Ammonia losses estimated by an open collector from urea applied to sugarcane straw

The quantification of ammonia (NH3) losses from sugarcane straw fertilized with urea can be performed with collectors that recover the NH3 in acid-treated absorbers. Thus, the use of an open NH3 collector with a polytetrafluoroethylene (PTFE)-wrapped absorber is an interesting option since its cost is low, handling easy and microclimatic conditions irrelevant. The aim of this study was to evaluate the efficiency of an open collector for quantifying NH3-N volatilized from urea applied over the sugarcane straw. The experiment was carried out in a sugarcane field located near Piracicaba, São Paulo, Brazil. The NH3-N losses were estimated using a semi-open static collector calibrated with 15N (reference method) and an open collector with an absorber wrapped in PTFE film. Urea was applied to the soil surface in treatments corresponding to rates of 50, 100, 150 and 200 kg ha-1 N. Applying urea-N fertilizer on sugarcane straw resulted in losses NH3-N up to 24 % of the applied rate. The amount of volatile NH3-N measured in the open and the semi-open static collector did not differ. The effectiveness of the collection system varied non-linearly, with an average value of 58.4 % for the range of 100 to 200 kg ha-1 of urea-N. The open collector showed significant potential for use; however, further research is needed to verify the suitability of the proposed method.

Isotope geochemical and geochronologic studies of basement units in the Central Western Carpathians (Slovakia)

In dieser Arbeit werden geochronologische und isotopen-geochemische Daten zur Entwicklung der Zentralen Westlichen Karpathen präsentiert. Die Karpathen bilden die östliche Fortsetzung der Alpen und können in drei Alpine Grundgebirgsdecken unterteilt werden, von denen zwei, die Veporische und die Gemerische, bearbeitet wurden. In der Veporischen Einheit wurden polymetamorphe Grundgebirgseinheiten untersucht, um deren genaue Altersstellung zu definieren und sie isotopengeochemisch zu klassifizieren. Dagegen wurde in der der Gemerischen Einheit, welche die Veporische Einheit überlagert, ein spezialisierter S-Typ Granit im Detail untersucht, um die petrogenetischen Prozesse, die zur magmatischen Entwicklung dieses Granits geführt haben, zu identifizieren. U-Pb Datierungen an Zirkonen der Veporischen Grundgebirgseinheiten zeigen für die gesamte Veporische Einheit ordovizische Entsehungsalter an (440-470 Ma). Diese Datierungen revidieren publizierte kambrische Entstehungsalter dieses Grundgebirges. Die Isotopensignatur (epsilon Nd und 87Sr/86Sr) der ordovizischen Grundgebirgseinheiten, bestehend aus stark überprägten Amphiboliten und Gneissen, ist von der Signatur der sich im Norden anschliessenden Tatrischen Einheit gut unterscheidbar. Die Bleiisotopenzusammensetzung dieser Gesteine ist stark krustal geprägt und überschneidet sich mit der der Tatrischen Einheit. Zusammen mit den T-DM Altern sind diese Einheiten vergleichbar mit prävariskischen Einheiten der Alpen. Somit kann das ordovizische Grundgebirge zu den peri-Gondwana Terranen gezählt werden, die an einem aktiven Kontinentalrand im Norden von Gondwana gebildet wurden. In den Gesteinen der Veporischen Einheit wurde im Weiteren eine starke metamorphe überprägung und intensiver felsischer Magmatismus karbonischen Alters erkannt (320-350 Ma). Dieses Ereignis ist zeitgleich mit dem Magmatismus, welcher hauptsächlich in der sich im Norden anschliessenden Tatrischen Einheit beobachtet wird. Dieser gehört der variskischen Orogenese an. Intensive alpine Deformation und Metamorphose konnte in der südlichen Veporischen Einheit anhand der Einzelzirkondatierungen und der Isotopendaten der ordovizischen Einheiten nachgewiesen werden. Am Dlha Dolina Granit in der Gemerischen Einheit können starke Fraktionierungs- und Auto-Metasomatose-Effekte beobachtet werden. Durch die magmatische Fraktionierung wird eine Anreicherung der SEE erzeugt, wogegen die Metasomatose die SEE stark verarmt. Es kommt sogar zur Ausbildung eines Tetraden Effektes im SEE Muster, welche den starken Einfluss von Fluiden während der spät-magmatischen Phase belegt. Gesamtgesteins Pb-Pb Daten beschränken das minimale Intrusionsalter dieses Granites auf 240 Ma. Dieses Alter ist in guter übereinstimmung mit den Sr-Isotopendaten der magmatisch dominierten Gesteine, wohingegen die stark metasomatisch geprägten Gesteine ein zu radiogenes 87Sr/86Sri aufweisen. Während dieser Arbeit wurde intensiv mit der Blei-Isotopenzusammensetzung von Gesamtgesteinsproben gearbeitet. Um die Auswertung dieser Daten optimieren zu können wurde ein Computerscript für das GPL Programm Octave erstellt. Die Hauptaufgabe dieses Scripts besteht darin, Regressionen für geochronologische Anwendungen gemäss York (1969) zu berechnen. Ausserdem können mu und kappa-Werte für diese Regressionen berechnet und eine Hauptkomponentenanalyse, welche hilfreich für den Vergleich von zwei Datensätzen ist, durchgeführt werden. Am Ende der vorliegenden Arbeit wird die analytische Methode für einen Mikrowellen beschleunigten Säureaufschluss von granitoidem Material zur Bestimmung der Sr- und Nd-Isotopenzusammensetzung und der Elementkonzentrationen vorgestellt. Diese kombinierte Methode nutzt ein TIMS für die Sr und Nd Isotopenmessungen und eine Einzelkollektor-ICPMS zur Bestimmung der SEE, Rb und Sr Konzentrationen, welche mithilfe von relativen Sensitivitätsfaktoren gegenüber einem internen Standard quantifiziert werden. Diese Methode wird durch Messungen von internationalen Referenzmaterialien bewertet. Die Ergebnisse zeigen eine Reproduzierbarkeit von <10% für die Elementkonzentrationen und von <5% für Elementverhältnisse.

