Oxidation kinetics of nickel nano crystallites obtained by controlled thermolysis of diaquabis(ethylenediamine) nickel(II) nitrate

The metal complex, [Ni(en)2(H2O)2](NO3)2 (en = ethylenediamine), was decomposed in a static furnace at 200 C by autogenous decomposition to obtain phase pure metallic nickel nanocrystallites. The nickel metal thus obtained was studied by XRD, IR spectra, SEM and CHN analysis. The nickel crystallites are in the nanometer range as indicated by XRD studies. The IR spectral studies and CHN analyses show that the surface is covered with a nitrogen containing species. Thermogravimetric mass gain shows that the product purity is high (93%). The formed nickel is stable and resistant to oxidation up to 350 C probably due to the coverage of nitrogen containing species. Activation energy for the oxidation of the prepared nickel nanocrystallites was determined by non-isothermal methods and was found to depend on the conversion ratio. The oxidation kinetics of the nickel crystallites obeyed a Johnson–Mehl–Avrami mechanism probably due to the special morphology and crystallite strain present on the metal.

A Chloride Ion-Selective Potentiometric Sensor Based on a Polymeric Schiff Base Complex

This paper describes the fabrication of an ion-selective electrode in which a polymeric Schiff base complex of cobalt(II) is used as the ionophore.The main advantage of the electrode is that it is mechanically stable upto 3 months..The electrode shows a linear response in the range of 2.5 × 10-5-0.5 × 10-1 mol dm-3. The response time of the electrode is 30 s.The pH range at which the electrode works is 3.8 to 6.8. The electrode was found to be selective towards chloride ion in the presence of ions like Na+, Ca2+, Mn2+, ,Fe3+, Co2+, Ni2+, Cu2+, Zn2+, CH3COO-, NO3-, SO42- ,Br- and NO2-.

Structural and spectral studies of novel Co(III) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde

Seven bis(ligand) Co(III) complexes {[CoL21] NO3 · H2 O (1), [CoL21] Cl · 2 H2 O (2),[CoL21] ClO4 (3), [CoL22] NO3 (4), [CoL22] Cl · 2 H2 O (5), [CoL23] Br · 2 H2 O (6), [CoL23] ClO4 · H2 O (7)} of three thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenylethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde-N(4)-(methyl),N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. All complexes are assigned octahedral geometries on the basis of spectral studies. The ligands deprotonate and coordinate by means of pyridine nitrogen, azomethine nitrogen, and thiolate sulfur atoms. The single crystal X-ray structures of HL3 and two nitrate compounds are discussed. The structural studies corroborate the spectral characterization.

Transition metal complexes derived from ketone based N(4)-substituted thiosemicarbazones: Crystal structures and spectral studies

Thiosemicarbazones have recently attracted considerable attention due to their ability to form tridentate chelates with transition metal ions through either two nitrogen and sulfur atoms, N–N–S or oxygen, nitrogen and sulfur atoms, O–N–S. Considerable interest in thiosemicarbazones and their transition metal complexes has also grown in the areas of biology and chemistry due to biological activities such as antitumoral, fungicidal, bactericidal, antiviral and nonlinear optical properties. They have been used for metal analyses, for device applications related to telecommunications, optical computing, storage and information processing.The versatile applications of metal complexes of thiosemicarbazones in various fields prompted us to synthesize the tridentate NNS-donor thiosemicarbazones and their metal complexes. As a part of our studies on transition metal complexes with these ligands, the researcher undertook the current work with the following objectives. 1. To synthesize and physico-chemically characterize the following thiosemicarbazone ligands: a. Di-2-pyridyl ketone-N(4)-methyl thiosemicarbazone (HDpyMeTsc) b. Di-2-pyridyl ketone-N(4)-ethyl thiosemicarbazone (HDpyETsc) 2. To synthesize oxovanadium(IV), manganese(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes using the synthesized thiosemicarbazones as principal ligands and some anionic coligands. 3. To study the coordination modes of the ligands in metal complexes by using different physicochemical methods like partial elemental analysis, thermogravimetry and by different spectroscopic techniques. 4. To establish the structure of compounds by single crystal XRD studies

