TY - JOUR A1 - Blüthgen, Nico A1 - Dormann, Carsten F. A1 - Prati, Daniel A1 - Klaus, Valentin H. A1 - Kleinebecker, Till A1 - Hoelzel, Norbert A1 - Alt, Fabian A1 - Boch, Steffen A1 - Gockel, Sonja A1 - Hemp, Andreas A1 - Müller, Jörg A1 - Nieschulze, Jens A1 - Renner, Swen C. A1 - Schöning, Ingo A1 - Schumacher, Uta A1 - Socher, Stephanie A. A1 - Wells, Konstans A1 - Birkhofer, Klaus A1 - Buscot, Francois A1 - Oelmann, Yvonne A1 - Rothenwöhrer, Christoph A1 - Scherber, Christoph A1 - Tscharntke, Teja A1 - Weiner, Christiane N. A1 - Fischer, Markus A1 - Kalko, Elisabeth K. V. A1 - Linsenmair, Karl Eduard A1 - Schulze, Ernst-Detlef A1 - Weisser, Wolfgang W. T1 - A quantitative index of land-use intensity in grasslands integrating mowing, grazing and fertilization JF - Basic and applied ecology : Journal of the Gesellschaft für Ökologie N2 - Land use is increasingly recognized as a major driver of biodiversity and ecosystem functioning in many current research projects. In grasslands, land use is often classified by categorical descriptors such as pastures versus meadows or fertilized versus unfertilized sites. However, to account for the quantitative variation of multiple land-use types in heterogeneous landscapes, a quantitative, continuous index of land-use intensity (LUI) is desirable. Here we define such a compound, additive LUI index for managed grasslands including meadows and pastures. The LUI index summarizes the standardized intensity of three components of land use, namely fertilization, mowing, and livestock grazing at each site. We examined the performance of the LUI index to predict selected response variables on up to 150 grassland sites in the Biodiversity Exploratories in three regions in Germany(Alb, Hainich, Schorlheide). We tested the average Ellenberg nitrogen indicator values of the plant community, nitrogen and phosphorus concentration in the aboveground plant biomass, plant-available phosphorus concentration in the top soil, and soil C/N ratio, and the first principle component of these five response variables. The LUI index significantly predicted the principal component of all five response variables, as well as some of the individual responses. Moreover, vascular plant diversity decreased significantly with LUI in two regions (Alb and Hainich). Inter-annual changes in management practice were pronounced from 2006 to 2008, particularly due to variation in grazing intensity. This rendered the selection of the appropriate reference year(s) an important decision for analyses of land-use effects, whereas details in the standardization of the index were of minor importance. We also tested several alternative calculations of a LUI index, but all are strongly linearly correlated to the proposed index. The proposed LUI index reduces the complexity of agricultural practices to a single dimension and may serve as a baseline to test how different groups of organisms and processes respond to land use. In combination with more detailed analyses, this index may help to unravel whether and how land-use intensities, associated disturbance levels or other local or regional influences drive ecological processes. KW - Agro-ecosystems KW - Biodiversity exploratories KW - Grassland management KW - Land-use impacts KW - Livestock density KW - Meadows KW - Nitrogen KW - Pastures Y1 - 2012 U6 - https://doi.org/10.1016/j.baae.2012.04.001 SN - 1439-1791 VL - 13 IS - 3 SP - 207 EP - 220 PB - Elsevier CY - Jena ER - TY - JOUR A1 - Reverey, Florian A1 - Großart, Hans-Peter A1 - Premke, Katrin A1 - Lischeid, Gunnar T1 - Carbon and nutrient cycling in kettle hole sediments depending on hydrological dynamics: a review JF - Hydrobiologia : acta hydrobiologica, hydrographica, limnologica et protistologica N2 - Kettle holes as a specific group of isolated, small lentic freshwater systems (LFS) often are (i) hot spots of biogeochemical cycling and (ii) exposed to frequent sediment desiccation and rewetting. Their ecological functioning is greatly determined by immanent carbon and nutrient transformations. The objective of this review is to elucidate effects of a changing hydrological regime (i.e., dry-wet cycles) on carbon and nutrient cycling in kettle hole sediments. Generally, dry-wet cycles have the potential to increase C and N losses as well as P availability. However, their duration and frequency are important controlling factors regarding direction and intensity of biogeochemical and microbiological responses. To evaluate drought impacts on sediment carbon and nutrient cycling in detail requires the context of the LFS hydrological history. For example, frequent drought events induce physiological adaptation of exposed microbial communities and thus flatten metabolic responses, whereas rare events provoke unbalanced, strong microbial responses. Different potential of microbial resilience to drought stress can irretrievably change microbial communities and functional guilds, gearing cascades of functional responses. Hence, dry-wet events can shift the biogeochemical cycling of organic matter and nutrients to a new equilibrium, thus affecting the dynamic balance between carbon burial and mineralization in kettle holes. KW - Drought KW - Rewetting KW - Temporary pond KW - Kettle hole KW - Organic matter KW - Nitrogen KW - Phosphorus Y1 - 2016 U6 - https://doi.org/10.1007/s10750-016-2715-9 SN - 0018-8158 SN - 1573-5117 VL - 775 SP - 1 EP - 20 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Olas, Justyna Jadwiga A1 - Apelt, Federico A1 - Watanabe, Mutsumi A1 - Höfgen, Rainer A1 - Wahl, Vanessa T1 - Developmental stage-specific metabolite signatures in Arabidopsis thaliana under optimal and mild nitrogen limitation JF - Plant science : an international journal of experimental plant biology N2 - Metabolites influence flowering time, and thus are among the major determinants of yield. Despite the reported role of trehalose 6-phosphate and nitrate signaling on the transition from the vegetative to the reproductive phase, little is known about other metabolites contributing and responding to developmental phase changes. To increase our understanding which metabolic traits change throughout development in Arabidopsis thaliana and to identify metabolic markers for the vegetative and reproductive phases, especially among individual amino acids (AA), we profiled metabolites of plants grown in optimal (ON) and limited nitrogen (N) (LN) conditions, the latter providing a mild but consistent limitation of N. We found that although LN plants adapt their growth to a decreased level of N, their metabolite profiles are strongly distinct from ON plant profiles, with N as the driving factor for the observed differences. We demonstrate that the vegetative