Stable isotopes indicate population structuring in the Southwest Atlantic population of right whales

From the early 17th century to the 1970s southern right whales, Eubalaena australis, were subject to intense exploitation along the Atlantic coast of South America. Catches along this coast recorded by whalers originally formed a continuum from Brazil to Tierra del Fuego. Nevertheless, the recovery of the population has apparently occurred fragmentarily, and with two main areas of concentration, one off southern Brazil (Santa Catarina) and another off central Argentina (Peninsula Valdés). This pattern suggests some level of heterogeneity amongst the population, which is apparently contradicted by records that traced individuals moving throughout the whole geographical extension covered by the species in the Southwest Atlantic. To test the hypothesis of the potential occurrence of discrete subpopulations exploiting specific habitats, we investigated N, C and O isotopic values in 125 bone samples obtained from whaling factories operating in the early 1970s in southern Brazil (n = 72) and from contemporary and more recent strandings occurring in central Argentina (n = 53). Results indicated significant differences between the two sampling areas, being δ13C and δ18O values significantly higher in samples from southern Brazil than in those from central Argentina. This variation was consistent with isotopic baselines from the two areas, indicating the occurrence of some level of structure in the Southwest Atlantic right whale population and equally that whales more likely feed in areas commonly thought to exclusively serve as nursing grounds. Results aim at reconsidering of the units currently used in the management of the southern right whale in the Southwest Atlantic Ocean. In the context of the current die-off affecting the species in Peninsula Valdés, these results also highlight the necessity to better understand movements of individuals and precisely identify their feeding areas.

Biogeochemical processes controlling oxygen and carbon isotopes of diatom silica in Late Glacial to Holocene lacustrine rhythmites

Biogeochemical cycles and sedimentary records in lakes are related to climate controls on hydrology and catchment processes. Changes in the isotopic imposition of the diatom frustules (δ 18 O diatom and δ 13 C diatom ) in lacustrine sediments can be used to reconstruct palaeoclimatic and palaeoenvironmental changes. The Lago Chungará (Andean Altiplano, 18°15 ′ S, 69°10 ′ W, 4520 masl) diatomaceous laminated sediments are made up of white and green multiannual rhythmites. White laminae were formed during short-term diatom super-blooms, and are composed almost exclusively of large-sized Cyclostephanos andinus.These diatoms bloom during mixing events when recycled nutrients from the bottom waters are brought to the surface and/or when nutrients are introduced from the catchment during periods of strong runoff. Conversely, the green laminae are thought to have been deposited over several years and are composed of a mixture of diatoms (mainly smaller valves of C. andinus and Discostella stelligera ) and organic matter. These green laminae reflect the lake's hydrological recovery from a status favouring the diatom super-blooms (white laminae) towards baseline conditions. δ 18 O diatom and δ 13 C diatom from 11,990 to 11,530 cal years BP allow us to reconstruct shifts in the precipitation/evaporation ratio and changes in the lake water dissolved carbon concentration, respectively. δ 18 O diatom values indicate that white laminae formation occurred mainly during low lake level stages, whereas green laminae formation generally occurred during high lake level stages. The isotope and chronostratigraphical data together suggest that white laminae deposition is caused by extraordinary environmental events. El Niño-Southern Oscillation and changes in solar activity are the most likely climate forcing mechanisms that could trigger such events, favouring hydrological changes at interannual-to-decadal scale. This study demonstrates the potential for laminated lake sediments to document extreme pluriannual events.

Buccal dental microwear and stable isotopes of El Collado: A mesolithic site from Spain,

This study examines the correlation between buccal dental microwear and stable isotopes. The buccal surface of post-canine teeth casts from El Collado, the largest Mesolithic site in Spain, were examined under Scanning Electron Microscope; photomicrographs were taken from the middle third of the buccal surface with magnification 100X. Only six individuals passed the criteria for buccal dental microwear analysis. The photomicrographs were treated by adobe Photoshop 8.01 to cover an area 0.56 mm² of middle third of buccal surface, the output photomicrographs were digitized using Sigmascan Pro 5 by SPSS. Then the correlation between buccal microwear pattern and stable isotopes of the same individuals, of the previous study of Guixe et al., 2006, was examined using a Pearson test. Statistical analysis revealed that there is no significant correlation between stable isotopes and buccal dental microwear of the people of the Mesolithic site of El Collado. The historical and archaeological documentation suggest that the Mesolithic people tended to consume marine food. Fish-drying techniques were used during the Mesolithic period which allowed the introduction of dust and sand to the fish. These abrasive particles affected the buccal dental microwear pattern, so that no correlation between the isotopes and microwear may be expected. This also suggests that the buccal dental microwear pattern exceeds dietary reconstruction to reconstruct food processing techniques.

