Quality and safety of oils and fats obtained as co-products or by-products of the food chain and destined to animal production

The aim of the first part of this thesis was to evaluate the effect of trans fatty acid- (TFA), contaminant, polycyclic aromatic hydrocarbon (PAH)- and oxidation productenriched diets on the content of TFA and conjugated linoleic acid (CLA) isomers in meat and liver of both poultry and rabbit. The enriched feedings were prepared with preselected fatty co-and by-products that contained low and high levels of TFA (low, palm fatty acid distillate; high, hydrogenated palm fatty acid distillate), environmental contaminants (dioxins and PCBs) (two different fish oils), PAH (olive oil acid oils and pomace olive oil from chemical refining, for low and high levels) and oxidation products (sunflower-olive oil blend before and after frying), so as to obtain single feedings with three enrichment degrees (high, medium and low) of the compound of interest. This experimental set-up is a part of a large, collaborative European project (http://www.ub.edu/feedfat/), where other chemical and health parameters are assessed. Lipids were extracted, methylated with diazomethane, then transmethylated with 2N KOH/methanol and analyzed by GC and silver-ion TLC-GC. TFA and CLA were determined in the fats, the feedings, meat and liver of both poultry and rabbit. In general, the level of TFA and CLA in meat and liver mainly varied according to those originally found in the feeding fats. It must be pointed out, though, that TFA and CLA accumulation was different for the two animal species, as well as for the two types of tissues. The TFA composition of meat and liver changes according to the composition of the oils added to the feeds with some differences between species. Chicken meat with skin shows higher TFA content (2.6–5.4 fold) than rabbit meat, except for the “PAH” trial. Chicken liver shows higher TFA content (1.2–2.1 fold) than rabbit liver, except for the “TRANS” and “PAH” trials. In both chicken and rabbit meats, the TFA content was higher for the “TRANS” trial, followed by the “DIOXIN” trial. Slight differences were found on the “OXIDATION” and “PAH” trends in both types of meats. In both chicken and rabbit livers, the TFA content was higher for the “TRANS” trial, followed by those of the “PAH”, “DIOXIN” and “OXIDATION” trials. This trend, however, was not identical to that of feeds, where the TFA content varied as follows: “TRANS” > “DIOXIN” >“PAH” > “OXIDATION”. In chicken and rabbit meat samples, C18:1 TFA were the most abundant, followed by C18:2 TFA and C18:3 TFA, except for the “DIOXIN” trial where C18:3 TFA > C18:2 TFA. In chicken and rabbit liver samples of the “TRANS” and “OXIDATION” trials, C18:1 TFA were the most abundant, followed by C18:2 TFA and C18:3 TFA, whereas C18:3 TFA > C18:2 in the “DIOXIN” trial. Slight differences were found on the “PAH” trend in livers from both species. The second part of the thesis dealt with the study of lipid oxidation in washed turkey muscle added with different antioxidants. The evaluation on the oxidative stability of muscle foods found that oxidation could be measured by headspace solid phase microestraction (SPME) of hexanal and propanal. To make this method effective, an antioxidant system was added to stored muscle to stop the oxidative processes. An increase in ionic strength of the sample was also implemented to increase the concentration of aldehydes in the headspace. This method was found to be more sensitive than the commonly used thiobarbituric acid reactive substances (TBARs) method. However, after antioxidants were added and oxidation was stopped, the concentration of aldehydes decreased. It was found that the decrease in aldehyde concentration was due to the binding of the aldehydes to muscle proteins, thus decreasing the volatility and making them less detectable.

Spatial and temporal variation in settlement, growth and condition of the rockfish species Sebastes caurinus and Sebastes carnatus in the Channel Islands region, Santa Barbara, CA

Survival during the early life stages of marine species, including nearshore temperate reef fishes, is typically very low, and small changes in mortality rates, due to physiological and environmental conditions, can have marked effects on survival of a cohort and, on a larger scale, on the success of a recruitment season. Moreover, trade offs between larval growth and accumulation of energetic resources prior to settlement are likely to influence growth and survival until this critical period and afterwards. Rockfish recruitment rates are notoriously variable between years and across geographic locations. Monitoring of rates of onshore delivery of pelagic juveniles (defined here as settlement) of two species of nearshore rockfishes, Sebastes caurinus and Sebastes carnatus, was done between 2003-2009 years using artificial collectors placed at San Miguel and Santa Cruz Island, off Southern California coast. I investigated spatiotemporal variation in settlement rate, lipid content, pelagic larval duration and larval growth of the newly settled fishes; I assessed relationships between birth date, larval growth, early life-history characteristics and lipid content at settlement, considering also interspecific differences; finally, I attempt to relate interannual patterns of settlement and of early life history traits to easily accessible, local and regional indices of ocean conditions including in situ ocean temperature and regional upwelling, sea surface temperature (SST) and Chlorophyll-a (Chl-a) concentration. Spatial variations appeared to be of low relevance, while significant interannual differences were detected in settlement rate, pelagic larval duration and larval growth. The amount of lipid content of the newly settled fishes was highly variable in space and time, but did not differ between the two species and did not show any relationships with early life history traits, indicating that no trade off involved these physiological processes or they were masked by high individual variability in different periods of larval life. Significant interspecific differences were found in the timing of parturition and settlement and in larval growth rates, with S. carnatus growing faster and breeding and settling later than S. caurinus. The two species exhibited also different patterns of correlations between larval growth rates and larval duration. S. carnatus larval duration was longer when the growth in the first two weeks post-hatch was faster, while S. caurinus had a shorter larval duration when grew fast in the middle and in the end of larval life, suggesting different larval strategies. Fishes with longer larval durations were longer in size at settlement and exhibited longer planktonic phase in periods of favourable environmental conditions. Ocean conditions had a low explanatory power for interannual variation in early life history traits, but a very high explanatory power for settlement fluctuations, with regional upwelling strength being the principal indicator. Nonetheless, interannual variability in larval duration and growth were related to great phenological changes in upwelling happened during the period of this study and that caused negative consequences at all trophic levels along the California coast. Despite the low explanatory power of the environmental variables used in this study on the variation of larval biological traits, environmental processes were differently related with early life history characteristics analyzed to species, indicating possible species-specific susceptibility to ocean conditions and local environmental adaptation, which should be further investigated. These results have implications for understanding the processes influencing larval and juvenile survival, and consequently recruitment variability, which may be dependent on biological characteristics and environmental conditions.

