La région Centre Ouest du Brésil possède des massifs ultrabasiques (UB) avec des manteaux latéritiques représentants des réserves et ainsi des ressources économiques importantes de Ni. Ces massifs nickélifères permettent d’étudier le cycle du Ni sous contraintes anthropiques par une approche pluridisciplinaire, associant caractérisations chimiques, mesures physiques de sa spéciation solide, et traçage isotopique des sources et des processus affectant le nickel. Cette thèse focalisée sur l’utilisation des isotopes du Ni comme traceur a eu pour but d’identifier la signature isotopique au sein de plusieurs compartiments en interactions les uns avec les autres (roche mère, saprolite, latérite, sol et plantes) et d’associer les fractionnements observés aux processus biogéochimiques. De plus, du fait de leurs ressources économiques, les massifs étudiés, Barro Alto et Niquelândia, subissent une pression anthropique importante, minière et métallurgique. Ainsi, ils offrent une opportunité unique d’étudier le fractionnement isotopique du nickel associé à son cycle anthropique, et voir s’il est possible d’identifier la contribution anthropique dans le cycle naturel du Ni par sa signature isotopique. Les résultats ont montré que l’altération de roches UB conduit à un fractionnement isotopique du Ni, se traduisant par une perte en isotopes lourds de la phase solide, soit un Δ⁶⁰Ni de - 0,47 ‰ entre la roche mère et le top-sol. Ce fractionnement semble associé au moins en partie à l’incorporation et à la sorption des isotopes légers du Ni sur les oxydes de Fe lors de la remobilisation du Ni au cours de l’altération. Cet enrichissement en isotopes légers du Ni dans la partie solide conduit à une composition isotopique en Ni plus lourde dans la phase dissoute (eaux du massifs : 0.50 ‰ < δ⁶⁰Ni < 0,70 ‰). La zone saprolitique présente une variation importante de signature isotopique allant pour δ⁶⁰Ni de -0,04 ‰ à 1,41 ‰. Pour les échantillons présentant une signature isotopique lourde, le Ni se trouve principalement au sein de la serpentine fortement substitué, quand les signatures plus légères sont en lien avec une proportion de Ni plus importante au sein de la goethite. Dans un système comme celui-ci avec un nombre important de phases porteuses de Ni, il est cependant très difficile d’établir un lien entre la spéciation solide et l’isotopie du Ni. Le rôle des plantes dans le cycle du Ni a été abordé en étudiant le fractionnement isotopique du Ni dans trois espèces de plantes hyperaccumulatrices de Ni et deux espèces de plantes tolérantes. Il existe un fractionnement isotopique lors du transfert de Ni de la tige vers la feuille, qui est systématiquement enrichie en isotopes lourds du Ni. Les feuilles sont les compartiments des plantes où les teneurs en Ni sont les plus importantes. L’enrichissement en isotopes lourds du Ni des feuilles par rapport aux sols (- 1,05 ± 0,03 ‰ < Δ⁶⁰Ni_sol-feuilles < - 0,06 ± 0,12 ‰) semble indiquer que la restitution et la décomposition de cette matière organique au niveau du sol s’accompagnera d’un apport en isotopes lourds du Ni dans le sol. L’activité pyrométallurgique entraîne un fractionnement isotopique lors du processus de fusion en conditions réductrices qui conduit à la formation des scories de réduction. Ces résidus présentent un enrichissement en isotopes lourds (δ⁶⁰Ni = 0,18 ± 0,05 ‰) par rapport au matériel entrant (δ⁶⁰Ni = 0,08 ± 0,08 ‰) et au produit final, le FeNi (δ⁶⁰Ni = 0,06 ± 0,02 ‰). Enfin, cette étude montre que l’utilisation des isotopes du Ni pour tracer le Ni « anthropique » et le distinguer du Ni naturel possède certaines limites en raison du faible fractionnement induit par les processus pyrométallurgiques aux regards de la grande variabilité des échantillons naturels au sein de la littérature (-1.03 ‰ < δ⁶⁰Ni < 2.50 ‰). / The Centre region the West of Brazil possesses ultramafic massifs (UM) with coats lateritic representatives of the reserves and so the important economic resources of Ni. These nickelifere massifs allow to study the cycle of Ni under anthropological constraints by a multidisciplinary approach, associating chemical characterizations, physical measures, solid speciation, and the isotopic drawing of sources and the processes affecting the nickel. This work focused on the use of the isotopes of Ni as tracer aimed at identifying the isotopic signature within several compartments in interactions some with the others (source rock, saprolite, laterite, soil and plants) and to associate the fractionation observed in the biogeochemical processes. Furthermore, because of their economic resources, the studied massifs, Barro Alto and Niquelândia, undergo an important, mining and metallurgical anthropological pressure. So, they offer an opportunity to study the isotopic fractionation of the nickel associated with its anthropological cycle, and to see if it is possible to identify the anthropological contribution in the natural cycle of Ni by its isotopic signature. The results showed that the weathering of rocks UB leads to an isotopic fractionation of Ni, being translated by a loss in heavy isotopes of the solid phase with a Δ⁶⁰Ni of - 0,47 ‰ between the bedrock and the top-soil. This division seems associated at least partially with the incorporation and with the sorption of the light isotopes in iron oxides during the remobilization of Ni. This enrichment in light isotopes in the solid part leads to a heavier isotopic composition in the dissolved phase (waters of massifs: 0.50 ‰ < δ⁶⁰Ni < 0,70 ‰). The saprolitic zone presents an important variation of isotopic signature (δ⁶⁰Ni) from -0,04 ‰ to 1,41 ‰. For samples presenting a heavy isotopic signature, Ni is mainly within the serpentine strongly substituted, when the lighter signatures are in connection with a proportion of Ni more important within the goethite. In a system as this one with a significant number of Ni-bearing phases, it is however very difficult to establish a link between the solid speciation and the isotopic composition. The role of plants in the cycle of Ni was approached by studying the isotopic fractionation of Ni in three species of hyperaccumulating plants of Ni and two species of tolerant plants. There is an isotopic fractionation during the transfer of Ni between the stem and the leaf, which is systematically enriched in heavy isotopes of Ni. The leaves are the compartments of the plants where the Ni contents are the most important. The enrichment in heavy isotopes of Ni in leaves with regard to soils (- 1,05 ± 0,03 ‰ < Δ⁶⁰Ni_sol-feuilles < - 0,06 ± 0,12 ‰) seems to indicate that the return and the decomposition of this organic matter at soil level will come along with a contribution in heavy isotopes of Ni in the soil. The pyrometallurgical activity lead to an isotopic fractionation during the smelting process in reducing conditions which leads to the formaton of the reduction slag. These slags present an enrichment in heavy isotopes (δ⁶⁰Ni = 0,18 ± 0,05 ‰) compared with the feeding material (δ⁶⁰Ni = 0,08 ± 0,08 ‰) and the end product, the FeNi (δ⁶⁰Ni = 0,06 ± 0,02 ‰). Finally, this study shows that the use of the isotopes of Ni to decipher the Ni anthropogenic and natural is limited because of the low fractionation induced by the pyrometallurgical processes in the looks of the big variability of the natural samples within the literature (-1.03 ‰ < δ⁶⁰Ni < 2.50 ‰).

