U-Pb dating by zircon dissolution method using chemical abrasion

Chemical abrasion was carried out on zircons grains of the Temora II standard for U-Pb dating prior to analyses using in situ Laser Ablation-MultiCollector Ion Coupled Plasma Mass Spectrometer (LA-ICPMS) followed by the Isotope Dissolution Thermal Ionization Mass Spectrometer (ID-TIMS) method. The proposed methodology was herein applied in order to reduce primarily the effects of secondary Pb loss, the presence of common lead and/or silicate impurities. Nine Temora II zircon grains were analyzed by the laser ablation method yielding an age of 418.3±4.3 Ma. Zircon grains of a same population were separated for chemical abrasion before dissolution and mass spectrometry analyses. Six fractions of them were separated for isotope dissolution using 235U-205Pb mixed spike after we have checked and assured the laboratory conditions of low blank values for total Pb of less than 2 pg/g. The obtained U-Pb zircon age by the ID-TIMS method was 415.7±1.8 Ma (error 0.43 %) based on four successful determinations. The results are consistent with the published ages for the Temora diorite (Temora I â 416.75±1.3 Ma; Temora II â 416.78±0.33 Ma) and established as 416±0.33 Ma. The technique is thus recommended for high precision U-Pb zircon analyses (error < 1 %), mainly for high resolution stratigraphic studies of Phanerozoic sequences.

Estudo por espectrometria de massas de soluções de hidróxi(tosilóxi)iodobenzeno: propostas para mecanismos de desproporção

Solutions of [hydroxy(tosyloxy)iodo]benzene (HTIB or Koser's reagent) in acetonitrile were analyzed using high resolution electrospray ionization mass spectrometry (ESI-MS) and electrospray ionization tandem mass spectrometry (ESI-MS/MS) under different conditions. Several species were characterized in these analyses. Based on these data, mechanisms were proposed for the disproportionation of the iodine(III) compounds in iodine(V) and iodine(I) species.

Aplicação de espectrometria de massas com ionização por elétron na análise de alcaloides do mulungu

Erythrina verna is a medicinal plant used to calm agitation popularly known as mulungu. We purchased the barks of E. verna from a commercial producer and analyzed the alkaloid fraction of the bark by CG-MS and HRESI-MS. Five erythrinian alkaloids were identified: erysotrine, erythratidine, erythratidinone, epimer, and 11-hydroxieritratidinone. Here we report the compound 11-hydroxieritratidinone for the first time as a natural product.

Cooking effects on iron and proteins content of beans (Phaseolus Vulgaris L.) by GF AAS and MALDI-TOF MS

The effects of domestic cooking on proteins, organic compounds and Fe distribution in beans (Phaseolus vulgaris L.) were investigated. Sequential extraction with different extractant solutions (mixture of methanol and chloroform 1:2 v/v, water, 0.5 mol L-1 NaCl, 70% v/v ethanol and 0.5 mol L-1 NaOH) were used for extracting lipids, albumins, globulins, prolamins and glutelins, respectively. Iron determination by graphite furnace atomic absorption spectrometry (GF AAS), proteins by Bradford method and organic compounds by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) were carried out in this work. High concentration of albumins, globulins and glutelins were found in raw beans, while in the cooked beans, albumins and glutelins are main proteins types. The MALDI-TOF MS spectra of raw and cooked beans revealed that the domestic cooking altered the molecular weight of the organic compounds, since that in the cooked beans were found compounds between 2 and 3.5 kDa, which were not presented in the raw beans. Besides this, in cooked beans were also observed the presence of four compounds of high molecular weight (12-16 kDa), being that in the raw grains there is only one (ca. 15.2 kDa). In raw grains is possible to observe that Fe is mainly associated to albumins, globulins and glutelins. For cooked grains, Fe is associated to albumins and globulins.

