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Li and B in ascending magmas: an experimental study on their mobility and isotopic fractionation
(2022)
This research study focuses on the behaviour of Li and B during magmatic ascent, and decompression-driven degassing related to volcanic systems. The main objective of this dissertation is to determine whether it is possible to use the diffusion properties of the two trace elements as a tool to trace magmatic ascent rate. With this objective, diffusion-couple and decompression experiments have been performed in order to study Li and B mobility in intra-melt conditions first, and then in an evolving system during decompression-driven degassing.
Synthetic glasses were prepared with rhyolitic composition and an initial water content of 4.2 wt%, and all the experiments were performed using an internally heated pressure vessel, in order to ensure a precise control on the experimental parameters such as temperature and pressure.
Diffusion-couple experiments were performed with a fix pressure 300 MPa. The temperature was varied in the range of 700-1250 °C with durations between 0 seconds and 24 hours. The diffusion-couple results show that Li diffusivity is very fast and starts already at very low temperature. Significant isotopic fractionation occurs due to the faster mobility of 6Li compared to 7Li. Boron diffusion is also accelerated by the presence of water, but the results of the isotopic ratios are unclear, and further investigation would be necessary to well constrain the isotopic fractionation process of boron in hydrous silicate melts. The isotopic ratios results show that boron isotopic fractionation might be affected by the speciation of boron in the silicate melt structure, as 10B and 11B tend to have tetrahedral and trigonal coordination, respectively.
Several decompression experiments were performed at 900 °C and 1000 °C, with pressures going from 300 MPa to 71-77 MPa and durations of 30 minutes, two, five and ten hours, in order to trigger water exsolution and the formation of vesicles in the sample. Textural observations and the calculation of the bubble number density confirmed that the bubble size and distribution after decompression is directly proportional to the decompression rate.
The overall SIMS results of Li and B show that the two trace elements tend to progressively decrease their concentration with decreasing decompression rates. This is explained because for longer decompression times, the diffusion of Li and B into the bubbles has more time to progress and the melt continuously loses volatiles as the bubbles expand their volumes.
For fast decompression, Li and B results show a concentration increase with a δ7Li and δ11B decrease close to the bubble interface, related to the sudden formation of the gas bubble, and the occurrence of a diffusion process in the opposite direction, from the bubble meniscus to the unaltered melt. When the bubble growth becomes dominant and Li and B start to exsolve into the gas phase, the silicate melt close to the bubble gets depleted in Li and B, because of a stronger diffusion of the trace elements into the bubble.
Our data are being applied to different models, aiming to combine the dynamics of bubble nucleation and growth with the evolution of trace elements concentration and isotopic ratios. Here, first considerations on these models will be presented, giving concluding remarks on this research study. All in all, the final remarks constitute a good starting point for further investigations. These results are a promising base to continue to study this process, and Li and B can indeed show clear dependences on decompression-related magma ascent rates in volcanic systems.
Variation of deuterium excess in surface waters across a 5000-m elevation gradient in eastern Nepal
(2020)
The strong elevation gradient of the Himalaya allows for investigation of altitude and orographic impacts on surface water delta O-18 and delta D stable isotope values. This study differentiates the time- and altitude-variable contributions of source waters to the Arun River in eastern Nepal. It provides isotope data along a 5000-m gradient collected from tributaries as well as groundwater, snow, and glacial-sourced surface waters and time-series data from April to October 2016. We find nonlinear trends in delta O-18 and delta D lapse rates with high-elevation lapse rates (4000-6000 masl) 5-7 times more negative than low-elevation lapse rates (1000-3000 masl). A distinct seasonal signal in delta O-18 and delta D lapse rates indicates time-variable source-water contributions from glacial and snow meltwater as well as precipitation transitions between the Indian Summer Monsoon and Winter Westerly Disturbances. Deuterium excess correlates with the extent of snowpack and tracks melt events during the Indian Summer Monsoon season. Our analysis identifies the influence of snow and glacial melt waters on river composition during low-flow conditions before the monsoon (April/May 2016) followed by a 5-week transition to the Indian Summer Monsoon-sourced rainfall around mid-June 2016. In the post-monsoon season, we find continued influence from glacial melt waters as well as ISM-sourced groundwater.
Partial melting is a first order process for the chemical differentiation of the crust (Vielzeuf et al., 1990). Redistribution of chemical elements during melt generation crucially influences the composition of the lower and upper crust and provides a mechanism to concentrate and transport chemical elements that may also be of economic interest. Understanding of the diverse processes and their controlling factors is therefore not only of scientific interest but also of high economic importance to cover the demand for rare metals.
