Water masses and circulation in the surface layers of the Caribbean at 66ºW

[EN] A meridional hydrographic section was made in August–September 1997 at 66°W from the coast of Venezuela to Woods Hole aboard the R/V Knorr. In this report, we concentrate on near surface measurements in the Caribbean. The data show two distinct water masses with different origins. From approximately 14°N to Puerto Rico, Caribbean Surface Water and Subtropical Under Water with their source in the North Atlantic are found, as previously observed. From Venezuela to approximately 13°N, a less saline water mass with its source in the Tropics and South Atlantic is found. Within the southern portion of the section, two different velocity patterns are observed, namely, an eastward flow with a subsurface maximum near the coast of Venezuela, and a surface intensified westward jet with Velocities of 130 cm s−1 in midbasin.

Distribution of water masses and diapycnal mixing in the Cape Verde Frontal Zone

[EN]The Cape Verde Frontal Zone separates North and South Atlantic Central Waters in the eastern North Atlantic Subtropical Gyre. CTD-O2 and shipboard ADCP data from three hydrographic sections carried out in September 2003 are used to study the structure of the front. Results show the relation between spatial variations of water masses and currents, demonstrating the importance of advection in the distribution of water masses. Diapycnal diffusivities due to double diffusion and vertical shear instabilities are also estimated. Existence of competition between the two processes through the water column is shown. Depth-averaged diffusivities suggest that salt fingering dominates diapycnal mixing, except areas of purest South Atlantic Central Water. Here, double diffusion processes are weak and, consequently, shear of the flow is the main process. Results also show that strong mixing induced by vertical shear is associated with a large intrusion found near the front.

Sistema per l'estrazione e purificazione di sostanze antiossidanti naturali nelle acque di vegetazione delle olive

The olive oil extraction industry is responsible for the production of high quantities of vegetation waters, represented by the constitutive water of the olive fruit and by the water used during the process. This by-product represent an environmental problem in the olive’s cultivation areas because of its high content of organic matter, with high value of BOD5 and COD. For that reason the disposal of the vegetation water is very difficult and needs a previous depollution. The organic matter of vegetation water mainly consists of polysaccharides, sugars, proteins, organic acids, oil and polyphenols. This last compounds are the principal responsible for the pollution problems, due to their antimicrobial activity, but, at the same time they are well known for their antioxidant properties. The most concentrate phenolic compounds in waters and also in virgin olive oils are secoiridoids like oleuropein, demethyloleuropein and ligstroside derivatives (the dialdehydic form of elenolic acid linked to 3,4-DHPEA, or p-HPEA (3,4-DHPEA-EDA or p-HPEA-EDA) and an isomer of the oleuropein aglycon (3,4-DHPEA-EA). The management of the olive oil vegetation water has been extensively investigated and several different valorisation methods have been proposed, such as the direct use as fertilizer or the transformation by physico-chemical or biological treatments. During the last years researchers focused their interest on the recovery of the phenolic fraction from this waste looking for its exploitation as a natural antioxidant source. At the present only few contributes have been aimed to the utilization for a large scale phenols recovery and further investigations are required for the evaluation of feasibility and costs of the proposed processes. The present PhD thesis reports a preliminary description of a new industrial scale process for the recovery of the phenolic fraction from olive oil vegetation water treated with enzymes, by direct membrane filtration (microfiltration/ultrafiltration with a cut-off of 250 KDa, ultrafiltration with a cut-off of 7 KDa/10 KDa and nanofiltration/reverse osmosis), partial purification by the use of a purification system based on SPE analysis and by a liquid-liquid extraction system (LLE) with contemporary reduction of the pollution related problems. The phenolic fractions of all the samples obtained were qualitatively and quantitatively by HPLC analysis. The work efficiency in terms of flows and in terms of phenolic recovery gave good results. The final phenolic recovery is about 60% respect the initial content in the vegetation waters. The final concentrate has shown a high content of phenols that allow to hypothesize a possible use as zootechnic nutritional supplements. The purification of the final concentrate have garanteed an high purity level of the phenolic extract especially in SPE analysis by the use of XAD-16 (73% of the total phenolic content of the concentrate). This purity level could permit a future food industry employment such as food additive, or, thanks to the strong antioxidant activity, it would be also use in pharmaceutical or cosmetic industry. The vegetation water depollutant activity has brought good results, as a matter of fact the final reverse osmosis permeate has a low pollutant rate in terms of COD and BOD5 values (2% of the initial vegetation water), that could determinate a recycling use in the virgin olive oil mechanical extraction system producing a water saving and reducing thus the oil industry disposal costs .

