Photothermal Investigations on Certain Plasma Polymerized Thin Films and Near IR Overtone Studies of Some Organic Molecules

Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and is detected using a position sensitive detector and its output is fed to a lock-in amplifier from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

Lipase production by marine fungus Aspergillus Awamori Nagazawa

The present study indicate the scope for the utilization of the marine fungus Aspergillus awamori Nagazawa BTMFW 032 for extracellular lipase production employing submerged fermentation. To the best of our knowledge this is the first report on lipase production by a marine fungus employing statistical modeling towards industrial production. The characterization of purified lipase produced by A. awamori showed stability in organic solvents, oxidizing agent and reducing agents, I,3-regiospecificity and hydrolytic activity. These properties make this lipase an ideal candidate for biocatalysis in organic media for the production of novel compounds such as biodiesel and sugar fatty esters. 91.4 % reduction in oil and grease content in ayurvedic oil by the treatment of A. awamori lipase indicates that there is a scope for this enzyme in the treatment of oil effluents and bioremediation. There is ample scope for further research on the biochemistry of the enzyme, structure elucidation and enzyme engineering towards a wide range of further applications, besides enriching scientific knowledge on marine enzymes.

Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds

Catalysis is a very important process from an industrial point of view since the production of most industrially important chemicals involves catalysis.Solid acid catalysts are appealing since the nature of acid sites is known and their chemical behavior in acid catalyzed reactions can be rationalized by means of existing theories and models. Mixed oxides crystallizing in spinel structure are of special interest because the spinel lattice imparts extra stability to the catalyst under various reaction conditions so that theses systems have sustained activities for longer periods. The thesis entitled" Catalysis By Ferrites And Cobaltites For The Alkylation And Oxidation Of Organic Compounds " presents the preparation ,characterization ,and activity studies of the prepared spinels were modified by incorporating other ions and by changing the stoichiometry.The prepared spinels exhibiting better catalytic activity towards the studied reactions with good product selectivity.Acid-base properties and cation distribution of the spinels were found to control the catalytic activity.

Triterpenoids as Biomarkers of Mangrove Organic Matter in Cochin Estuarine System

This thesis entitled triterpenoids as biomarkers of mangrove organic matter in cochin estuarine system.Mangrove forests, known as rainforests of the sea are one of the most important coastal ecosystems in the world in terms of primary production and coastal protection.Estuaries, the important areas of world’s coastal zones link the carbon cycle of the oceans to the continents.Three mangrove ecosystems and three estuarine stations around Cochin region, southwest coast of India were selected for the present study. The thesis is divided into five chapters. Chapter 1 is the Introduction and it deals with the aim and scope of the present study. Chapter 2 is Materials and Methods. This chapter deals with the nature and general geographical features of the study area. It also contains the details of the sampling and analytical methodology.the present study. Chapter 3 is Geochemistry and it includes the seasonal and spatial variations of the geochemical parameters in the surface sediments.Chapter 4 is Biochemical Composition. It covers the biochemical composition of organic matter in the surface sediments to examine the quality and quantity of organic matter.Chapter 5, Triterpenoid Biomarkers in Sediments, characterize the organic matter in the sediments of the mangrove and estuarine ecosystems under study, to assess the possible sources with the help of triterpenoid biomarkers along with other lipid biomarkers.

Microbial production of antibiotics from mangrove ecosystem

The present study on "Microbial production of antibiotics from mangrove ecosystem” was carried out for a period of one year in four selected Stations, Mangalavana, Narakkal, Puthuvyppu and light house area of Puthuvyppu (9°55' — 10°10'N and 76°10‘ - 76°20'E) from January to December 1991. Though much emphasis has been given to occurrence and distribution of actinomycetes, an attempt was also made to understand the distribution patterns of other micro flora in the sediments. Data on physico-chemical parameters were also collected to find out their relationship if any with the microflora. The principle interest of the present investigation is to determineseasonal variations of antagonistic actinomycetes in selected mangrove ecosystem. The microbial interrelationship in mangrove sediments was found out by constructing the ratio between bacteria and actinomycetes, bacteria and fungi, fungi and actinomycetes. In addition temperature, pH, salinity, dissolved oxygen and organic carbon were determined seasonally and their possible relationship was statistically analyzed and the results are presented. Isolated actinomycetes were subjected to cross streak assay to know their nature of antibiotic activity against test fish pathogens and crude antibiotics were extracted from selected isolates and their inhibitory activity is studied and the results are discussed.