Effect of rearing techniques and feed composition on productive traits, bird welfare and quality of poultry products

The PhD project was focused on the study of the poultry welfare conditions and improvements. The project work was divided into 3 main research activities. A) Field evaluation of chicken meat rearing conditions kept in intensive farms. Considering the lack of published reports concerning the overall Italian rearing conditions of broiler chickens, a survey was carried out to assess the welfare conditions of broiler reared in the most important poultry companies in Italy to verify if they are in accordance with the advices given in the European proposal COM (2005) 221 final. Chicken farm conditions, carcass lesions and meat quality were investigated. 1. The densities currently used in Italy are in accordance with the European proposal COM 221 final (2005) which suggests to keep broilers at a density lower than 30-32 kg live weight/m2 and to not exceed 38-40 kg live weight/m2. 2. The mortality rates in summer and winter agree with the mortality score calculated following the formula reported in the EU Proposal COM 221 final (2005). 3. The incidence of damaged carcasses was very low and did not seem related to the stocking density. 4. The FPD scores were generally above the maximum limit advised by the EU proposal COM 221 final (2005), although the stocking densities were lower than 30-32 kg live weight per m2. 5. It can be stated that the control of the environmental conditions, particularly litter quality, appears a key issue to control the onset of foot dermatitis. B) Manipulation of several farm parameters, such litter material and depth, stocking density and light regimen to improve the chicken welfare conditions, in winter season. 1. Even though 2 different stocking densities were established in this study, the performances achieved from the chickens were almost identical among groups. 2. The FCR was significantly better in Standard conditions contrarily to birds reared in Welfare conditions with lower stocking density, more litter material and with a light program of 16 hours light and 8 hours dark. 3. In our trial, in Standard groups we observed a higher content of moisture, nitrogen and ammonia released from the litter. Therefore it can be assumed that the environmental characteristics have been positively changed by the improvements of the rearing conditions adopted for Welfare groups. 4. In Welfare groups the exhausted litters of the pens were dryer and broilers showed a lower occurrence of FPD. 5. The prevalence of hock burn lesions, like FPD, is high with poor litter quality conditions. 6. The combined effect of a lower stocking density, a greater amount of litter material and a photoperiod similar to the natural one, have positively influenced the chickens welfare status, as a matter of fact the occurrence of FPD in Welfare groups was the lowest keeping the score under the European threshold of the proposal COM 221 final(2005). C) The purpose of the third research was to study the effect of high or low stocking density of broiler chickens, different types of litter and the adoption of short or long lighting regimen on broiler welfare through the evaluation of their productivity and incidence of foot pad dermatitis during the hot season. 1. The feed efficiency was better for the Low Density than for High Density broilers. 2. The appearance of FPD was not influenced by stocking density. 3. The foot examination revealed that the lesions occurred more in birds maintained on chopped wheat straw than on wood shaving. 4. In conclusion, the adoptions of a short light regimen similar to that occurring in nature during summer reduces the feed intake without modify the growth rate thus improving the feed efficiency. Foot pad lesion were not affected neither by stocking densities nor by light regimens whereas wood shavings exerted a favourable effect in preserving foot pad in good condition. D) A study was carried out to investigate more widely the possible role of 25-hydroxycholecalciferol supplemented in the diet of a laying hen commercial strain (Lohmann brown) in comparison of diets supplemented with D3 or with D3 + 25- hydroxycholecalciferol. Egg traits during a productive cycle as well as the bone characteristics of the layers have been as well evaluated to determine if there the vitamin D3 may enhance the welfare status of the birds. 1. The weight of the egg and of its components is often greater in hens fed a diet enriched with 25-hydroxycholecalciferol. 2. Since eggs of treated groups are heavier and a larger amount of shell is needed, a direct effect on shell strength is observed. 3. At 30 and at 50 wk of age hens fed 25 hydroxycholecalciferol exhibited greater values of bone breaking force. 4. Radiographic density values obtained in the trial are always higher in hens fed with 25-hydroxycholecalciferol of both treatments: supplemented for the whole laying cycle (25D3) or from 40 weeks of age onward (D3+25D3).

Oceanic crust and island arc formation in Central Asia during late Neoproterozoic times - evidence from petrological and geochemical studies

