<p> In this thesis, the rate-limiting step is determined in a biofuel cell with a bio-anode, a Nation membrane and a conventional, platinum-based cathode using reference electrode method. It was discovered by surprise that the cathode overpotential dominated the cell overpotential. Na + in the membrane was found to hinder the W transport. The cathode overpotential increased due to the presence of Na + in the membrane and at the cathode. The limited H+ transport causes the increase of the cathode overpotential. H+ transport is the rate-limiting step in our biofuel cell, rather than commonly believed electron transport. Moreover, the cell power output degradation is not due to the conventionally believed depletion of the fuel substrate, inter-penetration of the fuel and oxidizer and the degradation of the biocatalysts, but the limited W transport in our biofuel cell. </p> <p> The existing oxygen reduction mechanism at the cathode was questioned and revised. When Na+ occupies all sulfonate groups in the membrane, only the Na+ from the buffer can pass through the membrane. The oxygen reacts with the water transported with Na+ and electrons to produce OH", which balances with the transported Na+ to keep electroneutrality at the cathode. </p> <p> Tris buffer without Na + was utilized as alternative anolyte in the biofuel cell. It was found that the cell with Tris buffer had a poorer performance in comparison with sodium phosphate buffer due to the increases of the anode and cathode overpotentials. Tris buffer does not constitute a solution to the problem. </p> <p> This work represents a step toward a more complete understanding of the properties of biofuel cells. To improve biofuel cell output, the herein identified H+ transport limitation in Na + contained Nation needs to be overcome. </p> / Thesis / Master of Applied Science (MASc)

The aspiration for producing algal biofuel is motivated by the desire to replace conventional petroleum fuels, produce fuels domestically, and reduce greenhouse gas emissions. Although, in theory, algae have the potential to produce a large amount of petroleum fuel substitutes and capture carbon emissions, in practice, profitable algal biofuel production has proven quite challenging. This dissertation characterizes the production pathways for producing petroleum fuel substitutes from algae and evaluates constraints on algal biofuel production. Chapter 8 provides a summary of the entire dissertation. The first chapter provides a framework for reporting the production of renewable diesel from algae in a consistent way by using data that are specific and by presenting information with relevant metrics. The second chapter presents a review of analytical tools (i.e., microscopy, spectroscopy, and chromatography) that can be used to analyze the structure and composition of intermediate products in an algal biofuel production pathway. In chapters 3 through 6, the energy return on investment, water intensity, and financial return on investment are presented for three cases: 1) an Experimental Case in which data were measured during five batches of algal biocrude production with a combined processed volume of about 7600 L, 2) a hypothetical Reduced Case that assumes the same energy output as the Experimental Case, with reduced energy and material inputs, and 3) a Highly Productive Case that assumes higher energy outputs than the Experimental Case, with reduced energy and material inputs, similar to the Reduced Case. For all three cases, the second-order energy return on investment was determined to be significantly less than 1, which means that all three cases are energy negative. The water intensity (consumption and withdrawal) for all cases was determined to be much greater than that of conventional petroleum fuels and biofuels produced from non-irrigated crops. The financial return on investment was also found to be significantly less than 1 for all cases, indicating production would be unprofitable. Additionally, it was determined that large-scale algal biofuel production would be constrained by the availability of critical energy and material inputs (e.g., nitrogen and carbon dioxide). The final part of this dissertation presents a first-principles thermodynamic analysis that represents an initial attempt at characterizing the thermodynamic limits for algal biofuel production. In that analysis, the energy, entropy, and exergy is calculated for each intermediate product in the algal biofuel production pathway considered here. Based on the results presented in this body of work, game-changing technology and biotechnology developments are needed for sustainable and profitable algal biofuel production. / text

Darbe siekiama apibendrinti kietojo biokuro rinkos plėtros aspektus nagrinėjant jos struktūrinius pokyčius bei rinkos dalyvių elgseną. Teorinėje dalyje analizuojamas rinkodaros sprendimų priėmimo procesas ir inovatyviosios rinkodaros priemonių svarba siekiant šios verslo sistemos vystymo. Kietojo biokuro rinkos segmentų valdymo moksliniai-praktiniai sprendimai yra orientuoti taikyti tokias rinkodaros priemones, kurios padėtų gerinti tiekimo sistemos struktūriškumą. Tiriamojoje dalyje, remiantis kietojo biokuro rinkos dalyvių sąveikos įvertinimu, atliekamas jų veiklos plėtros galimybių vertinimas. Empirinio tyrimo pagrindas – apklausa. / The final thesis aims to examine the development aspects of solid biofuel market by summarizing the structural changes and the behavior of market entities. The theoretical analysis includes the marketing decision-making process and innovative marketing tools to achieve development of solid biofuel market. The scientific-practical managerial solutions are oriented towards the application of marketing tools that improve the supply system for the segments of solid biofuel market, which is structural complex and undeveloped. The research covers the basis of solid biofuel market interactions including activities of entities with the feasibility development assessment. The empirical basis of the study – a survey by questionnaire.

