Thesis advisor: Ethan Baxter / Serpentinites assume a critical role in geochemical and geophysical cycles, from recycling fluid into the sub-arc mantle to facilitating exhumation within subduction zones. Rodingite dikes can be used as a lens to investigate the hydration of the oceanic lithosphere as their development is synchronous with serpentinization, and while serpentinites lack sufficient mineral phases for geochronology, rodingite dikes are rich in andradite and grossular garnet which are potentially amenable for geochronology. This research seeks to constrain the timescales and duration of hydration of the oceanic lithosphere within the Alpine Tethys ocean basin, and associated serpentinization, by examining Apennines rodingites from the Internal Ligurides (Italy). These rodingites experienced seafloor hydrothermal alteration and were obducted onto the continental margin during Alpine orogenesis. As a result, they are ideal for studying seafloor metasomatism as they were not affected by prograde subduction zone metamorphism and dehydration. Sr isotopic and trace element profiles were constructed across two rodingite-serpentinite transects, revealing a complex, multi-stage hydration history consisting of 1) Widespread serpentinization, 2) Gabbroic intrusions, 3) Rodingitization, and 4) Localized, late-stage advective fluid flow. Serpentinizing fluids locally display strong continental crustal isotopic signatures, while rodingitization fluids are characterized by seawater-like values. U-Pb geochronology on rodingite garnets produced an age of 96.1 ± 8.9 Ma, which could represent either the main rodingitization phase or the late-stage advective alteration. / Thesis (MS) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

Integrated sequence stratigraphy and geochemistry has significantly improved our knowledge of the formation and distribution of early and late diagenetic products in North American Mississippian carbonates. Deposition of the Madison Limestone occurred in concert with a major perturbation to the global C-pool, the timing of which was constrained by comparing secular variations in the delta13C values from the Madison Limestone with limited biostratigraphy. These early constraints were then improved by peak matching of 87Sr/86Sr values from this study with European brachiopod 87Sr/86Sr. The secular variations in the delta13C values were then applied as a chronostratigraphic tool to outcrops and subsurface core. As a result, our sequence stratigraphic interpretations and knowledge regarding lateral facies variability in carbonate rocks is significantly improved. Geographic variability in the magnitude of the delta13C values is also documented along the dip-transects which suggests that marine waters experienced increasing restriction in a landward direction. These results show how local changes to the C-pool are controlled by the morphology of the depositional system which can significantly affect the original signal of the global carbon pool. The geographic variability in the delta13C and delta18O values from reservoir quality dolomites along the mid-to-upper Madison ramp suggest they also precipitated from a restricted water mass with increased salinity, temperature and alkalinity which in turn, were responsible for the distribution of massive quantities of strataform dolomite deposited during the continental transgression at the beginning of the Mississippian. Trace element and 87Sr/86Sr values from strataform dolomite suggest initial formation from Mississippian seawater and slight resetting during shallow burial diagenesis. Petrography indicates that the formation of this dolomite ceased in the shallow burial environment, between the Mississippian and Permian. These dolomites are cross-cut by comparatively small volumes of geothermal-hydrothermal dolomite associated with Laramide-age breccias and fractures. Tectonic-hydrothermal activity associated with the Laramide Orogeny was responsible for late stage calcite cemented fractures and breccias which cross-cut all carbonate rocks discussed in this thesis. Radiogenic 87Sr/86Sr, depleted delta18O and enriched delta13C values and the hottest fluid inclusions measured in this study suggest the late stage calcite formed in the hydrothermal environment and under the most open-system and water-dominated conditions. Tectonic-diagenesis is ultimately responsible for establishing vertical barriers in the otherwise porous and permeable strataform dolomites.

