O impacto da remoção de peixes sobre a dinâmica e estrutura dos grupos funcionais fitoplanctônicos em um lago raso tropical durante uma seca severa

The artifi cial eutrophication is one of the biggest t h reat for the quality of aquatic ecosystems in the whole world. The expectations for the future climatic scenarios in arid and semi - arid regions are intense and frequent droughts enhancing the risk of eutrophicati on and cyanobacterial blooms. Restoration techniques of eutrophic lakes were proposed to reduce nutrient loading and improve the water quality. A successful technique used in temperate regions is the biomanipulation by benthivorous fish removal . Our hypoth esis is that the benthivorous fish removal reduces phytoplankton total biomass and change the composition of phytoplankton functional groups, improving water quality. The aim of the study was evaluate the impact of biomanipulation on phytoplankton function al groups and in the water quality. We applied the technique of biomanipulation in the artificial lake ESEC, in a semi - arid region of Brazil and analyzed the physical and chemical variables and the dynamic of phytoplankton functional groups monthly during November 2012 to August 2013. With the removal of benthivorous fish we observed a significant increase of the euphotic depth, phytoplankton richness and the recruitment of green algae (groups F and J ), indicators of good water quality. However, we did not observe significant differences on total phosphorous concentration and on phytoplankton biomass and diversity. The drought effect in the region during the study was evident , promoting a drastic reduction on water level which influenced the availability of resource and affected phytoplankton community before the biomanipulation. To evaluate the effect of severe drought on the dynamic of phytoplankton functional groups and test if the drought periods are favorable to dominance of cyanobacterial groups, we stu died two artificial neighbors lakes (ESEC and Pocinhos) in a semi - arid tropical region during May 2012 to February 2013. We observed a temporal differentiation of biotic and abiotic variables caused by drought. Both lakes presented reduction of 2 meters of water level and increase on conductivity, turbidity, nutrients concentration and a reduction on water transparency, during the severe drought. The deeper lake (Pocinhos) increased phytoplankton total biomass and presented cyanobacterial functional group d ominance (group S N ) and the shallower lake (ESEC) reduced phytoplankton total biomass and presented dominance of mixotrophic and flagellate functional groups (groups W 1 e W 2 ). Summarizing, the knowledge of the effects of benthivorous fish removal in semi - a rid tropical lakes still unknown and this study had limitations caused by the impact of drought. Thus, it is necessary a long term monitoring to investigate the real effects of biomanipulation on the functioning of the studied ecosystems. Otherwise, period s of drought could have opposite effects (increase or reduction) on total biomass and composition of phytoplankton functional groups. Drought not always leads to dominance of cyanobacterial groups.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Land Use and Water Quality Correlations in Miami-Dade, Florida

South Florida continues to become increasingly developed and urbanized. My exploratory study examines connections between land use and water quality. The main objectives of the project were to develop an understanding of how land use has affected water quality in Miami-Dade canals, and an economic optimization model to estimate the costs of best management practices necessary to improve water quality. Results indicate Miami-Dade County land use and water quality are correlated. Through statistical factor and cluster analysis, it is apparent that agricultural areas are associated with higher concentrations of nitrogen, while urban areas commonly have higher levels of phosphorous than agricultural areas. The economic optimization model shows that urban areas can improve water quality by lowering fertilizer inputs. Agricultural areas can also implement methods to improve water quality although it may be more expensive than urban areas. It is important to keep solutions in mind when looking towards future water quality improvements in South Florida.