Assessment of trophic change and its probable impact on tropical estuarine environment (the Kodungallur-Azhikode estuary, India)

The cumulative effects of global change, including climate change, increased population density and domestic waste disposal, effluent discharges from industrial processes, agriculture and aquaculture will likely continue and increases the process of eutrophication in estuarine environments. Eutrophication is one of the leading causes of degraded water quality, water column hypoxia/anoxia, harmful algal bloom (HAB) and loss of habitat and species diversity in the estuarine environment. The present study attempts to characterize the trophic condition of coastal estuary using a simple tool; trophic index (TRIX) based on a linear combination of the log of four state variables with supplementary index Efficiency Coefficient (Eff. Coeff.) as a discriminating tool. Numerically, the index TRIX is scaled from 0 to10, covering a wide range of trophic conditions from oligotrophic to eutrophic. Study area Kodungallur-Azhikode Estuary (KAE) was comparatively shallow in nature with average depth of 3.6±0.2 m. Dissolve oxygen regime in the water column was ranged from 4.7±1.3 mgL−1 in Station I to 5.9±1.4 mgL−1 in Station IV. The average nitrate-nitrogen (NO3-N) of KAE water was 470 mg m−3; values ranged from Av. 364.4 mg m−3 at Station II to Av. 626.6 mg m−3at Station VII. The mean ammonium-nitrogen (NH4 +-N) varied from 54.1 mg m−3 at Station VII to 101 mg m−3 at Station III. The average Chl-a for the seven stations of KAE was 6.42±3.91 mg m−3. Comparisons over different spatial and temporal scales in the KAE and study observed that, estuary experiencing high productivity by the influence of high degree of eutrophication; an annual average of 6.91 TRIX was noticed in the KAE and seasonal highest was observed during pre monsoon period (7.15) and lowest during post monsoon period (6.51). In the spatial scale station V showed high value 7.37 and comparatively low values in the station VI (6.93) and station VII (6.96) and which indicates eutrophication was predominant in land cover area with comparatively high water residence time. Eff. Coeff. values in the KAE ranges from −2.74 during monsoon period to the lowest of −1.98 in pre monsoon period. Present study revealed that trophic state of the estuary under severe stress and the restriction of autochthonous and allochthonous nutrient loading should be keystone in mitigate from eutrophication process

Role of chlorine on the opto-electronic properties of β-In2S3 thin films

Effect of chlorine doping on the opto-electronic properties of β-In2S3 thin film, deposited by spray pyrolysis technique is studied for the first time. Chlorine was incorporated in the spray solution, using HCl. Pristine sample prepared using In(NO3)3 and thiourea as the precursors showed very low photosensitivity. But upon adding optimum quantity of chlorine, the photosensitivity increased by 3 orders. X-ray analysis revealed that crystallinity was also increasing up to this optimum level of Cl concentration. It was also observed that samples with high photosensitivity were having higher band gap. The present study proved that doping with chlorine was beneficial as this could result in forming crystalline and photosensitive films of indium sulfide.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Effects of manure quality and application forms on soil C and N turnover of a subtropical oasis soil under laboratory conditions

Our knowledge of the agricultural sustainability of the millennia-old mountain oases in northern Oman is restricted in particular with respect to C and N turnover. A laboratory study was conducted (1) to analyse the effects of rewetting and drying on soil microorganisms after adding different manures, (2) to investigate the effects of mulching or incorporating of these manures, and (3) to evaluate the relationships between C and N mineralisation rates and manure quality indices. During the first 9-day rewetting and drying cycle, i.e. the “mulch” period, the content of extractable organic C decreased by approximately 40% in all four treatments. During the second 9-day rewetting and drying cycle, i.e. the “incorporation” period, this fraction decreased insignificantly in almost all treatments. The control and mature manure treatments form the first pair with a low percentage of total organic C evolved as CO2 (0.3% in 18 days) and a considerable percentage of total N mineralised as NH4 and NO3 (1% in 18 days), the fresh and immature manure treatments form the second pair with a higher amount of total organic C evolved as CO2 (0.5% in 18 days) and no net N mineralisation. During the first 9-day rewetting and drying cycle, the contents of microbial biomass C and biomass N increased by approximately 150% in all four treatments. During the second 9-day rewetting and drying cycle, no further increase was observed in the control and immature manure treatments and a roughly 30% increase in the other two treatments.

