Räumliche Verbreitung geogener Schwermetallgehalte in Böden des Taunus: Einfluss von periglazialer Deckschichtengenese

Während der Glazialphasen kam es in den europäischen Mittelgebirgen bedingt durch extensive solifluidale Massenbewegungen zur Bildung von Deckschichten. Diese Deckschichten repräsentieren eine Mischung verschiedener Substrate, wie anstehendes Ausgangsgestein, äolische Depositionen und lokale Erzgänge. Die räumliche Ausdehnung der Metallkontaminationen verursacht durch kleinräumige Erzgänge wird durch die periglaziale Solifluktion verstärkt. Das Ziel der vorliegenden Untersuchung war a) den Zusammenhang zwischen den Reliefeigenschaften und den Ausprägungen der solifluidalen Deckschichten und Böden aufzuklären, sowie b) mittels Spurenelementgehalte und Blei-Isotopen-Verhältnisse als Eingangsdaten für Mischungsmodelle die Beitrage der einzelnen Substrate zum Ausgangsmaterial der Bodenbildung zu identifizieren und quantifizieren und c) die räumliche Verteilung von Blei (Pb) in Deckschichten, die über Bleierzgänge gewandert sind, untersucht, die Transportweite des erzbürtigen Bleis berechnet und die kontrollierenden Faktoren der Transportweite bestimmt werden. Sechs Transekte im südöstlichen Rheinischen Schiefergebirge, einschließlich der durch periglaziale Solifluktion entwickelten Böden, wurden untersucht. Die bodenkundliche Geländeaufnahme erfolgte nach AG Boden (2005). O, A, B und C-Horizontproben wurden auf ihre Spurenelementgehalte und teilweise auf ihre 206Pb/207Pb-Isotopenverhältnisse analysiert. Die steuernden Faktoren der Verteilung und Eigenschaften periglazialer Deckschichten sind neben der Petrographie, Reliefeigenschaften wie Exposition, Hangneigung, Hangposition und Krümmung. Die Reliefanalyse zeigt geringmächtige Deckschichten in divergenten, konvexen Hangbereichen bei gleichzeitig hohem Skelettgehalt. In konvergent, konkaven Hangbereichen nimmt die Deckschichtenmächtigkeit deutlich zu, bei gleichzeitig zunehmendem Lösslehm- und abnehmendem Skelettgehalt. Abhängig von den Reliefeigenschaften und -positionen reichen die ausgeprägten Bodentypen von sauren Braunerden bis hin zu Pseudogley-Parabraunerden. Des Weiteren kommen holozäne Kolluvien in eher untypischen Reliefpositionen wie langgestreckten, kaum geneigten Hangbereichen oder Mittelhangbereichen vor. Außer für Pb bewegen sich die Spurenelementgehalte im Rahmen niedriger Hintergrundgehalte. Die Pb-Gehalte liegen zwischen 20-135 mg kg-1. Abnehmende Spurenelementgehalte und Isotopensignaturen (206Pb/207Pb-Isotopenverhältnisse) von Pb zeigen, dass nahezu kein Pb aus atmosphärischen Depositionen in die B-Horizonte verlagert wurde. Eine Hauptkomponentenanalyse (PCA) der Spurenelementgehalte hat vier Hauptsubstratquellen der untersuchten B-Horizonte identifiziert (Tonschiefer, Löss, Laacher-See-Tephra [LST] und lokale Pb-Erzgänge). Mittels 3-Komponenten-Mischungsmodell, das Tonschiefer, Löss und LST einschloss, konnten, bis auf 10 Ausreißer, die Spurenelementgehalte aller 120 B-Horizontproben erklärt werden. Der Massenbeitrag des Pb-Erzes zur Substratmischung liegt bei <0,1%. Die räumliche Pb-Verteilung zeigt Bereiche lokaler Pb-Gehaltsmaxima hangaufwärtiger Pb-Erzgänge. Mittels eines 206Pb/207Pb-Isotopenverhältnis-Mischungsmodells konnten 14 Bereiche erhöhter lokaler Pb-Gehaltsmaxima ausgewiesen werden, die 76-100% erzbürtigen Bleis enthalten. Mit Hilfe eines Geographischen Informationssystems wurden die Transportweiten des erzbürtigen Bleis mit 30 bis 110 m bestimmt. Die steuerenden Faktoren der Transportweite sind dabei die Schluffkonzentration und die Vertikalkrümmung. Diese Untersuchung zeigt, dass Reliefeigenschaften und Reliefposition einen entscheidenden Einfluss auf die Ausprägung der Deckschichten und Böden im europäischen Mittelgebirgsbereich haben. Mischungsmodelle in Kombination mit Spurenelementanalysen und Isotopenverhältnissen stellen ein wichtiges Werkzeug zur Bestimmung der Beiträge der einzelnen Glieder in Bodensubstratmischungen dar. Außerdem können lokale Bleierzgänge die natürlichen Pb-Gehalte in Böden, entwickelt in periglazialen Deckschichten der letzten Vereisungsphase (Würm), bis über 100 m Entfernung erhöhen.

