The Antarctic Intermediate Water (AAIW) plays an important role on controlling globally climatic change. Numbers of researchers attempted to discuss whether AAIW across the equator or notduring glacial- interglacial transitions. In this study, we analyzed Mg/Ca and £UREE/Ca on benthic foraminiferal species, Cibicidoides wuellerstorfi, from core MD052922C, which retrieved from western equatorial Pacific region, for revealing the long-term variations of Paleohydrology in intermediate water depths of tropical Pacific. Our evaluated results reveal that the Mg/Ca ratios ranging from 1.27 to 2.04 mmol/mol, and ranging between 2.2 and 3.2¢J when calculating into paleotemoeratures.Highest Mg/Ca can be observed in MIS 6. This finding implies that the present AAIW mean temperature is colder than glacials, and the present AAIW is well-ventilated than that in glacials.Higher £UREEs/Ca values are usually well correlated with old and poor ventilated water masses. In our record, higher £UREEs/Ca values are observed at MIS 5 impling that the intermediate depth water mass of the western tropical Pacific is poor ventilated when comparing to glacials.

Understanding the formation conditions of seep carbonate is crucial to better constrain the dynamic fluid flow and chemical fluxes associate with cold seeps on the seafloor. Rare earth element (REE) in seep carbonates collected from modern cold seeps of Gulf of Mexico, Black Sea, Congo Fan, ancient seeps of Beauvoisin (Oxfordian, J3, Southeastern France) and Marmorito (Miocene, Northern Italy) were studied. Our focus has been on 5% HNO3-treated solution (authigenic carbonate minerals) of carbonates. Several crystalline forms of carbonate minerals have been selected for analysis. Total REE (ΣREE) contents in seep carbonates varies widely, from 0.068 to 43.655 ppm, but the common trend is that the ΣREE in microcrystalline phases is highest and lowest of in sparite, suggesting that the ΣREE of seep carbonates may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates show varied Ce anomalies across several seep sites and even within one site, suggesting that the formation condition of seep carbonate is variable and complex. Overall, our results show that apart from anoxic, oxic formation condition is also common at hydrocarbon seep environments.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23999号 / エネ博第435号 / 新制||エネ||82(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 野平 俊之, 教授 萩原 理加, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22011号 / 工博第4623号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 酒井 伸一, 教授 高岡 昌輝, 准教授 平井 康宏 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22452号 / 工博第4713号 / 新制||工||1736(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 三浦 清貴, 教授 藤田 晃司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Le craton archéen de l’In Ouzzal représente une succession d'événements intrusifs et métamorphiques depuis l’Eburnéen qui en font un marqueur important des processus géodynamiques à travers les temps géologiques. La région d’Ihouhaouene située au N-W du terrane de l’In Ouzzal en Algérie est unique de par la présence d’intrusions protérozoïques de carbonatites associées à des roches alcalines saturées. Ces carbonatites intracontinentales comptent parmi les plus anciennes et inhabituelles de par leurs diversités et la présence de minéraux à terres rares. Les carbonatites sont pegmatitiques ou bréchiques avec des fragments de syénite. Elles sont des calciocarbonatites composées de calcite (>50 vol.%), apatite, clinopyroxène et wollastonite et sont associées à des syénites rouges ou blanches présentes sous forme massive. Les syénites sont composées d’alternance de niveaux clairs de feldspaths alcalins rouges ou de wollastonites associées aux feldspaths blancs et de niveaux sombres d’apatites et de clinopyroxènes. Les carbonatites et syénites forment une suite cogénétique caractérisée par une augmentation en SiO2 et une diminution en CaO et CO2. Les carbonatites ont des compositions en silice comprises entre 5 et 35 pds.%, 28 et 53 pds.% CaO et 11 à 36 pds.% CO2. Les syénites montrent une forte teneur en K2O (12 pds.%) et des teneurs très faibles en Na2O (1 pds.%). Les carbonatites et syénites sont riches en éléments incompatibles avec des teneurs en REE supérieures à 7000 fois les chondrites et 1000 fois les chondrites dans les syénites, respectivement, et de fortes teneurs en U, Sr et Th. Les éléments en trace dans les minéraux magmatiques (apatite et pyroxène) mettent en évidence des processus complexes à l’origine de ces roches impliquant plusieurs étapes de cristallisation fractionnée et d’immiscibilité à partir d’un magma mélilititique riche en CO2. Les minéraux des carbonatites riches en silice et des syénites blanches ont des signatures géochimiques similaires et se caractérisent par des rapports élevés en Nb/Ta typiques de magmas riches en carbonate par immiscibilité. Les syénites rouges ont des caractéristiques de liquides silicatés évolués par différentiation. Les minéraux des carbonatites pauvres en silice ont des rapports Nb/Ta très