Organic potatoes for processing

Drei Feldversuche auf zwei Standorten (DFH: 51°4, 9°4’, BEL: 52°2’, 8°08’) wurden in den Jahren 2002 bis 2004 durchgeführt, um den Einfluss der Vorfrucht, des Vorkeimens, der N- und K-Düngung und der Sorte auf Nährstoffverfügbarkeit, Gesamt- und sortierte Knollenerträge sowie die Qualität von Kartoffeln und deren Eignung für die industrielle Verarbeitung zu Pommes frites und Chips zu untersuchen. Bestimmt wurden die N- und K-Verfügbarkeit im Boden, die N- und K-Aufnahme von Kraut und Knollen, gesamte Frisch- und Trockenmasseerträge, sortierte Frischmasseerträge für die Verarbeitung, sowie die Gehalte der Knollen an Trockensubstanz und reduzierenden Zuckern. In einer sensorischen Prüfung wurden Qualitätsparameter von Pommes frites (Aussehen/Farbe, Textur und Geschmack/Geruch) bewertet, die gewichtet in einen Qualitätsindex eingingen. Die Qualität der Chips wurde maschinell durch den L-Wert (Helligkeit) des Produktes quantifiziert. Der Gehalt des Bodens an mineralisiertem Nitrat-Stickstoff hing von der Vorfrucht und dem Jahr ab. Nach Erbsen wurden zum Auflaufen der Kartoffeln in den Versuchsjahren 2003 und 2004 (187 und 132 kg NO3-N ha-1) die höchsten NO3-N-Werte in 0-60 cm Boden gemessen verglichen mit Kleegras (169 bzw. 108 kg NO3-N ha-1 oder Getreide (112 kg bzw. 97 kg NO3-N ha-1), obgleich die Differenz nicht in allen Fällen signifikant war. Entsprechend wurden nach Erbsen die höchsten Knollen-Frischmasseerträge (414 und 308 dt ha-1) geerntet. Dasselbe galt für die Trockenmasserträge, was belegt, dass der Trockensubstanzgehalt der Knollen bei verbesserter N-Versorgung nicht im selben Maße sinkt, wie der Frischmasseertrag steigt. Das Vorkeimen der Pflanzknollen führte zu einer rascheren phänologischen Entwicklung im Jugendstadium der Pflanze, beschleunigter Trockenmassebildung des Krautes und einer früheren Einlagerung von Assimilaten vom Kraut in die Knollen. Obwohl die positive Wirkung des Vorkeimens auf den Gesamtertrag bis Ende Juli (+ 26 in 2003 bzw. 34 dt ha-1 in 2004) im Jahr ohne Krautfäuleepidemie von den nicht vorgekeimten Varianten bis zur Endernte im September kompensiert wurde, konnte in diesem Jahr durch Vorkeimen dennoch ein erhöhter Ertragsanteil (+ 12%) der besonders nachgefragten Übergrößen (>50 mm für Pommes frites) erzielt werden. Die durchschnittliche Knollenmasse reagierte positiv auf Vorkeimen (+ 5,4 g), Sortenwahl (Sorte Agria) und ein erhöhtes N-Angebot (Leguminosenvorfrucht). Generell wurde deutlich, dass die Knollengesamterträge unter den Bedingungen des Ökologischen Landbaus (geringe bis mittlere Nährstoffversorgung, verkürzte Vegetationsdauer) sehr stark vom Anbaujahr abhängen. Die Ergebnisse