A restauração ecológica visa o estabelecimento de ecossistemas semelhantes aos que originalmente ocupavam uma determinada área que foi degradada. Todavia, os resultados dos esforços envolvidos na restauração e no retorno dos processos ecológicos naturais são difíceis de serem medidos, pois faltam métodos apropriados. Os bioindicadores são ferramentas baratas e confiáveis para o diagnóstico das características ambientais e ecológicas, cujo princípio consiste em medidas simples de grupos biológicos especialmente sensíveis às mudanças no meio. Os Arthropoda que ocorrem no solo e na serapilheira, em especial as formigas, mediam processos ecológicos importantes e apresentam características que os tornam bioindicadores potenciais, mas seu uso ainda necessita de conhecimentos específicos. Assim, o presente estudo teve como objetivo testar o potencial indicador da comunidade de Arthropoda edáfico-epígea na restauração ecológica, com maior enfoque sobre as formigas. Foram avaliadas as comunidades de um gradiente sucessional formado por doze reflorestamentos com diferentes idades e três remanescentes florestais, localizados nas bacias dos rios Pardo e Mogi-Guaçu. O objetivo foi identificar quais os parâmetros que melhor refletem a resposta dessas comunidades ao desenvolvimento florestal. Os resultados indicaram que tanto a mirmecofauna como o restante da comunidade são influenciadas pelos estádios de desenvolvimento florestal. As comunidades variaram em composição e estrutura. A evolução das comunidades mostrou-se direcional, formando um padrão convergente de acordo com o avanço da sucessão. Os resultados indicaram forte efeito da sazonalidade e das técnicas de coleta na interpretação dos resultados. A comunidade edáfico-epígea encontrada no período seco mostrou-se especialmente sensível ao desenvolvimento florestal, enquanto a resposta da mirmecofauna foi mais evidente durante o período chuvoso. Os resultados indicaram também que as comunidades de diferentes regiões, Mogi-Guaçu e Ribeirão Preto, responderam ao processo sucessional, embora tenham apresentado diferenças na composição e no padrão de resposta. As análises com formigas classificadas em grupos funcionais indicaram que a resposta da mirmecofauna ao desenvolvimento florestal ocorre também no nível funcional. As mudanças nos padrões da comunidade e seus módulos estão relacionadas às mudanças nos filtros ambientais e à disponibilidade de nichos. Em conclusão, (1) a riqueza de espécies da fauna edáfico-epígea encontrada na serapilheira do período seco foi um bom preditor geral do desenvolvimento florestal; (2) a riqueza de grupos raros proporcionou o melhor modelo de prognóstico do estádio sucessional, indicando ainda que os reflorestamentos tendem a atingir patamares semelhantes aos encontrados nos remanescentes florestais por volta dos 27 anos após o plantio; (3) na comunidade edáfico-epígea, o avanço no desenvolvimento florestal levou à convergência entre padrões de composição, (4) enquanto na mirmecofauna a convergência ocorreu para os padrões de estrutura, sendo que em ambos os casos (3 e 4), quanto mais avançado o estádio sucessional, mais parecidos entre si são os padrões de locais diferentes; (5) a Equabilidade J das formigas amostradas por iscas decresceu ao longo do desenvolvimento florestal, sendo considerado também um indicador do processo sucessional (6) as classificações funcionais das formigas também permitiram boa predição dos estádios sucessionais, com destaque para formigas capturadas com iscas quando classificadas pelo sistema proposto por Andersen (1995), devido a boa relação custo/benefício. Portanto, foi confirmado o potencial bioindicador da mirmecofauna de comunidade edáfico-epígea geral, que podem ser utilizados como ferramentas de diagnóstico e monitoramento do processo sucessional. O uso mais apropriado deve ser feito por métodos comparativos, através de parâmetros provenientes de ecossistemas referência, ou por medidas repetidas ao longo do tempo, pela observação do deslocamento dos padrões da comunidade e interpretação da proporção dos grupos. / Ecological restoration objective is to promote the return of chemical, physical and biological natural properties as those similar to the native features as possible. However, the restoration projects cannot be well evaluated due to the fact that there are no appropriated tools to do that. Plantations using native species are a prominent technique used in São Paulo state, promoting the fast rising of a plant community, but it is very expensive and hard to measure if ecological processes are returning. Bioindicators are cheap tools to evaluate environmental conditions and ecological processes because they respond to all ecosystem characteristics acting together and the responses of a single group make possible to infer properties of the total biodiversity or the full ecosystem health. Epigeic and hipogeic Arthropoda, especially ants, are potential bioindicators, due to their high abundance, ubiquitousness and their straight relationship to some important ecological processes, even to other community components, but they have not been used because it lacks information about