Stable isotopes provide insight into population structure and segregation in eastern North Atlantic sperm whales

In pelagic species inhabiting large oceans, genetic differentiation tends to be mild and populations devoid of structure. However, large cetaceans have provided many examples of structuring. Here we investigate whether the sperm whale, a pelagic species with large population sizes and reputedly highly mobile, shows indication of structuring in the eastern North Atlantic, an ocean basin in which a single population is believed to occur. To do so, we examined stable isotope values in sequential growth layer groups of teeth from individuals sampled in Denmark and NW Spain. In each layer we measured oxygen- isotope ratios (δ18O) in the inorganic component (hydroxyapatite), and nitrogen and carbon isotope ratios (δ15N: δ13C) in the organic component (primarily collagenous). We found significant differences between Denmark and NW Spain in δ15N and δ18O values in the layer deposited at age 3, considered to be the one best representing the baseline of the breeding ground, in δ15N, δ13C and δ18O values in the period up to age 20, and in the ontogenetic variation of δ15N and δ18O values. These differences evidence that diet composition, use of habitat and/or migratory destinations are dissimilar between whales from the two regions and suggest that the North Atlantic population of sperm whales is more structured than traditionally accepted.

Stable isotopes unveil habitat partitioning among the marine mammals off NW Africa and reveal unique trophic niches for two globally threatened species.

Stable isotope abundances of carbon (δ13C) and nitrogen (δ15N) in the bone of 13 species of marine mammals from the northwest coast of Africa were investigated to assess their positions in the local trophic web and their preferred habitats. Also, samples of primary producers and potential prey species from the study area were collected to characterise the local isotopic landscape. This characterisation indicated that δ13C values increased from offshore to nearshore and that δ15N was a good proxy for trophic level. Therefore, the most coastal species were Monachus monachus and Sousa teuszii, whereas the most pelagic were Physeter macrocephalus and Balaenoptera acutorostrata. δ15N values indicated that marine mammals located at the lowest trophic level were B. acutorostrata, Stenella coeruleoalba and Delphinus sp., and those occupying the highest trophic level were M. monachus and P. macrocephalus. The trophic level of Orcinus orca was similar to that of M. monachus, suggesting that O. orca preys on fish. Conservation of coastal and threatened species (M. monachus and S. teuszii) off NW Africa should be a priority because these species, as the main apex predators, cannot be replaced by other marine mammals.

CERN-MEDICIS: une nouvelle infrastructure pour la production de radioisotopes a usage medical [CERN-MEDICIS (Medical Isotopes Collected from ISOLDE): a new facility].

CERN-MEDICIS (Medical Isotopes Collected from ISOLDE) est une plateforme de recherche destinée à la production de radioisotopes biomédicaux. Inauguré en 2014, il produira progressivement un nombre croissant de radioisotopes grâce au faisceau de protons ISOLDE déjà existant. Ce projet réunit des spécialistes du cancer, des chirurgiens, des experts en médecine nucléaire, en radiochimie et radiopharmacie et les scientifiques du CERN. Les radioisotopes ainsi produits seront destinés à la recherche fondamentale contre le cancer, à des études précliniques ainsi qu'au développement de protocoles d'imagerie et de thérapie destinés aux patients.Le CERN, les HUG, le CHUV, l'ISREC et l'EPFL qui soutiennent ce projet seront les premiers bénéficiaires de ces radioisotopes novateurs dont la distribution sera ensuite étendue à d'autres centres européens. CERN-MEDICIS is a facility dedicated to research and development in life science and medical applications. The research platform was inaugurated in October 2014 and will produce an increasing range of innovative isotopes using the proton beam of ISOLDE for fundamental studies in cancer research, for new imaging and therapy protocols in cell and animal models and for preclinical trials, possibly extended to specific early phase clinical studies (phase 0) up to phase I trials. CERN, the University Hospital of Geneva (HUG), the University Hospital of Lausanne (CHUV), the Swiss Institute for Experimental Cancer (ISREC) at Swiss Federal Institutes of Technology (EPFL) that currently support the project will benefit of the initial production that will then be extended to other centers.