and the reproductive phase are not only marked by growth parameters such as biomass and rosette area, but also by specific metabolite signatures including specific single AA. In summary, we identified N-dependent and -independent indicators manifesting developmental stages, indicating that the plant's metabolic status also reports on the developmental phases. KW - Amino acids KW - Floral induction KW - Flowering time KW - Nitrogen KW - Metabolites KW - Vegetative phase KW - Reproductive phase Y1 - 2021 U6 - https://doi.org/10.1016/j.plantsci.2020.110746 SN - 0168-9452 SN - 1873-2259 VL - 303 PB - Elsevier Science CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Klaus, Valentin H. A1 - Kleinebecker, Till A1 - Prati, Daniel A1 - Gossner, Martin M. A1 - Alt, Fabian A1 - Boch, Steffen A1 - Gockel, Sonja A1 - Hemp, Andreas A1 - Lange, Markus A1 - Müller, Jörg A1 - Oelmann, Yvonne A1 - Pasalic, Esther A1 - Renner, Swen C. A1 - Socher, Stephanie A. A1 - Türke, Manfred A1 - Weisser, Wolfgang W. A1 - Fischer, Markus A1 - Hölzel, Norbert T1 - Does organic grassland farming benefit plant and arthropod diversity at the expense of yield and soil fertility? JF - Agriculture, ecosystems & environment : an international journal for scientific research on the relationship of agriculture and food production to the biosphere N2 - Organic management is one of the most popular strategies to reduce negative environmental impacts of intensive agriculture. However, little is known about benefits for biodiversity and potential worsening of yield under organic grasslands management across different grassland types, i.e. meadow, pasture and mown pasture. Therefore, we studied the diversity of vascular plants and foliage-living arthropods (Coleoptera, Araneae, Heteroptera, Auchenorrhyncha), yield, fodder quality, soil phosphorus concentrations and land-use intensity of organic and conventional grasslands across three study regions in Germany. Furthermore, all variables were related to the time since conversion to organic management in order to assess temporal developments reaching up to 18 years. Arthropod diversity was significantly higher under organic than conventional management, although this was not the case for Araneae, Heteroptera and Auchenorrhyncha when analyzed separately. On the contrary, arthropod abundance, vascular plant diversity and also yield and fodder quality did not considerably differ between organic and conventional grasslands. Analyses did not reveal differences in the effect of organic management among grassland types. None of the recorded abiotic and biotic parameters showed a significant trend with time since transition to organic management, except soil organic phosphorus concentrations which decreased with time. This implies that permanent grasslands respond slower and probably weaker to organic management than crop fields do. However, as land-use intensity and inorganic soil phosphorus concentrations were significantly lower in organic grasslands, overcoming seed and dispersal limitation by re-introducing plant species might be needed to exploit the full ecological potential of organic grassland management. We conclude that although organic management did not automatically increase the diversity of all studied taxa, it is a reasonable and useful way to support agro-biodiversity. KW - Agri-environmental schemes KW - Fertilization KW - Fodder quality KW - Land-use intensity KW - Nitrogen KW - Biomass nutrient concentrations KW - Organic farming KW - Phosphorus KW - Species richness KW - Nutrient availability Y1 - 2013 U6 - https://doi.org/10.1016/j.agee.2013.05.019 SN - 0167-8809 VL - 177 IS - 3 SP - 1 EP - 9 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Reverey, Florian A1 - Ganzert, Lars A1 - Lischeid, Gunnar A1 - Ulrich, Andreas A1 - Premke, Katrin A1 - Grossart, Hans-Peter T1 - Dry-wet cycles of kettle hole sediments leave a microbial and biogeochemical legacy JF - The science of the total environment : an international journal for scientific research into the environment and its relationship with man N2 - Understanding interrelations between an environment's hydrological past and its current biogeochemistry is necessary for the assessment of biogeochemical and microbial responses to changing hydrological conditions. The question how previous dry-wet events determine the contemporary microbial and biogeochemical state is addressed in this study. Therefore, sediments exposed to the atmosphere of areas with a different hydrological past within one kettle hole, i.e. (1) the predominantly inundated pond center, (2) the pond margin frequently desiccated for longer periods and (3) an intermediate zone, were incubated with the same rewetting treatment. Physicochemical and textural characteristics were related to structural microbial parameters regarding carbon and nitrogen turnover, i.e. abundance of bacteria and fungi, denitrifiers (targeted by the nirK und nirS functional genes) and nitrate ammonifiers (targeted by the nrfA functional gene). Our study reveals that, in combination with varying sediment texture, the hydrological history creates distinct microbial habitats with defined boundary conditions within the kettle hole, mainly driven by redox conditions, pH and organic matter (OM) composition. OM mineralization, as indicated by CO2-outgassing, was most efficient in exposed sediments with a less stable hydrological past. The potential for nitrogen retention via nitrate ammonification was highest in the hydrologically rather stable pond center, counteracting nitrogen loss due to denitrification. Therefore, the degree of hydrological stability is an important factor leaving a microbial and biogeochemical legacy, which determines carbon and nitrogen losses from small lentic freshwater systems in the long term run. KW - Desiccation KW - DNRA KW - Denitrifiers KW - Organic matter mineralization KW - Carbon KW - Nitrogen Y1 - 2018 U6 - https://doi.org/10.1016/j.scitotenv.2018.01.220 SN - 0048-9697 SN - 1879-1026 VL - 627 SP - 985 EP - 996 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Hancock, Christine A1 - Wäschke, Nicole A1 - Schumacher, Uta A1 - Linsenmair, Karl Eduard A1 - Meiners, Torsten A1 - Obermaier, Elisabeth T1 - Fertilizer application decreases insect abundance on Plantago lanceolata - a large-scale experiment in three geographic regions JF - Arthropod-plant interactions : an international journal devoted to studies on interactions of insects, mites, and other arthropods with plants N2 - Humans have substantially altered the nitrogen cycle of ecosystems through the application of agricultural fertilizer. Fertilization may not only affect plant species diversity, but also insect dynamics by altering plant