Multiscale study on hydrogen mobility in metallic fusion divertor material

For achieving efficient fusion energy production, the plasma-facing wall materials of the fusion reactor should ensure long time operation. In the next step fusion device, ITER, the first wall region facing the highest heat and particle load, i.e. the divertor area, will mainly consist of tiles based on tungsten. During the reactor operation, the tungsten material is slowly but inevitably saturated with tritium. Tritium is the relatively short-lived hydrogen isotope used in the fusion reaction. The amount of tritium retained in the wall materials should be minimized and its recycling back to the plasma must be unrestrained, otherwise it cannot be used for fueling the plasma. A very expensive and thus economically not viable solution is to replace the first walls quite often. A better solution is to heat the walls to temperatures where tritium is released. Unfortunately, the exact mechanisms of hydrogen release in tungsten are not known. In this thesis both experimental and computational methods have been used for studying the release and retention of hydrogen in tungsten. The experimental work consists of hydrogen implantations into pure polycrystalline tungsten, the determination of the hydrogen concentrations using ion beam analyses (IBA) and monitoring the out-diffused hydrogen gas with thermodesorption spectrometry (TDS) as the tungsten samples are heated at elevated temperatures. Combining IBA methods with TDS, the retained amount of hydrogen is obtained as well as the temperatures needed for the hydrogen release. With computational methods the hydrogen-defect interactions and implantation-induced irradiation damage can be examined at the atomic level. The method of multiscale modelling combines the results obtained from computational methodologies applicable at different length and time scales. Electron density functional theory calculations were used for determining the energetics of the elementary processes of hydrogen in tungsten, such as diffusivity and trapping to vacancies and surfaces. Results from the energetics of pure tungsten defects were used in the development of an classical bond-order potential for describing the tungsten defects to be used in molecular dynamics simulations. The developed potential was utilized in determination of the defect clustering and annihilation properties. These results were further employed in binary collision and rate theory calculations to determine the evolution of large defect clusters that trap hydrogen in the course of implantation. The computational results for the defect and trapped hydrogen concentrations were successfully compared with the experimental results. With the aforedescribed multiscale analysis the experimental results within this thesis and found in the literature were explained both quantitatively and qualitatively.

Rot bilong mipela

In my master's thesis I explore the political significance of logging in Papua New Guinea (PNG). In commercial logging the post-colonial state of PNG, its local communities, transnational companies and non-governmental organizations come interestingly together. The central research questions are what forms of political awareness and mobilization does commercial logging bring up in the small scale communities and how – if at all – does logging change the relationship between these communities and the state of PNG. The thesis is based on three months of ethnographic fieldwork conducted in 2007 in a village located in the East New Britain province of PNG. The village, inhabited mainly by the Mengen people, was an interesting case, because logging operations had been conducted in the area with the permission of the people, while on the other hand some villagers had formed a conservation association of their own. Parliamentary elections were also held in PNG during the time of my fieldwork. During my stay in the village I took part in the village life and conducted interviews. In addition to this, much of my material is based on informal discussions with people. On my way to and from the village I also interviewed several Papua New Guinean NGO-workers in the national and provincial capitals. In my thesis I show that environmental conservation in the village is part of a larger attempt to protect local autonomy, culture and the environment, i.e. it is a ”localistic” movement. Locals supporting conservation, as well as those supporting logging, take actively part in national parliamentary as well as local level politics. In my thesis I have attempted to unpack the notion of ”local” by examining internal power relations of the community and describing various lines of thought and opinions that base on local cultural values. Along with this, commercial logging seems also to elicit the role of the state in two-fold way in East New Britain. On the one hand, the government seeks to use logging roads built by logging companies as the basis of its own national infrastructure, even though the company roads are often of manifestably poor quality and short-lived. On the other hand, problems caused by logging, such as land disputes, create a need among local communities for the state and its services. Central themes in my thesis are the local values invested in the environment, as well as the ways in which the locals produce their environment both conceptually as well as physically. As subsistence farmers the locals depend economically on the condition of their environment. However, the value of the environment goes beyond economical questions. For example, the environment holds proof of the history of the community. Conversely, also the state and companies attempt to conceptualize, modify and administer the environment. This is done through processes such as mapping and road building, both crucial political questions in East New Britain. Here the anthropological discussion about space and place, as well as political geography are central. The diverse ways of conceptualizing the environment, as well as logging, cause often disputes about the ownership of land areas. Because of this I discuss local ways of holding the land communally, as well as PNG's land legislation and ways of dispute management. Land tenure and disputes are political questions that the locals have to deal with and in some cases these questions also create a need for the judiciary system of the state. The disputes affect also political activity, which I discuss at some length in my thesis as well. Interestingly, the locals, regardless of their political views and affiliations, establish transnational connections ranging from NGOs to government departments and multinational companies.

