Afghanistan connection : heroin production, distribution, and consumption

Heroin prices are a reflection of supply and demand, and similar to any other market, profits motivate participation. The intent of this research is to examine the change in Afghan opium production due to political conflict affecting Europe’s heroin market and government policies. If the Taliban remain in power, or a new Afghan government is formed, the changes will affect the heroin market in Europe to a certain degree. In the heroin market, the degree of change is dependent on many socioeconomic forces such as law enforcement, corruption, and proximity to Afghanistan. An econometric model that examines the degree of these socioeconomic effects has not been applied to the heroin trade in Afghanistan before. This research uses a two-stage least squares econometric model to reveal the supply and demand of heroin in 36 different countries from the Middle East to Western Europe in 2008. An application of the two-stage least squares model to the heroin market in Europe will attempt to predict the socioeconomic consequences of Afghanistan opium production.

Retention of canopy trees as biological legacies for balancing woody biomass production and biodiversity in managed aspen forests of the Great Lakes Region

Green-tree retention under the conceptual framework of ecological forestry has the potential to provide both biomass feedstock for industry and maintain quality wildlife habitat. I examined the effects of retained canopy trees as biological legacies (“legacy trees”) in aspen (Populus spp.) forests on above-ground live woody biomass, understory plant floristic quality, and bird diversity. Additionally, I evaluated habitat quality for a high conservation priority species, the Golden-winged Warbler (Vermivora chrysoptera). I selected 27 aspen-dominated forest stands in northern Wisconsin with nine stands in each of three legacy tree retention treatments (conifer retention, hardwood retention, and clearcuts or no retention) across a chronosequence (4-36 years post-harvest). Conifer retention stands had greater legacy tree and all tree species biomass but lower regenerating tree biomass than clearcuts. Coniferous but not hardwood legacy trees appeared to suppress regenerating tree biomass. I evaluated the floristic quality of the understory plant assemblage by estimating the mean coefficient of conservatism (C). Mean C was lower in young stands than in middle-age or old stands; there was a marginally significant (p=0.058) interaction effect between legacy tree retention treatment and stand age. Late-seral plant species were positively associated with stand age and legacy tree diameter or age revealing an important relationship between legacy tree retention and stand development. Bird species richness was greatest in stands with hardwood retention particularly early in stand development. Six conservation priority bird species were indicators of legacy tree retention or clearcuts. Retention of legacy trees in aspen stands provided higher quality nest habitat for the Golden-winged Warbler than clearcuts based on high pairing success and nesting activity. Retention of hardwoods, particularly northern red oak (Quercus rubra), yielded the most consistent positive effects in this study with the highest bird species richness and the highest quality habitat for the Golden-winged Warbler. This treatment maintained stand biomass comparable to clearcuts and did not suppress regenerating tree biomass. In conclusion, legacy tree retention can enhance even-aged management techniques to produce a win-win scenario for the conservation of declining bird species and late-seral understory plants and for production of woody biomass feedstock from naturally regenerating aspen forests.

