Speciation of butyltin derivatives in surface sediments of three southern Brazilian harbors

For the first time, organotin compounds were determined in surface sediment samples collected from Sao Francisco do Sul, Itajai-Navegantes and Imbituba Harbors, located in Santa Catarina State, Brazil. Butyltins (BTs) were determined by gas chromatography with a pulsed flame photometric detector (GC-PFPD) after being modified using the Grignard derivatization method. The concentrations of BTs derivatives ranged from n.d. to 1136.6 ng (Sn) g(-1) of dry weight (dw) sediment for tributyltin (TOT), n.d. to 394.4 ng (Sn)g(-1) dw for dibutyltin (DOT) and n.d. to 312.2 ng (Sn)g(-1) dw for monobutyltin (MBT). The highest concentration of total BTs was found at the Itajai-Acu River dockyard, indicating intense inputs of antifouling paints to the environment. The relative difference in the BTs levels is a particular characteristic of sediments from harbors and may be related to the shipyards and the boat traffic which still use TBT-based antifouling paints.

Combustion of coal, bagasse and blends thereof Part II: Speciation of PAH emissions

This work reports on emissions of unburned hydrocarbon species from batch combustion of fixed beds of coal, sugar-cane bagasse, and blends thereof in a pre-heated two-stage laboratory furnace operated in the temperature range of 800-1000 degrees C. The effects of fuel blending, combustion staging, and operating furnace temperatures on emissions of pollutants were assessed. Furnace effluents were analyzed for products of incomplete combustion (PICs) including CO, volatile and semi-volatile hydrocarbons, and particulate matter, as has been reported in Ref. [1]. Emitted unburned hydrocarbons include traces of potentially health-hazardous Polycyclic Aromatic Hydrocarbons (PAHs), which are the focus of this work. Under the batch combustion conditions implemented herein, PAH were only generated during the volatile combustion phase of the fuels. The most prevalent species were in descending order: naphthalene, acenaphthylene, phenanthrene, fluoranthene, pyrene, dibenzofuran, benzofuran, byphenyl, fluorene, 9H-fluoren-9-one, acephenantrylene, benzo[b] fluoranthene, 1-methyl-naphthalene; 2-methyl-naphthalene, benz[a] anthracene and benzo[a] pyrene. PAH yields were the highest from combustion of neat bagasse. Combustion of the blends resulted in lower yields of PAH, than combustion of either of their neat fuel constituents. Increasing the furnace operating temperature enhanced the PAH emissions from bagasse, but had little effect on those from the coal or from the blends. Flue gas treatment in a secondary-stage furnace, upon with additional air, typically reduced PAH yields by promoting oxidation of the primary-stage furnace effluents. (C) 2011 Elsevier Ltd. All rights reserved.

Selenate and selenite on yield and agronomic biofortification with selenium in rice

The objective of this work was to evaluate the effect of doses of selenate and selenite on rice (Oryza sativa) biofortification with Se, as well the influence of these forms of Se in the levels of P, S, Fe, and Zn in grains. The experiment was conducted in a greenhouse, in pots with 4 dm(3) of a sandy clay loam Latosol, with medium texture, in a 5x2 factorial arrangement with five doses of Se (0, 0.75, 1.50, 3.0, and 6.0 mg dm(-3)) and two forms of Se (selenate and selenite). Selenate provided greater efficiency of root uptake of Se, plant-use efficiency, translocation from roots to shoots, and content of this element in rice grains. The application of Se during fertilization influences the levels of P, S, and Zn, but does not affect those of Fe in rice grains.

Rapid sample preparation procedure for As speciation in food samples by LC-ICP-MS

This paper describes a rapid method for arsenic (As) speciation by LC-ICP-MS in several types of food samples. Prior to analysis, samples were milled and the As species extracted from biological tissues by sonication in only 2 min with a solution containing MeOH (10%, v/v) plus HNO3 (2%, v/v). As species were separated by LC using an anion exchange column. Method detection limits for AsB, As3+,DMA, MMA and As5+ were 1.3, 0.9, 0.6, 0.7 and 0.8 ng g(-1), respectively. Method accuracy and precision were traceable to Certified Reference Materials SRM1577 bovine liver from the National Institute of Standards and Technology, CE278 mussel tissue from the Institute of Reference Materials and Measurements and DOLT-3 dogfish liver tissue and DORM-3 fish protein from the National Research Council of Canada. Finally, the method was applied to speciate As in food samples (egg, fish muscle, beef and chicken) purchased in Brazilian markets.

