Soil organic carbon stocks in estuarine and marine mangrove ecosystems are driven by nutrient colimitation of P and N

Mangroves play an important role in carbon sequestration, but soil organic carbon (SOC) stocks differ between marine and estuarine mangroves, suggesting differing processes and drivers of SOC accumulation. Here, we compared undegraded and degraded marine and estuarine mangroves in a regional approach across the Indonesian archipelago for their SOC stocks and evaluated possible drivers imposed by nutrient limitations along the land-to-sea gradients. SOC stocks in natural marine mangroves (271–572 Mg ha-1 m-1 were much higher than under estuarine mangroves (100–315 Mg ha-1 m-1 with a further decrease caused by degradation to 80–132 Mg ha-1 m-1. Soils differed in C/N ratio (marine: 29–64; estuarine: 9–28), δ15N (marine: 0.6 to 0.7‰; estuarine: 2.5 to 7.2‰), and plant-available P (marine: 2.3–6.3 mg kg-1; estuarine: 0.16–1.8 mg kg-1). We found N and P supply of sea-oriented mangroves primarily met by dominating symbiotic N2 fixation from air and P import from sea, while mangroves on the landward gradient increasingly covered their demand in N and P from allochthonous sources and SOM recycling. Pioneer plants favored by degradation further increased nutrient recycling from soil resulting in smaller SOC stocks in the topsoil. These processes explained the differences in SOC stocks along the land-to-sea gradient in each mangrove type as well as the SOC stock differences observed between estuarine and marine mangrove ecosystems. This first large-scale evaluation of drivers of SOC stocks under mangroves thus suggests a continuum in mangrove functioning across scales and ecotypes and additionally provides viable proxies for carbon stock estimations in PES or REDD schemes.

Development of Zirconia based phosphors for application in lighting and as luminescent bioprobes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure sensors are explored taking into account their studied characteristics.

Proton conductivity and luminiscence properties of lanthanide aminotriphosphonates

Metal phosphonates are multifunctional solids with tunable properties, such as internal H-bond networks, and high chemical and thermal stability [1]. In the present work, we describe the synthesis, structural characterization, luminescent properties and proton conduction performance of a new family of isostructural cationic compounds with general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La3+, Pr3+, Sm3+, Gd3+, Tb3+, Dy3+, Ho3+, H6NMP = nitrilotris(methylphosphonic acid)]. These solids are formed by positively charge layers, which consist of isolated LnO8 polyhedra and bridge chelating NMP2- ligands, held apart by chloride ions and water molecules. This arrangement result in extended interlayer hydrogen networks with possible proton transfer pathways. The proton conductivity of Gd3+ sample, selected as prototype of the series, was measured. In the range between range 25º and 80 ºC, the conductivity increase with the temperature up to a maximum value of 3.10-4 S·cm-1, at relative humidity of 95 %. The activation energy obtained from the Arrhenius plot (Figure 1) is in the range corresponding to a Grotthuss transfer mechanism.

Adubação de capim-elefante com composto orgânico produzido com resíduos animais.

Resumo: A utilização do composto orgânico proveniente de resíduos da criação e abate de pequenos ruminantes pode elevar a produção de matéria seca do capim-elefante, tendo em vista o teor de nutrientes contidos nesse fertilizante orgânico, diminuindo os impactos da produção animal sobre o ambiente e reduzindo os custos de produção na área de capineira de capim-elefante. Dada à escassez de informações na literatura e a importância do manejo adequado da adubação orgânica na agropecuária, objetivou-se avaliar os atributos químicos e físicos do solo, o estado nutricional e a produção do capim-elefante submetido à aplicação de doses do composto orgânico proveniente de resíduos da produção e abate de pequenos ruminantes. O delineamento experimental adotado foi em parcelas subdivididas, com medidas repetidas no tempo, sendo as parcelas as doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) de composto orgânico e um tratamento adicional com adubos minerais e as subparcelas os ciclos (1, 2, 3 e 4) com 4 blocos, totalizando 28 parcelas. As variáveis mensuradas foram atributos físicos e químicos do solo, a diagnose foliar e a produtividade de capim-elefante. Para o fator ciclo, a adubação orgânica incrementou a umidade gravimétrica e umidade volumétrica e ainda houve diminuição da densidade de partículas em função dos ciclos. Com as doses do fertilizante orgânico houve aumento nas concentrações da matéria orgânica, amônio, nitrato, amônio + nitrato, fósforo e saturação por base; houve redução do valor da acidez potencial, além da elevação dos teores de nitrogênio e fósforo nas plantas. As doses de composto orgânico aumentaram a biomassa de forragem total de capim elefante. A adubação mineral proporcionou maior incremento da produção do capim em relação à adubação orgânica no decorrer dos ciclos. Abstract: The use of organic compost from residues of production and slaughter of small ruminants can increase dry matter production of elephant grass, in due function of quantity nutrients in this compost, thus reducing the animal production impacts in the environment and production costs in elephant grass fields. Due to the Lack of information in literature and the importance regarding organic fertilization in agriculture, the aim of this work was evaluate chemical and physical soil attributes, nutritional status in plants and production of elephant grass in function of doses of organic compound of residues of production and slaughter of small ruminants. The experimental design was in split-plot, with the main treatment the doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) of organic compost and one additional treatment with mineral fertilization and secondary treatments was the cycles (1, 2, 3 and 4) with 4 blocks, and 28 plots. The measured variables were physical and chemical attributes in the soil, nutritional diagnosis in plants and production of elephant grass. For cycle factor the organic fertilization increased gravimetric and volumetric humidity, yet, occurred decrease of density in function of cycles. With the doses of organic compost increased organic matter, ammonium, nitrate, ammonium + nitrate, phosphor and base saturation; and decreased the value of potential acidity; and increased content of N and P in plants. The doses of organic compost increased the elephant grass production. The mineral fertilization increased the elephant grass production in relation of organic fertilization over the cycles.