nitrogen supplies. We investigated the effect of experimental fertilization on the vegetation, with the ribwort plantain as the focal plant, and on higher trophic levels on differently managed grasslands throughout Germany. Over a period of 2 years, we examined two specialist herbivores and their parasitoid on Plantago lanceolata L., and the composition and structure of the surrounding vegetation. Over 70 sites in three geographic regions, within the large-scale project "German Biodiversity Exploratories", were included in the study. The model system consisted of the host plant P. lanceolata L., the monophagous weevils Mecinus labilis Herbst and M. pascuorum Gyllenhal, and their parasitoid Mesopolobus incultus Walker. Fertilization decreased plant species richness and host plant abundance, whereas it enhanced the total vegetation growth. The increased size and heigher leaf nitrogen content did not improve herbivore performance. On the contrary, the abundance of the two herbivores was decreased by fertilization. The parasitoid depended on the abundance of one of its hosts, M. pascuorum (positively density-dependent). Reduced herbivore abundance due to fertilization might be explained by a lower abundance of the host plant, a lower stalk number, and by changed patterns of host localization within higher vegetation. Fertilization negatively affected the third trophic level by cascading up via host abundance. The relationships between fertilization, surrounding vegetation and the tritrophic system were measured throughout the three regions and over the 2-year period. Our findings present consequences of intensification for a plant-herbivore-parasitoid system, and may have significant implications for the conservation of multitrophic systems in managed grasslands. KW - Fertilization KW - Nitrogen KW - Tritrophic interaction KW - Plant species richness KW - Grassland management KW - Vegetation structure Y1 - 2013 U6 - https://doi.org/10.1007/s11829-012-9237-9 SN - 1872-8855 SN - 1872-8847 VL - 7 IS - 2 SP - 147 EP - 158 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Eckert, Sebastian A1 - Mascarenhas, Eric Johnn A1 - Mitzner, Rolf A1 - Jay, Raphael Martin A1 - Pietzsch, Annette A1 - Fondell, Mattis A1 - Vaz da Cruz, Vinicius A1 - Föhlisch, Alexander T1 - From the free ligand to the transition metal complex BT - FeEDTA(-) formation seen at ligand K-Edges JF - Inorganic chemistry N2 - Chelating agents are an integral part of transition metal complex chemistry with broad biological and industrial relevance. The hexadentate chelating agent ethylenediaminetetraacetic acid (EDTA) has the capability to bind to metal ions at its two nitrogen and four of its carboxylate oxygen sites. We use resonant inelastic X-ray scattering at the 1s absorption edge of the aforementioned elements in EDTA and the iron(III)-EDTA complex to investigate the impact of the metal-ligand bond formation on the electronic structure of EDTA. Frontier orbital distortions, occupation changes, and energy shifts through metal- ligand bond formation are probed through distinct spectroscopic signatures. KW - Energy KW - Ligands KW - Metals KW - Nitrogen KW - Oxygen Y1 - 2022 U6 - https://doi.org/10.1021/acs.inorgchem.2c00789 SN - 0020-1669 SN - 1520-510X VL - 61 IS - 27 SP - 10321 EP - 10328 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Post, Joachim T1 - Integrated process-based simulation of soil carbon dynamics in river basins under present, recent past and future environmental conditions T1 - Prozessbasierte Modellierung der Bodenkohlenstoffdynamik in Flusseinzugsgebieten unter heutigen und zukünftigen Umweltbedingungen N2 - Soils contain a large amount of carbon (C) that is a critical regulator of the global C budget. Already small changes in the processes governing soil C cycling have the potential to release considerable amounts of CO2, a greenhouse gas (GHG), adding additional radiative forcing to the atmosphere and hence to changing climate. Increased temperatures will probably create a feedback, causing soils to release more GHGs. Furthermore changes in soil C balance impact soil fertility and soil quality, potentially degrading soils and reducing soils function as important resource. Consequently the assessment of soil C dynamics under present, recent past and future environmental conditions is not only of scientific interest and requires an integrated consideration of main factors and processes governing soil C dynamics. To perform this assessment an eco-hydrological modelling tool was used and extended by a process-based description of coupled soil carbon and nitrogen turnover. The extended model aims at delivering sound information on soil C storage changes beside changes in water quality, quantity and vegetation growth under global change impacts in meso- to macro-scale river basins, exemplary demonstrated for a Central European river basin (the Elbe). As a result this study: ▪ Provides information on joint effects of land-use (land cover and land management) and climate changes on croplands soil C balance in the Elbe river basin (Central Europe) presently and in the future. ▪ Evaluates which processes, and at what level of process detail, have to be considered to perform an integrated simulation of soil C dynamics at the meso- to macro-scale and demonstrates the model’s capability to simulate these processes compared to observations. ▪ Proposes a process description relating soil C pools and turnover properties to readily measurable quantities. This reduces the number of model parameters, enhances the comparability of model results to observations, and delivers same performance simulating long-term soil C dynamics as other models. ▪ Presents an extensive assessment of the parameter and input data uncertainty and their importance both temporally and spatially on modelling soil C dynamics. For the basin scale assessments it is estimated that croplands in the Elbe basin currently act as a net source of carbon (net annual C flux of 11 g C m-2 yr-1, 1.57 106 tons CO2 yr-1 entire croplands on average). Although this highly depends on the amount of harvest by-products remaining on the field. Future anticipated climate change and observed climate change in the basin already accelerates soil C loss and increases source strengths (additional 3.2 g C m-2 yr-1, 0.48 106 tons CO2 yr-1 entire croplands). But anticipated changes of agro-economic conditions, translating to altered crop share distributions, display stronger effects on soil C storage than climate change. Depending on future use of land expected to fall out of agricultural use in the future (~ 30 % of croplands area as “surplus” land), the basin either considerably looses soil C and the net annual C flux to