A multiproxy assessment of organic pollution in shore sediments from the Río de la Plata Estuary, SW Atlantic

The study of organic pollution in estuaries is very relevant as they are transitional zones, which control the fluxes of water, nutrients, particles and organisms from and to the continental margins, rivers and oceans. The aims of this study are:(1) to evaluate organic pollution in coastal sediments of Montevideo, Río de la Plata Estuary by a multi-biomarker approach, (2) to identify major sources of organic pollutants through qualitative analysis using molecular indices, (3) to assess the relative contribution of different sources of hydrocarbons through quantitative source apportionment employing (PCA/MLR) as chemometric technique. Sampling surveys were carried out in July 2009, January 2010 and March 2011 in 37 stations along the middle portion of the Río de la Plata Estuary across the coast of Montevideo. In each station surface (0–2 cm depth) sediment samples were taken with a 0.05 m2 van Veen grab. The Soxhlet extracted organic compounds included aliphatic hydrocarbons (AHs) and steroids, analysed by gas chromatograph with flame ionization detector (GC-FID), linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs) quantified by gas chromatograph with mass spectrometer (GC/MS). All biomarkers presented the highest concentrations in the stations of Montevideo Bay indicating high levels of organic pollution. The combination of molecular indices and the chemometric technique showed that major sources of AHs and PAHs are petroleum inputs and combustion, due to oil transport and refinement, harbour activities and vehicular emissions.Major sources of LABs and steroids are urban and domestic sewage. Identification, quantification and source assignment of those organic compounds are very important to assess pollution and to give tools to help minimize the inputs into the environment

Equilibrium topology for plasmas with reversed current density.

Actually, transition from positive to negative plasma current and quasi-steady-state alternated current (AC) operation have been achieved experimentally without loss of ionization. The large transition times suggest the use of MHD equilibrium to model the intermediate magnetic field configurations for corresponding current density reversals. In the present work we show, by means of Maxwell equations, that the most robust equilibrium for any axisymmetric configuration with reversed current density requires the existence of several nonested families of magnetic surfaces inside the plasma. We also show that the currents inside the nonested families satisfy additive rules restricting the geometry and sizes of the axisymmetric magnetic islands; this is done without restricting the equilibrium through arbitrary functions. Finally, we introduce a local successive approximations method to describe the equilibrium about an arbitrary reversed current density minimum and, consequently, the transition between different nonested topologies is understood in terms of the eccentricity of the toroidal current density level sets.

Solid-phase Microextraction and Detection of Organophosphate Triesters in Indoor air

In the work underlying this thesis solid-phase microextraction (SPME) was evaluated as a passive sampling technique for organophosphate triesters in indoor air. These compounds are used on a large scale as flame-retarding and plastizicing additives in a variety of materials and products, and have proven to be common pollutants in indoor air. The main objective of this work was to develop an accurate method for measuring the volatile fraction. Such a method can be used in combination with active sampling to obtain information regarding the vapour/particulate distribution in different indoor environments. SPME was investigated under both equilibrium and non-equilibrium conditions and parameters associated with these different conditions were estimated. In Paper I, time-weighted average (TWA) SPME under dynamic conditions was investigated in order to obtain a fast air sampling method for organophosphate triesters. Among the investigated SPME coatings, the absorptive PDMS polymer had the highest affinity for the organophosphate triesters and was consequently used in all further work. Since the sampling rate is dependent on the agitation conditions, the linear airflow rates had to be carefully considered. Sampling periods as short as 1 hour were shown to be sufficient for measurements in the ng-μg m-3 range when using a PDMS 100-μm fibre and a linear flow rate above 7 cm s-1 over the fibre. SPME under equilibrium conditions is rather time-consuming, even under dynamic conditions, for slowly partitioning compounds such as organophosphate triesters. Nevertheless, this method has some significant advantages. For instance, the limit of detection is much lower compared to 1 h TWA sampling. Furthermore, the sampling time can be ignored as long as equilibrium has been attained. In Paper II, SPME under equilibrium conditions was investigated and evaluated for organophosphate triester vapours. Since temperature and humidity are closely associated with the distribution constant a simple study of the effect of these parameters was performed. The obtained distribution constants were used to determine the air levels in a common indoor environment. SPME and parallel active sampling on filters yielded similar results, indicating that the detected compounds were almost entirely associated with the vapour phase To apply dynamic SPME method in the field a sampler device, which enables controlled linear airflow rates to be applied, was constructed and evaluated (Paper III). This device was developed for application of SPME and active sampling in parallel. A GC/PICI-MS/MS method was developed and used in combination with active sampling of organophosphate triesters in indoor air (Paper IV). The combination of MS/MS and the soft ionization achieved with methanol as reagent gas yielded high selectivity and detection limits comparable to those provided by GC with nitrogen-phosphorus detection (NPD). The method limit of detection, when sampling 1.5 m3 of air, was in the range 0.1-1.4 ng m-3. In Paper V, the developed MS method was used in combination with SPME for indoor air measurements. The levels detected in the investigated indoor environments range from a few ng to μg m-3. Tris(2-chloropropyl) phosphate was detected at a concentration as high as 7 μg m-3 in a newly rebuilt lecture room.

