京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19517号 / 理博第4177号 / 新制||理||1600(附属図書館) / 32553 / 京都大学大学院理学研究科化学専攻 / (主査)教授 藤井 紀子, 教授 三木 邦夫, 教授 杉山 弘 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The redox cycling of iron is intimately linked to the cycling of C, S, N, P as well as the speciation, mobility, and bioavailability of various toxic contaminants in soils and sediments. Within these environments, the cycling of iron is catalytically driven by iron-oxidizing (FeOB) and iron reducing bacteria (FeRB) which mediate the formation, transformation, and dissolution of various iron-bearing minerals. Under oxic conditions, FeOB promote the formation of iron oxides on or in close proximity of their cell walls and extracellular polymeric substances, and such composite, termed biogenic iron oxides (BIOS), offers highly reactive heterogenous sites that efficiently immobilize trace metals and contaminants alike. However, under reducing conditions, FeRB mediate the reductive dissolution of BIOS and in turn lead to the remobilization of associated contaminants. Conversely, contaminants may become immobilized by secondary iron minerals that form from the metabolic activity of FeRB. Therefore, determining the factors that influence the reactivity of BIOS, as well as the formation of secondary iron minerals is of critical importance to develop a better understanding of the geochemical cycling of iron and in turn the transport of contaminants in the environment. This thesis investigated (1) the impact of simulated diagenesis (ageing for ~5 years at 4ºC) on the mineral stability and reactivity of BIOS towards reduction by Shewanella putrefaciens CN32, (2) the effects of phosphate at an environmentally relevant (10µM) and excess (3.9mM) concentration on the rates and extent of microbial reduction of synthetic 2-line ferrihydrite and BIOS, as well as the formation of secondary iron minerals, and (3) the impact of sterilization by γ-irradiation on the mineral stability and reactivity of BIOS. It was found that simulated diagenesis did not affect the mineralogical composition of BIOS but significantly lowered the reactivity of BIOS towards microbial reduction. The concentration of phosphate was found to have contrasting effects on the rates of reduction of ferrihydrite and BIOS, but in general, excess concentration of phosphate enhanced the extent of Fe(III) reduction. The formation of a specific secondary iron mineral was also found to depend on the concentration of phosphate, as well as, in the case for BIOS, the presence of intermixed cell derived organic matter. γ-irradiation did not alter the mineralogy and reactivity of BIOS towards microbial reduction, and it was concluded to be a suitable technique to sterilize BIOS.