Emerging contaminants in agricultural ecosystems: impact of selected pharmaceutical on water and soil ecology and pratical implications

Pharmaceuticals are useful tools to prevent and treat human and animal diseases. Following administration, a significant fraction of pharmaceuticals is excreted unaltered into faeces and urine and may enter the aquatic ecosystem and agricultural soil through irrigation with recycled water, constituting a significant source of emerging contaminants into the environment. Understanding major factors influencing their environmental fate is consequently needed to value the risk, reduce contamination, and set up bioremediation technologies. The antiviral drug Tamiflu (oseltamivir carboxylate, OC) has received recent attention due to the potential use as a first line defence against H5N1 and H1N1 influenza viruses. Research has shown that OC is not removed during conventional wastewater treatments, thus having the potential to enter surface water bodies. A series of laboratory experiments investigated the fate and the removal of OC in surface water systems in Italy and Japan and in a municipal wastewater treatment plant. A preliminary laboratory study investigated the persistence of the active antiviral drug in water samples from an irrigation canal in northern Italy (Canale Emiliano Romagnolo). After an initial rapid decrease, OC concentration slowly decreased during the remaining incubation period. Approximately 65% of the initial OC amount remained in water at the end of the 36-day incubation period. A negligible amount of OC was lost both from sterilized water and from sterilized water/sediment samples, suggesting a significant role of microbial degradation. Stimulating microbial processes by the addition of sediments resulted in reduced OC persistence. Presence of OC (1.5 μg mL-1) did not significantly affect the metabolic potential of the water microbial population, that was estimated by glyphosate and metolachlor mineralization. In contrast, OC caused an initial transient decrease in the size of the indigenous microbial population of water samples. A second laboratory study focused on basic processes governing the environmental fate of OC in surface water from two contrasting aquatic ecosystems of northern Italy, the River Po and the Venice Lagoon. Results of this study confirmed the potential of OC to persist in surface water. However, the addition of 5% of sediments resulted in rapid OC degradation. The estimated half-life of OC in water/sediment of the River Po was 15 days. After three weeks of incubation at 20 °C, more than 8% of 14C-OC evolved as 14CO2 from water/sediment samples of the River Po and Venice Lagoon. OC was moderately retained onto coarse sediments from the two sites. In water/sediment samples of the River Po and Venice Lagoon treated with 14C-OC, more than 30% of the 14C-residues remained water-extractable after three weeks of incubation. The low affinity of OC to sediments suggests that the presence of sediments would not reduce its bioavailability to microbial degradation. Another series of laboratory experiments investigated the fate and the removal of OC in two surface water ecosystems of Japan and in the municipal wastewater treatment plant of the city of Bologna, in Northern Italy. The persistence of OC in surface water ranged from non-detectable degradation to a half-life of 53 days. After 40 days, less than 3% of radiolabeled OC evolved as 14CO2. The presence of sediments (5%) led to a significant increase of OC degradation and of mineralization rates. A more intense mineralization was observed in samples of the wastewater treatment plant when applying a long incubation period (40 days). More precisely, 76% and 37% of the initial radioactivity applied as 14C-OC was recovered as 14CO2 from samples of the biological tank and effluent water, respectively. Two bacterial strains growing on OC as sole carbon source were isolated and used for its removal from synthetic medium and environmental samples, including surface water and wastewater. Inoculation of water and wastewater samples with the two OC-degrading strains showed that mineralization of OC was significantly higher in both inoculated water and wastewater, than in uninoculated controls. Denaturing gradient gel electrophoresis and quantitative PCR analysis showed that OC would not affect the microbial population of surface water and wastewater. The capacity of the ligninolytic fungus Phanerochaete chrysosporium to degrade a wide variety of environmentally persistent xenobiotics has been largely reported in literature. In a series of laboratory experiments, the efficiency of a formulation using P. chrysosporium was evaluated for the removal of selected pharmaceuticals from wastewater samples. Addition of the fungus to samples of the wastewater treatment plant of Bologna significantly increased (P < 0.05) the removal of OC and three antibiotics, erythromycin, sulfamethoxazole, and ciprofloxacin. Similar effects were also observed in effluent water. OC was the most persistent of the four pharmaceuticals. After 30 days of incubation, approximately two times more OC was removed in bioremediated samples than in controls. The highest removal efficiency of the formulation was observed with the antibiotic ciprofloxacin. The studies included environmental aspects of soil contamination with two emerging veterinary contaminants, such as doramectin and oxibendazole, wich are common parasitic treatments in cattle farms.

