Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.
Um aktuelle Umwelt- und Klimaveränderungen in einem längeren zeitlichen Kontext bewerten zu können, insbesondere anthropogene und natürliche Einflüsse auf den atmosphärischen Aerosoleintrag in die Atmosphäre zu verstehen, werden Informationen über die Zusammensetzung der Atmosphäre in der Vergangenheit benötigt. Eisbohrkerne aus den Polarregionen oder Gletschern sind wertvolle Umwelt- und Klimaarchive, da sie unter anderem das mit dem Schnellfall deponierte Aerosol enthalten. Daher kann die Analyse von partikel-gebundenen Spurenstoffen in Eisbohrkernen stoffliche Informationen über zurückliegende Umwelt- und Klimabedingungen liefern. Bis heute konzentrieren sich diese Bemühungen auf anorganische Substanzen und nur wenige organische Analyten. Ein Großteil der in diesen Bohrkernen enthaltenen Informationen geht dadurch verloren. Dies charakterisiert das Hauptziel des Vorhabens, durch Erarbeitung organischer spurenanalytischer Methoden basierend auf LC-HRMS (Flüssigchromatographie in Kombination mit hochauflösender Massenspektrometrie) eine ausgewählte Palette von Markersubstanzen zu quantifizieren. Zielmoleküle sind insbesondere neue Marker für biogene sekundäre organische Aerosole (biogenic SOA) und Biomasseverbrennungs-Marker. Die Auswahl dieser Verbindungen basiert einerseits auf dem zu erwartenden Informationsgewinn über die Quellen und deren Zusammensetzung (terrestrische Vegetation/Waldbrände), andererseits auf der atmosphärischen Lebensdauer der Marker, da nur langlebige Marker weit entfernt liegende Regionen erreichen können. Zusätzlich zur Analyse dieser Zielanalyten sollen auch ââ‚ Ìnon-target screening-Methoden zum Einsatz kommen. In enger Zusammenarbeit mit einem etablierten Eisbohrkernlabor am PSI in der Schweiz werden die entwickelten Analysetechniken auf einen Eisbohrkern aus dem Belukha-Gletscher im Sibirischen Altai Gebirge angewendet.
Atmospheric CO2 concentrations present a repetitive pattern of gradual decline and rapid increase during the last climate cycles, closely related to temperature and sea level change. During the Last Glacial Maximum (LGM; 23-19 kyr BP), when sea level was ca. 120 m below present, the ocean must have stored additionally about 750 Gt carbon. There is consensus that the Southern Ocean represents a key area governing past and present CO2 change. The latter is not only of high scientific but also of socio-economic and political concern since the Southern Ocean provides the potential for an efficient sink of anthropogenic carbon. However, the sensitivity of this carbon sink to climate-change induced reorganizations in wind patterns, ocean circulation, stratification, sea ice extent and biological production remains under debate. Models were not yet able to reproduce the necessary mechanisms involved, potentially due to a lack of the dynamic representation/resolution of atmospheric and oceanic circulation as well as missing carbon cycling. Data on past Southern Ocean hydrography and productivity are mainly from the Atlantic sector, thus do not adequately document conditions in the Pacific sector. This sector is not only the largest part of the Southern Ocean, but it also represents the main drainage area of the marine-based West Antarctic Ice Sheet (WAIS). In the proposed study we aim to generate paleo-data sets with a newly established proxy method from sediment core transects across the Pacific Southern Ocean. This will enhance the baselines for the understanding and modeling of the Southern Ocean's role in carbon cyling, i.e. ocean/atmosphere CO2 exchange and carbon sequestration. It will also allow insight into the response of the WAIS to past warmer than present conditions. Paired isotope measurements (oxygen, silicon) will be made on purified diatoms and radiolarians to describe glacial/interglacial contrasts in physical and nutrient properties at surface and subsurface water depth. This will be