Grass-dominated ecosystems in many regions around the world have experienced increased abundance of woody plants during the past 100 yrs. In the Rio Grande Plains of southern Texas, subtropical woodlands, dominated by C3 trees/shrubs capable of symbiotic N2-fixation, have become significant components of landscapes that were once dominated by C4 grasslands. Upland areas in this region now consist of small discrete clusters and large groves of woody vegetation embedded in a grassy matrix, while lower-lying portions of the landscape are dominated by closed-canopy woodlands. I used soil δ13C in conjunction with aerial photography and geostatistics to quantify landscape-scale vegetation dynamics in uplands of this savanna parkland. Spatial patterns of soil δ13C in grids and transects traversing woody patches indicated larger woody groves were formed from small discrete clusters of woody plants that spread laterally and eventually coalesced. Soil δ13C contour maps revealed some clusters are currently growing rapidly towards each other and might coalesce into groves in the near future, while some clusters remained relatively stable. Kriged maps of soil δ13C provided a strong spatial context for future studies aimed at understanding the functional consequences of this change in landscape structure. The dominant invading woody plant, honey mesquite (Prosopis glandulosa), was important in determining the spatial pattern of soil δ13C, supporting the hypothesis that they serve as recruitment foci and facilitate the establishment of subordinate woody species. Leaf δ15N values suggested that the N2-fixing mesquite influenced the N nutrition of nearby non-N2-fixing shrubs, thus, suggesting a mechanism by which mesquite could facilitate establishment of other woody species. In closed-canopy drainage woodlands, however, spatial patterns of soil δ13C were no longer controlled by the presence of mesquite, but by the amount of soil organic carbon and soil texture. The positive correlation between silt+clay and soil δ13C indicates that the formation of organomineral complexes and microaggregates may slow SOC turnover rates and favor the persistence of C4-derived SOC from the original grassland. This study enhances our understanding of potential patterns, causes and consequences of grassland to woodland conversions which are underway today in many grass-dominated ecosystems around the world.

