A laboratory investigation into foam separation processes, as applied to kraft pulping and bleaching effluents is described. Two methods, foam fractionation and ion flotation were tested in the laboratory. The procedures developed concentrated primarily on the removal of effluent colour because this property lent itself most readily to the available analytical methods, and because effluent colour removal presents one of the greatest waste water treatment problems facing the industry today. The foam fractionation technique was not successful. Substantial colour removals were obtained, but it was subsequently shown that the mechanism of removal was really an ion flotation. Positive results were obtained with the use of the ion flotation process for removal of effluent colour. At optimum conditions, the recovery of flotable material and the corresponding removal of effluent colour were in excess of 95 per cent. Variation of surfactant dosage showed that below a critical level no colour was removed. As concentrations increased above this value the amount of colour removed increased rapidly, reaching a high removal level beyond which increases in surfactant concentration were of little value. The rate of flotation recovery was found to be significantly affected by the air sparge rate and the sparger pore size, both parameters which would determine the area available for adsorption. The pH of the flotation cell solution had a marked effect on the system. Optimum pH was clearly defined as 5.1. Removal of material other than just the chromophoric fraction was apparent. Biological oxygen demand data, while not extensive, demonstrate a significant reduction in the bio-degradable portion of the effluent. The possible future development of the process into a viable candidate for industrial application is discussed. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Autocausticizing, a new method to regenerate sodium hydroxide from the sodium carbonate, is intended to replace the conventional Kraft Recovery System which uses calcium hydroxide produced in a lime kiln for this purpose. It is defined as the self-induced expulsion of carbon dioxide bound in the smelt by using certain amphoteric oxides. Thus autocausticizing can eliminate the need for a lime cycle and hence reduce the Kraft process capital and operating costs. The reactions between sodium carbonate and a number of amphoteric oxides have been reported in the literature. Patents have been issued on the use of titanium dioxide, iron oxide and sodium borates for this purpose. The sodium borates have the advantage of a high reaction rate, but are totally soluble and must be carried throughout the whole Kraft cycle. In this research colemanite (calcium borate) which is mined as a cheap mineral in California and in Turkey was studied as an autocausticizing agent. Since it is partially soluble and most likely can be recycled, it would eliminate the problems associated with the use of soluble borates. Experiments were performed both isothermally and under constant heating rate conditions. Isothermal studies were made with Ti0₂, alumina and colemanite to compare their performances as autocausticizing agents at 900°C and 1000°C for various reaction times in an electric furnace. The second group of experiments was made using a differential Chermogravimetric (TG) analyzer. In these experiments mixtures with 20 to 80 weight percent colemanite in sodium carbonate were heated at a constant heating rate of 10°K/min in the range of 190-1000°C. The results indicate that two reaction were involved. Above the stoichiometric colemanite concentration the colemanite and sodium carbonate had reacted completely by a temperature of about 700°C. Above that temperature the impurities in the colemanite appeared to catalyze the decomposition of sodium carbonate if the colemanite concentration was less than the stoichiometric amount needed. TG data were analyzed for the first and second reactions between the temperature ranges of 190-700°C and 700-1000°C respectively. Kinetic models were developed In terms of the reaction order, activation energy and frequency factor. The first reaction was found to be zero order on sodium carbonate concentration. The results also showed that the activation energy and frequency factor were functions of the colemanite concentration in the mixtures. As a result the rate was affected by the amount of colemanite used. The same was true for the second reaction except the reaction was first order. The concentrations predicted for the isothermal tests by the model were compared with the results of the isothermal study for various colemanite concentrations. Reasonable agreement was found except for the values at lower conversions, which might be due to the Increased importance of the diffusion of CO₂ from the mixtures in the case of Isothermal runs. It was also found that it is possible to obtain conversions as high as 85 percent with 40 percent colemanite in 20 minutes. Promising results were obtained from the recycle tests as well. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第21998号 / 医博第4512号 / 新制||医||1038(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 柳田 素子, 教授 松田 文彦, 教授 木村 剛 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

There are many advantages and some disadvantages associated with the fall application of nitrogen fertilizers. The advantages of applying fertilizer at this time appear very convincing. It is easier to get onto the land in the fall. During the fall, famers usually have more time to apply fertilizer than they do in the spring. In the fall the fertilizer companies offer better service. This is because the fall application of fertilizer lengthens out their season, thus making it possible for them to handle more fertilizer.