the atmosphere increases (surplus used as black fallow) or the basin converts to a net sink of C (sequestering 0.44 106 tons CO2 yr-1 under extensified use as ley-arable) or reacts with decrease in source strength when using bioenergy crops. Bioenergy crops additionally offer a considerable potential for fossil fuel substitution (~37 PJ, 1015 J per year), whereas the basin wide use of harvest by-products for energy generation has to be seen critically although offering an annual energy potential of approximately 125 PJ. Harvest by-products play a central role in soil C reproduction and a percentage between 50 and 80 % should remain on the fields in order to maintain soil quality and fertility. The established modelling tool allows quantifying climate, land use and major land management impacts on soil C balance. New is that the SOM turnover description is embedded in an eco-hydrological river basin model, allowing an integrated consideration of water quantity, water quality, vegetation growth, agricultural productivity and soil carbon changes under different environmental conditions. The methodology and assessment presented here demonstrates the potential for integrated assessment of soil C dynamics alongside with other ecosystem services under global change impacts and provides information on the potentials of soils for climate change mitigation (soil C sequestration) and on their soil fertility status. N2 - Böden speichern große Mengen Kohlenstoff (C) und beeinflussen wesentlich den globalen C Haushalt. Schon geringe Änderungen der Steuergrößen des Bodenkohlenstoffs können dazu führen, dass beträchtliche Mengen CO2, ein Treibhausgas, in die Atmosphäre gelangen und zur globalen Erwärmung und dem Klimawandel beitragen. Der globale Temperaturanstieg verursacht dabei höchstwahrscheinlich eine Rückwirkung auf den Bodenkohlenstoffhaushalt mit einem einhergehenden erhöhten CO2 Fluss der Böden in die Atmosphäre. Weiterhin wirken sich Änderungen im Bodenkohlenstoffhaushalt auf die Bodenfruchtbarkeit und Bodenqualität aus, wobei eine Minderung der Bodenkohlenstoffvorräte wichtige Funtionen des Bodens beeinträchtigt und folglich den Boden als wichtige Ressource nachhaltig beinflusst. Demzufolge ist die Quantifizierung der Bodenkohlenstoffdynamik unter heutigen und zukünftigen Bedingungen von hohem Interesse und erfordert eine integrierte Betrachtung der wesentlichen Faktoren und Prozesse. Zur Quantifizierung wurde ein ökohydrologisches Flusseinzugsgebietsmodell erweitert. Ziel des erweiterten Modells ist es fundierte Informationen zu Veränderungen des Bodenkohlenstoffhaushaltes, neben Veränderungen der Wasserqualität, der Wasserverfügbarkeit und des Vegetationswachstums unter Globalem Wandel in meso- bis makroskaligen Flusseinzugsgebieten bereitzustellen. Dies wird am Beispiel eines zentraleuropäischen Flusseinzugsgebietes (der Elbe) demonstriert. Zusammenfassend ergibt diese Arbeit: ▪ eine Quantifizierung der heutigen und zukünftigen Auswirkungen des Klimawandels sowie von Änderungen der Landnutzung (Bodenbedeckung und Bodenbearbeitung) auf den Bodenkohlenstoffhaushalt agrarisch genutzter Räume im Einzugsgebiet der Elbe. ▪ eine Beurteilung welche Prozesse, und zu welchem Prozessdetail, zur integrierten Simulation der Bodenkohlenstoffdynamik in der meso- bis makroskala zu berücksichtigen sind. Weiterhin wird die Eignung der Modellerweiterung zur Simulation dieser Prozesse unter der Zuhilfenahme von Messwerten dargelegt. ▪ darauf begründet wird eine Prozessbeschreibung vorgeschlagen die die Eigenschaften der Bodenkohlenstoffspeicher und deren Umsetzungsrate mit in der betrachteten Skala zur Verfügung stehenden Messdaten und Geoinformationen verbindet. Die vorgeschlagene Prozessbeschreibung kann als robust hinsichtlich der Parametrisierung angesehen werden, da sie mit vergleichsweise wenigen Modelparametern eine ähnliche Güte wie andere Bodenkohlenstoffmodelle ergibt. ▪ eine umfassende Betrachtung der Modell- und Eingangsdatenunsicherheiten von Modellergebnissen in ihrer räumlichen und zeitlichen Ausprägung. Das in dieser Arbeit vorgestellte Modellsystem erlaubt eine Quantifizierung der Auswirkungen des Klima- und Landnutzungswandels auf den Bodenkohlenstoffhaushalt. Neu dabei ist, dass neben Auswirkungen auf den Bodenkohlenstoffhaushalt auch Auswirkungen auf Wasserverfügbarkeit, Wasserqualität, Vegetationswachstum und landwirtschaftlicher Produktivität erfasst werden können. Die im Rahmen dieser Arbeit dargelegten Ergebnisse erlauben eine integrierte Betrachtung der Auswirkungen des Globalen Wandels auf wichtige Ökosystemfunktionen in meso- bis makro-skaligen Flusseinzugsgebieten. Weiterhin können hier gewonnene Informationen zur Potentialabschätzung der Böden zur Linderung des Klimawandels (durch C Festlegung) und zum Erhalt ihrer Fruchtbarkeit genutzt werden. KW - Kohlenstoff KW - Stickstoff KW - Anthropogene Klimaänderung KW - Bioenergie KW - Unsicherheit KW - Ökohydrologie KW - Ökosystemmodellierung KW - Landnutzungsänderung KW - Modellsensitivität KW - eco-hydrology KW - Ecosystem modelling KW - Carbon KW - Nitrogen KW - land use change KW - climate change KW - terrestrial carbon balance KW - model uncertainty Y1 - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-11507 ER - TY - JOUR A1 - Schmidt, Martin A1 - Lischeid, Gunnar A1 - Nendel, Claas T1 - Microclimate and matter dynamics in transition zones of forest to arable land JF - Agricultural and forest meteorology N2 - Human-driven fragmentation of landscapes leads to the formation of transition zones between ecosystems that are characterised by fluxes of matter, energy and information. These transition zones may offer rather inhospitable habitats that could jeopardise biodiversity. On the other hand, transition zones are also reported to be hotspots for biodiversity and even evolutionary processes. The general mechanisms and influence of processes in transition zones are poorly understood. Although heterogeneity and diversity of land use of fragments and the transition zones between them play an important role, most studies only refer to forested transition zones. Often, only an extrapolation of measurements in the different fragments themselves is reported to determine gradients in transition zones. This paper contributes to a quantitative understanding of agricultural landscapes beyond individual ecotopes, and towards connected ecosystem mosaics that may be beneficial for the provision of ecosystem services. KW - Edge effects KW - Environmental gradients KW - Fragmentation KW - Ecosystem services KW - Carbon KW - Nitrogen Y1 - 2019 U6 - https://doi.org/10.1016/j.agrformet.2019.01.001 SN - 0168-1923 SN - 1873-2240 VL - 268 SP - 1 EP - 10 PB - Elsevier CY - Amsterdam ER - TY - THES