Doctor of Philosophy / Department of Agronomy / Nathan O. Nelson / Augustine K. Obour / Emerging sustainability issues with summer-fallow period has prompted producers to identify fallow replacement crops in wheat (Triticum aestivum) production systems. Camelina [Camelina sativa (L.) Crantz] has been identified as a potential fallow replacement crop in the semiarid Great Plains. Camelina has uses in animal and human nutrition, biofuel production, and bio-based products. Three field experiments were conducted to develop production recommendations for camelina in wheat production systems in the semiarid Great Plains. In the first study, three camelina cultivars were evaluated in mid-March (March 17, 2014; March 18, 2015), early-April (April 3, 2013; April 1, 2014 and 2015), and mid-April (April 16, 2013; April 15, 2014 and 2015) at Hays, KS. Findings from this study showed delaying camelina planting until early- or mid-April resulted in 34% increase in seed yield. Planting date affected oil concentration, saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), polyunsaturated fatty acids (PUFA), and linolenic acid concentration. The concentrations of SFA, MUFA, PUFA, linoleic acid, and linolenic acid were also different among cultivars. A second study was conducted to evaluate the response of camelina to nitrogen (N), and sulfur (S) fertilizer application. Nitrogen rates (0, 22, 45 and 90 kg ha⁻¹), and S rates (0 and 20 kg ha⁻¹) were applied in a randomized complete block design with a split-plot arrangement. The main plots were S application rates and the subplot factor was N rates. Sulfur application did not affect seed yield, oil, protein, or seed nutrient concentration. The agronomic optimum N rate was 49 kg N ha⁻¹, however, the economic optimum N rate ranged from 25 to 31 kg N ha⁻¹ based on current N fertilizer cost, and camelina seed price. Nitrogen application had no effect on SFA, MUFA, and PUFA. Moderate N application increased seed calcium (Ca) concentration, whereas higher N rate increased zinc (Zn), and manganese (Mn) concentration in the seed. There was a general negative relation between N application with copper (Cu), and molybdenum (Mo) in camelina seed. Our study shows that camelina needed to be applied with a minimum of 25 kg N ha⁻¹ for optimum production. A third study investigated effects of crop rotation on crop yield, soil water, soil CO₂ flux, and soil health in wheat-camelina rotation systems. Rotation systems in this study were wheat-fallow (W-F), wheat-sorghum (Sorghum bicolor) -fallow (W-S-F), wheat-spring camelina (W-SC), and wheat-sorghum-spring camelina (W-S-SC). Crop rotation had no effect on sorghum grain yield. However, winter wheat yield decreased by 15% when fallow was replaced by camelina in the rotation system. Camelina yield in W-SC was 2-fold greater than that in W-S-SC. Soil water content in the more intensified rotations were less than rotations with fallow, irrespective of sampling period. Soil pH, phosphorus (P), and total nitrogen (TN) were not different among rotation systems. Nonetheless, soil profile N, soil organic carbon (SOC), microbial biomass carbon and N (MBC and MBN), and potentially mineralizable nitrogen (PMN) were different among rotation systems. Soil particle aggregation increased with increasing cropping intensity. This suggests improved soil structure with cropping intensification.

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Biotechnology of sulphate reducing bacteria has developed rapidly in recent years with the recognition of their extensive and diverse biocatalytic potential. However, their application in a number of areas has been constrained due to problems including poor cell retention within the continuous bioprocess reactor environment, and contamination of the treated stream with residual organic feed components and cell biomass. These problems have so far excluded the application of biological sulphate reduction in the treatment of ‘clean’ inorganic waste streams where components such as sulphate, acidity and heavy metal contamination require treatment. This study investigated the effective immobilisation of sulphate reducing bacterial cultures and proposed that the disarticulation of the electron donor and carbon source supply using such systems would create the basis for their application in the treatment of ‘clean’ inorganic waste streams. A functional and stable sulphate reducing culture was selected and following evaluation using a number of techniques, was immobilised by encapsulation within a calcium-alginate-xanthum gum membrane to give robust capsules with good sulphate reduction activity. The concept of disarticulation was investigated in a swing-back cycle where the carbon source was excluded and the electron donor supplied in the form of hydrogen gas in a continuous up-flow capsule-packed column reactor. Following a period of operation in this mode (4-12 days), the system was swung back to a carbon feed to supply requirements of cell maintenance (2-3 days). Three types of synthetic ‘clean’ inorganic waste stream treatments were investigated, including sulphate removal, neutralisation of acidity and heavy metal (copper and lead) removal. The results showed: • Sulphate removal at a rate of 50 mg SO₄²⁻L/day/g initial wet mass of capsules during three 4-day cycles of electron donor phase. This was comparable to the performance of free cell systems; • Neutralisation of acidity where influent pH values of 2.4 and 4.0 were elevated to above pH 7.5; • Copper removal of 99 and 85 % was achieved with initial copper concentrations of 2 and 60 mg/L respectively; • Percentage lead removal values of 49 and 78 % were achieved; This first report on the application of the concept of capsular immobilisation and disarticulation in the treatment of ‘clean’ inorganic waste streams will require future studies in order to extend the development of the full potential of the concept.