Propyl Gallate Synthesis Using Acidophilic Tannase and Simultaneous Production of Tannase and Gallic Acid by Marine Aspergillus awamori BTMFW032

Marine Aspergillus awamori BTMFW032, recently reported by us, produce acidophilic tannase as extracellular enzyme. Here, we report the application of this enzyme for synthesis of propyl gallate by direct transesterification of tannic acid and in tea cream solubilisation besides the simultaneous production of gallic acid along with tannase under submerged fermentation by this fungus. This acidophilic tannase enabled synthesis of propyl gallate by direct transesterification of tannic acid using propanol as organic reaction media under low water conditions. The identity of the product was confirmed with thin layer chromatography and Fourier transform infrared spectroscopy. It was noted that 699 U/ml of enzyme could give 60% solubilisation of tea cream within 1 h. Enzyme production medium was optimized adopting Box–Behnken design for simultaneous synthesis of tannase and gallic acid. Process variables including tannic acid, sodium chloride, ferrous sulphate, dipotassium hydrogen phosphate, incubation period and agitation were recognized as the critical factors that influenced tannase and gallic acid production. The model obtained predicted 4,824.61 U/ml of tannase and 136.206 μg/ml gallic acid after 48 h of incubation, whereas optimized medium supported 5,085 U/ml tannase and 372.6 μg/ml of gallic acid production after 36 and 84 h of incubation, respectively, with a 15-fold increase in both enzyme and gallic acid production. Results indicated scope for utilization of this acidophilic tannase for transesterification of tannic acid into propyl gallate, tea cream solubilisation and simultaneous production of gallic acid along with tannase

Protease Production by haloarchaea Natrinema sp. BTSH10 isolated from salt pan of South India

The present study led to the recognition of Natrinema sp. BTSH 10 isolated from saltern ponds, as an ideal candidate species for production of gelatinase, which was noted as a halozyme capable of showing enzyme activity in the presence of 15% NaCl. Results obtained during the course of the present study indicated potential for application of this enzyme in industrial catalysis that are performed in the presence of high concentrations of salt. The enzyme characteristics noted with this gelatinase also indicate the scope for probable applications in leather industry, meat tenderization, production of fish sauce and soy sauce. Since halophilic proteases are tolerant to organic solvents, they could be used in antifouling coating preparations used to prevent biofouling of submarine equipments. The gelatinase from haloarchaea could be considered as a probable candidate for peptide synthesis. However, further studies are warranted on this haloarcheal gelatinase particularly on structure elucidation and enzyme engineering to suit a wide range of applications. There is immense scope for developing this halozyme as an industrial enzyme once thorough biochemistry of this gelatinase is studied and a pilot scale study is conducted towards industrial production of this enzyme under fermentation is facilitated. Based on the present study it is concluded that haloarchaea Natrinema sp. that inhabit solar saltern ponds are ideal source for deriving industrially important halozymes and molecular studies on enzymes are prerequisite for their probable industrial applications. This is the first time this species of archaea is recognized as a source of gelatinase enzyme that has potential for industrial applications.

Provenance, Isolation and Characterisation of Organic Matter in the Cochin Estuarine Sediment-“a Diagenetic Amino Acid Marker Scenario