A1 - Wriedt, Gunter T1 - Modelling of nitrogen transport and turnover during soil and groundwater passage in a small lowland catchment of Northern Germany N2 - Stoffumsatzreaktionen und hydraulische Prozesse im Boden und Grundwasser können in Tieflandeinzugsgebieten zu einer Nitratretention führen. Die Untersuchung dieser Prozesse in Raum und Zeit kann mit Hilfe geeigneter Modelle erfolgen. Ziele dieser Arbeit sind: i) die Entwicklung eines geeigneten Modellansatzes durch Kombination von Teilmodellen zur Simulation des N-Transportes im Boden und Grundwasser von Tieflandeinzugsgebieten und ii) die Untersuchung von Wechselwirkungen zwischen Gebietseigenschaften und N-Transport unter besonderer Berücksichtigung der potentiellen N-Zufuhr in die Oberflächengewässer. Der Modellansatz basiert auf der Kombination verschiedener Teilmodelle: das Bodenwasser- und -stickstoffmodell mRISK-N, das Grundwassermodell MODFLOW und das Stofftransportmodell RT3D. Zur Untersuchung der Wechselwirkungen mit den Gebietseigenschaften muss die Verteilung und Verfügbarkeit von Reaktionspartnern berücksichtigt werden. Dazu wurde ein Reaktionsmodul entwickelt, welches chemische Prozesse im Grundwasser simuliert. Hierzu gehören die Mineralisation organischer Substanz durch Sauerstoff, Nitrat und Sulfat sowie die Pyritoxidation durch Sauerstoff und Nitrat. Der Modellansatz wurde in verschiedenen Einzelstudien angewandt, wobei jeweils bestimmte Teilmodelle im Vordergrund stehen. Alle Modellstudien basieren auf Daten aus dem Schaugrabeneinzugsgebiet (ca. 25 km²), in der Nähe von Osterburg(Altmark) im Norden Sachsen-Anhalts. Die folgenden Einzelstudien wurden durchgeführt: i) Evaluation des Bodenmodells anhand von Lysimeterdaten, ii) Modellierung eines Tracerexperimentes im Feldmaßstab als eine erste Anwendung des Reaktionsmoduls, iii) Untersuchung hydraulisch-chemischer Wechselwirkungen an einem 2D-Grundwassertransekt, iv) Flächenverteilte Modellierung von Grundwasserneubildung und Bodenstickstoffaustrag im Untersuchungsgebiet als Eingangsdaten für nachfolgende Grundwassersimulationen, und v) Untersuchung der Ausbreitung von Nitrat im Grundwasser und des Durchbruchs in die Oberflächengewässer im Untersuchungsgebiet auf Basis einer 3D-Modellierung von Grundwasserströmung und reaktivem Stofftransport. Die Modellstudien zeigen, dass der Modellansatz geeignet ist, die Wechselwirkungen zwischen Stofftransport und –umsatz und den hydraulisch-chemischen Gebietseigenschaften zu modellieren. Die Ausbreitung von Nitrat im Sediment wird wesentlich von der Verfügbarkeit reaktiver Substanzen sowie der Verweilzeit im Grundwasserleiter bestimmt. Bei der Simulation des Untersuchungsgebietes wurde erst nach 70 Jahren eine der gegebenen Eintragssitutation entsprechende Nitratkonzentration im Grundwasserzustrom zum Grabensystem erreicht (konservativer Transport). Die Berücksichtigung von reaktivem Stofftransport führt zu einer deutlichen Reduktion der Nitratkonzentrationen. Die Modellergebnisse zeigen, dass der Grundwasserzustrom die beobachtete Nitratbelastung im Grabensystem nicht erklären kann, da der Großteil des Nitrates durch Denitrifikation verloren geht. Andere Quellen, wie direkte Einträge oder Dränagenzuflüsse müssen ebenfalls in Betracht gezogen werden. Die Prognosefähigkeit des Modells für das Untersuchungsgebiet wird durch die Datenunsicherheiten und die Schätzung der Modellparameter eingeschränkt. Dennoch ist der Modellansatz eine wertvolle Hilfe bei der Identifizierung von belastungsrelevanten Teilflächen (Stoffquellen und -senken) sowie bei der Modellierung der Auswirkungen von Managementmaßnahmen oder Landnutzungsveränderungen auf Grundlage von Szenario-Simulationen. Der Modellansatz unterstützt auch die Interpretation von Beobachtungsdaten, da so die lokalen Informationen in einen räumlichen und zeitlichen Zusammenhang gestellt werden können. N2 - Chemical transformations and hydraulic processes in soil and groundwater often lead to an apparent retention of nitrate in lowland catchments. Models are needed to evaluate the interaction of these processes in space and time. The objectives of this study are i) to develop a specific modelling approach by combining selected modelling tools simulating N-transport and turnover in soils and groundwater of lowland catchments, ii) to study interactions between catchment properties and nitrogen transport. Special attention was paid to potential N-loads to surface waters. The modelling approach combines various submodels for water flow and solute transport in soil and groundwater: The soil-water- and nitrogen-model mRISK-N, the groundwater flow model MODFLOW and the solute transport model RT3D. In order to investigate interactions of N-transport and catchment characteristics, the distribution and availability of reaction partners have to be taken into account. Therefore, a special reaction-module is developed, which simulates various chemical processes in groundwater, such as the degradation of organic matter by oxygen, nitrate, sulphate or pyrite oxidation by oxygen and nitrate. The model approach is applied to different simulation, focussing on specific submodels. All simulation studies are based on field data from the Schaugraben catchment, a pleistocene catchment of approximately 25 km², close to Osterburg(Altmark) in the North of Saxony-Anhalt. The following modelling studies have been carried out: i) evaluation of the soil-water- and nitrogen-model based on lysimeter data, ii) modelling of a field scale tracer experiment on nitrate transport and turnover in the groundwater as a first application of the reaction module, iii) evaluation of interactions between hydraulic and chemical aquifer properties in a two-dimensional groundwater transect, iv) modelling of distributed groundwater recharge and soil nitrogen leaching in the study area, to be used as input data for subsequent groundwater simulations, v) study of groundwater nitrate distribution and nitrate breakthrough to the surface water system in the Schaugraben catchment area and a subcatchment, using three-dimensional modelling of reactive groundwater transport. The various model applications prove the model to be capable of simulating interactions between transport, turnover and hydraulic and chemical catchment properties. The distribution of nitrate in the sediment and the resulting loads to surface waters are strongly affected by the amount of reactive substances and by the residence time within the aquifer. In the Schaugraben catchment simulations, it is found that a period of 70 years is needed to raise the average seepage concentrations of nitrate to a level corresponding to the given input situation, if no reactions are considered. Under reactive transport conditions, nitrate