With diet being such a huge factor in the development of diseases, emerging research has supported that apple consumption is a promising candidate for disease prevention due to the high phenolic content it possesses. These polyphenols can be found in two forms: extractable polyphenols (EP) and non-extractable polyphenols (NEP). Polyphenols have been shown to have strong anti-inflammatory and anti-oxidant properties, but up until this point, most researchers focus on EP fractions, while NEP are neglected. After the EP extraction using acetone and acetic acid (99:1) from the Apple Boost powder, three additional extraction methods were conducted on the remaining powder residue to extract the NEP. These extractions put the residue in three different environments for hydrolysis to compare their extraction abilities: enzyme, alkaline, and acid. After analyzing the EP and NEP total phenolic content (TPC) levels, oxygen radical absorbance capacity (ORAC) assay was conducted to measure anti-oxidation capacity of each extraction, and in vitro anti-inflammatory assay was performed to evaluate the anti-inflammation capacity of each extraction where inflammation was induced by LPS. The results showed that the NEP obtained from acid hydrolysis had the highest readings in both the TPC and ORAC assay, but did not show any anti-inflammatory effects in vitro. The EP extraction had the second highest readings in the TPC, ORAC and anti-inflammatory assays. The NEP enzyme extraction had the second lowest TPC and ORAC assay performance, but highest performance in the anti-inflammatory assay. The NEP alkaline extraction had the lowest TPC and performed poorly in both the anti-inflammatory assay and ORAC assay.

Amending litter with aluminum sulfate (Al-S) has proven to be effective in reducing water-soluble P but there are concerns that it could result in soil pH reduction and increase levels of extractable soil Al if applied to acidic soils. A glasshouse study with soybean (Glycine max, L Merr) and cotton (Gossypium hirsutum L) as test crops was conducted to determine the impact of applying litter amended with Al-S at 0, 10 and 20% to an acidic sandy loam soil. These treatments were applied to meet N needs of a crop grown in soil with pH levels of 4.5, 5.0, 5.5 and 6.5. The experimental design was a randomized complete block. Application of BL + 20% Al-S to soil with initial pH of 4.5 or 5.0 significantly decreased the pH compared to BL. The decrease in soil pH with application of BL + 20% Al-S was attributed to high concentrations of geochemically labile Al which released hydrogen ions upon hydrolysis. Both BL and BL + 10% Al-S increased the initial soil pH and decreased extractable soil Al. Application of BL + 20% Al-S resulted in significant higher levels of extractable soil Al than BL and the differences were greater in the lower pH soils. Mehlich-3 extractable soil P, K, Mg, Ca, and Cu decreased with BL + 10 or 20% Al-S relative to BL. Soybean or cotton biomass from BL + 20% Al-S fertilization was significantly decreased relative to BL fertilized soils with initial pH of 4.5 or 5.0. Biomass with BL + 10% Al-S application were not statistically different from those fertilized with BL. Fertilizing cotton or soybean with BL + Al-S decreased tissue Al, N and P concentration. BL and BL + 10% Al-S showed the potential to increase soil pH and reduce extractable soil Al in acid soils but need further field evaluation.

The rise of cryptocurrencies has brought with it new math problems with new sets of constraints. The MEV problem entails solving for the ordering of pending trades that maximizes a block creator's profit. In decentralized finance, time is a big constraint, so an exhaustive search of all possible orderings is impossible. I propose a solution to the MEV problem that gives a near optimal result that can be solved in a reasonable amount of time. I layout the method and the formulas required for my solution. Additionally, I test my solution on synthesized data to show that it works as desired.