Cochin estuarine system is among the most productive aquatic environment along the Southwest coast of India, exhibits unique ecological features and possess greater socioeconomic relevance. Serious investigations carried out during the past decades on the hydro biogeochemical variables pointed out variations in the health and ecological functioning of this ecosystem. Characterisation of organic matter in the estuary has been attempted in many investigations. But detailed studies covering the degradation state of organic matter using molecular level approach is not attempted. The thesis entitled Provenance, Isolation and Characterisation of Organic Matter in the Cochin Estuarine Sediment-“ A Diagenetic Amino Acid Marker Scenario” is an integrated approach to evaluate the source, quantity, quality, and degradation state of the organic matter in the surface sediments of Cochin estuarine system with the combined application of bulk and molecular level tools. Sediment and water samples from nine stations situated at Cochin estuary were collected in five seasonal sampling campaigns, for the biogeochemical assessment and their distribution pattern of sedimentary organic matter. The sampling seasons were described and abbreviated as follows: April- 2009 (pre monsoon: PRM09), August-2009 (monsoon: MON09), January-2010 (post monsoon: POM09), April-2010 (pre monsoon: PRM10) and September- 2012 (monsoon: MON12). In order to evaluate the general environmental conditions of the estuary, water samples were analysed for water quality parameters, chlorophyll pigments and nutrients by standard methods. Investigations suggested the fact that hydrographical variables and nutrients in Cochin estuary supports diverse species of flora and fauna. Moreover the sedimentary variables such as pH, Eh, texture, TOC, fractions of nitrogen and phosphorous were determined to assess the general geochemical setting as well as redox status. The periodically fluctuating oxic/ anoxic conditions and texture serve as the most significant variables controlling other variables of the aquatic environment. The organic matter in estuary comprise of a complex mixture of autochthonous as well as allochthonous materials. Autochthonous input is limited or enhanced by the nutrient elements like N and P (in their various fractions), used as a tool to evaluate their bioavailability. Bulk parameter approach like biochemical composition, stoichiometric elemental ratios and stable carbon isotope ratio was also employed to assess the quality and quantity of sedimentary organic matter in the study area. Molecular level charactersation of free sugars and amino acids were carried out by liquid chromatographic techniques. Carbohydrates are the products of primary production and their occurrence in sediments as free sugars can provide information on the estuarine productivity. Amino acid biogeochemistry provided implications on the system productivity, nature of organic matter as well as degradation status of the sedimentary organic matter in the study area. The predominance of carbohydrates over protein indicated faster mineralisation of proteinaceous organic matter in sediments and the estuary behaves as a detrital trap for the accumulation of aged organic matter. The higher lipid content and LPD/CHO ratio pointed towards the better food quality that supports benthic fauna and better accumulation of lipid compounds in the sedimentary environment. Allochthonous addition of carbohydrates via terrestrial run off was responsible for the lower PRT/CHO ratio estimated in thesediments and the lower ratios also denoted a detrital heterotrophic environment. Biopolymeric carbon and the algal contribution to BPC provided important information on the better understanding the trophic state of the estuarine system and the higher values of chlorophyll-a to phaeophytin ratio indicated deposition of phytoplankton to sediment at a rapid rate. The estimated TOC/TN ratios implied the combined input of both terrestrial and autochthonous organic matter to sedimentsAmong the free sugars, depleted levels of glucose in sediments in most of the stations and abundance of mannose at station S5 was observed during the present investigation. Among aldohexoses, concentration of galactose was found to be higher in most of the stationsRelative abundance of AAs in the estuarine sediments based on seasons followed the trend: PRM09-Leucine > Phenylalanine > Argine > Lysine, MON09-Lysine > Aspartic acid > Histidine > Tyrosine > Phenylalanine, POM09-Lysine > Histadine > Phenyalanine > Leucine > Methionine > Serine > Proline > Aspartic acid, PRM10-Valine > Aspartic acid > Histidine > Phenylalanine > Serine > Proline, MON12-Lysine > Phenylalanine > Aspartic acid > Histidine > Valine > Tyrsine > MethionineThe classification of study area into three zones based on salinity was employed in the present study for the sake of simplicity and generalized interpretations. The distribution of AAs in the three zones followed the trend: Fresh water zone (S1, S2):- Phenylalanine > Lysine > Aspartic acid > Methionine > Valine ῀ Leucine > Proline > Histidine > Glycine > Serine > Glutamic acid > Tyrosine > Arginine > Alanine > Threonine > Cysteine > Isoleucine. Estuarine zone (S3, S4, S5, S6):- Lysine > Aspartic acid > Phenylalanine > Leucine > Valine > Histidine > Methionine > Tyrosine > Serine > Glutamic acid > Proline > Glycine > Arginine > Alanine > Isoleucine > Cysteine > Threonine. Riverine /Industrial zone (S7, S8, S9):- Phenylalanine > Lysine > Aspartic acid > Histidine > Serine > Arginine > Tyrosine > Leucine > Methionine > Glutamic acid > Alanine > Glycine > Cysteine > Proline > Isoleucine > Threonine > Valine. The abundance of AAs like glutamic acid, aspartic acid, isoleucine, valine, tyrosine, and phenylalanine in sediments of the study area indicated freshly derived organic matter.

