TY - THES A1 - Steeples, Elliot T1 - Amino acid-derived imidazolium salts: platform molecules for N-Heterocyclic carbene metal complexes and organosilica materials T1 - Imidazolium-Salze aus Aminosäure: Bausteine für N-Heterozyklische-Carben Metallkomplexe und Organosilicamaterialien N2 - In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes. The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer. The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts. N2 - Um Katalysatoren aus nachhaltigen Chemikalien herzustellen, wurden 1,3-Dicarbonsäure-Imidazolium-Salze, welche aus Aminosäuren synthetisiert wurden als N-heterozyklische-Carben-Liganden (NHC) in Metallkomplexen modifiziert. Liganden aus Glycin, Alanin, β-Alanin und Phenylalanin wurden wiederum genutzt, um Metallkomplexe aus Silber(I), Palladium(II) und Iridium(I) darzustellen. Alle Komplexverbindungen wurden mit Röntgenkristallographie charakterisiert. Die Palladiumkomplexe wurden als Katalysatoren in der Suzuki-Miyaura Reaktion eingesetzt. Durch zusätzliche Hydrolyse der Ester-Gruppen konnte eine gute Wasserlöslichkeit erreicht werden. Die hohe Aktivität der Mono-NHC–Palladium-Komplexe konnte bei der Kupplung von Arylbromiden mit Phenylboronsäuren aufgezeigt werden. Die aktive Spezies wurde hauptsächlich Pd(0) Nanopartikeln zugeschrieben. Nach erfolgreichem Recycling konnte der Katalysator noch einmal wiederverwendet werden. Die Imidazolium-Salze wurden ebenfalls herangezogen, um Organosilicamaterialien zu synthetisieren. Die Herstellung wurde durch zwei Methoden erreicht. Zum einen durch nachträgliches Aufbringen auf kommerzielle Siliziummaterialien, sowie durch Co-Kondensation auf das entsprechende Organosilan. Diese Co-Kondensation birgt Potential zur Herstellung von festen Trägerkatalysatoren. KW - synthesis KW - Synthese KW - sustainable chemistry KW - nachhaltige Chemie KW - organometallics KW - Metallorganischen KW - water KW - Wasser Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-101861 ER - TY - GEN A1 - Steeples, Elliot A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Esposito, Davide T1 - Amino acid-derived N-heterocyclic carbene palladium complexes for aqueous phase Suzuki–Miyaura couplings N2 - In this work, three ligands produced from amino acids were synthesized and used to produce five bis- and PEPPSI-type palladium–NHC complexes using a novel synthesis route from sustainable starting materials. Three of these complexes were used as precatalysts in the aqueous-phase Suzuki–Miyaura coupling of various substrates displaying high activity. TEM and mercury poisoning experiments provide evidence for Pd-nanoparticle formation stabilized in water. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 319 KW - transition-metal-complexes KW - imidazolium salts KW - green chemistry KW - water KW - catalysts KW - nhc KW - hydrogenation KW - isomerization KW - nanoparticles KW - precatalysts Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-394488 SP - 4922 EP - 4930 ER - TY - GEN A1 - Block, Inga A1 - Günter, Christina A1 - Rodrigues, Alysson Duarte A1 - Paasch, Silvia A1 - Hesemann, Peter A1 - Taubert, Andreas T1 - Carbon Adsorbents from Spent Coffee for Removal of Methylene Blue and Methyl Orange from Water T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1155 KW - water KW - spent coffee KW - dye adsorption KW - methylene blue KW - methyl orange KW - calcium carbonate KW - activated carbon KW - water treatment KW - dye removal Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-521653 SN - 1866-8372 IS - 14 ER - TY - JOUR A1 - Block, Inga A1 - Günter, Christina A1 - Rodrigues, Alysson Duarte A1 - Paasch, Silvia A1 - Hesemann, Peter A1 - Taubert, Andreas T1 - Carbon Adsorbents from Spent Coffee for Removal of Methylene Blue and Methyl Orange from Water JF - Materials N2 - Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed. KW - water KW - spent coffee KW - dye adsorption KW - methylene blue KW - methyl orange KW - calcium carbonate KW - activated carbon KW - water treatment KW - dye removal Y1 - 2021 U6 - https://doi.org/10.3390/ma14143996 SN - 1996-1944 VL - 14 IS - 14 PB - MDPI CY - Basel ER - TY - JOUR A1 - Pietzsch, Annette A1 - Niskanen, Johannes A1 - Vaz da Cruz, Vinicius A1 - Büchner, Robby A1 - Eckert, Sebastian A1 - Fondell, Mattis A1 - Jay, Raphael Martin A1 - Lu, Xingye A1 - McNally, Daniel A1 - Schmitt, Thorsten A1 - Föhlisch, Alexander T1 - Cuts through the manifold of molecular H2O potential energy surfaces in liquid water at ambient conditions JF - Proceedings of the National Academy of Sciences of the United States of America N2 - The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H2O molecular moieties. This is mirrored in a manifold of the H2O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H2O symmetric normal mode and the local asymmetric O-H bond coordinate up to 1 and 1.5 angstrom, respectively. The comparison of the single H2O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H2O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O-H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen ls to 4a(1) resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2b(2) resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H2O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O-H, H-H, and O-O correlation lengths from neutron scattering. KW - water KW - potential ene rgy surface KW - RIXS Y1 - 2022 U6 - https://doi.org/10.1073/pnas.2118101119 SN - 1091-6490 VL - 119 IS - 28 PB - National Acad. of Sciences CY - Washington, DC ER - TY - BOOK A1 - Bahouth, Chadi T1 - Der Konflikt um Wasser in Israel und Palästina BT - Konfliktstoff trotz Friedensquells – die vergebene Chance einer nachhaltigen und gerechten Lösung N2 - Wasser ist rar im Nahen Osten. Die knappe Ressource wird immer häufiger zum Gegenstand politischer Konflikte in der ohnehin instabilen Region. Der Konflikt zwischen Israel und Palästina gilt als eines der gravierendsten Beispiele für diese Entwicklung: Wasser als umkämpftes Menschenrecht, Wasser als strategisches Mittel der Besetzungspolitik und Wasser als Gegenstand langwieriger Verhandlungen. Der Wasserkonflikt ist so alt wie der Nahostkonflikt selbst. Sogar mit Beginn des Oslo-Prozesses 1993 hat es weder einen grundlegenden Wandel im Wasserkonflikt, noch in der Aussicht auf Veränderung der Wasserknappheit gegeben. Immerhin können die Palästinenser in der momentanen Situation ihre eigene Wasserversorgung dort selbst verwalten, wo es ihnen laut der Übereinkünfte erlaubt ist. Jedoch ist diese Freiheit eine sehr begrenzte und eine endgültige Klärung dieses Streitpunktes wurde, zusammen mit Jerusalem, den Flüchtlingen, den Siedlungen und der Staatsbildung auf die Endstatusverhandlungen verschoben. Chadi Bahouth, Absolvent des Otto-Suhr-Instituts der Freien Universität Berlin, untersucht in seiner Doktorarbeit die Gründe für die ungelöste Wasserfrage. Er analysiert die historische und rechtliche Chronologie des Konfliktes, bietet Lösungsvorschläge für die Wasserkrise an und erklärt, warum die Region dennoch für Generationen nicht zur Ruhe kommen wird. N2 - Water is rare at the Middle East and becomes more and more a matter of political conflicts in the already instable region. The conflict between Israel and Palestine is a serious noticeable example of this development: water as a hard-fought human right, water as a strategic mean of the politics of occupation and water as a matter of protracted negotiations. The battles for water are as old as the Middle East conflict itself. Even with the beginning of the Oslo-Process in 1993 there has not been a fundamental change containing the water conflict. After all, the Palestinians in the actual situation can administrate their own water supply, where they are allowed to concern the accords. But this freedom is strictly confined and a clarification of the controversial subject, together with Jerusalem, the refugees, the settlements and the building of the state were adjusted to the negotiations of the permanent status. Chadi Bahouth, alumnus of the Otto-Suhr-Institute (Free University Berlin), inspects in his doctoral thesis the reasons for the unsolved water politics. He analyses the historical and judicial chronology of the conflict, offers proposals for solution and explains, why the region will not be steadied for generations, nevertheless. T3 - Horizonte 21 : Umwelt · Energie · Sicherheit - 