Biogenic emission of halocarbons

Within this doctoral thesis, biogenic emissions of several globally relevant halocarbons (methyl chloride, methyl bromide, methyl iodide, dibromomethane, chloroform and bromoform) have been investigated in different environments. An airborne study was focused on the tropical rainforest ecosystem, while shipborne measurements investigated naturally occurring oceanic plankton blooms. Laboratory experiments using dried plant material were made to elucidate abiotic production mechanisms occurring in organic matter. Airborne measurements over the tropical rainforest of Suriname and French Guyana (3 - 6 °N, 51 - 59 °W) revealed net fluxes of 9.5 (± 3.8 2σ) µg m-2 h-1 methyl chloride and 0.35 (± 0.15 2σ) µg m-2 h-1 chloroform emitted in the long dry season (October) 2005. An extrapolation of these numbers to all tropical forests helped to narrow down the range of the recently discovered and poorly quantified methyl chloride source from tropical ecosystems. The value for methyl chloride obtained (1.5 (± 0.6 2σ) Tg yr-1) affirms that the contribution of the tropical forest ecosystem is the major source in the global budget of methyl chloride. The extrapolated global net chloroform flux from tropical forests (56 (± 23 2σ) Gg yr-1) is of minor importance (5 - 10 %) compared to the global sources. A source of methyl bromide from this region could not be verified. The abiotic formation of methyl chloride and methyl bromide from dead plant material was tested in a laboratory study. The release from plant tissue representative of grassland, deciduous forest, agricultural areas and coastal salt marshes (hay, ash, tomato and saltwort) has been monitored. Incubations at different temperatures (25 - 50 °C) revealed significant emissions even at ambient temperature, and that the emissions increased exponentially with temperature. The strength of the emission was found to be additionally dependent on the availability of halide and the methoxyl group within the plant tissue. However, high water content in the plant material was found to inhibit methyl halide emissions. The abiotic nature of the reaction yielding methyl halides was confirmed by its high activation energy calculated via Arrhenius plots. Shipborne measurements of the atmospheric mixing ratios of methyl chloride, methyl bromide, methyl iodide, dibromomethane and bromoform have been conducted along a South Atlantic transect from the 27.01. - 05.02.2007 to characterize halocarbon emissions from a large-scale natural algae bloom encountered off the coast of Argentina. Mixing ratios of methyl chloride and methyl bromide were not significantly affected by the occurrence of the phytoplankton bloom. Emissions of methyl iodide, dibromomethane and bromoform showed pronounced mixing ratio variations, triggered by phytoplankton abundance. Methyl iodide was strongly correlated with dimethyl sulfide throughout the sampled region. A new technique combining satellite derived biomass marker (chlorophyll a) data with back trajectory analysis was successfully used to attribute variations in mixing ratios to air masses, which recently passed over areas of enhanced biological production.

Advanced spectroscopic techniques and chemometric analysis for atmospheric organic aerosol characterization and source apportionment

Atmospheric aerosol particles directly impact air quality and participate in controlling the climate system. Organic Aerosol (OA) in general accounts for a large fraction (10–90%) of the global submicron (PM1) particulate mass. Chemometric methods for source identification are used in many disciplines, but methods relying on the analysis of NMR datasets are rarely used in atmospheric sciences. This thesis provides an original application of NMR-based chemometric methods to atmospheric OA source apportionment. The method was tested on chemical composition databases obtained from samples collected at different environments in Europe, hence exploring the impact of a great diversity of natural and anthropogenic sources. We focused on sources of water-soluble OA (WSOA), for which NMR analysis provides substantial advantages compared to alternative methods. Different factor analysis techniques are applied independently to NMR datasets from nine field campaigns of the project EUCAARI and allowed the identification of recurrent source contributions to WSOA in European background troposphere: 1) Marine SOA; 2) Aliphatic amines from ground sources (agricultural activities, etc.); 3) Biomass burning POA; 4) Biogenic SOA from terpene oxidation; 5) “Aged” SOAs, including humic-like substances (HULIS); 6) Other factors possibly including contributions from Primary Biological Aerosol Particles, and products of cooking activities. Biomass burning POA accounted for more than 50% of WSOC in winter months. Aged SOA associated with HULIS was predominant (> 75%) during the spring-summer, suggesting that secondary sources and transboundary transport become more important in spring and summer. Complex aerosol measurements carried out, involving several foreign research groups, provided the opportunity to compare source apportionment results obtained by NMR analysis with those provided by more widespread Aerodyne aerosol mass spectrometers (AMS) techniques that now provided categorization schemes of OA which are becoming a standard for atmospheric chemists. Results emerging from this thesis partly confirm AMS classification and partly challenge it.

