Progress 10/01/13 to 09/18/18

Outputs
Target Audience:Researchers, agricultural producers, forest products industries, government agencies. People who are involved in promoting green energy and operations. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Two PhD students and one MS student were involved in the project. How have the results been disseminated to communities of interest?Presentations in international/national/state conferences and meetings. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Using pine heartwood as a model and by uniquely combining thermochemical and mechanical treatments, we developed methods to efficiently synthesize cellulosic nanomaterials from woody biomass not only with high purity and yield but also with better controls over their physiochemical properties. The developed synthesis process of cellulose nanomaterials was optimized using Response Surface Methodology (RSM). The optimized method was generalized to other woody biomass in Arkansas, including sweetgum, oak and poplar, to determine the best source for cellulose nanomaterial extraction.

Publications

• Type: Journal Articles Status: Published Year Published: 2018 Citation: RanguMagar, A.B., Chhetri, B.P., Paremesharam-Thanknam, A., Watanabe, F., Kim, J.-W., Bris, A.S. & Ghosh, A. Visible light induced rapid nitrophenols mineralization using nitrogen doped TiO2 supported on carbonaceous material derived from nanocellulose and dopamine. ACS Omega 3, 8111-8121 (2018).
• Type: Journal Articles Status: Published Year Published: 2018 Citation: Seo, Y.-R., Kim, J.-W., Hoon, S., Kim, J., Chung, J.H. & Lim, K.-T. Cellulose-based nanocrystals: sources and applications via agricultural byproducts. J. Biosystems Eng. 43, 59-71 (2018).
• Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: G. Kandhola, A. Djioleu, K. Rajan, B.A. Babst, W.L. Headlee, D.J. Carrier, and J.-W. Kim. 2018. Effect of Source and Purity of Cellulose Pulp on the Yield and Properties of Cellulose Nanocrystals Extracted from Forest Biomass. 256th ACS National Meeting, August 19-23, Boston, MA.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Kandhola, G., Djioleu, A., Carrier, D.J. & Kim, J.-W. Pretreatments for enhanced enzymatic hydrolysis of pinewood: a review. Bioenergy Res. 10, 1138-1154 (2017)
• Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: G. Kandhola, A. Djioleu, K. Rajan, B.A. Babst, W.L. Headlee, D.J. Carrier, and J.-W. Kim. 2018. Source-Yield-Property Interrelations for Cellulose Nanomaterials Extracted from Forest Biomass. 2018 ASABE Annual International Meeting, July 29- August 1, Detroit, MI.
• Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: J. Batta-Mpouma, A. Sinha, A. Djioleu, J.-M. Lim, J. Sakon, H. Han, and J.-W. Kim. 2017. Engineering Liquid-Phase Stability of Cellulose Nanocrystal Films for Biological Applications. IEEE International Conference on Nano/Molecular Medicine and Engineering (IEEE-NANOMED), December 1-4, Shenzhen, China.
• Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: G. Kandhola, A. Djioleu, K. Rajan, D.J. Carrier, and J.-W. Kim. 2017. Optimized Production of Cellulose Nanocrystals from Loblolly Pine Biomass. 25th NSF EPSCoR National Conference, November 5-8, Missolua, MT.

Progress 10/01/16 to 09/30/17

Outputs
Target Audience:Researchers, agricultural producers, forest products industries, government agencies. People who are involved in promoting green energy and operations. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The project has involved undergraduate and graduate students who learning about technology related to the bio-based economy and sustainable practices. How have the results been disseminated to communities of interest?Publications. Participation in scientific conferences. What do you plan to do during the next reporting period to accomplish the goals?We are continuing the work into cellulosic nanocrystals. Searching for efficient ways to convert, purify, quantify and improve yields,efficeincies and maximization of useful/profitable properties.

Impacts
What was accomplished under these goals? The project has continued in the evaluation of pre-treatment process to promote economically feasible conversion of lignocellulosic residues into biofuels through yeast fermentation. This includes thermal treatments as well as exploration of the use of fungii to open up the cellulose and hemicellulose. We are also investigating utilization of these same residues in processes to yield nanocellulose and other materials that will have strctural/mechanical or other useful properties. Unless woody residues are utilized, incorporated into useful materials or converted into usable energy, then the carbohydrates will result in GHG emissions. Althought the emissions would be biogenic, there is a missed opportunity to offset fossil fuel consumption or to provide some carbon sequestration in durable material.

