Ab-initio calculations of the proton location in topaz-OH, Al2SiO4(OH)2

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4-H1... O1, O4-H2... O2, O4-H3... O3 and O4-H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton-proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4-H3... O3 and O4-H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4-H1... O1 and O4-H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm−1 was assigned to the OH-stretching of the O4-H3... O3 bond, while the band at 3600 cm−1 was attributed to OH-stretching of the O4-H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100-150 cm−1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4-H3... O3 and O4-H4... O4 bonds at 670 K occur at a rate of about 1.96 TH

Hope for Bohemian ecologists – comments on “A possible role of social activity to explain differences in publication output among ecologists?” by Tomáš Grim, Oikos 2008

No abstract available

The dynamics of solo self-employment: Persistence and transition to employership

This study examines dynamics of solo self-employment. In particular, we investigate the extent of true state dependence and cross state dependence, i.e., whether experiencing solo self-employment causally affects the probability of becoming an employer in the future. We use data from the German Socio-Economic Panel to estimate dynamic multinomial logit models. Our results show that the extent of true (cross) state dependence is rather small. The observed persistence in solo self-employment as well as transitions from solo self-employment to employership can largely be explained by observed and unobserved heterogeneity.Diese Studie untersucht die Dynamik der Solo-Selbständigkeit (Verbleib,Zu- und Abgänge). Wir berechnen das Ausmaß genuiner Zustandsabhängigkeit für den Verbleib in Solo-Selbständigkeit und schätzen den kausalen Effekt der Solo-Selbstständigkeit auf die Wahrscheinlichkeit, Arbeitgeber zu werden. Die Berechungen basieren auf dynamischen multinomialen Logit-Modellen, die mit Daten des Sozio-oekonomischen Panels geschätzt wurden. Unsere Ergebnisse deuten auf eine nur geringe genuine Zustandsabhängigkeit hin: Sowohl die beobachtete Persistenz in Solo-Selbständigkeit als auch die Übergänge zum Arbeitgeber-Status lassen sich größtenteils durch (beobachtete und unbeobachtete) individuelle Merkmale erklären

Using ocean models to predict spatial and temporal variation in marine carbon isotopes

Natural-abundance stable isotope ratios provide a wealth of ecological information relating to food web structure, trophic level, and location. The correct interpretation of stable isotope data requires an understanding of spatial and temporal variation in the isotopic compositions at the base of the food web. In marine pelagic environments, accurate interpretation of stable isotope data is hampered by a lack of reliable, spatio-temporally distributed measurements of baseline isotopic compositions. In this study, we present a relatively simple, process-based carbon isotope model that predicts the spatio-temporal distributions of the carbon isotope composition of phytoplankton (here expressed as δ13CPLK) across the global ocean at one degree and monthly resolution. The model is driven by output from a coupled physics-biogeochemistry model, NEMO-MEDUSA, and operates offline; it could also be coupled to alternative underlying ocean model systems. Model validation is challenged by the same lack of spatio-temporally explicit data that motivates model development, but predictions from our model successfully reproduce major spatial patterns in carbon isotope values observed in zooplankton, and are consistent with simulations from alternative models. Model predictions represent an initial hypothesis of spatial and temporal variation in carbon isotopic baselines in ocean areas where a few data are currently available, and provide the best currently available tool to estimate spatial and temporal variation in baseline isotopic compositions at ocean basin to global scales

Molecular imaging: novel tools in visualizing rheumatoid arthritis

Molecular imaging is a rapidly emerging field in biomedical research, aiming at the visualization, characterization and quantification of molecular and cellular processes non-invasively within intact living organisms. To sense biological processes such as gene expression, angiogenesis, apoptosis or cell trafficking in vivo, imaging reporter agents that interact specifically with molecular targets and appropriate imaging systems are currently under development. In rheumatoid arthritis, these novel tools will be used to evaluate physiological and pathophysiological processes, to facilitate diagnosis and monitor therapeutic regimens, to enable reliable prognosis and to support the development of new therapies. In this review, we summarize the basic principles of molecular imaging, such as the development of molecular imaging agents, the actual capabilities of different imaging modalities and the most recent advances in molecular imaging, demonstrating the potential of this technology. With regard to their applicability in rheumatic diseases, we discuss potential molecular targets, current experimental approaches and the future prospects for molecular imaging in rheumatoid arthriti

Analysis of margin classification systems for assessing the risk of local recurrence after soft tissue sarcoma resection

