Capability of a prototype of miniature collection device based on a strip of the molybdenum foil for collecting hydride forming elements (As, Se, Sb and Bi) was studied. The device was combined with a miniature hydrogen diffusion flame for detection by atomic absorption spectrometry. The conditions for trapping and subsequent vaporization of analytes of interest were optimized. A twin-channel hydride generation system was used for study of mutual interference effects of co-generated hydride forming elements. The influence of modification of the molybdenum surface with noble metals - Rh, Pt and Ir on trapping and vaporization processes was also studied and changes of microstructure of the foil surface after modification were investigated using scanning electron microscope equipped with energy dispersive x-ray analyzer and electron backscattered diffraction system. Complementary radiotracer and radiography experiments were performed in order to determine trapping efficiency and to assess the spatial distribution of collected analytes within the device. Practical application of the method was demonstrated on determination of antimony in water samples at trace level. Possibility of multi-element analysis was demonstrated by combining the collection device with atomization and excitation of the analyte in microwave induced plasma and with detection by atomic emission spectrometry method. The results of the experiments proved that tested miniature collection device is capable of trapping analytes that form volatile hydrides. This device can be coupled to various types of atomizers, typically used in spectrometry methods. Thus, very sensitive and specific detection of hydride forming elements can be performed.

The presented dissertation thesis deals with the use of UV-photochemical generation of volatile compounds (UV-PVG) as a derivatization technique for the combination of high-performance liquid chromatography (HPLC) and atomic absorption spectrometry (AAS) detection. Two model elements arsenic and mercury and their compounds were selected for the speciation analysis. The work was divided into several parts that follow. In the first part of the research, the apparatus for the UV-photochemical generation of the volatile mercury compounds and their detection with a new continuum source and high-resolution atomic absorption spectrometer (HR-CS AAS) with an externally heated detection tube was constructed. The analytical method was adapted for use with atomic fluorescence detection with the aim to improve sensitivity of the determination. Furthermore, apparatus for the electrochemical generation of cold mercury vapor with AAS detection was built. The construction of the apparatus was followed by optimization of the reaction conditions (concentration and flow of electrochemical reagents: sulfuric and hydrochloric acid, mobile phase, carrier medium, flow rate of the carrier gas and localization of its introduction), determination of the analytical figures of merit, and comparation of the methods. Both...

Die Vorhersage und Identifizierung von stabilen und metastabilen Stoffen ist ein wichtiges Instrument zur Bildung neuer Werkstoffe. Vor diesem Hintergrund gewinnen Konzepte einer rationalen Synthese zunehmend an Bedeutung: Die Berechnung der elektrochemischen Spannungsreihe für Festkörper und flüchtiger Phasen ermöglicht eine einfache Vorhersage der Reaktionswege. Unter Verwendung der elektrochemischen Spannungsreihe der Systeme As / P / O und As / P / X (X = F, Cl, Br, I) kann die Bildung von Elementallotropen über die Oxid- und Halogenidverbindungen in thermitischen Reaktionen abgeleitet werden. Die Analyse der Phasenbildung wird mit einer In-situ-Methode zur Überwachung von Gasphasenreaktionen gewonnen. Im Verlauf der Phasenformationen - zur Erreichung des Fest-Gas-Gleichgewichtes - können charakteristische Effekte beobachtet werden. / The prediction and identification of stable and metastable substances is an important tool to achieve new materials. With this objective in mind, concepts of a rational synthesis are gaining increasing importance: calculation of electromotive series of solids allows easy prediction of reaction pathways. Using the electromotive series of systems As/P/O and As/P/X (X = F, Cl, Br, I) the formation of element allotropes via the oxide and halide compounds in thermite type reactions can be deduced. The analysis of phase formation is acquired with an in situ method for monitoring gas-phase reactions. In the course of phase formations - attaining the solid-gas equilibrium state - characteristic effects can be observed.

The concomitant occurrence and reported discrepant behavior of uranium and arsenic in water bodies is a major health and environmental concern. This study combined batch and column experiments, hydrogeochemical simulations and XAFS spectroscopy to uncover the exchange mechanisms governing uranium fate between water and scrap metallic iron, minerals and Shewanella putrefaciens surfaces in the presence of arsenic. The main results suggest that both water chemistry and the solid phase composition influence uranium fate in the presence of arsenic. The importance of uranyl-arsenate species as a major control of uranium behavior in the presence of arsenic is shown. The toxicity of arsenic and the presence of nitrate are interpreted as limiting factors of the enzymatic reduction of both toxins. Besides, XANES fingerprinting and EXAFS modeling have confirmed precipitation/co-precipitation of uranyl-arsenates as a major mechanism controlling uranium behavior in the presence of arsenic.

