Neue Methoden zur Computersimulation von Polymersystemen auf verschiedenen Längenskalen und ihre Anwendungen

In dieser Dissertation stellen wir einen neuen Ansatz zurModellierungvon Polymersystemen vor. Es werden (von methodischer Seiteher) zweiautomatisierte Iterationschemata dazu eingeführt,Kraftfeldparametermesoskopischer Polymersysteme systematisch zu optimieren:DasSimplex-Verfahren und das Struktur-Differenzen-Verfahren. Sowerdendiejenigen Freiheitsgrade aus Polymersystemen eliminiert,die einehohe Auflösung erfordern, was die Modellierung größerersystemeermöglicht. Nach Tests an einfachen Flüssigkeiten werdenvergröberteModelle von drei prototypischen Polymeren (Polyacrylsäure,Polyvinylalkohol und Polyisopren) in unterschiedlichenUmgebungen(gutes Lösungsmittel und Schmelze) entwickelt und ihrVerhalten aufder Mesoskala ausgiebig geprüft. Die zugehörige Abbildung(vonphysikalischer Seite her) so zu gestalten, daß sie dieunverwechselbaren Charakteristiken jedes systems auf diemesoskopischeLängenskala überträgt, stellt eine entscheidende Anforderungan dieautomatisierten Verfahren dar. Unsere Studien belegen, daß mesoskopische Kraftfeldertemperatur- unddichtespezifisch sind und daher bei geändernden Bedingungennachoptimiert werden müssen. Gleichzeitig läßt sichabschätzen, beiwelchen Umgebungsbedingungen dies noch nicht notwendig wird.In allenFällen reichen effektive Paarpotentiale aus, einrealistischesmesoskopisches Modell zu konstruieren. VergröberteSimulationenwerden im Falle der Polyacrylsäure erfolgreich gegenexperimentelleLichtstreudaten getestet. Wir erzielen für Molmassen bis zu300000g/mol eine hervorragende Übereinstimmung für denhydrodynamischenRadius. Unsere Ergebnisse erklären auch Korrekturen zudessenVerhalten als Funktion der Kettenlänge ('Skalenverhalten'). Im Fallevon Polyisopren untersuchen wir sowohl statische als auchdynamischeGrößen und stellen klare Unterschiede unserer Ergebnisse zudeneneines einfachen semi-flexiblen Mesoskalenmodells fest. InderProteinforschung werden aus Datenbanken gewonnene effektivePaarwechselwirkungen dazu verwendet, die freie Energie einesneuensystems vorherzusagen. Wir belegen in einem Exkurs mittelsGittersimulationen, daß es selbst in einfachsten Fällennicht gelingt,dies auch nur qualitativ korrekt zu bewerkstelligen.

Effetto della temperatura di conservazione del latte, dalla raccolta all'affioramento, sulla microflora del latte, del sieroinnesto e del formaggio Trentingrana

