Oxidation of hexacyanoferrate(II) ion by hydrogen peroxide: evidence of free radical intermediacy

The redox reaction between hexacyanoferrate(II) ion as the reducing agent and hydrogen peroxide as the oxidizing one, in slightly acid (pH 4.36-6.65) aqueous solutions containing phosphate ions, has been studied by means of an UV-Vis spectrophotometer monitoring the formation of Fe(III) at 420 nm. The initial hydrolysis of the Fe(II)-cyanide complex reactant to yield a pentacyanoaquaferrate(II) intermediate, as well as a decrease in the solution pH (acid catalysis), had both a positive effect on the reaction rate, whereas an increase in the concentrations of Fe(III), phosphate and chloride ions, and d-mannitol had a negative effect (inhibition). A computer program, specifically designed for this purpose, allowed arriving at a complex eight-coefficient experimental rate law by application of the initial rate method, accounting for the dependences of the reaction rate on the concentrations of Fe(II), H2O2 and Fe(III). The reaction was characterized by a low value of the apparent activation energy (28.9 ± 2.7 kJ mol−1). Finally, a multi-step reaction mechanism, involving the participation of a penta-coordinated Fe(II) complex, and hydroxyl, superoxide and other free radicals as intermediates, has been proposed. This mechanism was supported by the available experimental information and confirmed by numerical simulations performed via the fourth order Runge-Kutta integration method

Sediment supply explains long-term and large-scale patterns in saltmarsh lateral expansion and erosion

Salt marshes often undergo rapid changes in lateral extent, the causes of which lack common explanation. We combine hydrological, sedimentological, and climatological data with analysis of historical maps and photographs to show that long‐term patterns of lateral marsh change can be explained by large‐scale variation in sediment supply and its wave‐driven transport. Over 150 years, northern marshes in Great Britain expanded while most southern marshes eroded. The cause for this pattern was a north to south reduction in sediment flux and fetch‐driven wave sediment resuspension and transport. Our study provides long‐term and large‐scale evidence that sediment supply is a critical regulator of lateral marsh dynamics. Current global declines in sediment flux to the coast are likely to diminish the resilience of salt marshes and other sedimentary ecosystems to sea level rise. Managing sediment supply is not common place but may be critical to mitigating coastal impacts from climate change

External conditions drive optimal planting configurations for salt marsh restoration

Coastal salt marshes are threatened by erosion from storminess and sea level rise, with resulting losses in flood protection, wildlife and recreational space. Although more than $1 billion has been spent to reconcile losses, restoration has had varying success because of poor survival of planted patches in challenging wave and current conditions. Marsh expansion after colonization or replanting is regulated by positive and negative feedbacks between vegetation density and sediment capture. Dense vegetation stimulates sediment capture and vertical patch growth, but negatively constrains patch expansion by concentrating hydrological energy into erosion gullies along patch edges. Conversely, low-density vegetation may not simulate enough sediment capture, which increases plant dislodgement mortality. The strengths of positive and negative feedbacks will vary with wave exposure, but this has never been tested in natural conditions. We observed density-dependent sediment feedbacks, survival and lateral expansion by Sporobolus anglicus patches (0.8 × 0.8 m) planted at three levels of vegetation density, at each of three levels of wave forcing (three sites). We found interactive effects of plant density and forcing on the strength of positive and negative feedbacks. Density-dependent feedbacks only emerged in moderate and exposed conditions: classic marsh tussock patch shapes, which arise due to combined positive (vertical growth) and negative (gullies) feedbacks, were only associated with high density vegetation under exposed conditions. At high exposure, survival was enhanced by dense planting, which diverted energy away from the vegetation. In sheltered conditions, expansion was the greatest at medium density, while dense patches had high mortality and erosion. Synthesis and applications. Success of wetland restoration clearly hinges on considering interactions between environmental stress and planting density. In challenging high-exposure settings, dense planting in large patches should maximize success, as plant facilitation boosts sediment capture and negative edge effects (gullies) will represent a diminished proportion of larger patches. Yet, benefits of dense planting will switch from positive (facilitation) to negative (competition) with reduced environmental stress, when moderate-density planting might be optimal. Switches along stress gradients between positive and negative feedbacks are common across ecosystems. We call for wider integration of facilitation and stress–gradient principles into restoration design to safeguard restoration successes

Hidromedusas profundas del Mediterráneo: Un estudio que incluye la descripción de dos nuevas especies recolectadas en cañones submarinos del Mediterráneo Occidental

Two new species of hydromedusae (Foersteria antoniae and Cunina simplex) are described from plankton collected in sediment traps placed in the Lacaze-Duthiers Submarine Canyon and along Banyuls-sur-Mer coast (northwestern Mediterranean). The Mediterranean hydromedusan deep-water fauna contains 41 species which represent 45.5 % of the world-wide deep-sea hydromedusae fauna (90) and 20% of the total number of Mediterranean hydromedusae (204). The Mediterranean deep-water hydromedusan fauna is characterised by a large percentage of holoplanktonic species (61%), mainly Trachymedusae. Nevertheless, contrary to the general opinion, the percentage of meroplanktonic species is equally high. The most original features of this fauna lies however in the importance of the number of endemic species (22%) and in the fact that the majority of them are meroplanktonic Leptomedusae with a supposed bathybenthic stage. Some of the endemic species could still represent relics of the primitive Tethys fauna having survived to the Messinian crisis. The origin of the Mediterranean deep-water hydromedusan fauna is discussed and a general hypothesis is proposed.Se describen dos especies nuevas a partir de ejemplares recolectados mediante trampas de sedimento del cañón submarino de Lacaze-Duthiers situado en frente de la costa de Banyuls-sur-Mer (Mediterráneo noroccidental). La fauna profunda de hydromedusas en el Mediterráneo contiene 41 especies que representan 45.5 % de la fauna mundial del grupo y el 20% de la fauna de hydromedusas del Mediterráneo. La fauna Mediterránea de hydromedusas profundas se caracteriza por un gran porcentaje de especies holoplanctónicas (61%), fundamentalmente Trachymedusas, sin embargo, contrario a la opinión generalizada, el porcentaje de especies meroplanctónicas es igualmente importante (39%). La característica más interesante de esta fauna es el número de especies endémicas (22%) y el hecho de que la mayoría de estas especies son meroplanctónicas (Leptomedusas) con una supuesta fase bentónica. Algunas de estas especies endémicas, podrían ser especies relictas (endémica insular) de la fauna primitiva del Tetis que sobrevivieron a la crisis Mesiniana. Se discute el origen de la fauna de hydromedusas profundas en el Mediterráneo y se presenta una nueva hipótesis

