Algal Photosynthetic Dynamics in Urban Lakes under Stress Conditions

Urban lakes form vital ecosystems supporting livelihood with social, economic and aesthetic benefits that are essential for quality life. This depends on the biotic and abiotic components in an ecosystem. The structure of an ecosystem forms a decisive factor in sustaining its functional abilities which include nutrient cycling, oxygen production, etc. A community assemblage of primary producers (algae) plays a crucial role in maintaining the balance as they form the base of energy pyramid in the ecosystem. Algae assimilate carbon in the environment via photosynthetic activities and releases oxygen for the next level of biotic elements in an ecosystem. Besides these, algal cells rich in protein serve as food and feed, used as manure and for production of biofuels. Understanding algal photosynthetic dynamics helps in assessing the level of dissolved oxygen (DO), food (fish, etc.), waste assimilation, etc. Algal chlorophyll content, algal biomass, primary productivity and algal photosynthetic quotient are some of the parameters that help in assessing the status of urban lakes. Chlorophyll content gives a measure of the growth, spread and quantity of algae. Unplanned rapid urbanization in Bangalore in recent times has resulted in either disappearance of lake ecosystems or deteriorated the lake water quality impairing the ecological processes. This paper computes algal growth, community structure, primary productivity and composition for three major lakes (T G Halli, Bellandur and Varthur lakes) under contrast levels of anthropogenic influences.

Biofuel production and implications for land use, food production and environment in India

There is a large interest in biofuels in India as a substitute to petroleum-based fuels, with a purpose of enhancing energy security and promoting rural development. India has announced an ambitious target of substituting 20% of fossil fuel consumption by biodiesel and bioethanol by 2017. India has announced a national biofuel policy and launched a large program to promote biofuel production, particularly on wastelands: its implications need to be studied intensively considering the fact that India is a large developing country with high population density and large rural population depending upon land for their livelihood. Another factor is that Indian economy is experiencing high growth rate, which may lead to enhanced demand for food, livestock products, timber, paper, etc., with implications for land use. Studies have shown that area under agriculture and forest has nearly stabilized over the past 2-3 decades. This paper presents an assessment of the implications of projected large-scale biofuel production on land available for food production, water, biodiversity, rural development and GHG emissions. The assessment will be largely focused on first generation biofuel crops, since the Indian program is currently dominated by these crops. Technological and policy options required for promoting sustainable biofuel production will be discussed. (C) 2010 Elsevier Ltd. All rights reserved.

Lipid composition in microalgal community under laboratory and outdoor conditions

Microalgae are the most sought after sources for biofuel production due to their capacity to utilize carbon and synthesize it into high density liquid. Current energy crisis have put microalgae under scanner for economical production of biodiesel. Modifications like physiological stress and genetic variation is done to increase the lipid yield of the microalgae. A study was conducted using a microalgal consortium for a period of 15 days to evaluate the feasibility of algal biomass from laboratory as well as outdoor culture conditions. Native algal strains were isolated from a tropical freshwater lake. Preliminary growth studies indicated the relationship between the nitrates and phosphates to the community structure through the days. The lipid profile done using Gas chromatography – Mass spectrometry, revealed the profile of the algal community. Resource competition led to isolation of algae, aided in the lipid profile of a single alga. However, further studies on the application of the mixed population are required to make this consortium approach economically viable for producing algae biofuels.