The redistribution of major and trace elements during partial melting represents a central step for the understanding how granite-bound mineralization develops (Hedenquist and Lowenstern, 1994). The partial melt generation and mobilization of ore elements (e.g. Sn, W, Nb, Ta) into the melt depends on the composition of the sedimentary source and melting conditions. Distinct source rocks have different compositions reflecting their deposition and alteration histories. This specific chemical “memory” results in different mineral assemblages and melting reactions for different protolith compositions during prograde metamorphism (Brown and Fyfe, 1970; Thompson, 1982; Vielzeuf and Holloway, 1988). These factors do not only exert an important influence on the distribution of chemical elements during melt generation, they also influence the volume of melt that is produced, extraction of the melt from its source, and its ascent through the crust (Le Breton and Thompson, 1988). On a larger scale, protolith distribution and chemical alteration (weathering), prograde metamorphism with partial melting, melt extraction, and granite emplacement are ultimately depending on a (plate-)tectonic control (Romer and Kroner, 2016). Comprehension of the individual stages and their interaction is crucial in understanding how granite-related mineralization forms, thereby allowing estimation of the mineralization potential of certain areas. Partial melting also influences the isotope systematics of melt and restite. Radiogenic and stable isotopes of magmatic rocks are commonly used to trace back the source of intrusions or to quantify mixing of magmas from different sources with distinct isotopic signatures (DePaolo and Wasserburg, 1979; Lesher, 1990; Chappell, 1996). These applications are based on the fundamental requirement that the isotopic signature in the melt reflects that of the bulk source from which it is derived. Different minerals in a protolith may have isotopic compositions of radiogenic isotopes that deviate from their whole rock signature (Ayres and Harris, 1997; Knesel and Davidson, 2002). In particular, old minerals with a distinct parent-to-daughter (P/D) ratio are expected to have a specific radiogenic isotope signature. As the partial melting reaction only involves selective phases in a protolith, the isotopic signature of the melt reflects that of the minerals involved in the melting reaction and, therefore, should be different from the bulk source signature. Similar considerations hold true for stable isotopes.
Groundwater transit time is an essential hydrologic metric for groundwater resources management. However, especially in tropical environments, studies on the transit time distribution (TTD) of groundwater infiltration and its corresponding mean transit time (mTT) have been extremely limited due to data sparsity. In this study, we primarily use stable isotopes to examine the TTDs and their mTTs of both vertical and horizontal infiltration at a riverbank infiltration area in the Vietnamese Mekong Delta (VMD), representative of the tropical climate in Asian monsoon regions. Precipitation, river water, groundwater, and local ponding surface water were sampled for 3 to 9 years and analysed for stable isotopes (delta O-18 and delta H-2), providing a unique data set of stable isotope records for a tropical region. We quantified the contribution that the two sources contributed to the local shallow groundwater by a novel concept of two-component lumped parameter models (LPMs) that are solved using delta O-18 records. The study illustrates that two-component LPMs, in conjunction with hydrological and isotopic measurements, are able to identify subsurface flow conditions and water mixing at riverbank infiltration systems. However, the predictive skill and the reliability of the models decrease for locations farther from the river, where recharge by precipitation dominates, and a low-permeable aquitard layer above the highly permeable aquifer is present. This specific setting impairs the identifiability of model parameters. For river infiltration, short mTTs (<40 weeks) were determined for sites closer to the river (<200 m), whereas for the precipitation infiltration, the mTTs were longer (>80 weeks) and independent of the distance to the river. The results not only enhance the understanding of the groundwater recharge dynamics in the VMD but also suggest that the highly complex mechanisms of surface-groundwater interaction can be conceptualized by exploiting two-component LPMs in general. The model concept could thus be a powerful tool for better understanding both the hydrological functioning of mixing processes and the movement of different water components in riverbank infiltration systems.