the local scale responses to successional process and which standards can be used as parameters. Hence, we have tried to understand the main standards and responses from soil and litter community, as well as the mirmecofauna responses, under a successional gradient constituted by twelve planted forests in different ages and three forest remainders (semi-deciduous forest), all located at the hydrographic basins, Pardo and Mogi-Guaçu, searching for trustful bioindicators of forest development. General fauna was sampled from litter and soil and ants were additionally sampled by attractive baits, using glucose and sardine. Results have showed that forest development makes influence on structure and composition of general communities and ant communities found in restoration sites, so that over time, these community parameters progressively have become more similar to those found in forest remainders, consisting in a directional shifting. Epigeic and hipogeic general fauna showed to be more sensitive to forest development through dry season, while ants presented critical responses in wet season. Communities from different regions were influenced by successional process but they have presented differences among fauna compositions. The analyses using ants classified in functional groups indicated that forest development makes influence also on fauna functional pattern. Groups occupying specialized niches tend to increase their relative amount throughout forest development. The shifting of ant community functionality may be related to changes in environmental filters plus the increase of niche availability through forest development. As conclusions, under experiment features (1) species richness of litter fauna of dry season is a good predictor of forest development; (2) the richness of rare taxa allowed the best prognosis about sucessional stage, also indicating that fauna found in forest plantations reaches similar fauna standards of forest remainders close to 27 years after the deployment; (3) over time, the composition of general edaphic-epigeic community found in restoration sites becomes more similar to composition of communities found in forest remainders, (4) while for ant communities, the structure standards found in restoration sites progressively become more similar of respective parameter found in forest remainders. (5) the Equitability J of ants communities sampled using baits decreases over forest development and it may be considered a bioindicator of sucessional process; (6) ant functional groups also provided good prediction of sucessional stages, highlighting ant sampling using baits and ant functional classification according to Andersen (1995), due to best benefit-cost ratio. For appropriated application of all bioindicators, the use of comparative techniques may be considered, including ecosystem references, and rather than it uses fixed values of fauna parameters (as fixed goals to be achieved), it is better to consider which parameters of the community are changing over time and if their tendencies are in accordance to the expected.

Ce travail est axé sur l’étude d’un profil de sol et des solutions de sol prélevés sur une parcelle expérimentale couvertes d’épicéas. Tous ces échantillons proviennent du Bassin Versant du Strengbach (Observatoire HydroGéochimique de l’Environnement – OHGE), ont été échantillonnés à différentes profondeurs (5, 10, 30 et 60 cm) et durant la période comprise entre 2009 et 2013.Les caractérisations des extraits des sols par spectroscopie Infra-Rouge ont permis de mettre en évidence les modifications des groupements fonctionnels organiques avec la profondeur et que ces modifications ont une forte incidence sur le comportement des cations (majeurs et traces) dans le sol. Des expérimentations d’ultra-filtration ont permis d’identifier les flux colloïdaux et dissous du carbone organique ainsi que ceux des éléments majeurs et traces présents dans les solutions de sol. L’utilisation conjointe des traceurs isotopiques (87Sr/86Sr et δ44/40Ca) et chimiques (Terres Rares) ont mis en évidence des processus ayant lieu aux interfaces eau-sol-plante, comme le prélèvement racinaire ou l’altération des sols. / This work is focused on the study of a profile of soil and soil solutions collected on an experimental plot covered with spruce. All these samples come from the watershed of the Strengbach (environment - OHGE Hydrogeochimique Observatory), were sampled at different depths (5, 10, 30 and 60 cm) and during the period between 2009 and 2013. Characterizations of soil extracts by infrared spectroscopy allowed to highlight changes in the organic functional groups with depth and that these changes have a significant impact on the behaviour of the cations (major and trace) in the soil. Ultrafiltration experiments helped to identify flows of colloidal and dissolved organic carbon as well as those of the major and trace-element present in soil solutions. The joint use of isotope tracers (87Sr / 86Sr and δ44 / 40 Ca) and chemical (Rare Earth Elements) have highlighted processes taking place at the water-soil-plant interface, as the uptake by root or soil alteration.