Arabinoxylans (AX’s) are the predominant non-starch polysaccharides found in the structural matrix of cell walls in wheat grains, being present in large quantities in wheat bran, accounting for up to 25% of its composition. Their physicochemical properties define their functionality which can be beneficial in cereal-based products such as bread, where their addition could enhance the gluten matrix responsible for the aerated structure and quality of bread. Bioethanol production has grown rapidly, however, to be economically viable, cereal-derived first generation biorefineries need to adopt the process integration approaches employed in petrochemical refineries, and exploit the interaction opportunities arising from multiple product streams. A potential source of AX is its extraction from the wheat bran based low value animal feed produced as an end product of the bioethanol distillation process. The benefits of extraction are twofold, to enhance feed nutritional value by reducing fibre content and produce a high value product for use as a functional ingredient in the breadmaking industry. Extraction of AX involves precipitation with ethanol, giving opportunity for integration and economic extraction in the context of a bioethanol plant. Currently no commercial supply of AX is available in sufficient quantities to conduct functionality trials; therefore the objective of the current work was to study the feasibility of extracting AX from animal feed and, by developing a scaled-up extraction process based on that of Hollmann and Lindhauer (2005) and Du et al. (2009), to produce sufficient quantities to conduct functionality trials into its effects on the breadmaking process. Two animal feeds, representative of contrasting biorefinery operations, were used for AX extraction, Distillers’ Dried Grains with Solubles (DDGS) and C*Traffordgold®, with water and alkaline AX being extracted from each. Monosaccharide analysis of the feedstocks confirmed the presence of arabinoxylans, with DDGS containing 12.5% AX and TG 13% AX, with A/X ratios of 0.55 and 0.61, respectively. The purity of AX extracted at both lab scale and on scale up was consistent, with 29.5% and 23% extracted at lab scale and 30% and 25% extracted in the scaled up process for WEAX from DDGS and TG, respectively. The purity of AEAX was lower, with 18% and 14% at lab scale and 15% and 14% for scale up for DDGS and TG, respectively. The results indicate that the same purity of crude extract can be achieved at both lab and larger scale extraction, however lower yields and absolute yields were observed at scale up and anticipated to be due to the crude nature of the process, which needs further optimisation. Addition of crude AX extracts to bread dough gave insights into its effects and potential benefits and issues. The type and origin of AX was found to affect bread dough characteristics in different ways. WEAX from both DDGS and TG exhibited effects on all stages of the breadmaking process, by improving stability and reducing softening at mixing, and slowing proving allowing the dough to retain a better aerated structure, leading to an open aerated finished loaf structure. AEAX from both types of animal feed generally caused destabilization of gas cells and coalescence, resulting in loaves with a tighter crumb structure. The AX dosage appeared to have a non-linear effect, with some positive changes at 1% addition turning to negative changes when added at 2%. This work has provided insights into the functionality of AX in bread dough, and a process has been developed to allow greater than lab scale production of arabinoxylan. The effects of AX need to be understood more clearly to retain beneficial effects, whilst supressing detrimental ones, preferably while avoiding the need for extensive purification. The work supports the possibility for AX extracts to be produced commercially as bread ingredients that could enhance bread structure and nutritional quality, and provides an elegant solution for synergy between two wheat-based industries serving both the food and non-food needs of society.

Soluble organic matter represent less than 1% of total soil organic matter (SOM) - but it contributes to many terrestrial ecosystem processes, due to its high mobility and reactivity in soil. Although it has been suggested that soluble organic matter (OM) may serve as an early indicator of soil quality changes as a result of shifts in land-use and management practices, only a few studies have addressed the dynamics of soluble OM in relation to land-use and specifically soil depth. This study focuses on two aspects of soluble OM. In the first part, I hypothesized that extractable OM obtained by aqueous solutions is a continuum of substances that depending on the extraction method can be separated into two operationally different fractions. The size and properties of these fractions may consistently differ among different land uses and at different soil depths. The objective of this part of the study was then to assess dynamics (size and properties, biodegradability and seasonality) of