Chemistry of eastern tropical Atlantic porewater

Distributions of pore water O2, NO-2, NO-3, NH+4, Si(OH)4, PO[3-]4, Mn[2+], F-, and T.A. were determined at 15 stations in the eastern equatorial Atlantic. While overall profile characteristics are consistent with previous models of organic matter diagenesis, profile shapes suggest that a deep reaction layer, rich in organic C, is also present at many sites. While it is unlikely that the oxidation of organic C in this layer has had a major effect on the ocean C cycle, pore water profile shapes are significantly altered. Despite exposure to seawater SO[2-]4 concentrations for > 1000 years, decomposition of the organic matter in the layer appears to be restricted to oxic and suboxic processes. These results suggest major differences in organic carbon decomposition and preservation under oxic/suboxic and anoxic conditions. Present-day benthic fluxes are largest adjacent to the eastern boundary coastal upwelling region and similar in magnitude to values reported for the eastern Pacific. Preliminary estimates suggest that the benthic respiration in the eastern 1/3 of the North Atlantic south of 20°N may alone account for >20% of the total deep North Atlantic respiration. Combining these results with estimates of organic C burial and deep water-column decomposition suggests that this region is a major location of organic C input into the deep sea.

A 5 million year reconstruction of sea level, temperature, and sea water d18O

Marine sediment records from the Oligocene and Miocene reveal clear 400,000-year (400-kyr) climate cycles related to variations in orbital eccentricity. These cycles are also observed in the Plio-Pleistocene records of the global carbon cycle. However they are absent in the Late Pleistocene ice-age record over the past 1.5 million years. Here, we present a simulation of global ice volume over the past 5 million years with a coupled system of four 3-D ice-sheet models. Our simulation shows that the 400-kyr long eccentricity cycles of Antarctica vary coherently with d13C records during the Pleistocene suggesting that they drive the long-term carbon cycle changes throughout the past 35 million years. The 400-kyr response of Antarctica is eventually suppressed by the dominant 100-kyr glacial cycles of the large ice sheets in the Northern Hemisphere (NH).

R-ArcticNet, A Regional Hydrographic Data Network for the Pan-Arctic Region (ISO-image of CD-ROM)

We describe the contemporary hydrography of the pan-Arctic land area draining into the Arctic Ocean, northern Bering Sea, and Hudson Bay on the basis of observational records of river discharge and computed runoff. The Regional Arctic Hydrographic Network data set, R-ArcticNET, is presented, which is based on 3754 recording stations drawn from Russian, Canadian, European, and U.S. archives. R-ArcticNET represents the single largest data compendium of observed discharge in the Arctic. Approximately 73% of the nonglaciated area of the pan-Arctic is monitored by at least one river discharge gage giving a mean gage density of 168 gages per 106 km2. Average annual runoff is 212 mm yr?1 with approximately 60% of the river discharge occurring from April to July. Gridded runoff surfaces are generated for the gaged portion of the pan-Arctic region to investigate global change signals. Siberia and Alaska showed increases in winter runoff during the 1980s relative to the 1960s and 1970s during annual and seasonal periods. These changes are consistent with observations of change in the climatology of the region. Western Canada experienced decreased spring and summer runoff.

Sea surface temperatures, alkenones and sedimentation rates at the Alboran basin

Sea surface temperatures (SSTs) recorded by alkenones and oxygen isotopes in the Alboran basin are used here to describe, at an unprecedented fine temporal resolution, the present interglaciation (PIG, initiated at 11.7 ka BP), the last interglaciation (LIG, onset approximately at 129 ka) and respective deglaciations. Similarities and dissimilarities in the progression of these periods are reviewed in comparison with ice cores and stalagmites. Cold spells coeval with the Heinrich events (H) described in the North Atlantic include multi-decadal scale oscillations not previously obvious (up to 4 °C in less than eight centuries within the stadials associated with H1 and H11, ca 133 ka and 17 ka respectively). These abrupt oscillations precede the accumulation of organic rich layers deposited when perihelion moves from alignment with NH spring equinox to the summer solstice, a reference for deglaciations. Events observed during the last deglaciation at 17 ka, 14.8 ka and 11.7 ka are reminiscent of events occurred during the penultimate deglaciation at ca 136 ka, 132 ka and 129 ka, respectively. The SST trend during the PIG is no more than 2 °C (from 20 °C to 18 °C; up to ?0.2 °C/ka). The trend is steeper during the LIG, i.e. up to a 5 °C change from the early interglaciation to immediately before the glacial inception (from 23 °C to 18 °C; up to -0.4 °C/ka). Events are superimposed upon a long term trend towards colder SSTs, beginning with SST maxima followed by temperate periods until perihelion aligned with the NH autumn equinox (before ca 5.3 ka for the PIG and 121 ka for the LIG). A cold spell of around eight centuries at 2.8 ka during the PIG was possibly mimicked during the LIG at ca 118 ka by a SST fall of around 1 °C in a millennium. These events led interglacial SST to stabilise at around 18 °C. The glacial inception, barely evident at the beginning ca 115 ka (North Atlantic event C25, after perihelion passage in the NH winter solstice), culminated with a SST drop of at least 2 °C in two millennia (event C24, ca 111 ka). The Little Ice Age (0.7 ka) also occurred after the latest perihelion passage in the NH winter solstice and could be an example of how a glacial pre-inception event following an interglaciation might be.