variables, sub-chondritiques (<10), indiquant une cristallisation à partir de liquides très évolués et la présence de magmas carbonatitiques tardifs. Les apatites, en particuliers, enregistrent divers épisodes magmatiques et également supergènes. Elles présentent dans certaines roches une redistribution et un enrichissement en terres rares variables qui se caractérisent par des exsolutions de britholite dans les carbonatites riches en silice et monazite dans les carbonatites pauvres en silice. Ces exsolutions traduisent des rééquilibrations locales sub-solidus avec des fluides tardi-magmatiques de composition riche en Cl-Th-REE pour l’exsolution de la britholite et S-Ca-P-CO2 pour les inclusions de monazite. L’apatite et le zircon présents dans ces roches alcalines et carbonatites, ont permis de déterminer l’âge de mise en place du complexe magmatique de Ihouahouene à 2100 Ma syn-métamorphique et de confirmer l’âge panafricain de son exhumation. L’étude pétrologique, géochimique et géochronologique des carbonatites et syénites d’Ihouhaouene a permis de mettre en évidence l’origine magmatique de ces roches et de définir les interactions fluides-roches supergènes à l’origine des enrichissements en REE. Les carbonatites et syénites d’Ihouahouene proviennent d’un faible taux de fusion partielle d’un manteau Précambrien riche en CO2. Plusieurs étapes de cristallisation fractionnée et d'immiscibilité ont permis la genèse de ces roches hybrides, piégées le long de grandes zones de cisaillement durant la période de transition Archéen /Eburnéen dans un régime extensif à l’In Ouzzal caractérisé par un environnement granulitique d’ultra-haute-température. / The In Ouzzal Archaean craton represents a succession of intrusive and metamorphic events since Eburnean, and an important marker of geodynamic processes through geological time. The Ihouhaouene area located in the N-W of In Ouzzal terrane in Algeria is unique by the presence of Proterozoic carbonatite intrusions associated with silica-saturated alkaline rocks. These intracontinental carbonatites are among the oldest and exceptional because of their diversity and the presence of unusual rare earth minerals. Carbonatites are pegmatitic or brecciated with fragments of syenite. They are calciocarbonatites with calcite (> 50 vol.%), apatite, clinopyroxene and wollastonite and are associated with red or white syenites in massive outcrops. Syenites are composed of alternating light levels of red alkaline feldspar or wollastonite associated with white feldspar and dark levels of apatite and clinopyroxene. Carbonatites and syenites form a cogenetic suite characterized by an increase in silica and decrease in calcium and CO2 content. The carbonatites have silica content ranging from 5 to 35 wt.%, 28 to 53 wt.% CaO, and 11 to 36 wt.% CO2. Syenites have high K2O (12 wt.%) and low Na2O content (1 wt.%). Carbonatites and syenites have high incompatible element concentrations with high REE content (7000*chondrites and 1000*chondrites, respectively) and high U, Pb, Sr and Th content. Trace elements (eg. Rare Earths, Nb-Ta, Zr-Hf) in magmatic minerals (apatite-pyroxene) of carbonatites and syenites reveal complex magmatic processes at the origin of these rocks involving several stages of fractional crystallization and immiscibility from a CO2-rich melilititic magma. Silica-rich carbonatites and white syenites are characterized by high Nb/Ta, Y/Zr and Rb/Sr ratios, typical of carbonate-rich magmas by immiscibility. The red syenites have characteristics of immiscible differentiated silicate melt. Silica-poor carbonatite minerals have variable subchondritic Nb/Ta (<10) indicating crystallization from highly evolved liquids and the presence of late carbonatitic magmas. Apatites, in particular, record various magmatic and supergene processes. They present, in some rocks, redistribution and enrichment in rare earth elements, which are characterized by exsolutions of britholite in silica-rich carbonatites and monazite-quartz-calcite inclusions in silica-poor carbonatites. These minerals reflect local sub-solidus re-equilibration with late-magmatic fluids rich in Cl-Th-REE for the exsolution of britholite and S-Ca-P-CO2 for monazite inclusions. The apatite and zircon present in these alkaline and carbonatite rocks, allow determination of the syn-metamorphic crystallization age of the Ihouahouene magmatic complex at 2100 Ma and confirm the pan-African age of its exhumation. The petrological, geochemical and geochronological study of Ihouhaouene carbonatites and syenites highlights the magmatic origin of these rocks and constrains the fluid-rock interactions at sub-solidus conditions leading to REE-enrichment. The carbonatites and syenites result from a low partial melting rate of a CO2-rich Precambrian mantle. Several fractional crystallization and immiscibility stages allowed the genesis of these hybrid magmas, trapped along large shear-zones during the Archean/Eburnean transition period in the In Ouzzal terrane, characterized by extensive deformation in ultra-high-temperature granulitic environment.