Contenido de radón en aguas subterráneas del noreste de Gran Canaria

[ES] En este trabajo se han determinado los niveles de 222Rn en el agua subterránea en la zona noreste de Gran Canaria a partir de 28 muestras de pozos en bombeo. La concentración de actividad de radón en una muestra de agua se determina mediante un sistema en circuito cerrado que consta de un monitor AlphaGUARD que mide la concentración de radón en aire por medio de una cámara de ionización y un conjunto AquaKIT que se utiliza para transferir el radón disuelto en la muestra de agua al aire del circuito. Los valores de la concentración de radón en agua de las muestras estudiadas varían entre 0.9 y 76.9 Bq/L. Debido a la peligrosidad radiológica del radón, en España se ha establecido un límite de actividad de 100 Bq/L de 222Rn para las aguas de consumo humano. Los valores obtenidos para todas las muestras analizadas se encuentran por debajo de este límite.

Metrologia dei campi di radiazioni di bassa energia

The conversion coefficients from air kerma to ICRU operational dose equivalent quantities for ENEA’s realization of the X-radiation qualities L10-L35 of the ISO “Low Air Kerma rate” series (L), N10-N40 of the ISO “Narrow spectrum” series (N) and H10-H60 of the ISO “High Air-kerma rate” (H) series and two beams at 5 kV and 7.5 kV were determined by utilising X-ray spectrum measurements. The pulse-height spectra were measured using a planar high-purity germanium spectrometer (HPGe) and unfolded to fluence spectra using a stripping procedure then validate with using Monte Carlo generated data of the spectrometer response. HPGe portable detector has a diameter of 8.5 mm and a thickness of 5 mm. The entrance window of the crystal is collimated by a 0.5 mm thick Aluminum ring to an open diameter of 6.5 mm. The crystal is mounted at a distance of 5 mm from the Berillium window (thickness 25.4 micron). The Monte Carlo method (MCNP-4C) was used to calculate the efficiency, escape and Compton curves of a planar high-purity germanium detector (HPGe) in the 5-60 keV energy. These curves were used for the determination of photon spectra produced by the X-ray machine SEIFERT ISOVOLT 160 kV in order to allow a precise characterization of photon beams in the low energy range, according to the ISO 4037. The detector was modelled with the MCNP computer code and validated with experimental data. To verify the measuring and the stripping procedure, the first and the second half-value layers and the air kerma rate were calculated from the counts spectra and compared with the values measured using an a free-air ionization chamber. For each radiation quality, the spectrum was characterized by the parameters given in ISO 4037-1. The conversion coefficients from the air kerma to the ICRU operational quantities Hp(10), Hp(0.07), H’(0.07) and H*(10) were calculated using monoenergetic conversion coefficients. The results are discussed with respect to ISO 4037-4, and compared with published results for low-energy X-ray spectra. The main motivation for this work was the lack of a treatment of the low photon energy region (from a few keV up to about 60 keV).

Mass spectrometry-based protein profiling strategies for biomarker discovery in liver and inflammatory bowel diseases

