Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Plant oil-based raw materials have become more attractive alternatives in polymer industry as fossil resources depletion and environmental concerns continue to arise. Camelina (camelina sativa L.) seed contains about 45% of oil and about 90% of the oil is unsaturated fatty acids such as linoleic acid, α-linolenic acid, and erucic acids. It also provides the advantages of low cost and low fertilizer demand. Functionalized oils such as epoxidized camelina oil (ECO) and di-hydroxyl camelina oil (DCO) can be used for resins, adhesives, coatings, etc. The objectives of this work were to synthesize and characterize ECO and DCO from camelina oil. The epoxidation reaction of camelina oil was completed with formic acid and hydrogen peroxide. Catalyst ratio, reaction time, and temperature effects on the epoxidation reaction were studied. The optimum epoxy content of 7.52 wt% with a conversion rate of 76.34% was obtained from camelina oil using excess hydrogen peroxide and a molar ratio of formic acid of less than 1 for 5 hours in 50 °C. Camelina oil yields higher epoxy content (7.52 wt%) than soybean oil (6.53 wt%); however, soybean oil had a higher conversion rate of 80.16% compared to camelina oil because of uniform fatty acids distribution. In this study, we found that epoxidation efficiency is significantly affected by fatty acids composition, structure, and distribution. DCO was synthesized from ECO with different reaction parameters. The ring opening of ECO was performed with water, perchloric acid, and THF as proton donor, catalyst, and solvent respectively. Hydroxyl value of DCO was measured, and the maximal hydroxyl value was 369.24 mg KOH/g. physical properties of DCO were characterized by acid value and moisture content; thermal properties of DCO were obtained using different scanning calorimeter (DSC), thermalgravimetric analysis (TGA). Amount of solvent and acid catalyst addition affected the hydroxyl value and residual acid in DCO. Heat capacity, phase transition temperatures, and thermal stability of DCO were obtained and showed higher values than ECO’s. The DCO showed higher peel adhesion when it was formulated with epoxidized soybean oils through UV curing because camelina oil allows higher epoxy content, which results in higher hydroxyl values.

Doctor of Philosophy / Department of Biological and Agricultural Engineering / Donghai Wang / Sorghum distillers dried grains with solubles (DDGS), canola and camelina meals are the main co-products resulting from grain-based ethanol or oil production. The main objective of this research was to study physicochemical properties of proteins isolated from DDGS, canola and camelina meals and their adhesion performance. Acetic acid-extracted sorghum protein (PI) from DDGS had superior adhesion performance in terms of dry, wet and soak adhesion strength compared to acetic acid-extracted sorghum protein (PF) from sorghum flour and aqueous ethanol-extracted sorghum protein (PII) from DDGS. PI had a significantly higher wet strength (3.15 MPa) than PII (2.17 MPa), PF (2.59 MPa), and soy protein without modification (1.63 MPa). The high content of hydrophobic amino acids in PI (57%) was likely the key factor responsible for high water resistance. Canola protein was extracted from canola meal and modified with different concentrations of NaHSO3 (0 to 15 g/L) during protein isolation. Unmodified canola protein showed the highest wet shear strength of 3.97 MPa cured at 190 °C. Adhesion strength of canola protein fractions extracted at pH 5.5 and pH 3.5 (3.9-4.1 MPa) was higher than the fraction extracted at pH 7.0. NaHSO3 slightly weakened adhesion performance of canola protein; however, it improved handling and flow-ability due to breaking of disulfide bonds in proteins. Albumin, globulin, and glutelins were isolated from camelina meal. Adhesion performance of globulin fraction behaved better than glutelin fraction. The greatest wet shear strength of globulin was 3.3 MPa at curing a temperature of 190 °C. Glutelin had a more protein aggregation compared with globulin, as indicated by higher crystallinity and thermal stability, and dense protein aggregate. This compact structure of glutelins may partially contribute to lower adhesion strength as compared to globulin.