Adaptación del sector turístico al cambio climático en España. La importancia de las acciones a escala local y en empresas turísticas

El 5º Informe del IPCC (Panel Intergubernamental de Cambio Climático, 2014) señala que el turismo será una de las actividades económicas que mayores efectos negativos experimentará en las próximas décadas debido al calentamiento térmico del planeta. En España, el turismo es una fuente principal de ingresos y de creación de puestos de trabajo en su economía. De ahí que sea necesaria la puesta en marcha de medidas de adaptación a la nueva realidad climática que, en nuestro país, va a suponer cambios en el confort climático de los destinos e incremento de extremos atmosféricos. Frente a los planes de adaptación al cambio climático en la actividad turística, elaborados por los gobiernos estatal y regional, que apenas se han desarrollado en España, la escala local muestra interesantes ejemplos de acciones de adaptación al cambio climático, desarrolladas tanto por los municipios (energía, transporte, vivienda, planificación urbanística) como por la propia empresa turística (hoteles, campings, apartamentos). Medidas de ahorro de agua y luz, fomento del transporte público y de las energías limpias, creación de zonas verdes urbanas y adaptación a los extremos atmosféricos destacan como acciones de mitigación del cambio climático en los destinos turísticos principales de nuestro país.

New insights into Plagiogrammaceae (Bacillariophyta) based on multigene phylogenies and morphological characteristics with the description of a new genus and three new species.

Plagiogrammaceae, a poorly described family of diatoms, are common inhabitants of the shallow marine littoral zone, occurring either in the sediments or as epiphytes. Previous molecular phylogenies of the Plagiogrammaceae were inferred but included only up to six genera: Plagiogramma, Dimeregramma, Neofragilaria, Talaroneis, Psammogramma and Psammoneis. In this paper, we describe a new plagiogrammoid genus, Orizaformis, obtained from Bohai Sea (China) and present molecular phylogenies of the family based on three and four genes (nuclear-encoded large and small subunit ribosomal RNAs and chloroplast-encoded rbcL and psbC). Also included in the new phylogenies is Glyphodesmis. The phylogenies suggest that the Plagiogrammaceae is composed of two major clades: one consisting of Talaroneis, Orizaformis and Psammoneis, and the second of Glyphodesmis, Psammogramma, Neofragilaria, Dimeregramma and Plagiogramma. In addition, we describe three new species within established genera: Psammoneis obaidii, which was collected from the Red Sea, Saudi Arabia; and Neofragilaria stilus and Talaroneis biacutifrons from the Mozambique Channel, Indian Ocean, and illustrate two new combination taxa: Neofragilaria anomala and Neofragilaria lineata. Our observations suggest that the biodiversity of the family is strongly needed to be researched, and the phylogenetic analyses provide a useful framework for future studies of Plagiogrammaceae.

New insights into Plagiogrammaceae (Bacillariophyta) based on multigene phylogenies and morphological characteristics with the description of a new genus and three new species.