Here we present high-resolution delta O-18 records obtained from speleothems collected in the eastern Bolivian Andes. The stable isotope records are related to the regional- to large-scale atmospheric circulation over South America and allow interpreting changes in delta O-18 during the last 1400 yr as a function of changes in precipitation regimes over the southern tropical Andes. Two distinct phases with more negative delta O-18 values, interpreted as periods of increased convective activity over the eastern Andean Cordillera in Bolivia are observed concomitantly with periods of global climate anomalies during the last millennium, such as the Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA) respectively. Changes in the Bolivian delta O-18 record during the LIA are apparently related to a southward displacement of the Intertropical Convergence Zone (ITCZ), which acts as a main moisture driver to intensify convection over the tropical continent. During the MCA, however, the increased convective activity observed in the Bolivian record is likely the result of a different mechanism, which implies moisture sourced mainly from the southern tropical Atlantic. This interpretation is consistent with paleoclimate records further to the north in the tropical Andes that show progressively drier conditions during this time period, indicating a more northerly position of the ITCZ. The transition period between the MCA and the LIA shows a slight tendency toward increased delta O-18 values, indicating weakened convective activity. Our results also reveal a non-stationary anti-phased behavior between the delta O-18 reconstructions from Bolivia and northeastern Brazil that confirms a continental-scale east-west teleconnection across South America during the LIA.
Changes in topography on Earth, particularly the growth of major mountain belts like the Central Andes, have a fundamental impact on regional and global atmospheric circulation patterns. These patterns, in turn, affect processes such as precipitation, erosion, and sedimentation. Over the last two decades, various geochemical, geomorphologic, and geologic approaches have helped identify when, where, and how quickly topography has risen in the past. The current spatio-temporal picture of Central Andean growth is now providing insight into which deep-Earth processes have left their imprint on the shape of the Earth's surface.
The global carbon cycle is closely linked to Earth’s climate. In the context of continuously unchecked anthropogenic CO₂ emissions, the importance of natural CO₂ bond and carbon storage is increasing. An important biogenic mechanism of natural atmospheric CO₂ drawdown is the photosynthetic carbon fixation in plants and the subsequent longterm deposition of plant detritus in sediments.
The main objective of this thesis is to identify factors that control mobilization and transport of plant organic matter (pOM) through rivers towards sedimentation basins. I investigated this aspect in the eastern Nepalese Arun Valley. The trans-Himalayan Arun River is characterized by a strong elevation gradient (205 − 8848 m asl) that is accompanied by strong changes in ecology and climate ranging from wet tropical conditions in the Himalayan forelad to high alpine tundra on the Tibetan Plateau. Therefore, the Arun is an excellent natural laboratory, allowing the investigation of the effect of vegetation cover, climate, and topography on plant organic matter mobilization and export in tributaries along the gradient.
Based on hydrogen isotope measurements of plant waxes sampled along the Arun River and its tributaries, I first developed a model that allows for an indirect quantification of pOM contributed to the mainsetm by the Arun’s tributaries. In order to determine the role of climatic and topographic parameters of sampled tributary catchments, I looked for significant statistical relations between the amount of tributary pOM export and tributary characteristics (e.g. catchment size, plant cover, annual precipitation or runoff, topographic measures). On one hand, I demonstrated that pOMsourced from the Arun is not uniformly derived from its entire catchment area. On the other, I showed that dense vegetation is a necessary, but not sufficient, criterion for high tributary pOM export. Instead, I identified erosion and rainfall and runoff as key factors controlling pOM sourcing in the Arun Valley. This finding is supported by terrestrial cosmogenic nuclide concentrations measured on river sands along the Arun and its tributaries in order to quantify catchment wide denudation rates. Highest denudation rates corresponded well with maximum pOM mobilization and export also suggesting the link between erosion and pOM sourcing.
The second part of this thesis focusses on the applicability of stable isotope records such as plant wax n-alkanes in sediment archives as qualitative and quantitative proxy for the variability of past Indian Summer Monsoon (ISM) strength. First, I determined how ISM strength affects the hydrogen and oxygen stable isotopic composition (reported as δD and δ18O values vs. Vienna Standard Mean Ocean Water) of precipitation in the Arun Valley and if this amount effect (Dansgaard, 1964) is strong enough to be recorded in potential paleo-ISM isotope proxies. Second, I investigated if potential isotope records across the Arun catchment reflect ISM strength dependent precipitation δD values only, or if the ISM isotope signal is superimposed by winter precipitation or glacial melt. Furthermore, I tested if δD values of plant waxes in fluvial deposits reflect δD values of environmental waters in the respective catchments.