concentrations are reduced effectively. Simulation results show that groundwater exfiltration does not contribute considerably to the nitrate pollution of surface waters, as most nitrate entering soils and groundwater is lost by denitrification. Additional sources, such as direct inputs or tile drains have to be taken into account to explain surface water loads. The prognostic value of the models for the study site is limited by uncertainties of input data and estimation of model parameters. Nevertheless, the modelling approach is a useful aid for the identification of source and sink areas of nitrate pollution as well as the investigation of system response to management measures or landuse changes with scenario simulations. The modelling approach assists in the interpretation of observed data, as it allows to integrate local observations into a spatial and temporal framework. KW - Stickstoff KW - Nitrat KW - Modellierung KW - Grundwasser KW - Einzugsgebiet KW - Reaktiver Stofftransport KW - Denitrifikation KW - Nitrogen KW - Nitrate KW - modelling KW - groundwater KW - catchment KW - reactive transport KW - denitrification Y1 - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001307 ER - TY - JOUR A1 - Klaus, Valentin H. A1 - Kleinebecker, Till A1 - Boch, Steffen A1 - Müller, Jörg A1 - Socher, Stephanie A. A1 - Prati, Daniel A1 - Fischer, Markus A1 - Hoelzel, Norbert T1 - NIRS meets Ellenberg's indicator values prediction of moisture and nitrogen values of agricultural grassland vegetation by means of near-infrared spectral characteristics JF - Ecological indicators : integrating monitoring, assessment and management N2 - Ellenberg indicator values are widely used ecological tools to elucidate relationships between vegetation and environment in ecological research and environmental planning. However, they are mainly deduced from expert knowledge on plant species and are thus subject of ongoing discussion. We researched if Ellenberg indicator values can be directly extracted from the vegetation biomass itself. Mean Ellenberg "moisture" (mF) and "nitrogen" (mN) values of 141 grassland plots were related to nutrient concentrations, fibre fractions and spectral information of the aboveground biomass. We developed calibration models for the prediction of mF and mN using spectral characteristics of biomass samples with near-infrared reflectance spectroscopy (NIRS). Prediction goodness was evaluated with internal cross-validations and with an external validation data set. NIRS could accurately predict Ellenberg mN, and with less accuracy Ellenberg mF. Predictions were not more precise for cover-weighted Ellenberg values compared with un-weighted values. Both Ellenberg mN and mF showed significant and strong correlations with some of the nutrient and fibre concentrations in the biomass. Against expectations, Ellenberg mN was more closely related to phosphorus than to nitrogen concentrations, suggesting that this value rather indicates productivity than solely nitrogen. To our knowledge we showed for the first time that mean Ellenberg indicator values could be directly predicted from the aboveground biomass, which underlines the usefulness of the NIRS technology for ecological studies, especially in grasslands ecosystems. KW - Biodiversity exploratories KW - Cover-weighting KW - Near-infrared reflectance spectroscopy (NIRS) KW - Nitrogen KW - Nutrient concentrations KW - Phosphorus Y1 - 2012 U6 - https://doi.org/10.1016/j.ecolind.2011.07.016 SN - 1470-160X VL - 14 IS - 1 SP - 82 EP - 86 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Balcke, Gerd U. A1 - Hahn, M. A1 - Oswald, Sascha T1 - Nitrogen as an indicator of mass transfer during in-situ gas sparging JF - Journal of contaminant hydrology N2 - Aiming at the stimulation of intrinsic microbial activity, pulses of pure oxygen or pressurized air were recurrently injected into groundwater polluted with chlorobenzene. To achieve well-controlled conditions and intensive sampling, a large, vertical underground tank was filled with the local unconfined sandy aquifer material. In the course of two individual gas injections, one using pure oxygen and one using pressurized air, the mass transfer of individual gas species between trapped gas phase and groundwater was studied. Field data on the dissolved gas composition in the groundwater were combined with a kinetic model on gas dissolution and transport in porous media. Phase mass transfer of individual gas components caused a temporary enrichment of nitrogen, and to a lower degree of methane, in trapped gas leading to the formation of excess dissolved nitrogen levels downgradient from the dissolving gas phase. By applying a novel gas sampling method for dissolved gases in groundwater it was shown that dissolved nitrogen can be used as a partitioning tracer to indicate complete gas dissolution in porous media. KW - Inter-phase mass transfer KW - Groundwater KW - Remediation KW - Gas sparging KW - Nitrogen KW - Methane KW - Kinetics KW - Bitterfeld Y1 - 2011 U6 - https://doi.org/10.1016/j.jconhyd.2011.05.005 SN - 0169-7722 VL - 126 IS - 1-2 SP - 8 EP - 18 PB - Elsevier CY - Amsterdam ER - TY - THES A1 - Czechowski, Tomasz T1 - Nitrogen signalling in Arabidopsis thaliana T1 - Stickstoff Signalling in Arabidopsis thaliana N2 - Nitrogen is an essential macronutrient for plants and nitrogen fertilizers are indispensable for modern agriculture. Unfortunately, we know too little about how plants regulate their use of soil nitrogen, to maximize fertilizers-N use by crops and pastures. This project took a dual approach, involving forward and reverse genetics, to identify N-regulators in plants, which may prove useful in the future to improve nitrogen-use efficiency in agriculture. To identify nitrogen-regulated transcription factor genes in Arabidopsis that may control N-use efficiency we developed a unique resource for qRT-PCR measurements on all Arabidpsis transcription factor genes. Using closely spaced, gene-specific primer pairs and SYBR® Green to monitor amplification of double-stranded DNA, transcript levels of 83% of all target genes could be measured in roots or shoots of young Arabidopsis wild-type plants. Only 4% of reactions produced non-specific PCR products, and 13% of TF transcripts were undetectable in these organs. Measurements of transcript abundance were quantitative over six orders of magnitude, with a detection limit equivalent to one transcript molecule in 1000 cells. Transcript levels for different TF genes ranged between 0.001-100 copies per cell. Real-time RT-PCR revealed 26 root-specific and 39 shoot-specific TF genes, most of which have not been identified as organ-specific previously. An enlarged and improved