Die vorliegende Arbeit behandelt die Entwicklung des 570 Ma alten, neoproterozoischen Agardagh - Tes-Chem Ophioliths (ATCO) in Zentralasien. Dieser Ophiolith liegt südwestlich des Baikalsees (50.5° N, 95° E) und wurde im frühen Stadium der Akkretion des Zentralasiatischen Mobilgürtels auf den nordwestlichen Rand des Tuvinisch-Mongolischen Mikrokontinentes aufgeschoben. Bei dem Zentralasiatische Mobilgürtel handelt es sich um einen riesigen Akkretions-Subduktionskomplex, der heute das größte zusammenhängende Orogen der Erde darstellt. Im Rahmen dieser Arbeit wurden eine Reihe plutonischer und vulkanischer Gesteine, sowie verschiedene Mantelgesteine des ATCO mittels mikroanalytischer und geochemischer Verfahren untersucht (Elektronenstrahlmikrosonde, Ionenstrahlmikrosonde, Spurenelement- und Isotopengeochemie). Die Auswertung dieser Daten ermöglichte die Entwicklung eines geodynamisch-petrologischen Modells zur Entstehung des ATCO. Die vulkanischen Gesteine lassen sich aufgrund ihrer Spurenelement- und Isotopenzusammensetzung in inselbogenbezogene und back-arc Becken bezogene Gesteine (IA-Gesteine und BAB-Gesteine) unterscheiden. Darüber hinaus gibt es eine weitere, nicht eindeutig zuzuordnende Gruppe, die hauptsächlich mafische Gänge umfasst. Der grösste Teil der untersuchen Vulkanite gehört zur Gruppe der IA-Gesteine. Es handelt sich um Al-reiche Basalte und basaltische Andesite, welche aus einem evolvierten Stammmagma mit Mg# 0.60, Cr ~ 180 µg/g und Ni ~ 95 µg/g hauptsächlich durch Klinopyroxenfraktionierung entstanden sind. Das Stammmagma selbst entstand durch Fraktionierung von ca. 12 % Olivin und geringen Anteilen von Cr-Spinell aus einer primären, aus dem Mantel abgeleiteten Schmelze. Die IA-Gesteine haben hohe Konzentrationen an inkompatiblen Spurenelementen (leichte-(L)- Seltenerdelement-(SEE)-Konzentrationen etwa 100-fach chondritisch, chondrit-normierte (La/Yb)c von 14.6 - 5.1), negative Nb-Anomalien (Nb/La = 0.37 - 0.62) und niedrige Zr/Nb Verhältnisse (7 - 14) relativ zu den BAB-Gesteinen. Initiale eNd Werte liegen bei etwa +5.5, initiale Bleiisotopenverhältnisse sind: 206Pb/204Pb = 17.39 - 18.45, 207Pb/204Pb = 15.49 - 15.61, 208Pb/204Pb = 37.06 - 38.05. Die Anreicherung lithophiler inkompatibler Spurenelemente (LILE) in dieser Gruppe ist signifikant (Ba/La = 11 - 130) und zeigt den Einfluss subduzierter Komponenten an. Die BAB-Gesteine repräsentieren Schmelzen, die sehr wahrscheinlich aus der gleichen Mantelquelle wie die IA-Gesteine stammen, aber durch höhere Aufschmelzgrade (8 - 15 %) und ohne den Einfluss subduzierter Komponenten entstanden sind. Sie haben niedrigere Konzentrationen an inkompatiblen Spurenelementen, flache SEE-Muster ((La/Yb)c = 0.6 - 2.4) und höhere initiale eNd Werte zwischen +7.8 und +8.5. Nb Anomalien existieren nicht und Zr/Nb Verhältnisse sind hoch (21 - 48). Um die geochemische Entwicklung der vulkanischen Gesteine des ATCO zu erklären, sind mindestens drei Komponenten erforderlich: (1) eine angereicherte, ozeaninselbasalt-ähnliche Komponente mit hoher Nb Konzentration über ~ 30 µg/g, einem niedrigen Zr/Nb Verhältnis (ca. 6.5), einem niedrigen initialen eNd Wert (um 0), aber mit radiogenen 206Pb/204Pb-, 207Pb/204Pb- und 208Pb/204Pb-Verhältnissen; (2) eine N-MORB ähnliche back-arc Becken Komponente mit flachem SEE-Muster und einem hohen initialen eNd Wert von mindestens +8.5, und (3) eine Inselbogen-Komponente aus einer verarmten Mantelquelle, welche durch die abtauchende Platte geochemisch modifiziert wurde. Die geochemische Entstehung der ATCO Vulkanite lässt sich dann am besten durch eine Kombination aus Quellenkontamination, fraktionierte Kristallisation und Magmenmischung erklären. Geodynamisch gesehen entstand der ATCO sehr wahrscheinlich in einem intraozeanischen Inselbogen - back-arc System. Bei den untersuchten Plutoniten handelt es sich um ultramafische Kumulate (Wehrlite und Pyroxenite) sowie um gabbroische Plutonite (Olivin-Gabbros bis Diorite). Die geochemischen Charakteristika der mafischen Plutonite sind deutlich unterschiedlich zu denen der vulkanischen Gesteine, weshalb sie sehr wahrscheinlich ein späteres Entwicklungsstadium des ATCO repräsentieren. Die Spurenelement-Konzentrationen in den Klinopyroxenen der ultramafischen Kumulate sind extrem niedrig, mit etwa 0.1- bis 1-fach chondritischen SEE-Konzentrationen und mit deutlich LSEE-verarmten Mustern ((La/Yb)c = 0.27 - 0.52). Berechnete Gleichgewichtsschmelzen der ultramafischen Kumulate zeigen grosse Ähnlichkeit zu primären boninitischen Schmelzen. Die primären Magmen waren daher boninitischer Zusammensetzung und entstanden in dem durch vorausgegangene Schmelzprozesse stark verarmten Mantelkeil über einer Subduktionszone. Niedrige Spurenelement-Konzentrationen zeigen einen geringen Einfluss der abtauchenden Platte an. Die Spurenelement-Konzentrationen der Gabbros sind ebenfalls niedrig, mit etwa 0.5 - 10-fach chondritischen SEE-Konzentrationen und mit variablen SEE-Mustern ((La/Yb)c = 0.25 - 2.6). Analog zu den Vulkaniten der IA-Gruppe haben alle Gabbros eine negative Nb-Anomalie mit Nb/La = 0.01 - 0.31. Die initialen eNd Werte der Gabbros variieren zwischen +4.8 und +7.1, mit einem Mittelwert von +5.9, und sind damit identisch mit denen der IA-Vulkanite. Bei den untersuchten Mantelgesteinen handelt es sich um teilweise serpentinisierte Dunite und Harzburgite, die alle durch hohe Mg/Si- und niedrige Al/Si-Verhältnisse gekennzeichnet sind. Dies zeigt einen refraktären Charakter an und steht in guter Übereinstimmung mit den hohen Cr-Zahlen (Cr#) der Spinelle (bis zu Cr# = 0.83), auf deren Basis der Aufschmelzgrad der residuellen Mantelgesteine berechnet wurde. Dieser beträgt etwa 25 %. Die geochemische Zusammensetzung und die petrologischen Daten der Ultramafite und Gabbros lassen sich am besten erklären, wenn man für die Entstehung dieser Gesteine einen zweistufigen Prozess annimmt. In einer ersten Stufe entstanden die ultramafischen Kumulate unter hohem Druck in einer Magmenkammer an der Krustenbasis, hauptsächlich durch Klinopyroxen-Fraktionierung. Bei dieser Magmenkammer handelte es sich um ein offenes System, dem von unten laufend neue Schmelze zugeführt wurde, und aus dem im oberen Bereich evolviertere Schmelzen geringerer Dichte entwichen. Diese evolvierten Schmelzen stiegen in flachere krustale Bereiche auf und bildeten dort meist isolierte Intrusionskörper. Diese Intrusionskörper erstarrten ohne Magmen-Nachschub, weshalb petrographisch sehr unterschiedliche Gesteine entstehen konnten. Eine geochemische Modifikation der abkühlenden Schmelzen erfolgte allerdings durch die Assimilation von Nebengestein. Da innerhalb der Gabbros keine signifikante Variation der initalen eNd Werte existiert, handelte es sich bei dem assimilierten Material hauptsächlich um vulkanische Gesteine des ATCO und nicht um ältere, möglicherweise kontinentale Kruste.