Rapid urbanization has led to the generation of enormous wastewater after independence. The domestic wastewater generated in municipalities is rich in nutrients such as carbon, nitrogen and phosphorus along with other ions. The generated wastewater due to lack of adequate appropriate infrastructure including low treatment efficiencies are either untreated or partially treated and are let into water bodies. Present sewage treatment plants (STP’s) in the city are either under capacity or malfunctioning and hence are unable to meet the growing demand of burgeoning urban population. Water bodies have the ability to uptake nutrients (remediation by algae, bacteria, macrophytes) provided the wastewater inflow does not exceed the threshold. However, the sustained flow of wastewater beyond the water body’s treatment ability has led to the serious problem of nutrient enrichment in surface water bodies which is evident from algal bloom and profuse growth of invasive exotic macrophytes. This necessitates cost effective environmentally sound treatment options. The current research focuses on the characterisation of domestic wastewater fed ponds/lakes, understanding of nutrient regimes in wastewaters, pond dynamics, nutrient transformation and resource recovery. This has aided in devising an algae based treatment system for Bangalore city. The interplay between various biotic and abiotic factors governs water quality in a water body. Regular monitoring helps in characterisation of the water body and also helps in identifying the sources of external input (if any) to the system. Wastewater generated in urban localities in India, due to lack of adequate appropriate infrastructure including low treatment efficiencies are untreated or partially treated and are let into water bodies. Understanding the nature of the wastewater flow regimes and the turnover of biota with prevalent nutrient conditions is required to design treatment systems. Treatment involves breakdown of complex organism forms into simpler forms and transformations of organic nutrients into inorganic forms that are finally absorbed and assimilated by microbes as algae and bacteria. In wastewater fed urban pond systems, an array of microphytes as well as macrophytes grow and help in nutrient cycling in the system and still manage to remove nutrients to satisfactory levels. However, sustained inflow of wastewater with high nutrients results in the deterioration of the system as nutrient input exceed the supportive and assimilative capability resulting in proliferation of macrophytes, algal blooms, froth formations rendering the system anoxic that results in the loss of functional abilities of the urban pond systems. This biota in the system plays a major role in nutrient removal and recycles. Understanding the nutrient cycling aspects of urban wastewater fed systems is essential to find out the key players in treatment and for devising a sustainable treatment option with resource recovery. The review of wastewater generation, treatment systems highlight shortfall of the treatment systems and need for sustainable treatment for removal and recovery of nutrients such as C, N and P. Characterisation of Varthur water body (spatial extent 220 ha) located in the south of Bangalore city has been done through monthly monitoring for 18 months with the analyses of physico-chemical and biological. The analysis showed BOD removal of 70% (filterable) when the lake functioned as an anaerobic–aerobic lagoon for 6 months at an estimated residence time of 5 days. During this period, the biota of the lake, especially primary producers such as algae, treat the water through remediation of nutrients to nearly standard water quality levels. However, the growth and spread of invasive exotic macrophytes such as water hyacinth rendered the lake anaerobic which reduces its ability (due to absence of low algae) to treat the water. This highlights the role of algae especially Chlorophycean members as Chlorococcum sp., Chlorella sp. and Monoraphidium sp. in treating urban domestic wastewater and the scope for introducing algal ponds/lagoons to treat wastewater treatment and it may be used in a larger number of small towns to enable local reuse of water. The entire pond systems comprises of various components that are deeply affected by the biotic and abiotic factors in the system. Hence, studies on major biotic components were conducted especially on algae and macrophytes and the impact of abiotic factors as wind, light, and precipitation with seasonality’s. The diurnal and spatio-temporal variations in the dissolved oxygen as well other treatment parameters were used for zonation through multivariate analysis. Physico-chemical parameters confirm the nutrient enrichment (high Amm.-N) in the water body due to the sustained inflow of wastewater. High levels of nutrients together with BOD have resulted in the lower DO levels affecting the biological life. Study on biota revealed macrophytes altering the photosynthetic regime in the algae in water bodies thus, creating anoxia and nutrient re-suspension. The multivariate analysis showed three distinct zones (clusters) on the basis of physico-chemical variables and nutrient concentrations in the lake. The sedimentary C and N analysis showed a steady increase in the C: N ratio as a function of residence time. Importance of the various sub-systems in the water body in terms of nutrient uptake and accumulation showed algal systems to be efficient. C budgeting accounted to ~ 7 t/d i.e. ~2574 t/y, indicated that the lake is an accumulator of C. An estimated relatively high gas emission across the water/air interface (17 t/d) to carbon burial into sediments (2.3 t/d) further indicates very high emissions compared to sedimentation showing the dominance of internal C cycles. The overall mass balance, gas exchange and carbon burial balance showed Varthur water body as a major emitter of C due to high primary production, substantive allochthonous carbon inputs and intensive anthropogenic activities in the water body. Gaseous carbon emission accounted for 28 % of the total Influx C. The spatial profile of N in sediment ranged from 2280-3539 mg/kg of sediment