This PhD research is part of a project addressed to improve the quality of Grana Trentino production. The objectives were to evaluated if milk storage and collection procedures may affect cheese-making technology and quality. Actually the milk is collected and delivered to the cheese factory just after milking in 50 L cans without refrigeration or in tanks cooled at 18 °C. This procedure is expensive (two deliveries each day) and the milk quality is difficult to preserve as temperatures are not controlled. The milk refrigeration at the farm could allow a single delivery to the dairy. Therefore it could be a good strategy to preserve raw milk quality and reduce cheese spoilage. This operation may, however, have the drawbacks of favouring the growth of psychrotrophic bacteria and changing the aptitude of milk to coagulation. With the aim of studying the effect on milk and cheese of traditional and new refrigerated technologies of milk storage, two different collection and creaming technologies were compared. The trials were replicated in three cheese factories manufacturing Grana Trentino. Every cheese-making day, about 1000 milk liters were collected from always the same two farms in the different collection procedures (single or double). Milk was processed to produce 2 wheels of Grana trentino every day. During the refrigerated trials, milk was collected and stored at the farm in a mixed tank at 12 or 8 °C and then was carried to the dairy in truck once a day. 112 cheese making day were followed: 56 for traditional technology and 56 for the refrigerated one. Each one of these two thechnologies lead to different ways of creaming: long time in the traditional one and shorter in the new one. For every cheese making day we recorded time, temperatures and pH during the milk processing to cheese. Whole milk before ceraming, cream and skim milk after creaming, vat milk and whey were sampled during every cheese-making day for analysis. After 18 months ripening we opened 46 cheese wheels for further chemical and microbiological analyses. The trials were performed with the aim of: 1 estimate the effect of storage temperatures on microbial communities, physico-chemical or/and rheological differences of milk and skim milk after creaming. 2 detect by culture dependent (plate counts) and indipendent (DGGE) methodolgies the microbial species present in whole, skimmed milk, cream and cheese sampled under the rind and in the core; 3 estimate the physico-chemical characteristics, the proteolytic activity, the content of free aminoacids and volatile compounds in 18 months ripened Grana Trentino cheeses from different storing and creaming of milk technologies. The results presented are remarkable since this is the first in-deep study presenting microbiological and chemical analysis of Grana Trentino that even if belonging to Grana Padano Consortium, it is clearly different in the milk and in the manufacturing technology.

Ophiolites of the eastern Vardar Zone, N. Greece

In the present thesis, the geochemistry, petrology and geochronology of ophiolite complexes from central northern Greece were studied in detail in order to gain insights on the petrogenetic pathways and geodynamic processes that lead to their formation and evolution. The major- and trace-element content of minerals and whole rocks from all four ophiolite complexes was determined using high-precision analytical equipment. These results were then coupled with Nd and Sr isotopic measurements. In order to precisely place the evolution of these ophiolites in time, U-Pb geochronology on zircons was conducted using a SHRIMP-II. The data obtained suggest that the ophiolites studied invariably show typical characteristics of subduction-zone magmatism (e.g. negative Nb anomalies, Th enrichment). In N-MORB-normalised multielement profiles the high field-strength elements display patterns that vary from depleted to N-MORB-like. Chondrite-normalised rare-earth element (REE) profiles show flat heavy-REE patterns suggesting a shallow regime of source melting for all the ophiolites, well within the stability field of spinel lherzolite. The majority of the samples have light-REE depleted patterns. 87Sr/86Sr isotopic ratios range from 0.703184 to 0.715853 and are in cases influenced by alteration. The εNd values are positive (the majority of the mafic samples is typically 7.1-3.1) but lower than N-MORB and depleted mantle. With the exception of the Thessaloniki ophiolite that has uniform island-arc tholeiitic chemical characteristics, the rest of the ophiolites show dual chemistry consisting of rocks with minor subduction-zone characteristics that resemble chemically back-arc basin basalts (BABB) and rocks with more pronounced subduction-zone characteristics. Tectonomagmatic discrimination schemes classify the samples as island-arc tholeiites and back-arc basin basalts or N-MORB. Melting modelling carried out to evaluate source properties and degree of melting verifies the dual nature of the ophiolites. The samples that resemble back-arc basin basalts require very small degrees of melting (<10%) of fertile sources, whereas the rest of the samples require higher degrees (25-15%) of melting. As deduced from the present geochemical and petrological investigation, the ophiolites from Guevguely, Oraeokastro, Thessaloniki, and Chalkidiki represent relics of supra-subduction zone crust that formed in succeeding stages of island-arc rifting and back-arc spreading as well as in a fore arc setting. The geochronological results have provided precise determination of the timing of formation of these complexes. The age of the Guevguely ophiolite has been determined as 167±1.2 Ma, that of Thessaloniki as 169±1.4 Ma, that of Kassandra as 167±2.2 Ma and that of Sithonia as 160±1.2 Ma.

Individuazione di tecniche di gestione idrica-agronomica e di ricarica dell’acquifero freatico costiero per limitare la salinizzazione delle acque sotterranee e dei suoli.