Effect of topical clay application on the synthesis of collagen in skin: an experimental study

Background. Clay is often used in cosmetic treatments, although little is known about its action. Aim. To evaluate the effect of topical clay application on the histoarchitecture of collagen fibres in rat skin. Methods. Animals received a daily application of clay and retinoic acid (RA) 0.025% to the dorsal skin over 7 and 14 days, under vaporization at 37 degrees C for 40 min. Control skin was not vaporized. Samples from each region were excised, and stained with picrosirius red for collagen evaluation. Results. Seven days after clay treatment, an increase in the number of collagen fibres was observed in treated skin compared with control skin (51.74 +/- 1.28 vs. 43.39 +/- 1.79%, respectively, P < 0.01), whereas RA did not alter the collagen level (45.66 +/- 1.10%). Clay application over 14 days did not induce a further increase in skin collagen, whereas treatment with RA did (58.07 +/- 1.59%; P = 0.001 vs. control). Conclusion. Clay application promotes an increase in the number of collagen fibres, which may account for its beneficial effects.

Cassava starch biodegradable films: Influence of glycerol and clay nanoparticles content on tensile and barrier properties and glass transition temperature

In this this study, glycerol content and its incorporation method on tensile and barrier properties of biodegradable films (BF) based on cassava starch were analyzed. ANOVA showed that the glycerol incorporation method did not influence the results (P > 0.05), however the glycerol content influenced significantly the tensile and barrier properties of the films (P < 0.05). Films prepared with lower glycerol content presented better tensile and barrier properties than films with higher content. Films were then prepared with addition of clay nanoparticles and their tensile and barrier properties and glass transition temperature were measured. ANOVA indicated that both glycerol and clay nanoparticles influenced significantly the tensile and barrier properties (P < 0.05), diminishing film permeability when clay nanoparticles were present, while the glass transition temperature was not influenced (P > 0.05). (C) 2011 Elsevier Ltd. All rights reserved.

Clay-containing block copolymer nanocomposites with aligned morphology prepared by extrusion

Clay-containing nanocomposites of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) copolymers having cylindrical domains were obtained by melt extrusion using a tape die. One type of sample (SEBS-MA) had maleic anhydride attached to the middle block. Two types of organoclays were added, namely Cloisite 20A and Cloisite 30B. Small angle X-ray scattering and transmission electron microscopy (TEM) analyses showed that the addition of 20A clay to SEBS and SEBS-MA resulted in nanocomposites with intercalated and partially exfoliated structures, respectively. The addition of 30B clay to SEBS and SEBS-MA promoted the formation of composites containing relatively large micron-sized and partially exfoliated clay particles, respectively. Our TEM analysis revealed that clay particles embedded in SEBS are preferably in contact with the polystyrene cylindrical domains, while in SEBS-MA they are in contact with the maleated matrix. The extrusion processing promoted alignment of the axes of the polystyrene cylinders along the extrusion direction in all samples, and the basal planes of the clay particles were mostly parallel to the main external surfaces of the extruded tapes. © 2013 Society of Chemical Industry.

Molecular dynamics of poly(Ethylene Glycol) intercalated in clay, studied using 13C solid-state NMR

In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na+ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.