Purpose: To compare the ability of margin classification systems to determine local recurrence (LR) risk after soft tissue sarcoma (STS) resection. Methods: Two thousand two hundred seventeen patients with nonmetastatic extremity and truncal STS treated with surgical resection and multidisciplinary consideration of perioperative radiotherapy were retrospectively reviewed. Margins were coded by residual tumor (R) classification (in which microscopic tumor at inked margin defines R1), the R+1mm classification (in which microscopic tumor within 1 mm of ink defines R1), and the Toronto Margin Context Classification (TMCC; in which positive margins are separated into planned close but positive at critical structures, positive after whoops re-excision, and inadvertent positive margins). Multivariate competing risk regression models were created. Results: By R classification, LR rates at 10-year follow-up were 8%, 21%, and 44% in R0, R1, and R2, respectively. R+1mm classification resulted in increased R1 margins (726 v 278, P < .001), but led to decreased LR for R1 margins without changing R0 LR; for R0, the 10-year LR rate was 8% (range, 7% to 10%); for R1, the 10-year LR rate was 12% (10% to 15%) . The TMCC also showed various LR rates among its tiers (P < .001). LR rates for positive margins on critical structures were not different from R0 at 10 years (11% v 8%, P = .18), whereas inadvertent positive margins had high LR (5-year, 28% [95% CI, 19% to 37%]; 10-year, 35% [95% CI, 25% to 46%]; P < .001). Conclusion: The R classification identified three distinct risk levels for LR in STS. An R+1mm classification reduced LR differences between R1 and R0, suggesting that a negative but < 1-mm margin may be adequate with multidisciplinary treatment. The TMCC provides additional stratification of positive margins that may aid in surgical planning and patient education

Development of consumption-based land use indicators

With this UFOPLAN project on land use indicators, the German Federal Environment Agency aimed at further developing indicators from a consumption perspective in support of Germany’s sustainability strategy, covering both area-based and impact-oriented land footprint indicators.The project also aimed at calculating selected land footprint indicators for Germany and the EU. These indicators should provide an improved understanding of the global teleconnections of consumption and land use relevant for policy making towards achieving sustainable land use. This synthesis report presents the key results from this project. First, we present a structured overview of existing approaches for estimating land footprintsand describe their technical and structural characteristicsas well as their strengths and weaknesses. This leads to the specification of a hybrid methodology as the preferred calculation approach. In the second part, we present the developed innovative hybrid land footprint method, consisting of a global land flow accounting and trade model capturing commodity flows in physical units to track embodied land along global supply chains. For non-food commodities the supply chains were complemented by an environmental input-output model. This method was used to calculate the cropland, grassland and forestland footprint of Germany and the EU. Finally, an overview of existing indicator systems for representing the environmental impacts of land use was provided and their complementary usage to extend area-based land footprints was discussed. A few of these complementary indicators were also quantified, most notably the deforestation footprint. The synthesis report closes with an overview of the thematic areas that need to be addressed in future research

Extending land footprints towards characterizing sustainability of land use

The global trade of biomass-based products leads to an increasing regional decoupling of the area of production and consumption. Area-based land footprint calculations attribute the extents of land use required to prevailing national consumption patterns. Another report (Fischer et al., 2016) of the present study describes the methodology for the calculation of area-based footprints and presents results for Germany and the EU. Beyond area extents, additional information is needed to assess the sustainability of land use, requiring further analyses regarding environmental impacts and preservation of land quality and ecosystem services. This report discusses extensions of area-based land footprints with meaningful impact-oriented indicators for the assessment of the effects of different consumption patterns on the ecosystems and sustainability of land use. First, existing indicators for representing the environmental impacts of land use are introduced in the context of their linkages and complementarity to area-based land footprints. The report discusses the following key indicators, which were identified as particularly relevant during an export workshop: System indicators, which qualify the area-based footprints across globally very different potential land productivities,deforestation footprint, energy use in agriculture, and irrigation water use in agriculture classified by degree of water scarcity. We introduce the methods developed for the quantification of system indicators for cropland and grassland footprints and for the deforestation footprint, and present results for Germany and the EU

A Policy Maker’s Guide to Designing Payments for Ecosystem Services

Over the past five years, there has been increasing interest around the globe in payment schemes for the provision of ecosystem services, such as water purification, carbon sequestration, flood control, etc. Written for an Asian Development Bank project in China, this report provides a user-friendly guide to designing payments for the provision of ecosystem services. Part I explains the different types of ecosystem services, different ways of assessing their value, and why they are traditionally under-protected by law and policy. This is followed by an analysis of when payments for services are a preferable approach to other policy instruments. Part II explains the design issues underlying payments for services. These include identification of the service as well as potential buyers and sellers, the level of service needed, payment timing, payment type, and risk allocation. Part II contains a detailed analysis of the different types of payment mechanisms, ranging from general subsidy and certification to mitigation and offset payments. Part III explores the challenges to designing a payment scheme. These include the ability to monitor service provision, secure property rights, perverse incentives, supporting institutions, and poverty alleviation