Optimization of ethanol production by yeasts from lignocellulosic feedstocks

Ethanol from lignocellulosic feedstocks is not currently competitive with corn-based ethanol in terms of yields and commercial feasibility. Through optimization of the pretreatment and fermentation steps this could change. The overall goal of this study was to evaluate, characterize, and optimize ethanol production from lignocellulosic feedstocks by the yeasts Saccharomyces cerevisiae (strain Ethanol Red, ER) and Pichia stipitis CBS 6054. Through a series of fermentations and growth studies, P. stipitis CBS 6054 and S. cerevisiae (ER) were evaluated on their ability to produce ethanol from both single substrate (xylose and glucose) and mixed substrate (five sugars present in hemicellulose) fermentations. The yeasts were also evaluated on their ability to produce ethanol from dilute acid pretreated hydrolysate and enzymatic hydrolysate. Hardwood (aspen), softwood (balsam), and herbaceous (switchgrass) hydrolysates were also tested to determine the effect of the source of the feedstock. P. stipitis produced ethanol from 66-98% of the theoretical yield throughout the fermentation studies completed over the course of this work. S. cerevisiae (ER) was determined to not be ideal for dilute acid pretreated lignocellulose because it was not able to utilize all the sugars found in hemicellulose. S. cerevisiae (ER) was instead used to optimize enzymatic pretreated lignocellulose that contained only glucose monomers. It was able to produce ethanol from enzymatically pretreated hydrolysate but the sugar level was so low (>3 g/L) that it would not be commercially feasible. Two lignocellulosic degradation products, furfural and acetic acid, were evaluated for whether or not they had an inhibitory effect on biomass production, substrate utilization, and ethanol production by P. stipitis and S. cerevisiae (ER). It was determined that inhibition is directly related to the concentration of the inhibitor and the organism. The final phase for this thesis focused on adapting P. stipitis CBS 6054 to toxic compounds present in dilute acid pretreated hydrolysate through directed evolution. Cultures were transferred to increasing concentrations of dilute acid pretreated hydrolysate in the fermentation media. The adapted strains’ fermentation capabilities were tested against the unadapted parent strain at each hydrolysate concentration. The fermentation capabilities of the adapted strain were significantly improved over the unadapted parentstrain. On media containing 60% hydrolysate the adapted strain yielded 0.30 g_ethanol/g_sugar ± 0.033 (g/g) and the unadapted parent strain yielded 0.11 g/g ±0.028. The culture has been successfully adapted to growth on media containing 65%, 70%, 75%, and 80% hydrolysate but with below optimal ethanol yields (0.14-0.19 g/g). Cell recycle could be a viable option for improving ethanol yields in these cases. A study was conducted to determine the optimal media for production of ethanol from xylose and mixed substrate fermentations by P. stipitis. Growth, substrate utilization, and ethanol production were the three factors used to evaluate the media. The three media tested were Yeast Peptone (YP), Yeast Nitrogen Base (YNB), and Corn Steep Liquor (CSL). The ethanol yields (g/g) for each medium are as follows: YP - 0.40-0.42, YNB -0.28-.030, and CSL - 0.44-.051. The results show that media containing CSL result in slightly higher ethanol yields then other fermentation media. P. stipitis was successfully adapted to dilute acid pretreated aspen hydrolysate in increasing concentrations in order to produce higher ethanol yields compared to the unadapted parent strain. S. cerevisiae (ER) produced ethanol from enzymatic pretreated cellulose containing low concentrations of glucose (1-3g/L). These results show that fermentations of lignocellulosic feedstocks can be optimized based on the substrate and organism for increased ethanol yields.

Decentralized or centralized production : impacts to the environment, industry, and the economy

Since product take-back is mandated in Europe, and has effects for producers worldwide including the U.S., designing efficient forward and reverse supply chain networks is becoming essential for business viability. Centralizing production facilities may reduce costs but perhaps not environmental impacts. Decentralizing a supply chain may reduce transportation environmental impacts but increase capital costs. Facility location strategies of centralization or decentralization are tested for companies with supply chains that both take back and manufacture products. Decentralized and centralized production systems have different effects on the environment, industry and the economy. Decentralized production systems cluster suppliers within the geographical market region that the system serves. Centralized production systems have many suppliers spread out that meet all market demand. The point of this research is to help further the understanding of company decision-makers about impacts to the environment and costs when choosing a decentralized or centralized supply chain organizational strategy. This research explores; what degree of centralization for a supply chain makes the most financial and environmental sense for siting facilities; and which factories are in the best location to handle the financial and environmental impacts of particular processing steps needed for product manufacture. This research considered two examples of facility location for supply chains when products are taken back; the theoretical case involved shoe resoling and a real world case study considered the location of operations for a company that reclaims multiple products for use as material inputs. For the theoretical example a centralized strategy to facility location was optimal: whereas for the case study a decentralized strategy to facility location was best. In conclusion, it is not possible to say that a centralized or decentralized strategy to facility location is in general best for a company that takes back products. Each company’s specific concerns, needs, and supply chain details will determine which degree of centralization creates the optimal strategy for siting their facilities.