Nel Comune di Ravenna, oltre 6.800 ettari di terreni agricoli sono a rischio salinizzazione, a causa dell’alta salinità delle acque sotterranee presenti all’interno dell’acquifero freatico costiero. L'area è interessata da subsidenza naturale, per compattazione dei sedimenti alluvionali e antropica, causata dall’estrazione di gas e dall’eccessivo sfruttamento delle acque sotterranee. Ne deriva che la maggior parte di questo territorio è sotto il livello medio del mare e l'agricoltura, così come ogni altra attività umana, è possibile grazie ad una fitta rete di canali di drenaggio che garantiscono il franco di coltivazione. L’agricoltura è una risorsa importante per la zona, ma a causa della scarsa disponibilità di acque dolci e per l’aumento dei processi di salinizzazione dei suoli, necessita di un cambiamento. Servono pratiche agricole sostenibili, con idonei requisiti irrigui, di drenaggio del suolo, di resistenza alla salinizzazione e di controllo del suolo. Dopo un’analisi generale sulle condizioni dell’acquifero, è stato monitorato un transetto di 10km rappresentativo della parte costiera di Ravenna. Infine, con l'obiettivo di comprendere l'interazione tra un canale d'irrigazione e le acque sotterranee, una piccola area agricola (12 ettari), è stata monitorata nel corso del 2011 utilizzando metodi idrologici, geochimici e geofisici. I risultati di questo lavoro mostrano una diffusa salinizzazione della falda freatica, ma anche la presenza di una lente d'acqua dolce spessa 5m, a 400m dalla linea di riva, con caratteristiche chimiche (hydrofacies) tipici di acque continentali e con dimensioni variabili stagionalmente. Questa bolla di acqua dolce si è originata esclusivamente dalle infiltrazioni dal canale d’irrigazione presente, in quanto, il contributo dell’irrigazione superficiale è stato nullo. Sfruttando la rete di canali di drenaggio già presente sarebbe possibile estendere questo processo d’infiltrazione da canale in altre porzioni dell’acquifero allo scopo di ricaricare l’acquifero stesso e limitare la salinizzazione dei suoli.

Functional hydrogels

Hydrogels are used in a variety of applications in daily life, such as super absorbers, contact lenses and in drug delivery. Functional hydrogels that allow the incorporation of additional functionalities have enormous potential for future development. The properties of such hydrogels can be diversified by introducing responsiveness to external stimuli. These crosslinked polymers are known to respond to changes in temperature, pH and pressure, as well as chemical and electrical stimuli, magnetic fields and irradiation. From this responsive behavior possible applications arise in many fields like drug delivery, tissue engineering, purification and implementation as actuators, biosensors or for medical coatings. However, their interaction with biomaterial and way of functioning are yet not fully understood. Therefore, thorough investigations regarding their optical, mechanical and chemical nature have to be conducted. A UV-crosslinkable polymer, consisting of N-isopropylacrylamide, methacrylic acid and the UV-crosslinker 4-benzoylphenyl methacrylate was synthesized. Its composition, determined by a comprehensive NMR study, is equivalent to the composition of the monomer mixture. The chemical characteristics were preserved during the subsequently formation of hydrogel films by photo-crosslinking as proved by XPS. For the optical characterization, e.g. the degree of swelling of very thin films, the spectroscopy of coupled long range surface plasmons is introduced. Thicker films, able to guide light waves were analyzed with combined surface plasmon and optical waveguide mode spectroscopy (SPR/OWS). The evaluation of the data was facilitated by the reverse Wentzel-Kramers-Brillouin (WKB) approximation. The meshsize and proper motion of the surface anchored hydrogels were investigated by fluorescence correlation spectroscopy (FCS), micro photon correlation spectroscopy (µPCS) and SPR/OWS. The studied gels exhibit a meshsize that allowed for the diffusion of small biomolecules inside their network. For future enhancement of probing diffusants, a dye that enables FRET in FCS was immobilized in the gel and the diffusion of gold-nanoparticles embedded in the polymer solution was studied by PCS. These properties can be conveniently tuned by the crosslinking density, which depends on the irradiation dose. Additionally, protocols and components for polymer analogous reactions based on active ester chemistry of the hydrogel were developed. Based on these syntheses and investigations, the hydrogel films are applied in the fields of medical coatings as well as in biosensing as matrix and biomimetic cushion. Their non-adhesive properties were proved in cell experiments, SPR/OWS and ToF-SIMS studies. The functionality and non-fouling property of the prepared hydrogels allowed for adaption to the needs of the respective application.