Complexes cationiques POCOP de nickel : synthèse, caractérisation, réactivité et étude catalytique

Ce mémoire traite de la chimie des complexes pinceurs de nickel (II) cationiques ayant un ligand de type POCOP. Elle se divise en deux parties. La première traite de la synthèse, de la caractérisation et de la réactivité des complexes cationiques pinceurs de Ni(II) de type POCOP (POCOP = 1,3-bis(phosphinitobenzene), où C fait partie d’un cycle benzénique et est lié au métal, et P est un ligand phosphoré aussi lié au métal). Ces complexes ont un ligand acétonitrile coordonné au centre métallique et sont du type [(R-POCOPR’)Ni(NCMe)][OSO2CF3], où R est un substituant du cycle benzénique et R’ est un substituant sur le ligand phosphoré (R’ = iPr: R = H (1), p-Me(2), p-OMe(3), p-CO2Me(4), p-Br(5), m,m-tBu2(6), m-OMe(7), m-CO2Me(8); R’ = t-Bu : R = H (9), p-CO2Me(10)). Les complexes cationiques sont préparés en faisant réagir le dérivé Ni(II) neutre correspondant R-(POCOPR’)Ni-Br avec Ag(OSO2CF3¬) dans l’acétonitrile à température ambiante. L’impact des groupements R et R’ du ligand POCOP sur la structure et sur les propriétées électroniques du complexe a été étudié par spectroscopies RMN, UV-VIS et IR, analyse électrochimique, et diffraction des rayons X. Les valeurs de fréquence du lien C≡N (ν(C≡N)) augmentent avec le caractère électroattracteur du complexe, dans l’ordre 7 < 3 ~ 2 ~ 6 < 1 < 5 ~ 8 < 4 et 9 < 10. Ces résultats sont en accord avec le fait qu’une augmentation du caractère électrophile du centre métallique devrait résulter en une augmentation de la donation σ MeCN→Ni. De plus, les complexes cationiques montrent tous un potentiel d’oxydation Ni(II)/Ni(III) plus élevé que leurs analogues neutres Ni-Br. Ensuite, une étude d’équilibre entre un complexe neutre (R-POCOPR’)NiBr et un complexe cationique [(R-POCOPR’)Ni(NCMe)][OSO2CF3] démontre l’échange facile des ligands MeCN et Br. La deuxième partie de ce mémoire consiste en deux chapitres. Le premier (Chapitre 3) est une étude structurelle permettant une meilleure compréhension du mécanisme d’hydroamination des oléfines activées promue par les complexes présentés au chapitre 1, suivi de tentatives de synthèse de nouveaux composés POCOP cationiques comportant un ligand amine et nitrile, et de déplacement du groupement amine par un groupement nitrile. Le deuxième chapitre (4) décrit la réactivité et la cinétique de la réaction d’hydroamination et d’hydroalkoxylation d’oléfines activées, qui permet ainsi de mieux comprendre l’impact des différentes variables du système (groupements R et R’, température, substrats, solvent, etc.) sur la réactivité catalytique.

Complexes cationiques POCOP de nickel : synthèse, caractérisation, réactivité et étude catalytique