Farmer land allocation for maize, groundnut and cotton production in Chipata District, Eastern Province, Zambia

Small-scale farmers in the Chipata District of Zambia rely on their farm fields to grow maize and groundnuts for food security. Cotton production and surplus food security crops are used to generate income to provide for their families. With increasing population pressure, available land has decreased and farmers struggle to provide the necessary food requirements and income to meet their family’s needs. The purpose of the study was to determine how a farmer can best allocate his land to produce maize, groundnuts and cotton when constrained by labor and capital resources to generate the highest potential for food security and financial gains. Data from the 2008-2009 growing season was compiled and analyzed using a linear programming model. The study determined that farmers make the most profit by allocating all additional land and resources to cotton after meeting their minimum food security requirements. The study suggests growing cotton is a beneficial practice for small-scale subsistence farmers to generate income when restricted by limited resources.

Economic viability of shale gas production in the Marcellus Shale; indicated by production rates, costs and current natural gas prices

The U.S. natural gas industry has changed because of the recent ability to produce natural gas from unconventional shale deposits. One of the largest and most important deposits is the Marcellus Shale. Hydraulic fracturing and horizontal drilling have allowed for the technical feasibility of production, but concerns exist regarding the economics of shale gas production. These concerns are related to limited production and economic data for shale gas wells, declines in the rates of production, falling natural gas prices, oversupply issues coupled with slow growth in U.S. natural gas demand, and rising production costs. An attempt to determine profitability was done through the economic analysis of an average shale gas well using data that is representative of natural gas production from 2009 to 2011 in the Marcellus Shale. Despite the adverse conditions facing the shale gas industry it is concluded from the results of this analysis that a shale gas well in the Marcellus Shale is profitable based on NPV, IRR and breakeven price calculations.

Planting and production of switchgrass (Panicum virgatum L.) as a bioenergy crop in Michigan's Upper Peninsula

Switchgrass (Panicum virgatum L.) is a perennial grass holding great promise as a biofuel resource. While Michigan’s Upper Peninsula has an appropriate land base and climatic conditions, there is little research exploring the possibilities of switchgrass production. The overall objectives of this research were to investigate switchgrass establishment in the northern edge of its distribution through: investigating the effects of competition on the germination and establishment of switchgrass through the developmental and competitive characteristics of Cave-in-Rock switchgrass and large crabgrass (Digitaria sanguinalis L.) in Michigan’s Upper Peninsula; and, determining the optimum planting depths and timing for switchgrass in Michigan’s Upper Peninsula. For the competition study, a randomized complete block design was installed June 2009 at two locations in Michigan’s Upper Peninsula. Four treatments (0, 1, 4, and 8 plants/m2) of crabgrass were planted with one switchgrass plant. There was a significant difference between switchgrass biomass produced in year one, as a function of crabgrass weed pressure. There was no significant difference between the switchgrass biomass produced in year two versus previous crabgrass weed pressure. There is a significant difference between switchgrass biomass produced in year one and two. For the depth and timing study, a completely randomized design was installed at two locations in Michigan’s Upper Peninsula on seven planting dates (three fall 2009, and four spring 2010); 25 seeds were planted 2 cm apart along 0.5 m rows at depths of: 0.6 cm, 1.3 cm, and 1.9 cm. Emergence and biomass yields were compared by planting date, and depths. A greenhouse seeding experiment was established using the same planting depths and parameters as the field study. The number of seedlings was tallied daily for 30 days. There was a significant difference in survivorship between the fall and spring planting dates, with the spring being more successful. Of the four spring planting dates, there was a significant difference between May and June in emergence and biomass yield. June planting dates had the most percent emergence and total survivorship. There is no significant difference between planting switchgrass at depths of 0.6 cm, 1.3 cm, and 1.9 cm. In conclusion, switchgrass showed no signs of a legacy effect of competition from year one, on biomass production. Overall, an antagonistic effect on switchgrass biomass yield during the establishment period has been observed as a result of increasing competing weed pressure. When planting switchgrass in Michigan’s Upper Peninsula, it should be done in the spring, within the first two weeks of June, at any depth ranging from 0.6 cm to 1.9 cm.