Methane production through anaerobic digestion of dedicated energy crops

Methane yield of ligno-cellulosic substrates (i.e. dedicated energy crops and agricultural residues) may be limited by their composition and structural features. Hence, biomass pre-treatments are envisaged to overcome this constraint. This thesis aimed at: i) assessing biomass and methane yield of dedicated energy crops; ii) evaluating the effects of hydrothermal pre-treatments on methane yield of Arundo; iii) investigating the effects of NaOH pre-treatments and iv) acid pre-treatments on chemical composition, physical structure and methane yield of two dedicated energy crops and one agricultural residue. Three multi-annual species (Arundo, Switchgrass and Sorghum Silk), three sorghum hybrids (Trudan Headless, B133 and S506) and a maize, as reference for AD, were studied in the frame of point i). Results exhibit the remarkable variation in biomass yield, chemical characteristics and potential methane yield. The six species alternative to maize deserve attention in view of a low need of external inputs but necessitate improvements in biodegradability. In the frame of point ii), Arundo was subjected to hydrothermal pre-treatments at different temperature, time and acid catalyst (with and without H2SO4). Pre-treatments determined a variable effect on methane yield: pre-treatments without acid catalyst achieved up to +23% CH4 output, while pre-treatments with H2SO4 catalyst incurred a methanogenic inhibition. Two biomass crops (Arundo and B133) and an agricultural residue (Barley straw) were subject to NaOH and acid pre-treatments, in the frame of point iii) and iv), respectively. Different pre-treatments determined a change of chemical and physical structure and an increase of methane yield: up to +30% and up to +62% CH4 output in Arundo with NaOH and acid pre-treatments, respectively. It is thereby demonstrated that pre-treatments can actually enhance biodegradability and subsequent CH4 output of ligno-cellulosic substrates, although pre-treatment viability needs to be evaluated at the level of full scale biogas plants in a perspective of profitable implementation.

Silk Fibroin: a biopolymer platform for innovative pharmaceutical formulation and biomedical devices.

The protein silk fibroin (SF) from the silkworm Bombyx mori is a FDA-approved biomaterial used over centuries as sutures wire. Importantly, several evidences highlighted the potential of silk biomaterials obtained by using so-called regenerated silk fibroin (RSF) in biomedicine, tissue engineering and drug delivery. Indeed, by a water-based protocol, it is possible to obtain protein water-solution, by extraction and purification of fibroin from silk fibres. Notably, RSF can be processed in a variety of biomaterials forms used in biomedical and technological fields, displaying remarkable properties such as biocompatibility, controllable biodegradability, optical transparency, mechanical robustness. Moreover, RSF biomaterials can be doped and/or chemical functionalized with drugs, optically active molecules, growth factors and/or chemicals In this view, activities of my PhD research program were focused to standardize the process of extraction and purification of protein to get the best physical and chemical characteristics. The analysis of the chemo-physical properties of the fibroin involved both the RSF water-solution and the protein processed in film. Chemo-physical properties have been studied through: vibrational (FT-IR and Raman-FT) and optical (absorption and emission UV-VIS) spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermal analysis and thermo-gravimetric scan (DSC and TGA). In the last year of my PhD, activities were focused to study and define innovative methods of functionalization of the silk fibroin solution and films. Indeed, research program was the application of different methods of manufacturing approaches of the films of fibroin without the use of harsh treatments and organic solvents. New approaches to doping and chemical functionalization of the silk fibroin were studied. Two different methods have been identified: 1) biodoping that consists in the doping of fibroin with optically active molecules through the addition of fluorescent molecules in the standard diet used for the breeding of silkworms; 2) chemical functionalization via silylation.