dry mass. Very low value of N:P ratio in sediments suggested possible N limitation. The determination of ammonification and nitrification showed lower nitrification rates than the ammonification rates. The potentially mineralisable nitrogen content in Varthur pond sediments varied greatly from 21.65% to 75.54% and was strongly correlated (r2=0.85) to sedimentary TN. N budgeting showed NH4-N as the predominant Nr form for microbial uptake and is the major mechanism for nitrogen removal, followed by the sedimentation process. Bacterial biomass, algal biomass and macrophyte biomass accounted for 14, 4 and 1% N removal, respectively. Ammonium concentration and nitrification accounted for 27% and 2%, respectively. While bacterial uptake remained fairly constant throughout the year, micro-algae was the major player during monsoon and winter and macrophytes dominated Nr capture during summer among autotrophs. From the estimates, it has been observed that nearly 55% Nr was recovered, recycled as cell mass and transferred to a crop system when such N-captured water is used for irrigating fodder crops. About 45% of N input into the system was lost and methods to reduce this loss need to be evolved in the future. The spatial profile of P in sediment ranged from 2111.35-3982.03 mg/kg of sediment dry mass. Inorganic-P (IP) ranging from 1270.27-3505.73 mg/kg was found to be the major fraction (61.16-91.56%) of sedimentary P. High p values in both water columns and sediments showed potential P excess conditions. P concentrations in micro and macro-algae collected during the due course of the study (on dry biomass basis) were 0.347% and 0.939% P respectively. The P fractionation revealed metal oxide bound P (NaOH-P) and constituted major fraction of IP indicating, high concentrations of Fe and Al in sediments. High concentrations of sedimentary N and P indicated possible higher trophic status (bio-productivity/unit volume) signifying its towering nutrient status evidenced from the rank order of P fractions: NaOH-P > HCl-P > NH4Cl-P, which is specific for highly enriched water bodies. P budgeting showed that bulk of the P is trapped in sediment layer with a potential of ~50 % recovery from the sediments indicating, ~70% P retention within the system. The biotic components such as bacteria, algae and macrophytes accumulates a substantial amount of P, immobilising ~139, ~482 and ~131 tonness/yr of P. The sequential P extraction shows that ~70 % of sediment bound P is readily reducible during anoxic conditions which can potentially become bio-available to trigger algal growth. Assessment of treatment efficiency of facultative algal ponds, showed moderate treatment levels with 60 % total COD removal, 50% of filterable COD removal; 82% of total BOD removal and 70% of filterable BOD removal. The N removal efficiency was lower. However, a rapid decrease in the suspended solids after a faster euglenoids growth indicated particulate C removal by algal ingestion. Euglenoides dominated the facultative pond and Chlorophycean members were more abundant in the maturation ponds owing to variable surface BOD loadings. Significant correlations between algal biomass and nutrients indicate the importance of the type and nature of algal communities that can be used as an efficient tool for predicting the dynamics of various phases in wastewater treatment systems. Detailed morphological analysis of dominant algal species i.e. euglenoides was also performed. Euglenophycean members (>14 species) sampled from various locations in the facultative pond based system showed various striae patterns and distinct nano channels on the cell surface that might have possible role in cell secretions. Comparative assessment of treatment systems reveal that algal pond systems performed well under higher organic load with a COD removal efficiency of 70%, TN removal efficiency of 73% and TP removal efficiency of 22%. However, the facultative pond based systems were effective in suspended solid (SS) removal up to 93% and BOD removal up to 82%. The conventional wastewater treatment systems were efficient in terms of SS removal up to 88%, COD removal up to 74% and BOD removal up to 63%, but were highly ineffective in nutrient removal. The evaluation of treatment processes in mechanically aerated systems, facultative ponds and large shallow lake based systems in terms of capital and annual O&M costs, COD removal cost and land requirements reveals that the mechanical systems require 5 times more capital and O&M costs than ponds. The treatment systems were also ranked in terms of the total annual cost (e.g., capital, manpower, chemical, repair, electricity, land). It showed that algal pond systems followed by facultative pond based system are economically better choice than mechanical technologies. Finally, it was found that the large pond based systems could be economically the best option for the developing countries considering all factors, including economic viability and treatment efficiency. The treatment efficiency analysis showed that algal pond systems were the most effective options for treating urban wastewater. Culturing native wastewater species in growth media and wastewaters, assessment of efficient cell disruption and solvent systems, lipid profiles of wastewater algal species were studied. Wastewater grown algal species as Euglena sp., Spirogyra sp., Phormidium sp., Lepocinclis ovum, and Chlorococcum sp. are comparatively rich in lipids. These algae grow mixotrophically and can store substantial amount of wastewater carbon as TAG’s in varied environments. Among the different cell disruption methods used for the study, sonication was the most effective. The combination of maceration and methanol: chloroform: water (2:1:0.8, v/v) (Bligh and Dyer’s, solvent) gave highest lipid extraction yield among other combinations. Further more these wastewater algae as Lepocinclis ovum and Chlorococcum sp. were found to grow better in wastewaters. Increased lipid content was recorded during the cell cultures with accumulation of quality FAME with high saturates predominated by C16-C18 fatty acids. These wastewater algal lipids are suitable for bio-energy generation