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.

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.

Effect of management strategies on the performance of ruminant livestock production systems and the safety of plant and animal products in the city of Sikasso, Mali

The regional population growth in West Africa, and especially its urban centers, will bring about new and critical challenges for urban development policy, especially in terms of ensuring food security and providing employment for the growing population. (Peri-) urban livestock and vegetable production systems, which can contribute significantly to these endeavours, are limited by various constraints, amongst them limited access to expensive production factors and their (in)efficient use. To achieve sustainable production systems with low consumer health risks, that can meet the urban increased demand, this doctoral thesis determined nutrient use efficiencies in representative (peri-) urban livestock production systems in three West African cities, and investigated potential health risks for consumers ensuing from there. The field study, which was conducted during July 2007 to December 2009, undertook a comparative analysis of (peri-) urban livestock production strategies across 210 livestock keeping households (HH) in the three West African cities of Kano/Nigeria (84 HH), Bobo Dioulasso/Burkina Faso (63 HH) and Sikasso/Mali (63 HH). These livestock enterprises were belonging to the following three farm types: commercial gardening plus field crops and livestock (cGCL; 88 HH), commercial livestock plus subsistence field cropping (cLsC; 109 HH) and commercial gardening plus semi-commercial livestock (cGscL; 13 HH) which had been classified in a preceding study; they represented the diversity of (peri-) urban livestock production systems in West Africa. In the study on the efficiency of ruminant livestock production, lactating cowsand sheep herd units were differentiated based on whether feed supplements were offered to the animals at the homestead (Go: grazing only; Gsf: mainly grazing plus some supplement feeding). Inflows and outflows of nutrients were quantified in these herds during 18 months, and the effects of seasonal variations in nutrient availability on animals’ productivity and reproductive performance was determined in Sikasso. To assess the safety of animal products and vegetables, contamination sources of irrigated lettuce and milk with microbiological contaminants, and of tomato and cabbage with pesticide residues in (peri-) urban agriculture systems of Bobo Dioulasso and Sikasso were characterized at three occasions in 2009. Samples of irrigation water, organic fertilizer and ix lettuce were collected in 6 gardens, and samples of cabbage and tomato in 12 gardens; raw and curdled milk were sampled in 6 dairy herds. Information on health risks for consumers of such foodstuffs was obtained from 11 health centers in Sikasso. In (peri-) urban livestock production systems, sheep and goats dominated (P<0.001) in Kano compared to Bobo Dioulasso and Sikasso, while cattle and poultry were more frequent (P<0.001) in Bobo Dioulasso and Sikasso than in Kano. Across cities, ruminant feeding relied on grazing and homestead supplementation with fresh grasses, crop residues, cereal brans and cotton seed cake; cereal grains and brans were the major ingredients of poultry feeds. There was little association of gardens and livestock; likewise field cropping and livestock were rarely integrated. No relation existed between the education of the HH head and the adoption of improved management practices (P>0.05), but the proportion of HH heads with a long-term experience in (peri-) urban agriculture was higher in Kano and in Bobo Dioulasso than in Sikasso (P<0.001). Cattle and sheep fetched highest market prices in Kano; unit prices for goats and chicken were highest in Sikasso. Animal inflow, outflow and dairy herd growth rates were significantly higher (P<0.05) in the Gsf than in the Go cattle herds. Maize bran and cottonseed expeller were the main feeds offered to Gsf cows as dry-season supplement, while Gsf sheep received maize bran, fresh grasses and cowpea pods. The short periodic transhumance of Go dairy cows help them maintaining their live weight, whereas Gsf cows lost weight during the dry season despite supplement feeding at a rate of 1506 g dry matter per cow and day, resulting in low productivity and reproductive performance. The daily live weight gains of calves and lambs, respectively, were low and not significantly different between the Go and the Gsf system. However, the average live weight gains of lambs were significantly higher in the dry season (P<0.05) than in the rainy season because of the high pressure of gastrointestinal parasites and of Trypanosoma sp. In consequence, 47% of the sheep leaving the Go and Gsf herds died due to diseases during the study period. Thermo-tolerant coliforms and Escherichia coli contamination levels of irrigation water significantly exceeded WHO recommendations for the unrestricted irrigation of vegetables consumed raw. Microbial contamination levels of lettuce at the farm gate and the market place in Bobo Dioulasso and at the farm gate in Sikasso were higher than at the market place in Sikasso (P<0.05). Pesticide residues were detected in only one cabbage and one tomato sample and were below the maximum residue limit for consumption. Counts of thermo-tolerant coliforms and Escherichia coli were higher in curdled than in raw milk (P<0.05). From 2006 to x 2009, cases of diarrhea/vomiting and typhoid fever had increased by 11% and 48%, respectively, in Sikasso. For ensuring economically successful and ecologically viable (peri-) urban livestock husbandry and food safety of (peri-) urban foodstuffs of animal and plant origin, the dissemination and adoption of improved feeding practices, livestock healthcare and dung management are key. In addition, measures fostering the safety of animal products and vegetables including the appropriate use of wastewater in (peri-) urban agriculture, restriction to approve vegetable pesticides and the respect of their latency periods, and passing and enforcement of safety laws is required. Finally, the incorporation of environmentally sound (peri-) urban agriculture in urban planning by policy makers, public and private extension agencies and the urban farmers themselves is of utmost importance. To enable an efficient (peri-) urban livestock production in the future, research should concentrate on cost-effective feeding systems that allow meeting the animals’ requirement for production and reproduction. Thereby focus should be laid on the use of crop-residues and leguminous forages. The improvement of the milk production potential through crossbreeding of local cattle breeds with exotic breeds known for their high milk yield might be an accompanying option, but it needs careful supervision to prevent the loss of the local trypanotolerant purebreds.