Regio- e stereocontrollo nell'addizione viniloga di alchilidenossindoli a nitrostireni via organocatalisi.

The topic of this work is the simultaneous activation, promoted by 9-epi-NH2-DHQA-TU, of alkylideneoxindole and nistirene derivatives, respectively via base catalysis and hydrogen-bond catalysis. The chosen substrates, of high biological interest, are used as starting materials for a vinylogous Michael addition where we wish to control the stereochemistry of the two asymmetric carbons far away from the active site, respectively in γ and δ position. Due to the particular structure of the starting oxindoles, it is hereby presented the first variant of this reaction performed at its highest level of stereochemical complexity. It is possible as a matter of fact, to generate 24 isomers of the product. Specifically, given that the nucleophilic attack can occur from various, non equivalent regions of the starting molecule, our main goal was to achieve a complete regio- and stereocontrol of the reaction. We have verified that the reported organocatalyzed vinylogous reaction represents a valid integration of the metal-catalyzed one, since it affords highly stereochemically complex products in good to high yields and excellent optical purity.

Gespeicherte Ionen in der Paulfalle: Voruntersuchungen zur Lebensdauermessung des metastabilen 6D-3/2-Zustands des 226 Ra +, Speichereigenschaften von 138 Ba + und 28 N 2 + bei Variation des Puffergasdrucks

