Browsing by Author "Hockaday, William C."
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Item Carbon Sequestration through Biochar Soil Amendment: Experimental studies and mathematical modeling(2012-09-05) Sun, Hao; Zygourakis, Kyriacos; Masiello, Caroline A.; Chapman, Walter G.; Hockaday, William C.Intentional amendment of soil with charcoal (called biochar) is a promising new approach to sequester atmospheric carbon dioxide and increase soil fertility. However, the environmental properties of biochars can vary with production conditions, making it challenging to engineer biochars that are simultaneously optimized for carbon sequestration, nutrient storage, and water-holding capacity. For this reason, I have undertaken a systematic study to (a) determine the pyrolysis conditions that lead to biochars with desired chemical and physical properties, and (b) find how these properties affect the water-holding capacity and nutrient adsorption in biochar-soil mixtures. First, a library of biochars was produced in a custom-built pyrolysis reactor under precisely controlled conditions. The chemical and physical structures of the produced biochars were characterized with various analytical techniques including 13C NMR, XPS, EA and BET pore surface analysis. My results suggest that the chemical composition and pore structure of biochars are determined not just by the maximum heat treatment temperature, but also by several other factors that include the pyrolysis heating rate, treatment time at the maximum temperature and particle size. I also tested a new approach that combines thermogravimetric reactivity measurements, diffusion-reaction theory and structural models to achieve a better characterization of the complicated multi-scale pore structure of biochars. The structural models treat biochars as porous solids having micro- and macropores of different shapes and exhibiting widely ranging pore-size distributions. Simulations results are then compared to experimental data to identify the presence of ordered or random pore networks and test their size distributions and connectivity. I then developed a multi-solid one-dimensional model that can use experimentally determined biochar properties to predict their field performance in beds packed with soil/biochar mixtures. The model used a system of coupled partial differential equations to describe the dynamic adsorption/elution of ammonium nitrate, a model fertilizer, in columns packed with biochar/soil mixtures and perfused with aqueous solutions of the fertilizer. The PDE system was solved using orthogonal collocation on finite elements. My chromatographic model accounted for all the important processes occurring in this system, including external mass transfer between the fluid phase and the solid particles, as well as intraparticle diffusion and adsorption of the solute on the pore surface area of the sorbents. To our knowledge, this is the first chromatographic model that accounted explicitly for the presence of two solid phases with widely different pore structures and adsorption capacities. A systematic parametric study was carried out to determine the importance of each system parameter. The adsorption equilibrium parameters and the intraparticle effective diffusivity of ammonium had the most significant effect on environmental performance. To complete the theoretical analysis, I also developed a model to describe the saturation and drainage of water from the packed column. The model accounted for all the important processes occurring in this system: (a) water exchange between the interstitial pore region and two different smaller pore regions and (b) water flow inside the larger pore region and the two different smaller pore regions. The transient mass balances led to a system of partial differential equations that was solved using block centered finite difference.Item Forest soil carbon oxidation state and oxidative ratio responses to elevated CO2(Wiley, 2015) Hockaday, William C.; Gallagher, Morgan E.; Masiello, Caroline A.; Baldock, Jeffrey A.; Iversen, Colleen M.; Norby, Richard J.The oxidative ratio (OR) of the biosphere is the stoichiometric ratio (O2/CO2) of gas exchange by photosynthesis and respiration—a key parameter in budgeting calculations of the land and ocean carbon sinks. Carbon cycle-climate feedbacks could alter the OR of the biosphere by affecting the quantity and quality of organic matter in plant biomass and soil carbon pools. This study considers the effect of elevated atmospheric carbon dioxide concentrations ([CO2]) on the OR of a hardwood forest after nine growing seasons of Free-Air CO2 Enrichment. We measured changes in the carbon oxidation state (Cox) of biomass and soil carbon pools as a proxy for the ecosystem OR. The OR of net primary production, 1.039, was not affected by elevated [CO2]. However, the Cox of the soil carbon pool was 40% higher at elevated [CO2], and the estimated OR values for soil respiration increased from 1.006 at ambient [CO2] to 1.054 at elevated [CO2]. A biochemical inventory of the soil organic matter ascribed the increases in Cox and OR to faster turnover of reduced substrates, lignin and lipids, at elevated [CO2]. This implicates the heterotrophic soil community response to elevated [CO2] as a driver of disequilibrium in the ecosystem OR. The oxidation of soil carbon pool constitutes an unexpected terrestrial O2 sink. Carbon budgets constructed under the assumption of OR equilibrium would equate such a terrestrial O2 sink to CO2 uptake by the ocean. The potential for climate-driven disequilibriua in the cycling of O2 and CO2 warrants further investigation.Item Nitrogen, biochar, and