Speciation and fractionation of Ca and the REE in fresh and marine waters

This study is concerned with speciation and fractionation of the rare earth elements (REE) and calcium (Ca) in aqueous solutions. The aim is to investigate the chemical states and physical sizes in which these elements can be present. The REE (including neodymium) and Ca have contrasting geochemical behavior in aqueous solutions. Ca is a major dissolved element, while the REE are trace components and highly reactive with aquatic particles. The major interests of the five papers included in this thesis are the following: · Papers I and V deal with the behavior of neodymium (Nd) and its isotopes in the Kalix River and some marine waters. · The diffusive gradients in thin-films (DGT) method is developed for measuring Ca and Mg in Paper II. · Paper III presents a speciation and fractionation study of Ca in the Kalix and Amazonian rivers. · The rare earth elements and their carrier phases are investigated in the Kalix river in Paper IV. For most elements a detailed study of speciation and fractionation can not be performed using only one method. This is due to the overall heterogeneity of the material, considering both size and chemical composition, which is present in aquatic solutions. During this project the aquatic geochemistry of the REE and Ca has been studied using mainly three methods; cross-flow filtration (CFF), field-flow fractionation (FFF) and diffusive gradients in thin-films (DGT). Field work has to a large part been conducted in the Kalix River, in northern Sweden, which is one of the last pristine river systems in Europe. Some field work has also been conducted in the Baltic Sea and the Arctic Ocean. Results from Amazonian rivers are also presented. These are the main conclusions from this work: The DGT technique works equally well for measuring Ca and Mg in natural waters as previously reported for trace metal. A significant colloidal phase for Ca could be detected in the Kalix River and in different Amazonian rivers. This was concluded independently using both CFF and FFF. Variations in REE signatures in the Kalix River suggests two different pathways for the REE during weathering and release form soil profiles and transport in the river. No significant variation in Nd-isotopic composition could be detected in the Kalix River although concentrations varied by a factor of ~10. This suggests that there is one major source for Nd in the river although different pathways for the REE may exist. A study of Nd in the Kalix River, the Baltic Sea and the Arctic Ocean showed that the isotopic compositions in the diffusible fractions were similar to water samples. However, the relative amount of diffusible Nd increased with salinity, probably reflecting the lower concentration of colloidal and particulate material in marine waters.

Heave of large excavations in clay: modelling and analysis of two british case-histories

ABSTRACT Il presente lavoro vuole introdurre la problematica del rigonfiamento del terreno a seguito di grandi scavi in argilla. Il sollevamento del terreno dopo lo scavo può passare inosservato ma sono numerosi i casi in cui il rigonfiamento dura per molti anni e addirittura decenni, Shell Centre, London, Lion Yard, Cambridge, Bell Common, London, ecc. Questo rigonfiamento il più delle volte è impedito dalla presenza di fondazioni, si genera quindi una pressione distribuita che se non considerata in fase di progetto può portare alla fessurazione della fondazione stessa. L’anima del progetto è la modellazione e l’analisi del rigonfiamento di grandi scavi in argilla, confrontando poi i risultati con i dati reali disponibili in letteratura. L’idea del progetto nasce dalla difficoltà di ottenere stime e previsioni attendibili del rigonfiamento a seguito di grandi scavi in argilla sovraconsolidata. Inizialmente ho esaminato la teoria e i fattori che influenzano il grado e la velocità del rigonfiamento, quali la rigidezza, permeabilità, fessurazione, struttura del suolo, etc. In seguito ho affrontato lo studio del comportamento rigonfiante di argille sovraconsolidate a seguito di scarico tensionale (scavi), si è evidenziata l’importanza di differenziare il rigonfiamento primario e il rigonfiamento secondario dovuto al fenomeno del creep. Il tema centrale del progetto è l’analisi numerica tramite Flac di due grandi scavi in argilla, Lion Yard, Cambridge, e, Bell Common, London. Attraverso una dettagliata analisi parametrica sono riuscito a trovare i migliori parametri che modellano il comportamento reale nei due casi in esame, in questo modo è possibile arrivare a stime e previsioni attendibili del fenomeno rigonfiante del terreno a seguito di grandi scavi. Gli scavi modellati Lion Yard e Bell Common sono rispettivamente in Gault Clay e London Clay, grazie a famosi recenti articoli scientifici sono riuscito a evidenziare la principali propietà che diversificano i due terreni in esame, tali propietà sono estremamente differenti dalle normali caratteristiche considerate per la progettazione in presenza di terreno argilloso; sono così riuscito a implementare i migliori parametri per descrivere il comportamento dei due terreni nei diversi modelli. Ho inoltre studiato l’interazione terreno-struttura, la pressione esercitata dal rigonfiamento del terreno è strettamente funzione delle caratteristiche di connesione tra fondazione superficiale e muro di sostegno, tale pressione non deve essere ignorata in fase progettuale poichè può raggiungere importanti valori. Nello scavo di Lion Yard, considerando la presenza delle fondazioni profonde ho evidenziato il fatto che il rigonfiamento crea una forza distribuita di taglio tra i pali di fondazione ed il terreno, anche tale sollecitazione dovrebbe essere considerata ai fini della progettazione. La problematica non si ferma solo sull’interazione terreno-fondazioni, infatti durante gli scavi di importanti fondazioni londinesi lo scarico tensionale ha creato uno spostamento significativo positivo verso la superfice di tratti di tunnel della metropolita, questo fenomeno può creare seri problemi di sicurezza nella rete dei trasporti pubblici. Infine sono stati messi a confronto i risultati del programma Flac con quelli di metodi semplificati, ho trovato che utilizzando il metodo iterativo di O’Brien i risultati sono simili alla realtà e il tempo di calcolo è molto inferiore di quello richiesto utilizzando Flac, 2-3 giorni. In conclusione posso affermare che grazie ad una dettagliata analisi parametrica è stato possibile stimare il rigonfiamento del terreno, argilla sovraconsolidata, nei due casi analizzati.