Three dimensional seismic imaging and earthquake locations in a complex, segmented fault region in Southern Apennines (Italy)

The southern Apennines of Italy have been experienced several destructive earthquakes both in historic and recent times. The present day seismicity, characterized by small-to-moderate magnitude earthquakes, was used like a probe to obatin a deeper knowledge of the fault structures where the largest earthquakes occurred in the past. With the aim to infer a three dimensional seismic image both the problem of data quality and the selection of a reliable and robust tomographic inversion strategy have been faced. The data quality has been obtained to develop optimized procedures for the measurements of P- and S-wave arrival times, through the use of polarization filtering and to the application of a refined re-picking technique based on cross-correlation of waveforms. A technique of iterative tomographic inversion, linearized, damped combined with a strategy of multiscale inversion type has been adopted. The retrieved P-wave velocity model indicates the presence of a strong velocity variation along a direction orthogonal to the Apenninic chain. This variation defines two domains which are characterized by a relatively low and high velocity values. From the comparison between the inferred P-wave velocity model with a portion of a structural section available in literature, the high velocity body was correlated with the Apulia carbonatic platforms whereas the low velocity bodies was associated to the basinal deposits. The deduced Vp/Vs ratio shows that the ratio is lower than 1.8 in the shallower part of the model, while for depths ranging between 5 km and 12 km the ratio increases up to 2.1 in correspondence to the area of higher seismicity. This confirms that areas characterized by higher values are more prone to generate earthquakes as a response to the presence of fluids and higher pore-pressures.

Synthesis and characterization of new discotic polycyclic aromatic hydrocarbons and related pyrolytic nanostructures

Diskotische Hexa-peri-hexabenzocoronene (HBC) als molekulare, definierte graphitische Substrukturen sind bereits seit langem Gegenstand von Untersuchungen zu der Delokalisierung von π-Elektronen. In dieser Arbeit wurden zusätzlich Platin-Komplexe in das periphere Substitutionsmuster von HBC eingeführt. Dies führte zu einer Verbesserung der Emission von dem angeregten Triplett-Zustand in den Singulett-Grundzustand mit einer zusätzlichen Verlängerung der Lebensdauer des angeregten Zustandes. Zusätzlich erlaubte diese Konfiguration ein schnelles Intersystem-Crossing mittels einer verstärkten Spin-Orbit Kopplung, die sowohl bei tiefen Temperaturen, als auch bei Raumtemperatur exklusiv zu Phosphoreszenz (T1→S0) führte. Das Verständniss über solche Prozesse ist auch essentiell für die Entwicklung verbesserter opto-elektronischer Bauteile. Die Erstellung von exakt definierten molekularen Strukturen, die speziell für spezifische Interaktionen hergestellt wurden, machten eine Inkorporation von hydrophoben-hydrophilen, wasserstoffverbrückten oder elektrostatischen funktionalisierten Einheiten notwendig, um damit den supramolekularen Aufbau zu kontrollieren. Mit Imidazolium-Salzen funktionalisierte HBC Derivate wurden zu diesem Zwecke hergestellt. Eine interessante Eigenschaft dieser Moleküle ist ihre Amphiphilie. Dies gestattete die Untersuchung ihrer Eigenschaften in einem polaren Solvens und sowohl der Prozessierbarkeit als auch der Faserbildung auf Siliziumoxid-Trägern. Abhängig vom Lösungsmittel und der gewählten Konditionen konnten hochkristalline Fasern erhalten werden. Durch eine Substitution der HBCs mit langen, sterisch anspruchsvollen Seitenketten, konnte durch eine geeignete Prozessierung eine homöotrope Ausrichtung auf Substraten erreicht werden, was dieses Material interessant für photovoltaische Applikationen macht. Neuartige Polyphenylen-Metall-Komplexe mit diskotischen, linearen und dendritischen Geometrien wurden mittels einer einfachen Reaktion zwischen Co2(CO)8 und Ethinyl-Funktionalitäten in Dichlormethan hergestellt. Nach der Pyrolyse dieser Komplexe ergaben sich unterschiedliche Kohlenstoff-Nanopartikel, inklusive Nanoröhren, graphitischen Nanostäben und Kohlenstoff/Metall Hybrid Komplexe, die durch Elektronenmikroskopie untersucht wurden. Die resultierenden Strukturen waren dabei abhängig von der Zusammensetzung und Struktur der Ausgangssubstanzen. Anhand dieser Resultate ergeben sich diverse Möglichkeiten, um den Mechanismus, der zur Herstellung graphitischer Nanopartikel führt, besser zu verstehen.

