Thesis advisor: Jeremy D. Shakun / The Arctic is one of the fastest warming regions on the planet. Currently, much of the Arctic is covered by permafrost, which contains approximately 1,700 gigatons of organic carbon. Permafrost thaw could release a substantial amount of this carbon as greenhouse gases into the atmosphere through microbial decomposition, potentially dramatically amplifying anthropogenic warming. However, the risk of permafrost thaw is uncertain, with models exhibiting a wide range of possibilities. Assessing the stability of permafrost during past interglacial periods enables evaluation of the sensitivity of permafrost to warming. Cave mineral deposits (speleothems) in areas currently covered with permafrost can act as a proxy for past permafrost thaw, as liquid water is one criterion for speleothem growth and thus speleothem deposition implies thawed ground conditions. Previous uranium-thorium (U-Th) dating of speleothems (n=73) from a wide range of latitudes and permafrost zones across the southern Canadian Rockies, Northwest Territories, and northern Yukon indicate that most of these formations exceed the U-Th dating limit of 500 ka. In this study, I apply uranium-lead (U-Pb) geochronology to several of these speleothems to extend the record of speleothem growth further back in time. Results include a U-Pb age of 412.8 ± 1.3 ka that replicates a previous U-Th age of 415.0 ± 11.5 ka, demonstrating the reliability of the U-Pb methodology. Additionally, U-Pb ages on six other speleothems are determined to be 876 ± 9 ka, 1501 ± 31 ka, 1570 ± 66 ka, 2046 ± 106 ka, 7636 ± 184 ka, and 7697 ± 185 ka. Further application of this technique could result in long records of past permafrost thaw and Arctic terrestrial climate extending back millions of years. / Thesis (MS) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

Trace element compositions, expressed as ratios relative to Ca (Mg/Ca, Sr/Ca and Ba/Ca), in drip water and modern speleothem calcite were measured at multiple sites within a single cave system (Natural Bridge Caverns) in central Texas. These measurements are used to investigate how water and calcite compositions respond to changes in climate. Drip water trace element ratios respond to changes in climate and in soil, vadose zone and/or in-cave processes, which are in turn influenced by climate. It is commonly assumed that speleothem calcite directly reflects these changes in the drip water composition. To test this assumption, this study quantifies the partitioning of trace elements into speleothem calcite in a natural cave setting. To determine the controls on calcite trace element ratios, empirical partition coefficients (K [subscript D]) for Mg, Sr, and Ba are measured using a unique time series of water and modern calcite geochemistry at two drip sites. One drip site, dominantly supplied by conduit flow, has relatively invariant calcite trace element compositions that reflect correspondingly small variations in drip water chemistry. A second drip site, supplied by a combination of conduit and diffuse flow, exhibits a seasonal change in drip water composition due to changes in cave-air CO₂ concentrations. The drip water seasonality at this site is recorded in the calcite trace element compositions; however the partitioning of Mg/Ca from drip water to calcite is not controlled by the same mechanism(s) that control Sr/Ca and Ba/Ca partitioning. Results of this study indicate that the partitioning of Mg changes with drip water Mg concentration, temperature and location of the calcite relative to the point of drip impact. Calcite Sr/Ca and Ba/Ca ratios are more strongly influenced by changes in cave-air CO₂ that cause changes in CO₂ degassing, affecting calcite precipitation. This element specific partitioning complicates the interpretation of speleothem trace element records, since calcite Mg/Ca and Sr/Ca may not always covary even at drip sites that experience PCP. Although there is a strong correlation between Mg/Ca and Sr/Ca ratios in the drip water at these sites, there is considerable scatter between these two values in calcite. Average K [subscript D] values at both sites fall within the range of previous theoretical and empirical studies and are 0.025, 0.12 and 0.15 for Mg, Sr and Ba respectively. It is important to note that not all trace element partitioning is controlled by the same mechanism, since this has implications for interpretations of hydrologic processes from speleothems. / text