belegen jedoch, dass organisch-mineralische N-K-Düngung den sortierten Ertrag an Knollen für die Verarbeitung signifikant erhöht: Höchste Gesamt- und sortierte Knollenfrischmasseerträge wurden nach kombinierter N (Horngrieß) und mineralischer K- (Kaliumsulfat) Gabe erzielt (348 dt ha-1 im Durchschnitt von 2002-2004). Im Gegensatz dazu kann eine Wirkung von Stallmist auf den Ertrag im Jahr der Ausbringung nicht unbedingt erwartet werden. Steigende Erträge nach Stallmistdüngung wurden lediglich in einem von drei Versuchsjahren (+58 dt ha-1) festgestellt und ließen sich eher auf eine K- als eine N-Wirkung zurückführen. Die Ergebnisse belegen, dass die Sortenwahl eine entscheidende Rolle spielt, wenn die Kartoffeln für die industrielle Verarbeitung zu den oben genannten Produkten angebaut werden. Insgesamt kann festgestellt werden, dass Kartoffelknollen aus ökologischen Anbauverfahren ausreichend hohe Trockensubstanzgehalte aufweisen, um für die Verarbeitung zu Pommes frites (>19%) geeignet zu sein und ohne dass dadurch die Konsistenz des Endproduktes gefährdet würde. Der Trockensubstanzgehalt der Referenzsorte für Chips, „Marlen“, unterschritt das in der Literatur geforderte Minimum für Chips von 23% lediglich, wenn die kombinierte Horngrieß-Kaliumsulfatdüngung zur Anwendung kam. Die Trockensubstanzgehalte der Knollen konnten durch Vorkeimen signifikant gesteigert werden und der Effekt war besonders groß (+1.2% absolut) in dem Jahr mit frühem Auftreten der Krautfäule (Phytophthora infestans), d.h. verkürzter Vegetationszeit. Die Knollen-Trockensubstanzgehalte waren in zwei von drei Experimenten nach Lagerung höher (+0.4 und 0.5% absolut) als noch zur Ernte. Sorten der sehr frühen und frühen Reifegruppe wiesen den größten relativen Anstieg der Gehalte an reduzierenden Zuckern (Glukose und Fruktose) während der Lagerung auf. Den mittelfrühen Sorten „Agria“ und „Marena“ hingegen kann aufgrund des von ihnen erreichten höchsten Qualitätsstandards (Pommes frites) zur Ernte eine sehr gute Eignung für die Bedingungen des Ökologischen Landbaus unterstellt werden. Die durchgehend beste Chipseignung wies die mittelfrühe Referenzsorte „Marlen“ auf. Insgesamt konnte nachgewiesen werden, dass durch gezielte Sortenwahl der Trockensubstanzgehalt und die Konzentration reduzierender Zucker, sowie die Qualität der Endprodukte (Pommes frites und Chips) gezielt beeinflusst werden kann. Im Gegensatz dazu haben acker- und pflanzenbauliche Maßnahmen wie Düngung, Wahl der Vorfrucht und Vorkeimen der Pflanzknollen einen eher geringen Einfluss. Dementsprechend sollte der Landwirt versuchen, durch die Wahl der Sorte den hohen Anforderungen der Industrie an die Rohware gerecht zu werden.