2 KW - Nahostkonflikt KW - Israel KW - Palästina KW - Wasser KW - Friedensprozess KW - Middle-East Conflict KW - Israel KW - Palestine KW - water KW - peace process Y1 - 2010 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-40747 SN - 978-3-86956-035-9 PB - Universitätsverlag Potsdam CY - Potsdam ER - TY - JOUR A1 - Lehr, Christian A1 - Lischeid, Gunnar T1 - Efficient screening of groundwater head monitoring data for anthropogenic effects and measurement errors JF - Hydrology and Earth System Sciences N2 - Groundwater levels are monitored by environmental agencies to support the sustainable use of groundwater resources. For this purpose continuous and spatially comprehensive monitoring in high spatial and temporal resolution is desired. This leads to large datasets that have to be checked for quality and analysed to distinguish local anthropogenic influences from natural variability of the groundwater level dynamics at each well. Both technical problems with the measurements as well as local anthropogenic influences can lead to local anomalies in the hydrographs. We suggest a fast and efficient screening method for the identification of well-specific peculiarities in hydrographs of groundwater head monitoring networks. The only information required is a set of time series of groundwater heads all measured at the same instants of time. For each well of the monitoring network a reference hydrograph is calculated, describing expected "normal" behaviour at the respective well as is typical for the monitored region. The reference hydrograph is calculated by multiple linear regression of the observed hydrograph with the "stable" principal components (PCs) of a principal component analysis of all groundwater head series of the network as predictor variables. The stable PCs are those PCs which were found in a random subsampling procedure to be rather insensitive to the specific selection of the analysed observation wells, i.e. complete series, and to the specific selection of measurement dates. Hence they can be considered to be representative for the monitored region in the respective period. The residuals of the reference hydrograph describe local deviations from the normal behaviour. Peculiarities in the residuals allow the data to be checked for measurement errors and the wells with a possible anthropogenic influence to be identified. The approach was tested with 141 groundwater head time series from the state authority groundwater monitoring network in northeastern Germany covering the period from 1993 to 2013 at an approximately weekly frequency of measurement. KW - streamflow variability KW - principal components KW - united states KW - time-seriesa KW - water KW - network KW - nonstationarity KW - fluctuations KW - rotation Y1 - 2020 U6 - https://doi.org/10.5194/hess-24-501-2020 SN - 1027-5606 SN - 1607-7938 VL - 24 IS - 2 SP - 501 EP - 513 PB - Copernicus CY - Göttingen ER - TY - GEN A1 - Lehr, Christian A1 - Lischeid, Gunnar T1 - Efficient screening of groundwater head monitoring data for anthropogenic effects and measurement errors T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Groundwater levels are monitored by environmental agencies to support the sustainable use of groundwater resources. For this purpose continuous and spatially comprehensive monitoring in high spatial and temporal resolution is desired. This leads to large datasets that have to be checked for quality and analysed to distinguish local anthropogenic influences from natural variability of the groundwater level dynamics at each well. Both technical problems with the measurements as well as local anthropogenic influences can lead to local anomalies in the hydrographs. We suggest a fast and efficient screening method for the identification of well-specific peculiarities in hydrographs of groundwater head monitoring networks. The only information required is a set of time series of groundwater heads all measured at the same instants of time. For each well of the monitoring network a reference hydrograph is calculated, describing expected “normal” behaviour at the respective well as is typical for the monitored region. The reference hydrograph is calculated by multiple linear regression of the observed hydrograph with the “stable” principal components (PCs) of a principal component analysis of all groundwater head series of the network as predictor variables. The stable PCs are those PCs which were found in a random subsampling procedure to be rather insensitive to the specific selection of the analysed observation wells, i.e. complete series, and to the specific selection of measurement dates. Hence they can be considered to be representative for the monitored region in the respective period. The residuals of the reference hydrograph describe local deviations from the normal behaviour. Peculiarities in the residuals allow the data to be checked for measurement errors and the wells with a possible anthropogenic influence to be identified. The approach was tested with 141 groundwater head time series from the state authority groundwater monitoring network in northeastern Germany covering the period from 1993 to 2013 at an approximately weekly frequency of measurement. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1424 KW - streamflow variability KW - principal components KW - united states KW - time-series KW - water KW - network KW - nonstationarity KW - fluctuations KW - rotation Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-511992 SN - 1866-8372 IS - 2 ER - TY - THES A1 - Sinn, Cornelia G. T1 - Ion binding to polymers and lipid membranes in aqueous solutions : Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen N2 - Ziel dieser Arbeit ist die Untersuchung der Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen. Im ersten Teil dieser Arbeit wurde der Einfluss verschiedener anorganischer Salze und Polyelektrolyte auf die Struktur des Wassers mit Hilfe Isothermer Mikrotitrationskalorimetrie (ITC) erforscht. Die Verdünnungswärme der Salze wurde als Maß für die Fähigkeit der Ionen, die geordnete Struktur des Wassers zu stabilisieren oder zu zerstören, verwendet. Die Verdünnungswärmen konnten auf Hofmeister Effekte zurückgeführt werden. Im Anschluss daran wurde die Bindung von Ca2+ an Natrium- Poly(acrylsäure) (NaPAA) untersucht. Mit Hilfe von ITC und einer Ca2+- selektiven Elektrode wurde die Reaktionsenthalpie und Bindungsisotherme gemessen. Es wurde gezeigt, dass die Binding von Ca2+ - Ionen an NaPAA stark endotherm und daher entropiegetrieben ist. Anschließend wurde die Bindung von Ca2+ an die eindimensionale Polymerkette mit der an ein Lipidvesikel mit denselben funktioniellen Gruppen verglichen. Es wurde beobachtet, dass die Ionenbindung –wie auch im Fall des Polymers- endotherm ist. Ein Vergleich der Ca2+- Bindung an die Lipidmembran mit der an das Polymer konnte zeigen, dass das Ion schwächer an die Membran bindet. Im Zusammenhang mit diesen Experimenten wurde auch beobachtet, dass Ca2+ nicht nur an geladene, sondern auch an zwitterionische Lipidvesikel bindet. Schließlich wurde die Wechselwirkung zweier Salze, KCl and NaCl, mit einem neutralen Polymergel, PNIPAAM, und dem geladenen Polymer PAA untersucht. Mit Hilfe von Kalorimetrie und einer kaliumselektiven Elektrode wurde beobachtet, dass die Ionen mit beiden Polymeren wechselwirken, unabhängig davon, ob diese Ladungen tragen, oder nicht. N2 - The goal of this work was to study the binding of ions to polymers and lipid bilayer membranes in aqueous solutions. In the first part of this work, the influence of various inorganic salts and polyelectrolytes on the structure of water was studied using Isothermal Titration Calorimetry (ITC). The heat of dilution of the salts was used as a scale of water structure making and breaking of the ions. The heats of dilution could be attributed to the Hofmeister Series. Following this, the binding of Ca2+ to poly(sodium acrylate) (NaPAA) was studied. ITC and a Ca2+ Ion Selective Electrode were used to measure the reaction enthalpy and binding isotherm. Binding of Ca2+ ions to PAA, was found to be highly endothermic and therefore solely driven by entropy. We then compared the binding of ions to the one-dimensional PAA polymer chain to the binding to lipid vesicles with the same functional groups. As for the polymer, Ca2+ binding was found to be endothermic. Binding of calcium to the