Chemische und physikalische Charakterisierung von Aerosolpartikeln aus besonderen anthropogenen Emissionsquellen : ein integrativer Ansatz mittels online (HR-ToF-AMS)- und komplementärer offline (ATR-FTIR-Spektroskopie)-Analytik

Die Gesundheitseffekte von Aerosolpartikeln werden stark von ihren chemischen und physikalischen Eigenschaften und somit den jeweiligen Bildungsprozessen und Quellencharakteristika beeinflusst. Während die Hauptquellen der anthropogenen Partikelemissionen gut untersucht sind, stellen die spezifischen Emissionsmuster zahlreicher kleiner Aerosolquellen, welche lokal und temporär zu einer signifikanten Verschlechterung der Luftqualität beitragen können, ein Forschungsdesiderat dar.rnIn der vorliegenden Arbeit werden in kombinierten Labor- und Feldmessungen durch ein integratives Analysekonzept mittels online (HR-ToF-AMS ) und filterbasierter offline (ATR-FTIR-Spektroskopie ) Messverfahren die weitgehend unbekannten physikalischen und chemischen Eigenschaften der Emissionen besonderer anthropogener Aerosolquellen untersucht. Neben einem Fußballstadion als komplexe Mischung verschiedener Aerosolquellen wie Frittieren und Grillen, Zigarettenrauchen und Pyrotechnik werden die Emissionen durch Feuerwerkskörper, landwirtschaftliche Intensivtierhaltung (Legehennen), Tief- und Straßenbauarbeiten sowie abwasserbürtige Aerosolpartikel in die Studie mit eingebunden. Die primären Partikelemissionen der untersuchten Quellen sind vorrangig durch kleine Partikelgrößen (dp < 1 µm) und somit eine hohe Lungengängigkeit gekennzeichnet. Dagegen zeigen die Aerosolpartikel im Stall der landwirtschaftlichen Intensivtierhaltung sowie die Emissionen durch die Tiefbauarbeiten einen hohen Masseanteil von Partikeln dp > 1 µm. Der Fokus der Untersuchung liegt auf der chemischen Charakterisierung der organischen Partikelbestandteile, welche für viele Quellen die NR-PM1-Emissionen dominieren. Dabei zeigen sich wichtige quellenspezifische Unterschiede in der Zusammensetzung der organischen Aerosolfraktion. Die beim Abbrand von pyrotechnischen Gegenständen freigesetzten sowie die abwasserbürtigen Aerosolpartikel enthalten dagegen hohe relative Gehalte anorganischer Substanzen. Auch können in einigen spezifischen Emissionen Metallverbindungen in den AMS-Massenspektren nachgewiesen werden. Über die Charakterisierung der Emissionsmuster und -dynamiken hinaus werden für einige verschiedenfarbige Rauchpatronen sowie die Emissionen im Stall der Intensivtierhaltung Emissionsfaktoren bestimmt, die zur quantitativen Bilanzierung herangezogen werden können. In einem weiteren Schritt werden anhand der empirischen Daten die analytischen Limitierungen der Aerosolmassenspektrometrie wie die Interferenz organischer Fragmentionen durch (Hydrogen-)Carbonate und mögliche Auswertestrategien zur Überwindung dieser Grenzen vorgestellt und diskutiert.rnEine umfangreiche Methodenentwicklung zur Verbesserung der analytischen Aussagekraft von organischen AMS-Massenspektren zeigt, dass für bestimmte Partikeltypen einzelne Fragmentionen in den AMS-Massenspektren signifikant mit ausgewählten funktionellen Molekülgruppen der FTIR-Absorptionsspektren korrelieren. Bedingt durch ihre fehlende Spezifität ist eine allgemeingültige Interpretation von AMS-Fragmentionen als Marker für verschiedene funktionelle Gruppen nicht zulässig und häufig nur durch die Ergebnisse der komplementären FTIR-Spektroskopie möglich. Des Weiteren wurde die Verdampfung und Ionisation ausgewählter Metallverbindungen im AMS analysiert. Die Arbeit verdeutlicht, dass eine qualitative und quantitative Auswertung dieser Substanzen nicht ohne Weiteres möglich ist. Die Gründe hierfür liegen in einer fehlenden Reproduzierbarkeit des Verdampfungs- und Ionisationsprozesses aufgrund von Matrixeffekten sowie der in Abhängigkeit vorangegangener Analysen (Verdampferhistorie) in der Ionisationskammer und auf dem Verdampfer statt-findenden chemischen Reaktionen.rnDie Erkenntnisse der Arbeit erlauben eine Priorisierung der untersuchten anthropogenen Quellen nach bestimmten Messparametern und stellen für deren Partikelemissionen den Ausgangpunkt einer Risikobewertung von atmosphärischen Folgeprozessen sowie potentiell negativen Auswirkungen auf die menschliche Gesundheit dar. rn