Uncovering poiesis : the role of production in technical communication, work, and public life

This dissertation is a report on a collaborative project between the Computer Science and the Humanities Departments to develop case studies that focus on issues of communication in the workplace, and the results of their use in the classroom. My argument is that case study teaching simulates real-world experience in a meaningful way, essentially developing a teachable way of developing phronesis, the reasoned capacity to act for the good in public. In addition, it can be read as a "how-to" guide for educators who may wish to construct their own case studies. To that end, I have included a discussion of the ethnographic methodologies employed, and how it was adapted to our more pragmatic ends. Finally, I present my overarching argument for a new appraisal of the concept of techné. This reappraisal emphasizes its productive activity, poiesis, rather than focusing on its knowledge as has been the case in the past. I propose that focusing on the telos, the end outside the production, contributes to the diminishment, if not complete foreclosure, of a rich concept of techné.

Ethanol Production from Hardboard Manufacturing Process Wastewater: Methods for Improving Product Yields from Hemicellulose Hydrolysates

Waste effluents from the forest products industry are sources of lignocellulosic biomass that can be converted to ethanol by yeast after pretreatment. However, the challenge of improving ethanol yields from a mixed pentose and hexose fermentation of a potentially inhibitory hydrolysate still remains. Hardboard manufacturing process wastewater (HPW) was evaluated at a potential feedstream for lignocellulosic ethanol production by native xylose-fermenting yeast. After screening of xylose-fermenting yeasts, Scheffersomyces stipitis CBS 6054 was selected as the ideal organism for conversion of the HPW hydrolysate material. The individual and synergistic effects of inhibitory compounds present in the hydrolysate were evaluated using response surface methodology. It was concluded that organic acids have an additive negative effect on fermentations. Fermentation conditions were also optimized in terms of aeration and pH. Methods for improving productivity and achieving higher ethanol yields were investigated. Adaptation to the conditions present in the hydrolysate through repeated cell sub-culturing was used. The objectives of this present study were to adapt S. stipitis CBS6054 to a dilute-acid pretreated lignocellulosic containing waste stream; compare the physiological, metabolic, and proteomic profiles of the adapted strain to its parent; quantify changes in protein expression/regulation, metabolite abundance, and enzyme activity; and determine the biochemical and molecular mechanism of adaptation. The adapted culture showed improvement in both substrate utilization and ethanol yields compared to the unadapted parent strain. The adapted strain also represented a growth phenotype compared to its unadapted parent based on its physiological and proteomic profiles. Several potential targets that could be responsible for strain improvement were identified. These targets could have implications for metabolic engineering of strains for improved ethanol production from lignocellulosic feedstocks. Although this work focuses specifically on the conversion of HPW to ethanol, the methods developed can be used for any feedstock/product systems that employ a microbial conversion step. The benefit of this research is that the organisms will the optimized for a company's specific system.

Production of liquid core-polymer shell microcapsules

Polylactide (PLA) is a biodegradable polymer that has been used in particle form for drug release, due to its biocompatibility, tailorable degradation kinetics, and desirable mechanical properties. Active pharmaceutical ingredients (APIs) may be either dissolved or encapsulated within these biomaterials to create micro- or nanoparticles. Delivery of an AIP within fine particles may overcome solubility or stability issues that can result in early elimination or degradation of the AIP in a hostile biological environment. Furthermore, it is a promising method for controlling the rate of drug delivery and dosage. The goal of this project is to develop a simple and cost-effective device that allows us to produce monodisperse micro- and nanocapsules with controllable size and adjustable sheath thickness on demand. To achieve this goal, we have studied the dual-capillary electrospray and pulsed electrospray. Dual-capillary electrospray has received considerable attention in recent years due to its ability to create core-shell structures in a single-step. However, it also increases the difficulty of controlling the inner and outer particle morphology, since two simultaneous flows are required. Conventional electrospraying has been mainly conducted using direct-current (DC) voltage with little control over anything but the electrical potential. In contrast, control over the input voltage waveform (i.e. pulsing) in electrospraying offers greater control over the process variables. Poly(L-lactic acid) (PLLA) microspheres and microcapsules were successfully fabricated via pulsed-DC electrospray and dual-capillary electrospray, respectively. Core shell combinations produced include: Water/PLLA, PLLA/polyethylene glycol (PEG), and oleic Acid/PLLA. In this study, we designed a novel high-voltage pulse forming network and a set of new designs for coaxial electrospray nozzles. We also investigated the effect of the pulsed voltage characteristics (e.g. pulse frequency, pulse amplitude and pulse width) on the particle’s size and uniformity. We found that pulse frequency, pulse amplitude, pulse width, and the combinations of these factors had a statistically significant effect on the particle’s size. In addition, factors such as polymer concentration, solvent type, feed flow rate, collection method, temperature, and humidity can significantly affect the size and shape of the particles formed.

