Environmental Geochemistry of Core Sediment in the Cochin Estuary (CE), India

Distribution of toxic metal in the sediment core is an important area of research for environmental impact studies. Sediment cores were collected from two prominent region(C1 and C2) of CE and subjected to geochemical analysis to determine distribution of toxic metals (Cd, Co, Cr, Cu and Pb ), texture characteristics, total organic carbon (TOC) and CHNS. Statistical analysis was done to understand the interrelationship between the components. In the studied cores, metal contamination level was identified for Pb, Cu; Cr, in C1 and C2 respectively. The metal distribution depends on the granulometric factor, geogenic mineral components and anthropogenic input. Correlation analysis (CA) and Principal component(PCA) analysis also support these results

Exploration of Novel Organic Reactions Catalyzed by Nucleophilic Heterocyclic Carbenes (NHCs)

The thesis entitled “Exploration of Novel Organic Reactions Catalyzed by Nucleophilic Heterocyclic Carbenes (NHCs)” embodies the results of the investigations carried out to explore the synthetic potential of N–heterocyclic carbenes (NHCs) as organocatalyst towards various electrophiles for the synthesis of heterocyclic and carbocyclic systems. Recent investigations in the generation of homoenolates by the addition of NHCs to conjugated aldehydes have made it possible to study the reactivity of this unique three carbon synthon.

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Molecular Epidemiology of Escherichia coli isolates from Environmental, Food and Clinical Sources

In the present study diversity of E. coli in the water samples of Cochin estuary were studied for a period of 3 years ranging from January 2010- December 2012. The stations were selected based on the closeness to satellite townships and waste input. Two of the stations (Chitoor and Thevara) were fixed upstream, two in the central part of the estuary namely Bolgatty and Off Marine Science Jetty, and one at the Barmouth. Diversity was assessed in terms of serotypes, phylogenetic groups and genotypes. Two groups of seafood samples such as fish and shellfish collected from the Cochin estuary were used for isolation of E. coli. One hundred clinical E. coli isolates were collected from one public health centre, one hospital and five medical labs in and around Cochin City, Kerala. From our results it was clear that pathogen cycling is occurring through food, water and clinical sources. Pathogen cycling through food is very common and fish and shellfish that harbour these strains might pose potential health risk to consumer. Estuarine environment is a melting pot for various kinds of wastes, both organic and inorganic. Mixing up of waste water from various sources such as domestic, industries, hospitals and sewage released into these water bodies resulting in the co-existence of E. coli from various sources thus offering a conducive environment for horizontal gene transfer. Opportunistic pathogens might acquire genes for drug resistance and virulence turning them to potential pathogens. Prevalence of ExPEC in the Cochin estuary, pose threat to people who use this water for fishing and recreation. Food chain also plays an important role in the transit of virulence genes from the environments to the human. Antibiotic resistant E. coli are widespread in estuarine water, seafood and clinical samples, for reasons well known such as indiscriminate use of antibiotics in animal production systems, aquaculture and human medicine. Since the waste water from these sources entering the estuary provides selection pressure to drug resistant mutants in the environment. It is high time that the authorities concerned should put systems in place for monitoring and enforcement to curb such activities. Microbial contamination can limit people’s enjoyment of coastal waters for contact recreation or shellfish-gathering. E. coli can make people sick if they are present in high levels in water used for contact recreation or shellfish gathering. When feeding, shellfish can filter large volumes of seawater, so any microorganisms present in the water become accumulated and concentrated in the shellfish flesh. If E. coli contaminated shellfish are consumed the impact to human health includes gastroenteritis, urinary tract infections (UTIs), and bacteraemia. In conclusion, the high prevalence of various pathogenic serotypes and phylogenetic groups, multidrug-resistance, and virulence factor genes detected among E. coli isolates from stations close to Cochin city is a matter of concern, since there is a large reservoir of antibiotic resistance genes and virulence traits within the community, and that the resistance genes and plasmid-encoded genes for virulence were easily transferable to other strains. Given the severity of the clinical manifestations of the disease in humans and the inability and/or the potential risks of antibiotic administration for treatment, it appears that the most direct and effective measure towards prevention of STEC and ExPEC infections in humans and ensuring public health may be considered as a priority.