Jatropha cultivation in southern India: assessing farmers' experiences

Together with 106 farmers who started growing Jatropha (Jatropha curcas L.) in 20042006, this research sought to increase the knowledge around the real-life experience of Jatropha farming in the southern India states of Tamil Nadu and Andhra Pradesh. Launched as an alternative for diesel in India, Jatropha has been promoted as a non-edible plant that could grow on poor soils, yield oil-rich seeds for production of bio-diesel, and not compete directly with food production. Through interviews with the farmers, information was gathered regarding their socio-economic situation, the implementation and performance of their Jatropha plantations, and their reasons for continuing or discontinuing Jatropha cultivation. Results reveal that 82% of the farmers had substituted former cropland for their Jatropha cultivation. By 2010, 85% (n = 90) of the farmers who cultivated Jatropha in 2004 had stopped. Cultivating the crop did not give the economic returns the farmers anticipated, mainly due to a lack of information about the crop and its maintenance during cultivation and due to water scarcity. A majority of the farmers irrigated and applied fertilizer, and even pesticides. Many problems experienced by the farmers were due to limited knowledge about cultivating Jatropha caused by poor planning and implementation of the national Jatropha program. Extension services, subsidies, and other support were not provided as promised. The farmers who continued cultivation had means of income other than Jatropha and held hopes of a future Jatropha market. The lack of market structures, such as purchase agreements and buyers, as well as a low retail price for the seeds, were frequently stated as barriers to Jatropha cultivation. For Jatropha biodiesel to perform well, efforts are needed to improve yield levels and stability through genetic improvements and drought tolerance, as well as agriculture extension services to support adoption of the crop. Government programs will -probably be more effective if implementing biodiesel production is conjoined with stimulating the demand for Jatropha biodiesel. To avoid food-biofuel competition, additional measures may be needed such as land-use restrictions for Jatropha producers and taxes on biofuels or biofuel feedstocks to improve the competitiveness of the food sector compared to the bioenergy sector. (c) 2012 Society of Chemical Industry and John Wiley & Sons, Ltd

Algal biofuel production and mitigation potential in India

Energy and energy services are the backbone of growth and development in India and is increasingly dependent upon the use of fossil based fuels that lead to greenhouse gases (GHG) emissions and related concerns. Algal biofuels are being evolved as carbon (C)-neutral alternative biofuels. Algae are photosynthetic microorganisms that convert sunlight, water and carbon dioxide (CO2) to various sugars and lipids Tri-Acyl-Glycols (TAG) and show promise as an alternative, renewable and green fuel source for India. Compared to land based oilseed crops algae have potentially higher yields (5-12 g/m(2)/d) and can use locations and water resources not suited for agriculture. Within India, there is little additional land area for algal cultivation and therefore needs to be carried out in places that are already used for agriculture, e.g. flooded paddy lands (20 Mha) with village level technologies and on saline wastelands (3 Mha). Cultivating algae under such conditions requires novel multi-tier, multi-cyclic approaches of sharing land area without causing threats to food and water security as well as demand for additional fertilizer resources by adopting multi-tier cropping (algae-paddy) in decentralized open pond systems. A large part of the algal biofuel production is possible in flooded paddy crop land before the crop reaches dense canopies, in wastewaters (40 billion litres per day), in salt affected lands and in nutrient/diversity impoverished shallow coastline fishery. Mitigation will be achieved through avoidance of GHG, C-capture options and substitution of fossil fuels. Estimates made in this paper suggest that nearly half of the current transportation petro-fuels could be produced at such locations without disruption of food security, water security or overall sustainability. This shift can also provide significant mitigation avenues. The major adaptation needs are related to socio-technical acceptance for reuse of various wastelands, wastewaters and waste-derived energy and by-products through policy and attitude change efforts.

AN EXPERIMENTAL STUDY ON EFFERVESCENT ATOMIZATION OF BIO-OIL FUELS

This paper presents the work on detailed characterization of effervescent spray of Jatropha and Pongamia pure plant oils. The spray characteristics of these biofuels are compared with those of diesel. Both macroscopic and microscopic spray characteristics at different injection pressures and gas-to-liquid ratio (GLR) have been studied. The particle/droplet imaging analysis (PDIA) technique along with direct imaging methods are used for the purpose of spray characterization. Due to their higher viscosity, pure plant oils showed poor atomization compared to diesel and a blend of diesel and pure plant oil at a given GLR. Pure plant oil sprays showed a lower spray cone angle when compared to diesel and blends at lower GLRs. However, the difference is not significant at higher GLRs. Droplet size measurements at 100 mm downstream of the exit orifice showed reduction in Sauter mean diameter (SMD) diameter with increase in GLR. A radial variation in the SMD is observed for the blend and pure plant oils. Pure oils showed a larger variation when compared to the blend. Spray unsteadiness has been characterized based on the image-to-image variation in the mean droplet diameter and fluctuations in the spray cone angle. Results showed that pure plant oil sprays are more unsteady at lower GLRs when compared to diesel and blend. A critical GLR is identified at which the spray becomes steady. The three regimes of spray operation, namely ``steady spray,'' ``pulsating spray,'' and ``spray and unbroken liquid jet'' are identified in the injection pressure-GLR parameter space for these pure plant oils. Two-phase flow imaging inside the exit orifice shows that for the pure plant oils, the flow is highly transient at low GLRs and the bubbly, slug, and annular two-phase flow regimes are all observed. However, at higher GLRs where the spray is steady, only the annular flow regime is observed.

