969 resultados para country rock instantaneous point source solld-llquid interface
Market Prices and Food Aid Local and Regional Procurement and Distribution: A Multi-Country Analysis
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To date, no research has rigorously addressed the concern that local and regional procurement (LRP) of food aid could affect food prices and food price volatility in food aid source and recipient countries. We assemble spatially and temporally disaggregated data and estimate the relationship between food prices and their volatility and local food aid procurement and distribution across seven countries for several commodities. In most cases, LRP activities have no statistically significant relationship with either local price levels or food price volatility. The few exceptions underscore the importance of market monitoring. (C) 2013 Elsevier Ltd. All rights reserved.
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The posterior circulation Acute Stroke Prognosis Early CT Score (pc-ASPECTS) quantifies the extent of early ischemic changes in the posterior circulation with a 10-point grading system. We hypothesized that pc-ASPECTS applied to CT angiography source images predicts functional outcome of patients in the Basilar Artery International Cooperation Study (BASICS).
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This paper presents a novel mock circulation for the evaluation of ventricular assist devices (VADs), which is based on a hardware-in-the-loop concept. A numerical model of the human blood circulation runs in real time and computes instantaneous pressure, volume, and flow rate values. The VAD to be tested is connected to a numerical-hydraulic interface, which allows the interaction between the VAD and the numerical model of the circulation. The numerical-hydraulic interface consists of two pressure-controlled reservoirs, which apply the computed pressure values from the model to the VAD, and a flow probe to feed the resulting VAD flow rate back to the model. Experimental results are provided to show the proper interaction between a numerical model of the circulation and a mixed-flow blood pump.
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International migration has increased rapidly in the Czech Republic, with more than 150,000 legally registered foreign residents at the end of 1996. A large proportion of these are in Prague - 35% of the total in December 1996. The aim of this project was to enrich the fund of information concerning the "environment", reasons and "mechanisms" behind immigration to the Czech Republic. Mr. Drbohlav looked first at the empirical situation and on this basis set out to test certain well-known migration theories. He focused on four main areas: 1) a detailed description and explanation of the stock of foreign citizens legally settled in Czech territory, concentrating particularly on "economic" migrants; 2) a questionnaire survey targeting a total of 192 Ukrainian workers (98 in the fall 1995 and 94 in the fall 1996) working in Prague or its vicinity; 3) a second questionnaire survey of 40 "western" firms (20 in 1996 and 20 in 1997) operating out of Prague; 4) an opinion poll on how the Czech population reacts to foreign workers in the CR. Over 80% of economic immigrants at the end of 1996 were from European countries, 16% from Asia and under 2% from North America. The largest single nationalities were Ukrainians, Slovaks, Vietnamese and Poles. There has been a huge increase in the Ukrainian immigrant community over both space (by region) and time (a ten-fold increase since 1993), and at 40,000 persons this represents one third of all legal immigrants. Indications are that many more live and work there illegally. Young males with low educational/skills levels predominate, in contrast with the more heterogeneous immigration from the "West". The primary reason for this migration is the higher wages in the Czech Republic. In 1994 the relative figures of GDP adjusted for parity of purchasing power were US$ 8,095 for the Czech Republic versus US$ 3,330 for the Ukraine as a whole and US$ 1,600 for the Zakarpatye region from which 49% of the respondents in the survey came. On an individual level, the average Czech wage is about US$ 330 per month, while 50% of the Ukrainian respondents put their last monthly wage before leaving for the Czech Republic at under US$ 27. The very low level of unemployment in the latter country (fluctuating around 4%) was also mentioned as an important factor. Migration was seen as a way of diversifying the family's source of income and 49% of the respondents had made their plans together with partners or close relatives, while 45% regularly send remittances to Ukraine (94% do so through friends or relatives). Looking at Ukrainian migration from the point of view of the dual market theory, these migrants' type and conditions of work, work load and earnings were all significantly worse than in the primary sector, which employs well educated people and offers them good earnings, job security and benefits. 