Grass-dominated ecosystems in many regions around the world have experienced increased abundance of woody plants during the past 100 yrs. In the Rio Grande Plains of southern Texas, subtropical woodlands, dominated by C3 trees/shrubs capable of symbiotic N2-fixation, have become significant components of landscapes that were once dominated by C4 grasslands. Upland areas in this region now consist of small discrete clusters and large groves of woody vegetation embedded in a grassy matrix, while lower-lying portions of the landscape are dominated by closed-canopy woodlands. I used soil δ13C in conjunction with aerial photography and geostatistics to quantify landscape-scale vegetation dynamics in uplands of this savanna parkland. Spatial patterns of soil δ13C in grids and transects traversing woody patches indicated larger woody groves were formed from small discrete clusters of woody plants that spread laterally and eventually coalesced. Soil δ13C contour maps revealed some clusters are currently growing rapidly towards each other and might coalesce into groves in the near future, while some clusters remained relatively stable. Kriged maps of soil δ13C provided a strong spatial context for future studies aimed at understanding the functional consequences of this change in landscape structure. The dominant invading woody plant, honey mesquite (Prosopis glandulosa), was important in determining the spatial pattern of soil δ13C, supporting the hypothesis that they serve as recruitment foci and facilitate the establishment of subordinate woody species. Leaf δ15N values suggested that the N2-fixing mesquite influenced the N nutrition of nearby non-N2-fixing shrubs, thus, suggesting a mechanism by which mesquite could facilitate establishment of other woody species. In closed-canopy drainage woodlands, however, spatial patterns of soil δ13C were no longer controlled by the presence of mesquite, but by the amount of soil organic carbon and soil texture. The positive correlation between silt+clay and soil δ13C indicates that the formation of organomineral complexes and microaggregates may slow SOC turnover rates and favor the persistence of C4-derived SOC from the original grassland. This study enhances our understanding of potential patterns, causes and consequences of grassland to woodland conversions which are underway today in many grass-dominated ecosystems around the world.

Thesis (Ph. D.)--Florida State University, 2005. / Advisor: Jeffrey P. Chanton, Florida State University, College of Arts and Sciences, Dept. of Oceanography. Title and description from dissertation home page (viewed Jan. 26, 2006). Document formatted into pages; contains xii, 145 pages. Includes bibliographical references.