Der Austausch von Stickstoffmonoxid zwischen Boden und Atmosphäre unter besonderer Berücksichtigung des Bodenwassergehaltes

Stickstoffmonoxid (NO) ist als reaktives Spurengas eine wichtige Komponente atmosphärenchemischer Prozesse und hat somit einen bedeutenden Einfluss auf die Zusammensetzung der Atmosphäre. Eine Hauptquelle des Spurengases stellen bodenmikrobiologische Prozesse dar, deren regionaler und globaler Anteil weiterhin mit größeren Unsicherheiten geschätzt wird. Ursache für die schwere Abschätzbarkeit der NO-Freisetzung aus Böden ist die hohe räumliche Variabilität der steuernden Faktoren. Als einer der wichtigsten Faktoren, die die Freisetzung von NO aus Böden regeln, gilt der Bodenwassergehalt. Ziel der vorliegenden Arbeit ist es, den Zusammenhang zwischen NO-Freisetzung, Bodenwassergehalt, den Bodeneigenschaften und den Standortbedingungen zu untersuchen und diesen möglichst zu quantifizieren. Dazu sind Bodenproben unterschiedlicher Landnutzungen in einem kleineren Wassereinzugsgebiet im Rheingau im Labor, unter kontrollierten Bedingungen, untersucht. Der charakteristische Zusammenhang zwischen Bodenfeuchte und NO-Freisetzung, die sogenannte Bodenfeuchtekurve, kann demnach weitestgehend auf die gemessenen Bodenmerkmale der untersuchten Proben zurückgeführt werden. Anhand der Bodenmerkmale kann die Bodenfeuchtekurve zufriedenstellend vorhergesagt werden. Dabei zeigt vor allem der Humusgehalt der Böden einen dominierenden Einfluss. Er ist die Variable, die die Unterschiede der Böden beim Zusammenhang zwischen Bodenfeuchte und NO-Freisetzung am besten und hinreichend erklären kann. Zur Konstruktion der Bodenfeuchtekurve müssen die optimale Bodenfeuchte und die dabei herrschende Freisetzung, sowie die obere Bodenfeuchte, bei der keine NO-Freisetzung mehr stattfindet, bekannt sein. Diese charakteristischen Punkte lassen sich durch lineare Regressionsmodelle gut aus den Bodeneigenschaften ableiten. Auf räumlicher Ebene werden die Bodeneigenschaften durch die standörtlichen Bedingungen geprägt, die wiederum Ausdruck der landschaftlichen Ausstattung sind. In der Kulturlandschaft kann der Mensch aufgrund seiner Landnutzungsansprüche als der dominierende Faktor angesehen werden. Die Landnutzung orientiert sich an den landschaftlichen Bedingungen und bestimmt in hohem Maße wichtige Bodeneigenschaften, die zu den erklärenden Merkmalen bei der Beziehung zwischen Bodenwassergehalt und NO-Freisetzung gehören. Die in erster Linie wirtschaftlich orientierten Kartenwerke Bodenschätzung, Weinbergsbodenkartierung und forstliche Standortkartierung sind dementsprechend geeignete Grundlagen, um eine Regionalisierung der Landschaft in - bezüglich der NO-Freisetzung - weitgehend homogene Flächen durchführen zu können. Eine hierauf beruhende Regionalisierung ist dazu geeignet, die räumliche Variabilität der NO-Freisetzung in räumlich sinnvoller Auflösung besser abschätzen zu können.