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

High precision Mg isotope measurements of meteoritic samples by secondary ion mass spectrometry

The possibility of establishing an accurate relative chronology of the early solar system events based on the decay of short-lived Al-26 to Mg-26 (half-life of 0.72 Myr) depends on the level of homogeneity (or heterogeneity) of Al-26 and Mg isotopes. However, this level is difficult. to constrain precisely because of the very high precision needed for the determination of isotopic ratios, typically of +/- 5 ppm. In this study, we report for the first time a detailed analytical protocol developed for high precision in situ Mg isotopic measurements ((25)mg/(24)mg and (26)mg/Mg-24 ratios, as well as Mg-26 excess) by MC-SIMS. As the data reduction process is critical for both accuracy and precision of the final isotopic results, factors such as the Faraday cup (FC) background drift and matrix effects on instrumental fractionation have been investigated. Indeed these instrumental effects impacting the measured Mg-isotope ratios can be as large or larger than the variations we are looking for to constrain the initial distribution of Al-26 and Mg isotopes in the early solar system. Our results show that they definitely are limiting factors regarding the precision of Mg isotopic compositions, and that an under- or over-correction of both FC background instabilities and instrumental isotopic fractionation leads to important bias on delta Mg-25, delta(26)mg and Delta Mg-26 values (for example, olivines not corrected for FC background drifts display Delta Mg-26 values that can differ by as much as 10 ppm from the truly corrected value). The new data reduction process described here can then be applied to meteoritic samples (components of chondritic meteorites for instance) to accurately establish their relative chronology of formation.

Steric and Electronic Interactions Controlling the cis/trans Isomer Equilibrium at X-Pro Tertiary Amide Motifs in Solution

A systematic understanding of the noncovalent interactions that influence the structures of the cis conformers and the equilibrium between the cis and the trans conformers, of the X-Pro tertiary amide motifs, is presented based on analyses of H-1-, C-13-NMR and FTIR absorption spectra of two sets of homologous peptides, X-Pro-Aib-OMe and X-Pro-NH-Me (where X is acetyl, propionyl, isobutyryl and pivaloyl), in solvents of varying polarities. First, this work shows that the cis conformers of any X-Pro tertiary amide motif, including Piv-Pro, are accessible in the new motifs X-Pro-Aib-OMe, in solution. These conformers are uniquely observable by FTIR spectroscopy at ambient temperatures and by NMR spectroscopy from temperatures as high as 273 K. This is made possible by the persistent presence of n(i-1i)* interactions at Aib, which also influence the disappearance of steric effects at these cis X-Pro rotamers. Second, contrary to conventional understanding, the energy contribution of steric effects to the cis/trans equilibrium at the X-Pro motifs is found to be nonvariant (0.54 +/- 0.02 kcal/mol) with increase in steric bulk on the X group. Third, the current studies provide direct evidence for the weak intramolecular interactions namely the n(i-1i)*, the N-Pro center dot center dot center dot Hi+1 (C(5)a), and the C-7 hydrogen bond that operate and influence the structures, stabilities, and dynamics between different conformational states of X-Pro tertiary amide motifs. NMR and IR spectral data suggest that the cis conformers of X-Pro motifs are ensembles of short-lived rotamers about the C-X-N-Pro bond. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 66-77, 2014.