Publications

• Type: Theses/Dissertations Status: Accepted Year Published: 2017 Citation: Turay, Amandeep Singh. 2017. Mushroom Inoculation on Switchgrass Feedstock during Storage: Effects of Subsequent Pre-processing for Intended Biofuels Production. M.S. Thesis. Department of Biological and Agricultural Engineering, University of Arkansas.
• Type: Journal Articles Status: Published Year Published: 2017 Citation: Kandhola G., Rajan K., Labbe N., Chmely S., Heringer N., Kim JW, Hood H. and Carrier D.J. (2017). Beneficial effects of Trametes versicolor pretreatment on saccharification and lignin enrichment of organosolv-pretreated pinewood. RSC Advances 7: 45652-45661.

Progress 10/01/15 to 09/30/16

Outputs
Target Audience:Researchers, agricultural producers, government agencies and industry who are involved in promoting green energy and operations. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The project involves graduate students and undergraduate students. This provides good training for future workers in sustainability/biobased technology. How have the results been disseminated to communities of interest?Publications listed elsewhere in this report. Participation in scientific conferences. What do you plan to do during the next reporting period to accomplish the goals?We are looking into processes to convert woody biomass, mainly from forest floor, to useful products. The targetted pathway is through thermoconversion and the creation of biochar. We are doing preliminary studies and seeking major funding for this work.

Impacts
What was accomplished under these goals? Woodchips from Pinus taeda were subjected to biological pretreatment with white-rot fungus, Trametes versicolor, for 15, 30 and 45 days under solid state fermentation conditions in the presence of potato dextrose broth. Bio-pulping was coupled with the organosolv process, conducted at 170°C for 60 min, using 65% ethanol (v/v) and 1.1% sulfuric acid (v/v) at liquid-to-wood ratio of 10 (v/w). It was found that, a 15 day fungal pretreatment of loblolly pine with Trametes versicolor was enough to obtain 25% delignification and an improvement in the enzymatic hydrolysis yield by 23%, when sachharified for 72 h, at an enzyme loading of 15 FPU/g glucan. It was also found that fungal pretreated pine chips provided lower pulp yields, ranging between 13-19%, but higher Ethanol Organosolv Lignin (EOL) yields (55-56%) in the liquid hydrolyzate during the subsequent organosolv process, compared to 23% pulp yield and 40% EOL yield obtained from non-pretreated wood. However, 100% cellulose-to-glucose conversion was achieved within 24 h for both fungal-organosolv and organosolv-only pretreated woodchips when subjected to enzymatic hydrolysis with 60 FPU/g of cellulase. It was concluded that supplementing the organosolv process with fungal pretreatment did not display any advantage for improving enzymatic digestibility, but could be a valuable addition for increasing the EOL yields from softwoods. Work tooptimizethe synthesis of cellulose nanocrystals (CNCs) and their surface modifications. A protocol to extract CNCs from woody biomass was developed using pinewood as a model. Currently, we arein the process of not only further optimizing the protocol and generalizing it toother woody biomass, such as poplar, but also functionalizing the CNC surface with biochemical molecules, including peptides.

Publications

• Type: Journal Articles Status: Published Year Published: 2016 Citation: Sharma S, Adams J, Sakul R, Martin E, Ricke S, Gibson K, and Carrier DJ. (2016). Loblolly pine Pinus taeda L. of essential oil yields affected by environmental and physiological changes. Journal of Sustainable Forestry 35 http://dx.doi.org/10.1080/10549811.2016.1192046
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Djioleu A and Carrier DJ. (2016). Effects of dilute acid pretreatment parameters on sugar production during biochemical conversion of switchgrass using a full factorial design. ACS Sustainable Chemistry and Engineering 4: 4124-4130.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Frederick N, Li M, Carrier DJ, Buser and Wilkins M. (2016). Switchgrass storage effects on the recovery of carbohydrates after liquid hot water pretreatment and enzymatic hydrolysis. AIMS Bioengineering 3: 389-399.
• Type: Journal Articles Status: Published Year Published: 2016 Citation: Sharara, M. A., S. S. Sadaka, T. A. Costello, K. W. VanDevender, D. J. Carrier, M. Popp, G. Thoma and A. Djioleu. 2016. "Combustion kinetics of swine manure and algal solids." J. Thermal Analysis Calorimetry 123(1):687-696.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: Sinha, A., Martin, E.M., Lim, K.-T., Carrier, D.J., Han, H., Zharov, V.P. & Kim, J.-W. 2015. Cellulose nanocrystals as advanced green materials for biological and biomedical engineering. J. Biosystems Eng. 40, 373-393
• Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: G. Kandhola, K. Rajan, D.J. Carrier, and J.-W. Kim. 2016. Fungal-Organosolvent Delignification of Pinus taeda Softwood for Enhanced Enzymatic Hydrolysis and Lignin Extraction. 2016 ASABE Annual International Meeting, July 17-20, Orlando, FL.

