures with the anionic (SPPh2)3C− ligand bonded via the three sulphur atoms in a tripodal, tridentate fashion. Each metal centre completes its coordination environment with a η5-C5Me5 (3a) or a η6-MeC6H4Pri group (4a). A quite interesting result concerns the non-planarity of the methanide carbon which display P−C−P angles in the range 112.6–114.4(5)° in 3a and 111.9–113.6(4)° in 4a. The redox chemistry of the complexes was investigated by cyclic voltammetry. The Rh(III) complexes are quasi-reversibly reduced to Rh(I) and the Ir(III) complex is irreversibly reduced to IKD in acetonitrile solutions. The Ru(II) complex undergoes a quasi-reversible reduction to Ru(I) and a reversible oxidation to Ru(III).We thank the 'Fondo de Desarrollo Cientifico y Tecnologico, Chile' (Grant No. 460/93-95), Direccion de Investigacion y Postgrado, Pontificia Universidad Catolica de Chile (DlPUC), Fundacion Andes, Chile, and the Instituto de Cooperacion Iberoamericano, Spain, for financial support.Peer reviewe