Agri-environmental evaluation of traditional and alternative corn production systems in Chiapas, Mexico

This study evaluates the effects of environmental variables on traditional and alternative agroecosystems in three Ejidos (communal lands) in the Chiapas rainforest in Mexico. The tests occurred within two seasonal agricultural cycles. In spring-summer, experiments were performed with the traditional slash, fell and burn (S-F-B) system, no-burn systems and rotating systems with Mucuna deeringiana Bort., and in the autumn-winter agricultural cycle, three no-burn systems were compared to evaluate the effect of alternative sowing with corn (no-burn and topological modification of sowing). The results show a high floristic diversity in the study area (S_S = 4 - 23%), with no significant differences among the systems evaluated. In the first cycle, the analysis of the agronomical variables of the corn indicated better properties in the fallowing systems, with an average yield of 1950 kg ha^‑1, but there was variation related to the number of years left fallow. In the second cycle, the yields were positive for the alternative technology (average yield 3100 kg ha^‑1). The traditional S-F-B systems had reduced pests and increased organic matter and soil phosphorous content. These results are the consequence of fallow periods and adaptation to the environment; thus, this practice in the Chiapas rainforest constitutes an ethnocultural reality, which is unlikely to change in the near future if the agrosystems are managed based on historical principles.

Effects of red brick production on land use, household income, and greenhouse gas emissions in Khartoum, Sudan

In Khartoum (Sudan) a particular factor shaping urban land use is the rapid expansion of red brick making (BM) for the construction of houses which occurs on the most fertile agricultural Gerif soils along the Nile banks. The objectives of this study were to assess the profitability of BM, to explore the income distribution among farmers and kiln owners, to measure the dry matter (DM), nitrogen (N), phosphorus (P), potassium (K) and organic carbon (C_org) in cow dung used for BM, and to estimate the greenhouse gas (GHG) emissions from burned biomass fuel (cow dung and fuel wood). About 49 kiln owners were interviewed in 2009 using a semi-structured questionnaire that allowed to record socio-economic and variable cost data for budget calculations, and determination of Gini coefficients. Samples of cow dung were collected directly from the kilns and analyzed for their nutrients concentrations. To estimate GHG emissions a modified approach of the Intergovernmental Panel on Climate Change (IPCC) was used. The land rental value from red brick kilns was estimated at 5-fold the rental value from agriculture and the land rent to total cost ratio was 29% for urban farms compared to 6% for BM. The Gini coefficients indicated that income distribution among kiln owners was more equal than among urban farmers. Using IPCC default values the 475, 381, and 36 t DM of loose dung, compacted dung, and fuel wood used for BM emit annually 688, 548, and 60 t of GHGs, respectively.