The chemistry of homogeneous transition metal systems offer parallels to the reactions on the surfaces of industrial hydrodesulphurization catalysts. The reactions of several ruthenium complexes with sulphur-containing reagents are described, with an emphasis on the kinetics and mechanisms thereof. The complex Ru(CO)₂(PPh₃)₃ (2), for example, reacts quickly with thiols and disulphides, producing cct-RuH(SR)(CO)₂(PPh₃)₂ (9) and cct-Ru(SR)₂(CO)₂(PPh₃)₂ (14), respectively, although 2 fails to react with unstrained thioethers. Reactions of the related complex Ru(CO)₂(PPh₃)(dpm) (dpm=Ph₂PCH₂PPh₂) are complicated by the lability of all of the three different ligands. The two dihydrides cct-RuH₂(CO)₂(PPh₃)₂ (3) and RuH₂(dpm)₂, as a cis/trans mixture (7), react with thiols to produce the hydrido-thiolato complexes 9 and RuH(SR)(dpm)₂ (13). respectively. The mechanisms appear to depend on the basicity of the hydride ligands; the more basic dihydride, 7, is probably protonated by the thiol, giving an unobserved molecular hydrogen intermediate, while 3 reacts by slow reductive elimination of H₂. The same rate constant, rate law, and activation parameters are found for the reaction of 3 with thiols, CO or PPh₃. The reaction of 3 with RSSR produces mostly 9, with small amounts of 14. The complete characterization of several members of the series 9 and 14 is described, including the crystal structure of the p-thiocresolate example of each. The reactions of 9 with other thiols, P(C₆H₄pCH₃)₃, CO, RSSR, HCl, PPh₃, and H₂, are also reported. The first three of these reactions share the same rate law and rate constant, the common rate determining step probably being initial loss of PPh₃. Some equilibrium constants for the exchange reactions of 9d (R=CH₂CH₃) with other thiols were tetermined, the Keq values increasing with the acidity of the incoming thiol. The mercapto hydrogens of 9a and 14a (R=H) exchange with the acidic deuterons of added CD₃OD. The hydridic and ortho-phenyl hydrogens exchange more slowly, presumably by intramolecular processes. Complex 14b (R=C₆H₄pCH₃) is unstable in the presence of light, exchanges phosphines rapidly with added P(C₆H₄pCH₃)₃, exchanges thiolate groups with added thiols, and is converted by high pressures of H₂ to a mixture of 9b and 3. Intermediates proposed for the mechanism of the thiol exchange reactions of 9 and 14 contain two or three thiolate groups sharing a proton. A related complex, [Ru(CO)₂(PPh₃)(μSEt)₂(μ₃SEt)Na(THF)]₂, which contains three thiolate groups on a ruthenium centre sharing a sodium cation, was isolated from the reaction of cct-RuCl₂(CO)₂(PPh₃)₂ with sodium ethanethiolate. In acetone, 9b and 14b can be formed cleanly from cct-RuHCl(CO)₂(PPh₃)₂ and cct-RuCl₂(CO)₂(PPh₃)₂, respectively, by reaction with p-thiocresolate. Complex 3 or cheaper analogues could be used as catalysts for the reduction of disulphides by H₂, or as recyclable reagents for the non-oxidative extraction of thiols from thiol-containing mixtures such as oil fractions. The chemistry described above will help to guide future researchers to systems that more closely parallel the processes occurring on the surfaces of industrial hydrodesulphurization catalysts. / Science, Faculty of / Chemistry, Department of / Graduate

The effects of temperature and sulphur nutrition on the growth, yield and mineral composition (N, NO₃-N, S and SO₄-S) of Hordeum vulgare L. cv Olli, Pisum sativum L. cv Dark Skin Perfection and Brassica campestris L. cv Arlo, were investigated in controlled environments. The net CO₂ exchange rates and compensation points were also determined at two S levels (0 and 64 ppm) under various temperature regimes. When barley and rape plants were grown at 0 ppm S, deficiency symptoms developed in about two weeks, whereas pea plants at the same level developed deficiency symptoms in about three weeks. Plants at the lowest S level and the highest temperature took the shortest time to develop S deficiency symptoms. Fresh and dry weights, shoot length, number of nodes and number of fertile fruit increased with increasing S levels. Shoot growth in all three species was more depressed by S deficiency than root growth. Optimum growing temperature regimes for barley and peas were found to be 24/16 at the vegetative stage and 18/10°C at the mature stage as evident from increased weights, maximum fruit set and mineral uptake. Optimum temperature for rape plants was 29/21°C at both stages of growth. Detrimental effects of cotyledon or endosperm removal tended to mask the effects of temperature and S levels. This method was thus found to be unsatisfactory for the study of S nutrition in plants. Higher mineral concentration was observed at the vegetative