A Study of Single Stage Semi‐Dry Anaerobic Digestion of Organic Fraction of Municipal Solid Waste

Solid waste generation is a natural consequence of human activity and is increasing along with population growth, urbanization and industrialization. Improper disposal of the huge amount of solid waste seriously affects the environment and contributes to climate change by the release of greenhouse gases. Practicing anaerobic digestion (AD) for the organic fraction of municipal solid waste (OFMSW) can reduce emissions to environment and thereby alleviate the environmental problems together with production of biogas, an energy source, and digestate, a soil amendment. The amenability of substrate for biogasification varies from substrate to substrate and different environmental and operating conditions such as pH, temperature, type and quality of substrate, mixing, retention time etc. Therefore, the purpose of this research work is to develop feasible semi-dry anaerobic digestion process for the treatment of OFMSW from Kerala, India for potential energy recovery and sustainable waste management. This study was carried out in three phases in order to reach the research purpose. In the first phase, batch study of anaerobic digestion of OFMSW was carried out for 100 days at 32°C (mesophilic digestion) for varying substrate concentrations. The aim of this study was to obtain the optimal conditions for biogas production using response surface methodology (RSM). The parameters studied were initial pH, substrate concentration and total organic carbon (TOC). The experimental results showed that the linear model terms of initial pH and substrate concentration and the quadratic model terms of the substrate concentration and TOC had significant individual effect (p < 0.05) on biogas yield. However, there was no interactive effect between these variables (p > 0.05). The optimum conditions for maximizing the biogas yield were a substrate concentration of 99 g/l, an initial pH of 6.5 and TOC of 20.32 g/l. AD of OFMSW with optimized substrate concentration of 99 g/l [Total Solid (TS)-10.5%] is a semi-dry digestion system .Under the optimized condition, the maximum biogas yield was 53.4 L/kg VS (volatile solid).. In the second phase, semi-dry anaerobic digestion of organic solid wastes was conducted for 45 days in a lab-scale batch experiment for substrate concentration of 100 g/l (TS-11.2%) for investigating the start-up performances under thermophilic condition (50°C). The performance of the reactor was evaluated by measuring the daily biogas production and calculating the degradation of total solids and the total volatile solids. The biogas yield at the end of the digestion was 52.9 L/kg VS for the substrate concentration of 100 g/l. About 66.7% of volatile solid degradation was obtained during the digestion. A first order model based on the availability of substrate as the limiting factor was used to perform the kinetic studies of batch anaerobic digestion system. The value of reaction rate constant, k, obtained was 0.0249 day-1. A laboratory bench scale reactor with a capacity of 36.8 litres was designed and fabricated to carry out the continuous anaerobic digestion of OFMSW in the third phase. The purpose of this study was to evaluate the performance of the digester at total solid concentration of 12% (semi-dry) under mesophlic condition (32°C). The digester was operated with different organic loading rates (OLRs) and constant retention time. The performance of the reactor was evaluated using parameters such as pH, volatile fatty acid (VFA), alkalinity, chemical oxygen demand (COD), TOC and ammonia-N as well as biogas yield. During the reactor’s start-up period, the process is stable and there is no inhibition occurred and the average biogas production was 14.7 L/day. The reactor was fed in continuous mode with different OLRs (3.1,4.2 and 5.65 kg VS/m3/d) at constant retention time of 30 days. The highest volatile solid degradation of 65.9%, with specific biogas production of 368 L/kg VS fed was achieved with OLR of 3.1 kg VS/m3/d. Modelling and simulation of anaerobic digestion of OFMSW in continuous operation is done using adapted Anaerobic Digestion Model No 1 (ADM1).The proposed model, which has 34 dynamic state variables, considers both biochemical and physicochemical processes and contains several inhibition factors including three gas components. The number of processes considered is 28. The model is implemented in Matlab® version 7.11.0.584(R2010b). The model based on adapted ADM1 was tested to simulate the behaviour of a bioreactor for the mesophilic anaerobic digestion of OFMSW at OLR of 3.1 kg VS/m3/d. ADM1 showed acceptable simulating results.

