Applications and Potentials for Biogenic Methane Recovery Operations in Nebraska Agriculture, Industry, and Economic Development

ABSTRACT: This thesis report illustrates the applications and potentials of biogenic methane recovery in Nebraska’s agricultural and industrial sectors and as a means for increasing sustainable economic development in the state’s rural communities. As the nation moves toward a new green economy, biogenic methane recovery as a waste management strategy and renewable energy resource presents significant opportunities for Nebraska to be a national and world leader in agricultural and industrial innovation, advanced research and development of renewable energy technology, and generation of new product markets. Nebraska’s agricultural economy provides a distinct advantage to the state for supporting methane recovery operations that provide long-term economic and environmental partnerships among producers, industry, and communities. These opportunities will serve to protect Nebraska’s agricultural producers from volatile energy input markets and as well as creating new markets for Nebraska agricultural products. They will also serve to provide quality education and employment opportunities for Nebraska students and businesses. There are challenges and issues that remain for the state in order to take advantage of its resource potential. There is a need to produce a comprehensive Nebraska biogenic methane potential study and digital mapping system to identify high-potential producers, co-products, and markets. There is also a need to develop a web-based format of consolidated information specific to Nebraska to aid in connecting producers, service providers, educators, and policy-makers.

Development of the ovaries of the lobster Panulirus echinatus (Crustacea: Palinuridae) based on macroscopic and microscopic examination and gonadosomatic relation (GSR)

The developmental stages of the ovaries of the lobster Panulirus echinatus Smith, 1869 were characterized using macroscopic and microscopic features and the gonadosomatic relation (GSR). Based on monthly samples (November, 1999 to October, 2000), a total of 711 females were captured using gillnets. The dorsal region of the carapace was removed to evaluate the ovaries, which were dissected, weighted, preserved in Bouin`s solution, and submitted to histological procedures. The microscopic analysis of the ovaries was assessed by the presence of germinative cells in different developmental phases. When this analysis was combined with macroscopical observations (changes in color and volume of the gonads in the cephalothorax) and GSR, five developmental stages could be identified: immature (I), intermediate (II); pre-maturation (III); mature (IV) and post-spawning stage (V). Statistical analyses confirmed that GSR can be used as an indicator of developmental stage.

Development stages of the reproductive tract of male of Panulirus echinatus Smith (Decapoda : Palinuridae)

This paper characterizes the developmental stages of the testes and vasa deferentia of the Panulirus echinatus Smith, 1869 through comparisons between microscopic findings, macroscopic aspects, and gonadosomatic index (GSR). The lobsters were sampled monthly (November 1999 to October 2000) using seine nets and a total of 1716 males were obtained at Tamandare Bay. Each carapace was cut to allow evaluation of the reproductive organs; the testes and vasa deferentia were dissected, weighed, fixed in Bouin`s solution up to 12 hours and submitted for histological analysis to determine the presence and/or absence of spermatozoa. These measures, along with change in color, size, diameter, development of the spermatophores and the GSR allowed the caracterization of three development stages: immature, intermediate and ripe. In conclusion, the maturity of the testes precedes the maturity of the vasa deferentia. To evaluate if gonadosomatic relation was a good quantitative indicator of the maturity stage, t tests (alpha = 0,05) were used and verified significant difference in the averages of GSR. The statistics corroborated that GSR can be used as indicative of the developmental stages for P. echinatus.

Guidelines for the Brazilian ceramic sector strategic development, based on a comparison with the Italian market