The assemblage of ca. 6–4 Ma volcanic rocks exposed at the Sagehen Research station in the Truckee-Tahoe region of the northern Sierra Nevada, United States, is interpreted to be, within the Ancestral Cascades volcanic arc, a Lassen-type stratovolcano complex. Sagehen is of particular importance because it is one of the few Tertiary arc volcanic centres in California which has not been heavily glaciated during the Pleistocene. The volcanic rocks are variably porphyritic or aphanitic, including abundant plagioclase with clinopyroxene and amphibole. The rocks range from basalt to basaltic-andesite to andesite in composition. Basalts are olivineand clinopyroxene-bearing with minor phenocrysts of plagioclase. The basaltic-andesites are primarily pyroxene bearing while the andesites contain pyroxene-, plagioclase- and hornblende porphyritic phases. Sagehen arc lavas are calc-alkaline and enriched in the large ion lithophile elements and depleted in High Field Strength Elements. The basalts are depleted in Zr and Hf while the andesites are enriched with Zr and Hf relative to the middle rare earth elements. Compared to previously studied Ancestral Cascade arc samples, Sagehen region basalts have lower 143Nd/144Nd isotopic values that do not correspond to proposed mantle-lithosphere mixing lines, while the andesite samples appear to represent the interplay of these two components on a 87Sr/86Sr vs. 143Nd/144Nd. The trace element data and isotopic plots suggest that the melts that produced the basalts are from subduction modified mantle wedge peridotites that ponded near the base of the lithosphere similar to the generation of other subduction related calc-alkaline lavas along convergent continental margins. The andesitic samples appear to be the result of further modification through crustal assimilation as seen in the higher isotopic Sr contents in the andesites and Ce/Smpmn vs. Tb/Ybpmn plots. Finally, the proposed map units from Sylvester & Raines (2007) were found to contain various geochemical facies based on the samples collected indicating that some map units may have to be redefined or sub-divided.

Strontium isotope analysis has provided archaeologists with an unprecedented opportunity to study the mobility of humans and animals in the past. However, a lack of systematic environmental baseline data has seriously restricted the full potential of the analytical technique; there is little biosphere data available against which to compare measured skeletal data. This thesis examines the extent to which geographic variation in biosphere 87Sr/86Sr composition can be spatially resolved within the lowland terrain of England, in a geographically and geologically coherent study area. Systematically collected samples of vegetation, stream water and surface soils, including new and archived material have been used. The potential of these sample media to provide reliable estimates of the ⁸⁷Sr/⁸⁶Sr composition of bioavailable strontium are evaluated under both high-density and low-density sampling regimes, and against new analyses of local archaeological material. Areas lying south of the Anglian glacial limit, display a pattern of geographic ⁸⁷Sr/⁸⁶Sr biosphere variation (0.7080-0.7105) controlled by solid geology, as demonstrated by high-density biosphere mapping. Data collected at a wider geographic scale, including above superficial deposits, indicate the dominant influence of re-worked local rocks on the biosphere. These methods have enabled a reclassification of the archaeologically important Cretaceous Chalk domain. Analysis of rainwater and other indicators of atmospheric deposition show that, in this setting, local biosphere variation is not significantly perturbed by atmospheric inputs. Time-related data from archaeological cattle and sheep/goat tooth enamel suggest that the modern biosphere data can be used to understand livestock management regimes and that these are more powerful than using an average value from the enamel. A more complete understanding of possible patterns of mobility in a group of humans has been achieved through analysis of material from Winchester and comparison with the Chalk biosphere domain.