The demand for biofuels continues to increase due in part to government standards and promotion as well as the ambitious goals set by various companies and industries. Camelina is considered to be an ideal energy crop because of its low input requirements, suitability for marginal soils, and naturally competitiveness with weeds. A partial equilibrium model with a break-even price approach is used to estimate the potential supply curves for Camelina in Idaho, Montana, Oregon, and Washington. The supply curves are used to determine if the 50 million gallon goal set by the "Farm to Fly" initiative can be met. Given the current price of Camelina, $0.15/lb, the estimated supply of Camelina in all 4 states is 1,756,076,887 lbs and 1,493,684 acres. This estimation assumes that if the wheat-Camelina rotation is more profitable than the current crop rotation, then all of the acres will be converted to a wheat-Camelina rotation. When a 5% adoption rate is applied to the low and the intermediate rainfall zones and a 1% to the high rainfall zones, the number of acres converted to Camelina decreases to 72,213. These results suggest that given current market conditions, the supply of Camelina in the Northwest is not enough to meet the biofuel goal without an increase in yield and government promotion. / Graduation date: 2013

published_or_final_version / Biological Sciences / Master / Master of Philosophy

Finding the alternate biofuel feedstock(s) in addition to and/or replacement of traditional soybean feedstock is necessary to meet the future demand of biofuels. Two field studies were conducted in diverse environments in Texas during 2007-2011 to evaluate the yield, adaptation, and oil content of 4 cool-season crop species (rapeseed, safflower, flax, and camelina). In addition to the evaluation of yield and adaptation in these cool-season crops, two more studies were conducted during 2009-2011 to study flax yield components (field study) and the effect of vernalization and photoperiod on flowering of flax (growth chamber study). Out of two field studies conducted in Texas, the evaluation of four cool-season crops was designed as a randomized complete block with fifty-one genotypes (four species) and three replications in nine locations across the Texas. In addition to the evaluation of cool-season crops, an exclusive replicated study was conducted in flax to evaluate 20 genotypes for the yield, adaptation, and association between yield and its components in three locations in South Texas. Additionally, a growth chamber study was setup as a split-split plot design with twenty genotypes, two vernalized treatments (vernalized and unvernalized), and two photoperiods (10 hours and 14 hours). Spring rapeseed (canola) and safflower were the highest yielding crops with a maximum yield of 1372 kg ha-1 and 1240 kg ha-1, respectively. In South and Central Texas, fall - seeded flax yield averaged 1075 kg ha^-1 with a mean oil content of 38.3%. The flax genotype evaluation in Southeast Texas suggested that all genotypes developed in Texas showed relative cold tolerance compared to genotypes developed in other locations. A cross between Caldwell / Dillman (Texas genotype) was highly adapted to the environments of southeast Texas. Nekoma and York (genotypes developed in North Dakota) yielded well in non-cold years (> -2 degrees C) in College Station. Overall, flax is well adapted to growth in the area surrounding College Station, TX. The results of association of yield and its components in flax suggest that tiller number was the most significant contributing factor (p<0.05) affecting yield of flax in all three locations. However, the effect of tiller number was almost negated by the effect of pods per tiller (compensatory) in two out of three locations. The effect of vernalization and photoperiod on flowering of 20 genotypes of flax suggested that Texas genotypes delayed anthesis for 7 days or more in non-vernalized seedlings. These genotypes also delayed anthesis for 12 days or more in vernalized and short day conditions compared to vernalized and long day conditions. In summary, the spring rapeseed in diverse environments of Texas and fall-planted flax in South Texas showed promising yield and adaptation. Selection for more productive tiller number and intrinsic earliness of flowering to reduce the time of maturation would benefit the flax yields in Southeast Texas. Safflower was widely adapted to Texas and with increased oil content could have potential to the biofuel industry in Texas.