Urban water demand model: the case study of Emilia Romagna (Italy)

Water is the driving force in nature. We use water for washing cars, doing laundry, cooking, taking a shower, but also to generate energy and electricity. Therefore water is a necessary product in our daily lives (USGS. Howard Perlman, 2013). The model that we created is based on the urban water demand computer model from the Pacific Institute (California). With this model we will forecast the future urban water use of Emilia Romagna up to the year of 2030. We will analyze the urban water demand in Emilia Romagna that includes the 9 provinces: Bologna, Ferrara, Forli-Cesena, Modena, Parma, Piacenza, Ravenna, Reggio Emilia and Rimini. The term urban water refers to the water used in cities and suburbs and in homes in the rural areas. This will include the residential, commercial, institutional and the industrial use. In this research, we will cover the water saving technologies that can help to save water for daily use. We will project what influence these technologies have to the urban water demand, and what it can mean for future urban water demands. The ongoing climate change can reduce the snowpack, and extreme floods or droughts in Italy. The changing climate and development patterns are expected to have a significant impact on water demand in the future. We will do this by conducting different scenario analyses, by combining different population projections, climate influence and water saving technologies. In addition, we will also conduct a sensitivity analyses. The several analyses will show us how future urban water demand is likely respond to changes in water conservation technologies, population, climate, water price and consumption. I hope the research can contribute to the insight of the reader’s thoughts and opinion.

Exploring physical processes related to past climate proxies: lake sediments and stable water isotopes

Proxy data are essential for the investigation of climate variability on time scales larger than the historical meteorological observation period. The potential value of a proxy depends on our ability to understand and quantify the physical processes that relate the corresponding climate parameter and the signal in the proxy archive. These processes can be explored under present-day conditions. In this thesis, both statistical and physical models are applied for their analysis, focusing on two specific types of proxies, lake sediment data and stable water isotopes.rnIn the first part of this work, the basis is established for statistically calibrating new proxies from lake sediments in western Germany. A comprehensive meteorological and hydrological data set is compiled and statistically analyzed. In this way, meteorological times series are identified that can be applied for the calibration of various climate proxies. A particular focus is laid on the investigation of extreme weather events, which have rarely been the objective of paleoclimate reconstructions so far. Subsequently, a concrete example of a proxy calibration is presented. Maxima in the quartz grain concentration from a lake sediment core are compared to recent windstorms. The latter are identified from the meteorological data with the help of a newly developed windstorm index, combining local measurements and reanalysis data. The statistical significance of the correlation between extreme windstorms and signals in the sediment is verified with the help of a Monte Carlo method. This correlation is fundamental for employing lake sediment data as a new proxy to reconstruct windstorm records of the geological past.rnThe second part of this thesis deals with the analysis and simulation of stable water isotopes in atmospheric vapor on daily time scales. In this way, a better understanding of the physical processes determining these isotope ratios can be obtained, which is an important prerequisite for the interpretation of isotope data from ice cores and the reconstruction of past temperature. In particular, the focus here is on the deuterium excess and its relation to the environmental conditions during evaporation of water from the ocean. As a basis for the diagnostic analysis and for evaluating the simulations, isotope measurements from Rehovot (Israel) are used, provided by the Weizmann Institute of Science. First, a Lagrangian moisture source diagnostic is employed in order to establish quantitative linkages between the measurements and the evaporation conditions of the vapor (and thus to calibrate the isotope signal). A strong negative correlation between relative humidity in the source regions and measured deuterium excess is found. On the contrary, sea surface temperature in the evaporation regions does not correlate well with deuterium excess. Although requiring confirmation by isotope data from different regions and longer time scales, this weak correlation might be of major importance for the reconstruction of moisture source temperatures from ice core data. Second, the Lagrangian source diagnostic is combined with a Craig-Gordon fractionation parameterization for the identified evaporation events in order to simulate the isotope ratios at Rehovot. In this way, the Craig-Gordon model can be directly evaluated with atmospheric isotope data, and better constraints for uncertain model parameters can be obtained. A comparison of the simulated deuterium excess with the measurements reveals that a much better agreement can be achieved using a wind speed independent formulation of the non-equilibrium fractionation factor instead of the classical parameterization introduced by Merlivat and Jouzel, which is widely applied in isotope GCMs. Finally, the first steps of the implementation of water isotope physics in the limited-area COSMO model are described, and an approach is outlined that allows to compare simulated isotope ratios to measurements in an event-based manner by using a water tagging technique. The good agreement between model results from several case studies and measurements at Rehovot demonstrates the applicability of the approach. Because the model can be run with high, potentially cloud-resolving spatial resolution, and because it contains sophisticated parameterizations of many atmospheric processes, a complete implementation of isotope physics will allow detailed, process-oriented studies of the complex variability of stable isotopes in atmospheric waters in future research.rn