The purpose of this study was to provide new insights into the interpretation of speleothem (cave calcite deposit) δ13C values. We studied two caves in central Texas, which have been actively monitored for over 12 years. We compared δ13C values of soil CO2 (δ13Cs), cave drip water (δ13CDIC), and modern cave calcite (δ13Ccc). Measured average δ13C values of soil CO2 were -13.9 ± 1.4‰ under mixed, shallowly-rooted C3-C4 grasses and were -18.3 ± 0.7‰ under deeply-rooted ashe juniper trees (C3). The δ13CDIC value of minimally-degassed drip water in Natural Bridge Caverns was -10.7 ± 0.3‰. The carbon isotope composition of CO2 in equilibrium with this measured drip water is -18.1 ± 0.3‰. The agreement between juniper soil CO2 and drip water (within ~0.2‰) suggests that the δ13C value of drip water (δ13CDIC) that initially enters the cave is controlled by deeply-rooted plants and may be minimally influenced by host-rock dissolution and/or prior calcite precipitation (PCP). At Inner Space Caverns, δ13CDIC values varied with vegetation above the drip site, distance from the cave entrance, and distance along in-cave flow paths. Whereas CO2 derived from deeply-rooted plants defines the baseline for drip water δ13CDIC entering the caves, kinetic effects associated with the degassing of CO2 and simultaneous precipitation of calcite account for seasonal variability in δ13CDIC and δ13Ccc. We documented increases in δ13CDIC at a rate of up to 0.47‰/hour during the season of peak degassing (winter), suggesting that δ13CDIC variations may be controlled by total elapsed time of CO2 degassing from drip water (Ttotal). We also observed seasonal shifts in the δ13C values of modern calcite grown on glass substrates that are correlated with shifts in drip water δ13CDIC values and drip-rate. Therefore, we suggest that increased aridity at the surface above a given cave results in, slower drip-rates, higher Ttotal, and therefore higher δ13CDIC values. We propose that large variability (>2‰) in speleothem δ13Ccc values dominantly reflect major vegetation changes, and/or increasing Ttotal by slowing drip-rates. Based on these findings, variability in speleothem carbon isotope records may serve as a proxy for paleoaridity and/or paleovegetation change. / text

Three questions were asked during this research. 1) Does the Sr content of Caribbean speleothems have a direct relationship with the age of the host rock at the time of speleothem precipitation?; 2) do older speleothems contain less Sr than younger speleothems in the same climatic setting?; and 3) will speleothems record the change in Sr concentration of eogenetic carbonates as a faster depletion in climates of higher precipitation as opposed to drier climates? The speleothems and cave rocks in this study were analyzed with various methods in an attempt to understand the rock processes that affect speleothem Sr concentrations. Evidence to support the hypothesis that younger host rock contributes higher concentrations of Sr to speleothems was found in the stalagmites of Curacao while Bahamian stalagmites indicated climatic variations. The results have implications for using stalagmites from relatively young, eogenetic limestone as a proxy for Sr-related paleoclimate data.

<p> The distribution of Mg and Sr in speleothem from Yorkshire, England, Vancouver Island and West Virginia, was investigated. Concentrations of Mg range from 300 to greater than 3000 parts per million. Concentrations of Sr range from less than 100 to a few hundred parts per million. Sr partitioning between seepage water and calcite may be more rate sensitive than Mg partitioning.</p> <p> It is possible that Mg and Sr in speleothem could provide information on kinetics and mechanism of speleothem formation and on seepage water and source rock composition.</p> <p> It may be possible to interpret Mg concentration in speleothem in terms of temperature if equilibrium partitioning of Mg between calcite and seepage waters can be demonstrated.</p> / Thesis / Bachelor of Science (BSc)