used to test (i) the impact of yet unconsidered dust-borne micronutrient deposition on the glacial South Pacific on shifts of primary productivity, Si-uptake rates and carbon export, (ii) the 'silicic-acid leakage' hypothesis (SALH) and (iii) the formation and extent of surface water stratification. Diatom and radiolarian oxygen isotopes will provide information on the timing of surface ocean salinity anomalies resulting from WAIS melt water. Climate model simulations using a complex coupled atmosphere ocean general circulation model (AOGCM) in combination with a sophisticated ocean biogeochemical model including Si-isotopes will be used for comparison with the paleo records. The analysis will cover spatial as well as temporal variability patterns of Southern Ocean hydrography, nutrient cycling and air-sea CO2-exchange. With the help of the climate model we aim to better separate and statistically analyse the individual impacts of ocean circulation and bio
Der Verlauf der atmosphärischen CO2-Konzentrationen während der vergangenen Klimazyklen ist durch ein Sägezahnmuster mit Maxima in Warmzeiten und Minima in Kaltzeiten geprägt. Es besteht derzeit Konsens, dass insbesondere der Süd Ozean (SO) eine Schlüsselfunktion bei der Steuerung der CO2-Entwicklung einnimmt. Allerdings sind die dabei wirksamen Mechanismen, die in Zusammenhang mit Änderungen der Windmuster, Ozeanzirkulation, Stratifizierung der Wassersäule, Meereisausdehnung und biologischer Produktion stehen, noch nicht ausreichend bekannt. Daten zur Wirkung dieser Prozesse im Wechsel von Warm- und Kaltzeiten beziehen sich bislang fast ausschließlich auf den atlantischen SO. Um ein umfassendes Bild der Klimasteuerung durch den SO zu erhalten muss geklärt werden, wie weit sich die aus dem atlantischen SO bekannten Prozesswirkungen auf den pazifischen SO übertragen lassen. Dies ist deshalb von Bedeutung, da der pazifische SO den größten Teil des SO einnimmt. Darüber hinaus stellt er das hauptsächliche Abflussgebiet des Westantarktischen Eisschildes (WAIS) in den SO dar. Im Rahmen des Projektes sollen mit einer neu entwickelten Proxy-Methode Paläoumwelt-Zeitreihen an ausgewählten Sedimentkernen von latitudinalen Schnitten über den pazifischen SO hinweg gewonnen werden. Dabei handelt es sich um kombinierte Sauerstoff- und Siliziumisotopenmessungen an gereinigten Diatomeen und Radiolarien. Es sollen erstmalig die physikalischen Eigenschaften und Nährstoffbedingungen in verschiedenen Stockwerken des Oberflächenwassers aus verschiedenen Ablagerungsräumen und während unterschiedlicher Klimabedingungen beschrieben werden. Dies umfasst Bedingungen von kälter als heute (z.B. Letztes Glaziales Maximum) bis zu wärmer als heute (z.B. Marines Isotopen Stadium, MIS 5.5). Die Untersuchungen geben Hinweise zur (1) Sensitivität des antarktischen Ökosystems auf den Eintrag von Mikronährstoffen (Eisendüngung), (2) Oberflächenwasserstratifizierung und (3) 'Silicic-Acid leakage'-Hypothese, und tragen damit zur Überprüfung verschiedener Hypothesen zur Klimawirksamkeit von SO-Prozessen bei. Die neuen Proxies bilden überdies Oberflächen-Salzgehaltsanomalien ab, die Hinweise zur Stabilität des WAIS unter verschiedenen Klimabedingungen geben. Darüber hinaus kann die Hypothese getestet werden, nach der der WAIS während MIS 5.5 vollständig abgebaut war. Die Projektergebnisse sollen mit Simulationen mit einem kombinierten biogeochemischen (Si-Isotope beinhaltenden) Atmosphäre-Ozean-Zirkulations-Modell aus einem laufenden SPP1158-DFG Projekt an der CAU Kiel (PI B. Schneider) verglichen werden. Damit sollen die jeweiligen Beiträge der Ozeanzirkulation und der biologischen Produktion zum CO2-Austausch zwischen Ozean und Atmosphäre getrennt und statistisch analysiert werden. Informationen zu Staubeintrag, biogenen Flussraten, physikalischen Ozeanparametern und zur Erstellung von Altersmodellen stehen durch Zusammenarbeit mit anderen (inter)nationalen Projekten zur Verfügung.