Ce travail est consacré à l'élaboration de nano-complexes polyélectrolytes (CPEs) ayant une stabilité améliorée en milieux physiologiques et à l'exemplification de leur fort potentiel d'application comme système de délivrance de (macro) molécules bioactives. Le chitosane comme polycation a été compléxé avec quatre polyanions naturels ayant différents densités de charges et groupements fonctionnels(-COO- et SO3-) à savoir l'acide hyaluronique (HYA), le chondroïtine sulfate (ChonS), le sulfate de dextrane (DS) et l'héparine (HEP). Les facteurs qui influent sur la formation et les propriétés physico-chimiques des nano-complexes chitosane-HYA ont été étudiés. Ces nanovecteurs perdent leur caractère colloïdal en milieux physiologiques. Pour améliorer leur stabilité dans ces conditions, une stratégie innovante qui implique l'ajout de zinc a été conçue. Cette stratégie de stabilisation a été démontrée comme étant polyvalente et a été étendue aux complexes polyélectrolytes (CPEs) chitosane-ChonS. Même si de cette manière une stabilité à long terme a été observée, cette stratégie reste uniquement applicable aux CPEs cationiques. Pour cette raison, une approche alternative permettant l'amélioration de la stabilité des colloïdes à charges positives ou négatives a été mise en oeuvre en concevant des nano-complexes de type coeur-couronne ternaires composés de polyacides forts c'est-à-dire de DS ou d'HEP associés au chitosane en coeur et un complexe chitosane-HYA en couronne. Tous les nano-complexes stables obtenus peuvent encapsuler le ténofovir, une molécule antirétrovirale et être fonctionnalisés par des IgAs de ciblage. En in vitro, ces nanovecteurs montrent une inhibition de l'infection des PBMC par le virus VIH-1 supérieure à l'antirétrovirale seule / This work is devoted to the elaboration of nano-polyelectrolyte complexes (PECs) systems with improved stability in physiological media and to the establishment of their high potential of applications as bioactive (macro) molecule delivery systems. Chitosan as polycation were complexed with four natural polyanions of different charged groups and densities (-COO- and SO3 - as negative charges), namely hyaluronan (HYA), chondroitin sulfate (ChonS), dextran sulfate (DS) and heparin (HEP). The factors impacting the formation and physical-chemical properties of chitosan-HYA nanocomplexes were investigated. However, these nanovectors lost their colloidal character in physiological media. To improve their colloidal stability in physiological conditions, an innovative stabilization strategy was designed, involving zinc ion. This stabilization strategy proved versatile and was extended to chitosan-ChonS PECs. Though a long-term stability was achieved, this strategy was only applicable to cationic PECs. Therefore, an alternate approach enabled the improvement of the colloidal stability in physiological media of both positive and negative colloids by designing core-shell ternary polyelectrolyte nanocomplexes composed of strong polyacid (DS or HEP)-chitosan PECs as core and a chitosan-HYA complex as shell. Furthermore, all of the stabilized nanocomplexes allowed the encapsulation of active molecules anti-retroviral drug tenofovir and surface functionalization with targeting IgAs. In vitro, these nanovectors exhibited an inhibition of infection of PBMCs by HIV-1 virus which could be superior to the free drug

Indiana University-Purdue University Indianapolis (IUPUI) / Nanoparticles (NPs) are an emerging technology in biomedical engineering with opportunities in diagnostics, imaging, and drug delivery. NPs can be prepared from a wide range of organic and/or inorganic materials. They can be fabricated to exhibit different characteristics for biomedical applications. The goal of this thesis was to develop NPs with tunable surface properties for selective cell targeting. Specifically, polyelectrolyte complexes composed of heparin (Hep, a growth factor binding glycosaminoglycan) and poly-L-lysine (PLL, a homopolymeric lysine) were prepared via a pulse sonication method. The Hep/PLL core NPs were further layered with additional Hep, tetrazine (Tz) modified Hep, or dextran sulfate (DS). The addition of Tz handle on Hep backbone permitted easy modification of NP surface with norbornene (NB) modified motifs/ligands, including inert poly(ethylene glycol) (PEG), cell adhesive peptides (e.g., RGD), and/or fluorescent marker. Both Hep and DS coated NPs could be readily internalized by J774A.1 monocytes/macrophages, whereas PEGylated NPs effectively reduced cellular uptake/recognition. The versatility of this NP system was further demonstrated by laying DS on the Hep/PLL NP surface. DS-coated NPs were recognized by J774A.1 cells more effectively. Furthermore, DS-layered NPs seemed to reduce IL-10 production on a per cell basis, suggesting that these NPs could be used to alter polarization of macrophages.

No description available.