Spurenanalyse von Uran und Plutonium sowie Speziationsuntersuchungen an Plutonium mit massenspektrometrischen und kapillarelektrophoretischen Methoden

Die Elemente Uran und Plutonium besitzen seit Entdeckung der Kernspaltung und der technischen Nutzung der Kernenergie eine globale Bedeutung. So trägt Pu hauptsächlich zur Radiotoxizität von abgebrannten Brennelementen bei und erfordert im Falle einer Endlagerung in einer tiefen geologischen Formation einen sicheren Verschluss für bis zu einer Million Jahre. Das Wissen über die vorliegenden chemischen Spezies ist dabei entscheidend für das Verständnis der chemisch-physikalischen Wechselwirkungen im jeweiligen geochemischen System, insbesondere mit dem Wirtsgestein (hier Ton) und den allgegenwärtigen Huminstoffen (hier Fulvinsäure). Längerfristig sind so Vorhersagen über einen Transport des hochradioaktiven Abfalls nach Auslaugung und Austritt aus einem Endlager bis in die Biosphäre möglich. Gerade der Ultraspurenbereich, im Fernfeld eines Endlagers zu erwarten, ist dabei von besonderem Interesse. Darüber hinaus machen nuklearforensische Untersuchungen – in Hinblick auf illegal benutztes Nuklearmaterial, Schmuggel oder Nuklearterrorismus – zur Bestimmung der Herkunft, des Alters oder der Radiotoxizität isotopenselektive Nachweismethoden im Ultraspurenbereich notwendig. Im Rahmen dieser Arbeit wurden hierfür die Resonanzionisationsmassenspektrometrie (RIMS) zur isotopenselektiven Spuren- und Ultraspurenanalyse von U und Pu sowie die Kapillarelektrophorese (CE) gekoppelt an die induktiv gekoppelte Plasma (ICP)-Massenspektrometrie (CE-ICP-MS) zur Speziation von Pu eingesetzt. Für den isotopenselektiven Nachweis von Ultraspurenmengen von Uran mittels RIMS wurden vorbereitende Studien durchgeführt und mehrere zweifach resonante Anregungsleitern mit nicht-resonanter Ionisation untersucht. Eine Effizienz von ca. 10^-10 bei einer Nachweisgrenze von 10^12 Atomen U-238 konnte erzielt werden. In Zusammenarbeit mit dem Institut für Radiochemie, TU München, wurde mittels RIMS die Isotopenzusammensetzung von Plutonium, abgetrennt aus einem panzerbrechenden Urangeschoss aus dem Kosovokonflikt, bestimmt und dieses als Waffenplutonium mit einem Gehalt von 15 pg Pu-239/g Uran identifiziert. Rückschlüsse über Herkunft und Alter des Plutoniums konnten daraus gewonnen werden. Für Studien zur Umweltüberwachung von Plutonium in Rheinland-Pfalz wurden Grund-, Oberflächen- und Klärwasserproben mittels RIMS untersucht. Oberhalb der Nachweisgrenze von ca. 10^7 Atomen