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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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.