The development and deployment of FOTOS: a fast observation of trace organics system

Flüchtige organische Bestandteile (engl.: VOC) sind in der Atmosphäre in Spuren vorhanden, spielen aber trotzdem eine wichtige Rolle in der Luftchemie: sie beeinflussen das Ozon der Troposphäre, städtischen Smog, Oxidationskapazität und haben direkte und indirekte Auswirkungen auf die globale Klimaveränderung. Eine wichtige Klasse der VOC sind die Nicht-Methan-Kohlenwasserstoffe (engl.: NMHC), die überwiegend von anthropogenen Quellen kommen. Aus diesem Grund ist für Luftchemiker ein Messinstrument nötig, das die VOC, die NMHC eingeschlossen, mit einer höheren Zeitauflösung misst, besonders für Echtzeitmessungen an Bord eines Forschungsflugzeuges. Dafür wurde das System zur schnellen Beobachtung von organischen Spuren (engl.: FOTOS) entworfen, gebaut für den Einsatz in einem neuen Wissenschaftlichen Flugzeug, das in großen Höhen und über weite Strecken fliegt, genannt HALO. In der Folge wurde FOTOS in zwei Messkampagnen am Boden getestet. FOTOS wurde entworfen und gebaut mit einem speziell angefertigten, automatisierten, kryogenen Probensystem mit drei Fallen und einem angepassten, erworbenen schnellen GC-MS. Ziel dieses Aufbaus war es, die Vielseitigkeit zu vergrößern und das Störungspotential zu verringern, deshalb wurden keine chemischen Trocknungsmittel oder adsorbierenden Stoffe verwendet. FOTOS erreichte eine Probenfrequenz von 5.5 Minuten, während es mindestens 13 verschiedene C2- bis C5-NMHC maß. Die Drei-Sigma-Detektionsgrenze für n- und iso-Pentan wurde als 2.6 und 2.0 pptv ermittelt, in dieser Reihenfolge. Labortests bestätigten, dass FOTOS ein vielseitiges, robustes, hochautomatisiertes, präzises, genaues, empfindliches Instrument ist, geeignet für Echtzeitmessungen von VOC in Probenfrequenzen, die angemessen sind für ein Forschungsflugzeug wie HALO. Um die Leistung von FOTOS zu bestätigen, wurde vom 26. Januar bis 4. Februar 2010 ein Zwischenvergleich gemacht mit dem GC-FID-System am Meteorologischen Observatorium Hohenpeißenberg, einer WMO-GAW-globalen Station. Dreizehn verschiedene NMHC wurden innerhalb des Rahmens der GWA Data Quality Objectives (DQO) analysiert und verglichen. Mehr als 80% der Messungen von sechs C3- bis C5-NMHC erfüllten diese DQO. Diese erste Messkampagne im Feld hob die Robustheit und Messgenauigkeit von FOTOS hervor, zusätzlich zu dem Vorteil der höheren Probenfrequenz, sogar in einer Messung am Boden. Um die Möglichkeiten dieses Instrumentes im Feld zu zeigen, maß FOTOS ausgewählte leichte NMHC während einer Messkampagne im Borealen Waldgebiet, HUMPPA-COPEC 2010. Vom 12. Juli bis zum 12. August 2010 beteiligte sich eine internationale Gruppe von Instituten und Instrumenten an Messungen physikalischer und chemischer Größen der Gas- und Partikelphasen der Luft über dem Borealen Wald an der SMEAR II-Station nahe Hyyttiälä, Finnland. Es wurden mehrere Hauptpunkte von Interesse im Mischungsverhältnis der Alkane und im Isomerenverhätnis von Pentan identifiziert, insbesondere sehr unterschiedliche Perioden niedriger und hoher Variabilität, drei Rauchschwaden von Biomassen-Verbrennung von russischen Waldbränden und zwei Tage mit extrem sauberer Luft aus der Polarregion. Vergleiche der NMHC mit anderen anthropogenen Indikatoren zeigten mehrere Quellen anthropogener Einflüsse am Ort auf und erlaubten eine Unterscheidung zwischen lokalen und weiter entfernten Quellen. Auf einen minimalen natürlichen Beitrag zum 24h-Kreislauf von NOx wurde geschlussfolgert aus der Korrelation von NOx mit Alkanen. Altersschätzungen der Luftmassen durch das Isomerenverhältnis von Pentan wurden erschwert durch sich verändernde Verhältnisse der Quellen und durch Besonderheiten der Photochemie während des Sommers im hohen Norden. Diese Messungen zeigten den Wert des Messens leichter NMHC, selbst in abgelegenen Regionen, als einen zusätzlichen spezifischen Marker von anthropogenem Einfluss.