Agricultural practices and horizontal nutrient balances in urban gardens and the alternative use of urban agricultural land in Khartoum, Sudan

The surge in the urban population evident in most developing countries is a worldwide phenomenon, and often the result of drought, conflicts, poverty and the lack of education opportunities. In parallel with the growth of the cities is the growing need for food which leads to the burgeoning expansion of urban and peri-urban agriculture (UPA). In this context, urban agriculture (UA) contributes significantly to supplying local markets with both vegetable and animal produce. As an income generating activity, UA also contributes to the livelihoods of poor urban dwellers. In order to evaluate the nutrient status of urban soils in relation to garden management, this study assessed nutrient fluxes (inputs and outputs) in gardens on urban Gerif soils on the banks of the River Nile in Khartoum, the capital city of Sudan. To achieve this objective, a preliminary baseline survey was carried out to describe the structure of the existing garden systems. In cooperation with the author of another PhD thesis (Ms. Ishtiag Abdalla), alternative uses of cow dung in brick making kilns in urban Khartoum were assessed; and the socio-economic criteria of the brick kiln owners or agents, economical and plant nutritional value of animal dung and the gaseous emission related to brick making activities were assessed. A total of 40 household heads were interviewed using a semi-structured questionnaire to collect information on demographic, socio-economic and migratory characteristics of the household members, the gardening systems used and the problems encountered in urban gardening. Based on the results of this survey, gardens were divided into three groups: mixed vegetable-fodder gardens, mixed vegetable-subsistence livestock gardens and pure vegetable gardens. The results revealed that UA is the exclusive domain of men, 80% of them non-native to Khartoum. The harvested produce in all gardens was market oriented and represented the main source of income for 83% of the gardeners. Fast growing leafy vegetables such as Jew’s mallow (Corchorous olitorius L.), purslane (Portulaca oleracea L.) and rocket (Eruca sativa Mill.) were the dominant cultivated species. Most of the gardens (95%) were continuously cultivated throughout the year without any fallow period, unless they were flooded. Gardeners were not generally aware of the importance of crop diversity, which may help them overcome the strongly fluctuating market prices for their produce and thereby strengthen the contributions of UA to the overall productivity of the city. To measure nutrient fluxes, four gardens were selected and their nutrients inputs and outputs flows were monitored. In each garden, all plots were monitored for quantification of nutrient inputs and outputs. To determine soil chemical fertility parameters in each of the studied gardens, soil samples were taken from three selected plots at the beginning of the study in October 2007 (gardens L1, L2 and H1) and in April 2008 (garden H2) and at the end of the study period in March 2010. Additional soil sampling occurred in May 2009 to assess changes in the soil nutrient status after the River Nile flood of 2008 had receded. Samples of rain and irrigation water (river and well-water) were analyzed for nitrogen (N), phosphorus (P), potassium (K) and carbon (C) content to determine their nutrient inputs. Catchment traps were installed to quantify the sediment yield from the River Nile flood. To quantify the nutrient inputs of sediments, samples were analyzed for N, P, K and organic carbon (Corg) content, cation exchange capacity (CEC) and the particle size distribution. The total nutrient inputs were calculated by multiplying the sediment nutrient content by total sediment deposits on individual gardens. Nutrient output in the form of harvested yield was quantified at harvest of each crop. Plant samples from each field were dried, and analyzed for their N, P, K and Corg content. Cumulative leaching losses of mineral N and P were estimated in a single plot in garden L1 from December 1st 2008 to July 1st 2009 using 12 ion exchange resins cartridges. Nutrients