Development of methods for the determination of bismuth and thallium in geological materials and their significance for the Cretaceous-Tertiary boundary event : a thesis presented in partial fulfilment for the degree of Master of Science, Department of Chemistry and Biochemistry, Massey University, New Zealand

Solvent extraction methods have been developed for the determination of thallium and bismuth in rocks. The method for thallium is based on the extraction of the chlorocomplex into methylisobutyl ketone followed by removal of the interfering chloride ion as insoluble silver chloride. The method for bismuth is based on the extraction of a stable metal complex with ammonium pyrrolidine dithiocarbamate into methylisobutyl ketone. Both elements are analysed on a electrothermal graphite furnace atomic absorption spectrometer. Tests on the efficiencies of the methods showed a good precision and accuracy with limits of detection of 9.5 ng/ml (ppb) for thallium and 20 ng/ml (ppb) for bismuth. Recovery studies on synthetic samples showed recoveries of >99.9% for both elements. A geochemical study was performed on a Cretaceous-Tertiary boundary site located near Flaxbourne River, Ward, New Zealand. Investigations were carried out to determine the enrichment of thallium and bismuth in the stratigraphic column. The results show a good correlation between the iridium and thallium content throughout the rock sequence, but the samples have very low bismuth contents. This is indicative of the different geochemical behavior of bismuth to other chalcophiles. These findings do not contradict the impact theory initially hypothesized by Alvarez et al. (1980), and instead suggest that bismuth's mobility and solubility are far greater than those of thallium and the other chalcophile elements enriched in the Flaxbourne River sequence. This results in the leaching of bismuth from the stratigraphic column by sea water after deposition

The platinum group metals in iron meteorites : thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry, Department of Chemistry and Biochemistry, Massey University, Palmerston North, New Zealand

Solvent extraction methods have been developed for the determination of Ru, Pd and Pt in iron meteorites. The method for Ru is based on the oxidation of this element in HCl solutions with sodium periodate followed by extraction of the tetroxide into CHCl3. The CHCl3 phase is then removed to a HNO3-NaIO4 "keeper" solution for storage up to 17 hours prior to analysis. The method for Pd and Pt entails simultaneous extraction of their stable iodocomplexes into methylisobutyl ketone after removal of Fe(III) as the chlorocomplex. The digestion of the samples with reference to these elements has also been investigated. All three elements were determined by the graphite furnace atomic absorption spectrometry technique. The limit of detection was lowered by increasing the volume of organic phase placed in the graphite furnace. The lowest absolute detection limits achieved in this study were 0.5 ng for Ru, 0.5 ng for Pd and 5 ng for Pt. The platinum group metal values for 108 authentic iron meteorites were subjected to Principal Components Analysis and Discriminant Analysis. These procedures confirmed the validity of the classification of iron meteorites developed over the past 25 years, but highlighted poor fits for some individual iron meteorites within a group. Possible reclassification of these members was evaluated after consideration of the meteorite's morphological features. The cases for the merging of some groups were investigated and discussed with reference to the chemical features of those groups. The data obtained also revealed several cases of meteorite pairings (related members of a single meteorite shower catalogued as separate meteorites), instances of the mislabelling of museum fragments and two putative meteorites which proved to consist of man-made materials

Association study of transition of laboratory marker levels and transition of disease activity of atopic dermatitis patients treated with dupilumab

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Assessment Report of Doctoral Theses