Progress 10/01/14 to 09/30/15

Outputs
Target Audience:The target audiences for this project are researchers, agricultural producers, governmental agencies and industry that is interested in promoting green energy and operations. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project is providing the cadre to train on average five graduate students per cycle, working on sustainablility/biobased technology economy related topics. Some projects are focused to the poultry industry, as this is a major Arkansas job creator. Preliminary data is generated for subsequent proposal development How have the results been disseminated to communities of interest?Carrier, Costello and Sadaka results were disseminated at the 2015 American Society of Agriculture and BiologicalEngineering (ASABE) annual meeting as posters and oral presentations. What do you plan to do during the next reporting period to accomplish the goals?We will continue to work on lowering phosphate concentrations of animal agriculture waste effluents, on delineating inhibitors of biomass saccharification systems, and on cellulose extraction and modification for filters and permeable surfaces production.

Impacts
What was accomplished under these goals? Objective 2. Switchgrass hemicellulose can be converted into sugars, such as xylose, for biobased product manufacturing. However, during pretreatment, the hemicellulose can also be converted into xylose oligomers, furfural and formic acid, which are detrimental to subsequent enzymatic hydrolysis and fermentation. Pretreatment conditions that maximize xylose production from hemicellulose, while also minimizing xylose oligomers, furfural and formic acid generation, would improve the economics of biobased product manufacturing by increasing yields and reducing enzyme and microorganism costs. The current study utilized switchgrass purified-xylose oligomers as model compounds to follow xylose oligomers, and furfural generation during pretreatment, using 0 to 1% wt acid sulfuric acid at temperatures of 160 and 180 °C. The resulting kinetic data were used in simple first order rate expressions. Based on the empirically derived Arrhenius models but not verified by experimental data, maximum xylose yields can be obtained at low temperatures and high acid concentrations. Pretreatment conditions with high temperatures yielded high reaction rates and shortened reaction times, but at the expense of increased concentrations of degradation compounds. Objective 3: Kim is working on chemically grafting peptide moieties onto the surface of cellulose nanocrystals using coupling agents, such as 3-aminopropyl-triethoxysilane (APTES). Kim is capable of controlling the self-assembly of the system. Objective 4: Carrier is teaching the on-line class Overview of conversion which is a class that is part of the Bioenergy and Sustainable Technology (BST) Ag*Idea on-line graduate certificate.