Recycling and recovery of materials and energy from waste is a key factor to mitigate virgin material demands and reduce resource consumption by utilising waste as a resource for new products. However, some critical materials, such as neodymium, are barely recycled because of missing information on amount and disposition of these critical materials within the waste streams. The goal of the study is to quantify recycling potentials from small and electric motors originating from end-of-life vehicles (ELV), electric bicycles and industrial machinery in Germany and the EU with focus on currently lost rare earth elements. Furthermore, innovative approaches to improve recycling of these motors shall be investigated. Therefore, a calculation model to predict current and future waste streams and the incorporated recycling potentials has been developed. The results show an increasing trend of recycling potentials from small and electric motors for all waste streams. The recycling potential of neodymium is estimated at a range of 150 t to 240 t in 2020 in Germany. However, data inaccuracy and the calculation model are likely to cause overestimation of actually available recycling potential and have to be interpreted carefully. In conclusion, disassembly of small and electric motors from ELV and electric bicycles in combination with a subsequent specific recycling process has been identified as promising to improve utilisation of the recycling potentials of rare earth elements from small and electric motors. However, in case recycling quotas are the prior goal of improvement, the application and further optimisation of post shredder technology is more relevant.

No description available.

Grasslands provide fundamental ecosystem services in many arid and semi-arid regions of the world, but are experiencing rapid increases in fire activity making them highly susceptible to post-fire accelerated soil erosion by wind. A quantitative assessment that integrates fire-wind erosion feedbacks is therefore needed to account for vegetation change, soil biogeochemical cycling, air quality, and landscape evolution. We investigated the applicability of a novel tracer technique – the use of multiple rare earth elements (REE) - to quantify aeolian soil erosion and to identify sources and sinks of wind-blown sediments in a burned and unburned shrub-grass transition zone in the Chihuahuan desert, NM, USA. Results indicate that the horizontal mass flux of wind-borne sediment increased approximately three times following the fire. The REE-tracer analysis of aeolian sediments shows that an average 88% of the horizontal mass flux in the control area was derived from bare microsites, whereas at the burned site it was derived from shrub and bare microsites, 42% and 39% respectively. The vegetated microsites, which were predominantly sinks of aeolian sediments in the unburned areas, became sediment sources following the fire. The burned areas exhibited a spatial homogenization of sediment tracers, highlighting a potential negative feedback on landscape heterogeneity induced by shrub encroachment into grasslands. Though fires are known to increase aeolian sediment transport, accompanying changes in the sources and sinks of wind-borne sediments likely influence biogeochemical cycling and land degradation dynamics. Our experiment demonstrated that REEs can be used as reliable tracers for field-scale aeolian studies. / Geology / Accompanied by one compressed .zip file: MET_Tower_Data.zip

Karst aquifers are dynamic hydrologic systems which are sensitive to short-term recharge events (storms) and heterogeneous recharge characteristics (point recharge at sinks, irregular soil thicknesses). These aquifers are highly productive yet also vulnerable to contamination, in large part because the conduit network is a significant unknown for predicting karst flow paths. To address these uncertainties, two adjacent karst springs, Tippery Spring and Near Tippery Spring, were monitored to better understand flow and source mixing characteristics. The two springs in central Pennsylvania’s Nittany Valley have similar discharges and are only 65 meters apart, yet they show unique behaviors in terms of water chemistry and discharge response to storms. First examined for flow characterization in 1971 by Shuster and White, the springs were analyzed in this study using high-resolution logging and new tracers such as rare earth element (REEs) and Ca/Zr ratios. This research contributes to the field of karst