Stable isotopes reveal trophic segregation by sex and age in the southern giant petrel in two different foodwebs

We investigated trophic ecology variation among colonies as well as sex- and age-related differences in the diet of the southern giant petrel Macronectes giganteus, a long-lived seabird that is sexually dimorphic in size. We measured stable isotopes (δ13C, δ15N) in blood samples collected during breeding at Bird Island (South Georgia, Antarctica) in 1998 and at 2 colonies in the Argentinean area of Patagonia in 2000 and 2001. Individuals from South Georgia showed lower δ13C and δ15N values than those in Patagonia, as expected from the more pelagic location and the short length of the Antarctic food web. Males and females showed significant differences in the isotopic signatures at both localities. These differences agree with the sexual differences in diet found in previous studies, which showed that both sexes rely mainly on penguin and seal carrion, but females also feed extensively on marine prey, such as fish, squid and crustaceans. However, males from Patagonia showed significantly higher δ15N and δ13C values than females did, and the reverse trend was observed at South Georgia. This opposite trend is probably related to the different trophic level of carrion between locations: whereas penguins and pinnipeds in Patagonia rely mainly on fish and cephalopods, in South Georgia they rely mainly on krill. Stable isotope values of male and female chicks in Patagonia did not differ; both attained high values, similar to adult males and higher than adult females, suggesting that parents do not provision their single offspring differently in relation to sex; however, they seem to provide offspring with a higher proportion of carrion, probably of higher quality, and more abundant food, than they consume themselves. Stable isotopes at South Georgia were not affected by age of adults. We have provided new information on intraspecific segregation in the diet in a seabird species and have also underlined the importance of considering food web structure when studying intraspecific variability in trophic ecology.

Activity and sulfur resistance of Rh(I) and Pd(II) complexes

Two complexes of Rh(I) and Pd(II) with chloride and tridecylamine ligands were obtained and characterized by Elementary Analysis and by XPS and FTIR spectroscopies. Complexes anchored on γ-Al2O3 were tested in the styrene semi-hydrogenation reaction carried out in the absence or presence of a sulfur poison. Although both low loaded catalysts were highly selective, the Pd(II) complex was three times more active than the Rh(I) complex. The rhodium complex was more sulfur resistant but less active than the palladium complex. Differences in conversion and sulfur resistance between both complexes could be related to electronic and/or geometric effects.

Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904), and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15).

Flow injection visible diffuse reflectance quantitative analysis of total sulfur in biodiesel, in plant leaves and in natural waters

Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of total sulfur in the form of sulfate, precipitated in the form of barium sulfate, is presented. The method was applied to biodiesel, to plant leaves and to natural waters analysis. The analytical signal (S) correlates linearly with sulfate concentration (C) between 20 and 120 ppm, through the equation S=-1.138+0.0934 C (r = 0.9993). The experimentally observed limit of detection is about 10 ppm. The mean R.S.D. is about 3.0 %. Real samples containing sulfate were analyzed and the results obtained by the FI and by the reference batch turbidimetric method using the statistical Student's t-test and F-test were compared.

Determination of sulfur in diesel using ATR/FTIR and multivariate calibration

The aim of this present work was to provide a more fast, simple and less expensive to analyze sulfur content in diesel samples than by the standard methods currently used. Thus, samples of diesel fuel with sulfur concentrations varying from 400 and 2500 mgkg-1 were analyzed by two methodologies: X-ray fluorescence, according to ASTM D4294 and by Fourier transform infrared spectrometry (FTIR). The spectral data obtained from FTIR were used to build multivariate calibration models by partial least squares (PLS). Four models were built in three different ways: 1) a model using the full spectra (665 to 4000 cm-1), 2) two models using some specific spectrum regions and 3) a model with variable selected by classic method of variable selection stepwise. The model obtained by variable selection stepwise and the model built with region spectra between 665 and 856 cm-1 and 1145 and 2717 cm-1 showed better results in the determination of sulfur content.

Mantle- and crust-derived magmatism in the southern Fennoscandian Shield at c. 1.8 Ga; evidence from geochemistry, isotopes and geochronology