53% of respondents were working and/or staying in the Czech Republic illegally at the time of the research, 73% worked as unqualified, unskilled workers or auxiliary workers, 62% worked more than 12 hours a day, and 40% evaluated their working conditions as hard. 51% had no days off, earnings were low in relation to the number of hours worked. and 85% said that their earnings did not increase over time. Nearly half the workers were recruited in Ukraine and only 4% expressed a desire to stay in the Czech Republic. Network theories were also borne out to some extent as 33% of immigrants came together with friends from the same village, town or region in Ukraine. The number who have relatives working in the Czech Republic is rising, and many wish to invite relatives or children to visit them. The presence of organisations which organised cross-border migration, including some which resort to organising illegal documents, also gives some support for the institutional theory. Mr. Drbohlav found that all the migration theories considered offered some insights on the situation, but that none was sufficient to explain it all. He also points out parallels with many other regions of the world, including Central America, South and North America, Melanesia, Indonesia, East Africa, India, the Middle East and Russia. For the survey of foreign and international firms, those chosen were largely from countries represented by more than one company and were mainly active in market services such as financial and trade services, marketing and consulting. While 48% of the firms had more than 10,000 employees spread through many countries, more than two thirds had fewer than 50 employees in the Czech Republic. Czechs formed 80% plus of general staff in these firms although not more than 50% of senior management, and very few other "easterners" were employed. All companies absolutely denied employing people illegally. The average monthly wage of Czech staff was US$ 850, with that of top managers from the firm's "mother country" being US$ 6,350 and that of other western managers US$ 3,410. The foreign staff were generally highly mobile and were rarely accompanied by their families. Most saw their time in the Czech Republic as positive for their careers but very few had any intention of remaining there. Factors in the local situation which were evaluated positively included market opportunities, the economic and political environment, the quality of technical and managerial staff, and cheap labour and low production costs. In contrast, the level of appropriate business ethics and conduct, the attitude of local and regional authorities, environmental production conditions, the legal environment and financial markets and fiscal policy were rated very low. In the final section of his work Mr. Drbohlav looked at the opinions expressed by the local Czech population in a poll carried out at the beginning of 1997. This confirmed that international labour migration has become visible in this country, with 43% of respondents knowing at least one foreigner employed by a Czech firm in this country. Perception differ according to the region from which the workers come and those from "the West" are preferred to those coming from further east. 49% saw their attitude towards the former as friendly but only 20% felt thus towards the latter. Overall, attitudes towards migrant workers is neutral, although 38% said that such workers should not have the same rights as Czech citizens. Sympathy towards foreign workers tends to increase with education and the standard of living, and the relatively positive attitudes towards foreigners in the South Bohemia region contradicted the frequent belief that a lack of experience of international migration lowers positive perceptions of it.
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Mr. Pechersky set out to examine a specific feature of the employer-employee relationship in Russian business organisations. He wanted to study to what extent the so-called "moral hazard" is being solved (if it is being solved at all), whether there is a relationship between pay and performance, and whether there is a correlation between economic theory and Russian reality. Finally, he set out to construct a model of the Russian economy that better reflects the way it actually functions than do certain other well-known models (for example models of incentive compensation, the Shapiro-Stiglitz model etc.). His report was presented to the RSS in the form of a series of manuscripts in English and Russian, and on disc, with many tables and graphs. He begins by pointing out the different examples of randomness that exist in the relationship between employee and employer. Firstly, results are frequently affected by circumstances outside the employee's control that have nothing to do with how intelligently, honestly, and diligently the employee has worked. When rewards are based on results, uncontrollable randomness in the employee's output induces randomness in their incomes. A second source of randomness involves the outside events that are beyond the control of the employee that may affect his or her ability to perform as contracted. A third source of randomness arises when the performance itself (rather than the result) is measured, and the performance evaluation procedures include random or subjective elements. Mr. Pechersky's study shows that in Russia the third source of randomness plays an important role. Moreover, he points out that employer-employee relationships in Russia are sometimes opposite to those in the West. Drawing on game theory, he characterises the Western system as follows. The two players are the principal and the agent, who are usually representative individuals. The principal hires an agent to perform a task, and the agent acquires an information advantage concerning his actions or the outside world at some point in the game, i.e. it is assumed that the employee is better informed. In Russia, on the other hand, incentive contracts are typically negotiated in situations in which the employer has the information advantage concerning outcome. Mr. Pechersky schematises it thus. Compensation (the wage) is W and consists of a base amount, plus a portion that varies with the outcome, x. So W = a + bx, where b is used to measure the intensity