water extractable organic matter (WEOM) and salt extractable organic matter (SEOM) in a sequence of human dominated land-uses at topsoil and subsoil. At the second part of the study, I tested the regulatory gate hypothesis –abiotic solubilization of OM- as a primary controlling factor in soluble OM production. The objective of this study was to evaluate the impact of the microbial activity on the net production of dissolved organic matter (DOM) from the native SOM in the presence of added DOM and plant residue. For the first part of the experiment, the soil samples were collected from four land-uses under bog pine (Halocarpus bidwillii) woodland, tussock grassland (Festuca novae-zelandiae and Heiracium pilosella), cropland (Medicago sativa) and plantation forest (Pinus nigra). The selected land uses were located in the Mackenzie Basin, Canterbury, New Zealand and occurring on the same soils, topography and experienced similar climates. Soil samples were obtained from topsoil (0-20 cm) and subsoil (60-80 cm) at the end of each season (November, February, May and August) during 2007-2008. The sampled soils were adjusted to the same water status prior to extraction. While WEOM was obtained during a mild extraction procedure and using 0.01M CaCl2, SEOM was extracted with 0.5M K2SO4 at high temperature (75οC for 90 min). Both extracts were filtered through a 0.45 μm filter size. In the first part of the study, I assessed the biodegradation dynamics of WEOM and SEOM (spring samples), using a double-exponential decay model. The WEOM and SEOM were inoculated and incubated at 22°C for 90d under aerobic conditions. Subsamples were removed on days 1, 3, 7, 12, 16, 30, 42, 60, 75, and 90, filtered (0.22 μm), and analyzed for organic C and N content, UV absorption, and 13C natural abundance (δ13C). The results of the biodegradation experiment indicated a similar pattern for both C and N of SEOM and WEOM as that of previously shown for soil DOM. However, C and N mineralization rate were considerably larger in the WEOM than SEOM. The parameters of the double-exponential model suggested that regardless of the land-use and soil depth, both the WEOM and SEOM can be modeled in two biological pools, with a largely similar “fast decomposable” but different “slowly decomposable” pools. However, since the extraction was not sequentially followed, a very small portion of the SEOM was comprised of the WEOM and given the greater observed biodegradability of the WEOM, the overall biodegradable portion of the SEOM would be lower than the observed. Despite a greater biodegradability of the organic N than C of both WEOM and SEOM; mainly due to a longer HL of the slowly biodegradable pool of C; the C/N ratio of the samples did not change very much during the biodegradation. This led us to conclude that the biodegradation of soluble OM may occur as a function of N availability. Parallel to C and N loss, a considerable increase in SUVA254 of SEOM, and particularly WEOM occurred during the incubation period. The greater increase in the proportion of aromatic compounds (assessed by SUVA) in the WEOM than SEOM, implied consumption of simple compounds (vs. very humified) during decomposition and further supported the observed faster biodegradation rate of the WEOM. The data indicated a relatively strong correlation (R2=0.66 and 0.74 for the WEOM and SEOM, respectively) between the amount of biodegraded C and the increase in SUVA254. This suggested that SUVA254 can be used as a simple, low-cost but reliable approach for describing the biodegradability of soluble OM, as previously suggested by others. At the end of the bioassay, the 13C natural abundance of the WEOM was significantly depleted, and showed a clear relationship with the proportion of the biodegraded C. This confirmed the previously suggested preferential biodegradation of simple organic constituents (13C enriched), resulting in the accumulation of more depleted 13C compounds (often recalcitrant compounds). Moreover, the results of the δ13C technique revealed that the relatively greater 13C enrichment of the WEOM obtained from subsoil, seems to be due to the presence of root exudates (often highly 13C enriched). In contrast, a proportionally greater 13C depletion observed in the SEOM particularly at subsoil samples, suggests that there is a close relationship between the SEOM and the typically 13C depleted humified SOM. The results of the biodegradation model (half-life of both C and N), in addition to dynamics of SUVA254 and δ13C of the WEOM and SEOM were very comparable between top and subsoil samples. This implied that the potential biodegradability of soluble OM under laboratory conditions does not necessary reflect the reported lower in situ biodegradability at soil depth, in agreement with recent evidence suggested by others. Instead, this may be largely due to the lack of optimum conditions (oxygen, nutrients, and moisture) for the decomposer community at soil depth. Although there was a tendency for a generally greater biodegradability of the samples from the soils under the crop