Bentonite clay is intended to form one of the barriers in most repositories of spent nuclear fuel located in granite. One important function of the bentonite barrier is to retard transport of radionuclides in the event of waste canister failure. Bentonite has a high sorption capacity of cations and its main constituent is montmorillonite. In contact with groundwater of low ionic strength, montmorillonite colloids can be released from bentonite and thereby control transport of radionuclides sorbed onto the colloids. In colloid transport in bedrock fractures, size separation of clay colloids may occur due to physical and chemical interactions with the bedrock fracture surface. This may enhance or retard the overall transport of radionuclides, depending on the sorption capacities and stability of the differently sized clay colloids. The bentonite barrier will be exposed to γ-radiation from the spent nuclear fuel. Irradiation affects surface-related properties of bentonite. If an average sorption capacity value cannot be used for all colloid sizes or if sorption is affected by exposure to γ-irradiation, corrected sorption capacity values would give higher resolution in current reactive transport models. In order to study the size separation process, a protocol was developed and successfully applied to fractionate montmorillonite into different-sized colloid suspensions by means of sequential or direct centrifugation. The stability and sorption capacity were studied using these fractions. Both stability and sorption capacity were found to be similar for all colloid sizes. Bentonite exposed to γ-radiation sorbed less divalent cations with increasing radiation dose. The effect was not large enough to have any impact on diffusion. The presence of bentonite enhanced irradiation-induced corrosion of copper under anaerobic atmosphere. An average sorption capacity value for montmorillonite can be used for all colloid sizes in reactive transport models. The effect of γ-irradiation on sorption capacity is sufficiently large to require consideration in transport modelling. / Bentonite är planerad som en av barriärerna i de flesta slutförvar av använt kärnbränsle. Bentonite har en hög sorptionskapacitet för katjoner. Den huvudsakliga beståndsdelen av bentonit är montmorillonit. Montmorillonitkolloider kommer att frigöras från bentonitbufferten i kontakt med grundvatten av låg jonstyrka och på så vis styra transporten av sorberade radionuklider. Under den kolloidala transporten i bergsprickorna kan en separation med avseende på storlek uppstå genom interaktioner mellan kolloiderna och bergytan. Detta kan få till följd att den genomsnittliga transporten av radionuklider bromsas eller tilltar beroende på sorptionskapaciteten och stabiliteten av de olika kolloidstorlekarna. Bentonitbarriären kommer även att utsättas för γ-bestrålning från det använda kärnbränslet, vilket påverkar dess ytrelaterade egenskaper. Om inte ett medeltal för sorptionskapaciteten är giltigt för alla kolloidstorlekar eller om sorptionen påverkas av γ-bestrålning, behövs nya sorptionskapaciteter bestämmas och impliceras för noggrannare transportmodeller. En metod för att separera montmorillonitkolloider med avseende på storlek via direkt och stegvis centrifugering har utvecklats. Stabiliteten och sorptionskapaciteten för dessa fraktioner har studerats. Både stabilitet och sorptionskapacitet visade sig vara lika för alla kolloidstorlekar. Bestrålad bentonit sorberar mindre andel divalenta katjoner med ökad dos bestrålning. Effekten är dock inte stor nog för att slå igenom i diffusionsexperimenten. Förekomst av bentonit ökar även den strålningsinducerade korrosionen av koppar under anaeroba förhållanden. Ett medelvärde för sorptionskapaciteten kan användas för alla kolloidstorlekar i transportmodeller. Effekten av γ-bestrålning är dock stor nog för att implementeras i modellerna. / <p>QC 20150213</p>

Selected fungal strain for production of raw-starch-digesting enzyme by solid state fermentation was improved by sequential exposures to γ-irradiation of Co60, ultraviolet and treatments with Nmethyl-N'-nitrosoguanidine. Mutant Aspergillus sp. CXN2-3A was chosen and its production of raw-starch-digesting enzyme (RSDE) was improved 2 folds higher than that of wild type. Optimal condition for the production of the enzyme using wheat bran as the substrate was accomplished for the CXN2-3A. With the optimal fermentation condition and the solid medium supplemented with urea and NH4NO3, CoSO4, Tween 80, 1% glucose, CXN2-3A produced RSDE 19.23 folds higher than wild type cultured in pre-optimized condition and un-supplemented medium. / Chủng nấm chọn lọc sản xuất enzyme thủy phân tinh bột bằng cách lên men trạng thái rắn, chủng nấm được cải thiện bằng chiếu xạ tia cực tím, tia Co60 và các phương pháp xử lí với N-methyl-N'-nitrosoguanidine. Mutant Aspergillus sp. CXN2-3A, đã được lựa chọn để sản xuất enzyme (RSDE) thủy phân tinh bột sống cải thiện cao hơn 2 lần so với chủng dại. Điều kiện tối ưu cho việc sản xuất các enzyme bằng cách sử dụng cám, lúa mì đã được thực hiện cho CXN2-3A. Với điều kiện lên men xốp tối ưu và bổ sung urê và NH4NO3, CoSO4, Tween 80, 1% glucose, CXN2-3A đã sản xuất RSDE cao gấp 19,23 lần so với kiểu dại ở cùng điều kiện.