Plagiogrammaceae, a poorly described family of diatoms, are common inhabitants of the shallow marine littoral zone, occurring either in the sediments or as epiphytes. Previous molecular phylogenies of the Plagiogrammaceae were inferred but included only up to six genera: Plagiogramma, Dimeregramma, Neofragilaria, Talaroneis, Psammogramma and Psammoneis. In this paper, we describe a new plagiogrammoid genus, Orizaformis, obtained from Bohai Sea (China) and present molecular phylogenies of the family based on three and four genes (nuclear-encoded large and small subunit ribosomal RNAs and chloroplast-encoded rbcL and psbC). Also included in the new phylogenies is Glyphodesmis. The phylogenies suggest that the Plagiogrammaceae is composed of two major clades: one consisting of Talaroneis, Orizaformis and Psammoneis, and the second of Glyphodesmis, Psammogramma, Neofragilaria, Dimeregramma and Plagiogramma. In addition, we describe three new species within established genera: Psammoneis obaidii, which was collected from the Red Sea, Saudi Arabia; and Neofragilaria stilus and Talaroneis biacutifrons from the Mozambique Channel, Indian Ocean, and illustrate two new combination taxa: Neofragilaria anomala and Neofragilaria lineata. Our observations suggest that the biodiversity of the family is strongly needed to be researched, and the phylogenetic analyses provide a useful framework for future studies of Plagiogrammaceae.

Survival or death: a dual role of autophagy in stress-induced pericyte loss in diabetic retinopathy

Aims/hypothesis
Intra-retinal extravasation and modification of LDL have been implicated in diabetic retinopathy: autophagy may mediate these effects.
Methods
Immunohistochemistry was used to detect autophagy marker LC3B in human and murine diabetic and non-diabetic retinas. Cultured human retinal capillary pericytes (HRCPs) were treated with in vitro-modified heavily-oxidised glycated LDL (HOG-LDL) vs native LDL (N-LDL) with or without autophagy modulators: green fluorescent protein–LC3 transfection; small interfering RNAs against Beclin-1, c-Jun NH(2)-terminal kinase (JNK) and C/EBP-homologous protein (CHOP); autophagy inhibitor 3-MA (5 mmol/l) and/or caspase inhibitor Z-VAD-fmk (100 μmol/l). Autophagy, cell viability, oxidative stress, endoplasmic reticulum stress, JNK activation, apoptosis and CHOP expression were assessed by western blots, CCK-8 assay and TUNEL assay. Finally, HOG-LDL vs N-LDL were injected intravitreally to STZ-induced diabetic vs control rats (yielding 50 and 200 mg protein/l intravitreal concentration) and, after 7 days, retinas were analysed for ER stress, autophagy and apoptosis.
Results
Intra-retinal autophagy (LC3B staining) was increased in diabetic vs non-diabetic humans and mice. In HRCPs, 50 mg/l HOG-LDL elicited autophagy without altering cell viability, and inhibition of autophagy decreased survival. At 100–200 mg/l, HOG-LDL caused significant cell death, and inhibition of either autophagy or apoptosis improved survival. Further, 25–200 mg/l HOG-LDL dose-dependently induced oxidative and ER stress. JNK activation was implicated in autophagy but not in apoptosis. In diabetic rat retina, 50 mg/l intravitreal HOG-LDL elicited autophagy and ER stress but not apoptosis; 200 mg/l elicited greater ER stress and apoptosis.
Conclusions
Autophagy has a dual role in diabetic retinopathy: under mild stress (50 mg/l HOG-LDL) it is protective; under more severe stress (200 mg/l HOG-LDL) it promotes cell death.

Sesamoids of the metatarsophalangeal joint of the big toe: a sistematic review

Abstract: The first metatarsal sesamoid bones are not always taken into consideration when making a diagnosis, in pathologies that affect the region of the first metatarsal head. This is due to the insufficient knowledge of all the pathologies that can affect the sesamoids and the relative little incidence that they have. With the increment of sports activities, in particular the running, increasingly affects of the symptoms concerning this region are observed. Methods: A literature search was performed in 5 databases (Medline, PubMed, Scopus, Cochrane Library and BUCEA). The terms included in the search were: sesamoids, anatomy, biomechanics, sesamoids review and sesamoids pathology. In the initial search articles with no more than 10 years, only humans and revision texts are considered. Results: 24 articles were selected and include different pathologies with diagnosis using imaging tests and treatments, both conservative and surgical; as well as aspects from the biomechanics of the metatarsal-sesamoid joint. Conclusion: Sesamoids due of his anatomy, topography and function can be involved in a lot of pathologies; with similar signs and symptoms that can confuse the podiatry when he has to make a correct diagnosis or treatment.