Chemical interaction between ocean and atmosphere

The exchange of chemical constituents between ocean and atmosphere provides potentially important feedback mechanisms in the climate system. The aim of this study is to develop and evaluate a chemically coupled global atmosphere-ocean model. For this, an atmosphere-ocean general circulation model with atmospheric chemistry has been expanded to include oceanic biogeochemistry and the process of air-sea gas exchange. The calculation of seawater concentrations in the oceanic biogeochemistry submodel has been expanded from DMS, CO₂

How different is water crystallization from polymer crystallization under confinement?

Ziel der vorliegenden Dissertation war es, Einblicke in das Kristallisationsverhalten weicher Materie („soft matter“), wie verschiedener Polymere oder Wasser, unter räumlicher Einschränkung („confinement“) zu erlangen. Dabei sollte untersucht werden, wie, weshalb und wann die Kristallisation in nanoporösen Strukturen eintritt. Desweiteren ist Kristallisation weicher Materie in nanoporösen Strukturen nicht nur aus Aspekten der Grundlagenforschung von großem Interesse, sondern es ergeben sich zahlreiche praktische Anwendungen. Durch die gezielte Steuerung der Kristallinität von Polymeren könnten somit Materialien mit verschiendenen mechanischen und optischen Eigenschaften erhalten werden. Desweiteren wurde auch räumlich eingeschränktes Wasser untersucht. Dieses spielt eine wichtige Rolle in der Molekularbiologie, z.B. für das globuläre Protein, und als Wolkenkondensationskeime in der Atmosphärenchemie und Physik. Auch im interstellaren Raum ist eingeschränktes Wasser in Form von Eispartikeln anzutreffen. Die Kristallisation von eingeschränktem Wasser zu verstehen und zu beeinflussen ist letztlich auch für die Haltbarkeit von Baumaterialien wie etwa Zement von großem Interesse.rnUm dies zu untersuchen wird Wasser in der Regel stark abgekühlt und das Kristallisationsverhalten in Abhängigkeit des Volumens untersucht. Dabei wurde beobachtet, dass Mikro- bzw. Nanometer große Volumina erst ab -38 °C bzw. -70 °C kristallisieren. Wasser unterliegt dabei in der Regel dem Prozess der homogenen Nukleation. In der Regel gefriert Wasser aber bei höheren Temperaturen, da durch Verunreinigungen eine vorzeitige, heterogene Nukleation eintritt.rnDie vorliegende Arbeit untersucht die sachdienlichen Phasendiagramme von kristallisierbaren Polymeren und Wasser unter räumlich eingeschränkten Bedingungen. Selbst ausgerichtetes Aluminiumoxid (AAO) mit Porengrößen im Bereich von 25 bis 400 nm wurden als räumliche Einschränkung sowohl für Polymere als auch für Wasser gewählt. Die AAO Nanoporen sind zylindrisch und parallel ausgerichtet. Außerdem besitzen sie eine gleichmäßige Porenlänge und einen gleichmäßigen Durchmesser. Daher eignen sie sich als Modelsystem um Kristallisationsprozesse unter wohldefinierter räumlicher Einschränkung zu untersuchen.rnEs wurden verschiedene halbkristalline Polymere verwendet, darunter Poly(ethylenoxid), Poly(ɛ-Caprolacton) und Diblockcopolymere aus PEO-b-PCL. Der Einfluss der Porengröße auf die Nukleation wurde aus verschiedenen Gesichtspunkten untersucht: (i) Einfluss auf den Nukleationmechanismus (heterogene gegenüber homogener Nukleation), (ii) Kristallorientierung und Kristallinitätsgrad und (iii) Zusammenhang zwischen Kristallisationstemperatur bei homogener Kristallisation und Glasübergangstemperatur.rnEs konnte gezeigt werden, dass die Kristallisation von Polymeren in Bulk durch heterogene Nukleation induziert wird und das die Kristallisation in kleinen Poren hauptsächlich über homogene Nukleation mit reduzierter und einstellbarer Kristallinität verläuft und eine hohe Kristallorientierung aufweist. Durch die AAOs konnte außerdem die kritische Keimgröße für die Kristallisation der Polymere abgeschätzt werden. Schließlich wurde der Einfluss der Polydispersität, von Oligomeren und anderen Zusatzstoffen auf den Nukleationsmechanismus untersucht.rn4rnDie Nukleation von Eis wurde in den selben AAOs untersucht und ein direkter Zusammenhang zwischen dem Nukleationstyp (heterogen bzw. homogen) und der gebildeten Eisphase konnte beobachtet werden. In größeren Poren verlief die Nukleation heterogen, wohingegen sie in kleineren Poren homogen verlief. Außerdem wurde eine Phasenumwandlung des Eises beobachtet. In den größeren Poren wurde hexagonales Eis nachgewiesen und unter einer Porengröße von 35 nm trat hauptsächlich kubisches Eis auf. Nennenswerter Weise handelte es sich bei dem kubischem Eis nicht um eine metastabile sondern eine stabile Phase. Abschließend wird ein Phasendiagramm für räumlich eingeschränktes Wasser vorgeschlagen. Dieses Phasendiagramm kann für technische Anwendungen von Bedeutung sein, so z.B. für Baumaterial wie Zement. Als weiteres Beispiel könnten AAOs, die die heterogene Nukleation unterdrücken (Porendurchmesser ≤ 35 nm) als Filter für Reinstwasser zum Einsatz kommen.rnNun zur Anfangs gestellten Frage: Wie unterschiedlich sind Wasser und Polymerkristallisation voneinander unter räumlicher Einschränkung? Durch Vergleich der beiden Phasendiagramme kommen wir zu dem Schluss, dass beide nicht fundamental verschieden sind. Dies ist zunächst verwunderlich, da Wasser ein kleines Molekül ist und wesentlich kleiner als die kleinste Porengröße ist. Wasser verfügt allerdings über starke Wasserstoffbrückenbindungen und verhält sich daher wie ein Polymer. Daher auch der Name „Polywasser“.