Algal biofuel from urban wastewater in India: Scope and challenges

Rapidly depleting stocks of fossil fuels and increasing greenhouse gas (GHG) emissions have necessitated the exploration of cost effective sustainable energy sources focussing on biofuels through algae. Abundant wastewaters generated in urban localities every day provide the nourishment to nurture algae for biofuel generation. The present communication focuses on the lipid prospects of algae grown in wastewater systems. Euglena sp., Spirogyra sp. and Phormidium sp. were collected from selected locations of sewage fed urban lakes and sewage treatment plants of Bangalore and Mysore. The total lipid content of Euglena sp. was higher (24.6%) compared to Spirogyra sp. (18.4%) followed by Phormidium sp. (8.8%) and their annual lipid yield potential was 6.52, 1.94 and 2.856 t/ha/year, respectively. These species showed higher content of fatty acids (palmitate, stearate followed by oleic and linoleic acids) with the desirable biofuel properties. (C) 2013 Elsevier Ltd. All rights reserved.

Experimental investigation of biofuel drop impact on stainless steel surface

Blends of conventional fuels such as Jet-A1 (aviation kerosene) and diesel with bio-derived components, referred to as biofttels, are gradually replacing the conventional fuels in aircraft and automobile engines. There is a lack of understanding on the interaction of spray drops of such biofuels with solid surfaces. The present study is an experimental investigation on the impact of biofuel drops onto a smooth stainless steel surface. The biofuel is a mixture of 90% commercially available camelina-derived biofuel and 10% aromatics. Biofuel drops were generated using a syringe-hypodermic needle arrangement. On demand, the needle delivers an almost spherical drop with drop diameter in the range 2.05-2.15 mm. Static wetting experiments show that the biofuel drop completely wets the stainless steel surface and exhibits an equilibrium contact angle of 5.6. High speed video camera was used to capture the impact dynamics of biofuel drops with Weber number ranging from 20 to 570. The spreading dynamics and maximum spreading diameter of impacting biofuel drops on the target surface were analyzed. For the impact of high Weber number biofuel drops, the spreading law suggests beta similar to tau(0.5) where beta is the spread factor and tau, the nondimensionalized time. The experimentally observed trend of maximum spread factor, beta(max) of camelina biofuel drop on the target surface with We compares well with the theoretically predicted trend from Ukiwe-Kwok model. After reaching beta(max), the impacting biofuel drop undergoes a prolonged sluggish spreading due to the high wetting nature of the camelina biofuel-stainless steel system. As a result, the final spread factor is found to be a little more than beta(max). (C) 2014 Elsevier Inc. All rights reserved.

EXPERIMENTAL STUDIES ON AIR-ASSISTED ATOMIZATION OF JATROPHA PURE PLANT OIL

The present study focuses on exploring air-assisted atomization strategies for effective atomization of high-viscosity biofuels, such as pure plant oils (PPOs). The first part of the study concerns application of a novel air-assisted impinging jet atomization for continuous spray applications, and the second part concerns transient spray applications. The particle/droplet imaging analysis (PDIA) technique along with direct imaging methods are used for the purpose of spray characterization. In the first part, effective atomization of Jatropha PPO is demonstrated at gas-to-liquid ratios (GLRs) on the order 0.1. The effect of liquid and gas flow rates on the spray characteristics is evaluated, and results indicate a Sauter mean diameter (SMD) of 50 mu m is achieved with GLRs as low as 0.05. In the second part of the study, a commercially available air-assisted transient atomizer is evaluated using Jatropha PPO. The effect of the pressure difference across the air injector and ambient gas pressure on liquid spray characteristics is studied. The results indicate that it is possible to achieve the same level of atomization of Jatropha as diesel fuel by operating the atomizer at a higher pressure difference. Specifically, a SMD of 44 mu m is obtained for the Jatropha oil using injection pressures of <1 MPa. A further interesting observation associated with this injector is the near constancy of a nondimensional spray penetration rate for the Jatropha oil spray.