Aspetti meccanicistici della coordinazione di [(PPh3)3Ru(CO)(H2)] com Timina Acido Acetico

Ruthenium complexes have proved to exhibit antineoplastic activity related to the interaction of metal ion with DNA nucleobases. It is indeed of great interest to provide new insights on theses cutting-edge studies, such as the identification of distinct coordinative modes of DNA binding sites. During the investigation on the reaction between [(PPh3)3Ru(CO)(H)2], 1, and the Thymine Acetic Acid (THA) as model for nucleobases, we identified an unstable monohapto hydride acetate complex 2, which rapidly evolves into elusive intermediates whose nature was evidenced by NMR spectra and DFT calculations. We obtained crystals of [(PPh3)2Ru(CO)(k1-THA)(k2-THA)] 17, and [Ru(CO)(PPh3)2(k2-N,O)-[THA(A)];(k1-O)[THA(B)]2 18, phosphine ligands assuming cis conformation. The thesis deals on the analogue reactions of 1 with acetic acid by varying different parameters and operating conditions. The reaction yields to the hydride dihapto-acetate [(PPh3)2RuH(CO)(k2-Ac)] 8 through the related meridian monohapto, by releasing of phosphine ligand. However, the reaction yields a mixture of compounds, in which the dihapto hydride complex 8 is prevailing in any cases and does not provide any disclosure for the proposed mechanistic aspects. The reaction with two equivalents of acetic acid, affords the complex [(PPh3)2Ru(CO)(k1-Ac)(k2-Ac)] 11, exhibiting mutual trans:cis locations in 2:1 ratio for the phosphine. Such evidence agrees with the results obtained DFT calculations in vacuo, whereas it is in contrast with those obtained with the THA. Therefore we can inferred that the products obtained from the latter reaction is intermolecularly ruled by the hydrogen binding interactions between the functions [-NH•••(O)C-] in the two coordinated thymine ligands.

Peat Bog Ecosystems: Atmospheric pollution

Peatlands can be damaged by deposition of pollutants from the atmosphere – often termed ‘ acid rain ’ . This results from the release of sulphur and nitrogen pollutants into the atmosphere . Originally associated with the Industrial Revolution, ‘acid rain’ was first described by Robert Angus Smith, a Manchester chemist of the 1800s , whose obser vations were made in close proximity to the peatlands of the South Pennines. Sulphur dioxide (SO 2 ) pollution, which is mainly emitted from coal burning power stations, peaked in the 1970s and has since decreased by over 90% due to emission controls and ch anges in energy supply. N itrogen ous air pollutants have decreased less . N itrogen oxide (NO x ) emissions , which are mainly from vehicle s , have decreased by two thirds since their peak in 1990 , but the decrease in ammonia ( NH 3 ) emissions , which are mainly from intensive livestock farming, is much less certain and may be only about 20%.

Desenvolvimento de sensores químicos para aniões

O objectivo deste trabalho foi o desenvolvimento de sensores químicos para aniões em solução aquosa. Os sensores basearam-se em cristais piezoelétricos de quartzo revestidos com macrociclos pirrólicos. Sensores com porfirinas, hexafirinas, ftalocianinas e uma rede metalo-orgânica como filmes de reconhecimento foram avaliados no que respeita à reversibilidade, sensibilidade, seletividade e tempo de vida. A sensibilidade aos aniões presentes nas águas minerais destinadas ao consumo humano dos sensores com macrociclos pirrólicos dependia dos grupos substituintes na periferia do macrociclo. A presença de grupos substituintes NH potenciou a sensibilidade, sendo o valor mais elevado obtido com o grupo NH-tosilo. Técnicas espectroscópicas permitiram mostrar que a principal interação entre o anião e o composto se fazia por meio de pontes de hidrogénio entre o anião e o grupo NH. A sensibilidade destes compostos dependia ainda da quantidade do composto depositado sobre o cristal. Nenhum dos sensores era específico, mas apresentavam variações na seletividade com o composto pirrólico sobre o cristal. O sensor com uma membrana polimérica que incorporou uma rede metalo-orgânica construída com moléculas de uma ftalocianina de magnésio com grupos NH-tosilo ligados por iões cobre apresentou coeficientes de seletividade muito diferentes de todos os restantes sensores. Uma língua eletrónica construída com três dos novos sensores foi capaz de determinar simultaneamente as concentrações dos iões HCO3-, Cl- e SO42- em amostras de água mineral engarrafada, não tendo os valores obtidos sido estatisticamente diferentes (α=0,05) daqueles que foram obtidos por cromatografia iónica ou volumetria.