A study of air-sea interaction processes on water mass formation and upwelling in the Mediterranean sea

Air-sea interactions are a key process in the forcing of the ocean circulation and the climate. Water Mass Formation is a phenomenon related to extreme air-sea exchanges and heavy heat losses by the water column, being capable to transfer water properties from the surface to great depth and constituting a fundamental component of the thermohaline circulation of the ocean. Wind-driven Coastal Upwelling, on the other hand, is capable to induce intense heat gain in the water column, making this phenomenon important for climate change; further, it can have a noticeable influence on many biological pelagic ecosystems mechanisms. To study some of the fundamental characteristics of Water Mass Formation and Coastal Upwelling phenomena in the Mediterranean Sea, physical reanalysis obtained from the Mediterranean Forecating System model have been used for the period ranging from 1987 to 2012. The first chapter of this dissertation gives the basic description of the Mediterranean Sea circulation, the MFS model implementation, and the air-sea interaction physics. In the second chapter, the problem of Water Mass Formation in the Mediterranean Sea is approached, also performing ad-hoc numerical simulations to study heat balance components. The third chapter considers the study of Mediterranean Coastal Upwelling in some particular areas (Sicily, Gulf of Lion, Aegean Sea) of the Mediterranean Basin, together with the introduction of a new Upwelling Index to characterize and predict upwelling features using only surface estimates of air-sea fluxes. Our conclusions are that latent heat flux is the driving air-sea heat balance component in the Water Mass Formation phenomenon, while sensible heat exchanges are fundamental in Coastal Upwelling process. It is shown that our upwelling index is capable to reproduce the vertical velocity patterns in Coastal Upwelling areas. Nondimensional Marshall numbers evaluations for the open-ocean convection process in the Gulf of Lion show that it is a fully turbulent, three-dimensional phenomenon.