version of the TF qRT-PCR platform contains now primer pairs for 2256 Arabidopsis TF genes, representing 53 gene families and sub-families arrayed on six 384-well plates. Set-up of real-time PCR reactions is now fully robotized. One researcher is able to measure expression of all 2256 TF genes in a single biological sample in a just one working day. The Arabidopsis qRT-PCT platform was successfully used to identify 37 TF genes which transcriptionaly responded at the transcriptional level to N-deprivation or to nitrate per se. Most of these genes have not been characterized previously. Further selection of TF genes based on the responses of selected candidates to other macronutrients and abiotic stresses allowed to distinguish between TFs regulated (i) specifically by nitrogen (29 genes) (ii) regulated by general macronutrient or by salt and osmotic stress (6 genes), and (iii) responding to all major macronutrients and to abiotic stresses. Most of the N-regulated TF genes were also regulated by carbon. Further characterization of sixteen selected TF genes, revealed: (i) lack of transcriptional response to organic nitrogen, (ii) two major types of kinetics of induction by nitrate, (iii) specific responses for the majority of the genes to nitrate but not downstream products of nitrate assimilation. All sixteen TF genes were cloned into binary vectors for constitutive and ethanol inducible over expression, and the first generation of transgenic plants were obtained for almost all of them. Some of the plants constitutively over expressing TF genes under control of the 35S promoter revealed visible phenotypes in T1 generation. Homozygous T-DNA knock out lines were also obtained for many of the candidate TF genes. So far, one knock out line revealed a visible phenotype: retardation of flowering time. A forward genetic approach using an Arabidopsis ATNRT2.1 promoter : Luciferase reporter line, resulted in identification of eleven EMS mutant reporter lines affected in induction of ATNRT2.1 expression by nitrate. These lines could by divided in the following classes according to expression of other genes involved in primary nitrogen and carbon metabolism: (i) lines affected exclusively in nitrate transport, (ii) those affected in nitrate transport, acquisition, but also in glycolysis and oxidative pentose pathway, (iii) mutants affected moderately in nitrate transport, oxidative pentose pathway and glycolysis but not in primary nitrate assimilation. Thus, several different N-regulatory genes may have been mutated in this set of mutants. Map-based cloning has begun to identify the genes affected in these mutants. N2 - Stickstoff ist einer der wichtigsten Makroelemente in der Natur und sein eingeschränktes Vorkommen ist häufig ein limitierender Faktor für pflanzliches Wachstum. In der Landwirtschaft eingesetzte Stickstoff-Dünger werden häufig nicht vollständig von Getreide- oder anderen kultivierten Pflanzen genutzt, sondern in die umliegenden Gewässer oder das Grundwasser ausgewaschen. Das Verständnis von pflanzlichen Signalprozessen kann helfen, Stickstoffaufnahme und -assimilation zu kontrollieren und somit den Einsatz von stickstoffhaltigen Düngemitteln in der Landwirtschaft zu reduzieren. Die meisten der in den pflanzlichen Stickstoffstoffwechsel involvierten Gene werden auf Transkriptionsebene reguliert. Dies geschieht durch sogenannte Transkriptionsfaktoren (TFs), Proteine, die von Genen anderer Genfamilien kodiert werden. Im Rahmen dieser Promotion wurde eine einzigartige und neue Ressource zur Quantifizierung der Expressionsniveaus solcher Transkriptionsfaktoren der Modellpflanze Arabidopsis thaliana entwickelt und getestet. Dabei konnte die beispiellose Robustheit, Genauigkeit und Präzision dieser PCR-basierten Methode gezeigt werden. Mit Hilfe dieses experimentellen Aufbaus wurden Transkriptionsfaktoren, potentielle Regulatoren von Genen, die in Stickstoffmetabolismus involviert sind, identifiziert und charakterisiert. Um die Funktionsweise dieser Gene besser zu verstehen, wurden transgene Pflanzen erzeugt und identifiziert, die entweder erhöhte oder chemisch induzierbare Transkription und/oder einen partiellen oder vollständigen Verlust der Aktivität dieser Gene aufweisen. Die Analyse der Transkriptionsfaktoren, die unter die Kontrolle eines induzierbaren Promoters gestellt wurden, soll helfen, die genauen Zielgene dieser TFs zu identifizieren und ihre Rolle im Stickstoffmetabolismus zu erklären. Darüber hinaus bieten sie die Chance, Hierarchieebenen innerhalb der verschiedenen TFs zu erkennen. Überexpression von Transkriptionsfaktoren kann zur Generierung von Phänotypen führen, die von direktem biotechnologischen Interesse sind, wie z.B. Pflanzen mit erhöhtem Stickstoffgehalt (Aminosäuregehalt), die besser an Situationen mit Stickstoffmangel angepasst sind. Neben diesen Transkriptionsfaktoren wurden allerdings auch Mutanten mit einem genetischen Defekt in einem der wichtigsten Gene, das für den Nitrattransport in Wurzeln von Arabidopsis verantwortlich ist, identifiziert. KW - Stickstoff KW - Schmalwand KW - Transkriptionsfaktor KW - qRT-PCR KW - Nitrogen KW - Arabidopsis KW - Transcription facotrs KW - qRT-PCR Y1 - 2005 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-5445 ER - TY - JOUR A1 - Klaus, Valentin H. A1 - Kleinebecker, Till A1 - Hoelzel, Norbert A1 - Bluethgen, Nico A1 - Boch, Steffen A1 - Müller, Jörg A1 - Socher, Stephanie A. A1 - Prati, Daniel A1 - Fischer, Markus T1 - Nutrient concentrations and fibre contents of plant community biomass reflect species richness patterns along a broad range of land-use intensities among agricultural grasslands JF - Perspectives in plant ecology, evolution and systematics N2 - Understanding changes in biodiversity in agricultural landscapes in relation to land-use type and intensity is a major issue in current ecological research. In this context nutrient enrichment has been identified as a key mechanism inducing species loss in Central European grassland ecosystems. At the same time, insights into the linkage between agricultural land use and plant nutrient status are largely missing. So far, studies on the relationship between chemical composition of plant community biomass and biodiversity have mainly been restricted to wetlands and all these studies neglected the effects of land use. Therefore, we analyzed aboveground biomass of 145 grassland plots covering a gradient of land-use intensities in three regions across Germany. In particular, we explored relationships between vascular plant species richness and nutrient concentrations as well as fibre contents (neutral and acid detergent fibre and lignin) in the aboveground community biomass. We found the concentrations of several