Development and application of a GC system for NMHC analyses of air samples from the CARIBIC aircraft project

The subject of this thesis is the development of a Gaschromatography (GC) system for non-methane hydrocarbons (NMHCs) and measurement of samples within the project CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com). Air samples collected at cruising altitude from the upper troposphere and lowermost stratosphere contain hydrocarbons at low levels (ppt range), which imposes substantial demands on detection limits. Full automation enabled to maintain constant conditions during the sample processing and analyses. Additionally, automation allows overnight operation thus saving time. A gas chromatography using flame ionization detection (FID) together with the dual column approach enables simultaneous detection with almost equal carbon atom response for all hydrocarbons except for ethyne. The first part of this thesis presents the technical descriptions of individual parts of the analytical system. Apart from the sample treatment and calibration procedures, the sample collector is described. The second part deals with analytical performance of the GC system by discussing tests that had been made. Finally, results for measurement flight are assessed in terms of quality of the data and two flights are discussed in detail. Analytical performance is characterized using detection limits for each compound, using uncertainties for each compound, using tests of calibration mixture conditioning and carbon dioxide trap to find out their influence on analyses, and finally by comparing the responses of calibrated substances during period when analyses of the flights were made. Comparison of both systems shows good agreement. However, because of insufficient capacity of the CO2 trap the signal of one column was suppressed due to breakthroughed carbon dioxide so much that its results appeared to be unreliable. Plausibility tests for the internal consistency of the given data sets are based on common patterns exhibited by tropospheric NMHCs. All tests show that samples from the first flights do not comply with the expected pattern. Additionally, detected alkene artefacts suggest potential problems with storing or contamination within all measurement flights. Two last flights # 130-133 and # 166-169 comply with the tests therefore their detailed analysis is made. Samples were analyzed in terms of their origin (troposphere vs. stratosphere, backward trajectories), their aging (NMHCs ratios) and detected plumes were compared to chemical signatures of Asian outflows. In the last chapter a future development of the presented system with focus on separation is drawn. An extensive appendix documents all important aspects of the dissertation from theoretical introduction through illustration of sample treatment to overview diagrams for the measured flights.

