Source: RICE UNIVERSITY submitted to NRP
EFFECTS OF NITROGEN MANAGEMENT STRATEGIES ON BIOFUEL CROP BIOCHEMICAL AND SOIL CARBON STOCKS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
0224163
Grant No.
2011-67009-20074
Cumulative Award Amt.
$443,541.00
Proposal No.
2010-03848
Multistate No.
(N/A)
Project Start Date
Jan 1, 2011
Project End Date
Dec 31, 2013
Grant Year
2012
Program Code
[A6121]- Sustainable Bioenergy: Sustainable Bioenergy Research
Recipient Organization
RICE UNIVERSITY
PO BOX 1892
HOUSTON,TX 77251
Performing Department
(N/A)
Non Technical Summary
Increased fertilizer use from expanded biofuel production is a threat to watersheds, with studies linking increased corn-grain ethanol production to the growing dead zone in the Gulf of Mexico. Leaching in areas of heavy fertilizer application has also led to drinking water contamination in parts of the rural U.S. Finally, heavy application of fertilizer can cause soil microbes to release of the potent greenhouse gas nitrous oxide (N2O), leading some researchers to conclude that conversion of land to biofuel production could accelerate global warming. A central challenge of sustainable biofuel production is controlling the release of fertilizer to watersheds and reducing the greenhouse footprint of biofuel production while simultaneously maximizing crop yields. Because food crop yields (e.g. corn grain) are highest when ecosystems are heavily fertilized, it has been assumed that biofuel crop yields (e.g. switchgrass) will also perform best when N-saturated, setting up an apparent conflict between energy needs and environmental sustainability. However, this conflict may not exist for biofuel crops when considered from the perspective of maximizing biochemical yields instead of maximizing mass yields. Our preliminary data show that while corn plants make more grain when heavily fertilized, the amount of cellulose they make increases only slightly. The slight increase in cellulose resulting from heavy fertilizer application is not enough to justify the cash spent applying high levels of fertilizer. In this grant we are testing the need for fertilizer in future biofuel crops by measuring the yield of biochemicals needed for biofuel production. We are using a novel, highly accurate tool to assess crop lignin, carbohydrate, lipid, and protein yields: solid state 13C nuclear magnetic resonance (NMR) coupled to a molecular mixing model. This technique is more accurate than traditional analytical approaches, but the tool (an NMR spectrometer) is not widely available within the agricultural community. Therefore we will calibrate a second cheap, widely available tool (near infrared spectroscopy) to our NMR results to produce a measurement approach that is easy to operate in-field.
Animal Health Component
50%
Research Effort Categories
Basic
50%
Applied
50%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1021699200033%
1027299200034%
1010110200033%
Knowledge Area
102 - Soil, Plant, Water, Nutrient Relationships; 101 - Appraisal of Soil Resources;

Subject Of Investigation
1699 - Pasture and forage crops, general/other; 0110 - Soil; 7299 - Research equipment and methods, general/other;