Auf Paulfallen basierende Experimente spielen eine wichtige Rolle in verschiedenen Bereichen der Physik, z.B. der Atomphysik zum Test theoretischer Modelle und der Massenspektroskopie. Die vorliegende Arbeit widmet sich beiden Themengebieten und gliedert sich entsprechend in zwei Teilbereiche: 1) Erdalkali-Ionen sind aufgrund ihrer Energieniveaus optimale Kandidaten für Laserspektroskopie-Experimente mit Ionenfallen und bestens geeignet, um mittels der spektroskopischen Daten die theoretischen Modelle zu testen. Lediglich für Ra+ fehlen bislang als einzigem Erdalkali-Ion diese Daten wie z.B. die Lebensdauern der metastabilen Niveaus. Diese wären auch von Interesse für bereits geplante Radium-Experimente zur Paritätsverletzung. Im ersten Teil dieser Arbeit wird der Aufbau eines Laser-Paulfallenexperiments zur Messung der Lebensdauer des 6D3/2 Zustands von 226Ra+ dokumentiert und es werden Testmessungen mit 138Ba+ vorgestellt. 2) Für die Verwendung der Paulfalle in der Massenspektroskopie und zur Analyse von Reaktionsprodukten ist die Kenntnis der Lage der im Speicherbereich auftretenden nichtlinearen Resonanzen wesentlich, ebenso wie deren Veränderung durch Dämpfung und Raumladung. Im zweiten Teil dieser Arbeit werden detaillierte Untersuchungen der Speicherung großer puffergasgekühlter Ionenwolken an zwei unterschiedlichen Paulfallen-Experimenten vorgestellt. Am ersten wurden 138Ba+-Ionenwolken kontinuierlich durch Laserspektroskopie bzw. über einen elektronischen Nachweis beobachtet, während das zweite N2+-Molekülionen automatisiert destruktiv nachwies. Am N2+-Experiment wurden zwei hochaufgelöste Messungen des ersten Speicherbereichs durchgeführt, die erstmals eine direkte Überprüfung der theoretisch berechneten Verläufe der Resonanzen mit experimentellen Daten erlauben. Die Nachweiseichung ermöglichte dabei zum ersten Mal die Angabe absoluter Ionenzahlen. Im Gegensatz zu vergleichbaren früheren Messungen wurden hierbei die sich überlagernden Speicherbereiche von 4 simultan gespeicherten Ionensorten beobachtet und zur Analyse der Resonanzen herangezogen. Die nichtlinearen Resonanzen wurden untersucht bei Variation von Puffergasdruck und Ionenzahl, wobei kollektive Resonanzen ohne zusätzliche externe Anregung beobachtet wurden. Die gemessenen Raumladungsverschiebungen wurden mit theoretischen Modellen verglichen. Bei Variation des Puffergasdrucks wurde mit Bariumionen die räumliche Ausdehnung der Ionenwolke gemessen und mit Stickstoffionen die Verschiebung des Punktes optimaler Speicherung bestimmt. Dabei wurde festgestellt, daß der zum Ioneneinfang optimale Puffergasdruck kleiner ist als der, bei dem die längsten Speicherdauern erzielt werden. Mit gespeicherten N2+-Ionen wurde die Position extern angeregter kollektiver und individueller Resonanzen im Frequenzspektrum bei Änderung der Parameter Ionenzahl, Puffergasdruck und Dauer der Anregung untersucht, ebenso wie die Resonanzform, die mit theoretischen Linienformen verglichen wurde. Bei Änderung der Fallenparameter wurden verstärkende Effekte zwischen nahen kollektiven Resonanzen festgestellt. Die Beobachtung, welche der im Frequenzspektrum vorher identifizierten Bewegungs-Resonanzen sich bei Variation der Fallenparameter a bzw. q überlagern, ermöglicht eine bislang nicht beschriebene einfache Methode der Bestimmung von nichtlinearen Resonanzen im Stabilitätsdiagramm.

Geometric facial comparisons in speed-check photographs

In many cases, it is not possible to call the motorists to account for their considerable excess in speeding, because they deny being the driver on the speed-check photograph. An anthropological comparison of facial features using a photo-to-photo comparison can be very difficult depending on the quality of the photographs. One difficulty of that analysis method is that the comparison photographs of the presumed driver are taken with a different camera or camera lens and from a different angle than for the speed-check photo. To take a comparison photograph with exactly the same camera setup is almost impossible. Therefore, only an imprecise comparison of the individual facial features is possible. The geometry and position of each facial feature, for example the distances between the eyes or the positions of the ears, etc., cannot be taken into consideration. We applied a new method using 3D laser scanning, optical surface digitalization, and photogrammetric calculation of the speed-check photo, which enables a geometric comparison. Thus, the influence of the focal length and the distortion of the objective lens are eliminated and the precise position and the viewing direction of the speed-check camera are calculated. Even in cases of low-quality images or when the face of the driver is partly hidden, good results are delivered using this method. This new method, Geometric Comparison, is evaluated and validated in a prepared study which is described in this article.