land (both WEOC and SEOC), along with relatively greater increase in SUVA, there was not a consistent trend of the effect of land use on the biodegradation of either WEOM or SEOM. The lower C/N ratio of the soils under the crop land seemed to be related with the observed proportionally greater biodegradability of these soils. During the second part of the study, I assessed seasonal variations of the size and properties of the previously defined WEOM and SEOM, collected from top-and subsoil from the land-uses. I observed that 10-year after conversion of the degraded tussock grassland to cropland or plantation, the total C stock of topsoil (0-20 cm) when above- and below-ground plant biomass is excluded; has remained unchanged. This was attributed to the limited biomass production of the region, more likely as a result of low productivity of the soil, but also harsh climatic conditions. Not only soil depth, but land-use affected both C concentration and C/N ratio of soil organic matter (SOM), with the greatest C concentration of soils under grassland and plantation in topsoil and subsoil, respectively. Despite the WEOM, the size of SEOM was largely unaffected by land-use and soil depth; instead, the properties of SEOM was more consistent with the effect of soil depth. Given the observed large temporal and spatial variability of the WEOM, the study suggests that the SEOM more consistently reflects the influence of land use and soil depth. No consistent effect of seasonality was observed in terms of size or properties of the SOM and the WEOM and SEOM. Overall comparison of the size and properties of the WEOM and SEOM indicated that OM extraction efficiency may vary largely, depending on extraction conditions. Using more concentrated salt solutions consistently yielded greater amount of OM (N, and especially C) release from soil with properties resembling more those of total soil OM (more humified) compared to the WEOM. The SEOM was also less variable by time and space. The last part of the study was aimed to assess biotic vs. non-biotic solubilization of OM in the presence of added plant residue. Given the need to recognize the source of the solubilized OM during the experiment, I used enriched (13C) plant residue as the source of fresh OM. The above-ground part of ryegrass was added to soil either as plant residue or residue extract (extracted with CaCl2 followed by 0.45μm filtration) -termed DOM. These two forms of added OM (residue/DOM) were conceived to represent two levels of bioavailability for the decomposer community for further assessing possible biotic solubilization of OM. Two soils similar in their OM content and other properties, but different in mineralogy were selected for the experiment. Soils were incubated for 90d under sterilized vs. non-sterile conditions and leached regularly with a dilute aqueous solution (0.05M CaCl2). Plant residue was added to soil (1:100, residue: soil, w/w) prior to the start of the incubation, but DOM was frequently applied to the soils along with each leaching experiment. The greater C and N concentration in the leachates of both sterilized residue-amended and DOM-amended soils compared to that of living soils, indicated a high microbial activity, as determined by CO2 loss, in the living soils. However, the proportion of the solubilized C (determined by 13C) from sterilized soils was largely comparable to that of living soils. This supports the recently suggested “regulatory gate” hypothesis, stating that solubilisation of OM largely occurs independent of the size or community structure of microorganisms. In addition, I observed that even with the presence of adequate amount of added fresh OM (ryegrass residue), about 70% of the solubilized C consistently originated from the humified soil OM, highlighting the role of native soil OM as the source of soluble OM in soil. In addition, in the DOM-amended soils, there was strong evidence, indicating that in the sterilized soils, the added DOM was exchanged with the humified soil OM as observed by an increase in SUVA, and humification index (HI) of the leached OM. Although the results of the study did not show a considerable difference in the solubilisation rate of added OM as a function of biological activity (either in the residue- or DOM-amended soils), there was clear evidence that the presence of microbial activity has resulted in further decomposition of the solubilised OM through biological transformations. Together, the results suggested that the proposed fractionation method can be used to separate two operationally defined pools of soluble OM with consistent differences in their size (C and N), properties (δ13C, SUVA254, and C/N ratio) and biodegradability across the land-uses and soil depth. The second part of the study supported the primary role of abiotic factors on the production of soluble OM from native soil OM. Although the abiotic mechanisms involved in the solubilization remain to be addressed by future studies. Cons and pros of the methods with some suggestions for further works have been mentioned in the last chapter.