lipid bilayer was found to be weaker than to the polymer. In the context of these experiments, it was shown that Ca2+ not only binds to charged but also to zwitterionic lipid vesicles. Finally, we studied the interaction of two salts, KCl and NaCl, to a neutral polymer gel, PNIPAAM, and to the ionic polymer PAA. Combining calorimetry and a potassium selective electrode we observed that the ions interact with both polymers, whether containing charges or not. T2 - Ion binding to polymers and lipid membranes in aqueous solutions : Ionenbindung an Polymeren und Lipidmembranen in wässrigen Lösungen KW - Ionen KW - Bindung KW - Salz KW - Wasser KW - Struktur KW - Hofmeister KW - Polyelektrolyt KW - Isotherme Titrationskalorimetrie KW - ionenselektive Elektrode KW - Vesikel KW - Calcium KW - Micr KW - ions KW - binding KW - salt KW - water KW - structure KW - Hofmeister KW - polyelectrolyte KW - Isothermal Titration Calorimetry KW - ion selective electrode KW - vesicle KW - calcium KW - micro Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001778 ER - TY - JOUR A1 - Guzman, Diego A. A1 - Samprogna Mohor, Guilherme A1 - Mendiondo, Eduardo Mario T1 - Multi-year index-based insurance for adapting Water Utility Companies to hydrological drought BT - case study of a water supply system of the Sao Paulo metropolitan region, Brazil JF - Water N2 - The sustainability of water utility companies is threatened by non-stationary drivers, such as climate and anthropogenic changes. To cope with potential economic losses, instruments such as insurance are useful for planning scenarios and mitigating impacts, but data limitations and risk uncertainties affect premium estimation and, consequently, business sustainability. This research estimated the possible economic impacts of business interruption to the Sao Paulo Water Utility Company derived from hydrological drought and how this could be mitigated with an insurance scheme. Multi-year insurance (MYI) was proposed through a set of "change" drivers: the climate driver, through forcing the water evaluation and planning system (WEAP) hydrological tool; the anthropogenic driver, through water demand projections; and the economic driver, associated with recent water price policies adopted by the utility company during water scarcity periods. In our study case, the evaluated indices showed that MYI contracts that cover only longer droughts, regardless of the magnitude, offer better financial performance than contracts that cover all events (in terms of drought duration). Moreover, through MYI contracts, we demonstrate solvency for the insurance fund in the long term and an annual average actuarially fair premium close to the total expected revenue reduction. KW - multi-year insurance KW - climate change KW - hydrological drought KW - water KW - security and economy Y1 - 2020 U6 - https://doi.org/10.3390/w12112954 SN - 2073-4441 VL - 12 IS - 11 PB - MDPI CY - Basel ER - TY - JOUR A1 - Baritello, Omar A1 - Khajooei, Mina A1 - Engel, Tilman A1 - Kopinski, Stephan A1 - Quarmby, Andrew James A1 - Müller, Steffen A1 - Mayer, Frank T1 - Neuromuscular shoulder activity during exercises with different combinations of stable and unstable weight mass JF - BMC sports science, medicine and rehabilitation N2 - Background Recent shoulder injury prevention programs have utilized resistance exercises combined with different forms of instability, with the goal of eliciting functional adaptations and thereby reducing the risk of injury. However, it is still unknown how an unstable weight mass (UWM) affects the muscular activity of the shoulder stabilizers. Aim of the study was to assess neuromuscular activity of dynamic shoulder stabilizers under four conditions of stable and UWM during three shoulder exercises. It was hypothesized that a combined condition of weight with UWM would elicit greater activation due to the increased stabilization demand. Methods Sixteen participants (7 m/9 f) were included in this cross-sectional study and prepared with an EMG-setup for the: Mm. upper/lower trapezius (U.TA/L.TA), lateral deltoid (DE), latissimus dorsi (LD), serratus anterior (SA) and pectoralis major (PE). A maximal voluntary isometric contraction test (MVIC; 5 s.) was performed on an isokinetic dynamometer. Next, internal/external rotation (In/Ex), abduction/adduction (Ab/Ad) and diagonal flexion/extension (F/E) exercises (5 reps.) were performed with four custom-made-pipes representing different exercise conditions. First, the empty-pipe (P; 0.5 kg) and then, randomly ordered, water-filled-pipe (PW; 1 kg), weight-pipe (PG; 4.5 kg) and weight + water-filled-pipe (PWG; 4.5 kg), while EMG was recorded. Raw root-mean-square values (RMS) were normalized to MVIC (%MVIC). Differences between conditions for RMS%MVIC, scapular stabilizer (SR: U.TA/L.TA; U.TA/SA) and contraction (CR: concentric/eccentric) ratios were analyzed (paired t-test; p <= 0.05; Bonferroni adjusted alpha = 0.008). Results PWG showed significantly greater muscle activity for all exercises and all muscles except for PE compared to P and PW. Condition PG elicited muscular activity comparable to PWG (p > 0.008) with significantly lower activation of L.TA and SA in the In/Ex rotation. The SR ratio was significantly higher in PWG compared to P and PW. No significant differences were found for the CR ratio in all exercises and for all muscles. Conclusion Higher weight generated greater muscle activation whereas an UWM raised the neuromuscular activity, increasing the stabilization demands. Especially in the In/Ex rotation, an UWM increased the RMS%MVIC and SR ratio. This might improve training effects in shoulder prevention and rehabilitation programs. KW - EMG KW - instability KW - overhead athlete KW - unstable resistance training KW - water KW - pipe KW - rotator cuff Y1 - 2020 U6 - https://doi.org/10.1186/s13102-020-00168-x SN - 2052-1847 VL - 12 IS - 1 PB - BioMed Central CY - London ER - TY - JOUR A1 - Zamponi, Flavio A1 - Penfold, Thomas J. A1 - Nachtegaal, Maarten A1 - Lübcke, Andrea A1 - Rittmann, Jochen A1 - Milne, Chris J. A1 - Chergui, Majed A1 - van Bokhoven, Jeroen A. T1 - Probing the dynamics of plasmon-excited hexanethiol-capped gold nanoparticles by picosecond X-ray absorption spectroscopy JF - physical chemistry, chemical physics : PCCP N2 - Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1. KW - TiO2 nanoparticles KW - diimine-complexes KW - electron-transfer KW - supported gold KW - visible-light KW - water KW - surface KW - reactivity KW - nanoclusters KW - excitation Y1 - 2014 U6 - https://doi.org/10.1039/c4cp03301a SN - 1463-9076 SN - 1463-9084 VL - 2014 IS - 16 SP - 23157 EP - 23163 ER - TY - GEN A1 - Zamponi, Flavio A1 - Penfold, Thomas J. A1 - Nachtegaal, Maarten A1 - Lübcke, Andrea A1 - Rittmann, Jochen A1 - Milne, Chris J. A1 - Chergui, Majed A1 - van Bokhoven, Jeroen A. T1 - Probing the dynamics of plasmon-excited hexanethiol-capped gold nanoparticles by picosecond X-ray absorption spectroscopy N2 - Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 176 KW - TiO2 nanoparticles KW - diimine-complexes KW - electron-transfer KW - excitation KW - nanoclusters KW - reactivity KW - supported gold KW - surface KW - visible-light KW - water Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-74492 SP - 23157 EP - 23163 ER - TY - JOUR A1 - Neill, Christopher A1 - Jankowski, KathiJo A1 - Brando, Paulo M. A1 - Coe, Michael T. A1 - Deegan, Linda A. A1 - Macedo, Marcia N. A1 - Riskin, Shelby H. A1 - Porder, Stephen A1 - Elsenbeer, Helmut A1 - Krusche, Alex V. T1 - Surprisingly Modest Water Quality Impacts From Expansion and Intensification of Large-Sscale Commercial Agriculture in the Brazilian Amazon-Cerrado Region JF - Tropical conservation science N2 - Large-scale commercial cropping of soybeans expanded in the tropical Amazon and Cerrado biomes of Brazil after 1990. More recently, cropping intensified from single-cropping of soybeans to double-cropping of soybeans with corn or cotton. Cropland expansion and intensification, and the accompanying use of mineral fertilizers, raise concerns about whether nutrient runoff and impacts to surface waters will be similar to those experienced in commercial cropland regions at temperate latitudes. We quantified water infiltration through soils, water yield, and streamwater chemistry in watersheds draining native tropical forest and single-and