京都大学 / 0048 / 新制・論文博士 / 博士(医学) / 乙第13386号 / 論医博第2218号 / 新制||医||1048(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 椛島 健治, 教授 妻木 範行, 教授 安達 泰治 / 学位規則第4条第2項該当 / Doctor of Medical Science / Kyoto University / DFAM

The aim of this work was the evaluation and method optimalization for determination of sulfates in aqueous solutions with application on different kinds of waters. For determination of sulfates were used two different procedures, turbidimetric and volumetric. In turbidimetric procedure was use optimized conditions applicable determination of sulfates in range from 0 – 20 mg.l-1. For stabilization of the colloid was use glycerine, himself sulfates sedimentation is discharged in BaSO4 form. By volumetric methods are used titration on the dithizone like indicator while using Pb(NO3)2 like volumetric reagent. Other indicator bromsulfonazo III, whitch are used for determination of sulfates by the help of volumetric solutions Ba(ClO4)2 and BaCl2. All volumetric determinations proceeded in acidic medium. During research of interferences ions on the individual titraction was detected substantial effect Ca2+, Mg2+ and Fe3+, which was needing divide off on the exchanger resin. Ions aforementioned don't interfere turbidimetric determination of sulfates.

The energetics of cast calcium sulfate dihydrate-aluminium thermites was explored and its use as a potential metal-cutting tool was investigated. Thermite is a pyrotechnic composition that undergoes a highly exothermic reaction that burns relatively slowly. It is often used in cutting, welding and incendiary devices. Consolidation of thermite by casting was chosen to enable control of the burning front. The base case thermite comprised 60 wt-% calcium sulfate dihydrate oxidiser and 40 wt-% aluminium fuel. Addition of additives were considered for their effect on the cast thermite’s setting time, density, surface temperature, reaction products and burn rate. EKVI and FactSage thermodynamic simulations were used to determine optimum compositions for the various systems. The thermite powder compositions were sieved before mixing with water and casting in a mould. The casts were allowed to set for 3 days to form calcium sulfate dihydrate-aluminium compositions. The copper sulfate pentahydrate additive was found to significantly decrease the setting time of the casts. The heat of hydration of the base case was 59 ± 8 J g−1 . The compressive strength reached 2.9 ± 0.2 MPa, the open air burn rate was 12.0 ± 1.6 mm s −1 and a maximum surface temperature of 1370 ± 64 °C was recorded using a pyrometer. Bomb calorimetry indicated an energy output of 7.96 ± 1.07 MJ kg−1 , slightly lower than predicted by the EKVI simulation. The density of the castings was varied by either adding hollow sodium borosilicate glass spheres or by adding excess water. The glass spheres resulted in a burn rate that decreased nonlinearly with decreasing cast density. The excess water made no changes to the burning, except for increasing the burn rate of the copper sulfate pentahydrate-based thermite. Calcium sulfate in the casts was also dehydrated by thermal treatments at 155 °C and 200 °C. This resulted in significant increases in the burn rate due to the porosity created by the evaporation of the hydration waters. Castings that were thermally treated in an oven at 155 °C were successful in puncturing part of an aluminium block in confined burn tests. A hole with a diameter of ~13.6 mm and depth of ~7 mm was produced. It is recommended that the composition with copper sulfate pentahydrate be used as a binder in further tests. / Dissertation (MEng)--University of Pretoria, 2018. / Chemical Engineering / MEng / Unrestricted