Nanopartikel basierte colorimetrische Assays bieten vielfältige Anwendungsmöglichkeiten vom Nachweis ionischer oder molekularer Spezies bis hin zu komplexen Strukturen, wie zum Beispiel Zellen oder Bakterien. Trotz der großen Anzahl von Anwendungsbeispielen in der Literatur gibt es nur sehr wenige Beispiele für den Fall, wenn Analyt und Sensorpartikel etwa gleich groß sind. Jedoch nimmt das Interesse an dem Nachweis solcher Analyten, wie zum Beispiel von Viren, in der Bioverfahrenstechnik, der Umwelttechnik und Medizin stetig zu. In der Dissertation wird anhand von drei unterschiedlichen Anwendungsbeispielen die lückenlose Anwendbarkeit des Nanopartikel basierten colorimetrischen Sensorprinzips für verschiedene Analyten aus dem gesamten interessierenden Größenspektrum nachgewiesen. Für die Detektion von Ionen bzw. Ionenkomplexen ist mit der Funktionalisierung der Goldnanopartikel mit bakteriellen Zellhüllenproteinen ein spezifisches Nachweisverfahren für spezielle Ionenkomplexe entwickelt worden. Erste Ergebnisse zum Nachweis von toxischen Arsen(V)-Komplexen in wässriger Lösung belegen das enorme Potential. Als Nachweisgrenze konnten Werte im Bereich herkömmlicher sensitiver Messverfahren ermittelt werden. Durch Untersuchung der Wechselwirkung von Au- und AuxAg1-x–Nanopartikeln mit dendritischen Polymerstrukturen mit Abmessungen im Größenbereich zwischen 2 und 5 nm konnten tiefere Einblicke in das Aggregationsverhalten der Partikel bei der Ausbildung größerer komplexer Strukturen erzielt werden, die eine sensorische Umsetzung ermöglichen. Derartige Betrachtungen existieren bisher nur für Ionen oder kleinere molekulare Spezies. Der Nachweis von Analyten mit zu den Nanopartikeln vergleichbarer Größe wird am Beispiel zweier unterschiedlicher viraler Proben, dem Rinder-Coronavirus (BCV) und einem humanen Influenzavirus (H3N2) in grundlegenden Experimenten demonstriert. Die Durchführung dieser Arbeiten mit prozessnahem Virusprobenmaterial ist mit besonderen Herausforderungen an die Signalgewinnung und Interpretation verbunden. Aufbauend auf diesen experimentellen Ergebnissen konnte in einer skalenübergreifenden Betrachtung für Analytgrößen vom Subnanometerbereich bis hin zu einigen hundert Nanometern die lückenlose, universelle Anwendbarkeit des colorimetrischen Sensorprinzips demonstriert werden. Diese Betrachtungen ermöglichen generelle Aussagen zur Lage des Farbumschlagbereiches sowohl in Abhängigkeit von der Analytgröße als auch der Funktionalisierung, der Konzentration und der Größe der Nanopartikel.