Publications

• Type: Journal Articles Status: Published Year Published: 2014 Citation: Rajan K and Carrier DJ. (2014). Characterization of rice straw prehydrolyzates and their effect on the hydrolysis of model substrates, using a commercial endo-cellulase, ?-glucosidase and cellulase cocktail. Sustainable Chemistry and Engineering 2:21242130.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Sadaka, S., M. Sharara, A. Ashworth, P. Keysser, F. Allen and A Wright. 2014. Characterization of Biochar from Switchgrass Carbonization. Energies. 7(2): 548-567.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Sadaka, S. 2013. Gasification of Raw and Torrefied Cotton Gin Wastes in an Auger System. Applied Engineering in Agriculture. 29(3): 405-414.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Sadaka, S., M. Sharara and G. Ubhi. 2014. Performance Assessment of an Allothermal Auger Gasification System for On-Farm Grain Drying. Journal for Sustainable Bioenergy Systems. 4:19-32. doi:10.4236/jsbs.2014.41003
• Type: Journal Articles Status: Awaiting Publication Year Published: 2014 Citation: Bunnell K, Lau C, Lay JO, Gidden J and Carrier DJ. (2014). Production and fractionation of xylose oligomers from switchgrass hemicelluloses using centrifugal partition chromatography. Journal of Chromatography and Related Technologies (In Press)
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Adams J, Martin E, Almeida G, Ricke S, Gibson K, Frederick N and Carrier DJ. (2014). Characterization and variation of essential oil from Pinus taeda L. and antimicrobial effects against antibiotic resistant and susceptible Staphyolococcus aureus.  Forest Products Research 64:161-165.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Frederick N, Zhang N, Ge X, Xu J, Pelkki M, Martin E and Carrier DJ. (2014). Poplar (Populus deltoides L.): The effect of washing pretreated biomass on enzymatic hydrolysis and fermentation to ethanol. Sustainable Chemistry and Engineering 2: 18351842
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Lau C, Clausen E, Thomas G and Carrier DJ (2014). Kinetic modeling of xylose oligomer degradation during pretreatment in dilute acid or in water. Industrial Research Engineering Chemistry 53:2219-2228.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Djioleu A, Sverzut C, Martin E, Childres E, Johnson C, West C and Carrier DJ. (2014). Effect of harvest and storage of switchgrass on the recovery of carbohydrates during dilute acid pretreatment and enzymatic hydrolysis. Forage and Grazinglands 12:1. doi:10.2134/FG-2013-0016-RS
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Rajan K and Carrier DJ. (2014). Effect of dilute acid pretreatment conditions and washing on the production of inhibitors and on recovery of sugars during wheat straw enzymatic hydrolysis. Biomass and Bioenergy 62: 222-227.
• Type: Journal Articles Status: Published Year Published: 2014 Citation: Djioleu A, Martin E, Pelkki M and Carrier DJ. (2014). Mixtures of sweetgum wood with sweetgum bark, oak wood and oak bark: Effects on xylose and glucose yields from dilute acid pretreatment and enzymatic hydrolysis.  Transactions of ASABE 57: 1175-1185.

Progress 10/01/13 to 09/30/14

Outputs
Target Audience: The target audiences for this project are researchers, agricultural producers, governmental agencies and industry that is interested in promoting green energy and operations. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This project is providing the cadre to train on average five graduate students per cycle, working on sustainablility/biobased technology economy related topics. Some projects are focused to the poultry industry, as this is a major Arkansas job creator. Preliminary data is generated for subsequent proposal development. How have the results been disseminated to communities of interest? Carrier, Costello and Sadaka results were disseminated at the 2014 American Society of Agriculture and Biological Engineering (ASABE) annual meeting as posters and oral presentations. What do you plan to do during the next reporting period to accomplish the goals? We will continue to work on lowering phosphate concentrations of animal agriculture waste effluents, on delineating inhibitors of biomass saccharification systems, on ...

Impacts
What was accomplished under these goals? Objective 2. Costello is working at converting confined animal agriculture waste into energy. Specifically, he is treating waste effluents with brown diatom species, cultured to a concentration of 17.68 g/ (m2 per day), which lower phosphorous concentrations. The produced algae is subsequently mixed with solid wastes and placed in an anaerobic digester. Carrier is working at understanding specific degradation by-products, which are formed during dilute acid pretreatment, that inhibit enzymatic hydrolysis critical to saccharification. Raw switchgrass is not a readily acceptable feedstock in existing power plants that were built to accommodate coal and peat. Characteristics of switchgrass biochar produced via carbonization such that it can be used as a solid fuel were explored. Biochar heating value and fixed carbon content increased from 17.6 to 21.9 MJ/kg and from 22.5 to 44.9%, under temperature levels of 300 oC and 400 oC, respectively. A Biomass Discoloration Index (BDI) was created to quantify changes in biochar colors as affected by temperature and residence time. A 10 kW thermal externally heated auger gasification reactor was constructed and tested in the Rice Research and Extension Center, University of Arkansas, Stuttgart, Arkansas. The reactor was used to achieve thermal decomposition of cotton gin wastes (CGW) into producer gas and biochar. Raw and torrefied CGW were gasified to assess the effects of the torrefaction process on the producer gas composition and yield. Increasing the reactor temperature resulted in an increase in the producer gas production rate and a decrease in char production rate. Gasification of torrefied CGW produced biochar with higher heating value (7.8%), as compared to those from gasification of raw CGW. The maximum higher heating value of gas reached 5.4 MJ/m3 from torrefied CGW. An allothermal, externally heated, auger gasifier capable of converting agricultural wastes to combustible gas for on-farm grain drying was operated. The system was used to convert soybean residues under different reactor temperature. The higher heating value of the producer gas reached 6.3 MJ/m3 at reactor temperature of 850 oC. Maximum carbon sequestration achieved, in the form of biochar-carbon, was 32% of the raw feedstock carbon. Gasification of collectable soybean residues from 1 acre would be sufficient to dry 1,132 kg of soybean seeds (the average yield from one acre) from moisture content of 22% to 13% (wet, weight basis). Objective 3: Kim is working on chemically grafting peptide moieties onto the surface of cellulose nanocrystals using coupling agents, such as 3-aminopropyl-triethoxysilane (APTES). Kim is capable of controlling the self-assembly of the system. Objective 4: Carrier is teaching the on-line class Overview of conversion which is a class that is part of the Bioenergy and Sustainable Technology Ag*Idea on-line graduate certificate.