Pu-239/500 mL konnte kein signifikanter Gehalt bestimmt werden. Zusätzlich wurden Klärschlammproben untersucht, wobei in einer Probe 5,1*10^7 Atome Pu-239/g gemessen wurde, was auf eine Anreicherung von Pu im Klärschlamm aus großen Wasservolumina hindeuten könnte. Speziationsuntersuchungen von Plutonium in Kontakt mit Fulvinsäure und dem Tonmineral Kaolinit wurden in Hinblick auf die Wechselwirkungen im Umfeld eines nuklearen Endlagers durchgeführt. Die Redoxkinetik von Pu(VI) in Kontakt mit Gorleben-Fulvinsäure zeigt eine mit steigendem pH zunehmend schnellere und vollständige Reduktion und ein vergleichbares Verhalten zur Huminsäure. Für ein Plutoniumgemisch aus allen vier umweltrelevanten Oxidationsstufen in Kontakt mit Gorleben-Fulvinsäure konnte nach ca. 1 Monat Kontaktzeit eine fasst vollständige Reduktion zum tri- und tetravalenten Pu beobachtet werden. Sorptionsuntersuchungen der stabilsten Oxidationsstufe, Pu(IV), in Kontakt mit Kaolinit bei pH = 0 bis 13 im Konzentrationsbereich 10^-7 bis 10^-9 mol/L verdeutlichen das ausgeprägte Sorptionsverhalten von Pu(IV) (ca. 60% bis 90% Sorption) im umweltrelevanten pH-Bereich bei einem Einsetzen der Sorption bei pH = 0 bis 2. Im Rahmen des "Colloid and Radionuclide Retardation" (CRR) Experiments im Felslabor Grimsel, Schweizer Alpen, wurde in Zusammenarbeit mit dem Institut für Nukleare Entsorgung, Karlsruhe, die kolloidgetragene Migration von Pu(IV) in einem Grundwasserstrom durch Scherzonen im Granitgestein unter umweltrelevanten Bedingungen untersucht. Bei Zugabe von im Grundwasser stabilen Bentonitkolloiden – Bentonit wird als ein geeignetes Verschlussmaterial für nukleare Abfälle erforscht – konnte ein erhöhter Transport des Pu(IV) beobachtet werden, der durch Sorption des Pu an die mobilen Kolloide hervorgerufen wird. Zur Speziation von Plutonium im Ultraspurenbereich wurde im Rahmen dieser Arbeit an der Entwicklung der Kopplung der CE mit der sehr sensitiven RIMS gearbeitet. Das Prinzip der offline-Kopplung basiert auf dem Sammeln der zu unterschiedlichen Zeiten am Ende der Kapillare eluierten Oxidationsstufen in einzelnen Fraktionen. Aus jeder Fraktion wird ein eigenes Filament hergestellt und mit RIMS auf seinen Plutoniumgehalt untersucht. Eine erste Validierung der Methode konnte durch Bestimmung der Oxidationsstufenzusammensetzung eines bekannten Gemischs erfolgreich für einen Gehalt von ca. 6*10^9 Atome Pu-239 durchgeführt werden. Dies stellt einen möglichen Zugang zu dem erwarteten Konzentrationsbereich im Fernfeld eines Endlagers dar.