Molecular Dynamics Perspective on the Protein Thermal Stability: A Case Study Using SAICAR Synthetase

The enzyme SAICAR synthetase ligates aspartate with CAIR (5'-phosphoribosyl-4-carboxy-5-aminoimidazole) forming SAICAR (5-amino-4-imidazole-N-succinocarboxamide ribonucleotide) in the presence of ATP. In continuation with our previous study on the thermostability of this enzyme in hyper-/thermophiles based on the structural aspects, here, we present the dynamic aspects that differentiate the mesophilic (E. coli, E. chaffeensis), thermophilic (G. kaustophilus), and hyperthermophilic (M. jannaschii, P. horikoshii) SAICAR synthetases by carrying out a total of 11 simulations. The five functional dimers from the above organisms were simulated using molecular dynamics for a period of 50 ns each at 300 K, 363 K, and an additional simulation at 333 K for the thermophilic protein. The basic features like root-mean-square deviations, root-mean-square fluctuations, surface accessibility, and radius of gyration revealed the instability of mesophiles at 363 K. Mean square displacements establish the reduced flexibility of hyper-/thermophiles at all temperatures. At the simulations time scale considered here, the long-distance networks are considerably affected in mesophilic structures at 363 K. In mesophiles, a comparatively higher number of short-lived (having less percent existence time) C alpha, hydrogen bonds, hydrophobic interactions are formed, and long-lived (with higher percentage existence time) contacts are lost. The number of time-averaged salt-bridges is at least 2-fold higher in hyperthermophiles at 363 K. The change in surface accessibility of salt-bridges at 363 K from 300 K is nearly doubled in mesophilic protein compared to proteins from other temperature classes.

A Comparative Study of Early Afterdepolarization-Mediated Fibrillation in Two Mathematical Models for Human Ventricular Cells

Early afterdepolarizations (EADs), which are abnormal oscillations of the membrane potential at the plateau phase of an action potential, are implicated in the development of cardiac arrhythmias like Torsade de Pointes. We carry out extensive numerical simulations of the TP06 and ORd mathematical models for human ventricular cells with EADs. We investigate the different regimes in both these models, namely, the parameter regimes where they exhibit (1) a normal action potential (AP) with no EADs, (2) an AP with EADs, and (3) an AP with EADs that does not go back to the resting potential. We also study the dependence of EADs on the rate of at which we pace a cell, with the specific goal of elucidating EADs that are induced by slow or fast rate pacing. In our simulations in two-and three-dimensional domains, in the presence of EADs, we find the following wave types: (A) waves driven by the fast sodium current and the L-type calcium current (Na-Ca-mediated waves); (B) waves driven only by the L-type calcium current (Ca-mediated waves); (C) phase waves, which are pseudo-travelling waves. Furthermore, we compare the wave patterns of the various wave-types (Na-Ca-mediated, Ca-mediated, and phase waves) in both these models. We find that the two models produce qualitatively similar results in terms of exhibiting Na-Ca-mediated wave patterns that are more chaotic than those for the Ca-mediated and phase waves. However, there are quantitative differences in the wave patterns of each wave type. The Na-Ca-mediated waves in the ORd model show short-lived spirals but the TP06 model does not. The TP06 model supports more Ca-mediated spirals than those in the ORd model, and the TP06 model exhibits more phase-wave patterns than does the ORd model.

Impact of lifetime control on the threshold of quantum dot lasers

Despite significant improvements in their properties as emitters, colloidal quantum dots have not had much success in emerging as suitable materials for laser applications. Gain in most colloidal systems is short lived, and needs to compete with biexcitonic decay. This has necessitated the use of short pulsed lasers to pump quantum dots to thresholds needed for amplified spontaneous emission or lasing. Continuous wave pumping of gain that is possible in some inorganic phosphors has therefore remained a very distant possibility for quantum dots. Here, we demonstrate that trilayer heterostructures could provide optimal conditions for demonstration of continuous wave lasing in colloidal materials. The design considerations for these materials are discussed in terms of a kinetic model. The electronic structure of the proposed dot architectures is modeled within effective mass theory.