A new approach in virtopsy: Postmortem ventilation in multislice computed tomography

Although postmortem imaging has gained prominence in the field of forensic medicine, evaluation of the postmortem lung remains problematic. Specifically, differentiation of normal postmortem changes and pathological pulmonary changes is challenging and at times impossible. In this study, five corpses were ventilated using a mechanical ventilator with a pressure of 40 mbar (40.8 cm H(2)O). The ventilation was performed via an endotracheal tube, a larynx mask or a continuous positive airway pressure mask. Postmortem computed tomographic images of the lungs before and with a ventilation of 40 mbar (40.8 cm H(2)O) were evaluated and the lung volumes were measured with segmentation software. Postmortem ventilation led to a clearly visible decrease of both the density in the dependant parts of the lungs and ground glass attenuation, whereas consolidated areas remained unchanged. Furthermore, a mean increase in the lung volume of 2.10 l was seen. Pathological changes such as septal thickening or pulmonary nodules in the lung parenchyma became more detectable with postmortem ventilation. Intracorporal postmortem mechanical ventilation of the lungs appears to be an effective method for enhancing detection of small pathologies of the lung parenchyma as well as for discriminating between consolidation, ground glass attenuation and position-dependent density.

Immediate Search in the IDE as an Example of Socio-Technical Congruence in Search-Driven Development

Search-driven development is mainly concerned with code reuse but also with code navigation and debugging. In this essay we look at search-driven navigation in the IDE. We consider Smalltalk-80 as an example of a programming system with search-driven navigation capabilities and explore its human factors. We present how immediate search results lead to a user experience of code browsing rather than one of waiting for and clicking through search results. We explore the socio-technical congruence of immediate search, ie unification of tasks and breakpoints with method calls, which leads to simpler and more extensible development tools. Eventually we conclude with remarks on the socio-technical congruence of search-driven development.

Seasonality as a core business of phenology

The best characteristics of phenological observations are their description of seasons and seasonal patterns. Specific phenological phases are used to define the beginning and the end of seasons that form phenological calendars. Phenological observations more closely capture the integrated seasonal rhythm than statistically derived means or thresholds from climate elements. They only provide approximate indicators of seasonal changes and cannot replace visible or directly measurable phenomena. Including abiotic observations such as the timing of frost, thawing, icing, snow and fog even provides seasonality descriptions beyond the vegetation period. The length and position of seasons within the year is a foundation for an integrated description of seasonality presented as a phenological season diagram. Phenological observations are the indispensable basis for an integral description of a seasonal classification and seasonality. A well designed phenological diagram could offer a comprehensive picture of the rhythm and amplitude of seasons.

Job Burnout in Public Accounting: Understanding Gender Differences

Job burnout is linked to job outcomes in public accounting professionals (Fogarty et al., 2000; Jones et al., 2010; Jones et al., 2012). Although women and men have entered the profession in relatively equal numbers, there is a significantly lower percentage of women partners (AICPA, 2011). Extant research has not sufficiently explored how burnout may affect the genders distinctly and whether these differences may lend insight as to women’s choices to exit. A large participant group with a similar proportion of women (n=836) and men (n=845) allowed examination of the burnout construct on a more profound level than extant studies. The three dimensions of job burnout in women and men public accountants were analyzed, not only in total, but also by functional area and position level. Overall findings are that women report higher levels of reduced personal accomplishment and men report higher levels of depersonalization. In light of these findings, suggestions are made for firm and individual actions that may mitigate the intensity of burnout experienced by both women and men public accountants.