Les macroinvertébrés benthiques entretiennent un ensemble complexe d’interactions. Les échelles spatiales et temporelles des processus formant la base de ces interactions ont traditionnellement limité leur étude empirique. Le premier chapitre du manuscrit tente une revue des outils de modélisation utilisés dans l’étude du benthos marin.Même si l’implémentation d’un modèle mécaniste semble s’ajuster aux communautés benthiques, son utilisation nécessite la création d’un nombre limité d’entités avec un rôle fonctionnel clair. Le second chapitre du manuscrit utilise l’hypothèse des groupes émergents, afin de faire cela via une procédure objective et testable. Le groupement est testé face aux postulats théoriques et les résultats supportent sa capacité à reproduire la diversité fonctionnelle dans l’estuaire de la Rance.Le manque de connaissances dans l’attribution des relations entre les composantes fonctionnelles reste important. Le troisième chapitre du manuscrit s’inscrit dans ce besoin, basé sur des théories écologiques qui prévoient l’existence de trade-offs fonctionnels opérant à grande et petite échelle. Dans un premier temps, ces éléments sont incorporés dans des modèles qualitatifs des groupes fonctionnels.Malgré l’intérêt du développement et de l’analyse de modèles qualitatifs, le but d’étudier la dynamique et le comportement spatialement explicite de la biodiversité ne peut être atteint que par un modèle avec ces mêmes caractéristiques. Le quatrième chapitre du manuscrit présente l’architecture d’un modèle individu-centré, en mettant l’accent sur le transfert des règles d’interactions des modèles qualitatifs vers un cadre dynamique et spatialement explicite. / Benthic macroinvertebrates are part of a complex network of interactions. The spatial and temporal scales of the processes that form the basis for these interactions have traditionally restricted their empirical investigation. The first chapter of the manuscript attempts a review of the modelling tools that have been employed for the study of the marine benthos.The implementation of a mechanistic modelling framework seems fitting, but it requires the derivation of a few model entities with a clear functional role. The second chapter of the manuscript employs the emergent group hypothesis to do that in a way that is objective and testable. The resulting grouping is tested against theoretical expectations and the results support its ability to represent functional diversity in the Rance estuary.The lack of knowledge for the attribution of relationships among functional components is still important. The third chapter of the manuscript addresses this issue based on ecological theories that predict the existence of functional trade-offs operating at both large and small spatial scales. In a first inception of the system, these elements are incorporated in the form of general rules of interaction into qualitative models of the functional groups.In spite of the interest in developing and analysing qualitative models, the goal of studying the dynamic and spatially explicit behaviour of benthic biodiversity can only be reached by a model with the same characteristics. The fourth chapter of the manuscript presents the architecture of an individual-based model, primarily transferring the rules of interaction from the qualitative models to a dynamic and spatially explicit framework.

Vor dem Hintergrund zukünftiger Sensoren, basierend auf dem piezoresistiven Effekt von einwandigen Kohlenstoffnanoröhren (SWCNT), werden in dieser Arbeit umfangreiche Ergebnisse zum mechanischen Verhalten von Grenzflächen zwischen SWCNTs und edlen Metallen am Beispiel von Pd und Au präsentiert. Im Fokus steht dabei die Synergie von rechnerischen und experimentellen Methoden Molekulardynamik (MD), nanoskalige Tests und Analytik , um (1) mit guter Genauigkeit maximale Kräfte von gezogenen SWCNTs, welche in Metall eingebettet sind, vorauszuberechnen und (2) einen wertvollen Beitrag zum Verständnis der zu Grunde liegenden Fehlermechanismen zu liefern. Es wurde ein MDModell eines in eine einkristalline Matrix eingebetteten SWCNTs mit Randbedingen eines Auszugsversuchs entwickelt. Mit diesem Modell können Kraft-Weg-Beziehungen und Energieverläufe für einen quasistatischen verschiebungsgesteuerten Auszugsversuch