Stream sediments analysis for geochemical mapping of Romagna Apennines (Northern Italy): monitoring and management tool of environmental resources at various scales

Geochemical mapping is a valuable tool for the control of territory that can be used not only in the identification of mineral resources and geological, agricultural and forestry studies but also in the monitoring of natural resources by giving solutions to environmental and economic problems. Stream sediments are widely used in the sampling campaigns carried out by the world's governments and research groups for their characteristics of broad representativeness of rocks and soils, for ease of sampling and for the possibility to conduct very detailed sampling In this context, the environmental role of stream sediments provides a good basis for the implementation of environmental management measures, in fact the composition of river sediments is an important factor in understanding the complex dynamics that develop within catchment basins therefore they represent a critical environmental compartment: they can persistently incorporate pollutants after a process of contamination and release into the biosphere if the environmental conditions change. It is essential to determine whether the concentrations of certain elements, in particular heavy metals, can be the result of natural erosion of rocks containing high concentrations of specific elements or are generated as residues of human activities related to a certain study area. This PhD thesis aims to extract from an extensive database on stream sediments of the Romagna rivers the widest spectrum of informations. The study involved low and high order stream in the mountain and hilly area, but also the sediments of the floodplain area, where intensive agriculture is active. The geochemical signals recorded by the stream sediments will be interpreted in order to reconstruct the natural variability related to bedrock and soil contribution, the effects of the river dynamics, the anomalous sites, and with the calculation of background values be able to evaluate their level of degradation and predict the environmental risk.

Modulation of network excitability and epileptiform activity in the hippocampus of immature rats by the activation of GlyRs

Epileptic seizures are the manifestations of epilepsy, which is a major neurological disorder and occurs with a high incidence during early childhood. A fundamental mechanism underlying epileptic seizures is loss of balance between neural excitation and inhibition toward overexcitation. Glycine receptor (GlyR) is ionotropic neurotransmitter receptor that upon binding of glycine opens an anion pore and mediates in the adult nervous system a consistent inhibitory action. While previously it was assumed that GlyRs mediate inhibition mainly in the brain stem and spinal cord, recent studies reported the abundant expression of GlyRs throughout the brain, in particular during neuronal development. But no information is available regarding whether activation of GlyRs modulates neural network excitability and epileptiform activities in the immature central nervous system (CNS). Therefore the study in this thesis addresses the role of GlyRs in the modulation of neuronal excitability and epileptiform activity in the immature rat brain. By using in vitro intact corticohippocampal formation (CHF) of rats at postnatal days 4-7 and electrophysiological methods, a series of pharmacological examinations reveal that GlyRs are directly implicated in the control of hippocampal excitation levels at this age. In this thesis I am able to show that GlyRs are functionally expressed in the immature hippocampus and exhibit the classical pharmacology of GlyR, which can be activated by both glycine and the presumed endogenous agonist taurine. This study also reveals that high concentration of taurine is anticonvulsive, but lower concentration of taurine is proconvulsive. A substantial fraction of both the pro- and anticonvulsive effects of taurine is mediated via GlyRs, although activation of GABAA receptors also considerably contributes to the taurine effects. Similarly, glycine exerts both pro- and anticonvulsive effects at low and high concentrations, respectively. The proconvulsive effects of taurine and glycine depend on NKCC1-mediated Cl- accumulation, as bath application of NKCC1 inhibitor bumetanide completely abolishes proconvulsive effects of low taurine and glycine concentrations. Inhibition of GlyRs with low concentration of strychnine triggers epileptiform activity in the CA3 region of immature CHF, indicating that intrinsically an inhibitory action of GlyRs overwhelms its depolarizing action in the immature hippocampus. Additionally, my study indicates that blocking taurine transporters to accumulate endogenous taurine reduces epileptiform activity via activation of GABAA receptors, but not GlyRs, while blocking glycine transporters has no observable effect on epileptiform activity. From the main results of this study it can be concluded that in the immature rat hippocampus, activation of GlyRs mediates both pro- and anticonvulsive effects, but that a persistent activation of GlyRs is required to prevent intrinic neuronal overexcitability. In summary, this study uncovers an important role of GlyRs in the modulation of neuronal excitability and epileptiform activity in the immature rat hippocampus, and indicates that glycinergic system can potentially be a new therapeutic target against epileptic seizures of children.