Structure-activity relationships from in vitro efficacies of the thiazolide series against the intracellular apicomplexan protozoan Neospora caninum

Nitazoxanide (2-acetolyloxy-N-(5-nitro 2-thiazolyl) benzamide; NTZ) represents the parent compound of a novel class of broad-spectrum anti-parasitic compounds named thiazolides. NTZ is active against a wide variety of intestinal and tissue-dwelling helminths, protozoa, enteric bacteria and a number of viruses infecting animals and humans. While potent, this poses a problem in practice, since this obvious non-selectivity can lead to undesired side effects in both humans and animals. In this study, we used real time PCR to determine the in vitro activities of 29 different thiazolides (NTZ-derivatives), which carry distinct modifications on both the thiazole- and the benzene moieties, against the tachyzoite stage of the intracellular protozoan Neospora caninum. The goal was to identify a highly active compound lacking the undesirable nitro group, which would have a more specific applicability, such as in food animals. By applying self-organizing molecular field analysis (SOMFA), these data were used to develop a predictive model for future drug design. SOMFA performs self-alignment of the molecules, and takes into account the steric and electrostatic properties, in order to determine 3D-quantitative structure activity relationship models. The best model was obtained by overlay of the thiazole moieties. Plotting of predicted versus experimentally determined activity produced an r2 value of 0.8052 and cross-validation using the "leave one out" methodology resulted in a q2 value of 0.7987. A master grid map showed that large steric groups at the R2 position, the nitrogen of the amide bond and position Y could greatly reduce activity, and the presence of large steric groups placed at positions X, R4 and surrounding the oxygen atom of the amide bond, may increase the activity of thiazolides against Neospora caninum tachyzoites. The model obtained here will be an important predictive tool for future development of this important class of drugs.

An integrative transcranial magnetic stimulation mapping technique using non-linear curve fitting

The aim of this study is to develop a new simple method for analyzing one-dimensional transcranial magnetic stimulation (TMS) mapping studies in humans. Motor evoked potentials (MEP) were recorded from the abductor pollicis brevis (APB) muscle during stimulation at nine different positions on the scalp along a line passing through the APB hot spot and the vertex. Non-linear curve fitting according to the Levenberg-Marquardt algorithm was performed on the averaged amplitude values obtained at all points to find the best-fitting symmetrical and asymmetrical peak functions. Several peak functions could be fitted to the experimental data. Across all subjects, a symmetric, bell-shaped curve, the complementary error function (erfc) gave the best results. This function is characterized by three parameters giving its amplitude, position, and width. None of the mathematical functions tested with less or more than three parameters fitted better. The amplitude and position parameters of the erfc were highly correlated with the amplitude at the hot spot and with the location of the center of gravity of the TMS curve. In conclusion, non-linear curve fitting is an accurate method for the mathematical characterization of one-dimensional TMS curves. This is the first method that provides information on amplitude, position and width simultaneously.

Associations with multiple pituitary hormone deficiency in patients with an ectopic posterior pituitary gland

INTRODUCTION: The presence of an ectopic posterior pituitary gland (EPP) on magnetic resonance imaging (MRI) is associated with hypopituitarism with one or more hormone deficiencies. We aimed to identify risk factors for having multiple pituitary hormone deficiency (MPHD) compared to isolated growth hormone deficiency (IGHD) in patients with an EPP. METHODS: In 67 patients (45 male) with an EPP on MRI, the site (hypothalamic vs. stalk) and surface area (SA) [ x (maximum diameter/2) x (maximum height/2), mm(2)] of the EPP were recorded and compared in patients with IGHD and MPHD in relation to clinical characteristics. RESULTS: In MPHD (n = 32) compared to IGHD (n = 35) patients: age of presentation was younger (1.4 [0.1-10.7]vs. 4.0 [0.1-11.3] years, P = 0.005), major incidents during pregnancy were increased (47%vs. 20%, P = 0.02) as were admissions to a neonatal intensive care unit (NICU) (60%vs. 26%, P = 0.04), whilst EPP SA was lower (12.3 [2.4-34.6]vs. 25.7 [6.9-48.2] mm(2), P < 0.001). In patients with a hypothalamic (n = 56) compared to a stalk sited EPP (n = 11): prevalence of MPHD was greater (55%vs. 9%,P = 0.05) and EPP surface area was smaller (17.3 [2.4-48.2]vs. 25.3 [11.8-38.5] mm(2), P < 0.001). In regression analysis, after adjusting for age, presence of MPHD was associated with: major incidents during pregnancy (RR 6.8 [95%CI 1.2-37.7]), hypothalamic EPP site (RR 10.9 [1.0-123.9]) and small EPP SA (RR 2.5 [1.0-5.0] for tertiles of SA). CONCLUSION: In patients with an EPP, adverse antenatal events, size (small) and position (hypothalamic) of the posterior pituitary gland on MRI were associated with MPHD. These findings suggest that adverse factors during pregnancy may be important for the development of an EPP.