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Thesis advisor: Corinne I. Wong / Investigating controls on past variability of South American hydroclimate is critical to assessing its response to future warming scenarios. δ¹⁸O records from South America offer insight into past variability of the South American Monsoon System (SAMS). The controls on precipitation δ¹⁸O values, however, can be decoupled from precipitation amount and thereby limit investigations of variability in local moisture conditions. Here we use a principle components analysis to assess the coherence of speleothem and lake core Holocene δ¹⁸O records in tropical South America to evaluate the extent to which δ¹⁸O variability reflects changes in SAMS intensity at different sites across the region. The main mode of variability across Holocene δ¹⁸O records (PC1) closely tracks austral summertime insolation, consistent with existing work. PC1 is strongly expressed at sites towards the periphery of the continent, while variability at interior sites bear little similarity that implicates controls, in addition to monsoon intensity, on these δ¹⁸O records. Further, we develop speleothem ⁸⁷Sr/⁸⁶Sr records spanning the Holocene from Tamboril Cave (Brazilian Highlands), Paraíso Cave (eastern Amazon Basin), Jaraguá Cave (Mato Grosso Plateau), and Botuverá Cave (Atlantic coastal plain) to investigate coupling between reconstructed monsoon variability and local moisture conditions. Speleothem ⁸⁷Sr/⁸⁶Sr variability is interpreted as a proxy of local moisture conditions, reflecting the degree of water-rock interaction with the cave host rock as driven by variations in water residence time. Speleothem ⁸⁷Sr/⁸⁶Sr records from all the sites, except Botuverá cave, do not co-vary with PC1, suggesting that local moisture conditions do not necessary follow variations in monsoon intensity at these interior sites. These speleothem ⁸⁷Sr/⁸⁶Sr records, however, generally suggest dry mid-Holocene conditions, consistent with interpretations of other paleo-moisture records in the region. These results highlight that dynamics, in addition to SAMS variability, might influence δ¹⁸O variability as well as local moisture conditions at interior sites, and highlight the need for δ¹⁸O-independent reconstructions of moisture conditions. / Thesis (MS) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

There is a strong concern about how water resources will be affected by future climate change. Investigation of how a hydrologic system might respond to climate change, however, requires a detailed understanding of the controls on and factors that might affect that system. The research presented in this dissertation focuses on improving the understanding of the Barton Springs segment of the Edwards aquifer in central Texas. The first three chapters of this dissertation present research investigating spatial and temporal controls on groundwater geochemistry. The fourth chapter focuses on characterizing and understanding the controls on long-term hydrologic variability by reconstructing past climate from a speleothem (cave mineral deposit) collected from a central Texas cave. On spatial scales, Edwards aquifer groundwater geochemistry is influenced by water-rock interaction (calcite and dolomite recrystallization, gypsum dissolution, and calcite precipitation) and mixing between fresh groundwater and saline groundwater. On temporal scales, variation in groundwater geochemistry is dictated by the extent to which fresh groundwater mixes with recharging stream water. The degree of mixing is sensitive to changes in climate conditions (i.e., more mixing under wetter conditions) and type of flow path (i.e., conduit or diffuse) that dominantly supplies a given site. The geochemistry of stream water, which provides the majority of recharge to the aquifer, is degrading over time and indirectly controlled by anthropogenic sources under both wet and dry conditions. Climate reconstructed from a speleothem suggests that central Texas moisture conditions were relatively constant from the mid to late Holocene (0 to 7 ka), except for an extended dry interval from 0.5 to 1.5 ka. Speleothem δ18O values spike during this dry interval, suggesting that decreases in Pacific-derived moisture or decreased tropical storm activity might have been coincident with the prolonged dry interval. This research has improved understanding of the natural variability of and controls on physical and geochemical components of hydrologic system in central Texas. / text