Processes influencing the nitrate concentration in an aquifer for drinking water production in Bremen-Nord - Northern Germany

Groundwater represents the most important raw material. Germany struggles to maintain the best water quality possible by providing advanced monitoring systems and legal measures to prevent further pollution. In areas involved in the intensive growing of plantations, one of the major contamination factors derives from nitrate. The aim of this master thesis is the characterisation of the Water Protection Area of Bremen (Germany). Denitrification is a natural process, representing the best means of natural reduction of the hazardous nitrate ion, which is dangerous both for human health and for the development of eutrophication. The study has been possible thanks to the collaboration with the University of Bremen, the Geological Service of Bremen (GDfB) and Peter Spiedt (Water Supply Company of Bremen). It will be defined whether nitrate amounts in the groundwater still overcome the threshold legally imposed, and state if the denitrification process takes place, thanks to new samples collected in 2015 and their integration with historical data. Gas samples have been gathered to test them with the “N2/Ar method”, which is able to estimate the denitrification rate quantitatively. Analyses stated the effective occurrence of the reaction, nevertheless showing that it only affects the chemical of the deep aquifers and not shallow ones. Temporal trends concentrations of nitrate have shown that no real improvement took place in the past years. It will be commented that despite the denitrification being responsible for an efficacious lowering in the nitrate ion, it needs reactive materials to take place. Since the latter are finite elements, it is not an endless process. It is thus believed that is clearly necessary to adopt a better attitude in order to maintain the best chemical qualities possible in such an important area, providing drinking water.

Habitat-specific demography and source-sink dynamics in a population of Siberian jays

P>1. There are a number of models describing population structure, many of which have the capacity to incorporate spatial habitat effects. One such model is the source-sink model, that describes a system where some habitats have a natality that is higher than mortality (source) and others have a mortality that exceeds natality (sink). A source can be maintained in the absence of migration, whereas a sink will go extinct. 2. However, the interaction between population dynamics and habitat quality is complex, and concerns have been raised about the validity of published empirical studies addressing source-sink dynamics. In particular, some of these studies fail to provide data on survival, a significant component in disentangling a sink from a low quality source. Moreover, failing to account for a density-dependent increase in mortality, or decrease in fecundity, can result in a territory being falsely assigned as a sink, when in fact, this density-dependent suppression only decreases the population size to a lower level, hence indicating a 'pseudo-sink'. 3. In this study, we investigate a long-term data set for key components of territory-specific demography (mortality and reproduction) and their relationship to habitat characteristics in the territorial, group-living Siberian jay (Perisoreus infaustus). We also assess territory-specific population growth rates (r), to test whether spatial population dynamics are consistent with the ideas of source-sink dynamics. 4. Although average mortality did not differ between sexes, habitat-specific mortality did. Female mortality was higher in older forests, a pattern not observed in males. Male mortality only increased with an increasing amount of open areas. Moreover, reproductive success was higher further away from human settlement, indicating a strong effect of human-associated nest predators. 5. Averaged over all years, 76% of the territories were sources. These territories generally consisted of less open areas, and were located further away from human settlement. 6. The source-sink model provides a tool for modelling demography in distinct habitat patches of different quality, which can aid in identifying key habitats within the landscape, and thus, reduce the risk of implementing unsound management decisions.

Applying erosion damage mapping to asses and quantify off-site effects of soil erosion in Switzerland

In order to fill existing knowledge gaps in the temporal and spatial distribution of soil erosion, its sources and causes, as well as in relation to its off-site impacts, erosion damage mapping of all visible erosion features was carried out at three study sites in Switzerland. The data illustrate that about one-quarter of the cultivated land was affected by water erosion. Observed mean annual soil loss rates are considered rather low (0.7–2.3 t/ha/y) compared to other European countries. However, substantial losses of >70 t/ha were recorded on individual plots. This paper focuses on the spatial aspects of soil erosion, by observing and comparing the study areas in a 1-year period from October 2005 to October 2006. The analyses illustrate that the sites differ considerably in average soil loss rates, but show similar patterns of off-site effects. In about one-third of the damaged plots an external source of surface runoff upslope contributed to the damage (run-on). Similarly, more than 50 per cent of the soil eroded on arable land deposited downslope on adjacent plots, roads, public/private infrastructure, etc., and 20 per cent of it reached open water bodies. Large amounts of eroded soil which deposit off-site, often related to slope depressions, are considered muddy floods and were frequently observed in Switzerland. Mapping, in conclusion, helps to sheds light on some of the important challenges of today, in particular: to comprehensively assess socioeconomic and ecological off-site effects of soil erosion, to attribute off-site impacts to on-site causes, and to raise awareness of all stakeholders involved, in order to improve ongoing discussions on policy formulation and implementation at the national and international levels.