Geokemi och isotopsammansättningarna hos ca 1,8 Ga (miljarder år) gamla mafiska bergartsintrusioner studerades i två huvudområden: i) Transskandinaviska magmatiska bältet (TMB) i Bergslagen, Småland och Blekinge, södra Sverige, inklusive några prov från det ca 1,87 Ga gamla Hedesunda-komplexet i östra Bergslagen, samt ii) mindre, postkollisionala komplex i södra Finland och ryska Karelen. I det senare fallet var även tillhörande granitoider inkluderade i studierna. TMB-bergarterna skiljer sig avsevärt i utvecklingsgrad och omfattar sammansättningsmässigt bergarter från ultramafiter till kvartsdioriter. Dessa bergarters geokemi är kännetecknande för kontinentala öbågar. För sydligaste TMB och Hedesunda antyder geokemin en något mera oceanisk öbågekaraktär. Tillsammans med tidigare data antyder de av Rutanen analyserade Nd- och Sr-isotopförhållanden för TMB en ’milt utarmad’ mantelsammansättning. De mafiska bergarterna i södra Finland och ryska Karelen varierar från ultramafiska till monzodioritiska, men med avsevärt högre alkalihalter jämfört med TMB. Källan för all den studerade mafiska magmatismen kan beskrivas som en utarmad mantel som i varierande grad påverkats av fluider och smältor ur subducerande litosfärplattor. Geokemin antyder infiltrering och påverkning av H2O-dominerande fluider i övre manteln för TMB. Den mafiska ca 1,8 Ga gamla magmatismen österut avspeglar en ökande påverkan av sedimentderiverade karbonatfluider och smältor inom allt djupare mantelområden. Denna subduktionsrelaterade mantelanrikning skedde under den föregående öbågeutvecklingen i södra delarna av Finland och Sverige, samt ryska Karelen. Geokemin för en grupp granitoider, associerade med de ca 1,8 Ga gamla intrusionerna i södra Finland visar både vulkanisk öbåge och synkollisional granitoidkaraktär. Denna grupp har ett blandat magmatiskt och sedimentärt Svekofenniskt ursprung, vilket kan antas p.g.a. deras Nd- och Sr-isotopförhållanden. En annan grupp av granitoider ligger geokemiskt mellan vulkanisk öbåge- och intraplatt-granitoider, och har magmatiskt ursprung. Geokemin och isotoperna hos dessa intrusioner kan förklaras med hybridisering mellan de kraftigt anrikade, mantelderiverade magmorna, och granitmagmor från den äldre skorpan. Den ca 1,8 Ga gamla TMB-magmatismen i Sverige skedde vid sammanslutning av kontinentalrandbågar, med kontinuerlig subduktion mot öster i Bergslagen, och mot norr i de sydligare delarna. Samtidigt i öster intruderade de postkollisionala intrusionerna i skorpan omedelbart efter kollisionen med den Volgo-Sarmatiska kontinenten från sydost. Denna invecklade paleotektoniska konfiguration orsakade en tektonisk regim där litosfäriska mantelkällor levererade de starkt anrikade magmorna, vilkas uppstigning troligen möjliggjordes av djupgående postkollisionala skjuvzoner. Intrusionerna orsakade uppsmältning av den omgivande skorpan, vilket framkallade den associerade granitoidmagmatismen.