were extracted and analyzed for nitrate (NO3--N), ammonium (NH4+-N) and phosphate PO4-3-P. Changes in soil nutrient balance were assessed as inputs minus outputs. The results showed that across gardens, soil N and P concentrations increased from 2007 to 2009, while particle size distribution remained unchanged. Sediment loads and their respective contents of N, P and Corg decreased significantly (P < 0.05) from the gardens of the downstream lowlands (L1 and L2) to the gardens of the upstream highlands (H1 and H2). No significant difference was found in K deposits. None of the gardens received organic fertilizers and the only mineral fertilizer applied was urea (46-0-0). This equaled 29, 30, 54, and 67% of total N inputs to gardens L1, L2, H1, and H2, respectively. Sediment deposits of the River Nile floods contributed on average 67, 94, 6 and 42% to the total N, P, K and C inputs in lowland gardens and 33, 86, 4 and 37% of total N, P, K and C inputs in highland gardens. Irrigation water and rainfall contributed substantially to K inputs representing 96, 92, 94 and 96% of total K influxes in garden L1, L2, H1 and H2, respectively. Following the same order, total annual DM yields in the gardens were 26, 18, 16 and 1.8 t ha-1. Annual leaching losses were estimated to be 0.02 kg NH4+-N ha-1 (SE = 0.004), 0.03 kg NO3--N ha-1 (SE = 0.002) and 0.005 kg PO4-3-P ha-1 (SE = 0.0007). Differences between nutrient inputs and outputs indicated negative nutrient balances for P and K and positive balances of N and C for all gardens. The negative balances in P and K call for adoptions of new agricultural techniques such as regular manure additions or mulching which may enhance the soil organic matter status. A quantification of fluxes not measured in our study such as N2-fixation, dry deposition and gaseous emissions of C and N would be necessary to comprehensively assess the sustainability of these intensive gardening systems. The second part of the survey dealt with the brick making kilns. A total of 50 brick kiln owners/or agents were interviewed from July to August 2009, using a semi-structured questionnaire. The data collected included general information such as age, family size, education, land ownership, number of kilns managed and/or owned, number of months that kilns were in operation, quantity of inputs (cow dung and fuel wood) used, prices of inputs and products across the production season. Information related to the share value of the land on which the kilns were built and annual income for urban farmers and annual returns from dung for the animal raisers was also collected. Using descriptive statistics, budget calculation and Gini coefficient, the results indicated that renting the land to brick making kilns yields a 5-fold higher return than the rent for agriculture. Gini coefficient showed that the kiln owners had a more equal income distribution compared to farmers. To estimate emission of greenhouse gases (GHGs) and losses of N, P, K, Corg and DM from cow dung when used in brick making, samples of cow dung (loose and compacted) were collected from different kilns and analyzed for their N, P, K and Corg content. The procedure modified by the Intergovernmental Panel on Climate Change (IPCC, 1994) was used to estimate the gaseous emissions of cow dung and fuel wood. The amount of deforested wood was estimated according to the default values for wood density given by Dixon et al. (1991) and the expansion ratio for branches and small trees given by Brown et al. (1989). The data showed the monetary value of added N and P from cow dung was lower than for mineral fertilizers. Annual consumption of compacted dung (381 t DM) as biomass fuel by far exceeded the consumption of fuel wood (36 t DM). Gaseous emissions from cow dung and fuel wood were dominated by CO2, CO and CH4. Considering that Gerif land in urban Khartoum supports a multifunctional land use system, efficient use of natural resources (forest, dung, land and water) will enhance the sustainability of the UA and brick making activities. Adoption of new kilns with higher energy efficiency will reduce the amount of biomass fuels (cow dung and wood) used the amount of GHGs emitted and the threat to the few remaining forests.