Master of Science / Biochemistry and Molecular Biophysics Interdepartmental Program / Timothy P. Durrett / Many Euonymus species express an acetyltransferase enzyme in their seeds which catalyzes the transfer of an acetyl group from acetyl-CoA to the sn-3 position of diacylglycerol (DAG) producing unusual acetyl-1,2-diacyl-sn-glycerols (acetyl-TAG). The presence of the sn-3 acetate group gives acetyl-TAG with unique physical properties over regular triacylglycerol (TAG) found in vegetable oils. The useful characteristics of acetyl-TAG oil offer advantages for its use as emulsifiers, lubricants, and 'drop-in' biofuels. One enzyme, Euonymus alatus diacylglycerol acetyltransferase (EaDAcT), responsible for acetyl-TAG synthesis in nature was previously isolated from the seeds of Euonymus alatus (burning bush) and expressed in the oilseed crop Camelina sativa. Expression of EaDAcT successfully led to production of high levels of acetyl-TAG in camelina seeds. To further increase acetyl-TAG accumulation in transgenic camelina seeds, multiple strategies were examined in this study. Expression of a new acetyltransferase enzyme (EfDAcT) isolated from the seeds of Euonymus fortunei, which was previously shown to possess higher in vitro activity and in vivo acetyl-TAG levels compared to EaDAcT, increased acetyl-TAG accumulation by 20 mol%. Suppression of the endogenous competing enzyme DGAT1 further enhanced acetyl-TAG accumulation to 90 mol% in selected transgenic line. Studying the regulation of EfDAcT transcript, protein, and acetyl-TAG levels during seed development further provided new insights on the factors limiting acetyl-TAG accumulation.

Master of Science / Department of Biological & Agricultural Engineering / Donghai Wang / Camelina sativa (L). Crantz that belongs to Brassicaceae family has been grown as a dicotyledonous oilseed crop in the cold places like America and Canada. Camelina seeds are widely used for the extraction of oil and protein. Recently, research found that camelina gum is an excellent candidate for food and industrial uses as thickener or stabilizer. The objectives of this research were 1) to increase camelina gum isolation efficiency using spray drying technology, and 2) to develop an innovative method to remove gum from seed bran to increase protein and oil extraction efficiency and quality. The camelina gums isolated using ethanol precipitation and spray drying method from the whole camelina seeds were compared. Effects of spray drying temperature on yield, gum morphology, and gum rheological and thermal properties were studied. The representative sample dried at 165°C was chosen to study the effects of concentration, temperature, pH and additives (NaCl, CaCl₂, sucrose, and ethanol) on viscosity and viscoelastic properties of the isolated gum. The gum showed a shear thinning behavior when shear rate increased gradually, higher concentrations of additives only slightly affect the rheological properties. Results showed that spray drying is an effective method in terms of saving time and energy, and provided positive rheology benefits on camelina gum isolation. Pre-removal of gum from camelina seeds can increase protein and oil yield and their quality. Decortication can separate 10-17% of the total camelina seed as bran. A wind tunnel was used to separate lighter bran particles from heavier endosperm and unbroken seeds. Camelina gum isolation from the separated seed bran using the traditional ethanol precipitation method was optimized using response surface methodology where the simultaneous effect of the three independent variables (seed bran to water ratio, isolation temperature, and isolation time) were investigated for gum yield, purity, and optimum rheological properties. Three independent quadratic modules were developed and the original data fitted the models fitted (R² = 0.995, 0.877, and 0.804). The optimal isolation conditions were seed bran to water ratio of 1:39, isolation temperature of 35 ºC, and isolation time of 1.5 h and 0.839 desirability was obtained by the rigorous statistics analysis. The protein yield and quality extracted from decorticated endosperm were improved significantly compared with that extracted from whole seeds meal without decortication. In addition, the degumming step can be eliminated before protein and oil extraction that increase protein and oil extraction efficiency.

No description available.