The reconstruction of paleoclimate variability in Northern Germany, during marine isotope stage 5

In order to obtain a better understanding about the influence of post-depositional diagenesis on speleothem 230Th/U-ages and paleoclimate variability during Marine Isotope Stage (MIS) 5 in northern Germany, four stalagmites from the Riesenberghöhle (RBH) were investigated by thin section analysis, 230Th/U-dating as well as stable oxygen and carbon isotope and laser ablation inductively coupled mass spectrometry (LA-ICPMS) trace element analysis. The RBH is located in the Weser Hills and is one of the northernmost limestone caves in Germany.rnMulti collector (MC) ICPMS 230Th/U-ages and thin section analysis of the RBH stalagmites shows that some growth phases of the stalagmites were diagenetically altered after their deposition. The impact of post-depositional diagenesis (PDD) on the 230Th/U-ages is modeled, and potential processes leading to PDD are discussed. In this context, it is suggested that PDD may be induced by rapid climate change at the inception of the GIS.rnDespite of the dating uncertainties resulting from PDD, 230Th/U-dating shows that the RBH stalagmites grew during the Eemian and most of the Greenland Interstadials (GIS) during MIS 5. Thus, the growth phases of the RBH stalagmites might be related to a reorganization of the Atlantic Meridional Overturning Circulation (AMOC). The stable isotope (δ13C and δ18O) and the trace element variability of the stalagmites reflects rapid changes of past temperature and precipitation on millennial and sub-millennial timescales. These past climate changes can be amplified by orbitally forced variations of the July solar insolation at 65°N.

The Presence of Words in Visual Art from Surrealism to Conceptualism

Without a doubt, one of the biggest changes that affected XXth century art is the introduction of words into paintings and, in more recent years, in installations. For centuries, if words were part of a visual composition, they functioned as reference; strictly speaking, they were used as a guideline for a better perception of the subject represented. With the developments of the XXth century, words became a very important part of the visual composition, and sometimes embodied the composition itself. About this topic, American art critic and collector Russell Bowman wrote an interesting article called Words and images: A persistent paradox, in which he examines the American and the European art of the XXth century in almost its entirety, dividing it up in six “categories of intention”. The aforementioned categories are not based on the art history timeline, but on the role that language played for specific artists or movements. Taking inspiration from Bowman's article, this paper is structured in three chapters, respectively: words in juxtaposition and free association, words as means of exploration of language structures, and words as means for political and personal messages. The purpose of this paper is therefore to reflect on the role of language in contemporary art and on the way it has changed from artist to artist.

Exhibit: "Michigan-I-O": Alan Lomax and the 1938 Library of Congress Folk-Song Expedition"

In 1938, a young folk music collector named Alan Lomax—destined to become one of the legendary folklorists of the 20th century recorded Michigan’s richly varied folk music traditions for the Archive of American Folk-Song at the Library of Congress. Michigan in the 1930s was experiencing a golden age of folksong collecting, as local folklorists mined the trove of ballads remembered by aging lumbermen and Great Lakes schoonermen. In addition to the ballads of these north woods singers, Lomax recorded a vibrant mix of ethnic music from Detroit to the western Upper Peninsula. The multimedia performance event Folksongs from Michigan-i-o combines live performance with historic images, color movie footage, and recorded sound from the Great Depression. Some of these materials haven’t been heard or seen by the general public for more than seven decades. The traveling exhibition Michigan Folksong Legacy: Grand Discoveries from the Great Depression brings Alan Lomax’s 1938 field trip to life through words, song lyrics, photographs, and sound recordings. Ten interpretive banners explore themes and each panel contains a QR code that links to related sound recordings from the Alan Lomax Collection at the American Folklife Center, Library of Congress.

Exhibit: "Michigan-I-O": Alan Lomax and the 1938 Library of Congress Folk-Song Expedition"

In 1938, a young folk music collector named Alan Lomax—destined to become one of the legendary folklorists of the 20th century recorded Michigan’s richly varied folk music traditions for the Archive of American Folk-Song at the Library of Congress. Michigan in the 1930s was experiencing a golden age of folksong collecting, as local folklorists mined the trove of ballads remembered by aging lumbermen and Great Lakes schoonermen. In addition to the ballads of these north woods singers, Lomax recorded a vibrant mix of ethnic music from Detroit to the western Upper Peninsula. The multimedia performance event Folksongs from Michigan-i-o combines live performance with historic images, color movie footage, and recorded sound from the Great Depression. Some of these materials haven’t been heard or seen by the general public for more than seven decades. The traveling exhibition Michigan Folksong Legacy: Grand Discoveries from the Great Depression brings Alan Lomax’s 1938 field trip to life through words, song lyrics, photographs, and sound recordings. Ten interpretive banners explore themes and each panel contains a QR code that links to related sound recordings from the Alan Lomax Collection at the American Folklife Center, Library of Congress.