Seawater carbonate chemistry and biological processes of Emiliania huxleyi (PML B92/11) during experiments, 2011

The present study investigates the combined effect of phosphorous limitation, elevated partial pressure of CO2 (pCO2) and temperature on a calcifying strain of Emiliania huxleyi (PML B92/11) by means of a fully controlled continuous culture facility. Two levels of phosphorous limitation were consecutively applied by renewal of culture media (N:P = 26) at dilution rates (D) of 0.3 d- and 0.1 d-1. CO2 and temperature conditions were 300, 550 and 900 µatm pCO2 at 14 °C and 900 µatm pCO2 at 18 °C. In general, the steady state cell density and particulate organic carbon (POC) production increased with pCO2, yielding significantly higher concentrations in cultures grown at 900 µatm pCO2 compared to 300 and 550 µatm pCO2. At 900 µatm pCO2, elevation of temperature as expected for a greenhouse ocean, further increased cell densities and POC concentrations. In contrast to POC concentration, C-quotas (pmol C cell-1) were similar at D = 0.3 d-1 in all cultures. At D = 0.1 d-1, a reduction of C-quotas by up to 15% was observed in the 900 µatm pCO2 at 18 °C culture. As a result of growth rate reduction, POC:PON:POP ratios deviated strongly from the Redfield ratio, primarily due to an increase in POC. Ratios of particulate inorganic and organic carbon (PIC:POC) ranged from 0.14 to 0.18 at D = 0.3 d-1, and from 0.11 to 0.17 at D = 0.1 d-1, with variations primarily induced by the changes in POC. At D = 0.1 d-1, cell volume was reduced by up to 22% in cultures grown at 900 µatm pCO2. Our results indicate that changes in pCO2, temperature and phosphorus supply affect cell density, POC concentration and size of E. huxleyi (PML B92/11) to varying degrees, and will likely impact bloom development as well as biogeochemical cycling in a greenhouse ocean.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Coordination of phosphido-boratabenzene ligands to transition metals

Environ 90% des composés produits industriellement sont fabriqués à l’aide de catalyseurs. C’est pourquoi la conception de catalyseurs toujours plus performants pour améliorer les procédés industriels actuels est toujours d’intérêt. De la grande variété de complexes avec des métaux de transition rapportés jusqu’à présent, les complexes zwitterioniques attirent notre attention par leurs activités catalytiques souvent supérieures aux complexes cationiques normaux. Un complexe métallique zwitterionique est un fragment métal-ligand neutre où la charge positive est située sur le centre métallique et où la charge négative est délocalisée sur un des ligands liés au métal. Nous proposons la synthèse de ligands anioniques phosphine comportant des groupements borates et boratabenzènes. Cette dernière espèce est un cycle à 6 membres où l’un des atomes de carbone est remplacé par un atome de bore et qui est négativement chargé. La capacité de ces phosphines anioniques à se lier à un centre métallique à l’aide de la paire libre du phosphore est due à la nature du lien P-B qui défavorise l’interaction entre la paire libre du phosphore et l’orbitale p vide du bore. Les propriétés de di-tert-butylphosphido-boratabenzène (DTBB) comme ligand phosphine anionique hautement donneur et encombré ainsi que la découverte de ses modes de coordination inhabituels pour stabiliser les métaux de transition insaturés ont été étudiés au cours de ce travail. De nouvelles perspectives sur les modes de coordination de phosphido-boratabenzène et la force de l’interaction du lien P-B seront discutées ainsi que les applications catalytiques. Nous avons d’abord étudié la coordination η1 avec des complexes de fer, ce qui nous a fourni des données quantitatives précieuses sur la capacité du DTBB d’agir comme ligand très donneur par rapport aux autres ligands donneurs bien connus. La capacité du DTBB à changer de mode de coordination pour soutenir les besoins électroniques du métal a été démontrée par la découverte d’une nouvelle espèce ferrocenyl phosphido-boratabenzène et sa nucléophilie a été étudiée. Au meilleur de notre connaissance, aucun exemple d’un ligand boratabenzène coordonné aux métaux du groupe 11 n’existe dans la littérature. Voilà pourquoi nous avons décidé d’explorer les modes de coordination du ligand DTBB avec Cu(I), Ag(I) et Au(I). A notre grande surprise, le ligand DTBB est capable de stabiliser les métaux du groupe 11 aux états d’oxydation faibles par une liaison MP qui est une coordination du type η1, un mode de coordination guère observé pour les ligands boratabenzène. Pendant nos travaux, notre attention s’est tournée vers la synthèse d’un complexe de rhodium(I) afin de tester son utilité en catalyse. A notre grande satisfaction, le complexe Rh-DTBB agit comme un précatalyseur pour l’hydrogénation des alcènes et alcynes à la température ambiante et à pression atmosphérique et son activité est comparable à celle du catalyseur de Wilkinson. Dans un désir d’élargir les applications de notre recherche, notre attention se tourna vers l’utilisation des composés du bore autres que le boratabenzène. Nous avons décidé de synthétiser une nouvelle espèce phosphido-borate encombrée. Lorsqu’elle réagit avec des métaux, l’espèce phosphido-borate subit un clivage de la liaison P-B. Toutefois, cette observation met en évidence la singularité et les avantages de la stabilité de la liaison P-B lors de l’utilisation du fragment boratabenzène. Ces observations enrichissent notre compréhension des conditions dans lesquelles la liaison P-B du ligand DTBB peut être clivée. Ces travaux ont mené à la découverte d’un nouveau ligand ansa-boratabenzène avec une chimie de coordination prometteuse.