Population characteristics of gulf menhaden, Brevoortia patronus

The status of the Gulf menhaden, Brevoortia patronus, fishery was assessed with purse-seine landings data from 1946 to 1997 and port sampling data from 1964 to 1997. These data were analyzed to determine growth rates, biological reference points for fi shing mortality from yield per recruit and maximum spawning potential analyses, spawner-recruit relationships, and maximum sustainable yield (MSY). The separable virtual population approach was used for the period 1976–97 (augmented by earlier analyses for 1964–75) to obtain point estimates of stock size, recruits to age 1, spawning stock size, and fishing mortality rates. Exploitation rates for age-1 fi sh ranged between 11% and 45%, for age-2 fi sh between 32% and 72%, and for age-3 fi sh between 32% and 76%. Biological reference points from yield per recruit (F0.1: 1.5–2.5/yr) and spawning potential ratio (F20: 1.3–1.9/yr and F30: 0.8–1.2/yr) were obtained for comparison with recent estimates of F (0.6–0.8/yr). Recent spawning stock estimates (as biomass or eggs) are above the long-term average, while recent recruits to age 1 are comparable to the long-term average. Parameters from Ricker-type spawner-recruit relations were estimated, although considerable unexplained variability remained. Recent survival to age-1 recruitment has generally been below that expected based on the Ricker spawner-recruit relation. Estimates of long-term MSY from PRODFIT and ASPIC estimation of production model ranged between 717,000 t and 753,000 t, respectively. Declines in landings between 1988 and 1992 raised concerns about the status of the Gulf menhaden stock. Landings have fl uctuated without trend since 1992, averaging about 571,000 t. However, Gulf menhaden are short lived and highly fecund. Thus, variation in recruitment to age 1, largely mediated by environmental conditions, infl uences fi shing success over the next two years (as age-1 and age-2 fi sh). Comparisons of recent estimates of fi shing mortality to biological reference points do not suggest overfishing. (PDF file contains 22 pages.)

Population Characteristics of Gulf Menhaden, Brevoortia patronus

The status of the gulf menhaden, Brevoortia patronus, fishery was assessed with purseseine landing data from 1946 to 1992 and port sampling data from 1964 to 1992. These data were analyzed to determine growth rates, biological reference points for fishing mortality from yield per recruit and maximum spawning potential analyses, spawner-recruit relationships, and maximum sustainable yield (MSY). Virtual population approaches were used to obtain point estimates of stock size, recruits to age I, spawning stock size, and fishing mortality rates. Exploitation rates ranged between 14% and 45% for age-1 fish, between 30% and 72% for age-2 fish, and between 36% and 71% for age-3 fish. Biological reference points from yield per recruit (FO. I: 0.7-0.9 yr-1) and maximum spawning potential (F20: 1.62.9 yr-l and F30: 1.0-2.1 yr-1) were obtained for comparison with recent estimates of F (0.4-0.8 yr-l). Parameters from Ricker-type spawner-recruit relations were estimated, although considerable unexplained variability remained. Estimates of long-term MSY from fits of the generalized production model ranged between 664,000 metric tons (t) and 897,000 t. Declines in landings since 1988 have raised concerns about the status of the gulf menhaden stock. However, gulf menhaden are short lived and highly fecund. Thus, variation in recruitment to age 1 largely mediated by environmental conditions influences fishing success over the next two years (as age-1 and age-2 fish). Comparisons of recent estimates of fishing mortality to biological reference points do not suggest overfishing. (PDF file contains 26 pages.)