Application of biogas slurries from energy crops to arable soils and their impact on carbon and nitrogen dynamics

The use of renewable primary products as co-substrate or single substrate for biogas production has increased consistently over the last few years. Maize silage is the preferential energy crop used for fermentation due to its high methane (CH4) yield per hectare. Equally, the by-product, namely biogas slurry (BS), is used with increasing frequency as organic fertilizer to return nutrients to the soil and to maintain or increase the organic matter stocks and soil fertility. Studies concerning the application of energy crop-derived BS on the carbon (C) and nitrogen (N) mineralization dynamics are scarce. Thus, this thesis focused on the following objectives: I) The determination of the effects caused by rainfall patterns on the C and N dynamics from two contrasting organic fertilizers, namely BS from maize silage and composted cattle manure (CM), by monitoring emissions of nitrous oxide (N2O), carbon dioxide (CO2) and CH4 as well as leaching losses of C and N. II) The investigation of the impact of differences in soil moisture content after the application of BS and temperature on gaseous emissions (CO2, N2O and CH4) and leaching of C and N compounds. III) A comparison of BS properties obtained from biogas plants with different substrate inputs and operating parameters and their effect on C and N dynamics after application to differently textured soils with varying application rates and water contents. For the objectives I) and II) two experiments (experiment I and II) using undisturbed soil cores of a Haplic Luvisol were carried out. Objective III) was studied on a third experiment (experiment III) with disturbed soil samples. During experiment I three rainfall patterns were implemented including constant irrigation, continuous irrigation with periodic heavy rainfall events, and partial drying with rewetting periods. Biogas slurry and CM were applied at a rate of 100 kg N ha-1. During experiment II constant irrigation and an irrigation pattern with partial drying with rewetting periods were carried out at 13.5°C and 23.5°C. The application of BS took place either directly before a rewetting period or one week after the rewetting period stopped. Experiment III included two soils of different texture which were mixed with ten BS’s originating from ten different biogas plants. Treatments included low, medium and high BS-N application rates and water contents ranging from 50% to 100% of water holding capacity (WHC). Experiment I and II showed that after the application of BS cumulative N2O emissions were 4 times (162 mg N2O-N m-2) higher compared to the application of CM caused by a higher content of mineral N (Nmin) in the form of ammonium (NH4+) in the BS. The cumulative emissions of CO2, however, were on the same level for both fertilizers indicating similar amounts of readily available C after composting and fermentation of organic material. Leaching losses occurred predominantly in the mineral form of nitrate (NO3-) and were higher in BS amended soils (9 mg NO3--N m-2) compared to CM amended soils (5 mg NO3--N m-2). The rainfall pattern in experiment I and II merely affected the temporal production of C and N emissions resulting in reduced CO2 and enhanced N2O emissions during stronger irrigation events, but showed no effect on the cumulative emissions. Overall, a significant increase of CH4 consumption under inconstant irrigation was found. The time of fertilization had no effect on the overall C and N dynamics. Increasing temperature from 13.5°C to 23.5°C enhanced the CO2 and N2O emissions by a factor of 1.7 and 3.7, respectively. Due to the increased microbial activity with increasing temperature soil respiration was enhanced. This led to decreasing oxygen (O2) contents which in turn promoted denitrification in soil due to the extension of anaerobic microsites. Leaching losses of NO3- were also significantly affected by increasing temperature whereas the consumption of CH4 was not affected. The third experiment showed that the input materials of biogas plants affected the properties of the resulting BS. In particular the contents of DM and NH4+ were determined by the amount of added plant biomass and excrement-based biomass, respectively. Correlations between BS properties and CO2 or N2O emissions were not detected. Solely the ammonia (NH3) emissions showed a positive correlation with NH4+ content in BS as well as a negative correlation with the total C (Ct) content. The BS-N application rates affected the relative CO2 emissions (% of C supplied with BS) when applied to silty soil as well as the relative N2O emissions (% of N supplied with BS) when applied to sandy soil. The impacts on the C and N dynamics induced by BS application were exceeded by the differences induced by soil texture. Presumably, due to the higher clay content in silty soils, organic matter was stabilized by organo-mineral interactions and NH4+ was adsorbed at the cation exchange sites. Different water contents induced highest CO2 emissions and therefore optimal conditions for microbial activity at 75% of WHC in both soils. Cumulative nitrification was also highest at 75% and 50% of WHC whereas the relative N2O emissions increased with water content and showed higher N2O losses in sandy soils. In summary it can be stated that the findings of the present thesis confirmed the high fertilizer value of BS’s, caused by high concentrations of NH4+ and labile organic compounds such as readily available carbon. These attributes of BS’s are to a great extent independent of the input materials of biogas plants. However, considerably gaseous and leaching losses of N may occur especially at high moisture contents. The emissions of N2O after field application corresponded with those of animal slurries.