Electrolytes for ceramic oxide fuel cells

The main objective of this dissertation is the development and processing of novel ionic conducting ceramic materials for use as electrolytes in proton or oxide-ion conducting solid oxide fuel cells. The research aims to develop new processing routes and/or materials offering superior electrochemical behavior, based on nanometric ceramic oxide powders prepared by mechanochemical processes. Protonic ceramic fuel cells (PCFCs) require electrolyte materials with high proton conductivity at intermediate temperatures, 500-700ºC, such as reported for perovskite zirconate oxides containing alkaline earth metal cations. In the current work, BaZrO3 containing 15 mol% of Y (BZY) was chosen as the base material for further study. Despite offering high bulk proton conductivity the widespread application of this material is limited by its poor sinterability and grain growth. Thus, minor additions of oxides of zinc, phosphorous and boron were studied as possible sintering additives. The introduction of ZnO can produce substantially enhanced densification, compared to the un-doped material, lowering the sintering temperature from 1600ºC to 1300ºC. Thus, the current work discusses the best solid solution mechanism to accommodate this sintering additive. Maximum proton conductivity was shown to be obtained in materials where the Zn additive is intentionally adopted into the base perovskite composition. P2O5 additions were shown to be less effective as a sintering additive. The presence of P2O5 was shown to impair grain growth, despite improving densification of BZY for intermediate concentrations in the range 4 – 8 mol%. Interreaction of BZY with P was also shown to have a highly detrimental effect on its electrical transport properties, decreasing both bulk and grain boundary conductivities. The densification behavior of H3BO3 added BaZrO3 (BZO) shows boron to be a very effective sintering aid. Nonetheless, in the yttrium containing analogue, BaZr0.85Y0.15O3- (BZY) the densification behavior with boron additives was shown to be less successful, yielding impaired levels of densification compared to the plain BZY. This phenomenon was shown to be related to the undesirable formation of barium borate compositions of high melting temperatures. In the last section of the work, the emerging oxide-ion conducting materials, (Ba,Sr)GeO3 doped with K, were studied. Work assessed if these materials could be formed by mechanochemical process and the role of the ionic radius of the alkaline earth metal cation on the crystallographic structure, compositional homogeneity and ionic transport. An abrupt jump in oxide-ion conductivity was shown on increasing operation temperature in both the Sr and Ba analogues.

Mössbauer Spectroscopic Study andMagnetic Investigation of Iron(III) Complexes on a DendrimericBasis

The functionalization of the molecular surface of various dendrimer generations with a phosphorous core and external amine groups is obtained by converting those amine groups into the corresponding imines of salicylaldehyde creating multiple coordination sites for the iron atoms. Treatment with iron(III) chloride yields multinuclear iron(III) complexes on a dendrimeric basis. The obtained multinuclear molecular systems exhibit extremely high total spin values. The influence of the generation growth on this type of coordination compounds is investigated by Mossbauer spectroscopy and SQUIDmagnetometry.