The study of protein expression profiles for biomarker discovery in serum and in mammalian cell populations needs the continuous improvement and combination of proteins/peptides separation techniques, mass spectrometry, statistical and bioinformatic approaches. In this thesis work two different mass spectrometry-based protein profiling strategies have been developed and applied to liver and inflammatory bowel diseases (IBDs) for the discovery of new biomarkers. The first of them, based on bulk solid-phase extraction combined with matrix-assisted laser desorption/ionization - Time of Flight mass spectrometry (MALDI-TOF MS) and chemometric analysis of serum samples, was applied to the study of serum protein expression profiles both in IBDs (Crohn’s disease and ulcerative colitis) and in liver diseases (cirrhosis, hepatocellular carcinoma, viral hepatitis). The approach allowed the enrichment of serum proteins/peptides due to the high interaction surface between analytes and solid phase and the high recovery due to the elution step performed directly on the MALDI-target plate. Furthermore the use of chemometric algorithm for the selection of the variables with higher discriminant power permitted to evaluate patterns of 20-30 proteins involved in the differentiation and classification of serum samples from healthy donors and diseased patients. These proteins profiles permit to discriminate among the pathologies with an optimum classification and prediction abilities. In particular in the study of inflammatory bowel diseases, after the analysis using C18 of 129 serum samples from healthy donors and Crohn’s disease, ulcerative colitis and inflammatory controls patients, a 90.7% of classification ability and a 72.9% prediction ability were obtained. In the study of liver diseases (hepatocellular carcinoma, viral hepatitis and cirrhosis) a 80.6% of prediction ability was achieved using IDA-Cu(II) as extraction procedure. The identification of the selected proteins by MALDITOF/ TOF MS analysis or by their selective enrichment followed by enzymatic digestion and MS/MS analysis may give useful information in order to identify new biomarkers involved in the diseases. The second mass spectrometry-based protein profiling strategy developed was based on a label-free liquid chromatography electrospray ionization quadrupole - time of flight differential analysis approach (LC ESI-QTOF MS), combined with targeted MS/MS analysis of only identified differences. The strategy was used for biomarker discovery in IBDs, and in particular of Crohn’s disease. The enriched serum peptidome and the subcellular fractions of intestinal epithelial cells (IECs) from healthy donors and Crohn’s disease patients were analysed. The combining of the low molecular weight serum proteins enrichment step and the LCMS approach allowed to evaluate a pattern of peptides derived from specific exoprotease activity in the coagulation and complement activation pathways. Among these peptides, particularly interesting was the discovery of clusters of peptides from fibrinopeptide A, Apolipoprotein E and A4, and complement C3 and C4. Further studies need to be performed to evaluate the specificity of these clusters and validate the results, in order to develop a rapid serum diagnostic test. The analysis by label-free LC ESI-QTOF MS differential analysis of the subcellular fractions of IECs from Crohn’s disease patients and healthy donors permitted to find many proteins that could be involved in the inflammation process. Among them heat shock protein 70, tryptase alpha-1 precursor and proteins whose upregulation can be explained by the increased activity of IECs in Crohn’s disease were identified. Follow-up studies for the validation of the results and the in-depth investigation of the inflammation pathways involved in the disease will be performed. Both the developed mass spectrometry-based protein profiling strategies have been proved to be useful tools for the discovery of disease biomarkers that need to be validated in further studies.

EoR in alternative cosmological scenarios

The aim of this Thesis is to investigate the possibility that the observations related to the epoch of reionization can probe not only the evolution of the IGM state, but also the cosmological background in which this process occurs. In fact, the history of the IGM ionization is indeed affected by the evolution of the sources of ionizing photons that, under the assumption of a structure formation paradigm determined by the hierarchic growth of the matter uctuations, results strongly dependent on the characteristics of the background universe. For the purpose of our investigation, we have analysed the reionization history in innovative cosmological frameworks, still in agreement with the recent observational tests related to the SNIa and the CMB probes, comparing our results with the reionization scenario predicted by the commonly used LCDM cosmology. In particular, in this Thesis we have considered two different alternative universes. The first one is a at universe dominated at late epochs by a dynamic dark energy component, characterized by an equation of state evolving in time. The second cosmological framework we have assumed is a LCDM characterized by a primordial overdensity field having a non-Gaussian probability distribution. The reionization scenario have been investigated, in this Thesis, through semi-analytic approaches based on the hierarichic growth of the matter uctuations and on suitable assumptions concerning the ionization and the recombination of the IGM. We make predictions for the evolution and the distribution of the HII regions, and for the global features of reionization, that can be constrained by future observations. Finally, we brie y discuss the possible future prospects of this Thesis work.