of the incentives provided to the employee. This means that one contract will be said to provide stronger incentives than another if it specifies a higher value for b. This is the incentive contract as it operates in the West. The key feature distinguishing the Russian example is that x is observed by the employer but is not observed by the employee. So the employer promises to pay in accordance with an incentive scheme, but since the outcome is not observable by the employee the contract cannot be enforced, and the question arises: is there any incentive for the employer to fulfil his or her promises? Mr. Pechersky considers two simple models of employer-employee relationships displaying the above type of information symmetry. In a static framework the obtained result is somewhat surprising: at the Nash equilibrium the employer pays nothing, even though his objective function contains a quadratic term reflecting negative consequences for the employer if the actual level of compensation deviates from the expectations of the employee. This can lead, for example, to labour turnover, or the expenses resulting from a bad reputation. In a dynamic framework, the conclusion can be formulated as follows: the higher the discount factor, the higher the incentive for the employer to be honest in his/her relationships with the employee. If the discount factor is taken to be a parameter reflecting the degree of (un)certainty (the higher the degree of uncertainty is, the lower is the discount factor), we can conclude that the answer to the formulated question depends on the stability of the political, social and economic situation in a country. Mr. Pechersky believes that the strength of a market system with private property lies not just in its providing the information needed to compute an efficient allocation of resources in an efficient manner. At least equally important is the manner in which it accepts individually self-interested behaviour, but then channels this behaviour in desired directions. People do not have to be cajoled, artificially induced, or forced to do their parts in a well-functioning market system. Instead, they are simply left to pursue their own objectives as they see fit. Under the right circumstances, people are led by Adam Smith's "invisible hand" of impersonal market forces to take the actions needed to achieve an efficient, co-ordinated pattern of choices. The problem is that, as Mr. Pechersky sees it, there is no reason to believe that the circumstances in Russia are right, and the invisible hand is doing its work properly. Political instability, social tension and other circumstances prevent it from doing so. Mr. Pechersky believes that the discount factor plays a crucial role in employer-employee relationships. Such relationships can be considered satisfactory from a normative point of view, only in those cases where the discount factor is sufficiently large. Unfortunately, in modern Russia the evidence points to the typical discount factor being relatively small. This fact can be explained as a manifestation of aversion to risk of economic agents. Mr. Pechersky hopes that when political stabilisation occurs, the discount factors of economic agents will increase, and the agent's behaviour will be explicable in terms of more traditional models.
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The AEGISS (Ascertainment and Enhancement of Gastrointestinal Infection Surveillance and Statistics) project aims to use spatio-temporal statistical methods to identify anomalies in the space-time distribution of non-specific, gastrointestinal infections in the UK, using the Southampton area in southern England as a test-case. In this paper, we use the AEGISS project to illustrate how spatio-temporal point process methodology can be used in the development of a rapid-response, spatial surveillance system. Current surveillance of gastroenteric disease in the UK relies on general practitioners reporting cases of suspected food-poisoning through a statutory notification scheme, voluntary laboratory reports of the isolation of gastrointestinal pathogens and standard reports of general outbreaks of infectious intestinal disease by public health and environmental health authorities. However, most statutory notifications are made only after a laboratory reports the isolation of a gastrointestinal pathogen. As a result, detection is delayed and the ability to react to an emerging outbreak is reduced. For more detailed discussion, see Diggle et al. (2003). A new and potentially valuable source of data on the incidence of non-specific gastro-enteric infections in the UK is NHS Direct, a 24-hour phone-in clinical advice service. NHS Direct data are less likely than reports by general practitioners to suffer from spatially and temporally localized inconsistencies in reporting rates. Also, reporting delays by patients are likely to be reduced, as no appointments are needed. Against this, NHS Direct data sacrifice specificity. Each call to NHS Direct is classified only according to the general pattern of reported symptoms (Cooper et al, 2003). The current paper focuses on the use of spatio-temporal statistical analysis for early detection of unexplained variation in the spatio-temporal incidence of non-specific gastroenteric symptoms, as reported to NHS Direct. Section 2 describes our statistical formulation of this problem, the nature of the available data and our approach to predictive inference. Section 3 describes the stochastic model. Section 4 gives the results of fitting the model to NHS Direct data. Section 5 shows how the model is used for spatio-temporal prediction. The paper concludes with a short discussion.