Different aspects of interaction of metals other than iron with metallophore mixtures were elucidated. Metal chelation besides iron and greater than with pure desferrioxamine B is documented by enhanced performance of soil mineral dissolution following application of diverse metallophore mixtures. New insights from genome to product of metallophores from Gordonia rubripertincta CWB2 under different cultivation conditions and under metal stress, particularly induced by rare earth elements are given. This evaluation led to increase by a factor of 13. Structure analyses showed that the strain produces citrate and different desferrioxamines. A robust RP-HPLC-based method quantified metal complexation. Further metal immobilization methods for metallophores for metal extraction from solutions with low concentrations were established. Moreover, catechol and hydroxamate metallophores from Arthrobacter oxydans ATW2 and Kocuria rosea ATW4 demonstrate the enhancement of Ge and rare earth element bioavailability, plant growth promotion and phytoextraction potential.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191 / En este trabajo se han dilucidado diferentes aspectos de la interacción de los metales con las mezclas de metalóforos desde distintos ángulos. La quelación de metales por debajo del hierro se pone de manifiesto en la mejora del rendimiento de la disolución de los minerales del suelo debido a la aplicación de diversas mezclas de metanóforos en comparación con la deferoxamina B pura. Se ofrecen nuevos conocimientos desde el genoma hasta el producto de los metanóforos de Gordonia rubripertincta CWB2 en diferentes condiciones de cultivo y bajo estrés por metales, especialmente inducido por elementos de tierras raras. Esta evaluación condujo a una sobreproducción de un factor de 13. El análisis estructural muestra que la cepa produce citrato y diferentes desferrioxaminas. Un método robusto basado en RP-HPLC cuantificó la complejación de metales. Se establecieron otros métodos de inmovilización de metales para la extracción de metales a partir de soluciones poco concentradas. Además, los metalóforos de catecol e hidroxamato de Arthrobacter oxydans ATW2 y Kocuria rosea ATW4 demuestran la mejora de la biodisponibilidad de GE y REE, la promoción del crecimiento vegetal y el potencial de fitoextracción.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191 / Es wurden verschiedene Aspekte der Wechselwirkung von anderen Metallen als Eisen mit Metallophormischungen untersucht. Die Chelatbildung mit anderen Metallen als Eisen, die größer ist als bei reinem Desferrioxamin B, wird durch eine verbesserte Leistung bei der Auflösung von Bodenmineralien nach Anwendung verschiedener Metallophormischungen dokumentiert. Es werden neue Erkenntnisse vom Genom bis zum Produkt von Metallophoren aus Gordonia rubripertincta CWB2 unter verschiedenen Anbaubedingungen und unter Metallstress, insbesondere induziert durch Seltene Erden, gegeben. Diese Auswertung führte zu einer Steigerung um den Faktor 13. Strukturanalysen zeigten, dass der Stamm Citrat und verschiedene Desferrioxamine produziert. Eine robuste RP-HPLC-basierte Methode quantifizierte die Metallkomplexierung. Weitere Methoden zur Metallimmobilisierung von Metallophoren für die Metallextraktion aus Lösungen mit niedrigen Konzentrationen wurden etabliert. Darüber hinaus zeigen Catechol- und Hydroxamat-Metallophore aus Arthrobacter oxydans ATW2 und Kocuria rosea ATW4 die Verbesserung der Bioverfügbarkeit von Ge und Seltenen Erden, die Förderung des Pflanzenwachstums und das Phytoextraktionspotenzial.:CONTENTS Abstract ..........................................................................................................1 CHAPTER 1 Introduction ......................................................................................5 CHAPTER 2 Mobilization of trace elements in soil extracts by bacterial siderophores in dependence of the pH-value..................................31 CHAPTER 3 Cultivation dependent formation of siderophores by Gordonia rubripertincta CWB2........................................................................41 CHAPTER 4 Data on metal-chelating, -immobilization and biosorption properties by Gordonia rubripertincta CWB2 in dependency on rare earth adaptation.......................................................................................67 CHAPTER 5 Analysis of desferrioxamine-like siderophores and their capability to selectively bind metals and metalloids: development of a robust analytical RP-HPLC method. ..........................................................97 CHAPTER 6 Secondary metabolites released by the rhizosphere bacteria Arthrobacter oxydans and Kocuria rosea enhance plant availability and soil–plant transfer of germanium (Ge) and rare earth elements (REEs) .........................................................................................120 CHAPTER 7 Conclusion remarks and further perspectives ...............................154 References .......................................................................................................162 Acknowledgement .........................................................................................185 Curriculum Vitae ..........................................................................................187 List of publications ..........................................................................................189 List of oral and poster presentations ..........................................................190 List of proceedings ..........................................................................................191