Cross-Talk tra Bifidobacterium e intestino umano: impatto sulle attività health promoting

Bifidobacteria constitute up to 3% of the total microbiota and represent one of the most important healthpromoting bacterial groups of the human intestinal microflora. The presence of Bifidobacterium in the human gastrointestinal tract has been directly related to several health-promoting activities; however, to date, no information about the specific mechanisms of interaction with the host is available. The first health-promoting activities studied in these job was the oxalate-degrading activity. Oxalic acid occurs extensively in nature and plays diverse roles, especially in pathological processes. Due to its highly oxidizing effects, hyper absorption or abnormal synthesis of oxalate can cause serious acute disorders in mammals and be lethal in extreme cases. Intestinal oxalate-degrading bacteria could therefore be pivotal in maintaining oxalate homeostasis, reducing the risk of kidney stone development. In this study, the oxalate-degrading activity of 14 bifidobacterial strains was measured by a capillary electrophoresis technique. The oxc gene, encoding oxalyl-CoA decarboxylase, a key enzyme in oxalate catabolism, was isolated by probing a genomic library of B. animalis subsp. lactis BI07, which was one of the most active strains in the preliminary screening. The genetic and transcriptional organization of oxc flanking regions was determined, unravelling the presence of other two independently transcribed open reading frames, potentially responsible for B. animalis subsp. lactis ability to degrade oxalate. Transcriptional analysis, using real-time quantitative reverse transcription PCR, revealed that these genes were highly induced in cells first adapted to subinhibitory concentrations of oxalate and then exposed to pH 4.5. Acidic conditions were also a prerequisite for a significant oxalate degradation rate, which dramatically increased in oxalate pre-adapted cells, as demonstrated in fermentation experiments with different pH-controlled batch cultures. These findings provide new insights in the characterization of oxalate-degrading probiotic bacteria and may support the use of B. animalis subsp. lactis as a promising adjunct for the prophylaxis and management of oxalate-related kidney disease. In order to provide some insight into the molecular mechanisms involved in the interaction with the host, in the second part of the job, we investigated whether Bifidobacterium was able to capture human plasminogen on the cell surface. The binding of human plasminogen to Bifidobacterium was dependent on lysine residues of surface protein receptors. By using a proteomic approach, we identified six putative plasminogen-binding proteins in the cell wall fraction of three strain of Bifidobacterium. The data suggest that plasminogen binding to Bifidobactrium is due to the concerted action of a number of proteins located on the bacterial cell surface, some of which are highly conserved cytoplasmic proteins which have other essential cellular functions. Our findings represent a step forward in understanding the mechanisms involved in the Bifidobacterium-host interaction. In these job w studied a new approach based on to MALDI-TOF MS to measure the interaction between entire bacterial cells and host molecular target. MALDI-TOF (Matrix Assisted Laser Desorption Ionization-Time of Flight)—mass spectrometry has been applied, for the first time, in the investigation of whole Bifidobacterium cells-host target proteins interaction. In particular, by means of this technique, a dose dependent human plasminogen-binding activity has been shown for Bifidobacterium. The involvement of lysine binding sites on the bacterial cell surface has been proved. The obtained result was found to be consistent with that from well-established standard methodologies, thus the proposed MALDI-TOF approach has the potential to enter as a fast alternative method in the field of biorecognition studies involving in bacterial cells and proteins of human origin.

Methodische Entwicklung der MALDI-TOF-Massenspektrometrie für Grenzbereiche der Polymeranalytik