double-cropped areas on the level, deep, highly weathered soils where cropland expansion and intensification typically occurs. Although water yield increased four-fold from croplands, streamwater chemistry remained largely unchanged. Soil characteristics exerted important control over the movement of nitrogen (N) and phosphorus (P) into streams. High soil infiltration rates prevented surface erosion and movement of particulate P, while P fixation in surface soils restricted P movement to deeper soil layers. Nitrogen retention in deep soils, likely by anion exchange, also appeared to limit N leaching and export in streamwater from both single-and double-cropped watersheds that received nitrogen fertilizer. These mechanisms led to lower streamwater P and N concentrations and lower watershed N and P export than would be expected, based on studies from temperate croplands with similar cropping and fertilizer application practices. KW - water KW - quality KW - agriculture KW - intensification KW - impact Y1 - 2017 U6 - https://doi.org/10.1177/1940082917720669 SN - 1940-0829 VL - 10 PB - Sage Publ. CY - Thousand Oaks ER - TY - THES A1 - Hunke, Philip Paul T1 - The Brazilian Cerrado: ecohydrological assessment of water and soil degradation in heavily modified meso-scale catchments T1 - Der brasilianische Cerrado: ökohydrologische Analyse von Boden- und Wasserdegradierung in intensiv landwirtschaftlich genutzten mesoskaligen Einzugsgebieten N2 - The Brazilian Cerrado is recognised as one of the most threatened biomes in the world, as the region has experienced a striking change from natural vegetation to intense cash crop production. The impacts of rapid agricultural expansion on soil and water resources are still poorly understood in the region. Therefore, the overall aim of the thesis is to improve our understanding of the ecohydrological processes causing water and soil degradation in the Brazilian Cerrado. I first present a metaanalysis to provide quantitative evidence and identifying the main impacts of soil and water alterations resulting from land use change. Second, field studies were conducted to (i) examine the effects of land use change on soils of natural cerrado transformed to common croplands and pasture and (ii) indicate how agricultural production affects water quality across a meso-scale catchment. Third, the ecohydrological process-based model SWAT was tested with simple scenario analyses to gain insight into the impacts of land use and climate change on the water cycling in the upper São Lourenço catchment which experienced decreasing discharges in the last 40 years. Soil and water quality parameters from different land uses were extracted from 89 soil and 18 water studies in different regions across the Cerrado. Significant effects on pH, bulk density and available P and K for croplands and less-pronounced effects on pastures were evident. Soil total N did not differ between land uses because most of the cropland sites were N-fixing soybean cultivations, which are not artificially fertilized with N. By contrast, water quality studies showed N enrichment in agricultural catchments, indicating fertilizer impacts and potential susceptibility to eutrophication. Regardless of the land use, P is widely absent because of the high-fixing capacities of deeply weathered soils and the filtering capacity of riparian vegetation. Pesticides, however, were consistently detected throughout the entire aquatic system. In several case studies, extremely high-peak concentrations exceeded Brazilian and EU water quality limits, which pose serious health risks. My field study revealed that land conversion caused a significant reduction in infiltration rates near the soil surface of pasture (–96 %) and croplands (–90 % to –93 %). Soil aggregate stability was significantly reduced in croplands than in cerrado and pasture. Soybean crops had extremely high extractable P (80 mg kg–1), whereas pasture N levels declined. A snapshot water sampling showed strong seasonality in water quality parameters. Higher temperature, oxi-reduction potential (ORP), NO2–, and very low oxygen concentrations (<5 mg•l–1) and saturation (<60 %) were recorded during the rainy season. By contrast, remarkably high PO43– concentrations (up to 0.8 mg•l–1) were measured during the dry season. Water quality parameters were affected by agricultural activities at all sampled sub-catchments across the catchment, regardless of stream characteristic. Direct NO3– leaching appeared to play a minor role; however, water quality is affected by topsoil fertiliser inputs with impact on small low order streams and larger rivers. Land conversion leaving cropland soils more susceptible to surface erosion by increased overland flow events. In a third study, the field data were used to parameterise SWAT. The model was tested with different input data and calibrated in SWAT-CUP using the SUFI-2 algorithm. The model was judged reliable to simulate the water balance in the Cerrado. A complete cerrado, pasture and cropland cover was used to analyse the impact of land use on water cycling as well as climate change projections (2039–2058) according to the projections of the RCP 8.5 scenario. The actual evapotranspiration (ET) for the cropland scenario was higher compared to the cerrado cover (+100 mm a–1). Land use change scenarios confirmed that deforestation caused higher annual ET rates explaining partly the trend of decreased streamflow. Taking all climate change scenarios into account, the most likely effect is a prolongation of the dry season (by about one month), with higher peak flows in the rainy season. Consequently, potential threats for crop production with lower soil moisture and increased erosion and sediment transport during the rainy season are likely and should be considered in adaption plans. From the three studies of the thesis I conclude that land use intensification is likely to seriously limit the Cerrado’s future regarding both agricultural productivity and ecosystem stability. Because only limited data are available for the vast biome, we recommend further field studies to understand the interaction between terrestrial and aquatic systems. This thesis may serve as a valuable database for integrated modelling to investigate the impact of land use and climate change on soil and water resources and to test and develop mitigation measures for the Cerrado in the future. N2 - Ökohydrologische Interaktionen in Folge von exzessiver Bodenerosion auf landwirtschaftlich stark modifizierten Flächen können speziell in tropischen Gebieten einen großen Einfluss auf die Fruchtbarkeit und zukünftige Nutzbarkeit der Böden haben, wie dies im Cerrado geschieht. Der brasilianische Cerrado ist eine neotropische Savanne und stellt mit 2 Mio. km² das zweitgrößte Biom Südamerikas dar. Das Biom wird global unter den bedeutendsten aber auch meist gefährdetsten 25 Biodiversitätshotspots gelistet. Ein extremer Landnutzungswandel führt dazu, dass der Cerrado zu den weltweit bedeutendsten landwirtschaftlichen Gebieten zählt und mittlerweile > 50 % des Bioms abgeholzt sind. Durch staatliche Subventionsprogramme, Aufkalkung und Düngung der Böden werden mehrere Ernten (v.a. Soja, Mais, Zuckerrohr und Baumwolle) pro Jahr bei hohem Ertrag realisiert. Aufgrund weniger Untersuchungen ist bisher unklar, wie sich die Landnutzungsintensivierung mit dem Einsatz großer Mengen an Agrochemikalien auf die Boden- und Wasserressourcen auswirkt. Um die Zielsetzung zu erreichen, wurden in einer umfassenden Metaanalyse Boden- und Wasserqualitätsparameter von mehr als 100 Einzelstudien analysiert, mehrere Feldkampagnen zur Erhebung bodenphysikochemischer und Wasserqualitätsparameter für unterschiedliche Landnutzungen durchgeführt und Modellierungen mit SWAT zur Abschätzung des Landnutzungs- und Klimawandels vorgenommen. Die Literaturanalyse konnte zeigen, dass Erosion, Veränderungen des Nährstoffkreislaufs, Nährstoffanreicherungen und sehr hohe Pestizidkonzentrationen in den Gewässern des gesamten Cerrado auftreten, mit stärkster Ausprägung für Ackerflächen. Trotz hoher Düngemengen wird festgestellt, dass P nur in sehr geringen Konzentrationen in den Gewässern nachgewiesen wird, welches auf die P-Fixierung der Böden und die Filterleistung der Uferrandstreifen zurückzuführen ist. In einer Feldstudie bestätigen sich die Ergebnisse, dass der Landnutzungswandel zu