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The Michigan Department of Transportation is evaluating upgrading their portion of the Wolverine Line between Chicago and Detroit to accommodate high speed rail. This will entail upgrading the track to allow trains to run at speeds in excess of 110 miles per hour (mph). An important component of this upgrade will be to assess the requirement for ballast material for high speed rail. In the event that the existing ballast materials do not meet specifications for higher speed train, additional ballast will be required. The purpose of this study, therefore, is to investigate the current MDOT railroad ballast quality specifications and compare them to both the national and international specifications for use on high speed rail lines. The study found that while MDOT has quality specifications for railroad ballast it does not have any for high speed rail. In addition, the American Railway Engineering and Maintenance-of-Way Association (AREMA), while also having specifications for railroad ballast, does not have specific specifications for high speed rail lines. The AREMA aggregate specifications for ballast include the following tests: (1) LA Abrasion, (2) Percent Moisture Absorption, (3) Flat and Elongated Particles, (4) Sulfate Soundness test. Internationally, some countries do require a highly standard for high speed rail such as the Los Angeles (LA) Abrasion test, which is uses a higher standard performance and the Micro Duval test, which is used to determine the maximum speed that a high speed can operate at. Since there are no existing MDOT ballast specification for high speed rail, it is assumed that aggregate ballast specifications for the Wolverine Line will use the higher international specifications. The Wolverine line, however, is located in southern Michigan is a region of sedimentary rocks which generally do not meet the existing MDOT ballast specifications. The investigation found that there were only 12 quarries in the Michigan that meet the MDOT specification. Of these 12 quarries, six were igneous or metamorphic rock quarries, while six were carbonate quarries. Of the six carbonate quarries four were locate in the Lower Peninsula and two in the Upper Peninsula. Two of the carbonate quarries were located in near proximity to the Wolverine Line, while the remaining quarries were at a significant haulage distance. In either case, the cost of haulage becomes an important consideration. In this regard, four of the quarries were located with lake terminals allowing water transportation to down state ports. The Upper Peninsula also has a significant amount of metal based mining in both igneous and metamorphic rock that generate significant amount of waste rock that could be used as a ballast material. The main drawback, however, is the distance to the Wolverine rail line. One potential source is the Cliffs Natural Resources that operates two large surface mines in the Marquette area with rail and water transportation to both Lake Superior and Lake Michigan. Both mines mine rock with a very high compressive strength far in excess of most ballast materials used in the United States and would make an excellent ballast materials. Discussions with Cliffs, however, indicated that due to environmental concerns that they would most likely not be interested in producing a ballast material. In the United States carbonate aggregates, while used for ballast, many times don't meet the ballast specifications in addition to the problem of particle degradation that can lead to fouling and cementation issues. Thus, many carbonate aggregate quarries in close proximity to railroads are not used. Since Michigan has a significant amount of carbonate quarries, the research also investigated using the dynamic properties of aggregate as a possible additional test for aggregate ballast quality. The dynamic strength of a material can be assessed using a split Hopkinson Pressure Bar (SHPB). The SHPB has been traditionally used to assess the dynamic properties of metal but over the past 20 years it is now being used to assess the dynamic properties of brittle materials such as ceramics and rock. In addition, the wear properties of metals have been related to their dynamic properties. Wear or breakdown of railroad ballast materials is one of the main problems with ballast material due to the dynamic loading generated by trains and which will be significantly higher for high speed rails. Previous research has indicated that the Port Inland quarry along Lake Michigan in the Southern Upper Peninsula has significant dynamic properties that might make it potentially useable as an aggregate for high speed rail. The dynamic strength testing conducted in this research indicate that the Port Inland limestone in fact has a dynamic strength close to igneous rocks and much higher than other carbonate rocks in the Great Lakes region. It is recommended that further research be conducted to investigate the Port Inland limestone as a high speed ballast material.