The development of sustainable and efficient energy conversion processes at interfaces is at the center of the rapidly growing field of basic energy science. How successful this challenge can be addressed will ultimately depend on the acquired degree of molecular-level understanding. In this respect, the severe knowledge gap in electro- or photocatalytic conversions compared to corresponding thermal processes in heterogeneous catalysis is staggering. This discrepancy is most blatant in the present status of predictive-quality, viz. first-principles based modelling in the two fields, which largely owes to multifactorial methodological issues connected with the treatment of the electrochemical environment and the description of the surface redox chemistry driven by the photo-excited charges or external potentials.Successfully tackling these complexities will advance modelling methodology in (photo)electrocatalysis to a similar level as already established in heterogeneous catalysis, with an impact that likely even supersedes the one seen there in the last decade. A corresponding method development is the core objective of the present proposal, with particular emphasis on numerically efficient approaches that will ultimately allow to reach comprehensive microkinetic formulations. Synergistically combining the methodological expertise of the two participating groups we specifically aim to implement and advance implicit and mixed implicit/explicit solvation models, as well as QM/MM approaches to describe energy-related processes at solid-liquid interfaces. With the clear objective to develop general-purpose methodology we will illustrate their use with applications to hydrogen generation through water splitting. Disentangling the electro- resp. photocatalytic effect with respect to the corresponding dark reaction, this concerns both the hydrogen evolution reaction at metal electrodes like Pt and direct water splitting at oxide photocatalysts like TiO2. Through this we expect to arrive at a detailed mechanistic understanding that will culminate in the formulation of comprehensive microkinetic models of the light- or potential-driven redox process. Evaluating these models with kinetic Monte Carlo simulations will unambiguously identify the rate-determining and overpotential-creating steps and therewith provide the basis for a rational optimization of the overall process. As such our study will provide a key example of how systematic method development in computational approaches to basic energy sciences leads to breakthrough progress and serves both fundamental understanding and cutting-edge application.
Introduction: In Malaysia, excessive nutrients from livestock waste management systems are currently released to the environment. Particularly, large amounts of manure from intensive pig production areas are being excreted daily and are not being fully utilised. Alternatively, the excess manure can be applied as an organic fertiliser source in neighbouring cropping systems on the small landholdings of the pig farms to improve soil fertility so that its nutrients will be available for crop uptake instead of being discharged into water streams. Thus, there is a need for better tools to analyse the present situation, to evaluate and monitor alternative livestock production systems and manure management scenarios, and to support farmers in the proper management of manure and fertiliser application. Such tools are essential to quantify, and assess nutrient fluxes, manure quality and content, manure storage and application rate to the land as well as its environmental effects. Several computer models of animal waste management systems to assist producers and authorities are now available. However, it is felt that more development is needed to adopt such models to the humid tropics and conditions of Malaysia and other developing countries in the region. Objectives: The aim is to develop a novel model to evaluate nutrient emission scenarios and the impact of livestock waste at the landscape or regional level in humid tropics. The study will link and improve existing models to evaluate emission of N to the atmosphere, and leaching of nutrients to groundwater and surface water. The simulation outputs of the models will be integrated with a GIS spatial analysis to model the distribution of nutrient emission, leaching and appropriate manure application on neighbouring crop lands and as an information and decision support tool for the relevant users.
In the Bavarian Forest National Park a brief, but intense storm event on 1 August 1983 created large windfall areas. The windfall ecosystems within the protection zone of the park were left develop without interference; outside this zone windfall areas were cleared of dead wood but not afforested. A set of permanent plots (transect design with 10 to 10 m plots) was established in 1988 in spruce forests of wet and cool valley bottoms in order to document vegetation development. Resampling shall take place every five years; up to now it was done in 1993 and 1998. On cleared areas an initial raspberry (Rubus idaeus) shrub community was followed by pioneer birch (Betula pubescens, B. pendula) woodland, a sequence well known from managed forest stands. In contrast to this, these two stages were restricted to root plates of fallen trees in uncleared windfalls; here shade-tolerant tree species of the terminal forest stages established rather quickly from saplings that had already been present in the preceeding forest stand. Soil surface disturbances are identified to be causal to the management pathway of forest development, wereas the untouched pathway is caused by relatively low disturbance levels. The simulation model FORSKA-M is used to analyse different options of further stand development with a simulation time period of one hundred years.