deutlichen Änderungen der boden-physikochemischen Parameter führt, wie z.B. einer signifikanten Abnahme der hydraulischen Leitfähigkeit (> –90 %) und der Bodenaggregatstabilität. Außerdem werden erhöhte pH-Werte und Überdüngung anzeigende P und K-gehalte im Oberboden (9-fach natürlicher Hintergrund) mit der stärksten Ausprägung unter Soja gemessen. Die Niederschlagsintensitäten überschreiten die Infiltrationskapazität der landwirtschaftlich genutzten Böden, wodurch es zu erhöhtem Oberflächenabfluss, Bodenerosionsereignissen mit Gullyformierungen kommt und der Eintrag von Agrochemikalien in die zuvor pristinen Gewässer begünstigt wird. Verglichen mit natürlichen Gewässern konnten im gesamten Einzugsgebiet niedrigere O2-Werte (< 5 mg l–1) sowie erhöhte NO3– (0.5 mg l–1), NO2– (0.1 mg l–1) und in der Trockenzeit auf direkte Düngung zurückzuführende sehr hohe PO43– (0.8 mg l–1) Konzentrationen festgestellt werden. Da in den Bodenprofilen keine Tiefenakkumulation von NPK nachgewiesen wurde ist davon auszugehen, dass Dünger durch Oberflächenabflussprozesse in das Flusssystem gelangen. Auch wenn die Nährstoffkonzentrationen nach europäischen Maßstäben gering sind, ist anzunehmen, dass in einem nährstofflimitierten System wie dem Cerrado die um ein vielfach erhöhte Konzentration der natürlichen Hintergrundwerte den Metabolismus der Gewässer negativ beeinflusst. In einer dritten Studie wird mit SWAT untersucht wie sich der Landnutzungs- und Klimawandel auf die Wasserbilanz auswirkt. In Testläufen zeigt sich, dass sowohl die verwendeten Niederschlagseingangsdaten als auch die Vegetationsparameter des natürlichen Cerrados von hoher Relevanz sind. Die Simulation verschiedener Landnutzungsszenarien belegt, dass die im Gebiet beobachteten abnehmenden Abflüsse auf die Zunahme landwirtschaftlicher Produktion und einer damit einhergehenden Zunahme der Evapotranspiration zurückzuführen sind. Die Simulation extremer Klimaszenarien (RCP 8.5 2039-2058) verdeutlicht, dass sich die Trockenzeit verlängert, welches Auswirkungen auf die Aussaattermine haben könnte. Gleichzeitig nehmen die Spitzenabflüsse in der Regenzeit zu, welches ohne entsprechende Gegenmaßnahmen zu erhöhter Erosion und gesteigertem Nähr- und Schadstofftransport in die Gewässer führt. Kombiniert mit einer weiteren Landnutzungsintensivierung wird für die zukünftige Entwicklung des Cerrado geschlussfolgert, dass die Veränderungen des Wasser- und Nährstoffhaushalt durch die Landwirtschaft und die damit einhergehenden Degradierungserscheinungen die Produktivität und Ökosystemstabilität nicht dauerhaft gewährleisten werden können. Die vorliegende Dissertation liefert einen zentralen Beitrag zur ökohydrologischen Bewertung des Status quo und der zukünftigen Entwicklung des brasilianischen Cerrados. Sie kann einen Ausgangspunkt für weitere Forschungen und Modellierungen darstellen, um die in dieser Arbeit benannten offenen Fragen hinsichtlich der ökohydrologischen Interaktionen zu klären. KW - Cerrado KW - ecohydrology KW - water KW - soil KW - deforestation KW - Cerrado KW - Ökohydrologie KW - Landnutzung KW - Boden KW - Wasser Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-85110 ER - TY - THES A1 - Rohrmann, Alexander T1 - The role of wind and water in shaping earth's plateaus T1 - Die Rolle von Wind und Wasser bei der Bildung von Hochplateaus der Erde N2 - The overarching goal of this dissertation is to provide a better understanding of the role of wind and water in shaping Earth’s Cenozoic orogenic plateaus - prominent high-elevation, low relief sectors in the interior of Cenozoic mountain belts. In particular, the feedbacks between surface uplift, the build-up of topography and ensuing changes in precipitation, erosion, and vegetation patterns are addressed in light of past and future climate change. Regionally, the study focuses on the two world’s largest plateaus, the Altiplano-Puna Plateau of the Andes and Tibetan Plateau, both characterized by average elevations of >4 km. Both plateaus feature high, deeply incised flanks with pronounced gradients in rainfall, vegetation, hydrology, and surface processes. These characteristics are rooted in the role of plateaus to act as efficient orographic barriers to rainfall and to force changes in atmospheric flow. The thesis examines the complex topics of tectonic and climatic forcing of the surface-process regime on three different spatial and temporal scales: (1) bedrock wind-erosion rates are quantified in the arid Qaidam Basin of NW Tibet over millennial timescales using cosmogenic radionuclide dating; (2) present-day stable isotope composition in rainfall is examined across the south-central Andes in three transects between 22° S and 28° S; these data are modeled and assessed with remotely sensed rainfall data of the Tropical Rainfall Measuring Mission and the Moderate Resolution Imaging Spectroradiometer; (3) finally, a 2.5-km-long Mio-Pliocene sedimentary record of the intermontane Angastaco Basin (25°45’ S, 66°00’ W) is presented in the context of hydrogen and carbon compositions of molecular lipid biomarker, and oxygen and carbon isotopes obtained from pedogenic carbonates; these records are compared to other environmental proxies, including hydrated volcanic glass shards from volcanic ashes intercalated in the sedimentary strata. There are few quantitative estimates of eolian bedrock-removal rates from arid, low relief landscapes. Wind-erosion rates from the western Qaidam Basin based on cosmogenic 10Be measurements document erosion rates between 0.05 to 0.4 mm/yr. This finding indicates that in arid environments with strong winds, hyperaridity, exposure of friable strata, and ongoing rock deformation and uplift, wind erosion can outpace fluvial erosion. Large eroded sediment volumes within the Qaidam Basin and coeval dust deposition on the Chinese Loess plateau, exemplify the importance of dust production within arid plateau environments for marine and terrestrial depositional processes, but also health issues and fertilization of soils. In the south-central Andes, the analysis of 234 stream-water samples for oxygen and hydrogen reveals that areas experiencing deep convective storms do not show the commonly observed patterns of isotopic fractionation and the expected co-varying relationships between oxygen and hydrogen with increasing elevation. These convective storms are formed over semi-arid intermontane basins in the transition between the broken foreland of the Sierras Pampeanas, the Eastern Cordillera, and the Puna Plateau in the interior of the orogen. Here, convective rainfall dominates the precipitation budget and no systematic stable isotope-elevation relationship exists. Regions to the north, in the transition between the broken foreland and the Subandean foreland fold-and-thrust belt, the impact of convection is subdued, with lower degrees of storminess and a stronger expected isotope-elevation relationship. This finding of present-day fractionation trends of meteoric water is of great importance for paleoenvironmental studies in attempts to use stable isotope relationships in the reconstruction of paleoelevations. The third part of the thesis focuses on the paleohydrological characteristics of the Mio-Pliocene (10-2 Ma) Angastaco Basin sedimentary record, which reveals far-reaching environmental changes during Andean uplift and orographic barrier formation. A precipitation- evapotranspiration record identifies the onset of a precipitation regime related to the South American Low Level Jet at this latitude after 9 Ma. Humid foreland conditions existed until 7 Ma, followed by orographic barrier uplift to the east of the present-day Angastaco Basin. This was superseded by rapid (~0.5 Myr) aridification in an intermontane basin, highlighting the effects of eastward-directed deformation. A transition in vegetation cover from a humid C3 forest ecosystem to semi-arid C4-dominated vegetation was coeval with continued basin uplift to modern elevations. N2 - Das übergreifende Ziel dieser Dissertation ist es, ein besseres Verständnis des Einflusses von Wind und Wasser auf die Entstehung orogener Plateaus im Känozoikum zu erlangen. Orogene Plateaus sind hochgelegene, durch geringes Relief und oft endorheische Entwässerung charakterisierte trockene Hochgebirgsregionen. In dieser Arbeit wird vor allem die Rückkopplung zwischen tektonischer Hebung, dem Aufbau von Relief und den