Field Of Science
2000 - Chemistry;
Goals / Objectives
Increased fertilizer use from expanded biofuel production has been identified as a threat to watersheds, with studies linking increased corn-grain ethanol production to accelerated Gulf of Mexico anoxia [Burkart and James, 1999; Donner and Kucharik, 2008]. Fertilizer application also drives nonlinear increases in fluxes of nitrous oxide (N2O) [McSwiney and Robertson, 2005], leading some researchers to conclude that increased biofuel production will drive increased greenhouse gas emissions [Crutzen, et al., 2008]. A central challenge of sustainable biofuel production is controlling the release of reactive nitrogen to watersheds and reducing the greenhouse footprint of biofuel production while simultaneously maximizing crop yields. Because food crop yields are maximized when ecosystems are held in an N-saturated state, it has been implicitly assumed that biofuel crop yields will also perform best when N-saturated, setting up an apparent conflict between energy needs and environmental sustainability. However, this conflict may not exist in the same form for biofuel crops when considered from the perspective of maximizing biochemical yields instead of maximizing mass yields. Although fertilizer application increases the mass and grain yield of food crops, it does not always increase the Mg/ha yield of individual biochemicals like cellulose or lignin. Biochemicals relevant for biofuel production respond differently than grain to N fertilization, suggesting that it may not be necessary to fertilize biofuel crops to the extent that food crops are fertilized. In fact, the potential for different biochemical responses to N fertilization for each crop suggests that N management may be one mechanism to tune crop biochemistry to meet specific feedstock needs. Soil carbon profiles also respond to management practices, with the biochemistry of root compounds playing a major role in controlling the size and turnover time of intermediate soil carbon pools[Silver and Miya, 2001; Abiven, et al., 2005; Garten, 2009; Mendez-Millan, et al., 2010]. Root biochemical composition may be tuneable through fertilization, and managing the biochemistry of roots is a promising tool for improving soil carbon sequestration, especially in the case of tall grass biofuel feedstocks [Liebig, et al., 2005]. None of these optimizations are possible without a fast, accurate tool to screen crop biomass for bulk biochemical composition. Traditional wet chemical assays are time and labor-intensive, and since the pools they extract are operationally defined, questions exist about their accuracy [Jung, et al., 1997; Harmon, et al., 1999; Hatfield and Fukushima, 2005]. Here we propose applying highly accurate, and faster nuclear magnetic resonance (NMR) techniques to determine the biochemistry of crop biomass with the goals of 1) measuring the effects of N application on switchgrass above- and belowground biochemical profiles, 2) identifying N application levels that lead to optimized switchgrass biochemical yields for bio-oil production from pyrolysis, and 3) identifying management practices that optimize root carbon chemistry for efficient soil carbon sequestration.
Project Methods
We are applying highly accurate, and faster nuclear magnetic resonance (NMR) techniques to determine the biochemistry of crop biomass and roots with the goals of 1) measuring the effects of N application on switchgrass above- and belowground biochemical profiles, 2) identifying N application levels that lead to optimized switchgrass biochemical yields for bio-oil production from pyrolysis, and 3) identifying management practices that optimize root carbon chemistry for efficient soil carbon sequestration. The advantages of NMR are that it is fast (~10 samples/day) and accurate, but the disadvantage is that it is not widely available. For this reason, we also propose calibrating NMR-based plant biochemical measurements to a near-infrared (NIR) analyzer, a tool that can make even more rapid measurements (100/day), is portable, and does not need analytical infrastructure beyond electricity. We are measuring the effects of N fertilization on switchgrass above and belowground biochemistry at two switchgrass N rate trials, one located at the Kellogg Biological Station (KBS) in Hickory Corners, MI, and the other located at the University of Tennessee Research and Education Center in Milan, TN (UT-REC). By using two sites, our experiments will include two of the major switchgrass cultivars (Cave-in-Rock at KBS and Alamo at UT-REC).