Paleoclimate reconstruction using LA-ICP-MS analyses of ostracods and stalagmite

Als paläoklimatische Archive können unter anderem Stalagmiten und Klappen von Ostrakoden herangezogen werden. Bisher gab es noch keine veröffentlichten Ergebnisse räumlich hochaufgelöster Spurenelementverteilungen in einzelnen Ostrakodenklappen. Das gleiche gilt für die Bestimmung radiogener Blei-Isotope in Stalagmiten. Um klimatische Prozesse vergangener Zeiten zu untersuchen, wurde eine neue LA-ICP-MS (Laserablations – Massenspektrometrie mit induktiv gekoppeltem Plasma) Technik für hochaufgelöste in-situ Messungen von Spurenelementen und Bleiisotopen entwickelt. rnrnZunächst wurden geeignete Materialien für die Kalibrierung der Technik untersucht; als Proben dienten die Silikatreferenzgläser BAM-S005-A und BAM-S005B der Bundesanstalt für Materialforschung und –prüfung (BAM). Die Homogenität dieser Referenzgläser wurde mit LA-ICP-MS und den anderen mikroanalytischen Methoden EPMA (Elektronenmikrosonde) und SIMS (Ionensonde) überprüft. Die Ergebnisse zeigten, dass alle Haupt- und die meisten Spurenelemente in beiden Gläsern selbst im Mikrometerbereich homogen verteilt sind. Ausnahmen sind einige Spurenelemente, wie Cs, Cl, Cr, Mo und Ni, die heterogen in den Gläsern verteilt sind. Die Hauptelementzusammensetzung von BAM-S005-A und BAM-S005-B wurde mit Hilfe der EPMA bestimmt, wobei die Ergebnisse die Referenzwerte des BAM-Zertifikats bestätigten. Mit Ausnahme von Sr, Ba, Ce und Pb, stimmten die LA-ICP-MS-Spurenelementwerte mit den zertifizierten Werten innerhalb der angegebenen Fehlergrenzen überein. Gründe für die Diskrepanz der vier oben erwähnten Elemente sind noch unklar, aber sind möglicherweise durch fehlerhafte Referenzwerte zu erklären. Zusätzlich wurden 22 Spurenelemente gemessen, deren Gehalte von BAM nicht zertifiziert wurden. Aufgrund dieser Untersuchungen konnte festgestellt werden, dass beide BAM-Gläser für mikroanalytische Anwendungen geeignet sind.rnrnUm neuartige paläoklimatische Proxies im Calcit von Ostrakoden aus tibetanischen Seesedimenten zu untersuchen, wurde die Spurenelementvariabilität in einzelnen Ostrakodenklappen durch eine neue LA-ICP-MS-Technik bestimmt. Klappen von Ostrakoden der drei Arten (Leucocytherella sinensis Huang, 1982, ?Leucocythere dorsotuberosa Huang, 1982 und ?L. dorsotuberosa f. postilirata sensu Pang, 1985) wurden aus zwei Sedimentkernen des Nam Co Sees auf dem Hochplateau von Tibet gewonnen. Zwei LA-ICP-MS-Varianten, Spot- bzw. Linienanalyse, wurden verwendet, um die Elementkonzentrationen der Spurenelemente Mg, Sr, Ba, U und die der Seltenen Erdelemente (SEE) in den Klappen einzelner Ostrakoden zu bestimmen. Die Ergebnisse zeigten, dass die Linienanalyse präzisere Daten als die Spotanalyse liefert und sie wurde daher vorgezogen. Signifikante Unterschiede in der Spurenelementzusammensetzung zwischen den verschiedenen Arten der Ostrakoden wurden nicht gefunden. Variationen der Elementverhältnisse Mg/Ca und Sr/Ca in den Klappen stimmen mit veröffentlichten Seenspiegelschwankungen während des Holozäns überein, was zeigt, dass Mg- und Sr-Messungen in den Ostrakoden zur Untersuchung paläohydrochemischer Prozesse in diesem Gebiet herangezogen werden kann. Die gute Korrelation, die in dieser Arbeit zwischen Ba/Ca und Sr/Ca gefunden wurde, ist ein Hinweis darauf, dass der Einbau von Ba und Sr in die Klappen durch den gleichen Mechanismus erfolgte. Eine mögliche Beziehung zwischen dem U/Ca-Verhältnis in den Ostrakoden und den Redoxbedingungen auf dem Boden des Sees in der Vergangenheit wird diskutiert. Relativ geringe und konstante La/Ca-Verhältnisse wurden festgestellt, deren Ursache möglicherweise entweder auf der SEE-Charakteristik des Seewassers, auf biologischen Prozessen in den Ostrakoden oder auf Kontamination von Fe-Mn und/oder organischen Substanzen beruhen. Weitere Untersuchungen an Proben aus diesem Gebiet, speziell Klappen von lebenden Ostrakoden, sind notwendig, um den Gehalt von Ba, U und den SEE in Ostrakoden als paläoklimatische Proxies von Umweltbedingungen zu verwenden.

An inter-comparison between a VIS/IR and a MW satellite-based methods for cloud detection and classification

This thesis is aimed to assess similarities and mismatches between the outputs from two independent methods for the cloud cover quantification and classification based on quite different physical basis. One of them is the SAFNWC software package designed to process radiance data acquired by the SEVIRI sensor in the VIS/IR. The other is the MWCC algorithm, which uses the brightness temperatures acquired by the AMSU-B and MHS sensors in their channels centered in the MW water vapour absorption band. At a first stage their cloud detection capability has been tested, by comparing the Cloud Masks they produced. These showed a good agreement between two methods, although some critical situations stand out. The MWCC, in effect, fails to reveal clouds which according to SAFNWC are fractional, cirrus, very low and high opaque clouds. In the second stage of the inter-comparison the pixels classified as cloudy according to both softwares have been. The overall observed tendency of the MWCC method, is an overestimation of the lower cloud classes. Viceversa, the more the cloud top height grows up, the more the MWCC not reveal a certain cloud portion, rather detected by means of the SAFNWC tool. This is what also emerges from a series of tests carried out by using the cloud top height information in order to evaluate the height ranges in which each MWCC category is defined. Therefore, although the involved methods intend to provide the same kind of information, in reality they return quite different details on the same atmospheric column. The SAFNWC retrieval being very sensitive to the top temperature of a cloud, brings the actual level reached by this. The MWCC, by exploiting the capability of the microwaves, is able to give an information about the levels that are located more deeply within the atmospheric column.

Is hypoxia training good for muscles and exercise performance?

Altitude training has become very popular among athletes as a means to further increase exercise performance at sea level or to acclimatize to competition at altitude. Several approaches have evolved during the last few decades, with "live high-train low" and "live low-train high" being the most popular. This review focuses on functional, muscular, and practical aspects derived from extensive research on the "live low-train high" approach. According to this, subjects train in hypoxia but remain under normoxia for the rest of the time. It has been reasoned that exercising in hypoxia could increase the training stimulus. Hypoxia training studies published in the past have varied considerably in altitude (2300-5700 m) and training duration (10 days to 8 weeks) and the fitness of the subjects. The evidence from muscle structural, biochemical, and molecular findings point to a specific role of hypoxia in endurance training. However, based on the available performance capacity data such as maximal oxygen uptake (Vo(2)max) and (maximal) power output, hypoxia as a supplement to training is not consistently found to be advantageous for performance at sea level. Stronger evidence exists for benefits of hypoxic training on performance at altitude. "Live low-train high" may thus be considered when altitude acclimatization is not an option. In addition, the complex pattern of gene expression adaptations induced by supplemental training in hypoxia, but not normoxia, suggest that muscle tissue specifically responds to hypoxia. Whether and to what degree these gene expression changes translate into significant changes in protein concentrations that are ultimately responsible for observable structural or functional phenotypes remains open. It is conceivable that the global functional markers such as Vo(2)max and (maximal) power output are too coarse to detect more subtle changes that might still be functionally relevant, at least to high-level athletes.