Based on a structured literature review, the ceramic tiles sector of Italy (benchmark) and Brazil (2nd world producer and consumer) are compared, under four strategic factors: normative, market, technology and strategic management, in order to identify critical risks for a national strategic sector. The document aims to propose guidelines for a strategic re-planning of the Brazilian ceramic tiles sector, making the Brazilian producers aware of the national market fragility (in spite of its recent remarkable evolution) and helping the policy makers to reflect on the need of reviewing the strategic planning methods and practice, of designing new targeted programs (based on coherence between operation and business strategies), of providing improved management to strengthen the sector against unfair competition by low-cost producers, enhancing the necessary infrastructure in technology, work, marketing and quality management. The analysis is limited to the single-firing production technology. The wide-coverage strategic analysis of the Brazilian ceramic tiles sector, very little studied until now in a scientific way, emphasizes the importance of applying research methodology and may be valuable to both scholars and practitioners. Additionally, it highlights the need of investments in innovation (product design and production technology) and the fundamental role of the sector organization, identifying different dimensions. It is possible to conclude that the recent Brazilian production growth is not due to a natural strengthening because of the hit of the sector and of correct enterprises strategy, but it seems the result of a temporary and favorable economic contingency.

Development of Plurimetallic Electrocatalysts Prepared by Decomposition of Polymeric Precursors for EtOH/O-2 Fuel Cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal: carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Glycerol as a by-product of biodiesel production in Brazil: Alternatives for the use of unrefined glycerol

On January 1 2008, Brazil included yet another element into its energy matrix: biodiesel. The predominant biodiesel production process involves a phase of transesterification that yields glycerol as a by-product. The use of this glycerol is limited since it is considered an unrefined raw material that must be refined for its various types of use. Several studies have addressed identification of possible uses for unrefined glycerol. Given the diversity of uses, an overview is necessary. The purpose of this work is to present alternatives currently being considered for the use of unrefined glycerol as a by-product of biodiesel production, aiming to contribute to the sustainable consolidation of the biofuel market. Exploratory research was carried out to identify these viable alternatives for the use of this by-product. The possibilities include the production of chemical products, fuel additives, production of hydrogen, development of fuel cells, ethanol or methanol production, animal feed, co-digestion and co-gasification, and waste treatment among others. The present research reveals that there are promising possibilities for the use of unrefined glycerol, which may help consolidate the sustainability of the biofuel market. (C) 2012 Elsevier Ltd. All rights reserved.

Is missing maxillary lateral incisor in complete cleft lip and palate a product of genetics or local environment?

Objective: To test the null hypothesis: Subjects with isolated complete unilateral cleft lip and palate (UCLP) show no differences in overall frequency of tooth agenesis (hypodontia), comparing a subsample with cleft-side maxillary lateral incisor (MxI2) agenesis to a subsample without cleftside MxI2 agenesis. Findings could clarify the origins of cleft-side MxI2 agenesis. Materials and Methods: Tooth agenesis was identified from dental radiographs of 141 subjects with UCLP. The UCLP cohort was segregated into four categories according to the status and location of MxI2 in the region of the unilateral cleft: group M: subjects with one tooth, located on the mesial side of the alveolar cleft; group D: subjects with one tooth, located on the distal side of the alveolar cleft; group MD: subjects with two teeth present, one mesial and one distal to the cleft; and group ABS: subjects with lateral incisor absent (agenesis) in the cleft area. Results: The null hypothesis was rejected. Among UCLP subjects, there was a twofold increase (P < .0008) in overall frequency of tooth agenesis outside the cleft region in a subsample with cleftside MxI2 agenesis (ABS), compared to a subsample presenting with no agenesis of the cleft-side MxI2 (M+D+MD). Conclusions: Cleft-side MxI2 agenesis in CLP subjects appears to be largely a genetically controlled anomaly associated with cleft development, rather than a collateral environmental consequence of the adjacent cleft defect, since increased hypodontia involving multiple missing teeth observed remote from a cleft clearly has a significant genetic basis. (Angle Orthod. 2012;82:959-963.)