Population dynamics of the anchoveta, Cetengraulis mysticetus, in the Gulf of Panama, as determined by tagging experiments

ENGLISH: The anchoveta is the major constituent of the important bait and reduction fisheries of the Gulf of Panama. It is a short-lived species, the great majority of the catch consisting of fish in their first year of life. Fish for reduction are caught chiefly in the Isla Verde area, between Punta Chame and the entrance of the Panama Canal. In 1960 and 1961 anchovetas were tagged with metal internal tags and released in the major areas of occurrence of this species. The tags were recovered from the meal in the reduction plants with magnets. From the 53,380 fish tagged in 1960, 745 tags were returned during the 1960 season, 246 during the 1961 season, and 8 during the 1962 season. From the 113,202 tagged in 1961, 373 tags were returned during the 1961 season and 48 during the 1962 season. Complete catch statistics are available, and length-frequency and length-weight data were used to convert these from pounds to numbers of fish of each year class. The annual survival rate for the fish of the 1959 year class in the Isla Verde area was estimated to be 0.086 by the Chapman-Robson method, 0.102 by the year-class method, and 0.088 by the Jackson positive method. The first method is considered to give the best estimate. Six estimates of the population of fish of the 1959 year class in the Isla Verde area were obtained from the sample tag ratios of six experiments conducted in that area in 1960. The estimates differed due to the temporal decrease in the population, but the downward trend corresponded fairly well to what was expected from the total annual mortality rate. It was estimated that the population of 1959-year class fish was about 818 million on March 8, 1960, and about 70 million on March 8, 1961. As the population of anchovetas decreases during the season the effort increases sufficiently that the catch remains roughly constant. This is described as the "constant absolute catch" type fishery. Of the original population of fish in the Isla Verde area at the beginning of the 1960 season, about 11 per cent were caught and 81 per cent died of natural causes. Evaluation of growth and mortality data demonstrated that beginning the fishery for the youngest age group later than March 8 (the date it began in 1960) would reduce the yield per recruit, while increasing the fishing effort would greatly increase it. Further, it is believed unlikely that increases in the catch in the Isla Verde area alone would noticeably decrease the number of recruits to that area. Therefore there is no foreseeable need for regulation of the fishery. SPANISH: El principal constituyente de la importante pesquería para carnada y para reducción en el Golfo de Panamá es la anchoveta. Es una especie de vida corta cuya pesca, en su mayor parte, está constituida por peces que se encuentran en su primer año de vida. Para la industria de reducción los peces son capturados principalmente en el área de Isla Verde, entre Punta Chame y la entrada del Canal de Panamá. En 1960 y 1961 las anchovetas fueron marcadas con marcas metálicas internas y liberadas en las áreas más importantes en que se encuentra esta especie. Las marcas fueron recobradas de la harina en las plantas de reducción por medio de magnetos. De los 53,380 peces marcados en 1960, fueron devueltas 745 marcas durante la temporada pesquera de 1960, 246 durante la de 1961, y 8 durante la de 1962. De los 113,202 marcados en 1961, 373 marcas fueron devueltas durante la temporada pesquera de 1961 y 48 durante la de 1962. Se dispone de estadísticas completas de captura, y los datos de frecuencia-longitud y de longitud-peso fueron usados para convertir éstos de libras a números de peces de cada clase anual. La tasa anual de supervivencia correspondiente a la clase anual de 1959 en el área de Isla Verde estimó en 0.086 por medio del método Chapman-Robson; en 0.102 por método de la clase anual; y en 0.088 por el método positivo de Jackson. Se considera que el primer método dé la mejor estimación. Seis estimaciones de la población de peces de la clase anual 1959 en el área de Isla Verde fueron obtenidas según la proporción de marcas halladas en las muestras correspondientes a seis experimentos efectuados en aquella área en 1960. Las estimaciones variaron debido a la disminución temporal de la población, pero esta tendencia descendente correspondió bastante bien a lo que se esperaba según la tasa total de mortalidad anual. Se estimó que la población de peces de la clase anual de 1959 era de unos 818 millones el 8 de marzo de 1960, y aproximadamente de unos 70 millones el 8 de marzo de 1961. Conforme a que la población de anchovetas disminuye durante la temporada pesquera, el esfuerzo aumenta lo suficientemente como para que la pesca se mantenga más o menos constante. Este es el tipo de pesquería descrito como de "captura absoluta constante". De la población original de peces en el área de Isla Verde al comienzo de la temporada pesquera de 1960, cerca del 11 por ciento fue capturada y el 81 por ciento murió por causas naturales. La evaluación de los datos del crecimiento mortalidad demostraron que al comenzar la pesquería a explotar grupo de edad más joven en una fecha posterior al 8 de marzo (la fecha en que comenzó en 1960) se reduciría el rendimiento por recluta, mientras que al aumentar el esfuerzo de pesca lo aumentaría considerablemente. Más aún, se cree improbable que el aumento en la pesca en el área de Isla Verde de por sí disminuyera perceptiblemente el número de reclutas en esa área. En consecuencia no se prevé la necesidad de una reglamentación de la pesquería. (PDF contains 172 pages.)