Zusammenfassung der DoktorarbeitDie MALDI-TOF-Massenspektrometrie (Matrix Assisted Laser Desorption and Ionisation–Time Of Flight) ist in der Lage, Moleküle mit einem Molekulargewicht bis zu mehreren Hunderttausend Da intakt in die Gasphase zu überführen. Dabei wird die Fragmentierung des Analyten stark eingeschränkt bzw. gänzlich vermieden. Diese Methode findet daher zunehmend Verwendung für die Charakterisierung von Biopolymeren und synthetischen Polymeren. Ziel dieser Arbeit war, die MALDI-TOF-Massenspektrometrie zur Charakterisierung von Makromolekülen einzusetzen, bei denen die konventionellen polymeranalytischen Methoden nur unzureichende Informationen oder gar falsche bzw. gar keine Ergebnisse liefern. Mittels einer methodischen Entwicklung der MALDI-TOF-Massenspektrometrie gelang es, die bisherigen Grenzen der Methode zu erweitern und neue Anwendungsbereiche der Polymeranalytik aufzuzeigen. Anhand der erzielten Ergebnisse wurden darüber hinaus neue Erklärungsansätze formuliert, die zu einem besseren Verständnis des noch immer ungeklärten MALDI-Prozesses beitragen können. Besonders vielversprechend sind zum einen die Ergebnisse der Fragmentionenanalyse synthetischer Polymere und zum anderen die Charakterisierung von unlöslichen PAHs (Polycyclic Aromatic Hydrocarbons). Die Möglichkeiten und Aussagekraft der Fragmentionenanalyse wurde an synthetischen Polymeren getestet. Mit Hilfe dieser neuen Technik konnte die komplizierte Endgruppenverteilung einer Polycarbonat-Probe sowie die Zusammensetzung eines Poly-para-phenylenethynylen-b-Polyethylenoxid-Diblock-Copolymers eindeutig bestimmen werden, während die konventionellen MALDI-Massenspektren nur über einen wesentlich geringeren Informationsgehalt verfügten. Auf dem Gebiet der Analytik von unlöslichen PAHs wurde mit der Entwicklung einer neuen MALDI-Probenvorbereitung eine Methode gefunden, die über die PAH Analytik hinaus von großem Nutzen ist. Diese erstmalig angewendete Probenvorbereitung unterscheidet sich von den üblichen MALDI-Probenpräparationen, indem sie auf die Beteiligung eines Lösungsmittels vollkommen verzichtet. Damit konnte speziell ein unlöslicher, zuvor nicht nachweisbarer PAH von ca. 2700 Da mit MALDI eindeutig charakterisiert werden.

Resonante Laserionisations-Massenspektrometrie an Gadolinium zur Isotopenhäufigkeitsanalyse mit geringsten Mengen

Resonante Laserionisations-Massenspektrometrie an Gadolinium zur Isotopenhäufigkeitsanalyse mit geringsten Mengen Die selektive Spuren- und Ultraspurenanalyse des Erdalkalielements Gadolinium eröffnet eine Vielzahl von Anwendungen in der Biomedizin und Kosmochemie. Zum Erreichen der hohen Anforderungen bezüglich Isotopen- und Isobarenselektivität von S>10^7 sowie Gesamteffizienz von e>10^-6 wurde der Einsatz der resonanten Laserionisations-Massenspektrometrie untersucht. Dazu erfolgte die Weiterentwicklung und Anpassung des existierenden Diodenlaser-Quadrupolmassenspektrometersystems. Durch Ionenflugbahn-Simulationsrechnungen wurde für das Quadrupol-Massenspektrometer die erreichbare Nachbarmassenunterdrückung und Transmission in Abhängigkeit von der Auflösung theoretisch vorhergesagt. Die Werte wurden experimentell bestätigt. Aus der beobachteten Peakstruktur erfolgte die Ableitung einer Methode zur Bestimmung der Energieunschärfe des eingesetzten Ionisationsprozesses. Zum Auffinden eines effizienten dreifach resonanten Anregungsschemas wurden die Isotopieverschiebungen und Hyperfeinstrukturen aller stabilen Gadoliniumisotope in zahlreichen Übergängen für die einfach, zweifach und dreifach resonante Ionisation präzise vermessen. Das aufgenommene Spektrum autoionisierender Resonanzen zeigte etwa 150 bislang unbekannter Zustände mit Resonanzüberhöhungen von bis zu fünf Größenordnungen im Ionisationswirkungsquerschnitt. Die entwickelte Methode der Hyperfeinzustandsselektion ermöglichte die Bestimmung der Drehimpulsquantenzahl J der autoionisierenden Resonanzen. Die analytische Charakterisierung der dreistufig resonanten Ionisation von Gadolinium ergab eine Isotopen- und Isobarenselektivität von S(Isotop)>10^12 und S(Isobar)>10^7. Die mit dem Diodenlasersystem erreichte Nachweiseffizienz von e=1-3x10^-6 mit einer untergrundlimitierten Nachweisgrenze von wenigen 10^9 Atomen Gd-158 erlaubte erste Demonstrationsmessungen an medizinischen Gewebeproben.