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One of the original ocean-bottom time-lapse seismic studies was performed at the Teal South oil field in the Gulf of Mexico during the late 1990s. This work reexamines some aspects of previous work using modern analysis techniques to provide improved quantitative interpretations. Using three-dimensional volume visualization of legacy data and the two phases of post-production time-lapse data, I provide additional insight into the fluid migration pathways and the pressure communication between different reservoirs, separated by faults. This work supports a conclusion from previous studies that production from one reservoir caused regional pressure decline that in turn resulted in liberation of gas from multiple surrounding unproduced reservoirs. I also provide an explanation for unusual time-lapse changes in amplitude-versus-offset (AVO) data related to the compaction of the producing reservoir which, in turn, changed an isotropic medium to an anisotropic medium. In the first part of this work, I examine regional changes in seismic response due to the production of oil and gas from one reservoir. The previous studies primarily used two post-production ocean-bottom surveys (Phase I and Phase II), and not the legacy streamer data, due to the unavailability of legacy prestack data and very different acquisition parameters. In order to incorporate the legacy data in the present study, all three poststack data sets were cross-equalized and examined using instantaneous amplitude and energy volumes. This approach appears quite effective and helps to suppress changes unrelated to production while emphasizing those large-amplitude changes that are related to production in this noisy (by current standards) suite of data. I examine the multiple data sets first by using the instantaneous amplitude and energy attributes, and then also examine specific apparent time-lapse changes through direct comparisons of seismic traces. In so doing, I identify time-delays that, when corrected for, indicate water encroachment at the base of the producing reservoir. I also identify specific sites of leakage from various unproduced reservoirs, the result of regional pressure blowdown as explained in previous studies; those earlier studies, however, were unable to identify direct evidence of fluid movement. Of particular interest is the identification of one site where oil apparently leaked from one reservoir into a new reservoir that did not originally contain oil, but was ideally suited as a trap for fluids leaking from the neighboring spill-point. With continued pressure drop, oil in the new reservoir increased as more oil entered into the reservoir and expanded, liberating gas from solution. Because of the limited volume available for oil and gas in that temporary trap, oil and gas also escaped from it into the surrounding formation. I also note that some of the reservoirs demonstrate time-lapse changes only in the gas cap and not in the oil zone, even though gas must be coming out of solution everywhere in the reservoir. This is explained by interplay between pore-fluid modulus reduction by gas saturation decrease and dry-frame modulus increase by frame stiffening. In the second part of this work, I examine various rock-physics models in an attempt to quantitatively account for frame-stiffening that results from reduced pore-fluid pressure in the producing reservoir, searching for a model that would predict the unusual AVO features observed in the time-lapse prestack and stacked data at Teal South. While several rock-physics models are successful at predicting the time-lapse response for initial production, most fail to match the observations for continued production between Phase I and Phase II. Because the reservoir was initially overpressured and unconsolidated, reservoir compaction was likely significant, and is probably accomplished largely by uniaxial strain in the vertical direction; this implies that an anisotropic model may be required. Using Waltons model for anisotropic unconsolidated sand, I successfully model the time-lapse changes for all phases of production. This observation may be of interest for application to other unconsolidated overpressured reservoirs under production.
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Open source and European antitrust laws: An analysis of copyleft and the prohibition of software license fees on the basis of art. 101 TFEU and the block exemptions Open source software and open source licenses (like the GNU GPL) are not only relevant for computer nerds or activists they are already business. They are for example the fundament of LINUX, the only real rival of MICROSOFTs WINDOWS-line in the field of operating systems for IBM PC compatibles. Art. 101 TFEU (like the identical predecessor art. 81 TEC) as part of the EU antitrust laws prohibits contract terms like price fixing and some forms of technology control. Are copyleft the viral effect, the cancer and the interdiction of software license fees in the cross hairs of this legal rule? On the other side the European Union has since 2004 a new Technology Transfer Block Exemption with software license agreements for the first time in its scope: a safe harbour and a dry place under a umbrella for open source software? After the introduction (A) with a description of open source software the following text analyses the system of the European Unions competition law respectivley antitrust law and the requirements of the block exemptions (B). Starting point of antitrust analysis are undertakings but who are the untertakings (C) in the field of widespread, independent developers as part of the bazar organization? To see how much open source has to fear from the law of the European Union, at the end the anti competitive and pro competitive effects of open source are totalized within the legal framework (D). The conclusion (E) shows: not nothing, but not much.
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kobilanzierung von Produktsystemen dient der Abschtzung ihrer Wirkung auf die Umwelt. Eine vollstndige Lebenswegbetrachtung erfordert auch die Einbeziehung intralogistischer Transportprozesse bzw. -mittel. Fr die Erstellung von kobilanzen wird i. d. R. ein Computerprogramm verwendet. Die Demoversionen dreier kommerzieller Softwarelsungen (SimaPro, GaBi und Umberto NXT LCA) und die Vollversion einer Open Source Software (openLCA) wurden aus softwareergonomischer Sicht analysiert. Hierzu erfolgte u. a. der Nachbau der bereitgestellten Tutorials bzw. die Modellierung eigener Produktsysteme. Im Rahmen der Analyse wurden die Punkte Entstehung, Verbreitung, Zielgruppe, Eignung der Tutorials, Erlernbarkeit, Grafische Benutzeroberflche, Individualisierbarkeit der Software, Umsetzung der Anforderungen aus den kobilanzierungsnormen, Notwendige Arbeitsschritte zur Erstellung einer kobilanz einer vergleichenden Betrachtung unterzogen. Der Beitrag beinhaltet eine Einfhrung in die wesentlichen Prinzipien der kobilanzierung und die Grundstze der Softwareergonomie. Diese werden zu softwareergonomischen Eigenschaften fr kobilanzsoftwarelsungen subsumiert. Anschlieend werden die Ergebnisse des Softwarevergleiches dargestellt. Abschlieend erfolgt eine Zusammenfassung der Erkenntnisse.