with potential biomass productivity (6.52 t/ha/yr) of wastewater-grown species as Euglena. The studies on Euglena sp. showed mixotrophic mode that offers an efficient removal of TOC, N and P from domestic wastewater without any pre-treatment. Lipid profiles of the extracted algal oil were similar to the vegetative feedstock oils, indicating a good quality fuel for energy generation. Mixed algal consortia’s bioremediation potential (removal of nutrients) with the scope for biofuel production highlights self flocculating abilities of algal consortia aided in the effective treatment of wastewater with substantial algal harvest. Studies on cultivating wastewater algal consortia in novel cascading algal parcel flow reactor (CAPFR) operating in continuous mode showed 70-80 % nutrient and ~90 % C removal with in a residence time of ~4 days with highest cell densities (0.91 g/l) and productivities (0.26 g/l/d) in the last stages. The lipid contents varied from 26-28 % with highest lipid productivities ~58 mg/l/d in the 2nd phase of the bioreactor. Most of the lipids were associated with the pigments as chlorophyll and carotenoids. Furthermore, the algal rector removed bacteria up to 4 log orders. Essential cations and phosphates were responsible for self clumping of algal biomass in the final stages with a high internal P content within the cell. The algal biomass also showed substantial exothermic peaks and high heat values (~18 MJ/kg). Studies on continuous cultivation of Dictyosphaerium sp. showed that this species could adapt to wastewater conditions and also showed good nutrient removal at lower HRT (2.5 days). The high biomass productivities with high lipid content (~36%) at low HRT in the continuous mode offer potential options for economic and feasible nutrient removal with biofuel production. Investigations on city wastewaters showed low nutrient ratio indicating C limitations and possible scope for algal wastewater treatment. Integration of algal ponds in the present treatment network requires an additional land ranging from ~0.37 to 2.75 ha to treat an MLD of wastewater depending on the nutrient content and influent waters fed to algal systems. The treatment plants require an additional ~1.6 ha of land to treat 1 MLD of wastewater considering an average N and P values of 18 and 5 mg/l. The continuous algal bio-processes implemented at decentralised levels would help in the economical ways for nutrient removal and recycling of the nutrient free waters after treatment. This meets multiple objectives of low cost treatment of wastewater, nutrient recovery and fuel production. Algal nutrient capture and consequent biofuel production would ensure sustainability through i) water purification ii) nutrients capture and iii) biofuel to meet the growing energy demand, and would be an optimal treatment option for urban wastewater. The thesis consists of 10 chapters and basically deals with the development of a sustainable and economically viable bioprocess for wastewater treatment and biomass production. Chapter 1 provides a brief introduction to wastewater; domestic wastewater composition, generation and treatment in developing nations and in the country and review of the various techniques for treatment of domestic wastewaters, advantages of algal processes in nutrient removal (C, N and P) and production of valued by-product such as lipid generation, for its use as biofuel. Chapter 2 is based on primary field investigations in a wastewater fed urban water body/pond systems involving monthly sampling and analysis of various physico-chemical and biological parameters. Assessment of treatment capabilities of the continuous systems through detailed characterisation of treatment parameters is explained in the second chapter. Chapter 3 discusses the role of the major biotic (algae and macrophytes) and abiotic factors in nutrient transformations, the diurnal variations in parameters especially dissolved oxygen, multivariate spatio-temporal analysis of functional abilities for zoning, the activities in the sludge/sediment and transitions in the CN ratio as a function of residence time. Chapter 4 involves studies in C, N and P quantification and budgeting in such pond systems and partitioning of the nutrients and their distribution in various biotic and abiotic subsystems. This chapter also highlights the major nutrient losses from the system and un-utilised nutrient stocks, paving way for beneficial use of nutrients from such man made lagoon wastewater systems. Chapter 5 discusses the mechanisms and efficacies of algal pond based treatment systems through a detailed study and highlight its advantages over the mechanical ASP based systems. This has been done through a comparative assessment of treatment efficiency, economics and environmental externalities. This study also provides necessary insights and potential of wastewater algal species such as Euglena for its abilities in nutrient removal and biomass generation. This provides insights to algal treatment options for optimal resource recovery and utilisation from wastewaters. Chapter 6 focuses on testing the growth, biomass and lipid production of various wastewater algae isolated from treatment ponds. The chapter identifies suitable cell disruption and extraction routes for efficient lipid extraction and assesses the potential of these wastewater grown algae for regional and national biofuel production. Chapter 7 discusses the effectiveness of wastewater grown Euglena sp. and algal consortia in nutrient removal and as a source of lipids for biofuel generation. Chapter 8 involves the design and operation of a continuous algal (uni-algal/algal consortia) bioreactor devised taking insights from earlier field based studies and their potential as efficient urban wastewater treatment systems. Chapter 9 discusses the present nutrient levels in the city wastewaters and also an analysis of the temporal and spatial variation of nutrients in city sewers and elaborates the scope for integration of the algal modules i.e. continuous algal bioreactors (designed in the previous chapter) into existing STP’s. Chapter 10 elaborates significant contributions and outcome of the research.