Iodine speciation in atmospheric aerosols in the marine boundary layer

Iodine chemistry plays an important role in the tropospheric ozone depletion and the new particle formation in the Marine Boundary Layer (MBL). The sources, reaction pathways, and the sinks of iodine are investigated using lab experiments and field observations. The aims of this work are, firstly, to develop analytical methods for iodine measurements of marine aerosol samples especially for iodine speciation in the soluble iodine; secondly, to apply the analytical methods in field collected aerosol samples, and to estimate the characteristics of aerosol iodine in the MBL. Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) was the technique used for iodine measurements. Offline methods using water extraction and Tetra-methyl-ammonium-hydroxide (TMAH) extraction were applied to measure total soluble iodine (TSI) and total insoluble iodine (TII) in the marine aerosol samples. External standard calibration and isotope dilution analysis (IDA) were both conducted for iodine quantification and the limits of detection (LODs) were both 0.1 μg L-1 for TSI and TII measurements. Online couplings of Ion Chromatography (IC)-ICP-MS and Gel electrophoresis (GE)-ICP-MS were both developed for soluble iodine speciation. Anion exchange columns were adopted for IC-ICP-MS systems. Iodide, iodate, and unknown signal(s) were observed in these methods. Iodide and iodate were separated successfully and the LODs were 0.1 and 0.5 μg L-1, respectively. Unknown signals were soluble organic iodine species (SOI) and quantified by the calibration curve of iodide, but not clearly identified and quantified yet. These analytical methods were all applied to the iodine measurements of marine aerosol samples from the worldwide filed campaigns. The TSI and TII concentrations (medians) in PM2.5 were found to be 240.87 pmol m-3 and 105.37 pmol m-3 at Mace Head, west coast of Ireland, as well as 119.10 pmol m-3 and 97.88 pmol m-3 in the cruise campaign over the North Atlantic Ocean, during June – July 2006. Inorganic iodine, namely iodide and iodate, was the minor iodine fraction in both campaigns, accounting for 7.3% (median) and 5.8% (median) in PM2.5 iodine at Mace Head and over the North Atlantic Ocean, respectively. Iodide concentrations were higher than iodate in most of the samples. In the contrast, more than 90% of TSI was SOI and the SOI concentration was correlated significantly with the iodide concentration. The correlation coefficients (R2) were both higher than 0.5 at Mace Head and in the first leg of the cruise. Size fractionated aerosol samples collected by 5 stage Berner impactor cascade sampler showed similar proportions of inorganic and organic iodine. Significant correlations were obtained in the particle size ranges of 0.25 – 0.71 μm and 0.71 – 2.0 μm between SOI and iodide, and better correlations were found in sunny days. TSI and iodide existed mainly in fine particle size range (< 2.0 μm) and iodate resided in coarse range (2.0 – 10 μm). Aerosol iodine was suggested to be related to the primary iodine release in the tidal zone. Natural meteorological conditions such as solar radiation, raining etc were observed to have influence on the aerosol iodine. During the ship campaign over the North Atlantic Ocean (January – February 2007), the TSI concentrations (medians) ranged 35.14 – 60.63 pmol m-3 among the 5 stages. Likewise, SOI was found to be the most abundant iodine fraction in TSI with a median of 98.6%. Significant correlation also presented between SOI and iodide in the size range of 2.0 – 5.9 μm. Higher iodate concentration was again found in the higher particle size range, similar to that at Mace Head. Airmass transport from the biogenic bloom region and the Antarctic ice front sector was observed to play an important role in aerosol iodine enhancement. The TSI concentrations observed along the 30,000 km long cruise round trip from East Asia to Antarctica during November 2005 – March 2006 were much lower than in the other campaigns, with a median of 6.51 pmol m-3. Approximately 70% of the TSI was SOI on average. The abundances of inorganic iodine including iodine and iodide were less than 30% of TSI. The median value of iodide was 1.49 pmol m-3, which was more than four fold higher than that of iodate (median, 0.28 pmol m-3). Spatial variation indicated highest aerosol iodine appearing in the tropical area. Iodine level was considerably lower in coastal Antarctica with the TSI median of 3.22 pmol m-3. However, airmass transport from the ice front sector was correlated with the enhance TSI level, suggesting the unrevealed source of iodine in the polar region. In addition, significant correlation between SOI and iodide was also shown in this campaign. A global distribution in aerosol was shown in the field campaigns in this work. SOI was verified globally ubiquitous due to the presence in the different sampling locations and its high proportion in TSI in the marine aerosols. The correlations between SOI and iodide were obtained not only in different locations but also in different seasons, implying the possible mechanism of iodide production through SOI decomposition. Nevertheless, future studies are needed for improving the current understanding of iodine chemistry in the MBL (e.g. SOI identification and quantification as well as the update modeling involving organic matters).

Anwendung der CE-ICP-MS und RIMS sowie Entwicklung und Anwendung der CE-RIMS auf Umweltproben