ASTAXANTHIN PRODUCTION FROM HAEMATOCOCCUS PLUVIALIS UNDER VARIOUS LIGHT INTENSITIES AND CARBON DIOXIDE CONCENTRATIONS

The microalga Haematococcus pluvialis was cultivated in MES-volvox medium at various light intensities and CO2 concentrations. It was found that CO2 concentrations of 10 and 15%, in combination with high irradiance at initial pH =6.7, accelerate astaxanthin accumulation in H. pluvialis cells but obstruct cell growth. The purpose of this research study was to devise a one-stage process consisting of the simultaneous cultivation of H. pluvialis and astaxanthin production using high light intensity and high CO2 concentration. This could be achieved at 200 µE/m2s and 15% CO2 in growth medium at initial pH = 4.3. Compared to the traditional two-stage H. pluvialis cultivation system, this one-step process can save up to 8-9 days of astaxanthin production time. The astaxanthin content in H. pluvialis cells induced with high light intensity only or with a combination of high light intensity and high CO2 concentration had comparable astaxanthin content; 94 and 97 mg/g dry biomass, respectively. However, it was extremely low in nitrate-free medium at high irradiance alone or combined with high CO2 concentration, with an average value of 4 mg/g dry biomass. Cell density was 40% less in cultures under discontinuous illumination compared to continuous illumination. This process could serve as a microalgal CO2 mitigation system after further understanding of the CO2 fixation ability of H. pluvialis has been gained.

THE POTENTIAL OF INDUSTRIAL WASTE AND AGRICULTURAL FEEDSTOCK TOWARDS SUSTAINABLE BIOFUELS PRODUCTION: TECHNO-ECONOMIC AND ENVIRONMENTAL IMPACT PERSPECTIVES

This Ph.D. research is comprised of three major components; (i) Characterization study to analyze the composition of defatted corn syrup (DCS) from a dry corn mill facility (ii) Hydrolysis experiments to optimize the production of fermentable sugars and amino acid platform using DCS and (iii) Sustainability analyses. Analyses of DCS included total solids, ash content, total protein, amino acids, inorganic elements, starch, total carbohydrates, lignin, organic acids, glycerol, and presence of functional groups. Total solids content was 37.4% (± 0.4%) by weight, and the mass balance closure was 101%. Total carbohydrates [27% (± 5%) wt.] comprised of starch (5.6%), soluble monomer carbohydrates (12%) and non-starch carbohydrates (10%). Hemicellulose components (structural and non-structural) were; xylan (6%), xylose (1%), mannan (1%), mannose (0.4%), arabinan (1%), arabinose (0.4%), galatactan (3%) and galactose (0.4%). Based on the measured physical and chemical components, bio-chemical conversion route and subsequent fermentation to value added products was identified as promising. DCS has potential to serve as an important fermentation feedstock for bio-based chemicals production. In the sugar hydrolysis experiments, reaction parameters such as acid concentration and retention time were analyzed to determine the optimal conditions to maximize monomer sugar yields while keeping the inhibitors at minimum. Total fermentable sugars produced can reach approximately 86% of theoretical yield when subjected to dilute acid pretreatment (DAP). DAP followed by subsequent enzymatic hydrolysis was most effective for 0 wt% acid hydrolysate samples and least efficient towards 1 and 2 wt% acid hydrolysate samples. The best hydrolysis scheme DCS from an industry's point of view is standalone 60 minutes dilute acid hydrolysis at 2 wt% acid concentration. The combined effect of hydrolysis reaction time, temperature and ratio of enzyme to substrate ratio to develop hydrolysis process that optimizes the production of amino acids in DCS were studied. Four key hydrolysis pathways were investigated for the production of amino acids using DCS. The first hydrolysis pathway is the amino acid analysis using DAP. The second pathway is DAP of DCS followed by protein hydrolysis using proteases [Trypsin, Pronase E (Streptomyces griseus) and Protex 6L]. The third hydrolysis pathway investigated a standalone experiment using proteases (Trypsin, Pronase E, Protex 6L, and Alcalase) on the DCS without any pretreatment. The final pathway investigated the use of Accellerase 1500® and Protex 6L to simultaneously produce fermentable sugars and amino acids over a 24 hour hydrolysis reaction time. The 3 key objectives of the techno-economic analysis component of this PhD research included; (i) Development of a process design for the production of both the sugar and amino acid platforms with DAP using DCS (ii) A preliminary cost analysis to estimate the initial capital cost and operating cost of this facility (iii) A greenhouse gas analysis to understand the environmental impact of this facility. Using Aspen Plus®, a conceptual process design has been constructed. Finally, both Aspen Plus Economic Analyzer® and Simapro® sofware were employed to conduct the cost analysis as well as the carbon footprint emissions of this process facility respectively. Another section of my PhD research work focused on the life cycle assessment (LCA) of commonly used dairy feeds in the U.S. Greenhouse gas (GHG) emissions analysis was conducted for cultivation, harvesting, and production of common dairy feeds used for the production of dairy milk in the U.S. The goal was to determine the carbon footprint [grams CO2 equivalents (gCO2e)/kg of dry feed] in the U.S. on a regional basis, identify key inputs, and make recommendations for emissions reduction. The final section of my Ph.D. research work was an LCA of a single dairy feed mill located in Michigan, USA. The primary goal was to conduct a preliminary assessment of dairy feed mill operations and ultimately determine the GHG emissions for 1 kilogram of milled dairy feed.

TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION

Approximately 90% of fine aerosol in the Midwestern United States has a regional component with a sizable fraction attributed to secondary production of organic aerosol (SOA). The Ozark Forest is an important source of biogenic SOA precursors like isoprene (> 150 mg m-2 d-1), monoterpenes (10-40 mg m-2 d-1), and sesquiterpenes (10-40 mg m-2d-1). Anthropogenic sources include secondary sulfate and nitrate and biomass burning (51-60%), vehicle emissions (17-26%), and industrial emissions (16-18%). Vehicle emissions are an important source of volatile and vapor-phase, semivolatile aliphatic and aromatic hydrocarbons that are important anthropogenic sources of SOA precursors. The short lifetime of SOA precursors and the complex mixture of functionalized oxidation products make rapid sampling, quantitative processing methods, and comprehensive organic molecular analysis essential elements of a comprehensive strategy to advance understanding of SOA formation pathways. Uncertainties in forecasting SOA production on regional scales are large and related to uncertainties in biogenic emission inventories and measurement of SOA yields under ambient conditions. This work presents a bottom-up approach to develop a conifer emission inventory based on foliar and cortical oleoresin composition, development of a model to estimate terpene and terpenoid signatures of foliar and bole emissions from conifers, development of processing and analytic techniques for comprehensive organic molecular characterization of SOA precursors and oxidation products, implementation of the high-volume sampling technique to measure OA and vapor-phase organic matter, and results from a 5 day field experiment conducted to evaluate temporal and diurnal trends in SOA precursors and oxidation products. A total of 98, 115, and 87 terpene and terpenoid species were identified and quantified in commercially available essential oils of Pinus sylvestris, Picea mariana, and Thuja occidentalis, respectively, by comprehensive, two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC × GC-ToF-MS). Analysis of the literature showed that cortical oleoresin composition was similar to foliar composition of the oldest branches. Our proposed conceptual model for estimation of signatures of terpene and terpenoid emissions from foliar and cortical oleoresin showed that emission potentials of the foliar and bole release pathways are dissimilar and should be considered for conifer species that develop resin blisters or are infested with herbivores or pathogens. Average derivatization efficiencies for Methods 1 and 2 were 87.9 and 114%, respectively. Despite the lower average derivatization efficiency of Method 1, distinct advantages included a greater certainty of derivatization yield for the entire suite of multi- and poly-functional species and fewer processing steps for sequential derivatization. Detection limits for Method 1 using GC × GC- ToF-MS were 0.09-1.89 ng μL-1. A theoretical retention index diagram was developed for a hypothetical GC × 2GC analysis of the complex mixture of SOA precursors and derivatized oxidation products. In general, species eluted (relative to the alkyl diester reference compounds) from the primary column (DB-210) in bands according to n and from the secondary columns (BPX90, SolGel-WAX) according to functionality, essentially making the GC × 2GC retention diagram a Carbon number-functionality grid. The species clustered into 35 groups by functionality and species within each group exhibited good separation by n. Average recoveries of n-alkanes and polyaromatic hydrocarbons (PAHs) by Soxhlet extraction of XAD-2 resin with dichloromethane were 80.1 ± 16.1 and 76.1 ± 17.5%, respectively. Vehicle emissions were the common source for HSVOCs [i.e., resolved alkanes, the unresolved complex mixture (UCM), alkylbenzenes, and 2- and 3-ring PAHs]. An absence of monoterpenes at 0600-1000 and high concentrations of monoterpenoids during the same period was indicative of substantial losses of monoterpenes overnight and the early morning hours. Post-collection, comprehensive organic molecular characterization of SOA precursors and products by GC × GC-ToFMS in ambient air collected with ~2 hr resolution is a promising method for determining biogenic and anthropogenic SOA yields that can be used to evaluate SOA formation models.