Doctor of Philosophy / Department of Grain Science and Industry / Praveen V. Vadlani / Distillers Dried grain with Solubles (DDGS) is a co-product of grain-based ethanol and is primarily used as livestock feed. With increasing production of DDGS, it is imperative to produce value-added products and/or find new applications of DDGS to help sustain the biofuel industry. Carotenoids are expensive yet essential feed additives. Since animals cannot synthesize carotenoids and animal feeds including DDGS are generally poor in carotenoids, about 30-120 ppm of total carotenoids is added to animal feed to improve animal health. The objectives of this study were to 1) produce carotenoid (astaxanthin and β-carotene)-enriched DDGS by Phaffia rhodozyma and Sporobolomyces roseus monoculture and mixed culture submerged fermentation of whole stillage, 2) optimize fermentation media by response surface methodology (RSM) and mixture design followed by validation, 3) evaluate the nutritional profile of carotenoid-enriched DDGS, 4) improve carotenoid production by the use of precursors, and 5) develop carotenoid-enriched feeds namely, wheat bran, rice bran and soybean products. Carotenoid-enriched DDGS was produced from both monoculture and mixed culture fermentation with yields ranging from 17-233 µg/g. Upon media optimization, astaxanthin and β-carotene yields, especially in P. rhodozyma were enhanced by 177% and 164% to yield 98 and 275 µg/g respectively. Nutrition profiling of the carotenoid-enriched DDGS showed that the secondary fermentation resulted in low fiber, protein and %N and enhanced fat. Fiber was reduced by 77% and 66% by P. rhodozyma and S. roseus respectively, whereas the crude fat increased by 80% in mixed culture fermentation. Additionally, abundant vaccenic acid, a monounsaturated fatty acid was seen in S. roseus and mixed culture fermented DDGS. Vaccenic acid is a precursor of conjugated linolenic acid which is known to confer numerous health benefits. Fermentation of milo DDGS, wheat bran, rice bran and soybean products also resulted in carotenoid enrichment, with the best astaxanthin yield of 80 µg/g in rice bran, and best β-carotene yield of 837 µg/ g in soy flour. Precursors like mevalonic acid, apple pomace and tomato pomace increased carotenoid yield in DDGS and other substrates, with the yield increment depending on the substrate. Mevalonic acid resulted in the best astaxanthin and β-carotene yield increment by 140% and 236% resulting in 220 µg/g and 904 µg/g respectively in corn DDGS. Apple pomace and tomato pomace resulted in 29% carotenoid yield increment. Numerous studies thus far have used cheap agricultural substrates to produce carotenoids especially astaxanthin using P. rhodozyma with the intent of extracting the carotenoids for use in animal feed. However, by fermenting the animal feed directly, carotenoid-enriched feed can be produced without the need for extraction. By this simple yet novel carotenoid value addition, premium feeds or feed blends can be developed. Apart from carotenoid enrichment, low-fiber DDGS can help expand the market base of DDGS for use in non-ruminant feeds. Carotenoid value addition of DDGS can not only help sustain the biofuel industry but can also capture the aquaculture feed base which heavily relies on astaxanthin supplementation.

Master of Science / Department of Biology / Jesse B. Nippert / Jesse B. Nippert / Anthropogenic climate change is likely to alter the function and composition of ecosystems worldwide through increased precipitation variability and temperatures. To predict ecosystem responses, a greater understanding of the physiological and growth responses of plants is required. Dominant species drive ecosystem responses, and it is essential to understand how they respond to understand potential ecosystem changes. Dominant species, such as switchgrass (Panicum virgatum L.), posses large genotypic and phenotypic variability, which will impact the degree of responses to projected climate changes. I studied the physiological and growth responses of switchgrass, a common perennial warm-season C4 grass that is native to the tallgrass prairie, to alterations in precipitation amount and temperature. The first experiment I conducted focused on the responses of three ecotypes of P. virgatum to three precipitation regimes (average, 25% below, 25% above). I concluded that the physiological responses of photosynthesis, stomatal conductance, transpiration, dark-adapted fluorescence, and mid-day water potential in P. virgatum were explained by ecotypic differences. Robust responses to altered precipitation were seen in the water use efficiency, mid-day water potential, and aboveground biomass. Ecotypic differences were also seen in several aboveground biomass variables, and most strikingly in flowering times and rates. There were few interactions between ecotype and precipitation, suggesting precipitation is a strong driver of biomass production, whereas adaption of ecotypes to their local environment affects physiological processes. A second experiment studied the response of local populations of P. virgatum to nocturnal warming. Results showed significant differences in daytime E, daytime gs, and flowering phenology between treatments. Differences in aboveground biomass were between topographic positions. I concluded that water availability, based on topographic position, is a strong driver of P. virgatum aboveground biomass production, but nocturnal warming has the potential to impact flowering phenology, physiological responses, and exacerbate plant water stress. I also reviewed the literature on the ecological effects of implementing switchgrass cultivation for biofuel. From the literature review, I concluded that large-scale switchgrass cultivation will have widespread ecological impacts. If landscape heterogeneity is maintained through harvest rotations, no till farming, and mixed species composition, ecosystem services can be maintained while providing economic value.