Die vorliegende Arbeit wurde im Rahmen des Verbundprojektes „Wechselwirkung und Transport von Actiniden im natürlichen Tongestein unter Berücksichtigung von Huminstoffen und Tonorganika – Wechselwirkung von Neptunium und Plutonium mit natürlichem Tongestein“ durchgeführt. Diese Untersuchungen sollen die thermodynamische Datenbasis für Actiniden erweitern sowie Informationen zur Ableitung von Bewertungskriterien für die Endlagerung radioaktiver Abfälle in Ton als Wirtsgestein, insbesondere über das Rückhaltevermögen von Tongestein gegenüber Radionukliden, liefern. Dabei stand die Anwendung verschiedener Speziationstechniken wie CE-ICP-MS, UV/VIS und die apparative Entwicklung der CE-RIMS im Vordergrund. Es sollte das Verhalten von Plutonium in umweltrelevanten Medien und Konzentrationen, im Ultraspurenbereich, untersucht werden. Unabhängig davon sollten Uranproben aus dem 2. Weltkrieg und Umweltproben des Landesamts für Umwelt und Forsten Rheinland-Pfalz auf ihren Plutoniumgehalt analysiert werden. Dazu wurde zunächst ein neues ICP-MS-Gerät Agilent 7500ce in Betrieb genommen und auf die Verwendung in Kombination mit der Kapillarelektrophorese optimiert. Die erreichte Nachweisgrenze für die vier Oxidationsstufen des Pu beträgt 0,05 ppb des gesamten Plutoniums in Lösung. Mit Hilfe der CE-ICP-MS wurde die Redoxstabilität einer Mischung aus verschiedenen Oxidationszuständen des Plutoniums in Opalinus-Ton-Porenwasser und Vergleichsmedien unter aeroben und anaeroben Bedingungen mit der CE untersucht. Die Untersuchungen zeigen das Pu(III) bis zu 40 min im verwendeten Elektrolytsystem stabil ist und dann oxidiert wird. In Porenwasser wurde als vorherrschende Spezies Pu(V) bestimmt. Die Redoxstabilität von Pu(VI) wurde untersucht, dabei wurde festgestellt, dass sich Pu(VI) bereits durch einfaches Verdünnen reduzieren lässt. Weiterhin wurden die Kd-Werte für die Sorption von Plutonium an Opalinuston unter aeroben und anaeroben Bedingungen für Pu(III) und Pu(IV) im System Porenwasser/Opalinuston von Kd(aerob) Pu(III) ≈ 53 m3/kg, Kd(aerob) Pu(IV) ≈ 14 m3/kg, Kd(anaerob) Pu(III) ≈ 114 m3/kg, Kd(anaerob) Pu(IV) ≈ 178 m3/kg bestimmt. Ein weiterer Schwerpunkt der Arbeit war die Entwicklung, Optimierung und Anwendung der Kopplung CE-RIMS zur Speziation des Plutoniums im Ultraspurenbereich. Dies konnte erfolgreich in mehreren Schritten durchgeführt und an den Proben aus den Batchversuchen zur Kd-Wert Bestimmung angewandt werden. Der Memory-Effekt des an den Kapillarwänden sorbierenden Pu(IV) konnte mit der empfindlichen Kopplung CE-RIMS ebenfalls nachgewiesen werden.

Transposable elements dynamics in taxa with different reproductive strategies or speciation rate

In recent years the advances in genomics allowed to understand the importance of Transposable Elements (TE) in the evolution of eukaryotic genomes. In this thesis I face two aspects of the TE impact on the in the animal kingdom. The first part is a comparison of the dynamics of the TE dynamics in three species of stick-insects of the Genus Bacillus. I produced three random genomic libraries of 200 Kbps for the three parental species of the taxon: a gonochoric population of Bacillus rossius (facultative parthenogenetic), Bacillus grandii (gonochoric) and Bacillus atticus (obligate parthenogenetic). The unisexual taxon Bacillus atticus does not shows dramatic differences in TE total content and activity with respect to Bacillus grandii and Bacillus rossius. This datum does not confirm the trend observed in other animal models in which unisexual taxa tend to repress the activity of TE to escape the extinction by accumulation of harmful mutations. In the second part I tried to add a contribute to the debate initiated in recent years about the possibility that a high TE content is linked to a high rate of speciation. I designed an evolutionary framework to establish the different rate of speciation among two or more taxa, then I compared TE dynamics considering the different rates of speciation. The species dataset comprises: 29 mammals, four birds, two fish and two insects. On the whole the majority of comparisons confirms the expected trend. In particular the amount of species analyzed in Mammalia allowed me to get a statistical support (p<0,05) of the fact that the TE activity of recently mobilized elements is positively related with the rate of speciation.