hydrology through innovative water sampling and monitoring techniques to investigate karst recharge and flow behavior along with conduit flow models incorporating multiple calibration target datasets such as water temperature and dye tracing. Stable isotope signatures (δD & δ18O) of storm water samples at the two springs varied based on storm intensity, but also due to their unique recharge behaviors. Increased spring discharge preceded the arrival of storm water as conduits were purged of pre-storm water, indicated by no change in isotopic composition on the rising limb. The isotopic signature then became progressively more enriched at both springs, indicating storm water recharge. At Tippery, this enrichment began around peak flow, sooner than at Near Tippery where enrichment began during the descending limb. Thus, isotopes indicated a stronger surface connection at Tippery Spring. Storm intensity also affected the relative contribution of recharging water reaching both springs, with a larger storm producing a larger recharge signature compared to a smaller storm. At Tippery Spring, for a short time the majority of emerging water was storm water, which may indicate a reversal in water exchange between the conduits and the surrounding matrix, an important consideration in karst contaminant transport. Two natural tracers were applied in new ways for this study: Ca/Zr ratios and REE patterns. Both tracers provided additional information about flow paths and recharge sources as they varied during the storm hydrograph. Ca/Zr ratios changed in timing and intensity with storm intensity, and both springs exhibited a decline in Ca/Zr ratios as calcium-rich carbonate matrix water was displaced by zirconium-rich storm recharge water from sinking streams off the clastic upland ridges. Being a storm water arrival indicator in clastic-ridge-fed Valley and Ridge springs, this relationship made Ca/Zr ratios a useful substitute for stable water isotopes while also providing information on source area. In response to storm water recharge, REE concentrations increased with the arrival of storm water. The timing and magnitude of concentration increases were influenced both by the degree of surface connectivity intrinsic to each spring and the intensity of the recharge event. Elevated REE concentrations persisted after other parameters recovered to pre-storm levels, suggesting water which has interacted with either the local carbonate matrix or the upland siliciclastics. These slower flow paths recharging the two springs were not apparent from other geochemical parameters. This study illustrated the relationships among multiple tracers to understand source waters in different periods of storm hydrographs. A flow and transport model using the Finite Element Subsurface Flow Model (FEFLOW) was calibrated using quantitative dye trace and high resolution temperature data to simulate the connection between a sinking stream and Tippery Spring. Dye was injected at the sink and monitored at the spring while temperature data was collected using loggers at both the sink and the spring. FEFLOW was used to simulate the connection between sink and spring through varying conduit geometries, sink and spring discharges, conduit conductivity, conduit cross-sectional area, matrix transmissivity, matrix porosity, and dispersivity. Single conduit models reproduced larger peak and recession concentrations than observed. A forked conduit model diverted flow from the main conduit, reducing the concentration of dye reaching the spring, provided a better match. Latin Hypercube sensitivity analysis indicated that dye concentration breakthrough curves were most sensitive to conduit conductivity and less sensitive to other model parameters. Temperature data from high-resolution loggers at the sink and spring were then incorporated into the model scenarios to reproduce seasonal spring temperature using the conduit configuration fit to the dye trace. Simulated temperature signals at the spring were sensitive to parameters in addition to conduit conductivity, most notably matrix transmissivity and inflow rates at the sink. The dual approach to karst model calibration using a temperature model set up from an initial dye trace results in greater model confidence due to a limited possible range in conduit conductivity. This study improved conceptual and numerical models for karst by examining how data from storm events and tracers can be used to better understand recharge and flow paths. / Geoscience