Publications

• Type: Journal Articles Status: Published Year Published: 2014 Citation: 1. Rajan K and Carrier DJ. (2014). Characterization of rice straw prehydrolyzates and their effect on the hydrolysis of model substrates, using a commercial endo-cellulase, ?-glucosidase and cellulase cocktail. Sustainable Chemistry and Engineering 2:21242130. 2. Bunnell K, Lau C, Lay JO, Gidden J and Carrier DJ. (2014). Production and fractionation of xylose oligomers from switchgrass hemicelluloses using centrifugal partition chromatography. Journal of Chromatography and Related Technologies (In Press) 3. Adams J, Martin E, Almeida G, Ricke S, Gibson K, Frederick N and Carrier DJ. (2014). Characterization and variation of essential oil from Pinus taeda L. and antimicrobial effects against antibiotic resistant and susceptible Staphyolococcus aureus.  Forest Products Research 64:161-165. 4. Frederick N, Zhang N, Ge X, Xu J, Pelkki M, Martin E and Carrier DJ. (2014). Poplar (Populus deltoides L.): The effect of washing pretreated biomass on enzymatic hydrolysis and fermentation to ethanol. Sustainable Chemistry and Engineering 2: 18351842. 5. Lau C, Clausen E, Thomas G and Carrier DJ (2014). Kinetic modeling of xylose oligomer degradation during pretreatment in dilute acid or in water. Industrial Research Engineering Chemistry 53:2219-2228. 6. Djioleu A, Sverzut C, Martin E, Childres E, Johnson C, West C and Carrier DJ. (2014). Effect of harvest and storage of switchgrass on the recovery of carbohydrates during dilute acid pretreatment and enzymatic hydrolysis. Forage and Grazinglands 12:1. doi:10.2134/FG-2013-0016-RS 7. Rajan K and Carrier DJ. (2014). Effect of dilute acid pretreatment conditions and washing on the production of inhibitors and on recovery of sugars during wheat straw enzymatic hydrolysis. Biomass and Bioenergy 62: 222-227. 8. Djioleu A, Martin E, Pelkki M and Carrier DJ. (2014). Mixtures of sweetgum wood with sweetgum bark, oak wood and oak bark: Effects on xylose and glucose yields from dilute acid pretreatment and enzymatic hydrolysis.  Transactions of ASABE 57: 1175-1185. Sadaka, S., M. Sharara, A. Ashworth, P. Keysser, F. Allen and A Wright. 2014. Characterization of Biochar from Switchgrass Carbonization. Energies. 7(2): 548-567. Sadaka, S. 2013. Gasification of Raw and Torrefied Cotton Gin Wastes in an Auger System. Applied Engineering in Agriculture. 29(3): 405-414. Sadaka, S., M. Sharara and G. Ubhi. 2014. Performance Assessment of an Allothermal Auger Gasification System for On-Farm Grain Drying. Journal for Sustainable Bioenergy Systems. 4:19-32. doi:10.4236/jsbs.2014.41003.