Mannich-Type reactions in the Gas-Phase: the addition of Enol Silanes to cyclic N-Acyliminium Ions

The intrinsic gas-phase reactivity of cyclic N-acyliminium ions in Mannich-type reactions with the parent enol silane, vinyloxytrimethylsilane, has been investigated by double- and triple-stage pentaquadrupole mass spectrometric experiments. Remarkably distinct reactivities are observed for cyclic N-acyliminium ions bearing either endocyclic or exocyclic carbonyl groups. NH-Acyliminium ions with endocyclic carbonyl groups locked in s-trans forms participate in a novel tandem N-acyliminium ion reaction:  the nascent adduct formed by simple addition is unstable and rearranges by intramolecular trimethylsilyl cation shift to the ring nitrogen, and an acetaldehyde enol molecule is eliminated. An NSi(CH3)3-acyliminium ion is formed, and this intermediate ion reacts with a second molecule of vinyloxytrimethylsilane by simple addition to form a stable acyclic adduct. N-Acyl and N,N-diacyliminium ions with endocyclic carbonyl groups, for which the s-cis conformation is favored, react distinctively by mono polar [4+ + 2] cycloaddition yielding stable, ressonance-stabilized cycloadducts. Product ions were isolated via mass-selection and structurally characterized by triple-stage mass spectrometric experiments. B3LYP/6-311G(d,p) calculations corroborate the proposed reaction mechanisms.

Selenium in dysphagic patients who underwent endoscopic gastrostomy for long term enteral feeding

Background and aims - Endoscopic gastrostomy (PEG) patients usually present protein-energy malnutrition, but little is known about selenium deficiency. We aimed to assess serum selenium evolution when patients underwent PEG, after 4 and 12 weeks. We also evaluated the evolution of albumin, transferrin and Body Mass Index and the influence of the nature of the underlying disease. Methods - A blood sample was obtained before PEG (T0), after 4 (T1) and 12 (T3) weeks. Selenium was assayed using GFAAS (Furnace Atomic Absorption Spectroscopy). The PEG patients were fed through homemade meals. Patients were studied as a whole and divided into two groups: head and neck cancer (HNC) and neurological dysphagia (ND). Results - We assessed 146 patients (89 males), between 21-95 years old: HNC-56; ND-90. Normal values of selenium in 79% (n=115); low albumin in 77, low transferrin in 94, low values for both serum proteins in 66. Low BMI in 78. Selenium has slow evolution, with most patients still displaying normal Selenium at T3 (82%). Serum protein levels increase from T0 to T3, most patients reaching normal values. The nature of the underlying disease is associated with serum proteins but not with selenium. Conclusions - Low serum selenium is uncommon when PEG is performed, after 4 and 12 weeks of enteral feeding and cannot be related with serum proteins levels or dysphagia cause. Enteral nutrition using customized homemade kitchen meals is satisfactory to prevent or correct Selenium deficiency in the majority of PEG patients.

Nutrient fluxes on an intertidal mudflat in Marennes-Oleron Bay, and influence of the emersion period

Fluxes of nutrients (NH sub(4) super(+), NO sub(3) super(-), PO sub(4) super(3-) and Si(OH) sub(4)) were studied on an intertidal mudflat in Marennes-Oleron Bay, France, at two different seasons and at different times of the emersion period. Fluxes through the sediment-water interface were both calculated from vertical profiles of nutrient concentration in pore-water (diffusive fluxes, JD) and measured in light and dark benthic mini-chambers (measured fluxes, J sub(0)). Results indicate that ammonia was mainly released in summer while nitrate was mainly taken up in late winter. This uptake from the overlying water was probably due to the coupling of nitrification-denitrification within the sediment. The J sub(0) /J sub(D) ratio further indicates that bioturbation likely enhanced ammonia release in summer. Concerning phosphate, the comparison of diffusive and measured fluxes suggests that PO sub(4) super(3-) could be assimilated by the biofilm in winter while it was released in summer at a high rate due to both bioturbation and desorption because of the relative summer anoxic conditions. Silica was always released by the sediment, but at a higher rate in summer. Statistically significant differences in measured fluxes were detected in dark chambers at different times of low tide, thus suggesting a short-term variability of fluxes. Microphytobenthos preferred ammonia to nitrate, but assimilated nitrate when ammonia was not available. It also turned out that benthic cells could be limited in nitrogen during low tide in late winter. In summer, ammonia was not limiting and microphytobenthic activity significantly decreased the measured flux of NH sub(4) super(+) in the middle of low tide when its photosynthetic capacity was highest.