新規代替冷媒用ヒートポンプシステムの最適化に関する研究[平良]Wave-particle and wave-wave interactions in a high energy astrophysical plasma[松清]プラズマディスプレイ用マイクロ放電内の電子挙動のレーザー散乱法による研究[野口]Mechanical and Thermal Properties of Oxide Glasses[稲葉]シリカオパールを用いたフォトニッククリスタルの作製とその光学特性[隅岡]反応イオンを選別したメタン化学イオン化質量スペクトル[田中]磁気光学材料による送電線電流の光計測方法に関する研究[林]バルト系ペロブスカイト型酸化物を用いた酸素分離に関する研究[草場]フェムト秒過渡反射率測定による金単結晶電極／水溶液界面における伝導電子の超高速熱平衡化過程に関する研究[杉山]弱配位性の溶媒や対アニオン種によって活性化された\u22裸の\u22リチウムイオンのルイス酸性に関する研究[池田]トロポノイドッインの液晶性発現に及ぼす双極子モーメントの向きと連結鎖や末端基の長さに関する研究[武本]ルテニウム多核カルボニル錯体触媒を用いるシランの活性化と触媒的含酸素有機化合物化学変換反応の開発[井浦]アミジナート配位子を有する高反応性ルテニウム錯体の合成と反応[林田]ルイス酸触媒下でのオキシム，ヒドラゾン共役付加反応[仲間]Oxidation Mechanism of Tin Oxide Layer of Zircaloy and Zircaloy-type Alloys[Sosiati]極短パルス・高出力レーザー照射を受ける物質の熱過渡現象解析に関する研究[帆足]都市高温化の緩和とパッシブ手法による環境負荷低減に関する研究[三坂]磁場下における立方体容器内の液体金属の自然対流に及ぼすゼーベック係数の影響ならびに安定成層空気の磁場による対流誘起[金田]円筒容器内の空気の自然対流に及ぼす磁場効果[牧]純冷媒R134aおよび非共沸混合冷媒R407Cの千鳥配列フィン付き管群内凝縮に及ぼすフィン形状の影響に関する研究[金]臨界断面を有する矩形柱周囲流れに関する数値解析的研究[林]Acceleration and thermalization of charged particles by large amplitude MHD waves in space plasma[蔵満]Seasonal Variability of the Oceanic Condition around Java, Indonesia[Suhendar]日本海における中層水の形成と循環論文調査委員[川村]ニトリルオキシド環状付加による有用多官能基化合成ブロックの構築[松田]MOLECULAR ANALYSIS ON NON-COVALENT ASSOCIATION OF HYDROCARBON NETWORK AND TRANSFORMATION OF MoS COMPLEX CATALYST IN UP GRADING OF COAL AND HEAVY RESID[渡邉]冷媒R134aの扁平微細多孔管内凝縮に関する研究[中下]Measurements of Thermal Conductivity and Thermal Diffusivity of High Temperature Molten Materials using Transient Short-Hot-Wire Method[Hendro]重質油の非定常噴霧燃焼における問題点とその解決法に関する研究[石田]瀬戸内海の低次生物生産構造[林]Stereoselective Living Polymerization of Styrene Derivatives[川辺

学位論文審査報告

新規代替冷媒用ヒートポンプシステムの最適化に関する研究[平良]Wave-particle and wave-wave interactions in a high energy astrophysical plasma[松清]プラズマディスプレイ用マイクロ放電内の電子挙動のレーザー散乱法による研究[野口]Mechanical and Thermal Properties of Oxide Glasses[稲葉]シリカオパールを用いたフォトニッククリスタルの作製とその光学特性[隅岡]反応イオンを選別したメタン化学イオン化質量スペクトル[田中]磁気光学材料による送電線電流の光計測方法に関する研究[林]バルト系ペロブスカイト型酸化物を用いた酸素分離に関する研究[草場]フェムト秒過渡反射率測定による金単結晶電極／水溶液界面における伝導電子の超高速熱平衡化過程に関する研究[杉山]弱配位性の溶媒や対アニオン種によって活性化された"裸の"リチウムイオンのルイス酸性に関する研究[池田]トロポノイドッインの液晶性発現に及ぼす双極子モーメントの向きと連結鎖や末端基の長さに関する研究[武本]ルテニウム多核カルボニル錯体触媒を用いるシランの活性化と触媒的含酸素有機化合物化学変換反応の開発[井浦]アミジナート配位子を有する高反応性ルテニウム錯体の合成と反応[林田]ルイス酸触媒下でのオキシム，ヒドラゾン共役付加反応[仲間]Oxidation Mechanism of Tin Oxide Layer of Zircaloy and Zircaloy-type Alloys[Sosiati]極短パルス・高出力レーザー照射を受ける物質の熱過渡現象解析に関する研究[帆足]都市高温化の緩和とパッシブ手法による環境負荷低減に関する研究[三坂]磁場下における立方体容器内の液体金属の自然対流に及ぼすゼーベック係数の影響ならびに安定成層空気の磁場による対流誘起[金田]円筒容器内の空気の自然対流に及ぼす磁場効果[牧]純冷媒R134aおよび非共沸混合冷媒R407Cの千鳥配列フィン付き管群内凝縮に及ぼすフィン形状の影響に関する研究[金]臨界断面を有する矩形柱周囲流れに関する数値解析的研究[林]Acceleration and thermalization of charged particles by large amplitude MHD waves in space plasma[蔵満]Seasonal Variability of the Oceanic Condition around Java, Indonesia[Suhendar]日本海における中層水の形成と循環論文調査委員[川村]ニトリルオキシド環状付加による有用多官能基化合成ブロックの構築[松田]MOLECULAR ANALYSIS ON NON-COVALENT ASSOCIATION OF HYDROCARBON NETWORK AND TRANSFORMATION OF MoS COMPLEX CATALYST IN UP GRADING OF COAL AND HEAVY RESID[渡邉]冷媒R134aの扁平微細多孔管内凝縮に関する研究[中下]Measurements of Thermal Conductivity and Thermal Diffusivity of High Temperature Molten Materials using Transient Short-Hot-Wire Method[Hendro]重質油の非定常噴霧燃焼における問題点とその解決法に関する研究[石田]瀬戸内海の低次生物生産構造[林]Stereoselective Living Polymerization of Styrene Derivatives[川辺