Modelling of global crop production and resulting N2O emissions

Landwirtschaft spielt eine zentrale Rolle im Erdsystem. Sie trägt durch die Emission von CO2, CH4 und N2O zum Treibhauseffekt bei, kann Bodendegradation und Eutrophierung verursachen, regionale Wasserkreisläufe verändern und wird außerdem stark vom Klimawandel betroffen sein. Da all diese Prozesse durch die zugrunde liegenden Nährstoff- und Wasserflüsse eng miteinander verknüpft sind, sollten sie in einem konsistenten Modellansatz betrachtet werden. Dennoch haben Datenmangel und ungenügendes Prozessverständnis dies bis vor kurzem auf der globalen Skala verhindert. In dieser Arbeit wird die erste Version eines solchen konsistenten globalen Modellansatzes präsentiert, wobei der Schwerpunkt auf der Simulation landwirtschaftlicher Erträge und den resultierenden N2O-Emissionen liegt. Der Grund für diese Schwerpunktsetzung liegt darin, dass die korrekte Abbildung des Pflanzenwachstums eine essentielle Voraussetzung für die Simulation aller anderen Prozesse ist. Des weiteren sind aktuelle und potentielle landwirtschaftliche Erträge wichtige treibende Kräfte für Landnutzungsänderungen und werden stark vom Klimawandel betroffen sein. Den zweiten Schwerpunkt bildet die Abschätzung landwirtschaftlicher N2O-Emissionen, da bislang kein prozessbasiertes N2O-Modell auf der globalen Skala eingesetzt wurde. Als Grundlage für die globale Modellierung wurde das bestehende Agrarökosystemmodell Daycent gewählt. Neben der Schaffung der Simulationsumgebung wurden zunächst die benötigten globalen Datensätze für Bodenparameter, Klima und landwirtschaftliche Bewirtschaftung zusammengestellt. Da für Pflanzzeitpunkte bislang keine globale Datenbasis zur Verfügung steht, und diese sich mit dem Klimawandel ändern werden, wurde eine Routine zur Berechnung von Pflanzzeitpunkten entwickelt. Die Ergebnisse zeigen eine gute Übereinstimmung mit Anbaukalendern der FAO, die für einige Feldfrüchte und Länder verfügbar sind. Danach wurde das Daycent-Modell für die Ertragsberechnung von Weizen, Reis, Mais, Soja, Hirse, Hülsenfrüchten, Kartoffel, Cassava und Baumwolle parametrisiert und kalibriert. Die Simulationsergebnisse zeigen, dass Daycent die wichtigsten Klima-, Boden- und Bewirtschaftungseffekte auf die Ertragsbildung korrekt abbildet. Berechnete Länderdurchschnitte stimmen gut mit Daten der FAO überein (R2 = 0.66 für Weizen, Reis und Mais; R2 = 0.32 für Soja), und räumliche Ertragsmuster entsprechen weitgehend der beobachteten Verteilung von Feldfrüchten und subnationalen Statistiken. Vor der Modellierung landwirtschaftlicher N2O-Emissionen mit dem Daycent-Modell stand eine statistische Analyse von N2O-und NO-Emissionsmessungen aus natürlichen und landwirtschaftlichen Ökosystemen. Die als signifikant identifizierten Parameter für N2O (Düngemenge, Bodenkohlenstoffgehalt, Boden-pH, Textur, Feldfrucht, Düngersorte) und NO (Düngemenge, Bodenstickstoffgehalt, Klima) entsprechen weitgehend den Ergebnissen einer früheren Analyse. Für Emissionen aus Böden unter natürlicher Vegetation, für die es bislang keine solche statistische Untersuchung gab, haben Bodenkohlenstoffgehalt, Boden-pH, Lagerungsdichte, Drainierung und Vegetationstyp einen signifikanten Einfluss auf die N2O-Emissionen, während NO-Emissionen signifikant von Bodenkohlenstoffgehalt und Vegetationstyp abhängen. Basierend auf den daraus entwickelten statistischen Modellen betragen die globalen Emissionen aus Ackerböden 3.3 Tg N/y für N2O, und 1.4 Tg N/y für NO. Solche statistischen Modelle sind nützlich, um Abschätzungen und Unsicherheitsbereiche von N2O- und NO-Emissionen basierend auf einer Vielzahl von Messungen zu berechnen. Die Dynamik des Bodenstickstoffs, insbesondere beeinflusst durch Pflanzenwachstum, Klimawandel und Landnutzungsänderung, kann allerdings nur durch die Anwendung von prozessorientierten Modellen berücksichtigt werden. Zur Modellierung von N2O-Emissionen mit dem Daycent-Modell wurde zunächst dessen Spurengasmodul durch eine detailliertere Berechnung von Nitrifikation und Denitrifikation und die Berücksichtigung von Frost-Auftau-Emissionen weiterentwickelt. Diese überarbeitete Modellversion wurde dann an N2O-Emissionsmessungen unter verschiedenen Klimaten und Feldfrüchten getestet. Sowohl die Dynamik als auch die Gesamtsummen der N2O-Emissionen werden befriedigend abgebildet, wobei die Modelleffizienz für monatliche Mittelwerte zwischen 0.1 und 0.66 für die meisten Standorte liegt. Basierend auf der überarbeiteten Modellversion wurden die N2O-Emissionen für die zuvor parametrisierten Feldfrüchte berechnet. Emissionsraten und feldfruchtspezifische Unterschiede stimmen weitgehend mit Literaturangaben überein. Düngemittelinduzierte Emissionen, die momentan vom IPCC mit 1.25 +/- 1% der eingesetzten Düngemenge abgeschätzt werden, reichen von 0.77% (Reis) bis 2.76% (Mais). Die Summe der berechneten Emissionen aus landwirtschaftlichen Böden beträgt für die Mitte der 1990er Jahre 2.1 Tg N2O-N/y, was mit den Abschätzungen aus anderen Studien übereinstimmt.