Doctor of Philosophy / Department of Civil Engineering / Kyle A. Riding / The cement industry is an important component in the quest to reduce global greenhouse gas emissions because of vast amounts of cement used annually. Incorporating supplementary cementitious materials (SCMs) into concrete is one alternative to reduce cement production and thereby reduce greenhouse gas emissions. This study investigated three types of agricultural residues, namely corn stover, wheat straw, and rice straw, in addition to bioethanol byproducts as potential resources for SCM production for concrete applications. Pretreatments, commonly used in bioethanol production, were used to improve pozzolanic reactivity of corn stover ash (CSA), wheat straw ash (WSA), and rice straw ash (RSA) in cementitious systems. In the first part of this research, the impact of distilled water and dilute hydrochloric acid pretreatments on pozzolanic reactivity of WSA, RSA, and CSA were studied. Results showed that pretreatments, particularly dilute acid, improved pozzolanic properties of CSA, WSA, and RSA by removing potassium and phosphorous from the biomass prior to ashing. In addition, WSA and RSA were shown to have similar pozzolanic reactivity to that of silica fume. In the second part of this study, suitability of high lignin residue (HLR), a bioethanol byproduct, for SCM production was investigated. It was shown that burning high lignin residue produces HLR ash that is very reactive in cementitious materials and can be used as a reactive SCM in concrete. The impact of each step in the production of bioethanol on the quality of bioethanol byproduct for subsequent burning and use in concrete was also studied. Sodium hydroxide and sulfuric acid pretreatments and enzymatic hydrolysis were used. Results revealed that sodium hydroxide pretreatment of the biomass have negative impact on biomass ash properties for concrete use because sodium hydroxide pretreatment did not remove phosphorous and other crystalline phases out of the biomass. However, sulfuric acid pretreatment of biomass greatly improved ash properties. It was also shown that enzymatic hydrolysis could have beneficial impact on ash properties because, during enzymatic hydrolysis, some phosphorous was leached out of the biomass.

Master of Science / Department of Agronomy / Scott A. Staggenborg / Volatile energy prices, energy independency, and environmental concerns have increased the demand for renewable fuel production in the United States. The current renewable fuel industry in the United States has developed around the conversion of starch into ethanol fuel, supplied mainly by corn (Zea mays L.) grain. Future energy demands cannot be met by corn grain alone; therefore greater amounts of biomass from traditional and alternative crops must be utilized. Nutrient removal by selected biofuel crops is important in order to determine biomass quality, required fertilizer inputs, and economic viability of biofuel cropping systems. The objectives of this study were to evaluate grain, stover, total biomass, and estimated ethanol yields of annual and perennial C4 crops grown under the same soil and weather conditions; and fermentable carbohydrate (FC) yields from extracted sweet sorghum juice. In addition, nitrogen (N), phosphorus (P) and potassium (K) concentrations of biomass were evaluated to determine total nutrient removal for annual and perennial crops. Field trials, at two locations in northeast Kansas, included corn, sorghum [Sorghum bicolor (L.) Moench] and perennial warm-season grass cultivars. Yields and nutrient removal were greater for annual crops than perennial grasses. Annual crop yields varied among cultivars, but were similar between locations and years. Perennial grass yields improved significantly from the 2007 establishment year to 2008, however nutrient removal was not affected by the yield increase. The highest grain yield and grain nutrient removal amounts were observed for corn across both years and locations. Total biomass yields were greatest for sweet and photoperiod sensitive sorghum cultivars. Average extracted sweet sorghum FC yields were 4.8 Mg ha[superscript]1. Estimated ethanol yields of sweet sorghum were greater than all other crop cultivars. Overall, nutrient removal was most affected by biomass yield variation among crop cultivars; however P concentrations, and subsequent removal, were dependent upon soil P levels at individual locations. These results suggest that annual crops can achieve the greatest biomass yields for multiple renewable fuel conversion processes, but are associated with high nutrient removal levels which must be considered when evaluating biofuel energy cropping systems.