Methylmercury (MeHg) is a global pollutant and potent neurotoxin that bioaccumulates in aquatic and terrestrial foodwebs. As such, predicting the fate of MeHg in the environment is important in addressing ecosystem and human health concerns. Pollution that results from mining activities (i.e. ore roasting and smelting) is one way in which geochemistry of lakes can be altered, in turn altering the cycling of mercury (Hg) overall and the kinetics of MeHg production and bioaccumulation. My thesis is focused on examining the effect of different pollution gradients on the cycling of Hg at two different sites impacted by legacy mining in Canada. In Yellowknife (Northwest Territories, Canada) I assessed the effect of sulfate and arsenic (As) emissions on the production of MeHg in lake sediments, while in Sudbury (Ontario, Canada) I examined the effect of selenium (Se) emissions on the bioaccumulation of Hg and MeHg in freshwater biota. In Yellowknife, an environment polluted with both sulfate and As from mining activities, lakes were sampled using a factorial design which controlled for environmental variables known to affect MeHg production (i.e. sulfate, iron, productivity, pH, and dissolved organic matter). We used stable Hg isotope tracers to quantify Hg methylation and demethylation rate constants in sediments. Results showed that %MeHg in the water is best correlated with sulfate concentrations, while the rate at which Hg is methylated (Km) in sediments is negatively correlated with total As, and positively correlated with dissolved organic carbon, total phosphorus, and %MeHg in the water. Furthermore, a detailed examination of a lake with representative limnological characteristics of the area showed that addition of sulfate and organic carbon does increase the production of MeHg in the sediments, while addition of arsenate (0 to 10 mM) showed significant decrease in MeHg production, regardless of sulfate concentrations. Next, Se emissions in Sudbury (Ontario, Canada) correlated with lower total Hg and MeHg in tissues of zooplankton, amphipods (Hyalella azteca), mayflies (Stenonema femoratum), and young-of-the-year perch (Perca flavescens). However, despite ten years of emission reductions, results show that total Se concentrations in the majority of lakes have increased, most likely due to the long residence time of Se in the watershed and the water column. Consequently, Se continues to exhibit a protective effect on total Hg and MeHg bioaccumulation in biota, even a decade after emissions have greatly decreased. Canada’s numerous mining operations have left a legacy of pollution and it is important to understand the effects of these pollutants on the biogeochemistry of surrounding lakes. The results from my thesis demonstrate how mining emissions can alter the kinetics and bioaccumulation of MeHg in freshwater lakes, highlighting the complexity of Hg cycling in response to mining activities. My thesis is an important step in identifying and modeling the controls of MeHg production and bioaccumulation in environments impacted by emissions from mining operations.

Acid sulfate soils covers an area area about 600 km-2 along the coast line of Northern Sweden. These soils originate from land uplift and oxidized sulfide soils. The oxidation process releases sulfur and Fe(III) and will lower the pH-value and mobilize metals that will cause toxic environments for water living organisms. Concerns of how higher occurrence of extreme weather conditions will affect the mobilization of metals has occurred. Understanding of the mobilizations of metals in different catchment conditions is therefore important knowledge for preparation of risk analyzes to protect ecosystems from toxic effects. The aim of this study is to compare accumulation of metals in sediments from marine and limnic environments to investigate how lakes effects the mobilization of metals in catchments consisting of acid sulfate soil. Answering the questions of accumulation differences between the catchments and how organic matter affects the mobilization and accumulation of metals. Sediment cores were collected in two different catchment areas, known to be affected by acid sulfate soils, in Västerbotten county. 22 different elements were analyzed by x-ray fluorescence spectroscopy and Loss-on-ignition (LOI) was used as a proxy for organic matter. The results indicate that draining of land areas, often due to agriculture and deforestation, increases mobilization and accumulation of metals correlated with both organic and lithogenic fractions to a large extent. However, elements such as S, Ni, Zn, Fe, Cu, Na, Mg, Al, Rb, Sr and Zr are derived from mobilization from acid sulfate soils where elements with high correlation with organic matter accumulates in limnic environment conditions.

Preclinical results support the use of N-methyl D-aspartate receptor (NMDAR) modulators for cognition enhancement therapeutics. Pregnenolone sulfate (PregS) is a neuroactive steroid derived from cholesterol that augments long term potentiation (LTP) in hippocampal slices and improves memory performance in rats and mice. At micromolar concentrations, PregS is a subtype selective positive allosteric modulator of NMDARs at NR2A and NR2B containing receptors, and at concentrations ranging from pM - nM induces NMDAR-dependent dopamine release in the striatum and from striatal synaptosomes. In this report, we observe that micromolar [PregS] induces an increase in levels of neuronal intracellular calcium ([Ca^2+]i) and surface NMDARs in cortical neurons. Moreover, our results show that PregS stimulated upregulation of surface NR1 subunits in cortical neurons is dependent on NMDARs but independent of channel activity. As PregS has been detected in brain at bulk concentrations of 0.1 nM to 5 nM, we asked whether low, picomolar concentrations of PregS might alter [Ca^2+] levels. We report here that PregS increases [Ca^2+]i signal in cortical neurons in a voltage-gated Na^+ channel and NMDAR-NR2B dependent manner with an EC50 of ~2 pM, at least 6 orders of magnitude higher affinity than its rapid potentiating effect upon the NMDAR-mediated ionotropic response, and within the range of PregS detected in bulk brain tissue. Additionally, calcium (Ca^2+) activation of cyclic AMP response element binding protein (CREB) is critical to the protein synthesis-dependent component of LTP and important in associated behavioral measures of learning and memory. Increased [Ca^2+]i levels are known to induce CREB activation and we now show that 50 pM PregS induces a 44 ± 13% increase in the ratio of pCREB to total CREB that is dependent upon ERK signaling and canonical excitatory synaptic transmission: this includes voltage gated Na+ channels, NMDARs, and voltage-gated Ca^2+ channel activation. The results taken together indicate that PregS may be a useful platform for the development of high-affinity positive modulators of NMDAR-signaling that can be used as cognitive enhancers to treat a variety of neurological disorders: such as Alzheimer's disease, Parkinson's disease, and schizophrenia.