Multi-isotopic and compositional exploration of factors controlling nitrate pollution

In Catalonia, according to the nitrate directive (91/676/EU), nine areas have been declared as vulnerable to nitrate pollution from agricultural sources (Decret 283/1998 and Decret 479/2004). Five of these areas have been studied coupling hydro chemical data with a multi-isotopic approach (Vitòria et al. 2005, Otero et al. 2007, Puig et al. 2007), in an ongoing research project looking for an integrated application of classical hydrochemistry data, with a comprehensive isotopic characterisation (δ15N and δ18O of dissolved nitrate, δ34S and δ18O of dissolved sulphate, δ13C of dissolved inorganic carbon, and δD and δ18O of water). Within this general frame, the contribution presented explores compositional ways of: (i) distinguish agrochemicals and manure N pollution, (ii) quantify natural attenuation of nitrate (denitrification), and identify possible controlling factors. To achieve this two-fold goal, the following techniques have been used. Separate biplots of each suite of data show that each studied region has a distinct δ34S and pH signatures, but they are homogeneous with regard to NO3- related variables. Also, the geochemical variables were projected onto the compositional directions associated with the possible denitrification reactions in each region. The resulting balances can be plot together with some isotopes, to assess their likelihood of occurrence

Análisis de las estrategias de cooperación sur-sur para el desarrollo económico y social binacional. Estudio de caso: proyectos en materia agropecuaria en el marco del convenio de cooperación técnica y científica entre Brasil y Colombia, periodo 2007-2011

Las desigualdades económicas y sociales entre los Estados del Norte y del Sur son evidentes, ante esta premisa surge la Cooperación Sur-Sur como una herramienta eficaz para potencializar el desarrollo económico y social de las naciones del Sur bajos los principios de horizontalidad, consenso y equidad. En este sentido, se analizan las estrategias de Cooperación Sur-Sur entre Brasil y Colombia y su aplicación en uno de los sectores prioritarios de los Estados del Sur como es el sector agropecuario.

Análisis de la influencia de grandes ciudades en la transformación de sus entornos regionales para la provisión de bienes y servicios. Caso específico: influencia de Bogotá en Cundinamarca para la generación de infraestructura turística (2000-2012)

El crecimiento acelerado de las ciudades ha incidido en la transformación de las condiciones urbanas haciendo de la expansión y conformación de asentamientos más complejos algo inminente. Bogotá es un buen ejemplo de una ciudad ha crecido sobre su región, generando actividades económicas complementarias, que han venido especializando a los diferentes municipios en actividades productivas y de servicios. Una de las mayores demandas en la prestación de bienes y servicios, tiene que ver con el tema de la recreación, específicamente el Turismo.

Coco Chanel. El éxito y la perdurabilidad de su marca, en relación con el liderazgo

Este trabajo de investigación consiste en establecer si Coco Chanel puede ser considerada un líder, y de ser así se determinarán las características de su liderazgo. Coco Chanel además de ser una diseñadora exitosa que marcó tendencias entre 1901 y 1971, también fue una administradora que posicionó una marca y un estilo a nivel mundial. Lo anterior es particularmente relevante en una sociedad y en un tiempo en el que la gran mayoría de empresarios eran hombres. Para lograr el objetivo, se describirán diferentes momentos y situaciones de la vida de Chanel, las cuales le dejaron enseñanzas y experiencias que contribuyeron a su desarrollo como persona, a marcar una época con tendencias revolucionarias y a posicionar su marca, la cuales a pesar del tiempo siguen intactas. Para caracterizar a Chanel, se analizarán sus decisiones y la repercusión tanto a nivel personal como empresarial, su entorno, documentos académicos, documentales, biografías, páginas web oficiales y videos que permitirán establecer el tipo de discurso y lenguaje utilizado por ella para la toma de decisiones en su vida y en su marca, las características de su empresa y del contexto que influyó en el éxito de su marca y en qué medida tal éxito se debió a procesos de liderazgo; de igual forma se establecerá si ella utilizó comprensión descriptiva, (lenguaje que sigue a la realidad) o comprensión generativa (la realidad que sigue al lenguaje) (Barbosa, 2009). A lo largo de esta investigación, se podrá reflexionar en torno a las habilidades que resultan esenciales en un líder y si estas podrían utilizarse en el entorno cambiante al que nos enfrentamos hoy en día.