Fate of fuel-bound nitrogen and sulfur in biomass-fired Industrial boilers

Användning av biomassa som energikälla för produktion av el och värme är ett sätt att minska beroendet av fossila bränslen och höja självförsörjningen av energi. Fossila bränslen är den främsta källan till koldioxid utsläpp förorsakad av människan. Biomassa, å andra sidan, betraktas som en koldioxidneutral energikälla. Svavlet och kvävet i biomassan bildar dock föroreningar såsom kväveoxider (NOX) och svaveldioxid (SO2), som bidrar till försurning av mark och sjöar. Svavlet i bränslet kan även både förorsaka och förhindra korrosion i en förbränningsanläggning, beroende på förbränningen och bränslet. Huvudsyftet med detta arbete var att få en bättre förståelse om hur utsläppen av NOX och SO2 bildas från bränslebundet kväve och svavel vid förbränning av olika biobränslen. Mätkampanjer i fullskaliga förbränningsanläggningar utfördes, där gassammansättningen mättes i eldstaden och rökgasen. Förståelsen om gaskemin i eldstaden är viktig, för att möjliggöra utvecklandet av renare och effektivare förbränningsanläggningar. Ett annat syfte med arbetet var att klargöra om sulfatering av askkomponenter vid förbränning av biobränslen med olika askegenskaper. Alkaliklorider som bildas vid biomassaförbränning kan orsaka korrosion av värmeöverföringsytor. Svavlet i bränslet visade sig ha en viktig roll i att sulfatera alkaliklorider till mindre korrosiva alkalisulfater. Närvaron av gasformig svavelsyra i rökgaskanalen av förbränningsanläggningar studerades även. Kondensering av svavelsyra leder till korrosion av rökgaskanalen och dess delar. Om svavelsyrakoncentrationen i rökgasen är känd, kan daggpunktstemperaturen beräknas och kondensering av svavelsyra förhindras. I arbetet utvecklades en mätmetod för att mäta låga koncentrationer av gasformig svavelsyra i rökgaser. Denna metod användes för att undersöka risken av lågtemperaturkorrosion orsakad av svavelsyra i förbränningsanläggningar. ------------------------------------------------------------------------------------------------------------ Käyttämällä biomassaa energianlähteenä voidaan vähentää sähkön- ja lämmöntuotannon riippuvuutta fossiilisiin polttoaineisiin. Biomassan käytöllä voidaan myös lisätä energiantuotannon omavaraisuutta. Fossiiliset polttoaineet ovat pääasiallinen syy ihmisen aiheuttamiin hiilidioksidipäästöihin. Biomassa sen sijaan luetaan hiilidioksidineutraaleihin energianlähteisiin. Biopolttoaineiden käytössä tosin vapautuu typpi- ja rikkioksideja, jotka edesauttavat maaperän ja merien happamoitumista. Lisäksi biopolttoaineen rikki voi sekä vähentää että aiheuttaa laitteiden korroosiota energiantuotannossa riippuen biopolttoaineesta ja palamisesta. Tämän työn päätavoitteena oli selvittää mitä biopolttoaineeseen sitoutuneelle typelle ja rikille tapahtuu teollisissa polttolaitoksissa. Kyseisten oksidien muodostumista tutkittiin polttamalla eri biomassoja polttolaitoksissa. Tutkimukset toteutettiin mittauskampanjoilla useissa polttolaitoksissa. Kaasujen koostumusta mitattiin sekä tulipesässä, että savukaasuista. Kaasujen koostumus varsinkin tulipesässä on tärkeää, jotta tulevaisuudessa voidaan rakentaa puhtaampia ja tehokkaampia polttolaitoksia. Työn toisena tavoitteena oli selvittää biomassan polton yhteydessä tapahtuvaa tuhkan sulfatoitumista. Alkalikloridit, joita muodostuu biomassan poltossa, voivat aiheuttaa lämmönsiirtopintojen korroosiota. Rikki osoittautui tärkeäksi osaksi prosessia, jossa korroosiota aiheuttavat alkalikloridit sulfatoituivat vähemmän korrosoiviksi alkalisulfaateiksi. Myös kaasumaisen rikkihapon läsnäoloa savukaasuissa tutkittiin. On todettu, että kaasumuotoinen rikkihappo johtaa korroosioon savukaasukanavan kylmässä päässä ja sen eri osissa rikkihapon tiivistyessä lämpötilan laskiessa. Mikäli rikkihapon pitoisuus savukaasussa tiedetään, sen kastepiste voidaan laskea ja tiivistyminen estää. Tässä työssä kehitettiin mittausmenetelmä rikkihapon alhaisten pitoisuuksien mittaamiseen. Menetelmää hyödynnettiin polttolaitoksissa, joissa tutkittiin rikkihapon tiivistymisestä johtuvaa korroosiota.

Association of sulfur dioxide exposure with circulatory system deaths in a medium-sized city in Brazil

There is a demonstrable association between exposure to air pollutants and deaths due to cardiovascular diseases. The objective of this study was to estimate the effects of exposure to sulfur dioxide on mortality due to circulatory diseases in individuals 50 years of age or older residing in São José dos Campos, SP. This was a time-series ecological study for the years 2003 to 2007 using information on deaths due to circulatory disease obtained from Datasus reports. Data on daily levels of pollutants, particulate matter, sulfur dioxide (SO2), ozone, temperature, and humidity were obtained from the São Paulo State Environmental Agency. Moving average models for 2 to 7 days were calculated by Poisson regression using the R software. Exposure to SO2 was analyzed using a unipollutant, bipollutant or multipollutant model adjusted for mean temperature and humidity. The relative risks with 95%CI were obtained and the percent decrease in risk was calculated. There were 1928 deaths with a daily mean (± SD) of 1.05 ± 1.03 (range: 0-6). Exposure to SO2 was significantly associated with mortality due to circulatory disease: RR = 1.04 (95%CI = 1.01 to 1.06) in the 7-day moving average, after adjusting for ozone. There was an 8.5% decrease in risk in the multipollutant model, proportional to a decrease of SO2 concentrations. The results of this study suggest that residents of medium-sized Brazilian cities with characteristics similar to those of São José dos Campos probably have health problems due to exposure to air pollutants.