Atmospheric deposition of nitrogen has been implicated in the destruction of seagrass beds and in the decline of water quality of Tampa Bay, Florida. The objective of this research was to determine the tendency for air masses of different origins to wet-deposit nitrate and ammonium species to the bay. Precipitation chemistry data was obtained via the NADP AIRMoN Gandy Bridge monitoring site for the period of 1 August 1996 through 31 December 2000. Rainfall events were classified by using the NOAA HYSPLIT trajectory model, precipitation chemistry data, and tropical storm history data. Average nitrate and ammonium concentrations and nitrogen fluxes were calculated based upon the chosen categories. The average annual nitrogen flux for nitrate and ammonium were 2.1 kg/ha/yr and 1.4 kg/ha/yr, respectively. For trajectory-classified data, the lowest nitrate and ammonium nitrogen fluxes were observed with air masses from the west and south, over the Gulf of Mexico. The highest ammonium nitrogen flux was seen from trajectories from the east, while local trajectories demonstrated the highest average nitrate nitrogen flux. For chemically-classified data, the highest nitrate and ammonium fluxes were associated with the local combustion classification. Rainfall from tropical weather systems deposited lower average nitrate nitrogen fluxes than non-tropical events, but ammonium nitrogen fluxes were the same between tropical and non-tropical precipitation. Even the events representing the cleanest air masses contributing precipitation to Tampa Bay had nitrate and ammonium concentrations more than two times the background concentrations associated with the northern hemisphere.

A lead sensitive indicator electrode was constructed with a 70 percent lead and 30 percent mercury amalgam billet. Sulfate concentrations in pure solutions, natural waters, and soil saturation extracts were determined potentiometrically using the lead-mercury amalgam indicator electrode and a standard calomel reference electrode. Sulfate concentrations over the range 0.4 to 20 milliequivalents sulfate per liter were determined with an automatic titrator and compared to a turbidimetric method for accuracy and precision. The values obtained by the two methods from twelve saturation extracts and three subsurface drainage waters were not significantly different and the potentiometric method was generally more precise. The automatic sulfate titration method has the advantages of increased sensitivity and speed.

abstract: Humans are exposed up to thousands of per- and polyfluoroalkyl substances (PFAS) in the environment, but most of the research and action has been directed towards only two PFAS compounds. These two compounds are part of a subcategory of PFAS called perfluoroalkyl acids (PFAAs). It has been a challenge for the environmental community to mitigate risks caused by PFAAs due to their high persistence and lack of effective measures to remove them from the environment, especially in heavily impacted areas like fire-training sites. The goal of this work was to further answer some questions regarding the removal of PFAAs in the environment by looking at anion exchange resin characteristics and presence of a competing compound, natural organic matter (NOM), in the adsorption of environmentally relevant PFAS compounds including the two often monitored 8-carbon chain PFAAs. Two different resins were tested with two forms of counterions, in both groundwater and NOM impacted groundwater. Resin polymer matrix was the most important property in the adsorption of PFAAs, the two resins used A520E and A860 had similar properties except for their matrices polystyrene (PS) and polyacrylic (PA), respectively. The PS base is most effective at PFAAs adsorption, while the PA is most effective at NOM adsorption. The change in the counterion did not negatively affect the adsorption of PFAAs and is, therefore, a viable alternative for future studies that include regeneration and destruction of PFAAs. The presence of NOM also did not significantly affect the adsorption of PFAAs in the PS resin A520E, although for some PFAAs compounds it did affect adsorption for the PA resin. Ultimately, PS macroporous resins with a strong Type I or Type II base work best in PFAAs removal. / Dissertation/Thesis / Masters Thesis Engineering 2019

The green alga, Selenastrum capricornutum Printz, was used in an algal bioassay to determine the toxic properties of copper in various natural lake waters of Oregon. Lake water was collected and brought back to the laboratory where it was treated with various copper concentrations and inoculated with a cell suspension of the test alga. Growth of the alga was determined by direct cell counts. The copper ion activity, pH, and absorbance of the test cultures were also determined. The growth of the alga was ·found to depend upon the water tested and also upon the copper concentration used.