Exhibit: "Michigan-I-O": Alan Lomax and the 1938 Library of Congress Folk-Song Expedition

In 1938, a young folk music collector named Alan Lomax—destined to become one of the legendary folklorists of the 20th century recorded Michigan’s richly varied folk music traditions for the Archive of American Folk-Song at the Library of Congress. Michigan in the 1930s was experiencing a golden age of folksong collecting, as local folklorists mined the trove of ballads remembered by aging lumbermen and Great Lakes schoonermen. In addition to the ballads of these north woods singers, Lomax recorded a vibrant mix of ethnic music from Detroit to the western Upper Peninsula. The multimedia performance event Folksongs from Michigan-i-o combines live performance with historic images, color movie footage, and recorded sound from the Great Depression. Some of these materials haven’t been heard or seen by the general public for more than seven decades. The traveling exhibition Michigan Folksong Legacy: Grand Discoveries from the Great Depression brings Alan Lomax’s 1938 field trip to life through words, song lyrics, photographs, and sound recordings. Ten interpretive banners explore themes and each panel contains a QR code that links to related sound recordings from the Alan Lomax Collection at the American Folklife Center, Library of Congress.

Reliability and quality of water isotope data collected with a lowbudget rain collector

RATIONALELow-budget rain collectors for water isotope analysis, such as the `ball-in-funnel type collector' (BiFC), are widely used in studies on stable water isotopes of rain. To date, however, an experimental quality assessment of such devices in relation to climatic factors does not exist. METHODSWe used Cavity Ring-Down Spectrometry (CRDS) to quantify the effects of evaporation on the O-18 values of reference water under controlled conditions as a function of the elapsed time between rainfall and collection for isotope analysis, the sample volume and the relative humidity (RH: 31% and 67%; 25 degrees C). The climate chamber conditions were chosen to reflect the warm and dry end of field conditions that favor evaporative enrichment (EE). We also tested the performance of the BiFC in the field, and compared our H-2/O-18 data obtained by isotope ratio mass spectrometry (IRMS) with those from the Swiss National Network for the Observation of Isotopes in the Water Cycle (ISOT). RESULTSThe EE increased with time, with a 1 increase in the O-18 values after 10days (RH: 25%; 25 degrees C; 35mL (corresponding to a 5mm rain event); p <0.001). The sample volume strongly affected the EE (max. value +1.5 parts per thousand for 7mL samples (i.e., 1mm rain events) after 72h at 31% and 67% RH; p <0.001), whereas the relative humidity had no significant effect. Using the BiFC in the field, we obtained very tight relationships of the H-2/O-18 values (r(2) 0.95) for three sites along an elevational gradient, not significantly different from that of the next ISOT station. CONCLUSIONSSince the chosen experimental conditions were extreme compared with the field conditions, it was concluded that the BiFC is a highly reliable and inexpensive collector of rainwater for isotope analysis. Copyright (c) 2014 John Wiley & Sons, Ltd.

Revisiting the Nd-142 deficits in the 1.48 Ga Khariar alkaline rocks, India

The 146Sm–142Nd system plays a central role in tracing the silicate differentiation of the Earth prior to 4.1 Ga. After this time, given its initial abundance, the 146Sm can be considered to be extinct. Upadhyay et al. (2009) reported unexpected negative 142Nd anomalies in 1.48 Ga rocks of the Khariar nepheline syenite complex (India) and inferred that an early enriched, low-Sm/Nd reservoir must have contributed to the mantle source rocks of the Khariar complex. As 146Sm had been effectively extinct for about 2.6 billion years before the crystallisation of the Khariar samples, this Nd signature should have remained isolated from the convective mantle for at least that long. It was thus suggested that the source rock of Khariar samples had been sequestered in the lithospheric root of the Indian craton. Using a different chemical separation method, and a different Thermal Ionization Mass Spectrometry (TIMS) analysis protocol, the present study attempted to replicate these negative 142Nd anomalies, but none were found. To determine which data set is correct, we investigated three possible sources of bias between them: imperfect cancellation of Faraday collector efficiencies during multidynamic TIMS analysis, rapid sample fractionation between the sequential measurement of 146Nd/144Nd and 142Nd/144Nd, and non-exponential law behaviour resulting from so-called “domain mixing.” Incomplete cancellation of collector efficiencies was found unlikely to cause resolvable biases at the estimated level of variation among collector efficiencies. Even in the case of highly variable efficiency and resolvable biases, there is no reason to suspect that they would reproducibly affect only four rocks out of 10 analysed by Upadhyay et al. (2009). Although domain mixing may explain apparent “reverse” fractionation trends observed in some TIMS analyses, it cannot be the cause of the apparent negative anomalies in the study of Upadhyay et al. (2009). It was determined that rapid mass fractionation during the course of a multidynamic TIMS analysis can bias all measured Nd ratios. After applying an approximate correction for this effect, only one rock from Upadhyay et al. (2009) retained an apparent negative 142Nd anomaly. This, in conjunction with our new, anomaly-free data set measured at fractionation rates too low to cause bias, leads to the conclusion that the anomalies reported by Upadhyay et al. (2009) are a subtle and reproducible analytical artefact. The absence of negative 142Nd anomalies in these rocks relaxes the need for a mechanism (other than crust formation) that can isolate a Nd reservoir from the convective mantle for billions of years.