daraus resultierenden Veränderungen des Niederschlags, der Erosion und variierenden Vegetationsmustern im Zusammenhang mit vergangenen und zukünftigen Klimaveränderungen untersucht. Der regionale Fokus dieser Arbeit liegt auf den zwei größten Plateaus der Erde, das Altiplano-Puna-Plateau in den Anden und das Tibet Plateau. Beide besitzen eine durchschnittliche Höhe von > 4 km. Als effiziente orographische Barrieren und „Heizflächen“ beeinflussen Plateaus großräumig die atmosphärische Zirkulation und bewirken somit ausgeprägte Gradienten in Niederschlag, Vegetation, Hydrologie und Oberflächenprozessen. Vor diesem Hintergrund untersucht diese Arbeit das komplexe Zusammenspiel zwischen Tektonik und Klima und damit verbundene Auswirkungen auf Erdoberflächenprozesse auf drei verschiedenen zeitlichen und räumlichen Skalen: (1) die Quantifizierung von Wind-Erosionsraten im Festgestein des ariden Qaidam-Beckens von Nordwest-Tibet mittels kosmogener Nukliddatierungen über Zeiräume von mehreren 103 Jahren; (2) die heutige Isotopenzusammensetzung von Niederschläge wird entlang von drei Transekten über die Südzentralanden zwischen 22° und 28° S ermittelt; diese Daten werden modelliert und der Niederschlag mit satellitenbasierten Fernerkundungsdaten der Tropical Rainfall Measuring Mission und des Moderate Resolution Imaging Spectroradiometer ausgewertet; (3) eine 2,5 km mächtige mio-pliozäne Sedimentabfolge des intermontanen Angastaco-Beckens (25°45’ S, 66°00’ W) wird auf die Wasserstoff- und Kohlenstoffzusammensetzungen von molekularen Blattwachsen und hinsichtlich der Sauerstoff- und Kohlenstoffisotopie von Bodenkarbonaten untersucht; diese Datensätze werden mit anderen Umweltindikatoren verglichen, u.a. mit hydratisierten Gläsern vulkanischer Aschen, die in der Sedimentabfolge aufgeschlossen sind. Es gibt nur wenige quantitative Abschätzungen von Winderosionsraten im Festgestein arider Gebiete mit geringem Relief. Kosmogene 10Be-Messungen im westlichen Qaidam-Becken dokumentieren Erosionsraten zwischen 0,05 bis 0,4 mm/a. Diese Resultate zeigen, dass in ariden Gebieten mit hohen Windgeschwindigkeiten, leicht erodierbaren Gesteinen und andauernder Deformation und Hebung, Wind-Erosionsprozesse die Denudationsraten der fluvialen Erosion bei weitem übersteigen kann. Das große Volumen erodierter Gesteine im Qaidam-Becken und die gleichzeitige Lössablagerung im chinesischen Löss-Plateau veranschaulichen die wichtige Rolle der äolischen Sedimentproduktion in ariden Plateaugebieten und unterstreichen deren Bedeutung für marine und terrestrische Ablagerungsprozesse sowie Nährstoffeinträge in Böden und respiratorische Gesundheitsprobleme. Die Analyse der Sauerstoff- und Wasserstoffisotopie von 234 Flusswasserproben aus den Südzentralanden belegt, dass Gebiete mit starken konvektiven meteorologischen Ereignissen nicht die erwarteten Isotopenmuster zwischen der Abnahme der Isotopie und der Höhe aufweisen. Diese konvektiven Ereignisse werden über semiariden intermontanen Becken in der Übergangszone zwischen dem zerbrochenen Vorland der Sierras Pampeanas, der Ostkordillere und dem Puna-Plateau im Inneren des Orogens gebildet. Konvektiver Niederschlag dominiert hier den Niederschlagshaushalt und eliminiert jegliche systematische Beziehung zwischen der Isotopie und der Höhe. In den nördlichen Regionen, - in der Übergangszone zwischen dem zerbrochenen Vorland und dem subandinen Falten- und Überschiebungsgürtel, verringert sich der Einfluss konvektiver Niederschläge und hydrometeorologische Extremereignisse gegenüber den orographischen bedingten Niederschlagsmechanismen. Dieser Unterschied wirkt sich in einer besseren Beziehung zwischen Isotopenverhältnissen und Höhe aus. Eine bessere Kenntnis der meteorologischen Einflüsse auf die Wasserisotopie sind der Schlüssel für zukünftige Paläoumweltstudien und zukünftige Bestrebungen, mit Hilfe der Trends in der Isotopie meteorischer Wässer das vertikale Wachstum von Gebirgen zu quantifizieren. Der dritte Teil der Arbeit behandelt die Isotopenverhältnisse in Blattwachsen und daraus abgeleitete paläohydrologische Eigenschaften des Anagastaco-Beckens im Mio-Pliozän (10-2 Ma), welche weitreichende Umweltveränderungen während der Hebung der Anden und der Bildung von orografischen Barrieren im Vorland aufzeigen. Als Proxies für Niederschlag und Evapotranspiration dokumentieren Isotopenverhältnisse in Blattwachsen, Bodenkarbonaten und vulkanischen Gläsern den Beginn eines Niederschlagsystems in diesem Teil der Anden, welches durch feuchtebringende Winde des South American Low Level Jet ab 9 Ma etabliert war. Humide Bedingungen existierten bis 7 Ma im Vorland, gefolgt von einer Bildung einer orografischen Barriere im Osten des heutigen Angastaco-Beckens. Als Folge dieser Hebung folgte eine rasche Aridifikation (innerhalb ~0,5 Ma) des nun intermontanen Angastaco-Beckens. Ein Wechsel von einem feuchten C3-Wald-Ökosystem zu semiariden Umweltbedingungen mit einer C4-dominierten Vegetationsdecke vollzog sich gleichzeitig mit der fortlaufenden Hebung des Beckens auf heutige Höhen. KW - plateau KW - isotopes KW - erosion KW - water KW - leaf wax KW - Plateau KW - stabile Isotope KW - Wasser KW - Erosion KW - Blattwachse Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-77938 ER - TY - THES A1 - Mertoglu, Murat T1 - The synthesis of well-defined functional homo- and block copolymers in aqueous media via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization T1 - - N2 - New chain transfer agents based on dithiobenzoate and trithiocarbonate for free radical polymerization via Reversible Addition-Fragmentation chain Transfer (RAFT) were synthesized. The new compounds bear permanently hydrophilic sulfonate moieties which provide solubility in water independent of the pH. One of them bears a fluorophore, enabling unsymmetrical double end group labelling as well as the preparation of fluorescent labeled polymers. Their stability against hydrolysis in water was studied, and compared with the most frequently employed water-soluble RAFT agent 4-cyano-4-thiobenzoylsulfanylpentanoic acid dithiobenzoate, using UV-Vis and 1H-NMR spectroscopy. An improved resistance to hydrolysis was found for the new RAFT agents, providing good stabilities in the pH range between 1 and 8, and up to temperatures of 70°C. Subsequently, a series of non-ionic, anionic and cationic water-soluble monomers were polymerized via RAFT in water. In these experiments, polymerizations were conducted either at 48°C or 55°C, that are lower than the conventionally employed temperatures (>60°C) for RAFT in organic solvents, in order to minimize hydrolysis of the active chain ends (e.g. dithioester and trithiocarbonate), and thus to obtain good control over the polymerization. Under these conditions, controlled polymerization in aqueous solution was possible with styrenic, acrylic and methacrylic monomers: molar masses increase with conversion, polydispersities are low, and the degree of end group functionalization is high. But polymerizations of methacrylamides were slow at temperatures below 60°C, and showed only moderate control. The RAFT process in water was also proved to be a powerful method to synthesize di- and triblock copolymers including the preparation of functional polymers with complex structure, such as amphiphilic and stimuli-sensitive block copolymers. These include polymers containing one or even two stimuli-sensitive hydrophilic blocks. The hydrophilic character of a single or of several blocks was switched by changing the pH, the temperature or the salt content, to demonstrate the variability of the molecular designs suited for stimuli-sensitive polymeric amphiphiles, and to exemplify the concept of multiple-sensitive systems. Furthermore, stable colloidal block ionomer complexes were prepared by mixing anionic surfactants in aqueous media with a double hydrophilic block copolymer synthesized via RAFT in water. The block copolymer is composed of a noncharged hydrophilic block based on polyethyleneglycol and a cationic block. The complexes prepared with perfluoro decanoate were found so stable that they even withstand dialysis; notably they do not denaturate proteins. So, they are potentially useful for biomedical applications in vivo. N2 - Ziel der vorliegenden Arbeit war es, neue Kettenübertragungs Agenzien, basierend auf Dithiobenzoat- und Trithiocarbonatderivaten zu synthetisieren, welche