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The topic of this study was to evaluate state-dependent effects of diazepam on the frequency characteristics of 47-channel spontaneous EEG maps. A novel method, the FFT-Dipole-Approximation (Lehmann and Michel, 1990), was used to study effects on the strength and the topography of the maps in the different frequency bands. Map topography was characterized by the 3-dimensional location of the equivalent dipole source and map strength was defined as the spatial standard deviation (the Global Field Power) of the maps of each frequency point. The Global Field Power can be considered as a measure of the amount of energy produced by the system, while the source location gives an estimate of the center of gravity of all sources in the brain that were active at a certain frequency. State-dependency was studied by evaluating the drug effects before and after a continuous performance task of 25 min duration. Clear interactions between drug (diazepam vs. placebo) and time after drug intake (before and after the task) were found, especially in the inferior-superior location of the dipole sources. It supports the hypothesis that diazepam, like other drugs, has different effects on brain functions depending on the momentary functional state of the brain. In addition to the drug effects, clearly different source locations and Global Field Power were found for the different frequency bands, replicating earlier reports (Michel et al., 1992).
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The chloride and sulfate concentration profiles in a 260 m thick clay-rich Mesozoic sediment sequence have been analyzed by various methods. Chloride data generally indicate a good consistency between different methods if anion exclusion is accounted for in leaching tests. For sulfate, however, there is an apparent inconsistency between leaching data and those obtained from the other methods, which points to the dissolution of a sulfur-bearing mineral. Traces of diagenetic gypsum seem to be a likely source, but other sulfur minerals cannot be ruled out.
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The present study investigates life stories of established Italian workforce migrants living in the city of Berne, Switzerland, in regard to language related major life events (De Bot, 2007). These events are important in terms of changes happening in the linguistic setting during the life span and influence language development. In this sense, during the process of retirement, a new phase of life begins, which, amongst other things, has to be reorganized in relation to social contact and language use. One of my main questions is how the subjects handle the changes happening within and after the process of retirement in respect to the use of different languages and how this language related major life event is constructed and described by the migrants. One of these changes happens due to the fact that, after retirement, the social network at the workplace (the primary source of language input) can get (partially) lost and with it, the use of the local language. The fact that migrants living in Berne are confronted with diglossia (Standard German and Swissgerman), that the Canton of Berne is bilingual (German and French) and that the migrants' mother tongue (Italian) is one of the Swiss national languages, makes this question even more interesting. A second question will consider the influence of the fact that most of the subjects in question lived with the idea of return migration, but as shown in a previous study (Alter/Vieillesse/Anziani, NFP 32, 1999), only a third returned back while another third remained in the host country and the final third chose the commuting option. I will first examine these processes, changes and influences by using quantitative questionnaires in order to obtain general information on demographic data, the social situation, and a self-assessment of linguistic skills. Secondly, I will use qualitative interviews to get in-depth information of the subjects life stories and language biographies. The results of this project are meant to deliver insight into different aspects that have not been looked at in detail to this point: which factors of the life stories of Italian workforce migrants, who decided to remain in Switzerland after retirement, influence the linguistic changes in general and the ones happening around retirement in particular.
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The liquidvapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquidvapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquidvapor interface. XPS measurements over an experimental probe depth of 51 gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental 0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.
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The rate constants of simple electron transfer (ET) reactions in room temperature ionic liquids (ILs) available now are rather high, typically at the edge of experimental accuracy. To consider ET phenomena in these media in view of theory developed earlier for molecular solvents, it is crucial to provide quantitative comparison of experimental kinetic data for certain reactions. We report this comparison for ferrocene/ferrocenium reaction. The ET distance is fixed by Au surface modification by alkanethiol self-assembled monolayers, which were characterized by in situ scanning tunneling microscopy. The dependence of ln kapp on barrier thickness in the range of ca. 620 is linear, with a slope typical for the same plots in aqueous media. This result confirms diabatic mode of Fc oxidation at long distance. The data for shorter ET distances point to the adiabatic regime of ET at a bare gold surface, although more detailed computational studies are required to justify this conclusion.