The specificity of a medaka vitellogenin (Vtg) enzyme-linked immunosorbent assay (ELISA) kit was tested on adult hybrid tilapia to determine if vitellogenin could be successfully measured in tilapia using this method. Adult hybrid (Orechromis niloticus x Oreochromis mossambicus x Oreochromis aureus) tilapia were injected with 17â-estradiol (E2) at 5 ìg/g body weight (b.w.) in two separate experiments and exposed to 2.5 ìg/g b.w. E2 through aquaria water in a third experiment. All fish were exposed to solvent controls (50/50 PBS/ethanol, or 59/41 PBS/ ethanol) proportional to the volume of estradiol solvent used. Experiment 1 was terminated due to a decrease in fish health and unexpected mortalities. Experiment 2 was continued though there was again a decrease in fish health and mortalities before experiment was completed. According to one-way ANOVA, Experiment 2 treatment groups were significantly different (P<0.05); however, Tukey's pairwise comparisons showed no differences between treatment groups. Experiment 3 results showed statistical differences between some treatment groups (P<0.001). However, maximum vitellogenin levels reached 1250 ng/mL Vtg, which were much lower than induced vitellogenin levels from literature (0.002 mg/mL to 6 mg/mL). Typical induction trends should be as follows: male control<female control< induced male<induced female; however, these trends were not observed in this study. For these reasons, the medaka vitellogenin ELISA kit was determined not specific to tilapia vitellogenin. This research was performed due to the fact that tilapia are farmed worldwide, and to increase research with these fish, in order to better understand their response to xenobiotic chemicals, easier methods are desired for measuring their vitellogenin. Vitellogenin induction from exposure to the chemotherapeutics: oxytetracycline, Romet-30®, and copper sulfate was evaluate using Japanese medaka (Oryzias latipes). Medaka were exposed to E2 (0.0552 ìg/L) in aquaria water as a positive control. Medaka were fed oxytetracycline medicated feed at 0.0174 g, 0.0348 g, and 0.087 g, and Romet-30® medicated feed at 0.0261 g, 0.0522 g, and 0.1305 g daily for 11 days and 5 days as recommended. Medaka were exposed to copper sulfate at 1.85 mg/L for one hour (for 1 day, 7 consecutive days, and every three to five days for a total of 7 doses). Vitellogenin levels were measured using a sandwich ELISA. As expected, Vtg levels were induced from exposure to E2 (P<0.01); however, exposure to the chemotherapeutic compounds did not induce elevated Vtg levels. Alternately, copper sulfate exposure for one hour for 1 day did show a significant decrease in vitellogenin (P<0.01). Biological variation accounted for large portions of the variation within treatment groups in medaka vitellogenin in fish exposed to chemotherapeutics (as high as 41.01%). From this research we suggest that these chemicals do not have estrogenic properties capable of inducing vitellogenin in medaka. / Master of Science

Specific conductivity (SC) and total dissolved solids (TDS) are increasingly being used as a parameter used to judge the aquatic health of streams that are impacted by coal mining operations in the Appalachian region of the United States. Due to this, government environmental regulatory bodies have been considering issuing a regulation on SC for all mining operation outfalls. Sulfate typically has the greatest dissolved ion presence in coal mine waters. In literature examining the treatment of mine waters, SC and TDS analysis is typically not reported. The technologies examined in this study were nanofiltration membrane technology and biological sulfate reducing bioreactors. In the nanofiltration study, three different nanofiltration membranes were evaluated for SC reduction: NF270, DK, and NFX. The DK and NFX nanofilters were able to reduce SC levels by an average of 84 percent for both mine waters tested and were able to reach SC levels below the proposed limit of 500 S/cm. The SC levels achieved by the NF270 nanofilters were observed to have much higher variability. The inclusion of microfiltration and simulated-sand filtration were also introduced as a pre-treatment stage in order to determine whether or not nanofiltration performance would improve in terms of SC reduction. In the biological sulfate reducing bioreactor study, multiple bioreactors were established to identify the optimal organic mixture to foster both SC and sulfate reduction. Sulfate reduction began to occur approximately 20 days after the establishment of each bioreactor. SC levels were greater than 13,000 S/cm in each of the bioreactors sampled by the fortieth day of sampling. The probable cause of the increase SC was identified to be the manure/compost used in the study. Future testing should incorporate more sampling in the early phases of experimentation in order to ensure the ability to monitor changes in water quality. / MS

Risk management has been used regularly in the mining industry over the last few decades. The majority of those instances have focused on health and safety issues. Health and safety has improved in the United States, Australia, and other major mining districts because of the successful use of risk management and mitigation practices. Risk management has been used to a lesser extent to reduce or avoid environmental issues as well. There are a number of factors that make utilization of risk management analysis more applicable to health and safety than to environmental issues. This thesis explores the use of risk management in the context of environmental issues associated with mining. Specifically, two case studies are developed in two self-contained manuscripts: the first focuses on sequestering CO2 while the second focuses on wild rice in Minnesota with regards to the sulfate standard. Through the lens of risk management, an attempt is made to align project goals and efforts with mitigation potential to reduce the likelihood or result of particular risks. The end result is a reduction in risks due to mitigation. The first manuscript shows how risks disappear over time because they have been categorized and addressed. The project goals are keep on track by eliminating or reducing these risks. The second manuscript can be used by stakeholders to review their potential risks and mitigate those risks if possible/necessary. In contrast to the first manuscript that contains risks that are known and measurable, the second manuscript examines different risks based on four potential outcomes. / Master of Science