Doctor of Philosophy / Biochemistry and Molecular Biophysics Interdepartmental Program / Timothy P. Durrett / The direct use of vegetable oils as a biofuel suffers from problems such as high viscosity, low volatility and poor cold temperature properties. 3-acetyl-1,2-diacyl-sn-glycerols (acetyl-TAGs) have lower viscosity and freezing temperature than regular vegetable oils. However, by modifying their fatty acid composition, further improvement in their fuel properties is possible. Our goal was to develop plants that synthesize seed oils with further improved fuel properties. Euonymus alatus diacylglycerol acetyltransferase (EaDAcT) synthesizes acetyl-TAGs by the acetyl-CoA dependent acylation of diacylglycerol (DAG). Knowledge of the substrate specificity of EaDAcT for its acetyl-CoA donor and DAG acceptor substrates is important to generate the required acetyl-TAG composition in seed oil. A rapid method to quantify acetyl-TAGs was developed based on electrospray ionization mass spectrometry to gain information about the substrate specificity of EaDAcT. This method is as accurate and more rapid than the traditional radiolabeled substrate based assay and additionally provides information on acetyl-TAG molecular species present. Using this assay, EaDAcT specificity for different chain length acyl-CoA and DAGs was tested. It was found that although EaDAcT can use other short chain length acyl-CoAs as acyl donors, it has high preference for acetyl-CoA. Further, EaDAcT can acetylate a variety of DAGs with short, medium and long chain length fatty acids with high preference for DAGs containing unsaturated fatty acids. To generate acetyl-TAGs with lower molecular mass, EaDAcT was transformed into transgenic Camelina sativa lines producing high amounts of medium chain fatty acids (MCFAs). EaDAcT expression was also combined with the knockdown of DGAT1 and PDAT enzymes, which compete with EaDAcT for their common DAG substrate. High acetyl-TAG yielding homozygous T3 transgenic lines were generated but the incorporation of MCFAs into acetyl-TAGs was inefficient. A small increase in the viscosity of acetyl-TAGs from these lines was observed compared to acetyl-TAGs produced in wild type Camelina plant. The combined effect of insufficient lowering of molecular mass and increased fatty acid saturation levels of acetyl-TAGs might be responsible for this increased viscosity. Overall, it was concluded that the molecular mass and the saturation levels of fatty acids of acetyl-TAGs need to be considered at the same time in future attempts to further decrease their viscosity.

Aviation greenhouse gas (GHG) emissions have risen faster than any other transport sector to double between 1990 and 2005. Such emissions from aviation could increase another 700 percent globally, and at least 150 percent in the European Union (EU), by 2050 due to continuously increasing consumer demand. To reverse the trend of rising emissions writ large, the EU has set 2030 climate goals of reducing its GHG emissions by 40 percent (relative to 2005) and having 32 percent of gross final energy consumption from renewables. The EU’s recast Renewable Energy Directive (RED-II) calls for 14 percent of transport energy from renewables, gives multipliers to advanced biofuels, and restricts biomass that is from ecologically valuable lands or that causes land use change. Energy security and energy independence are also long-term EU goals. Many of these goals and targets have also been adopted by the European Free Trade Area (EFTA). Despite these efforts, options are limited to reduce aviation emissions compared to other transport sectors, leaving aviation biofuels, also known as renewable jet fuels (RJFs), as currently the only commercialized option. Against this backdrop, in this thesis scenario analyses were conducted to produce biomass from EU+EFTA lands, project RJF yields from this biomass, and estimate emissions savings of these RJFs compared to petroleum jet fuel. Particular effort was devoted to identifying biomass, biofuels, and EU+EFTA lands that comply with RED-II criteria. The two RJF pathways selected were hydroprocessed esters and fatty acid (HEFA) conversion of Camelina sativa vegetable oil and Fischer-Tropsch (FT) synthesis of forestry residue lignocellulosic biomass. Over 117 million hectares in the EU+EFTA was identified as available for Camelina sativa cultivation, which could yield over 64 Mt of RJF each year, or 113 percent of the total jet fuel consumed in the EU+EFTA in 2017. Conversely, if 50 percent of the forestry residues generated as by-products from EU+EFTA roundwood harvesting operations in 2017 were extracted from harvest sites, 40 Mt of forestry residues would be available as biomass, which would yield almost 7.6 Mt of RJF annually (13% of 2017 jet fuel consumption). If all 144 million hectares of EU+EFTA forest lands deemed available for wood supply were logged, 1,772 Mt of forestry residues would be produced in total (at 50 percent extraction), which could result in almost 337 Mt of RJF, or 590% of the jet fuel consumed in the region in 2017. Hence, RJF can be feasibly produced from biomass from EU+EFTA lands, in amounts that meet or exceed the annual jet fuel consumption of the EU+EFTA, and in ways that meet or exceed RED-II sustainability criteria. However, the proportion of these RJF yields to total annual EU+EFTA jet fuel consumption will decrease over time as the number of flights and their resulting emissions increase. The two RJFs also emit 67 percent and 91 percent fewer GHG emissions, respectively, than petroleum-based jet fuel, showing them to be important tools for the EU to meet its 2030 renewables and emissions reductions targets. Producing the biomass feedstocks and RJFs in these quantities will require the EU to make serious decisions on land use trade-offs, such as whether livestock production is more important than biofuel production.