Efeitos de manipulações ascendentes e descendentes sobre a comunidade fitoplanctônica em um reservatório eutrófico no semi-árido brasileiro

Top-down (grazing) and bottom-up (nutrient, light) controls are important in freshwater ecosystems regulation. Relative importance of these factors could change in space and time, but in tropical lakes bottom-up regulation has to been appointed as more influent. Present study aimed to test the hypothesis that phytoplankton growths rate in Armando Ribeiro reservoir, a huge eutrophic reservoir in semi-arid region of Rio Grande do Norte state, is more limited by nutrient available then zooplankton grazing pressure. Bioassay was conduced monthly from September (2008) to August (2009) manipulating two levels of nutrients (with/without addition) and two level of grazers (with/without removal). Experimental design was factorial 2X2 with four treatments (X5), (i) control with water and zooplankton from natural spot ( C ), (ii) with nutrient addition ( +NP ), (iii) with zooplankton remove ( -Z ) and (iv) with zooplankton remove and nutrient addition ( -Z+NP ). For bioassay confection transparent plastic bottles (500ml) was incubate for 4 or 5 days in two different depths, Secchi`s depth (high luminosity) and 3 times Secchi`s depth (low luminosity). Water samples were collected from each bottle in begins and after incubates period for chlorophyll a concentration analysis and zoopalnktonic organisms density. Phytoplankton growths rates were calculated. Bifactorial ANOVA was performance to test if had a significant effect (p<0,005) of nutrient addition and grazers remove as well a significant interaction between factors on phytoplankton growths rates. Effect magnitude was calculated the relative importance of each process. Results show that phytoplankton growth was in generally stimulated by nutrient addition, as while zooplankton remove rarely stimulated phytoplankton growth. Some significant interactions happening between nutrient additions and grazers remove on phytoplankton growth. In conclusion this study suggests that in studied reservoir phytoplankton growth is more controlled by ascendent factors than descendent

Bioremediation of phosphates in seawater: approach for recirculating marine aquaculture effluents

Marine Recirculating Aquaculture Systems (RAS) produce great volume of wastewater, which may be reutilized/recirculated or reutilized after undergoing different treatment/remediation methods, or partly discharged into neighbour water-bodies (DWW). Phosphates, in particular, are usually accumulated at high concentrations in DWW, both because its monitoring is not compulsory for fish production since it is not a limiting parameter, and also because there is no specific treatment so far developed to remove them, especially in what concerns saltwater effluents. As such, this work addresses two main scientific questions. One of them regards the understanding of the actual (bio)remediation methods applied to effluents produced in marine RAS, by identifying their advantages, drawbacks and gaps concerning their exploitation in saltwater effluents. The second one is the development of a new, innovative and efficient method for the treatment of saltwater effluents that potentially fulfil the gaps identified in the conventional treatments. Thereby, the aims of this thesis are: (i) to revise the conventional treatments targeting major contaminants in marine RAS effluents, with a particular focus on the bioremediation approaches already conducted for phosphates; (ii) to characterize and evaluate the potential of oyster-shell waste collected in Ria de Aveiro as a bioremediation agent of phosphates spiked into artificial saltwater, over different influencing factors (e.g., oyster-shell pre-treatment through calcination, particle size, adsorbent concentration). Despite the use of oyster-shells for phosphorous (P) removal has already been applied in freshwater, its biosorptive potential for P in saltwater was never evaluated, as far as I am aware. The results herein generated showed that NOS is mainly composed by carbonates, which are almost completely converted into lime (CaO) after calcination (COS). Such pre-treatment allowed obtaining a more reactive material for P removal, since higher removal percentages and adsorption capacity was observed for COS. Smaller particle size fractions for both NOS and COS samples also increased P removal. Kinetic models showed that NOS adsorption followed, simultaneously, Elovich and Intraparticle Difusion kinetic models, suggesting that P removal is both a diffusional and chemically rate-controlled process. The percentage of P removal by COS was not controlled by Intraparticle Diffusion and the Elovich model was the kinetic model that best fitted phosphate removal. This work demonstrated that waste oyster-shells, either NOS or COS, could be used as an effective biosorbent for P removal from seawater. Thereby, this biomaterial can sustain a cost-effective and eco-friendly bioremediation strategy with potential application in marine RAS.