stage than at the mature stage in peas and rape plants, while in barley the mineral concentration remained constant at both stages of growth. With increase in S supply there was an increase in uptake of both total S and SO₄-S. Uptake also increased with increasing temperatures. This increase was largely due to "concentration effects". Hence the use of SO₄-S level as a criterion for diagnosis of S deficiency may be unsatisfactory, unless plants are grown at optimum temperatures. S deficient plants had increased total N and NO₃-N concentrations in all three species. NO₃-N concentration also increased with an increase in temperature. The total N concentration did not increase appreciably with temperature. Consequently, at low S level (0 and 8 ppm) total N:total S ratios (N:S) tended to increase or decrease depending on low or high growing temperatures respectively. These changes in ratios were independent of actual size of the plants. Furthermore the ratios for all S levels at the vegetative stage were lower than those at the mature stage. Therefore both temperature and stage of growth are important factors to be considered in interpreting S deficiency from N:S ratios in plants. The net C0₂ exchange rates were generally higher at 20 days than at 30 days. At 0 ppm S level and at high temperature, the decline in net C0₂ exchange rate with age was greater. Maximum CO₂ exchange rates were observed at the optimum growing temperatures for both S levels. Increasing the measuring temperature above the growing temperature caused no further stimulation in CO₂ uptake, and at high temperatures there was a decrease in uptake. When CO₂ exchange rates were measured at two 5.5°C intervals above and below the growing temperatures the maximum rates were recorded at or below growing temperatures in all the species at both S levels. The CO₂ compensation values were higher with lower S level in the leaf tissue than at higher S levels. Increase in growing temperatures also caused larger CO₂ compensation values than at lower temperatures. Negative correlations between CO₂ compensation point and leaf tissue S level and positive correlations between CO₂ compensation point and temperature were observed in barley and peas. / Land and Food Systems, Faculty of / Graduate

Reduced organic sulfur (ROS) compounds are environmentally ubiquitous and play an important role in sulfur cycling as well as in biogeochemical cycles of toxic metals, in particular mercury. Development of effective methods for analysis of ROS in environmental samples and investigations on the interactions of ROS with mercury are critical for understanding the role of ROS in mercury cycling, yet both of which are poorly studied. Covalent affinity chromatography-based methods were attempted for analysis of ROS in environmental water samples. A method was developed for analysis of environmental thiols, by preconcentration using affinity covalent chromatographic column or solid phase extraction, followed by releasing of thiols from the thiopropyl sepharose gel using TCEP and analysis using HPLC-UV or HPLC-FL. Under the optimized conditions, the detection limits of the method using HPLC-FL detection were 0.45 and 0.36 nM for Cys and GSH, respectively. Our results suggest that covalent affinity methods are efficient for thiol enrichment and interference elimination, demonstrating their promising applications in developing a sensitive, reliable, and useful technique for thiol analysis in environmental water samples. The dissolution of mercury sulfide (HgS) in the presence of ROS and dissolved organic matter (DOM) was investigated, by quantifying the effects of ROS on HgS dissolution and determining the speciation of the mercury released from ROS-induced HgS dissolution. It was observed that the presence of small ROS (e.g., Cys and GSH) and large molecule DOM, in particular at high concentrations, could significantly enhance the dissolution of HgS. The dissolved Hg during HgS dissolution determined using the conventional 0.22 µm cutoff method could include colloidal Hg (e.g., HgS colloids) and truly dissolved Hg (e.g., Hg-ROS complexes). A centrifugal filtration method (with 3 kDa MWCO) was employed to characterize the speciation and reactivity of the Hg released during ROS-enhanced HgS dissolution. The presence of small ROS could produce a considerable fraction (about 40% of total mercury in the solution) of truly dissolved mercury (< 3 kDa), probably due to the formation of Hg-Cys or Hg-GSH complexes. The truly dissolved Hg formed during GSH- or Cys-enhanced HgS dissolution was directly reducible (100% for GSH and 40% for Cys) by stannous chloride, demonstrating its potential role in Hg transformation and bioaccumulation.