Progress 01/01/11 to 12/31/13

Outputs
Target Audience: Our primary target audience during this reporting period was other academic researchers and members of the petroleum and biofuels community. In addition, we have had internal university audiences whose education has been important. Both the PI and co-I are faculty at private universities which historically have not perceived agricultural science as part of their mission, but do see energy research as central to their research indentiies. However, it has become clear many institutions, including ours, that no research university will be able to develop a meaningful 21st century energy research portfolio without including food and water as an integrated component. Private universities do have a unique niche in this environment, with the ability to act as bridges between agricultural researchers and the energy industry, especially in Texas. This grant has allowed us the opportunity to educate our own communities on exactly how Texas private universities can contribute to the knotty questions of food, water, and energy in the 21st century. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? We proposed to train 1 postdoctoral researcher and 1 graduate student as part of this grant. We have significantly exceeded these numbers. This grant supported Dr. Morgan Gallagher (Rice and KBS) through her postdoc, and Zachary Valdez (Baylor) through a significant portion of his PhD. In addition, two more graduate students at Baylor trained as part of this grant: Dong Mei He and Justin Von Bargen. At Baylor 3 postdoctoral researchers participated collaboratively: Dr. K. Jugeshwar Singh, Dr. Nelson van der Velde, and Dr. Behrooz Zekavat (all in Baylor Department of Chemistry & Biochemistry). Finally, a total of 7 undergraduate researchers participated in sample preparation (3 at Rice and 4 at Baylor). How have the results been disseminated to communities of interest? K. Jugeshwar Singh, W.C. Hockaday, S.J. Kim, Nuclear Magnetic Resonance Studies on Solids-to-liquids Biomass Pyrolysis Oils, 245th American Chemical Society National Meeting, New Orleans, LA, April 7-11, 2013. Talk K. Jugeshwar Singh, W.C. Hockaday, Molecular transformations of biomass to pyrolysis liquids, Rice University Biochar Symposium, Houston, TX, March 20, 2013. Nelson A. van der Velde, W.C. Hockaday, Characterization of slow-pyrolysis bio-oils obtained from different biomass feed-stocks, 247th ACS National Meeting, Dallas, Texas, March 16-20, 2014. talk Valdez, Z.P., Hockaday, W.C., Gallagher, M.E., Masiello, C.A., Gao, X., Effects of nitrogen fertilizer on soil organic matter pools under switchgrass agriculture, Soil Science Society of America National Meeting, Cincinnati, OH, Oct. 21, 2012. poster Zachary P. Valdez; William C. Hockaday, Morgan E. Gallagher, Caroline A. Masiello, Effects of Nitrogen Fertilizer and Harvesting Frequency on Soil Organic Matter Pools Under Switchgrass Agriculture Soil Survey and Land Resource Workshop, College Station, TX, Feb 7, 2013. talk Zachary P. Valdez; William C. Hockaday; Morgan E. Gallagher; Caroline A. Masiello; Xiaodong Gao, Effects of Nitrogen Fertilizer and Harvesting Frequency on Soil Organic Matter Pools Under Switchgrass Agriculture, American Geophysical Union Fall Meeting, San Francisco, CA, Dec. 11, 2013. Poster B31C-0416 Zachary P. Valdez; William C Hockaday; Morgan E Gallagher; Caroline A. Masiello; Xiaodong Gao, Effects of Nitrogen Fertilizer and Harvesting Frequency on Soil Organic Matter Pools Under Switchgrass Agriculture, 247th American Chemical Society National Meeting, Dallas, TX, March 18, 2014. Talk #84 Rebecca M. Davis, Valdez, Z. P.; Hockaday, W.C., Impact of Farming Practices on Root Biochemistry Using 13C NMR, American Chemical Society Southwest Regional Meeting, Waco, TX, Nov. 9-11, 2013. Poster W. Hockaday, M. Gallagher, C. Masiello, W. Polley, L. Pyle, J. Baldock, Biochemical inventory as a means to assay ecosystem carbon cycling, Ecological Society of America, Austin, TX, August, 9, 2011. talk M. Gallagher, W. Hockaday, C. Masiello, Using 13C nuclear magnetic resonance spectroscopy to estimate biochemical stocks and biofuel feedstock quality, USDA Sustainable bioenergy project directors meeting, Washington DC, Oct 24-26, 2011 W.C. Hockaday, S.J. Kim, K. Jugeshwar Singh, Basic Nuclear Magnetic Resonance Spectroscopy of Solid Samples, Baylor University Advanced Instrumentation Workshop, Waco, TX, Sept. 21-22, 2012. Talk M. Gallagher, W. Hockaday, C. Masiello, Using 13C nuclear magnetic resonance spectroscopy to estimate biochemical stocks and biofuel feedstock quality, Soil Science Society of America, USDA bioenergy project directors meeting, Cincinnati, OH., Oct. 23-25, 2012. M.E. Gallagher, W.C. Hockaday, C.A. Masiello, Z.P. Valdez, and X. Gao, The Effects of N Fertilization and Harvest Frequency on Switchgrass Feedstock Quality for Biofuel Production, Soil Science Society of America National Meeting, Cincinnati, OH, Oct. 21, 2012. poster Gao, X., Masiello, C.A., Gallagher, M.A., Hockaday, W.C., Valdez, Z.P., Effect of Nitrogen Fertilization on Switchgrass Root Biochemistry and Soil Carbon Sequestration, 245th American Chemical Society National Meeting, New Orleans, LA, April 7-11, 2013. Talk He, D.M, Vogel, J.G., Jokela, E.J., Schuur, E.A.G., Ruan, H., Hockaday, W.C., Effects of Genetic Selection and Fertilization on the Constituents of Soil Organic Matter in Managed Loblolly Pine Forests, as Determined by Nuclear Magnetic Resonance, Soil Science Society of America National Meeting, Tampa, FL, Oct. 31, 2013. Poster Jason G. Vogel; Eric J. Jokela; Dongmei He; William C. Hockaday; Edward A. Schuur, The effect of fertilization levels and genetic deployment on soil organic matter chemistry and turnover in managed loblolly pine forests, American Geophysical Union Fall Meeting, San Francisco, CA, Dec. 10, 2013, poster B23B-0553 W.C. Hockaday, N.A. van der Velde, K.J. Singh, The influence of pyrolysis conditions on the organic chemistry of bio-oils and bio-chars: An overview, 247th ACS National Meeting that will be held in Dallas, Texas, March 16-20, 2014. Talk 18733 What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? This grant covered specifically the effects of N fertilization on switchgrass, and we have completely analyzed full sample suites from all field sites proposed (Kellogg Biological Station and UT Milan research station). In addition, we have two additional projects of opportunity in progress as part of this grant, both using the analytical tool described here (NMR) to understand the effects of cropping and land use practices on biofuel biochemistry. The first project measured the biochemical yields (lipids, carbohydrates, proteins, and lignin) of 8 cropping systems at KBS. All data have been collected for this project and it is in the process of being written up. The second project is an ongoing collaboration with Jason Wight at Texas A&M University looking at the effects of N fertilization on sorghum cultivars. Data are still being collected as part of this project.