Organic field-effect transistors and phototransistors based on amorphous materials

A comparison between the charge transport properties in low molecular amorphous thin films of spiro-linked compound and their corresponding parent compound has been demonstrated. The field-effect transistor method is used for extracting physical parameters such as field-effect mobility of charge carriers, ON/OFF ratios, and stability. In addition, phototransistors have been fabricated and demonstrated for the first time by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. The active materials used in this study can be divided into three classes, namely Spiro-linked compounds (symmetrically spiro-linked compounds), the corresponding parent-compounds, and photosensitive spiro-linked compounds (asymmetrically spiro-linked com-pounds). Some of symmetrically spiro-linked compounds used in this study were 2,2',7,7'-Tetrakis-(di-phenylamino)-9,9'-spirobifluorene (Spiro-TAD),2,2',7,7'-Tetrakis-(N,N'-di-p-methylphenylamino)-9,9'-spirobifluorene (Spiro-TTB), 2,2',7,7'-Tetra-(m-tolyl-phenylamino)-9,9'-spirobifluorene (Spiro-TPD), and 2,2Ž,7,7Ž-Tetra-(N-phenyl-1-naphtylamine)-9,9Ž-spirobifluorene (Spiro alpha-NPB). Related parent compounds of the symmetrically spiro-linked compound used in this study were N,N,N',N'-Tetraphenylbenzidine (TAD), N,N,N',N'-Tetrakis(4-methylphenyl)benzidine (TTB), N,N'-Bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), and N,N'-Diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (alpha-NPB). The photosensitive asymmetrically spiro-linked compounds used in this study were 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(biphenyl-4-yl)-9,9'-spirobifluorene (Spiro-DPSP), and 2,7-bis-(N,N'-diphenylamino)-2',7'-bis(spirobifluorene-2-yl)-9,9'-spirobifluorene (Spiro-DPSP^2). It was found that the field-effect mobilities of charge carriers in thin films of symmetrically spiro-linked compounds and their corresponding parent compounds are in the same order of magnitude (~10^-5 cm^2/Vs). However, the thin films of the parent compounds were easily crystallized after the samples have been exposed in ambient atmosphere and at room temperature for three days. In contrast, the thin films and the transistor characteristics of symmetrically spiro-linked compound did not change significantly after the samples have been stored in ambient atmosphere and at room temperature for several months. Furthermore, temperature dependence of the mobility was analyzed in two models, namely the Arrhenius model and the Gaussian Disorder model. The Arrhenius model tends to give a high value of the prefactor mobility. However, it is difficult to distinguish whether the temperature behaviors of the material under consideration follows the Arrhenius model or the Gaussian Disorder model due to the narrow accessible range of the temperatures. For the first time, phototransistors have been fabricated and demonstrated by using organic materials. In this case, asymmetrically spiro-linked compounds are used as active materials. Intramolecular charge transfer between a bis(diphenylamino)biphenyl unit and a sexiphenyl unit leads to an increase in charge carrier density, providing the amplification effect. The operational responsivity of better than 1 A/W can be obtained for ultraviolet light at 370 nm, making the device interesting for sensor applications. This result offers a new potential application of organic thin film phototransistors as low-light level and low-cost visible blind ultraviolet photodetectors.