nutrients in the biomass to be closely linked to plant species richness and land use. Whereas phosphorus concentrations increased with land-use intensity and decreased with plant species richness, nitrogen and potassium concentrations showed less clear patterns. Fibre fractions were negatively related to nutrient concentrations in biomass, but hardly to land-use measures and species richness. Only high lignin contents were positively associated with species richness of grasslands. The N:P ratio was strongly positively related to species richness and even more so to the number of endangered plant species, indicating a higher persistence of endangered species under P (co-)limited conditions. Therefore, we stress the importance of low P supply for species-rich grasslands and suggest the N:P ratio in community biomass to be a useful proxy of the conservation value of agriculturally used grasslands. KW - Biodiversity exploratories KW - Fertilization KW - Grazing KW - Land use KW - Mowing KW - Nitrogen KW - Nutrient limitation KW - Phosphorus KW - Productivity Y1 - 2011 U6 - https://doi.org/10.1016/j.ppees.2011.07.001 SN - 1433-8319 VL - 13 IS - 4 SP - 287 EP - 295 PB - Elsevier CY - Jena ER - TY - JOUR A1 - Leuschner, Christoph A1 - Wulf, Monika A1 - Bäuchler, Patricia A1 - Hertel, Dietrich T1 - Soil C and nutrient stores under Scots pine afforestations compared to ancient beech forests in the German Pleistocene - the role of tree species and forest history JF - Forest ecology and management N2 - In the diluvial lowlands of northern Germany, the Netherlands and northern Poland, an estimated similar to 5 Mio ha of Scots pine plantations (Pinus sylvestris) has been established on sandy soil in the last 250 years replacing the former temperate broad-leaved forests after extended periods of cultivation in the Middle Ages. We examined the effect of variable stand continuity of pine plantations (recent vs. ancient: 51-128 vs. >230 years) on the soil organic carbon (SOC) store and soil nutrient capital in comparison to ancient beech forests (>230 years of continuity) which represent the potential natural forest vegetation. Recent and ancient pine stands had c. 75% larger organic layer C stores than ancient beech forests, while the total C stock in the soil (organic layer and mineral soil to 100 cm) was similar to 25% larger in the beech forests due to higher C concentrations in 0-50 cm depth of the mineral soil. The soil stores of N-tot were similar to 50% and the exchangeable Ca, K and Mg pools about three times larger under beech than under the pine stands. Resin-exchangeable P was enriched in the soils under ancient pine stands probably due to manuring in the past. After clear-cut and long cultivation, it may take >230 years of forest presence to restore the greatly reduced mineral soil C and N pools. The C and N sequestration potential of the soils appeared to be particularly small under pine indicating a pronounced tree species (pine vs. beech) effect on soil C and N dynamics. We conclude that, in the face of rising greenhouse gas emissions, the limited soil C and nutrient storage potential of Scots pine plantations on sandy soils needs consideration when selecting suitable tree species for future forestry. (C) 2013 Elsevier B.V. All rights reserved. KW - Sandy soil KW - Pinus sylvestris KW - Fagus sylvatica KW - Forest continuity KW - Historic land use KW - Nitrogen Y1 - 2013 U6 - https://doi.org/10.1016/j.foreco.2013.08.043 SN - 0378-1127 SN - 1872-7042 VL - 310 IS - 6 SP - 405 EP - 415 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - López-Tarazón, José Andrés A1 - Lopez, Pilar A1 - Lobera, Gemma A1 - Batalla Villanueva, Ramon J. T1 - Suspended sediment, carbon and nitrogen transport in a regulated Pyrenean river JF - The science of the total environment : an international journal for scientific research into the environment and its relationship with man N2 - Regulation alters the characteristics of riversty transforming parts of them into lakes, affecting their hydrology and also the physical, chemical, and biological characteristics and dynamics. Reservoirs have proven to be very effective retaining particulate materials, thereby avoiding the downstream transport of suspended sediment and the chemical substances associated with it (e.g. Carbon, C or Nitrogen, N). The study of fluvial transport of C and N is of great interest since river load represents a major link to the global C and N cycles. Moreover, reservoirs are the most important sinks for organic carbon among inland waters and have a potential significance as nitrogen sinks. In this respect, this paper investigates the effects of a Pyrenean reservoir on the runoff, suspended sediment, C and N derived from the highly active Esera and Isabena rivets. Key findings indicate that the reservoir causes a considerable impact on the Esera-Isabena river fluxes, reducing them dramatically as almost all the inputs are retained within the reservoir. Despite the very dry study year (2011-2012), it can be calculated that almost 300,000 t of suspended sediment were deposited into the Barasona Reservoir, from which more than 16,000 were C (i.e. 2200 t as organic C) and 222 t were N. These values may not be seen as remarkable in a wider global context but, assuming that around 30 hm(3) of sediment are currently stored in the reservoir, figures would increase up to ca. 2.6 x 10(6) t of C (i.e. 360,000 t of organic C) and 35,000 t of N. Nevertheless, these values are indicative and should be treated with caution as there is incomplete understanding of all the processes which affect C and N. Further investigation to establish a more complete picture of C and N yields and budgets by monitoring the different processes involved is essential. (C) 2015 Elsevier B.V. All rights reserved. KW - Suspended sediment KW - Carbon KW - Nitrogen KW - Temporal dynamics KW - Barasona Reservoir KW - River Esera KW - Ebro basin Y1 - 2016 U6 - https://doi.org/10.1016/j.scitotenv.2015.06.132 SN - 0048-9697 SN - 1879-1026 VL - 540 SP - 133 EP - 143 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Vaz da Cruz, Vinicius A1 - Büchner, Robby A1 - Fondell, Mattis A1 - Pietzsch, Annette A1 - Eckert, Sebastian A1 - Föhlisch, Alexander T1 - Targeting individual tautomers in equilibrium by resonant inelastic X-ray scattering JF - The journal of physical chemistry letters N2 - Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the pi and sigma manifolds at the proton-transfer site. KW - Equilibrium KW - Molecular structure KW - Molecules KW - Nitrogen KW - Solvents Y1 - 2022 U6 - https://doi.org/10.1021/acs.jpclett.1c03453 SN - 1948-7185 VL - 13 IS - 10 SP - 2459 EP - 2466 PB - American Chemical Society CY - Washington ER -