I showed that surface water δD values in the Arun Valley and precipitation δD from south of the Himalaya both changed similarly during two consecutive years (2011 & 2012) with distinct ISM rainfall amounts (~20% less in 2012). In order to evaluate the effect of other water sources (Winter-Westerly precipitation, glacial melt) and evapotranspiration in the Arun Valley, I analysed satellite remote sensing data of rainfall distribution (TRMM 3B42V7), snow cover (MODIS MOD10C1), glacial coverage (GLIMSdatabase, Global Land Ice Measurements from Space), and evapotranspiration (MODIS MOD16A2). In addition to the predominant ISM in the entire catchment I found through stable isotope analysis of surface waters indications for a considerable amount of glacial melt derived from high altitude tributaries and the Tibetan Plateau. Remotely sensed snow cover data revealed that the upper portion of the Arun also receives considerable winter precipitation, but the effect of snow melt on the Arun Valley hydrology could not be evaluated as it takes place in early summer, several months prior to our sampling campaigns. However, I infer that plant wax records and other potential stable isotope proxy archives below the snowline are well-suited for qualitative, and potentially quantitative, reconstructions of past changes of ISM strength.
Two of the most controversial issues concerning the late Cenozoic evolution of the Andean orogen are the timing of uplift of the intraorogenic Puna plateau and its eastern border, the Eastern Cordillera, and ensuing changes in climatic and surface-process conditions in the intermontane basins of the NW-Argentine Andes. The Eastern Cordillera separates the internally drained, arid Puna from semi-arid intermontane basins and the humid sectors of the Andean broken foreland and the Subandean fold-and-thrust belt to the east. With elevations between 4,000 and 6,000 m the eastern flanks of the Andes form an efficient orographic barrier with westward-increasing elevation and asymmetric rainfall distribution and amount with respect to easterly moisture-bearing winds. This is mirrored by pronounced gradients in the efficiency of surface processes that erode and re-distribute sediment from the uplifting ranges. Although the overall pattern of deformation and uplift in this sector of the southern central Andes shows an eastward migration of deformation, a well-developed deformation front does not exist and uplift and associated erosion and sedimentary processes are highly disparate in space and time. In addition, periodic deformation within intermontane basins, and continued diachronous foreland uplifts associated with the reactivation of inherited basement structures furthermore make a rigorous assessment of the spatiotemporal uplift patterns difficult.
This thesis focuses on the tectonic evolution of the Eastern Cordillera of NW Argentina, the depositional history of its intermontane sedimentary basins, and the regional topographic evolution of the eastern flank of the Puna Plateau. The intermontane basins of the Eastern Cordillera and the adjacent morphotectonic provinces of the Sierras Pampeanas and the Santa Bárbara System are akin to reverse fault bounded, filled, and partly coalesced sedimentary basins of the Puna Plateau. In contrast to the Puna basins, however, which still form intact morphologic entities, repeated deformation, erosion, and re-filling have impacted the basins in the Eastern Cordillera. This has resulted in a rich stratigraphy of repeated basin fills, but many of these basins have retained vestiges of their early depositional history that may reach back in time when these areas were still part of a contiguous and undeformed foreland basin. Fortunately, these strata also contain abundant volcanic ashes that are not only important horizons to decipher tectono-sedimentary events through U-Pb geochronology and geochemical correlation, but they also represent terrestrial recorders of the hydrogen-isotope composition of ancient meteoric waters that can be compared to the isotopic composition of modern meteoric water. The ash horizons are thus unique recorders of past environmental conditions and lend themselves to tracking the development of rainfall barriers and tectonically forced climate and environmental change through time.
U-Pb zircon geochronology and paleocurrent reconstructions of conglomerate sequences in the Humahuaca Basin of the Eastern Cordillera at 23.5° S suggest that the basin was an integral part of a largely unrestricted depositional system until 4.2 Ma, which subsequently became progressively decoupled from the foreland by range uplifts to the east that forced easterly moisture-bearing winds to precipitate in increasingly eastward locations. Multiple cycles of severed hydrological conditions and drainage re-capture are identified together with these processes that were associated with basin filling and sediment evacuation, respectively. Moreover, systematic relationships among faults, regional unconformities and deformed landforms reveal a general pattern of intra-basin deformation that appears to be linked with basin-internal deformation during or subsequent to episodes of large-scale sediment removal. Some of these observations are supported by variations in the hydrogen stable isotope composition of volcanic glass from the Neogene to Quaternary sedimentary record, which can be related to spatiotemporal changes in topography and associated orographic effects. δDg values in the basin strata reveal two main trends associated with surface uplift in the catchment area between 6.0 and 3.5 Ma and the onset of semiarid conditions in the basin following the attainment of threshold elevations for effective orographic barriers to the east after 3.5 Ma. The disruption of sediment supply from western sources after 4.2 Ma and subsequent hinterland aridification, moreover, emphasize the possibility that these processes were related to lateral orogenic growth of the adjacent Puna Plateau. As a result of the hinterland aridification the regions in the orogen interior have been characterized by an inefficient fluvial system, which in turn has helped maintaining internal drainage conditions, sediment storage, and relief reduction within high-elevation basins.