Enquête auprès du public de la bibliothèque municipale de Bordeaux (2002)

Résultats de l\u27enquête de la Bibliothèque municipale de Bordeaux menée auprès du public en 2002. Questionnaire, résultats détaillés et analyse

The immune score as a new possible approach for the classification of cancer

The outcome prediction in cancer is usually achieved by evaluating tissue samples obtained during surgical removal of the primary tumor focusing on their histopathological characteristics. Tumor staging (AJCC/UICC-TNM classification) summarizes data on tumor burden (T), presence of cancer cells in draining and regional lymph nodes (N), and evidence for metastases (M). However, this classification provides limited prognostic information in estimating the outcome in cancer and does not predict response to therapy. It is recognized that cancer outcomes can vary significantly among patients within the same stage. Recently, many reports suggest that cancer development is controlled by the host's immune system underlying the importance of including immunological biomarkers for the prediction of prognosis and response to therapy. Data collected from large cohorts of human cancers demonstrated that the immune-classification has a prognostic value that may be superior to the AJCC/UICC TNM-classification. Thus, it is imperative to begin incorporating immune scoring as a prognostic factor and to introduce this parameter as a marker to classify cancers, as part of the routine diagnostic and prognostic assessment of tumors. At the same time, the inherent complexity of quantitative immunohistochemistry, in conjunction with variable assay protocols across laboratories, the different immune cell types analyzed, different region selection criteria, and variable ways to quantify immune infiltration underscore the urgent need to reach assay harmonization. In an effort to promote the immunoscore in routine clinical settings worldwide, the Society for Immunotherapy of Cancer (SITC), the European Academy of Tumor Immunology, the Cancer and Inflammation Program, the National Cancer Institute, National Institutes of Health, USA and "La Fondazione Melanoma" will jointly initiate a task force on Immunoscoring as a New Possible Approach for the Classification of Cancer that will take place in Naples, Italy, February 13th, 2012. The expected outcome will include a concept manuscript that will be distributed to all interested participants for their contribution before publication outlining the goal and strategy to achieve this effort; a preliminary summary to be presented during the "Workshop on Tumor Microenvironment" prior to the SITC annual meeting on October 24th - 25th 2012 in Bethesda, Maryland, USA and finally a "Workshop on Immune Scoring" to be held in Naples in December of 2012 leading to the preparation of a summary document providing recommendations for the harmonization and implementation of the Immune Score as a new component for the classification of cancer

Near-forward Raman selection rules of the phonon-polariton created by alloying in (Zn,Be)Se

The Raman selection rules of the (ZnSe, BeSe) mixed phonon polariton created by alloying in the three mode (1ZnSe, 2BeSe) ZnBeSe system, whose dramatic S like dispersion covers the large frequency gap between the ZnSe and BeSe spectral ranges, is studied in its wave vector dependence by near forward scattering. Both the collapse regime away from the Brillouin zone centre and the reinforcement regime near the Brillouin zone centre are addressed, using appropriate laser lines and Be contents. We find that in both regimes the considered phonon polariton, in fact a transverse mode with mixed mechanical and electrical character, obeys the same nominal Raman selection rules as its purely mechanical variant commonly observed in the backscattering geometry. Besides, marked differences in the phonon polariton Raman lineshapes in the two regimes give a hint about how the phonon polariton electrical field E develops while descending the S like dispersion towards the Brillouin zone centre. In the reinforcement regime E is large, leading to intramode on top of intermode transfers of oscillator strength mediated by E between the two BeSe modes, that both exhibit a fine structure on account of the alloy disorder. In contrast, in the collapse regime E remains weak, as testified by the absence of intramode transfer. The discussion is supported by contour modeling of the multi phonon polariton Raman lineshapes in their wave vector dependence within the linear dielectric approach.Comment: 16 pages, 7 figure

Factory Gate Pricing: An Analysis of the Dutch Retail Distribution

Factory Gate Pricing (FGP) is a relatively new phenomenon in retail distribution. Under FGP, products are no longer delivered at the retailer distribution center, but collected by the retailer at the factory gates of the suppliers. Owing to both the asymmetry in the distribution networks (the supplier sites greatly outnumber the retailer distribution centers) and the better inventory and transport coordination mechanisms, this is likely to result in high savings. A mathematical model was used to analyze the benefits of FGP for a case study in the Dutch retail sector. Extensive numerical results are presented to show the effect of the orchestration shift from supplier to retailer, the improved coordination mechanisms, and sector-wide cooperation