Abstract, key words The aim of this thesis was to perform a phytoextraction experiment with benzodiazepines chlordiazepoxide, diazepam, alprazolam and bromazepam on corn plant (Zea mays). After 14 days of growing of sterile cultivation, new medium (Murashige and Skoog) contaminated with benzodiazepine was added. The starting concentration of benzodiazepine was 10 mg · l-1. After every 24 hours, a sample of medium was collected. The actual concentration of benzodiazepine was measured on HPLC with UV detection. Extractable residues were also analysed to find out whether the benzodiazepine is being translocated to the upper parts of the plant. The same HPLC conditions were used for these samples. The greatest phytoextraction efficiency (the amount of drug extracted by 1 gram of biomass in 24 hours) was observed for chlordiazepoxide, followed by bromazepam, alprazolam and diazepam respectively. The extractable residues analysis confirmed the translocation to the upper parts of the plant for every of the benzodiazepines tested. That indicates a threat for the animals through the food chain contamination. Key words: phytoremediation, phytoextraction, benzodiazepines, extractable residuals, HPLC.

It is well documented that increases in soil organic matter (SOM) improve soil physical properties and increase the overall fertility and sustainability of the soil. Research in SOM storage has recently amplified following the proposal that agricultural soils may provide a significant carbon (C) sink that may aid in the mitigation of increasing atmospheric carbon dioxide. Observed differences in lint yield and nitrogen response from a cotton performance study at the Texas A&M University Experimental Farm near College Station, TX prompted us to examine the effects of tillage and rotation on soil organic C (SOC), soil microbial biomass C (SMBC), 38-day cumulative C mineralization (38-day CMIN), hot-water extractable organic C (hot-WEOC), carbohydrate C, and total glomalin. The treatments examined included conventional-till continuous cotton (CT), reduced-till continuous cotton (RT), and conventional-till cotton after corn rotation (CC) treatments. In pre-plant soil samples, SOC, SMBC, and 38-day CMIN in the top 5 cm were 33, 58, and 79 % greater in RT and 29, 32, and 36 % greater in CC vs. CT. Comparable differences were observed for hot-WEOC and carbohydrate C. Little seasonal variation was observed for labile-C pools throughout the growing season, suggesting minimal C input from cotton roots. Water-stable aggregation was not significantly affected by management, and did not correlate with labile-C pools or total glomalin. Labile-C pools were generally more responsive to management vs. SOC and were strongly correlated with one another. Carbohydrate C of hot-water extracts exhibited the strongest relationships with SMBC and 38-day CMIN, even though it comprised only 3 and 5 % of these pools, respectively. Our data suggest that increasing SOC in Texas cotton-cropping systems through conservation management is possible. Long-term data are still needed to fully address SOC storage potentials in Texas, but increases in labile-C pools resulting from conservation management are attainable and have the potential to positively impact soil fertility.

Iron (Fe) and zinc (Zn) deficiencies affect an estimated 3 billion people worldwide and are linked with cognitive and physical impairments, maternal and child mortality rates, and decreased adult work activity. To combat this "hidden" hunger, plant breeders in Mali are working to increase sorghum grain Fe and Zn concentrations. The objective of this study was to investigate soil and mold influences that affect Fe and Zn uptake and accumulation in sorghum grain. In southern Mali, soils from participatory sorghum variety trials and areas of different parent material and proximity to Shea (Vitellaria paradoxa) trees were analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Zn and related soil properties, and sorghum grain was analyzed for Zn concentration. An inoculation trial was also performed at College Station, TX to determine if sorghum grain infected by the mold Curvularia lunata significantly increased grain Fe concentrations. DTPA-extractable Zn concentration was highly variable with high concentrations found in soils under Shea tree canopies with high pH and organic carbon and derived from mafic, high Zn-content parent material. However, these high concentrations did not significantly affect grain Zn concentrations in sorghum grown outside of the canopy. Groundnut grown underneath the canopy is likely to be affected and warrants further investigation. In many cases, soil DTPA-extractable Zn concentrations were at deficient levels, thus hampering its correlation to sorghum grain Zn concentration and potentially limiting the expression of genetic Zn biofortification. Knowledge of soil DTPA-extractable Zn concentrations or basic soil properties such as pH, organic carbon, and soil parent material may aid in the location of suitable available Zn fields and overall biofortification efforts. Grain Fe concentration was not significantly related to Curvularia lunata percent recovery or grain mold rating, but instead showed a relatively high variance by panicle, digestion batch, and grain subsample. Additional work is needed to address these sources of Fe variation so as to determine better if mold affects grain Fe concentrations.