Cette thèse a pour objectif de tester l’intérêt des spéléothèmes en tant qu’archive pédologique dans le but de reconstruire l’histoire des sols à haute-résolution durant la période Holocène. Il s’appuie sur une partie expérimentale visant à tester la robustesse des proxies organiques comme indicateurs des variations environnementales au cours du temps, et sur l'utilisation des indicateurs robustes pour reconstruire l'évolution de l'environnement dans les Bauges durant les 6000 dernières années.Le d13C de la matière organique (MO, indicateur de la dynamique de la MO dans les sols) et les lipides (indicateurs des contributions des différentes sources) ont été analysés en complément du d13C de la calcite. Les Hydrocarbures Aromatiques Polycycliques (HAP) ont également été utilisés comme molécule sonde pour comprendre le transfert des différentes molécules organiques, et comme indicateur des combustions passées, naturelles ou anthropiques. Une attention particulière a été portée à l’optimisation de la méthode analytique, afin que la résolution temporelle des analyses soit compatible avec les questions environnementales. Les résultats obtenus pour ces proxies ne sont pas exploitables et montrent un manque de robustesse attribué à des problèmes analytiques (d13CMO, lipides), au type d’alimentation des spéléothèmes (HAP) ou a des effets de site (d13C calcite).L’analyse de fluorescence UV en phase solide a été utilisée pour obtenir un enregistrement haute-résolution des variations semi-quantitatives et qualitatives de la MO. Un protocole a été développé pour quantifier l’intensité de fluorescence en phase solide (FPS). L'intensité de fluorescence en phase liquide d'extraits de MO des sols et des spéléothèmes ont été couplées par un modèle non linéaire à la FPS à haute résolution. Cette méthode a permis d’obtenir une chronique des flux de MO exportée depuis les sols sur une stalagmite test, provenant du Vercors (Grotte de Choranche) et couvrant les 400 dernières années.Un enregistrement composite de l’intensité de fluorescence et du d18O a été créé à partir de trois spéléothèmes du massif des Bauges (salle du Précieux, réseau Garde-Cavale) se recoupant sur les derniers 6000 ans, et a permis l’interprétation des variations du paléoenvironnement. Celles-ci montrent une réponse de l’environnement aux forçages climatiques, basculant vers un forçage anthropique au cours du temps.Cette étude démontre qu’il est possible d’obtenir un enregistrement haute-résolution de l’histoire des sols à l’échelle de la période Holocène par l’utilisation de la FPS. Le couplage avec des proxies organiques plus informatifs a cependant montré la limite de l’utilisation de ces derniers, due à leur manque de robustesse. La combinaison du signal de FPS avec le d18O des spéléothèmes a tout de même permis de réaliser une interprétation des variations environnementales durant l’Holocène. Celle-ci pourrait être améliorée en intégrant d’autres traceurs inorganiques (terres rares, éléments traces) qui n’ont pu être analysés durant cette thèse. / This thesis aims to demonstrate the interest of speleothems as pedologic archives to reconstruct high resolution soil history during the Holocene. Experimental study was applied to test proxies robustness as environmental tracers. These robust tracers are used to reconstruct environmental evolution in the Bauges Massif during the last 6000 years.Organic matter (OM) d13C (tracer of OM dynamic in soils) and lipids (tracers of source contributors) were analyzed complementary to the d13C of calcite. Polycyclic Aromatic Hydrocarbons (PAH) were used as a “probe” to understand organic molecular transport from soils, and to record past natural and anthropogenic combustions. Attention was paid on the optimization of extraction method in order to obtain a temporal resolution suitable for environmental issues. Results obtained are not workable because of their lack of robustness attributed to analytical issues (d13COM, lipids), to speleothem water feeding type (PAH), or to site-specific effect (d13C).OM semi-quantitative and qualitative variations were recorded at high resolution using the solid-phase fluorescence (SPF) analysis. A protocol was developed to quantify the fluorescence intensity obtained with SPF. Liquid-phase fluorescence intensity of soil and stalagmite OM extracts was coupled with high resolution SPF using a non linear model. OM fluxes record was obtained for a stalagmite-test from the Vercors Massif (last 400 years).A composite record of SPF intensity and d18O was created from 3 stalagmites from the Bauges Massif (Précieux room, Garde-Cavale system), spanning the last 6000 years. It enabled the interpretation of paleoenvironmental variations which shows a change from a climatic to anthropogenic control.This study shows that SPF is a reliable tool to record soil history during Holocene with high resolution. However, organic proxies coupling highlights the limit of their use, induced by a weak robustness. Combination of SPF and d18O enabled to reconstruct environmental variations during the Holocene. This interpretation could be improved by integrating other proxies such as rare earths or trace elements, which could not have been tested during this work due to experimental issues.