Microbial use of organic substrates and maize growth, especially in saline and alkaline soils of Pakistani Punjab

This thesis consists of 4 main parts: (1) impact of growing maize on the decomposition of incorporated fresh alfalfa residues, (2) relationships between soil biological and other soil properties in saline and alkaline arable soils from the Pakistani Punjab, (3) decomposition of compost and plant residues in Pakistani soils along a gradient in salinity, and (4) interactions of compost and triple superphosphate on the growth of maize in a saline Pakistani soil. These 4 chapters are framed by a General Introduction and a Conclusions section. (1) In the first study, the effects of growing maize plants on the microbial decomposition of freshly chopped alfalfa residues was investigated in a 90-day pot experiment using a sandy arable soil. Assuming that the addition of alfalfa residues did not affect the decomposition of native soil organic matter, only 27% of the alfalfa residues were found as CO2. This suggests that a considerable part of alfalfa-C remained undecomposed in the soil. However, only 6% of the alfalfa residues could be recovered as plant remains in treatment with solely alfalfa residues. Based on d13C values, it was calculated that plant remains in treatment maize + alfalfa residues contained 14.7% alfalfa residues and 85.3% maize root remains. This means 60% more alfalfa-C was recovered in this treatment. (2) In the second study, the interactions between soil physical, soil chemical and soil biological properties were analysed in 30 Pakistani soils from alkaline and saline arable sites differing strongly in salinisation and in soil pH. The soil biological properties were differentiated into indices for microbial activity, microbial biomass, and community structure with the aim of assessing their potential as soil fertility indices. (3) In the third study, 3 organic amendments (compost, maize straw and pea straw) were added to 5 Pakistani soils from a gradient in salinity. Although salinity has depressive effects on microbial biomass C, biomass N, biomass P, and ergosterol, the clear gradient according to the soil salt concentration was not reflected by the soil microbial properties. The addition of the 3 organic amendments always increased the contents of the microbial indices analysed. The amendment-induced increase was especially strong for microbial biomass P and reflected the total P content of the added substrates. (4) The fourth study was greenhouse pot experiment with different combinations of compost and triple superphosphate amendments to investigate the interactions between plant growth, microbial biomass formation and compost decomposition in a strongly saline Pakistani arable soil in comparison to a non-saline German arable soil. The Pakistani soil had a 2 times lower content of ergosterol, a 4 times lower contents of microbial biomass C, biomass N and biomass P, but nearly a 20 times lower content of NaHCO3 extractable P. The addition of 1% compost always had positive effects on the microbial properties and also on the content of NaHCO3 extractable P. The addition of superphosphate induced a strong and similar absolute increase in microbial biomass P in both soils.

Vom Input zum Output

Infolge der durch die internationalen Schulvergleichstests eingeleiteten empirischen Wende in der Erziehungswissenschaft hat sich die Aufmerksamkeit vom Input schulischen Lehrens und Lernens zunehmend auf die Ergebnisse (Output) bzw. Wirkungen (Outcomes) verlagert. Die Kernfrage lautet nun: Was kommt am Ende in der Schule bzw. im Unterricht eigentlich heraus? Grundlegende Voraussetzung ergebnisorienterter Steuerung schulischen Unterrichts ist die Formulierung von Bildungsstandards. Wie Bildungsstandards mit Kompetenzmodellen und konkreten Aufgabenstellungen im Unterricht des Faches "Politik & Wirtschaft" verknüpft werden können, wird in diesem Beitrag einer genaueren Analyse unterzogen. Vor dem Hintergrund bildungstheoretischer Vorstellungen im Anschluss an Immanuel Kant kommen dabei das Literacy-Konzept der Pisa-Studie sowie die "Dokumentarische Methode" nach Karl Mannheim zur Anwendung.