Publications

  • Type: Journal Articles Status: Published Year Published: 2012 Citation: Koarashi, J., W. Hockaday, Trumbore, S., Masiello, C. Dynamics of decadally-cycling carbon in subsurface soils, Journal of Geophysical Research-Biogeosciences, 117, G03033, 2012.
  • Type: Journal Articles Status: Awaiting Publication Year Published: 2014 Citation: Abayomi D. Olaitan,Behrooz Zekavat, Birendra Dhungana, William C. Hockaday, C. Kevin Chambliss, Touradj Solouki, Analysis of Volatile Organic Compound Mixtures Using Radiofrequency Ionization/Mass Spectrometry, Chemical Analysis, 2014, in press: DOI: 10.1039/c3ay41729h.
  • Type: Journal Articles Status: Other Year Published: 2014 Citation: Xiaodong Gao, Caroline A. Masiello, Morgan E. Gallagher, William Hockaday, Zack Valdez, Donald D. Tyler. Effect of nitrogen fertilization and soil type on switchgrass root biochemistry and soil carbon sequestration. In prep 2014. Biomass and Bioenergy.
  • Type: Book Chapters Status: Published Year Published: 2014 Citation: Michael Nguyen, W. Hockaday, B.L.T. Lau, Probing Temperature-Dependent Organo-Mineral Interactions with molecular spectroscopy and Quartz Crystal Microgravimetry, pp. 189-195, in Soil Carbon, Progress in Soil Science series XXVI, Hartemink, A.E., McSweeney, K. (Eds.), Springer, 2014.


Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: During the first 9 months of funding, we have accomplished the following: hired a full-time postdoc (Dr. M. Gallagher) to work on this project; purchased, installed, and arranged for Gallagher to be trained on a near infrared spectrometer (NIR); conducted 3 field sampling trips, collecting above-ground biomass and soils from our field sites in Tennessee and Michigan; hired 3 undergrad researchers to assist Gallagher in sample processing; supervised 1 undergrad research project based on samples collected in June 2011. Additionally, Gallagher presented a methodological paper at the 2011 national ASA-CSSA-SSSA meeting: M.E. Gallagher, W.C. Hockaday, C.A. Masiello, J.A. Baldock, S. Snapp, C.P. McSwiney. Using 13C Nuclear Magnetic Resonance Spectroscopy to Estimate Biochemical Stocks and Biofuel Feedstock Quality. ASA-CSSA-SSSA Annual International Meeting: San Antonio, TX, October 2011. Finally, as a result of the fall 2011 principal investigator's meeting, we have begun a collaboration with Jason Wight from Texas A&M University, extending the scope of our project to include sorghum as well as switchgrass biochemical response to fertilization. PARTICIPANTS: Caroline Masiello, Rice U. Role: Project Director Overall project and employee management, coordination of Rice-Baylor research, field work planning. Method development for soil density separation, purchasing equipment, and hiring and arranging training of new employees. Hiring and managing undergraduates. Attended project director's meeting in Washington DC, October 2011. Morgan Gallagher, Rice U. Role: Postdoctoral Researcher On-site management of all field trips, sample collection, packaging, shipping. Purchase, install, learn to operate near infrared spectrometer. Manage NMR analysis of all samples. Day-to-day supervision of undergraduates. Attended project director's meeting in Washington DC, October 2011. Kate Ziegelgruber: assistance managing undergraduates, assistance with soil processing. Agar Woda, Nathaniel Lee, Tierra Moore, Rice U. Undergraduate researchers responsible for soil sieving and basic density extractions. William Hockaday, Baylor U. Role: Project Co-director Activities: Soil sample collection at the University of Tennessee Agriculture Research Station (soil core extraction, extrusion, and packaging) prior to switchgrass emergence in April 2011. Method development for soil fractionation procedures (e.g. density fractionation). Lab set-up and purchasing equipment, materials, and supplies for soil processing and analysis. Logistical arrangements for research assistants (airfare) and sample shipment (freight service for soil cores). Training graduate students in elemental analysis and 13C nuclear magnetic resonance (NMR) techniques. Attended project director's meeting in Washington DC, October 2011. Justin Von Bargen, Baylor U. Role: Graduate Research Assistant Activity: Soil sample collection at Kellogg Biological Station (soil core extraction, extrusion, and packaging) after mid-season switchgrass harvest, July 2011. Laboratory set-up and purchasing of equipment, and supplies needed for soil sample processing. Zack Valdez, Baylor U. Role: Graduate Research Assistant Activities: Soil collection at Kellogg Biological Station (soil core extraction, extrusion, and packaging) after post-season switchgrass harvest, November 2011. Soil processing in the lab: soil drying, root isolation, sieving, density fractionation, and grinding. Conducted preliminary sample analyses such as solid-state 13C NMR analysis of switchgrass roots for major biopolymer components (lignin, protein, etc) or roots, and genetic (PCR) analysis of root responses to nitrogen fertilization rate. Supervises one undergraduate researcher, who assists with soil processing. TARGET AUDIENCES: Our target audiences are agricultural extension agents, other researchers in the biofuels industry and academia, and undergraduates who would benefit from more knowledge about the fundamentals of biofuels and agriculture. Since receiving funding 10 months ago, we have given 2 presentations (one at ASA-CSSA-SSSA and another at the required biofuels principal investigators meeting). We have also involved a number of undergraduates at both Rice U and at Baylor. All the undergrad researchers at both universities attend weekly research planning meetings. This exposes them to the process of research at the university level, broadens their understanding of the breadth of science going on within our research team, and builds basic job skills. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
This grant has been funded for 10 months. In this time our primary outcomes and impacts have been: we have presented our preliminary data at a national meeting; we have incorporated 1 postdoc and 3 undergraduate researchers into the study; we have created an undergraduate research course focussed on the material in this study.

Publications

  • No publications reported this period