Ce mémoire traite de la chimie des complexes pinceurs de nickel (II) cationiques ayant un ligand de type POCOP. Elle se divise en deux parties. La première traite de la synthèse, de la caractérisation et de la réactivité des complexes cationiques pinceurs de Ni(II) de type POCOP (POCOP = 1,3-bis(phosphinitobenzene), où C fait partie d’un cycle benzénique et est lié au métal, et P est un ligand phosphoré aussi lié au métal). Ces complexes ont un ligand acétonitrile coordonné au centre métallique et sont du type [(R-POCOPR’)Ni(NCMe)][OSO2CF3], où R est un substituant du cycle benzénique et R’ est un substituant sur le ligand phosphoré (R’ = iPr: R = H (1), p-Me(2), p-OMe(3), p-CO2Me(4), p-Br(5), m,m-tBu2(6), m-OMe(7), m-CO2Me(8); R’ = t-Bu : R = H (9), p-CO2Me(10)). Les complexes cationiques sont préparés en faisant réagir le dérivé Ni(II) neutre correspondant R-(POCOPR’)Ni-Br avec Ag(OSO2CF3¬) dans l’acétonitrile à température ambiante. L’impact des groupements R et R’ du ligand POCOP sur la structure et sur les propriétées électroniques du complexe a été étudié par spectroscopies RMN, UV-VIS et IR, analyse électrochimique, et diffraction des rayons X. Les valeurs de fréquence du lien C≡N (ν(C≡N)) augmentent avec le caractère électroattracteur du complexe, dans l’ordre 7 < 3 ~ 2 ~ 6 < 1 < 5 ~ 8 < 4 et 9 < 10. Ces résultats sont en accord avec le fait qu’une augmentation du caractère électrophile du centre métallique devrait résulter en une augmentation de la donation σ MeCN→Ni. De plus, les complexes cationiques montrent tous un potentiel d’oxydation Ni(II)/Ni(III) plus élevé que leurs analogues neutres Ni-Br. Ensuite, une étude d’équilibre entre un complexe neutre (R-POCOPR’)NiBr et un complexe cationique [(R-POCOPR’)Ni(NCMe)][OSO2CF3] démontre l’échange facile des ligands MeCN et Br. La deuxième partie de ce mémoire consiste en deux chapitres. Le premier (Chapitre 3) est une étude structurelle permettant une meilleure compréhension du mécanisme d’hydroamination des oléfines activées promue par les complexes présentés au chapitre 1, suivi de tentatives de synthèse de nouveaux composés POCOP cationiques comportant un ligand amine et nitrile, et de déplacement du groupement amine par un groupement nitrile. Le deuxième chapitre (4) décrit la réactivité et la cinétique de la réaction d’hydroamination et d’hydroalkoxylation d’oléfines activées, qui permet ainsi de mieux comprendre l’impact des différentes variables du système (groupements R et R’, température, substrats, solvent, etc.) sur la réactivité catalytique.

Adubação de capim-elefante com composto orgânico produzido com resíduos animais.

A utilização do composto orgânico proveniente de resíduos da criação e abate de pequenos ruminantes pode elevar a produção de matéria seca do capim-elefante, tendo em vista o teor de nutrientes contidos nesse fertilizante orgânico, diminuindo os impactos da produção animal sobre o ambiente e reduzindo os custos de produção na área de capineira de capim-elefante. Dada à escassez de informações na literatura e a importância do manejo adequado da adubação orgânica na agropecuária, objetivou-se avaliar os atributos químicos e físicos do solo, o estado nutricional e a produção do capim-elefante submetido à aplicação de doses do composto orgânico proveniente de resíduos da produção e abate de pequenos ruminantes. O delineamento experimental adotado foi em parcelas subdivididas, com medidas repetidas no tempo, sendo as parcelas as doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1) de composto orgânico e um tratamento adicional com adubos minerais e as subparcelas os ciclos (1, 2, 3 e 4) com 4 blocos, totalizando 28 parcelas. As variáveis mensuradas foram atributos físicos e químicos do solo, a diagnose foliar e a produtividade de capim-elefante. Para o fator ciclo, a adubação orgânica incrementou a umidade gravimétrica e umidade volumétrica e ainda houve diminuição da densidade de partículas em função dos ciclos. Com as doses do fertilizante orgânico houve aumento nas concentrações da matéria orgânica, amônio, nitrato, amônio + nitrato, fósforo e saturação por base; houve redução do valor da acidez potencial, além da elevação dos teores de nitrogênio e fósforo nas plantas. As doses de composto orgânico aumentaram a biomassa de forragem total de capimelefante. A adubação mineral proporcionou maior incremento da produção do capim em relação à adubação orgânica no decorrer dos ciclos. Abstract: The use of organic compost from residues of production and slaughter of small ruminants can increase dry matter production of elephant grass, in due function of quantity nutrients in this compost, thus reducing the animal production impacts in the environment and production costs in elephant grass fields. Due to the Lack of information in literature and the importance regarding organic fertilization in agriculture, the aim of this work was evaluate chemical and physical soil attributes, nutritional status in plants and production of elephant grass in function of doses of organic compound of residues of production and slaughter of small ruminants. The experimental design was in split-plot, with the main treatment the doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) of organic compost and one additional treatment with mineral fertilization and secondary treatments was the cycles (1, 2, 3 and 4) with 4 blocks, and 28 plots. The measured variables were physical and chemical attributes in the soil, nutritional diagnosis in plants and production of elephant grass. For cycle factor the organic fertilization increased gravimetric and volumetric humidity, yet, occurred decrease of density in function of cycles. With the doses of organic compost increased organic matter, ammonium, nitrate, ammonium + nitrate, phosphor and base saturation; and decreased the value of potential acidity; and increased content of N and P in plants. The doses of organic compost increased the elephant grass production. The mineral fertilization increased the elephant grass production in relation of organic fertilization over the cycles.