Nitrogen excretion during embryonic development of the green iguana, Iguana iguana (Reptilia; Squamata)

Development within the cleidoic egg of birds and reptiles presents the embryo with the problem of accumulation of wastes from nitrogen metabolism. Ammonia derived from protein catabolism is converted into the less toxic product urea or relatively insoluble uric acid. The pattern of nitrogen excretion of the green iguana, Iguana iguana, was determined during embryonic development using samples from allantoic fluid and from the whole homogenized egg, and in hatchlings and adults using samples of blood plasma. Urea was the major excretory product over the course of embryonic development. It was found in higher concentrations in the allantoic sac, suggesting that there is a mechanism present on the allantoic membrane enabling the concentration of urea. The newly hatched iguana still produced urea while adults produced uric acid. The time course of this shift in the type of nitrogen waste was not determined but the change is likely to be related to the water relations associated with the terrestrial habit of the adult. The green iguana produces parchment-shelled eggs that double in mass during incubation due to water absorption: the eggs also accumulate 0.02 mM of urea, representing 82% of the total measured nitrogenous residues that accumulate inside the allantois. The increase in egg mass and urea concentration became significant after 55 days of incubation then were unchanged until hatching. (C) 2012 Elsevier Inc. All rights reserved.

Development of cassava cake enriched with its own bran and Spirulina platensis

The cassava cake was developed enriching it with a biomass of Spirulina platensis and a type of bran made out of its own starch. This biomass, a part from being rich in protein, also contains vitamins, essential fatty acids and minerals. Around Umuarama, in the State of Parana, there is an agricultural/industrial complex annually producing and processing tons of cassava. Baked goods can be elaborated based in cassava as a way to expand the use of this raw material and to produce food free of gluten to celiac people. In this complex a solid byproduct is generated, which is rich in starch and fibres, and because of its low commercial value it is used for animal feed or discarded. The bran was dehydrated and analysed microbiologically as well as physically and chemically so as to be used in applied research. Developed energetic food based on cassava lacks protein, but this can be supplied by adding the biomass of Spirulina platensis. Different formulations of this cassava cake were developed varying the concentration of Spirulina platensis and cassava bran. The formulation that presented the best features received chocolate before being submitted to sensory tests by children in the public education system. The results show an excellent acceptance which made viable the development of this product because of aspects like nutrition, technology and sensorial.

Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Development of Organocatalytic stereoselective SN1 type reactions

The proposal in my thesis has been the study of Stereoselective α-alkylation through SN1 type reaction. SN1 type reaction involves a stabilized and reactive carbocation intermediate By taking advantages of stability of particular carbocations, the use of carbocations in selective reactions has been important. In this work has been necessary to know the stability and reactivity of carbocations. And the work of Mayr group has helped to rationalize the behaviour and reactivity between the carbocations and nucleophiles by the use of Mayr’s scale of reactivity. The use of alcohols to performed the stable and reactive carbocations have been the key in my thesis. The direct nucleophilic substitution of alcohols has been a crucial scope in the field of organic synthesis, because offer a wide range of intermediates for the synthesis of natural products and pharmaceutics synthesis. In particular the catalytic nucleophilic direct substitution of alcohols represents a novel methodology for the preparation of a variety of derivatives, and water only as the sub-product in the reaction. The stereochemical control of the transformation C-H bond into stereogenic C-C bond adjacent to carbonyl functionalized has been studied for asymmetric catalysis. And the field of organocatalysis has introduced the use of small organic molecule as catalyst for stereoselective transformations. Merging these two concepts Organocatalysis and Mayr’s scale, my thesis has developed a new approach for the α-alkylation of aldehydes and ketones through SN1 type reaction.

Development of guidelines for microbiological control in microbrewery

Over the past 15 years the Italian brewing scene showed interesting changes, especially with regard to the creation of many breweries with an annual production of less than 10,000 hectoliters. The beers produced by microbreweries are very susceptible to attack by spoilage micro-organisms that cause the deterioration of beer quality characteristics. In addition, most of the microbreweries do not practice heat treatments of stabilization and do not carry out quality checks on the product. The high presence of beer spoilage bacteria is an economic problem for the brewing industry because it can damage the brand and it causes high costs of product retrieval. This thesis project was aimed to study the management of the production process in the Italian microbreweries within a production less than 10,000 hl. In particular, the annual production, type of plant, yeast management, process management, cleaning and sanitizing of a representative sample of microbreweries were investigated. Furthermore was made a collection of samples in order to identify, with simple methods, what are spoilage bacteria more present in the Italian craft beers. 21% of the beers analysed were positive at the presence of lactic acid bacteria. These analytical data show the importance of understanding what are the weak points of the production process that cause the development of spoilage bacteria. Finally, the thesis examined the actual production of two microbreweries in order to understand the process management that can promote the growth of spoilage bacteria in beer and production plant. The analysis of the data for the two case studies was helpful to understand what are the critical points where the microorganisms are most frequently in contact with the product. The hygiene practices are crucial to ensure the quality of the finished product, especially in the case of non-pasteurized beer.