The diachronous nature of basin formation and impacts on the fluvial system in the adjacent broken foreland is underscored by the results of detailed sediment provenance and paleocurrent analyses, as well as U-Pb zircon geochronology in the Lerma and Metán basins at ca. 25° S. This is particularly demonstrated by the isolated uplift of the Metán range at ~10 Ma, which is more than 50 km away from the presently active orogenic front along the eastern Puna margin and the Eastern Cordillera to the west. At about 5 Ma, Puna-sourced sediments disappear from the foreland record, documenting further range uplifts in the Eastern Cordillera and hydrological isolation of the neighboring Angastaco Basin from the foreland. Finally, during the late Pliocene and Quaternary, deformation has been accommodated across the entire foreland and is still active. To elucidate the interactions between tectonically controlled changes in elevation and their impact on atmospheric circulation processes in this region, this thesis provides additional, temporally well-constrained hydrogen stable isotope results of volcanic glass samples from the broken foreland, including the Angastaco Basin, and other intermontane basins farther south. The results suggest similar elevations of intermontane basins and the foreland sectors prior to ca. 7 Ma. In case of the Angastaco Basin the region was affected by km-scale surface uplift of the basin. A comparison with coeval isotope data collected from sedimentary sequences in the Puna plateau explains rapid shifts in the intermontane δDg record and supports the notion of recurring phases of enhanced deep convection during the Pliocene, and thus climatic conditions during the middle to late Pliocene similar to the present day.
Combined, field-based and isotope geochemical methods used in this study of the NW-Argentine Andes have thus helped to gain insight into the systematics, rate changes, interactions, and temporal characteristics among tectonically controlled deformation patterns, the build-up of topography impacting atmospheric processes, the distribution of rainfall, and resulting surface processes in a tectonically active mountain belt. Ultimately, this information is essential for a better understanding of the style and the rates at which non-collisional mountain belts evolve, including the development orogenic plateaus and their bordering flanks. The results presented in this study emphasize the importance of stable isotope records for paleoaltimetric and paleoenvironmental studies in mountain belts and furnishes important data for a rigorous interpretation of such records.
The hypersaline crater lake and its catchment on seabird island Isabel (Pacific, off Mexico) was studied to explore the influence of strong seasonal variations in rainfall/evaporation and guano contribution on its limnology. The hypersaline lake water (HSW, 78 %) is up to 2.2-times enriched in inert ions relative to mean seawater. Rainfall during summer dilutes the HSW to form a less saline rainwater body (RWB) above a chemolimnion between 2 and 4 m water depth. The RWB is inhabited first by diatoms and ostracods followed later on by cyanobacteria and ciliates. Evaporation of > 1.5 m depth of lake water over the dry season increases the salinity of the RWB until the water column becomes isohaline at HSW concentrations in the late dry season. Differences in the stable isotope composition of water and primary producers in RWB and HSW reflect this development. Introduction of seabird guano and the decrease of salinity fuel a high primary production in the RWB with higher delta(CDIC)-C-13 and delta(13)Corg of particulate organic matter than in the HSW. The high N supply leads to high delta N-15 NH4 values (+ 39 % in the HSW) as the consequence of ammonia volatilization that is strongest during guano maturation and with evaporative salinity increase from the HSW. Precipitation of carbonate (calcite and aragonite) from the RWB and the HSW is hindered by the high concentration of guano-derived P. This inhibition may be overcome with evaporative supersaturation during particularly dry conditions. Carbonate may also precipitate during particularly wet conditions from the dilute RWB, where the P-concentration is reduced during an active phytoplankton production that raises the pH. Differences in the stable isotope signatures of carbon and oxygen in HSW and RWB (+ 5 % delta(CDIC)-C-13 and -3 % d18OH2O) suggest the processes of carbonate precipitation can be distinguished based on the isotope signature of the carbonates deposited. Changes in the lake system are indicated when lower temperatures and higher rainfall in the 2006 wet season introduced more and less mature guano to the lake. The lower pH was accompanied by lower ammonia volatilization and carbonate precipitation as indicated by an increased concentration of NH4, Ca, Sr and DIC, while delta H-2, delta(NNH4)-N-15, and salinity were lower. According to our results, the observed sediment laminations should reflect the introduction of catchment material (including guano) with runoff, the RWB plankton production, and the carbonate precipitation in relation to its origin and seasonality.