mycorrhizae: Alteration of the symbiosis and oxidation of the char surface(Elsevier, 2014) LeCroy, Chase; Masiello, Caroline A.; Rudgers, Jennifer A.; Hockaday, William C.; Silberg, Jonathan J.In some cases amending soil with biochar improves fertility, although the exact mechanisms through which biochar alters soil processes are not well understood. In other cases, however, biochar amendment can have no effect on plant growth, or can have negative effects. When crop benefits occur, simultaneous amendment with biochar and mineral nutrients causes results that are not additive, suggesting that biochar may be capable of improving the efficiency of nutrient uptake by plants, but the mechanisms of this synergy remain unknown. One possible mechanism that has not been fully explored is alterations to the plant-mycorrhizal fungus mutualism, a relationship that occurs in most land plants. In a 4 week greenhouse experiment, we investigated possible effects of the presence of biochar, mycorrhizal fungi, and nitrogen fertilizer on sorghum seedling growth. Results indicated that the combined treatment of biochar, mycorrhizal fungi, and high nitrogen decreased aboveground plant biomass by 42% relative to the mycorrhizae and high nitrogen treatment, while simultaneously promoting mycorrhizal root colonization. This is evidence for an induced parasitism of the mycorrhizal fungus in the presence of nitrogen and biochar within the 4 week timescale of our experiments. Using x-ray photoelectron spectroscopy, we found evidence of increased surface oxidation on biochar particles over the 4 weeks of our trial, consistent with sorption of labile, plant derived dissolved organic matter or char oxidation, either via biotic or abiotic processes. Biochar in soils with mycorrhizae but without sufficient nitrogen showed more surface oxidation than other treatment combinations, and showed a significantly greater fraction of surface carbon present in carbonyl (ﾖCdouble bond; length as m-dashO) functionalities. Our results suggest that soil nitrogen acts as a switch controlling the ability of char to influence the mycorrhizal symbiosis and, in turn, the degree to which the fungi oxidize the char surface.Item Plant species, not climate, controls aboveground biomass O2:CO2 exchange ratios in deciduous and coniferous ecosystems(Wiley, 2017) Gallagher, Morgan E.; Liljestrand, Frasier L.; Hockaday, William C.; Masiello, Caroline A.The oxidative ratio (OR) is the O2:CO2 ratio associated with photosynthesis, respiration, and other ecosystem gas exchange processes and can be reported on the scale of an individual leaf, an ecosystem, up to the entire terrestrial biosphere. The OR of the terrestrial biosphere is used to partition anthropogenic CO2 between oceanic and terrestrial carbon sinks, and the ease of measurement of this property on smaller scales suggests its potential for other uses. However, controls on the natural variation of OR are not understood in either organic matter pools or fluxes, and this lack of basic information limits the use of the tracer. Here we assess the annual variability of the OR of photosynthesis over ~decade for two temperate forests, one coniferous and one deciduous, and show that the photosynthetic OR signature is strongly dominated by plant species. We determined the OR of this flux by measuring the OR of carbon pools that close on annual or shorter timescales (leaves and individual tree rings), via solid‐state 13C NMR spectroscopy and elemental analysis. Leaf litter OR is different between coniferous and deciduous forests, but tree bole OR is constant between species. There was no significant change in leaf litter OR with time, nor any correlations between leaf litter OR and temperature or precipitation. During this time growing season precipitation varied by 95% from the time period average, and growing season temperature by 22%, demonstrating that on the decadal scale photosynthetic OR is invariant over significant shifts in these climate parameters.Item Short‐Term Changes in Physical and Chemical Properties of Soil Charcoal Support Enhanced Landscape Mobility(Wiley, 2017) Pyle, Lacey A.; Magee, Kate L.; Gallagher, Morgan E.; Hockaday, William C.; Masiello, Caroline A.Charcoal is a major component of the stable soil organic carbon reservoir, and the physical and chemical properties of charcoal can sometimes significantly alter bulk soil properties (e.g., by increasing soil water holding capacity). However, our understanding of the residence time of soil charcoal remains uncertain, with old measured soil charcoal ages in apparent conflict with relatively short modeled and measured residence times. These discrepancies may exist because the fate of charcoal on the landscape is a function not just of its resistance to biological decomposition but also its physical mobility. Mobility may be important in controlling charcoal landscape residence time and may artificially inflate estimates of its degradability, but few studies have examined charcoal vulnerability to physical redistribution. Charcoal landscape redistribution is likely higher than other organic carbon fractions owing to charcoal's low bulk density, typically less than 1.0ﾠg/cm3. Here we examine both the physical and chemical properties of soil and charcoal over a period of two years following a 2011 wildfire in Texas. We find little change in properties with time; however, we find evidence of enhanced mobility of charcoal relative to other forms of soil organic matter. These data add to a growing body of evidence that charcoal is preferentially eroded, offering another explanation for variations observed in its environmental residence times.