Vaccine hypersensitivity--update and overview

Concerns about possible reactions to vaccines or vaccinations are frequently raised. However, the rate of reported vaccine-induced adverse events is low and ranges between 4.8-83.0 per 100,000 doses of the most frequently used vaccines. The number of true allergic reactions to routine vaccines is not known; estimations range from 1 per 500,000 to 1 per 1,000,000 doses for most vaccines. When allergens such as gelatine or egg proteins are components of the formulation, the rate for serious allergic reactions may be higher. Nevertheless, anaphylactic, potentially life-threatening reactions to vaccines are still a rare event (approximately 1 per 1,500,000 doses). The variety of reported vaccine-related adverse events is broad. Most frequently, reactions to vaccines are limited to the injection site and result from a non specific activation of the inflammatory system by, for example, aluminium salts or the active microbial components. If allergy is suspected, an accurate examination followed by algorithms is the key for correct diagnosis, treatment and the decision regarding revaccination in patients with immediate-type reactions to vaccines.

Regulation of placental growth by aldosterone and cortisol

During pregnancy, trophoblasts grow to adapt the feto-maternal unit to fetal requirements. Aldosterone and cortisol levels increase, the latter being inactivated by a healthy placenta. By contrast, preeclamptic placental growth is reduced while aldosterone levels are low and placental cortisol tissue levels are high due to improper deactivation. Aldosterone acts as a growth factor in many tissues, whereas cortisol inhibits growth. We hypothesized that in preeclampsia low aldosterone and enhanced cortisol availability might mutually affect placental growth and function. Proliferation of cultured human trophoblasts was time- and dose-dependently increased with aldosterone (P < 0.04 to P < 0.0001) and inhibited by spironolactone and glucocorticoids (P < 0.01). Mineralo- and glucocorticoid receptor expression and activation upon agonist stimulation was verified by visualization of nuclear translocation of the receptors. Functional aldosterone deficiency simulated in pregnant mice by spironolactone treatment (15 μg/g body weight/day) led to a reduced fetal umbilical blood flow (P < 0.05). In rat (P < 0.05; R(2) = 0.2055) and human (X(2) = 3.85; P = 0.0249) pregnancy, placental size was positively related to plasma aldosterone. Autocrine production of these steroid hormones was excluded functionally and via the absence of specific enzymatic transcripts for CYP11B2 and CYP11B1. In conclusion, activation of mineralocorticoid receptors by maternal aldosterone appears to be required for trophoblast growth and a normal feto-placental function. Thus, low aldosterone levels and enhanced cortisol availability may be one explanation for the reduced placental size in preeclampsia and related disorders.

Expression patterns of Bmi-1 and p16 significantly correlate with overall, disease-specific, and recurrence-free survival in oropharyngeal squamous cell carcinoma

BACKGROUND: The objective of this study was to link expression patterns of B-cell-specific Moloney murine leukemia virus integration site 1 (Bmi-1) and p16 to patient outcome (recurrence and survival) in a cohort of 252 patients with oral and oropharyngeal squamous cell cancer (OSCC). METHODS: Expression levels of Bmi-1 and p16 in samples from 252 patients with OSCC were evaluated immunohistochemically using the tissue microarray method. Staining intensity was determined by calculating an intensity reactivity score (IRS). Staining intensity and the localization of expression within tumor cells (nuclear or cytoplasmic) were correlated with overall, disease-specific, and recurrence-free survival. RESULTS: The majority of cancers were localized in the oropharynx (61.1%). In univariate analysis, patients who had OSCC and strong Bmi-1 expression (IRS >10) had worse outcomes compared with patients who had low and moderate Bmi-1 expression (P = .008; hazard ratio [HR], 1.82; 95% confidence interval [CI], 1.167-2.838); this correlation was also observed for atypical cytoplasmic Bmi-1 expression (P = .001; HR, 2.164; 95% CI, 1.389-3.371) and for negative p16 expression (P < .001; HR, 0.292; 95% CI, 0.178-0.477). The combination of both markers, as anticipated, had an even stronger correlation with overall survival (P < .001; HR, 8.485; 95% CI, 4.237-16.994). Multivariate analysis demonstrated significant results for patients with oropharyngeal cancers, but not for patients with oral cavity tumors: Tumor classification (P = .011; HR, 1.838; 95%CI, 1.146-2.947) and the combined marker expression patterns (P < .001; HR, 6.254; 95% CI, 2.869-13.635) were correlated with overall survival, disease-specific survival (tumor classification: P = .002; HR, 2.807; 95% CI, 1.477-5.334; combined markers: P = .002; HR, 5.386; 95% CI, 1.850-15.679), and the combined markers also were correlated with recurrence-free survival (P = .001; HR, 8.943; 95% CI, 2.562-31.220). CONCLUSIONS: Cytoplasmic Bmi-1 expression, an absence of p16 expression, and especially the combination of those 2 predictive markers were correlated negatively with disease-specific and recurrence-free survival in patients with oropharyngeal cancer. Therefore, the current results indicate that these may be applicable as predictive markers in combination with other factors to select patients for more aggressive treatment and follow-up. Cancer 2011;. © 2011 American Cancer Society.