Soil organic carbon management for sustainable land use in Sudano-Sahelian West Africa

Judged by their negative nutrient balances, low soil cover and low productivity, the predominant agro-pastoral farming systems in the Sudano-Sahelian zone of West Africa are highly unsustainable for crop production intensification. With kaolinite as the main clay type, the cation exchange capacity of the soils in this region, often less than 1 cmol_c kg^-1 soil, depends heavily on the organic carbon (Corg) content. However, due to low carbon sequestration and to the microbe, termite and temperature-induced rapid turnover rates of organic material in the present land-use systems, Corg contents of the topsoil are very low, ranging between 1 and 8 g kg^-1 in most soils. For sustainable food production, the availability of phosphorus (P) and nitrogen (N) has to be increased considerably in combination with an improvement in soil physical properties. Therefore, the adoption of innovative management options that help to stop or even reverse the decline in Corg typically observed after cultivating bush or rangeland is of utmost importance. To maintain food production for a rapidly growing population, targeted applications of mineral fertilisers and the effective recycling of organic amendments as crop residues and manure are essential. Any increase in soil cover has large effects in reducing topsoil erosion by wind and water and favours the accumulation of wind-blown dust high in bases which in turn improves P availability. In the future decision support systems, based on GIS, modelling and simulation should be used to combine (i) available fertiliser response data from on-station and on-farm research, (ii) results on soil productivity restoration with the application of mineral and organic amendments and (iii) our present understanding of the cause-effect relationships governing the prevailing soil degradation processes. This will help to predict the effectiveness of regionally differentiated soil fertility management approaches to maintain or even increase soil Corg levels.

Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Organic inputs and farmers' management strategies in millet fields of western Niger

Research on soil fertility management in sub-Saharan Africa was criticized lately for largely ignoring farmers’ management strategies and the underlying principles. To fill this gap of knowledge, detailed interviews were conducted with 108 farm households about their rationale in managing the soil fertility of 307 individual fields in the agro-pastoral village territory of Chikal in western Niger. To amplify the farmers’ information on manuring and corralling practices, repeated measurements of applied amounts of manure were carried out within six 1-km^2 monitoring areas from February to October 1998. The interviews revealed that only 2% of the fields were completely fallowed for a period of 1–15 years, but 40% of the fields were at least partially fallowed. Mulching of crop residues was mainly practiced to fight wind erosion but was restricted to 36% of the surveyed fields given the alternative use of straw as livestock feed. Manure application and livestock corralling, as most effective tools to enhance soil fertility, were targeted to less than 30% of the surveyed fields. The application of complete fallow and manuring and corralling practices were strongly related to the households’ endowment with resources, especially with land and livestock. Within particular fields, measures were mainly applied to spots of poor soil fertility, while the restoration of the productivity of hard pans was of secondary importance. Given the limited spatial coverage of indigenous soil fertility measures and their strong dependence on farmers’ wealth, supplementary strategies to restrict the decline of soil fertility in the drought prone areas of Niger with their heavily weathered soils are needed.

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.

Development of hybrid UV VCSEL with organic active material and dielectric DBR mirrors for medical, sensoric and data storage applications

Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.

Learning achievements of farmers during the transition to market-oriented organic agriculture in rural Uganda

Organic agriculture requires farmers with the ability to develop profitable agro-enterprises on their own. By drawing on four years of experiences with the Enabling Rural Innovation approach in Uganda, we outline how smallholder farmers transition to organic agriculture and, at the same time, increase their entrepreneurial skills and competences through learning. In order to document this learning we operationalised the Kirkpatrick learning evaluation model, which subsequently informed the collection of qualitative data in two study sites. Our analysis suggests that the Enabling Rural Innovation approach helps farmers to develop essential capabilities for identifying organic markets and new organic commodities, for testing these organic commodities under varying organic farm management scenarios, and for negotiating contracts with organic traders. We also observed several obstacles that confront farmers’ transition to organic agriculture when using the Enabling Rural Innovation approach. These include the long duration of agronomic experimentation and seed multiplication, expensive organic certification procedures and the absence of adequate mechanism for farmers to access crop finance services. Despite prevailing obstacles we conclude that the Enabling Rural Innovation approach provides a starting point for farmers to develop entrepreneurial competences and profitable agro-enterprises on their own.