Die Freiberger Mulde, die einen Teil des Freiberger Reviers entwässert, weist hohe Schwermetall‑, Arsen- und Sulfatbelastungen auf. Besonders der Abschnitt zwischen Berthelsdorf und Siebenlehn ist stark durch den Alterzbergbau sowie die Bunt- und Edelmetallurgie geprägt. Das Ziel von zwei Messkampagnen war die Identifikation aller punktueller Einleiter in diesem Abschnitt, um mittels einer Frachtbilanzierung die wesentlichen punktuellen Einleiter sowie mögliche diffuse Zutritte von Arsen, Blei, Cadmium, Kupfer, Eisen, Nickel, Nitrat, Sulfat und Zink zu identifizieren. Hierbei wurden acht punktuelle Einleiter identifiziert, die maßgeblich für eine entsprechende Frachtzunahme im Untersuchungsgebiet verantwortlich sind. Die Aufstellung der Frachtbilanzen erfolgte nach einem vereinfachten Ansatz, der Rückschlüsse auf mögliche diffuse Zutritte oder Verluste durch z. B. Rückhalt, Abbau und Versickerung erlaubt. Dabei zeigte eine Bilanzierung über das gesamte Untersuchungsgebiet nur eine geringe Aussagekraft. Erst durch eine abschnittsweise Bilanzierung entlang des Untersuchungsgebietes wird ersichtlich, dass sich Eintrags- und Rückhalteprozesse abwechseln und möglicherweise innerhalb der Abschnitte überlagern. Dies liefert nützliche Erkenntnisse für weitere Betrachtungen der Belastungsursachen und die Umsetzung der Wasserrahmenrichtlinie im Einzugsgebiet der Freiberger Mulde. / The Freiberg Mulde River, which drains part of the Freiberg mining district, has high levels of heavy metal, arsenic and sulfate pollution. The section between Berthelsdorf and Siebenlehn in particular is strongly influenced by historic mining as well as by non-ferrous and precious metal metallurgy. The aim of two large-scale monitoring campaigns was to identify all point sources in this area in order to identify the main emitters as well as possible diffuse (groundwater-borne) sources of arsenic, lead, cadmium, copper, iron, nickel, sulfate and zinc by means of load balances. Eight main emitters were identified, which are largely responsible for a corresponding increase in pollution in the study area. The pollution balances were carried out according to a simplified approach that allows conclusions to be drawn about possible diffuse influxes or losses due to, for example, retention, degradation and infiltration. In this context, a balance over the entire study area showed limited value. Only a section-by-section balance along the study area reveals that inflow and retention processes alternate and possibly overlap within the sections. This provides useful insights for further considerations of the causes of pollution and for the implementation of the Water Framework Directive in the catchment area of the Freiberg Mulde River.

The main aim of this thesis was the development of conjugation of existing methods for analysis of arsenic-glutathione complexes (As-GS complexes) together with simple arsenic species (iAs, MMAs, DMAs) during simple run. The basic technique for analysis of As-GS complexes was the HPLC-ICP-MS method with a reverse phase separation column (C18). The separation problem of simple species has been overcome by extending of system by postcolumn hydride generation with cryotrapping system (HG-CT). The resulting HPLC/HG-CT-ICP-MS system provides a complex analysis of all the above-mentioned analytes. According to the currently available resources, it is an innovative system, where for the first time all the simple arsenic species (iAs, MMAs, DMAs) and the As-GS complexes were separated. Under the given conditions, the detection limit for the As-GS complexes of 1.9 pg cm-3 in the RP-HPLC-ICP-MS system (a quantification limit of 6.5 pg cm-3 ) was achieved at a sensitivity of 468 CPS s pg-1 . The HG-CT-ICP-MS system provided a detection limit for iAs of 1.2 pg cm-3 at a sensitivity of 1121 CPS s pg-1 , for MMAs of 0.043 pg cm-3 at a sensitivity of 895 CPS s pg-1 and for DMAs of 0.076 pg.cm-3 at a sensitivity of 926 CPS s pg-1 . This method was applied to achieve another aim, studying the pathways of enzymatic...

(EN) The presented dissertation thesis summarizes the results contained in five original research papers that were published in prestigious international scientific journals in the field of analytical chemistry and atomic spectrometry. It is devoted to the method of generation of volatile compounds using a tetrahydroborate reaction and detection in a quartz multiatomizer by atomic absorption spectrometry. The thesis can be divided into two thematic parts - speciation analysis of arsenic based on hydride generation technique with collection and separation in a cryogenic trap and generation of volatile species of transition metals. In the first thematic part pre-reduction of pentavalent inorganic and methylated arsenicals has been studied. A simple setup for on-line pre-reduction employing thioglycolic acid as a fast pre-reductant has been developed, connected with a current hydride generator and applied/verified to oxidation state specific arsenic speciation analysis of human urine samples. In the same method the possibility of drying the gaseous phase from water vapor has been investigated to avoid incidental blocking the cryogenic trap by frozen water and to decrease fluctuations of signal baseline. Pronounced losses of methylated species have been discovered on Nafion tube dryer currently used in...

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