Aviation biofuel is technically viable and nearing the commercial stage. In the last 5 years aviation biofuel has moved from relative obscurity to become fully certified for commercial use in up to 50% blends with standard jet fuel. There have since been 15 successful commercial flight tests using aviation biofuels including Lufthansa s six month trial operating on a passenger revenue generating route in 2011. Airlines and biofuel companies such as British Airways and Solena are furthermore beginning to form partnerships to finance specialised aviation biofuel production facilities. However, aviation biofuels have yet to become widely commercialised. In fact, there are a series of issues preventing the emergence, development and uptake of aviation biofuels. The main issues are perceived as high costs of manufacture, limited availability of feedstocks, controversy surrounding the effect on food prices and the emissions output from land use change. Furthermore, there is a significant lack of academic peer reviewed literature which investigates these issues or offers solutions to support the development of the technology. This thesis aims to investigate the factors that affect the emergence, development and uptake of aviation biofuels by drawing upon in-depth stakeholder interviews and survey data. Strategic niche management (SNM) theory is used and extended to analyse the contemporary issues and develop recommendations to support the continued emergence, development and uptake of aviation biofuels. It is concluded that the emergence, development and uptake is being driven mainly by rising jet fuel prices, growing concern regarding aviation emissions legislation and fuel (in)security. Airlines, biofuel producers and specialised supply chain companies are driving emergence, development and uptake due to commercial opportunities. Despite these drivers, the emergence, development and uptake is being constrained by a combination of ineffective policy provision, high costs of production, limited feedstocks and uncertainty surrounding sustainability. Ineffective and unsuitable policy is exacerbating the issues of high production costs, limited feedstocks and sustainability. In particular, competition between aviation and road biofuels is limiting aviation biofuel expansion. Recommendations are to develop nurtured niche markets for aviation biofuels using principles from SNM. Within these markets, aviation biofuels are afforded commercial viability in order to learn about supply chain development, longer term infrastructural requirements and technological development. Information should be shared between the niche markets in order to maximise learning by doing and speed up efficiency gains. Once niche markets are established, the incentives and protection should be gradually reduced to allow a competitive aviation biofuel industry to develop.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Increasing oil prices along with the climate change threat have forced governments, society and the energy sector to consider alternative fuels. Biofuel presents itself as a suitable replacement and has received much attention over recent years. Thermochemical conversion processes such as pyrolysis is a topic of interest for conversion of cheap agricultural wastes into clean energy and valuable products. Fast pyrolysis of biomass is one of the promising technologies for converting biomass into liquid fuels and regarded as a promising feedstock to replace petroleum fuels. Corn residues, corn cob and corn stover, are some of the largest agricultural waste types in South Africa amounting to 8 900 thousand metric tonnes annually (1.7% of world corn production) (Nation Master, 2005). This study looked at the pyrolysis kinetics, the characterisation and quality of by-products from fast pyrolysis of the corn residues and the upgrading of bio-oil. The first objective was to characterise the physical and chemical properties of corn residues in order to determine the suitability of these feedstocks for pyrolytic purposes. Secondly, a study was carried out to obtain the reaction kinetic information and to characterise the behaviour of corn residues during thermal decomposition. The knowledge of biomass pyrolysis kinetics is of importance in the design and optimisation of pyrolytic reactors. Fast pyrolysis experiments were carried out in 2 different reactors: a Lurgi twin screw reactor and a bubbling fluidised bed reactor. The product yields and quality were compared for different types of reactors and biomasses. Finally, a preliminary study on the upgrading of bio-oil to remove the excess water and organics inorder to improve the quality of this liquid fuel was performed. Corn residues biomass are potential thermochemical feedstocks, with the following properties (carbon 50.2 wt. %, hydrogen 5.9 wt. % and Higher heating value 19.14 MJ/kg) for corn cob and (carbon 48.9 wt. %, hydrogen 6.01 wt. % and Higher heating value 18.06 MJ/kg) for corn stover. Corn cobs and corn stover contained very low amounts of nitrogen (0.41-0.57 wt. %) and sulphur (0.03-0.05 wt. %) compared with coal (nitrogen 0.8-1.9 wt. % and sulphur 0.7-1.2 wt. %), making them emit less sulphur oxides than when burning fossil fuels. The corn residues showed three distinct stages in the thermal decomposition process, with peak temperature of pyrolysis shifting to a higher value as the heating rate increased. The activation energies (E) for corn residues, obtained by the application of an iso-conversional method from thermogravimetric tests were in the range of 220 to 270 kJ/mol. The products obtained from fast pyrolysis of corn residues were bio-oil, biochar, water and gas. Higher bio-oil yields were produced from fast pyrolysis of corn residues in a bubbling fluidised bed reactor (47.8 to 51.2 wt. %, dry ash-free) than in a Lurgi twin screw reactor (35.5 to 37 wt. %, dry ash-free). Corn cobs produced