errechnet werden. Das Modell liefert kritische Kräfte bei Versagen des Systems. Des Weiteren können mit diesem Modell der Einfluss des SWCNT-Typus, der Einbettungslänge, der Temperatur, von intrinsischen Defekten und Oberflächengruppen (SFGs) auf das Grenzflächenverhalten untersucht werden. Zum Vergleich wurden kritische Kräfte experimentell durch in situ Auszugsversuche in einem Rasterelektronenmikroskop bestimmt. Es wurde eine sehr gute Übereinstimmung von rechnerischen und experimentellen Daten festgestellt. Der vorherrschende Fehler im Experiment ist der SWCNT-Bruch, jedoch wurden auch einige SWCNT-Auszüge beobachtet. Mit Hilfe der MD-Simulationen wurde gefunden, dass die SFGs als kleine Anker in der umgebenden metallischen Matrix wirken und somit die maximalen Kräfte signifikant erhöhen. Diese Grenzflächenverstärkung kann Zugspannungen verursachen, die genügend hoch sind, so dass SWCNT-Bruch initiert wird. Im Gegensatz dazu zeigten Simulationen von Auszugstests mit idealen SWCNTs nur kleine Auszugskräfte, welche meistens unabhängig von der Einbettungslänge des SWCNTs sind. Dieses Verhalten wird mit einer inkommensurablen Konfiguration der Kristallstrukturen an der Grenzfläche von SWCNTs und der einbettenden Edelmetalle interpretiert. Zur Qualifizierung der Existenz von carboxylatischen Oberflächengruppen auf dem genutzten SWCNT-Material wurden analytische Untersuchungen mittels Fluoreszenzmarkierung von Oberflächengruppen durchgeführt. In Übereinstimmung mit Literaturstellen zum gesicherten Nachweis von SFGs, bedingt durch technologische Behandlungen, weisen diese Experimente stark auf das Vorhandensein von carboxylatischen Oberflächengruppen auf dem genutzten SWCNT-Material hin. Demnach kann der dominante SWCNT-Bruch Fehler durch die Grenzflächenverstärkung auf Grund von SFGs erklärt werden. / In the light of future sensors, that are based upon the piezoresistive effect of singlewalled carbon nanotubes (SWCNTs), this work presents comprehensive results of studies on the mechanical behavior of interfaces between SWCNTs and noble metals using the examples of Pd and Au. With this contribution, the focus is on a synergy between computational and experimental approaches involving molecular dynamics (MD) simulations, nanoscale testing, and analytics (1) to predict to a good degree of accuracy maximum forces of pulled SWCNTs embedded in a noble metal matrix and (2) to provide valuable input to understand the underlying mechanisms of failure. A MD model of a SWCNT embedded in a single crystalline matrix with pull-out test boundary conditions was developed. With this model, force-displacement relations and energy evolutions for a quasi-static displacement controlled test can be computed. The model provides critical forces for failure of the system. Furthermore, the influence of SWCNT type, embedding length, temperature, intrinsic defects and surface functional groups (SFGs) on the interface behavior can be studied using this model. For comparison, critical forces were experimentally determined by conducting pull-out tests in situ, inside a scanning electron microscope. A very good agreement of computational and experimental values was discovered. The dominant failure mode in the experiment was a SWCNT rupture, although several pull-out failures were also observed. From MD simulations, it was found that SFGs act as small anchors in the metal matrix and significantly enhance the maximum forces. This interface reinforcement can lead to tensile stresses sufficiently high to initiate SWCNT rupture. In contrast, pull-out test simulations of ideal SWCNTs show only small pull-out forces, which are mostly independent on SWCNT embedding length. This behavior is interpreted with an incommensurate configuration of crystal structures at the interface between SWCNTs and embedding noble metals. To qualify the existence of carboxylic SFGs on the used SWCNT material, an analytical investigation by means of fluorescence labeling of surface species was performed. In agreement with literature reports on the secured verification of SFGs due to necessary technological treatments, these experiments strongly indicate the presence of carboxylic SFGs on the used SWCNT material. Thus, the dominant SWCNT rupture failure is explained with an interface reinforcement by SFGs.