Bestimmung der Ionisationsenergie von Actinium und Ultraspurenanalyse von Plutonium mit resonanter Ionisationsmassenspektrometrie (RIMS)

ZusammenfassungDie Resonanzionisationsmassenspektrometrie (RIMS) verbindet hohe Elementselektivität mit guter Nachweiseffizienz. Aufgrund dieser Eigenschaften ist die Methode für Ultraspurenanalyse und Untersuchungen an seltenen oder schwer handhabbaren Elementen gut geeignet. Für RIMS werden neutrale Atome mit monochromatischem Laserlicht ein- oder mehrfach resonant auf energetisch hoch liegende Niveaus angeregt und anschließend durch einen weiteren Laserstrahl oder durch ein elektrisches Feld ionisiert. Die Photoionen werden in einem Massenspektrometer massenselektiv registriert.Ein Beispiel für die Anwendung von RIMS ist die präzise Bestimmung der Ionisationsenergie als fundamentale physikalisch-chemische Eigenschaft eines bestimmten Elements; insbesondere bei den Actinoiden ist die Kenntnis der Ionisationsenergie von Interesse, da es dort bis zur Anwendung der laser-massenspektroskopischer Methode nur wenige experimentelle Daten gab. Die Bestimmung der Ionisationsenergie erfolgt durch die Methode der Photoionisation im elektrischen Feld gemäß dem klassischen Sattelpunktsmodell. Im Experiment werden neutrale Atome in einem Atomstrahl mittels Laserlicht zunächst resonant angeregt. Die angeregten Atome befinden sich in einem äußeren, statischen elektrischen Feld und werden durch einen weiteren Laserstrahl, dessen Wellenlänge durchgestimmt wird, ionisiert. Das Überschreiten der Laserschwelle macht sich durch einen starken Anstieg im Ionensignal bemerkbar. Man führt diese Messung bei verschiedenen elektrischen Feldstärken durch und erhält bei Auftragen der Ionisationsschwellen gegen die Wurzel der elektrischen Feldstärke durch Extrapolation auf die Feldstärke Null die Ionisationsenergie.Im Rahmen dieser Arbeit wurde die Ionisationsenergie von Actinium erstmalig zu 43398(3) cm-1 º 5,3807(4) eV experimentell bestimmt. Dazu wurden Actiniumatome zunächst einstufig resonant mit einem Laser mit einer Wellenlänge von 388,67 nm auf einen Zustand bei 25729,03 cm-1 angeregt und anschließend mit Laserlicht mit einer Wellenlänge von ca. 568 nm ionisiert. Damit sind die Ionisationsenergien aller Actinoiden bis einschließlich Einsteinium mit Ausnahme von Protactinium bekannt. Als Atomstrahlquelle wird ein spezielles 'Sandwichfilament' benutzt, bei dem das Actinoid als Hydroxid auf eine Tantalfolie aufgebracht und mit einer reduzierenden Deckschicht überzogen wird. Das Actinoid dampft bei Heizen dieser Anordnung atomar ab. Bei den schwereren Actinoiden wurde Titan als Deckschicht verwendet. Um einen Actiniumatomstrahl zu erzeugen, wurde aufgrund der hohen Abdampftemperaturen statt Titan erstmals Zirkonium eingesetzt. Bei Protactinium wurde Thorium, welches noch stärkere Reduktionseigenschaften aufweist, als Deckmaterial eingesetzt. Trotzdem gelang es mit der 'Sandwichtechnik' nicht, einen Protactiniumatomstrahl zu erzeugen. In der Flugzeitapparatur wurde lediglich ein Protactinium-monoxidionensignal detektiert. Um ein erst seit kurzem verfügbares Fest-körperlasersystem zu explorieren, wurden zusätzlich noch die bekannten Ionisations-ener-gien von Gadolinium und Plutonium erneut bestimmt. Die gemessenen Werte stimmen mit Literaturdaten gut überein.Ferner wurde noch ein bestehender Trennungsgang für Plutonium aus Umweltproben auf die Matrices Meerwasser und Hausstaub angepasst und für die Bestimmung von Plutonium und dessen Isotopenzusammensetzung in verschiedenen Probenreihen mittels RIMS eingesetzt. Der modifizierte Trennungsgang ermöglicht das schnelle Aufarbeiten von großen Probenmengen für Reihenuntersuchungen von Plutoniumkontaminationen. Die ermittelten Gehalten an 239Pu lagen zwischen 8,2*107 Atome pro 10 l Meerwasserprobe und 1,7*109Atome pro Gramm Staubprobe.