in der "Reversiblen Additions-Fragmentierungs Kettenübertragungs-Polymerisation" (RAFT) eingesetzt werden können. Die neu synthetisierten Verbindungen zeichnen sich durch permanent hydrophile Sulfonatgruppen aus, welche eine pH-unabhängige Löslichkeit in Wasser ermöglichen. Eine dieser Verbindungen trägt ein Fluorophore, wodurch eine asymmetrische doppelte Endgruppenmarkierung sowie die Herstellung von Fluoreszenzmarkierten Polymeren möglich ist. Die Hydrolysestabilität dieser Verbindungen in wässriger Lösung im Vergleich mit dem z. Zeit bekanntesten wasserlöslichen RAFT Agenz (4-Cyano-4-thiobenzoylsulfanylpentansäuredithiobenzoate) wurde unter Anwendung spektroskopischer Methoden (UV-Vis, 1H-NMR) untersucht. Dabei wurde festgestellt, dass diese neue Verbindungen deutlich bessere Hydrolysestabiltäten im pH-Bereich von 1-8 und bis zu einer Temperatur von 70°C besitzen. Die neuen RAFT-Verbindungen wurden ebenfalls bezgl. Ihrer Eignung in der Polymerisation von wasserlöslichen nichtionischen, anionischen und kationischen Monomeren in wässrigem Medium bei 48°C und 55°C getestet. Unter diesen Bedingungen konnten Vinylverbindungen wie z. B. Styrenderivate. Acrylate und Methacrylate kontrolliert polymerisiert werden: Die Molmasse stieg mit dem Umsatz, die Polydispersitäten waren niedrig und die isolierten Polymere zeigten Grad an Endgruppenfunktionalität. Bei der Polymerisation von Methacrylamiden wurde bei Polymerisationstemperaturen unter 60°C nur eine mäßige Kontrolle gefunden. Es konnte weiterhin die RAFT Polymerisation in Wasser als leistungsstarke Methode zur Herstellung definierter Di- und Triblockcopolymere, einschließlich der Synthese von funktionalen Polymeren mit komplexer Struktur – beispielsweise amphiphiler- und schaltbare (stimuli responsive) Blockcopolymere entwickelt werden. Dies beinhaltet auch Polymere, die einen oder zwei schaltbare hydrophile Polymerblöcke enthalten. Der hydrophile Eigenschaft eines oder mehrer Blöcke kann durch äußere Reize wie pH-Änderung, Temperatur oder Salzgehalt geändert werden. Diese Beispiele demonstrierten die Variabilität des für schaltbare Polyamphiphile notwendigen Designs und zeigten exemplarisch das Konzept für multi-sensitive Systeme. KW - RAFT KW - wasser KW - blockcopolymere KW - stimuli-sensitive KW - RAFT KW - water KW - blockcopolymer KW - stimuli-sensitive Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-2338 ER - TY - GEN A1 - Fondell, Mattis A1 - Eckert, Sebastian A1 - Jay, Raphael Martin A1 - Weniger, Christian A1 - Quevedo, Wilson A1 - Niskanen, Johannes A1 - Kennedy, Brian A1 - Sorgenfrei, Florian A1 - Schick, Daniel A1 - Giangrisostomi, Erika A1 - Ovsyannikov, Ruslan A1 - Adamczyk, Katrin A1 - Huse, Nils A1 - Wernet, Philippe A1 - Mitzner, Rolf A1 - Föhlisch, Alexander T1 - Time-resolved soft X-ray absorption spectroscopy in transmission mode on liquids at MHz repetition rates T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - We present a setup combining a liquid flatjet sample delivery and a MHz laser system for time-resolved soft X-ray absorption measurements of liquid samples at the high brilliance undulator beamline UE52-SGM at Bessy II yielding unprecedented statistics in this spectral range. We demonstrate that the efficient detection of transient absorption changes in transmission mode enables the identification of photoexcited species in dilute samples. With iron(II)-trisbipyridine in aqueous solution as a benchmark system, we present absorption measurements at various edges in the soft X-ray regime. In combination with the wavelength tunability of the laser system, the set-up opens up opportunities to study the photochemistry of many systems at low concentrations, relevant to materials sciences, chemistry, and biology. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 780 KW - l-edge xas KW - electronic-structure KW - molecular-structure KW - spin-state KW - dynamics KW - complexes KW - probe KW - water KW - iron(II) KW - spectra Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437529 SN - 1866-8372 IS - 780 ER - TY - GEN A1 - Lara, Mark J. A1 - Nitze, Ingmar A1 - Große, Guido A1 - McGuire, David T1 - Tundra landform and vegetation productivity trend maps for the Arctic Coastal Plain of northern Alaska T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Arctic tundra landscapes are composed of a complex mosaic of patterned ground features, varying in soil moisture, vegetation composition, and surface hydrology over small spatial scales (10-100 m). The importance of microtopography and associated geomorphic landforms in influencing ecosystem structure and function is well founded, however, spatial data products describing local to regional scale distribution of patterned ground or polygonal tundra geomorphology are largely unavailable. Thus, our understanding of local impacts on regional scale processes (e.g., carbon dynamics) may be limited. We produced two key spatiotemporal datasets spanning the Arctic Coastal Plain of northern Alaska (similar to 60,000 km(2)) to evaluate climate-geomorphological controls on arctic tundra productivity change, using (1) a novel 30m classification of polygonal tundra geomorphology and (2) decadal-trends in surface greenness using the Landsat archive (1999-2014). These datasets can be easily integrated and adapted in an array of local to regional applications such as (1) upscaling plot-level measurements (e.g., carbon/energy fluxes), (2) mapping of soils, vegetation, or permafrost, and/or (3) initializing ecosystem biogeochemistry, hydrology, and/or habitat modeling. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1035 KW - spatial-distribution KW - lake basins KW - microtopography KW - water KW - ice KW - accumulation KW - degradation KW - permafrost KW - dynamics KW - barrow Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-459875 SN - 1866-8372 IS - 1035 ER - TY - THES A1 - Numberger, Daniela T1 - Urban wastewater and lakes as habitats for bacteria and potential vectors for pathogens T1 - Urbane Abwässer und Seen als Habitat für Bakterien und potentielle Vektoren für Krankheitserreger N2 - Wasser ist lebensnotwendig und somit eine essentielle Ressource. Jedoch sind unsere Süßwasser-Ressourcen begrenzt und ihre Erhaltung daher besonders wichtig. Verschmutzungen mit Chemikalien und Krankheitserregern, die mit einer wachsenden Bevölkerung und Urbanisierung einhergehen, verschlechtern die Qualität unseres Süßwassers. Außerdem kann Wasser als Übertragungsvektor für Krankheitserreger dienen und daher wasserbürtige Krankheiten verursachen. Der Leibniz-Forschungsverbund INFECTIONS‘21 untersuchte innerhalb der interdisziplinären Forschungsgruppe III - „Wasser", Gewässer als zentralen Mittelpunkt für Krankheiterreger. Dabei konzentrierte man sich auf Clostridioides difficile sowie aviäre Influenza A-Viren, von denen angenommen wird, dass sie in die Gewässer ausgeschieden werden. Ein weiteres Ziel bestand darin, die bakterielle Gemeinschaften eines Klärwerkes der deutschen Hauptstadt Berlin zu charakterisieren, um anschließend eine Bewertung des potentiellen Gesundheitsrisikos geben zu können. Bakterielle Gemeinschaften des Roh- und Klarwassers aus dem Klärwerk unterschieden sich signifikant voneinander. Der Anteil an Darm-/Fäkalbakterien war relativ niedrig und potentielle Darmpathogene wurden größtenteils aus dem Rohwasser entfernt. Ein potentielles Gesundheitsrisiko konnte allerdings von potentiell pathogenen Legionellen wie L. lytica festgestellt werden, deren relative Abundanz im Klarwasser höher war als im Rohwasser. Es wurden außerdem drei C. difficile-Isolate aus den Klärwerk-Rohwasser und einem städtischen Badesee in Berlin (Weisser See) gewonnen und sequenziert. Die beiden Isolate aus dem Klärwerk tragen keine Toxin-Gene, wohingegen das Isolat aus dem See Toxin-Gene besitzt. Alle drei Isolate sind sehr nah mit humanen Stämmen verwandt. Dies deutet auf ein potentielles, wenn auch sporadisches Gesundheitsrisiko hin. (Aviäre) Influenza A-Viren wurden in 38.8% der untersuchten Sedimentproben mittels PCR detektiert, aber die Virusisolierung schlug fehl. Ein Experiment mit beimpften Wasser- und Sedimentproben zeigte, dass für die Isolierung aus Sedimentproben eine relativ hohe Viruskonzentration nötig ist. In Wasserproben ist jedoch ein niedriger Titer an Influenza A-Viren ausreichend, um eine Infektion auszulösen. Es konnte zudem auch festgestellt