Motiviert durch die Zunahme der weltweiten Nachfrage nach hochwertigen Humusstoffen wurde am Institut für Holz- und Pflanzenchemie ein neuartiger Humusersatzstoff entwickelt. Dieses N-modifizierte Produkt wird auf Basis eines patentierten Normaldruckverfahrens der oxidativen Ammonolyse (OA) aus ligninhaltigen Ausgangssubstanzen, im vorliegenden Fall Lausitzer Braunkohle, hergestellt. Ziel war, die bisher vorliegenden Erkenntnisse der strukturellen Eigenschaften solcher Humusstoffe zu erweitern. Im Fokus standen die Gehalte und Charakteristik der Huminstofffraktionen (Humine, Humin- und Fulvosäuren). Der Stickstoff und die Art seines Einbaus in die organische Substanz spielt hierbei eine besondere Rolle. Für die Huminstoffisolierung kam die hinsichtlich der Ausbeuten und des Zeitaufwandes optimierte IHSS-Methode zum Einsatz. Wesentliche Merkmale N-modifizierter Substanzen sind erhöhte Huminsäurengehalte, zeitlich differenziert wirksame N-Bindungsformen und damit eine Diversifizierung der Funktionalität. Zusätzlich mit dem geringen Aschegehalt unterscheidet dies N-modifizierte Lausitzer Braunkohle von anderen auf Braunkohlebasis erzeugten Bodenverbesserungsmitteln des Marktes. Es konnte gezeigt werden, dass Huminsäuren hinsichtlich der Bereitstellung von Stickstoff und Funktionalität (z.B. Austauscherplätze) eine Schlüsselrolle einnehmen. Die Veränderungen durch die OA basieren stofflich auf der Bildung regenerierter Huminsäuren und chemisch u.a. auf der oxidativen Ringspaltung von Aromaten an nicht veretherten phenolischer OH-Gruppen von Methoxyphenolstrukturen. Dabei ist diese Reaktion entgegen früherer Annahmen nicht an eine Demethoxylierung gebunden und erfordert auch keine verschärften Reaktionsbedingungen (z.B. erhöhter Druck). Diese und weitere Reaktionsmechanismen führen zu ammoniumartig, amidartig und fest organisch gebundenen N-Bindungsformen. 15N-NMR-Spektroskopische Untersuchungen an einem 15N-angereicherten Produkt, Py-GC/MS-Untersuchungen und nasschemische Experimente zeigen, dass in der Vergangenheit die Bedeutung heterocyclischer, insbesondere heteroaromatischer N-Bindungsformen überschätzt wurde. Amidartiger Stickstoff präsentiert sich dabei als außerordentlich heterogen hinsichtlich seiner Hydrolysestabilität bzw. Pflanzenverfügbarkeit. Für die effektive Beurteilung möglicher Ausgangssubstanzen hinsichtlich ihrer Eignung für die Herstellung von Humusdüngestoffen nach dem Prinzip der OA kann der Huminsäurengehalt herangezogen werden. Er wird mit Hilfe eines degradativen Verfahrens ermittelt. Die mit dem Huminsäurengehalt in Verbindung stehenden Stoffeigenschaften von Kohlen korrelieren gut mit dem N-Einbau. Aus Sicht der Verfahrensführung hängt die Intensität des N-Einbaus eng mit dem Oxidationsregime zusammen. Durch Anwendung von reinem Sauerstoff anstelle von Luft als sehr einfach und günstig zu realisierende Maßnahme kann die Reaktionszeit halbiert werden. / The development of a novel artificial humus material at the Institute of Wood- and Plant Chemistry was accounted by the increasing demand for high grade humic matter. This N-modified product base on a patented ambient pressure technology of the oxidative ammonolysis. of lignin containing substances, in particular Lusitian lignite. Objective of the work was to broadening the current knowledge of structural properties with focus on the contents and characteristics of humic substances fractions (humins, humic acids, fulvic acids). Especially attention was given to nitrogen and its way of incorporation into organic matter. For isolating humic substances the IHSS method was used. The procedure was adapted in order to increase the yield of humic acids and decrease time needed. Main characteristics of N-modified substances are higher contents of humic acids and subtly differenciateted effective N-binding forms with leads to higher diversity of the chemical functionality. This and the low ash content makes the differences to other brown coal based soil improving agents available on the marked. It has been shown that humic acids give the main part providing nitrogen and functionality (e.g. cation exchange capacity). The oxidative ammonolysis leads to regenerated humic acids as well as e.g. the clevage of aromatic structures by reactions of free phenolic groups. In contrast to former assumptions the cleavage is not strongly related to demethoxylation or strong reaction conditions like high pressure. This and other reactions lead to short, middle, and long lasting N-binding forms. 15N-NMR-spectroscopic investigations on a 15N-enriched product, Py-GC/MS-investigations and conventional investigations show an overestimation of heterocyclic, in particular heteroaromatic N-binding forms up to now. Consequently amide like nitrogen reveals as extraordinary according to its persistent behaviour to hydrolysis and plant availability respectively. Corresponding the correlation of the N-incorporation and humic acid content of raw materials the latter can be used for evaluating possible raw material for its usage for N-modification. It can be easy obtained in a degratadive way. From the process engineering point of view the success of N-incorporating is strongly correlated to the oxidation conditions during processing. Using pure oxygen instead of air shorts the needed reaction at 50%.