Perennial fodder cropping potentially increases subsoil biopore density by formation of extensive root systems and temporary soil rest. We will quantify root length density, earthworm abundance and biopore size classes after Medicago sativa, Cichorium intybus and Festuca arundinacea grown for 1, 2 and 3 years respectively in the applied research unit's Central Field Trial (CeFiT) which is established and maintained by our working group. Shoot parameters including transpiration, gas exchange and chlorophyll fluorescence will frequently be recorded. Precrop effects on oilseed rape and cereals will be quantified with regard to crop yield, nutrient transfer and H2-release. The soil associated with biopores (i.e. the driloshpere) is generally rich in nutrients as compared to the bulk soil and is therefore supposed to be a potential hot spot for nutrient acquisition. However, contact areas between roots and the pore wall have been reported to be low. It is still unclear to which extent the nutrients present in the drilosphere are used and which potential relevance subsoil biopores may have for the nutrient supply of crops. We will use a flexible videoscope to determine the root-soil contact in biopores. Nitrogen input into the drilosphere by earthworms and potential re-uptake of nitrogen from the drilosphere by subsequent crops with different rooting systems (oilseed rape vs. cereals) will be quantified using 15N as a tracer.
This project focuses on the long-term stability (or otherwise) of vegetation, based on a series of multi-proxy records in southern South America. We will build a network of sites suitable for high-resolution reconstructions of changes in vegetation since the Last Glacial Maximum, and use these to test a null hypothesis that changes in vegetation over the past 14,000 years are driven by internal dynamics rather than external forcing factors. The extent to which the null hypothesis can be falsified will reveal the degree to which we can expect to be able to predict how vegetation is affected by external events, including future climate change. The southern fringes of the South American landmass provide a rare opportunity to examine the development of moorland vegetation with sparse tree cover in a wet, cool temperate climate of the Southern Hemisphere. We present a record of changes in vegetation over the past 17,000 years, from a lake in extreme southern Chile (Isla Santa Inés, Magallanes region, 53°38.97S; 72°25.24W; Fontana, Bennett 2012: The Holocene), where human influence on vegetation is negligible. The western archipelago of Tierra del Fuego remained treeless for most of the Lateglacial period. Nothofagus may have survived the last glacial maximum at the eastern edge of the Magellan glaciers from where it spread southwestwards and established in the region at around 10,500 cal. yr BP. Nothofagus antarctica was likely the earlier colonizing tree in the western islands, followed shortly after by Nothofagus betuloides. At 9000 cal. yr BP moorland communities expanded at the expense of Nothofagus woodland. Simultaneously, Nothofagus species shifted to dominance of the evergreen Nothofagus betuloides and the Magellanic rain forest established in the region. Rapid and drastic vegetation changes occurred at 5200 cal. yr BP, after the Mt Burney MB2 eruption, including the expansion and establishment of Pilgerodendron uviferum and the development of mixed Nothofagus-Pilgerodendron-Drimys woodland. Scattered populations of Nothofagus, as they occur today in westernmost Tierra del Fuego may be a good analogue for Nothofagus populations during the Lateglacial in eastern sites. Climate, dispersal barriers and/or fire disturbance may have played a role controlling the postglacial spread of Nothofagus. Climate change during the Lateglacial and early Holocene was a prerequisite for the expansion of Nothofagus populations and may have controlled it at many sites in Tierra del Fuego. The delayed arrival at the site, with respect to the Holocene warming, may be due to dispersal barriers and/or fire disturbance at eastern sites, reducing the size of the source populations. The retreat of Nothofagus woodland after 9000 cal. yr BP may be due to competitive interactions with bog communities. Volcanic disturbance had a positive influence on the expansion of Pilgerodendron uviferum and facilitated the development of mixed Nothofagus-Pilgerodendron-Drimys woodland.
Early generation plant breeding trials are often laid out according to unreplicated designs. Replicated checks may be used for error control, for example in augmented designs based on an incomplete block design for checks which are augmented with unreplicated entries. Traditional augmented designs require considerable resources to be spent on genotypes that are not themselves of interest. Therefore, it has been suggested to replace checks with partially replicated entries, leading to so-called prep designs. In the present proposal we suggest combining both ideas to develop what we call augmented prep designs. A non-trivial design problem arises when trials are to be performed at multiple locations. The main challenge then is how to augment the blocks so as to balance the number of pairwise concurrences. This task can be tackled in different ways based on the use (-arrays which are well-known as the basis for (-designs in fully replicated experiments. Furthermore, we also explore the refinement of designs when analysis by spatial models is envisioned. Robustness of the designs to the presence of genotype-environment interaction is also investigated.
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