Analisi idrogeologica dell'area carsica dei Monti Alburni (Salerno, Campania)

The Alburni Massif is the most important karstic area in southern Italy and It contains about 250 caves. Most of these caves are located on the plateau, between 1500 m a.s.l. and 700 m a.s.l., and only a few reach the underground streams that feed the springs and the deep aquifer. The main springs are Grotta di Pertosa-Auletta (CP1) and Auso spring (CP31), both located at 280 m a.s.l., the first on the south-eastern margin whereas the second on south-west margin, and the springs present in Castelcivita area, the Castelcivita-Ausino system (CP2) and Mulino di Castelcivita spring (CP865), located at 60 m a.s.l.. Some other secondary springs are present too. We have monitored Pertosa-Auletta’s spring with a multiparameter logger. This logger has registered data from November 2014 to December 2015 regarding water level, electric conductivity and temperature. The hydrodynamic monitoring has been supported by a sampling campaign in order to obtain chemical water analyses. The work was done from August 2014 to December 2015, not only at Pertosa but also at all the other main springs, and in some caves. It was possible to clarify the behavior of Pertosa-Auletta’s spring, almost exclusively fed by full charge conduits, only marginally affected by seasonal rains. Pertosa-Auletta showed a characteristic Mg/Ca ratio and Mg2+ enrichment, as demonstrated by its saturation index that always showed a dolomite saturation. All other spring have characteristic waters from a chemical point of view. In particular, it highlights the great balance between the components dissolved in the waters of Mulino’ spring opposed to the variability of the nearby Castelcivita-Ausino spring. Regarding the Auso spring the variable behavior in terms of discharge and chemistry is confirmed, greatly influenced by rainfall and, during drought periods, by full charge conduits. Rare element concentrations were also analyzed and allowed to characterize further the different waters. Based on all these data an updated hydrogeological map of the Alburni massif has been drawn, that defines in greater detail the hydrogeological complexes on the basis of lithologies, and therefore of their chemical characteristics.

Contribution à l’étude de l’influence des caractères physico-chimiques du sol sur la stabilité structurale ; cas de la plaine de Sidi Bel Abbes

The aim of the study is to contribute to the knowledge and the identification of the main physical and chemical characteristics of the soil that affect the structural stability of soil types forming the soil cover of the plain of Sidi Bel Abbes region for agricultural use by excellence. Structural stability is an indicator of the cohesion of soil aggregates. This is a parameter that expresses the ability of soil aggregates to resist degradation in general the impact of rain or excess water. Measuring the structural stability makes it possible to evaluate the sensitivity a soil crusting and erosion. The results showed that soils subject of our study are stable and very stable with a slight difference. We have a statistical study made it possible to establish a correlation between the structural stability and other physical and chemical soil parameters measured )fersiallitic red soil and brown calcareous soil( such as organic matter content, the rate of total limestone and soil texture, to better explain the stability or instability of the soil structure and to establish a relationship between these parameters and the structural stability. // Keywords: Sidi Bel Abbes, chemical characteristics, physical, structural stability, soil, plain, fersiallitic red soil, brown calcareous soil