Sustainability of protein production by bioreactor processes using wind and solar power as energy sources

Food production account for significant share of global environmental impacts. Impacts are global warming, fresh water use, land use and some non-renewable substance consumption like phosphorous fertilizers. Because of non-sustainable food production, the world is heading to different crises. Both food- and freshwater crises and also land area and phosphorous fertilizer shortages are one of many challenges to overcome in near future. The major protein sources production amounts, their impacts on environment and uses are show in this thesis. In this thesis, a more sustainable than conventional way of biomass production for food use is introduced. These alternative production methods are photobioreactor process and syngas-based bioreactor process. The processes’ energy consumption and major inputs are viewed. Their environmental impacts are estimated. These estimations are the compared to conventional protein production’s impacts. The outcome of the research is that, the alternative methods can be more sustainable solutions for food production than conventional production. However, more research is needed to verify the exact impacts. Photobioreactor is more sustainable process than syngas-based bioreactor process, but it is more location depended and uses more land area than syngas-based process. In addition, the technology behind syngas-based application is still developing and it can be more efficient in the future.

Dinâmica do fósforo em cultivo heterotrófico e produção de compostos celulares por cianobactéria integrado a biorrefinarias agroindustriais

O objetivo desta tese foi avaliar a dinâmica do fósforo em cultivo heterotrófico e produção de compostos celulares por Aphanothece microscopica Nägeli visando avaliar a perspectiva de implementação de uma biorrefinaria microalgal. Desta forma, foi avaliado o comportamento do micro-organismo em estudo no cultivo heterotrófico, utilizando como meio de cultivo o efluente de laticínios. O trabalho foi desenvolvido em 3 etapas. Em um primeiro momento foi avaliada a influência da temperatura (20 e 30°C) e os valores máximos e mínimos de nutrientes, em especial do fósforo dissolvido reativo (PDR), disponíveis no efluente de laticínio, na remoção de nutrientes. Os resultados demonstraram que a concentração inicial de fósforo dissolvido e a temperatura exerceram influência no crescimento celular e na eficiência de remoção de nutrientes. Em termos de otimização de processo os cultivos conduzidos a 20°C e maiores concentrações de PDR (5,5 mg.L-1 ) no efluente de laticínio, foram os mais eficientes na conversão de poluentes em biomassa e remoção de nutrientes. A segunda etapa foi desenvolvida com o objetivo de avaliar a dinâmica de distribuição de fósforo na fase líquida e sólida do reator heterotrófico, quando o efluente de laticínio foi tratado pela Aphanothece microscopica Nägeli, a 20°C e nas máximas concentrações de fósforo dissolvido encontradas no efluente. Foi demonstrado que as formas fosforadas na fase líquida do reator se caracterizam pela predominância da fração dissolvida em comparação à particulada e por apresentar como fração predominante a de fósforo orgânico. No que se refere à fase sólida, ficou demonstrado que a Aphanothece microscopica Nägeli, quando cultivada heterotroficamente apresenta 3,8 vezes mais fósforo que o requerido para o crescimento celular. Ficando demonstrado ainda que a remoção biológica de fósforo por Aphanothece microscopica Nägeli pode resultar em substanciais aportes financeiros para as estações de tratamento de efluentes. Uma terceira etapa foi desenvolvida, a qual teve como objetivo avaliar a estimativa de produção de compostos celulares por Aphanothece microscopica Nägeli, a partir do efluente de laticínio, bem como o efeito da redução de temperatura de cultivo no teor de lipídios , no momento em que é obtida a máxima concentração deste componente celular, nas condições otimizadas.Foi obtido na fase logarítmica de crescimento, concentrações de 41,8 % de proteinas, carboidratos 28,5 %, lipídios 10,4 % e minerais 10,8 %. O maior teor de lipídio registrado a 20°C correspondeu a biomassa analisada na fase logarítmica.Com a redução da temperatura para 5°C por um período de 30 h é possível obter concentrações de lipídios 2,4 vezes superior ao registrado na fase logarítmica a 20 °C. No entanto, não foram indicadas diferenças significativas (p≤0,05) em função da temperatura entre as concentrações de lipídios obtidas para a biomassa a 10°C em 40 h. O perfil de ácidos graxos da biomassa gerada a 20°C, apresentou como ácidos graxos majoritários, os ácidos graxos: palmítico, oléico, γ-linolênico, palmitoleico e esteárico, resultando um aumento na concentração de ácidos graxos saturados as espensa dos insaturados, quando a temperatura é reduzida. Em paralelo,um reator heterotrófico descontinuo foi definido, ficando demonstrado que a extrapolação da operação em batelada para contínua requer um biorreator heterotrófico com volume útil de trabalho de 240,51 m 3 , permitindo tratar 950 m3 diários de efluente, gerando 11,8 kg.d-1 de biomassa útil para produção de compostos celulares por Aphanothece microscopica Nägeli, visando à simultânea remoção de matéria orgânica, nitrogênio total e fósforo total, gerando insumos que podem suportar a implementação de uma biorrefinaria microalgal.