werden, dass sich „Madin-Darby Canine Kidney (MDCK)―-Zellkulturen im Gegensatz zu embryonierten Hühnereiern besser eignen, um Influenza A-Viren aus Sediment zu isolieren. Zusammenfassend lässt sich sagen, dass diese Arbeit mögliche Gesundheitsrisiken aufgedeckt hat, wie etwa durch Legionellen im untersuchten Berliner Klärwerk, deren relative Abundanz in geklärtem Abwasser höher ist als im Rohwasser. Desweiteren wird indiziert, dass Abwasser und Gewässer als Reservoir und Vektor für pathogene Organismen dienen können, selbst für nicht-typische Wasser-Pathogene wie C. difficile. N2 - Water is essential to life and thus, an essential resource. However, freshwater resources are limited and their maintenance is crucial. Pollution with chemicals and pathogens through urbanization and a growing population impair the quality of freshwater. Furthermore, water can serve as vector for the transmission of pathogens resulting in water-borne illness. The Interdisciplinary Research Group III – "Water" of the Leibniz alliance project INFECTIONS‘21 investigated water as a hub for pathogens focusing on Clostridioides difficile and avian influenza A viruses that may be shed into the water. Another aim of this study was to characterize the bacterial communities in a wastewater treatment plant (WWTP) of the capital Berlin, Germany to further assess potential health risks associated with wastewater management practices. Bacterial communities of WWTP inflow and effluent differed significantly. The proportion of fecal/enteric bacteria was relatively low and OTUs related to potential enteric pathogens were largely removed from inflow to effluent. However, a health risk might exist as an increased relative abundance of potential pathogenic Legionella spp. such as L. lytica was observed. Three Clostridioides difficile isolates from wastewater inflow and an urban bathing lake in Berlin (‗Weisser See‘) were obtained and sequenced. The two isolates from the wastewater did not carry toxin genes, whereas the isolate from the lake was positive for the toxin genes. All three isolates were closely related to human strains. This indicates a potential, but rather sporadic health risk. Avian influenza A viruses were detected in 38.8% of sediment samples by PCR, but virus isolation failed. An experiment with inoculated freshwater and sediment samples showed that virus isolation from sediment requires relatively high virus concentrations and worked much better in Madin-Darby Canine Kidney (MDCK) cell cultures than in embryonated chicken eggs, but low titre of influenza contamination in freshwater samples was sufficient to recover virus. In conclusion, this work revealed potential health risks coming from bacterial groups with pathogenic potential such as Legionella spp. whose relative abundance is higher in the released effluent than in the inflow of the investigated WWTP. It further indicates that water bodies such as wastewater and lake sediments can serve as reservoir and vector, even for non-typical water-borne or water-transmitted pathogens such as C. difficile. KW - water KW - Wasser KW - bacteria KW - Bakterien KW - influenza A viruses KW - Influenza A Viren KW - pathogens KW - Krankheitserreger Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437095 ER - TY - JOUR A1 - Ugwuja, Chidinma G. A1 - Adelowo, Olawale O. A1 - Ogunlaja, Aemere A1 - Omorogie, Martins O. A1 - Olukanni, Olumide D. A1 - Ikhimiukor, Odion O. A1 - Iermak, Ievgeniia A1 - Kolawole, Gabriel A. A1 - Günter, Christina A1 - Taubert, Andreas A1 - Bodede, Olusola A1 - Moodley, Roshila A1 - Inada, Natalia M. A1 - Camargo, Andrea S.S. de A1 - Unuabonah, Emmanuel Iyayi T1 - Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites JF - ACS applied materials & interfaces N2 - This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Arhammar, C.; Jamstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, therrnogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 x 10(7) cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries. KW - disinfection KW - nanocomposite material KW - multidrug-resistant Escherichia coli KW - water KW - reactive oxygen species Y1 - 2019 U6 - https://doi.org/10.1021/acsami.9b01212 SN - 1944-8244 SN - 1944-8252 VL - 11 IS - 28 SP - 25483 EP - 25494 PB - American Chemical Society CY - Washington, DC ER - TY - GEN A1 - Duy, Nguyen Le A1 - Heidbüchel, Ingo A1 - Meyer, Hanno A1 - Merz, Bruno A1 - Apel, Heiko T1 - What controls the stable isotope composition of precipitation in the Mekong Delta? BT - a model-based statistical approach T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - This study analyzes the influence of local and regional climatic factors on the stable isotopic composition of rainfall in the Vietnamese Mekong Delta (VMD) as part of the Asian monsoon region. It is based on 1.5 years of weekly rainfall samples. In the first step, the isotopic composition of the samples is analyzed by local meteoric water lines (LMWLs) and single-factor linear correlations. Additionally, the contribution of several regional and local factors is quantified by multiple linear regression (MLR) of all possible factor combinations and by relative importance analysis. This approach is novel for the interpretation of isotopic records and enables an objective quantification of the explained variance in isotopic records for individual factors. In this study, the local factors are extracted from local climate records, while the regional factors are derived from atmospheric backward trajectories of water particles. The regional factors, i.e., precipitation, temperature, relative humidity and the length of backward trajectories, are combined with equivalent local climatic parameters to explain the response variables delta O-18, delta H-2, and d-excess of precipitation at the station of measurement. The results indicate that (i) MLR can better explain the isotopic variation in precipitation (R-2 = 0.8) compared to single-factor linear regression (R-2 = 0.3); (ii) the isotopic variation in precipitation is controlled dominantly by regional moisture regimes (similar to 70 %) compared to local climatic conditions (similar to 30 %); (iii) the most important climatic parameter during the rainy season is the precipitation amount along the trajectories of air mass movement; (iv) the influence of local precipitation amount and temperature is not sig-nificant during the rainy season, unlike the regional precipitation amount effect; (v) secondary fractionation processes (e.g., sub-cloud evaporation) can be identified through the d-excess and take place mainly in the dry season, either locally for delta O-18 and delta H-2, or along the air mass trajectories for d-excess. The analysis shows that regional and local factors vary in importance over the seasons and that the source regions and transport pathways, and particularly the climatic conditions along the pathways, have a large influence on the isotopic composition of rainfall. Although the general results have been reported qualitatively in previous studies (proving the validity of the approach), the proposed method provides quantitative estimates of the controlling factors, both for the whole data set and for distinct seasons. Therefore, it is argued that the approach constitutes an advancement in the statistical analysis of isotopic records in rainfall that can supplement or precede more complex studies utilizing atmospheric models. Due to its relative simplicity, the method can be easily transferred to other regions, or extended with other factors. The results illustrate that the interpretation of the isotopic composition of precipitation as a recorder of local climatic conditions, as for example performed for paleorecords of water isotopes, may not be adequate in the southern part of the Indochinese Peninsula, and likely neither in other regions affected by monsoon processes. However, the presented approach could open a pathway towards better and seasonally differentiated reconstruction of paleoclimates based on isotopic records. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 927 KW - Asian summer monsoon KW - interannuel variability KW - climate controls KW - deuterium excess KW - oxygen isotopes KW - paleoclimate KW - water KW - system KW - trajectories KW - circulation Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-445743 SN - 1866-8372 IS - 927 SP - 1239 EP - 1262 ER -