Development of innovative catalysts for the hydrodechlorination to fluoroethers

In this work the hydrodechlorination of CF3OCFClCF2Cl to produce unsaturated CF3OCF=CF2 was studied over a series of supported metal catalysts. Currently this molecule is produced from the precursor CF3OCFClCF2Cl by dechlorination with zinc powder. An important cost on the economic and environmental balance is represents by the large amount of ZnCl2 produced and to be disposed of. A new approach, based on gas-phase hydrodechlorination over supported catalysts can lead to a new sustainable process. During the feasibility step of this project, substantially two kind of materials were studied: metals supported over activated carbon and Pd/Cu species supported over MCM-41 mesoporous silica. Observed catalytic performances were strongly dependent on the metal and support used. All carbon-supported Ru, Pd, and bimetallic catalysts are fairly active and yielded the target product CF3OCF=CF2, the higher selectivity being obtained with ruthenium- and palladium-based materials. Nevertheless, Ru-based catalysts showed poor stability and this deactivation may be attributed to the deposition of chlorinated organic species blocking the active sites. On the other hand, palladium-containing catalysts showed high stability. Ru/Pd and Pd/Cu bimetallic catalysts exhibited long-term selectivity and stability, highlighting the possibility for these materials to be employed in the CF3OCF=CF2 production process. During the second part of this thesis, a series of bimetallic meso-structured Pd/Cu MCM-41 catalysts were studies to overcome possible mass transfer limitations. The materials were obtained by different synthesis methods. The incorporation of Pd and Cu during MCM-41 synthesis, did not destroy the typical hexagonal array and ordered pore system of MCM-41. However, the calcination for the removal of the template provoked significant segregation of oxides. The impregnation leads to pore-occlusion and formation of Cu particles and large bimetallic PdCu species. Larger metal particles leads to lower CF3OCFClCF2Cl conversion, while the monometallic particles can decrease the selectivity to CF3OCF=CF2, fostering the dehalogenation to CF3OCH=CF2.

Entrepreneurship influential factors in development of rural tourism as diversified rural activity in Republic of Macedonia

Rural tourism is relatively new product in the process of diversification of the rural economy in Republic of Macedonia. This study used desk research and life story interviews of rural tourism entrepreneurs as qualitative research method to identify prevalent success influential factors. Further quantitative analysis was applied in order to measure the strength of influence of identified success factors. The primary data for the quantitative research was gathered using telephone questionnaire composed of 37 questions with 5-points Likert scale. The data was analyzed using Partial Least Squares Structural Equation Modeling (PLS-SEM) by SmartPLS 3.1.6. Results indicated that human capital, social capital, entrepreneurial personality and external business environment are predominant influential success factors. However, human capital has non-significant direct effect on success (p 0.493) nonetheless the effect was indirect with high level of partial mediation through entrepreneurial personality as mediator (VAF 73%). Personality of the entrepreneur, social capital and business environment have direct positive affect on entrepreneurial success (p 0.001, 0.003 and 0.045 respectably). Personality also mediates the positive effect of social capital on entrepreneurial success (VAF 28%). Opposite to the theory the data showed no interaction between social and human capital on the entrepreneurial success. This research suggests that rural tourism accommodation entrepreneurs could be more successful if there is increased support in development of social capital in form of conservation of cultural heritage and natural attractions. Priority should be finding the form to encourage and support the establishment of formal and informal associations of entrepreneurs in order to improve the conditions for management and marketing of the sector. Special support of family businesses in the early stages of the operation would have a particularly positive impact on the success of rural tourism. Local infrastructure, access to financial instruments, destination marketing and entrepreneurial personality have positive effect on success.