This doctoral dissertation presents contributions advancing the state-of-the-art of secure two-party computation (S2PC) — a cryptographic primitive that allows two mutually distrustful parties, with respective private inputs, to evaluate a function of their combined input, while ensuring privacy of inputs and outputs and integrity of the computation, externally indistinguishable from an interaction mediated by a trusted party. The dissertation shows that S2PC can be made more practical by means of innovative cryptographic techniques, namely by engineered use of commitment schemes with special properties, enabling more efficient protocols, with provable security and applicable to make systems more dependable. This is one further step toward establishing S2PC as a practical tool for privacy-preserving applications. The main technical contribution is a new protocol for S2PC of Boolean circuits, based on an innovative technique called forge-and-lose.1 Building on top of a traditional cut-and-choose of garbled circuits (cryptographic versions of Boolean circuits), the protocol improves efficiency by reducing by a factor of approximately 3 the needed number of garbled circuits. This significantly reduces a major communication component of S2PC with malicious parties, for circuits of practical size. The protocol achieves simulatable S2PC-with-commitments, producing random commitments of the circuit input and output bits of both parties. The commitments also enable direct linkage of several S2PCs in a malicious adversarial setting. As second result, the dissertation describes an improvement to the efficiency of one of the needed sub-protocols: simulatable two-party coin-flipping.1 The sub-protocol is based on a new universally composable commitment scheme that for bit-strings of increasing size can achieve an asymptotic communication-complexity rate arbitrarily close to 1. The dissertation then discusses how S2PC-with-commitments can enable in brokered identification systems a difficult-to-achieve privacy property — a kind of unlinkability.1 This mitigates a vector of potential mass surveillance by an online central entity (a hub), which is otherwise empowered in systems being developed at nation scale for authentication of citizens. When the hub mediates between identity providers and service providers the authentication of users, an adequate S2PC (e.g., of a block-cipher) can prevent the hub from learning user pseudonyms that would allow linking transactions of the same user across different services providers. 1 Parts of these contributions were previously presented at ASIACRYPT 2013, PETS 2015 and PKC 2016.

Per- and polyfluoroalkyl substances (PFAS) are synthetic compounds that have beenaround since 1940. They can be used in a variety of products such as fire-fighting foam, food packaging and cosmetic products. Many PFAS have potential toxic effects on both humans and animals which poses a problem due to their wide distribution and persistency. Another problem concerns the remediation of PFAS, where the substances ends up circulating between the different disposal types (landfills, wastewater treatment and incineration). Active methods are therefore needed to remove or retain the contaminants. Some examples of these remediation technologies can be biomaterials, organoclays and more advanced methods such as activated carbon and ion exchange. The more advanced being suited for remediation of drinking water. In this study, the sorption efficiency of two pine bark fractions has been studied and also compared to the efficiency of activated carbon. The evaluation was done for both target analysis (PFAS-11) and non-specific analysis of extractable organofluorine (EOF) compounds in contaminated water from a hazardous waste management facility. The two pine bark fractions indicated similar sorption efficiencies, for both the PFAS-11 and the EOF compounds. The sorption efficiency ranged from 10% up to 75% for perfluorinated sulfonic acids (PFSA) and from below zero up to 40% for perfluorinated carboxylic acids (PFCA). A general pattern can be seen, the sorption efficiency increases with increasing length of the PFAS chain. The activated carbon had a higher sorption efficiency, where the majority of PFAS had an average sorption of 100%. In comparison, the PFAS-11 and total EOF analysis displayed high concentrations of unidentified EOF compounds. These compounds indicated a negative sorption, which might imply that non-targeted PFAS or other fluorinated organic compounds desorb from the bark. Therefore, the pine bark might be suitable as a rough remediation of long-chain PFAS (≥8C), but further studies on the sorption of unidentified fluorinated organic compounds are of interest.