THE EFFECTS OF SURFACTANT ON SIMPLEX NOZZLE SPRAY BEHAVIOR AND ITS COMPARISON TO LIQUID FUELS

Pressure-swirl nozzles (simplex nozzles) are used in various field applications such as aero-engines, power generation, spray painting and agricultural irrigation. For this particular nozzle, research in the past decade has dealt with the development of numerical models for predicting droplet distribution profiles. Although these results have been valuable, the experimental results have been contradictory, therefore fundamental understanding of the influence of properties in nozzle is important. This paper experimentally investigates the effect of surfactants on breakup and coalescence. Since most of the fuels and biofuels have low surface tension compared to water, a comparative analysis between a surfactant solution and a liquid fuel is imperative. For this experimental study, a simplex nozzle characterized as flow number 0.4 will be utilized. The injection pressures will range from 0.3 - 4Mpa while altering the surface tension from 72 to 28mN/m. By applying Phase Doppler Particle Anemometry (PDPA) which is a non-intrusive laser diagnostic technique, the differences in spray characteristics due to spray surface tension can be highlighted. The average droplet diameter decreases for a low surface tension fluid in the axial direction in comparison to pure water. The average velocity of droplets is surprisingly lower in the same spray zone. Measurements made in the radial direction show no significant changes, but at the locations close to the nozzle, water droplets have larger diameter and velocity. The results indicate the breakup and coalescence regimes have been altered when surface tension is lowered. A decrease in surface tension alters the breakup length while increasing the spray angle. Moreover, higher injection pressure shortens the breakup length and decrease in overall diameter of the droplets. By performing this experimental study the fundamentals of spray dynamics, such as spray formation, liquid breakup length, and droplet breakup regimes can be observed as a function of surface tension and how a surrogate fuel compares with a real fuel for experimental purposes. This knowledge potentially will lead to designing a better atomizer or new biofuels.

Lignin extraction, purification and depolymerization study

280 p. : il.

Engineering thermostable fungal cellobiohydrolases

Meeting the world's growing energy demands while protecting our fragile environment is a challenging issue. Second generation biofuels are liquid fuels like long-chain alcohols produced from lignocellulosic biomass. To reduce the cost of biofuel production, we engineered fungal family 6 cellobiohydrolases (Cel6A) for enhanced thermostability using random mutagenesis and recombination of beneficial mutations. During long-time hydrolysis, engineered thermostable cellulases hydrolyze more sugars than wild-type Cel6A as single enzymes and binary mixtures at their respective optimum temperatures. Engineered thermostable cellulases exhibit synergy in binary mixtures similar to wild-type cellulases, demonstrating the utility of engineering individual cellulases to produce novel thermostable mixtures. Crystal structures of the engineered thermostable cellulases indicate that the stabilization comes from improved hydrophobic interactions and restricted loop conformations by proline substitutions. At high temperature, free cysteines contribute to irreversible thermal inactivation in engineered thermostable Cel6A and wild-type Cel6A. The mechanism of thermal inactivation in this cellulase family is consistent with disulfide bond degradation and thiol-disulfide exchange. Enhancing the thermostability of Cel6A also increases tolerance to pretreatment chemicals, demonstrated by the strong correlation between thermostability and tolerance to 1-ethyl-3-methylimidazolium acetate. Several semi-rational protein engineering approaches – on the basis of consensus sequence analysis, proline stabilization, FoldX energy calculation, and high B-factors – were evaluated to further enhance the thermostability of Cel6A.

Alternative trajectories for decarbonizing urban transportation

4 p.

Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Decarbonising urban transportation

18 p.