Fischarten der westlichen Ostsee – Untersuchungen von 2000 bis 2002

Ichthyoplankton provides information on the species com-position in an area of investigation and leads to a better understanding of the entire fish community. Every year since 1993 May/June (from 2000 in April/May) an ichthyoplankton survey in ICES Subdivision 22 and 24 has been done to sample the plankton community in the western Baltic Sea. One objective was to acquire indicators of possible changes in the natural structures of the fish com-munity. The time series derived from the Bongo-Net samples is too short to show a trend in larval densities. Up to now samples in the western Baltic Sea yielded only low mean densities. According to the reproductive biology the fish species were divided in three major groups: •Fish species with a long developmental phase in the plankton community •Small short lived species with benthic eggs and a reduced planktonic phase •Guests without local spawning populations. Species were identified, which were absent in the plankton of the western Baltic Sea in the 1960s and 1970s.

Fischbestände der Ostsee, ihre Entwicklung seit 1970 und Schlussfolgerungen für ihre fischereiliche Nutzung - Teil 3: Sprotte

The sprat of the Baltic Sea is not as short-lived as inother Seas probably because fish predator species arerestricted mainly on cod and salmon. Sea bird popula-tions are much smaller and marine mammals are rare inthe Baltic Sea. The sprat stock biomass is fluctuatingstrongly. The fluctuation is mainly influenced by thestock recruitment and is also dependent on the strengthof the cod stock. After a strong decrease during the1980ies sprat catches increased again from 1992 onwardsand reached a peak with over half a million tonnes in 1997. At about the same time the character of the BalticSea sprat fishery changed from catches mainly for hu-man consumption to catches mainly for industrial pur-poses initiated by the fishery of Sweden. The recentrecord high catches of sprat have been possible only dueto the low level of the cod stock of the main Baltic SeaBasins over some years. A sprat fishery on such a highcatch level might cause conflicts with a recovering codstock in future.

Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Bird migration and the spread of Crustacea. [Translation from: Verhandlungen der Deutschen Zoologischen Gesellschaft 27, 311-316, 1963.]

The passive spread of a high percentage of freshwater organisms is one of the most important requirements in short-lived and insular communities for species to attai n and survive - and consequently to balance the lack of a topographical continuity of most inland waters. Unfortunately hardly anything is known about the amounts of seed material typical for any lake into which it is carried. The causes of passive dissemination - wind, water and animals as well as man - are confirmed by many examples. It has been assumed now for at least a hundered years that , among animals, birds play a prominent role, although also disappointingly few facts are at hand. The passage and spread through birds' intestines has up to now been supported only by some limited data. This paper reports on experimental research where the eggs of Daphnia magna, Triops cancriformis, Artemia salina, Diaptomus spinosus and Cypris pubera were introduced by means of gelatine capsules into the oesophagus of a drake. The bird's excrements were inspected under a microscope for eggs and resting stages, and these were transferred into corresponding cultures.