Biochemical Conversions of Lignocellulosic Biomass for Sustainable Fuel-Ethanol Production in the Upper Midwest

Biofuels are an increasingly important component of worldwide energy supply. This research aims to understand the pathways and impacts of biofuels production, and to improve these processes to make them more efficient. In Chapter 2, a life cycle assessment (LCA) is presented for cellulosic ethanol production from five potential feedstocks of regional importance to the upper Midwest - hybrid poplar, hybrid willow, switchgrass, diverse prairie grasses, and logging residues - according to the requirements of Renewable Fuel Standard (RFS). Direct land use change emissions are included for the conversion of abandoned agricultural land to feedstock production, and computer models of the conversion process are used in order to determine the effect of varying biomass composition on overall life cycle impacts. All scenarios analyzed here result in greater than 60% reduction in greenhouse gas emissions relative to petroleum gasoline. Land use change effects were found to contribute significantly to the overall emissions for the first 20 years after plantation establishment. Chapter 3 is an investigation of the effects of biomass mixtures on overall sugar recovery from the combined processes of dilute acid pretreatment and enzymatic hydrolysis. Biomass mixtures studied were aspen, a hardwood species well suited to biochemical processing; balsam, a high-lignin softwood species, and switchgrass, an herbaceous energy crop with high ash content. A matrix of three different dilute acid pretreatment severities and three different enzyme loading levels was used to characterize interactions between pretreatment and enzymatic hydrolysis. Maximum glucose yield for any species was 70% oftheoretical for switchgrass, and maximum xylose yield was 99.7% of theoretical for aspen. Supplemental β-glucosidase increased glucose yield from enzymatic hydrolysis by an average of 15%, and total sugar recoveries for mixtures could be predicted to within 4% by linear interpolation of the pure species results. Chapter 4 is an evaluation of the potential for producing Trichoderma reesei cellulose hydrolases in the Kluyveromyces lactis yeast expression system. The exoglucanases Cel6A and Cel7A, and the endoglucanase Cel7B were inserted separately into the K. lactis and the enzymes were analyzed for activity on various substrates. Recombinant Cel7B was found to be active on carboxymethyl cellulose and Avicel powdered cellulose substrates. Recombinant Cel6A was also found to be active on Avicel. Recombinant Cel7A was produced, but no enzymatic activity was detected on any substrate. Chapter 5 presents a new method for enzyme improvement studies using enzyme co-expression and yeast growth rate measurements as a potential high-throughput expression and screening system in K. lactis yeast. Two different K. lactis strains were evaluated for their usefulness in growth screening studies, one wild-type strain and one strain which has had the main galactose metabolic pathway disabled. Sequential transformation and co-expression of the exoglucanase Cel6A and endoglucanase Cel7B was performed, and improved hydrolysis rates on Avicel were detectable in the cell culture supernatant. Future work should focus on hydrolysis of natural substrates, developing the growth screening method, and utilizing the K. lactis expression system for directed evolution of enzymes.