Over one million hip prostheses are implanted in patients worldwide each year and the need is increasing as the patient group of younger and more active patients is increasing. Many parameters affect the longevity of the implant, where aseptic loosening caused by wear debris is the most common reason for revision. To be able to monitor wear in vivo and also to predict the longevity of new materials for hip prostheses are therefore important issues in this interdisciplinary research area. This thesis comprise a true non-invasive 3D method for determination of acetabular cup wear using Computed Tomography (CT) intended for clinical routine use in order to plan for a revision. It also comprises investigations of the influence of surface roughness and sterilization method in wear testing of materials for hip prostheses. Mainly wear of ultra high molecular weight polyethylene (UHMWPE) was investigated since it is the most common soft bearing in hip prostheses. The 3D-CT method was found to be easy to use and showed an accuracy and repeatability at a clinical relevant level for acetabular cup wear. It should lend itself well to semi-automation. The influence of surface roughness was investigated with both a multidirectional pin-on-disk machine and with a hip simulator. A new low friction coating, Micronite, was also evaluated with the pin-on-disk machine. This coating showed potential for use in artificial joints, but further investigations are needed. In the hip simulator test, it was found that not only a rougher counter surface increased wear, but also sterilization by γ-irradiation increased wear of UHMWPE cups. / QC 20101117

<p>Over one million hip prostheses are implanted in patients worldwide each year and the need is increasing as the patient group of younger and more active patients is increasing. Many parameters affect the longevity of the implant, where aseptic loosening caused by wear debris is the most common reason for revision. To be able to monitor wear in vivo and also to predict the longevity of new materials for hip prostheses are therefore important issues in this interdisciplinary research area. This thesis comprise a true non-invasive 3D method for determination of acetabular cup wear using Computed Tomography (CT) intended for clinical routine use in order to plan for a revision. It also comprises investigations of the influence of surface roughness and sterilization method in wear testing of materials for hip prostheses. Mainly wear of ultra high molecular weight polyethylene (UHMWPE) was investigated since it is the most common soft bearing in hip prostheses. The 3D-CT method was found to be easy to use and showed an accuracy and repeatability at a clinical relevant level for acetabular cup wear. It should lend itself well to semi-automation. The influence of surface roughness was investigated with both a multidirectional pin-on-disk machine and with a hip simulator. A new low friction coating, Micronite, was also evaluated with the pin-on-disk machine. This coating showed potential for use in artificial joints, but further investigations are needed. In the hip simulator test, it was found that not only a rougher counter surface increased wear, but also sterilization by γ-irradiation increased wear of UHMWPE cups.</p>

Selected fungal strain for production of raw-starch-digesting enzyme by solid state fermentation was improved by sequential exposures to γ-irradiation of Co60, ultraviolet and treatments with Nmethyl-N'-nitrosoguanidine. Mutant Aspergillus sp. CXN2-3A was chosen and its production of raw-starch-digesting enzyme (RSDE) was improved 2 folds higher than that of wild type. Optimal condition for the production of the enzyme using wheat bran as the substrate was accomplished for the CXN2-3A. With the optimal fermentation condition and the solid medium supplemented with urea and NH4NO3, CoSO4, Tween 80, 1% glucose, CXN2-3A produced RSDE 19.23 folds higher than wild type cultured in pre-optimized condition and un-supplemented medium. / Chủng nấm chọn lọc sản xuất enzyme thủy phân tinh bột bằng cách lên men trạng thái rắn, chủng nấm được cải thiện bằng chiếu xạ tia cực tím, tia Co60 và các phương pháp xử lí với N-methyl-N'-nitrosoguanidine. Mutant Aspergillus sp. CXN2-3A, đã được lựa chọn để sản xuất enzyme (RSDE) thủy phân tinh bột sống cải thiện cao hơn 2 lần so với chủng dại. Điều kiện tối ưu cho việc sản xuất các enzyme bằng cách sử dụng cám, lúa mì đã được thực hiện cho CXN2-3A. Với điều kiện lên men xốp tối ưu và bổ sung urê và NH4NO3, CoSO4, Tween 80, 1% glucose, CXN2-3A đã sản xuất RSDE cao gấp 19,23 lần so với kiểu dại ở cùng điều kiện.