Soil management system effects on N availability and tree productivity in chestnut planatations under Mediterranean conditions

Soil tillage with chisel ploughing is the conventional soil management system in chestnut stands for fruit production in Northern Portugal. A study was developed to assess the effects of three soil management systems on in situ soil N mineralization dynamics, tree nutrition status and fruit productivity, in a 50-yr old chestnut stand. The treatments were: conventional tillage with a chisel ploughing twice a year (CT), no-tillage with rainfed improved pasture with leguminous and grasses plants (NIP), and no-tillage with spontaneous herbaceous vegetation - natural pasture (NP). The CT treatment showed a strong increase of the soil N mineral concentration following soil disturbance by tillage, but the cumulative net N mineralized along the year was significantly lower (51.8 kg ha-1) than in the NIP (85.1 kg ha-1) treatment. The NP treatment (65.9 kg ha-1) did not cause a reduction in the soil N mineralization when compared to the CT treatment. The mineralization rate (g mineralized N kg-1 total N) in 2004 was about 26, 30 and 38 in the treatments CT, NP and NIP, respectively. Treatments showed different soil N dynamics, the proportion of mineralized NO3--N being lower in the NP (10-48%) than in CT and NIP treatments (53-74%). Our study indicates that no-tillage systems improve the tree nutrition status and enhance productivity

TGA/FTIR study of the pyrolysis of diammonium hydrogen phosphate–tobacco mixtures

Diammonium hydrogen phosphate (DAP) is commonly used as a flavor ingredient of commercial cigarettes. In addition, among its other uses, it is employed to expand the tobacco volume, to manufacture reconstituted tobacco sheet, and to denicotinize tobacco. However, the use of DAP as a cigarette ingredient is a controversial issue. Some authors have stated that ammonium compounds added to tobacco increase smoke ammonia and “smoke pH”, resulting in more free nicotine available in the smoke. On the other hand, other researchers have reported that the larger ammonium content of a cigarette blend due to the presence of DAP was not reflected in increased smoke ammonia. In this work, the thermal behavior of DAP, tobacco and DAP-tobacco mixtures has been studied by TGA/FTIR. The chemical processes involved in the different pyrolysis steps of DAP have been suggested. Marked changes in the pyrolytic behavior of both, tobacco and DAP have been detected when analyzing the behavior of the mixtures. A displacement of the decomposition steps mainly related to the glycerol and lignin from tobacco toward lower temperatures has been observed, whereas that associated with cellulose is displaced toward higher temperature. Additionally, no peak corresponding to the phosphorous oxides decomposition has been detected in the curves relating to the DAP-tobacco mixtures. All these features are indicative of the strong interactions between DAP and tobacco. The FTIR spectra show no significant qualitative differences between the qualitative overall composition of the gases evolved from the pyrolysis of tobacco in the absence and in the presence of DAP. Nevertheless, depending on the temperature considered, the addition of DAP contributes to a decrease in the generation of hydrocarbons and an increase in the formation of CO, CO2 and oxygenated compounds in terms of amount generated per mass of pyrolysed tobacco.