Pipes in Steel Ingots as Exemplified by Casting Wax

This paper presents some experimental data on the size and position of pipes steel ingots as exemp1ified by casting wax under various conditions and noting the size and location of the pipes formed. The results tend to show that the length of the pipe is decreased by: 1. Slow casting 2. By casting large end up instead of down 3. By retarding the cooling of the top

Use of gold markers for setup in image-guided fractionated high-dose-rate brachytherapy as a monotherapy for prostate cancer

BACKGROUND AND PURPOSE: In order to use a single implant with one treatment plan in fractionated high-dose-rate brachytherapy (HDR-B), applicator position shifts must be corrected prior to each fraction. The authors investigated the use of gold markers for X-ray-based setup and position control between the single fractions. PATIENTS AND METHODS: Caudad-cephalad movement of the applicators prior to each HDR-B fraction was determined on radiographs using two to three gold markers, which had been inserted into the prostate as intraprostatic reference, and one to two radiopaque-labeled reference applicators. 35 prostate cancer patients, treated by HDR-B as a monotherapy between 10/2003 and 06/2006 with four fractions of 9.5 Gy each, were analyzed. Toxicity was scored according to the CTCAE Score, version 3.0. Median follow-up was 3 years. RESULTS: The mean change of applicators positions compared to baseline varied substantially between HDR-B fractions, being 1.4 mm before fraction 1 (range, -4 to 2 mm), -13.1 mm before fraction 2 (range, -36 to 0 mm), -4.1 mm before fraction 3 (range, -21 to 9 mm), and -2.6 mm at fraction 4 (range, -16 to 9 mm). The original position of the applicators could be readjusted easily prior to each fraction in every patient. In 18 patients (51%), the applicators were at least once readjusted > 10 mm, however, acute or late grade > or = 2 genitourinary toxicity was not increased (p = 1.0) in these patients. CONCLUSION: Caudad position shifts up to 36 mm were observed. Gold markers represent a valuable tool to ensure setup accuracy and precise dose delivery in fractionated HDR-B monotherapy of prostate cancer.

Exploiting Runtime Information in the IDE

Developers rely on the mechanisms provided by their IDE to browse and navigate a large software system. These mechanisms are usually based purely on a system's static source code. The static perspective, however, is not enough to understand an object-oriented program's behavior, in particular if implemented in a dynamic language. We propose to enhance IDEs with a program's runtime information (eg. message sends and type information) to support program comprehension through precise navigation and informative browsing. To precisely specify the type and amount of runtime data to gather about a system under development, dynamically and on demand, we adopt a technique known as partial behavioral reflection. We implemented navigation and browsing enhancements to an IDE that exploit this runtime information in a prototype called Hermion. We present preliminary validation of our experimental enhanced IDE by asking developers to assess its usefulness to understand an unfamiliar software system.

Reliability of evaluations for the choice of system solutions at the example of automated order-picking systems for bagged goods

There is a steadily increasing pressure on cost-savings and productivity growth in sectors of order-picking such that the wish for rationalization by automation is rising. Special problems are faced trying to automatize handling operations of order-picking articles packed in bags. The mechanical properties of the objects and their hard-to-predict shape and position represent obstacles and are complicating handling operations. A systematic approach in system design is required. This article deals with the properties of such products under aspects of difficulties arising in automated handling and points out a useful system development methodology.