higher bio-oil yields than corn stover in both types of reactors. At the optimised operating temperature of 500-530 °C, higher biochar yields were obtained from corn stover than corn cobs in both types of reactors. There were no major differences in the chemical and physical properties of bio-oil produced from the two types of reactors. The biochar properties showed some variation in heating values, carbon content and ash content for the different biomasses. The fast pyrolysis of corn residues produced energy products, bio-oil (Higher heating value = 18.7-25.3 MJ/kg) and biochar (Higher heating value = 19.8-29.3 MJ/kg) comparable with coal (Higher heating value = 16.2-25.9 MJ/kg). The bio-oils produced had some undesirable properties for its application such as acidic (pH 3.8 to 4.3) and high water content (21.3 to 30.5 wt. %). The bio-oil upgrading method (evaporation) increased the heating value and viscosity by removal of light hydrocarbons and water. The corn residues biochar produced had a BET Brynauer-Emmet-Teller (BET) surface area of 96.7 to 158.8 m2/g making it suitable for upgrading for the manufacture of adsorbents. The gas products from fast pyrolysis were analysed by gas chromatography (GC) as CO2, CO, H2, CH4, C2H4, C2H6, C3H8 and C5+ hydrocarbons. The gases had CO2 and CO of more than 80% (v/V) and low heating values (8.82-8.86 MJ/kg). / AFRIKAANSE OPSOMMING: Die styging in olie pryse asook dreigende klimaatsveranderinge het daartoe gelei dat regerings, die samelewing asook die energie sektor alternatiewe energiebronne oorweeg. Biobrandstof as alternatiewe energiebron het in die afgope paar jaar redelik aftrek gekry. Termochemiese omskakelingsprosesse soos pirolise word oorweeg vir die omskakeling van goedkoop landbou afval na groen energie en waardevolle produkte. Snel piroliese van biomassa is een van die mees belowende tegnologië vir die omskakeling van biomassa na vloeibare brandstof en word tans gereken as ’n belowende kandidaat om petroleum brandstof te vervang. Mielieafval, stronke en strooi vorm ’n reuse deel van die Suid Afrikaanse landbou afval. Ongeveer 8900 duisend metrieke ton afval word jaarliks geproduseer wat optel na ongeveer 1.7% van die wêreld se mielie produksie uitmaak (Nation Master, 2005). Hierdie studie het gekk na die kinetika van piroliese, die karakterisering en kwaliteit van by-produkte van snel piroliese afkomstig van mielie-afval asook die opgradering van biobrandstof. Die eerste mikpunt was om die fisiese en chemiese karakteristieke van mielie-afval te bepaal om sodoende die geskiktheid van hierdie afval vir die gebruik tydens piroliese te bepaal. Tweendens is ’n kinetiese studie onderneem om reaksie parameters te bepaal asook die gedrag tydens termiese ontbinding waar te neem. Kennis van die piroliese kinetika van biomassa is van belang juis tydens die ontwerp en optimering van piroliese reaktore. Snel piroliese ekspermente is uitgevoer met behulp van twee verskillende reaktore: ’n Lurgi twee skroef reaktor en ’n borrelende gefluidiseerde-bed reaktor. Die produk opbrengs en kwaliteit is vergelyk. Eindelik is ’n voorlopige studie oor die opgradering van bio-olie uitgevoer deur te kyk na die verwydering van oortollige water en organiese materiaal om die kwaliteit van hierdie vloeibare brandstof te verbeter. Biomassa afkomstig van mielie-afval is ’n potensiële termochemiese voerbron met die volgende kenmerke: mielie stronke- (C - 50.21 massa %, H – 5.9 massa %, HHV – 19.14 MJ/kg); mielie strooi – (C – 48.9 massa %, H – 6.01 massa %, HHV – 18.06 MJ/kg). Beide van hierdie materiale bevat lae hoeveelhede N (0.41-0.57 massa %) and S (0.03-0.05 massa %) in vergelyking met steenkool N (0.8-1.9 massa %) and S (0.7-1.2 massa %). Dit beteken dat hieride bronne van biomassa laer konsentrasies van swael oksiedes vrystel in vergelyking met fossielbrandstowwe. Drie kenmerkende stadia is waargeneem tydens die termiese afbraak van mielie-afval, met die temperatuur piek van piroliese wat skuif na ’n hoër temperatuur soos die verhittingswaarde toeneem. Die waargenome aktiveringsenergie (E) van mielie-afval bereken met behulp van die iso-omskakelings metode van TGA toetse was in die bestek: 220 tot 270 kJ/mol. Die produkte verkry deur Snel Piroliese van mielie-afval was bio-olie, bio-kool en gas. ’n Hoër opbrengs van bio-olie is behaal tydens Snel Piroliese van mielie-afval in die borrelende gefluidiseerde-bed reakctor (47.8 na 51.2 massa %, droog as-vry) in vergelyking met die Lurgi twee skroef reakctor (35.5 na 37 massa %, droog as-vry). Mielie stronke sorg vir ’n hoër opbrengs van bio-olie as mielie strooi in beide reaktore. By die optimum bedryfskondisies is daar in beide reaktor ’n hoër bio-kool opbrengs verkry van mielie stingels teenoor mielie stronke. Geen aansienlike verskille is gevind in die chemise en fisiese kenmerke van van die bio-olie wat geproduseer is in die twee reaktore nie. Daar is wel variasie getoon in die bio-kool kenmerkte van die verskillende Snel Piroliese prosesse. Snel piroliese van mielie-afval lewer energie produkte, bio-olie (HVW = 18.7-25.3MJ/kg) en bio-kool (HVW = 19.8-29.3 MJ/kg) vergelykbaar met steenkool (HVW = 16.2-25.9 MJ/kg). Die bio-olies geproduseer het sommige ongewenste kenmerke getoon byvoorbeeld suurheid (pH 3.8-4.3) asook hoë water inhoud (21.3 – 30.5 massa %). Die metode (indamping) wat gebruik is vir die opgradering van bio-olie het gelei tot die verbetering van die verhittingswaarde asook die toename in viskositeit deur die verwydering van ligte koolwaterstowwe en water. Die mielie-afval bio-kool toon ’n BET (Brunauer-Emmet-Teller) oppervlakte area van 96.7-158.8 m2/g wat dit toepaslik maak as grondstof vir absorbante. The gas geproduseer tydens Snel Piroliese is geanaliseer met behulp van gas chromotografie (GC) as CO2, CO, H2, CH4, C2H4, C2H6, C3H8 and C5+ koolwaterstowwe. Die vlak van CO2 en CO het 80% (v/V) oorskry en met lae verhittingswaardes (8.82-8.86 MJ/kg).