Dans un contexte de perturbations du système Terre, il est important d'améliorer notre compréhension des cycles géochimiques déterminant la composition chimique de l'atmosphère. Les aérosols de sulfate sont directement émis par les sources (naturelle ou anthropique) ou bien produit par des gaz soufrés précurseurs. Ils participent à l'augmentation de la pollution urbaine impliquant des risques sanitaires élevés et à l'augmentation des particules atmosphériques qui détermine la chimie atmosphérique, le bilan radiatif terrestre et in fine l'évolution du climat. Pour ces raisons, le cycle du soufre est un enjeu scientifique fort. Les fractionnements isotopiques dépendant et indépendant de la masse de l'oxygène et du soufre sont des traceurs géochimiques performants qui permettent d'étudier quantitativement l'origine et le devenir des sulfates. Notre étude développe en premier lieu un outil analytique de pré traitement des échantillons. Ensuite, nous avons montré que les sulfates primaires d'origine volcanique (via une étude au Stromboli) ne présentent pas d'anomalie isotopique en soufre et en oxygène. Des résultats similaires sont observés pour les sulfates adsorbés sur les cendres fraiches du Popocatépetl (Mexique) indiquant des processus de formation primaires. Les sulfates de la ville de Mexico présentent des anomalies isotopiques de l'ordre de D17O=0.9 et D33S=0.3. Les valeurs en D17O sont interprétées par des processus d'oxydation secondaires via les oxydants atmosphérique OH, H2O2, O3 et O2-TMI. Les valeurs en D33S sont encore peu contraintes. Notre étude montre finalement une influence des émissions volcaniques sur le bilan global des sulfates urbains à Mexico City. / Currently in our environmental context it is important to better constraint the geochemical cycles that are a key factor for atmospheric composition and climate change. Sulfate aerosols are emitted directly by sources (anthropogenic or natural) or produced from sulfur precursor gases. In the atmosphere, sulfate aerosols are associated with the high level of urban pollutant that impact human health and with the increase of atmospheric particle that have radiative effect. For these reasons studies of sulfate aerosols from anthropogenic and volcanic emissions are an important scientific stake. First, our study develops a method to extract and purify sulfates from natural samples which is compulsory for ambiguous isotope analyses. Then, from a field project at Stromboli, we show that primary sulfate aerosols from volcano are mass dependent (i.e. D17O=0‰). Similar results are observed for sulfates adsorbed on fresh ash from Popocatépetl volcano (Mexico) suggesting primary processes during volcanic eruptions. For urban sulfate aerosols we observe significant oxygen and sulfur mass independent fractionation (MIF) (D17O=0.9‰ and D33S=0.3‰) which are interpreted as secondary oxidation processes from atmospheric oxidant (OH, H2O2, O3, O2-TMI) for O-MIF and perhaps stratospheric input for S-MIF but the quantitative processes remained poorly constraint. Finally we discuss the influence of volcanic emissions on the urban area of Mexico City.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22652号 / 工博第4736号 / 新制||工||1740(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 小池 克明, 教授 米田 稔, 准教授 柏谷 公希 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Includes bibliographical references. / Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Nuclear Engineering, 1980. / by Richard Keith Lester. / Ph.D.

No description available.

No description available.

Three simultaneous isotope effects have been determined for the Tschugaeff reaction, i.e., the thermal decomposition of an xanthate ester. The ratio of the rate constants, k32/k34, was found to be 1.009 for the thion sulphur atom and 1.002 for the thio-ether sulphur atom. The rate ratio k12/k13, for the xanthate carbon atom was found to have a value of 1.000. The findings of previous investigators of the Tschugaeff reaction had been consistent with either of two mechanisms. However, with the determination of the isotope effects referred to above, it has been possible to distinguish between the two possible mechanisms and to gain considerable information about the transition state of the Tschugaeff reaction. The measured isotope effects have been discussed in terms of Bigeleisen's isotopic rate equation. In addition, it has been possible to carry out theoretical calculations for each reaction mechanism by assuming an appropriate potential function and in this manner make the interpretation of the measured isotope effects more quantitative. / Thesis / Master of Science (MS)