The chironomid-temperature relationship: expression in nature and palaeoenvironmental implications

Fossils of chironomid larvae (non-biting midges) preserved in lake sediments are well-established palaeotemperature indicators which, with the aid of numerical chironomid-based inference models (transfer functions), can provide quantitative estimates of past temperature change. This approach to temperature reconstruction relies on the strong relationship between air and lake surface water temperature and the distribution of individual chironomid taxa (species, species groups, genera) that has been observed in different climate regions (arctic, subarctic, temperate and tropical) in both the Northern and Southern hemisphere. A major complicating factor for the use of chironomids for palaeoclimate reconstruction which increases the uncertainty associated with chironomid-based temperature estimates is that the exact nature of the mechanism responsible for the strong relationship between temperature and chironomid assemblages in lakes remains uncertain. While a number of authors have provided state of the art overviews of fossil chironomid palaeoecology and the use of chironomids for temperature reconstruction, few have focused on examining the ecological basis for this approach. Here, we review the nature of the relationship between chironomids and temperature based on the available ecological evidence. After discussing many of the surveys describing the distribution of chironomid taxa in lake surface sediments in relation to temperature, we also examine evidence from laboratory and field studies exploring the effects of temperature on chironomid physiology, life cycles and behaviour. We show that, even though a direct influence of water temperature on chironomid development, growth and survival is well described, chironomid palaeoclimatology is presently faced with the paradoxical situation that the relationship between chironomid distribution and temperature seems strongest in relatively deep, thermally stratified lakes in temperate and subarctic regions in which the benthic chironomid fauna lives largely decoupled from the direct influence of air and surface water temperature. This finding suggests that indirect effects of temperature on physical and chemical characteristics of lakes play an important role in determining the distribution of lake-living chironomid larvae. However, we also demonstrate that no single indirect mechanism has been identified that can explain the strong relationship between chironomid distribution and temperature in all regions and datasets presently available. This observation contrasts with the previously published hypothesis that climatic effects on lake nutrient status and productivity may be largely responsible for the apparent correlation between chironomid assemblage distribution and temperature. We conclude our review by summarizing the implications of our findings for chironomid-based palaeoclimatology and by pointing towards further avenues of research necessary to improve our mechanistic understanding of the chironomid-temperature relationship.

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.

Caracteres físico-químicos de efluentes de fábricas de aceite de oliva : Mendoza (Argentina)

La producción de aceite de oliva genera distintos subproductos entre los cuales el efluente o alpechín representa un serio problema mediambiental. En los países productores el alpechín es un residuo muy contaminante debido a su elevada composición orgánica, sus efectos inhibitorios y la tendencia de sus componentes a sufrir oxidación biológica. Estas características y la estacionalidad de su producción dificultan su eliminación. La industria del aceite de oliva está actualmente en expansión en Argentina. En Mendoza, dicha actividad tiene una gran tradición y un impacto ambiental considerable. El objetivo de este trabajo fue analizar los caracteres físico- químicos de los efluentes de fábricas de aceite oliva en Mendoza (Argentina) para conocer la realidad de la industria local y rever las especificaciones legales para efluentes. Los efluentes de dos fábricas fueron evaluados en tres puntos de muestreo: agua de entrada al proceso, salida de la fábrica y pileta de deposición final de los efluentes. Se analizó el contenido de iones, pH, conductividad eléctrica, DBO y DQO. Los resultados obtenidos permiten concluir que las características del efluente dependen del método de extracción utilizado y la eventual dilución con agua de lavado. La calidad del agua subterránea utilizada en el proceso no es un factor determinante para lograr un efluente fácilmente tratable. El problema medioambiental que se plantea es la producción de un efluente con alto contenido orgánico, salino y bajo pH, caracteres que impiden su vuelco en cursos de agua superficial o red de cloacas, por no cumplir con los requisitos indicados en la normativa vigente. Por lo tanto, las fábricas elaboradoras de aceite de oliva serán las encargadas de que dichos efluentes reciban un adecuado proceso de depuración que permita su eliminación o reutilización.