Iron uptake and ferrokinetics in healthy male subjects of an iron-based oral phosphate binder (SBR759) labeled with the stable isotope 58 Fe

SBR759 is a novel polynuclear iron(III) oxide–hydroxide starch·sucrose·carbonate complex being developed for oral use in chronic kidney disease (CKD) patients with hyperphosphatemia on hemodialysis. SBR759 binds inorganic phosphate released by food uptake and digestion in the gastro-intestinal tract increasing the fecal excretion of phosphate with concomitant reduction of serum phosphate concentrations. Considering the high content of ∼20% w/w covalently bound iron in SBR759 and expected chronic administration to patients, absorption of small amounts of iron released from the drug substance could result in potential iron overload and toxicity. In a mechanistic iron uptake study, 12 healthy male subjects (receiving comparable low phosphorus-containing meal typical for CKD patients: ≤1000 mg phosphate per day) were treated with 12 g (divided in 3 × 4 g) of stable 58Fe isotope-labeled SBR759. The ferrokinetics of [58Fe]SBR759-related total iron was followed in blood (over 3 weeks) and in plasma (over 26 hours) by analyzing with high precision the isotope ratios of the natural iron isotopes 58Fe, 57Fe, 56Fe and 54Fe by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Three weeks following dosing, the subjects cumulatively absorbed on average 7.8 ± 3.2 mg (3.8–13.9 mg) iron corresponding to 0.30 ± 0.12% (0.15–0.54%) SBR759-related iron which amounts to approx. 5-fold the basal daily iron absorption of 1–2 mg in humans. SBR759 was well-tolerated and there was no serious adverse event and no clinically significant changes in the iron indices hemoglobin, hematocrit, ferritin concentration and transferrin saturation.

Characterization of the Capacitance of a Rotating Ring–Disk Electrode

The use of rotating ring–disk electrodes as generator-collector systems has so far been limited to the detection of Faradaic currents at the ring. As opposed to other generator-collector configurations, non-Faradaic detection has not yet been carried out with rotating ring–disk electrodes. In this study, a.c. perturbation based detection for measurement of the ring impedance is introduced. By using a conducting polymer-modified disk electrode in combination with a bare gold ring as a model, it is shown that the measured ring capacitance correlates with the polarization of the polymer film, most probably due to counter-ion exchange. A method of calculating the ring capacitance based on a small-signal sinusoid perturbation is described and the most important instrumental limitations are identified.

Room for Experiment: The Countess of Arundel’s "Site of Medication"

The so-called Dutch Pranketing Room of Alethea Talbot, Countess of Arundel, at Tart Hall was a site of domestic experiments, courtly splendour and global ambition. Lady Arundel, the probable author of a famous recipe book, would have used Tart Hall for cooking and experiments as well as for impressive dinner parties, and she would have used large amounts of sugar to create intricate imitations of meat and vegetables to astonish, entertain and delight her guests. Linking household practice with global trade as well as artistic creation, Lady Arundel’s banquets are situated not only between a national tradition of cooking, as it appears in Markham’s manuals, and the new possibilities the arising global trade provided, but also played with a mismatch between taste and sight. This mediating role could be compared to that played by the artists the Countess employed. Within this context it is worth noting that a series of paintings displayed in the building’s gallery showed still lifes, markets, and a cook. The inventory of Tart Hall gives an insight into the world of the widely travelled collector and patron of Van Dyck and Rubens, but raises also a number of questions. In my talk I would like to explore the Countess’ Pranketing Room as a site of mediation between alimentary and painterly experiments, considering the use of recipes, experience, invention and transformation