Indiana University-Purdue University Indianapolis (IUPUI) / Recent innovations in portable electronics, electric vehicles and power generation by wind and solar have expanded the need for effcient battery storage. Lithium-ion batteries have been the frontline contender of battery storage yet are not able to match current demands. Alternatively, lithium-sulfur batteries are a promising technology to match the consumer demands. Elemental sulfur cathodes incur a variety of problems during cycling including the dissolution of intermediate lithium polysul- fides, an undesirable volume change (~ 80%) when completely reduced and a high dependence on liquid electrolyte, which quickly degrades the cell's available energy density. Due to these problems, the high theoretical capacity and energy density of lithium sulfur cells are unattainable. In this work, A new class of phenyl polysul- fides, C6H5SxC6H5(4 < x <6), are developed as liquid sulfur containing cathode materials. This technology was taken a step further to fulfill and emerging need for exible electronics in technology. Phenyl tetrasulfide (C6H5S4C6H5) was polymerized to form a high energy density battery with acute mobility. Lithium half-cell testing shows that phenyl hexasulfide (C6H5S6C6H5) can provide a specific capacity of 650mAh/g and capacity retention of 80% through 500 cycles at 1C rate along with superlative performance up to 10C. Furthermore, 1, 302W h/ kg and 1, 720W h/L are achievable at a low electrolyte/active material ratio. Electrochemical testing of polymer phenyl tetrasulfide reveals high specific capacities of 634mAh /g at 1C, while reaching 600mAh /g upon mechanical strain testing. This work introduces novel cathode materials for lithium-sulfur batteries and provides a new direction for the development of alternative high-capacity flexible cathode materials.

Lithium batteries have revolutionized emerging electronic applications and will play more important roles in the future. Unfortunately, the energy density of commercial lithium-ion batteries (100-265 Wh kg-1) cannot satisfy the fast-growing demand for energy storage technologies. Lithium-sulfur (Li-S) batteries stand out for high energy density (2567 Wh kg-1), low-cost, and environmentally benign attributes. However, the development of Li-S full-batteries is still hindered by the dissolution of polysulfides into the organic electrolytes and poor ions transfer at the interfaces of electrolytes and lithium-intercalated electrodes (e.g., lithiated graphite). Improving the electrolytes is a crucial aspect for the development of battery technologies, but the knowledge concerning the electrolyte microstructures remains elusive. This dissertation unravels the microstructures of organic electrolytes and paves the way to the development of Li-S batteries. Firstly, we demonstrate the key role of electrolyte chemistry in the battery performances by showing a synergetic effect of electrolytes coupled with designed sulfur cathodes. Secondly, we investigate the microstructure of electrolytes and discover previously unexplored solvent-solvent and solvent-anion interactions. We show that the interactions are useful to elucidate important battery operations, such as ions transfer at electrolyte-electrode interfaces, and reveal a potential probe for developing battery electrolytes. Thirdly, we optimize the electrolyte composition to obtain a highly reversible Li+ intercalation/deintercalation at the graphite anode, giving high performances of Li-S full-batteries in a dilute electrolyte concentration. Finally, we unravel the key role of additives in suppressing Li+ solvation in the electrolytes. Nitrate (NO3-) anions are observed to incorporate into the solvation shells, change the local environment of Li+ cations, and then lead to an effective Li+ desolvation followed by improved battery performances. Key significances of this dissertation are (i) observation of detailed electrolyte microstructures showing a potential probe for developing battery electrolytes; (ii) evidences of the electrolyte chemistry plays a predominant role in the electrolyte-electrode interfacial reactions, which prevails over the role of commonly believed solid electrolyte interphase (SEI); and (iii) new mechanistic insights into the key role of additives in the electrolyte microstructures. Furthermore, the presented methodology paves the way for developing electrolytes for broad electrochemical applications.