The assemblage of ca. 6–4 Ma volcanic rocks exposed at the Sagehen Research station in the Truckee-Tahoe region of the northern Sierra Nevada, United States, is interpreted to be, within the Ancestral Cascades volcanic arc, a Lassen-type stratovolcano complex. Sagehen is of particular importance because it is one of the few Tertiary arc volcanic centres in California which has not been heavily glaciated during the Pleistocene. The volcanic rocks are variably porphyritic or aphanitic, including abundant plagioclase with clinopyroxene and amphibole. The rocks range from basalt to basaltic-andesite to andesite in composition. Basalts are olivineand clinopyroxene-bearing with minor phenocrysts of plagioclase. The basaltic-andesites are primarily pyroxene bearing while the andesites contain pyroxene-, plagioclase- and hornblende porphyritic phases. Sagehen arc lavas are calc-alkaline and enriched in the large ion lithophile elements and depleted in High Field Strength Elements. The basalts are depleted in Zr and Hf while the andesites are enriched with Zr and Hf relative to the middle rare earth elements. Compared to previously studied Ancestral Cascade arc samples, Sagehen region basalts have lower 143Nd/144Nd isotopic values that do not correspond to proposed mantle-lithosphere mixing lines, while the andesite samples appear to represent the interplay of these two components on a 87Sr/86Sr vs. 143Nd/144Nd. The trace element data and isotopic plots suggest that the melts that produced the basalts are from subduction modified mantle wedge peridotites that ponded near the base of the lithosphere similar to the generation of other subduction related calc-alkaline lavas along convergent continental margins. The andesitic samples appear to be the result of further modification through crustal assimilation as seen in the higher isotopic Sr contents in the andesites and Ce/Smpmn vs. Tb/Ybpmn plots. Finally, the proposed map units from Sylvester & Raines (2007) were found to contain various geochemical facies based on the samples collected indicating that some map units may have to be redefined or sub-divided.

The assemblage of ca. 6–4 Ma volcanic rocks exposed at the Sagehen Research station in the Truckee-Tahoe region of the northern Sierra Nevada, United States, is interpreted to be, within the Ancestral Cascades volcanic arc, a Lassen-type stratovolcano complex. Sagehen is of particular importance because it is one of the few Tertiary arc volcanic centres in California which has not been heavily glaciated during the Pleistocene. The volcanic rocks are variably porphyritic or aphanitic, including abundant plagioclase with clinopyroxene and amphibole. The rocks range from basalt to basaltic-andesite to andesite in composition. Basalts are olivineand clinopyroxene-bearing with minor phenocrysts of plagioclase. The basaltic-andesites are primarily pyroxene bearing while the andesites contain pyroxene-, plagioclase- and hornblende porphyritic phases. Sagehen arc lavas are calc-alkaline and enriched in the large ion lithophile elements and depleted in High Field Strength Elements. The basalts are depleted in Zr and Hf while the andesites are enriched with Zr and Hf relative to the middle rare earth elements. Compared to previously studied Ancestral Cascade arc samples, Sagehen region basalts have lower 143Nd/144Nd isotopic values that do not correspond to proposed mantle-lithosphere mixing lines, while the andesite samples appear to represent the interplay of these two components on a 87Sr/86Sr vs. 143Nd/144Nd. The trace element data and isotopic plots suggest that the melts that produced the basalts are from subduction modified mantle wedge peridotites that ponded near the base of the lithosphere similar to the generation of other subduction related calc-alkaline lavas along convergent continental margins. The andesitic samples appear to be the result of further modification through crustal assimilation as seen in the higher isotopic Sr contents in the andesites and Ce/Smpmn vs. Tb/Ybpmn plots. Finally, the proposed map units from Sylvester & Raines (2007) were found to contain various geochemical facies based on the samples collected indicating that some map units may have to be redefined or sub-divided.

Strontium isotope analysis has provided archaeologists with an unprecedented opportunity to study the mobility of humans and animals in the past. However, a lack of systematic environmental baseline data has seriously restricted the full potential of the analytical technique; there is little biosphere data available against which to compare measured skeletal data. This thesis examines the extent to which geographic variation in biosphere 87Sr/86Sr composition can be spatially resolved within the lowland terrain of England, in a geographically and geologically coherent study area. Systematically collected samples of vegetation, stream water and surface soils, including new and archived material have been used. The potential of these sample media to provide reliable estimates of the 87Sr/86Sr composition of bioavailable strontium are evaluated under both high-density and low-density sampling regimes, and against new analyses of local archaeological material. Areas lying south of the Anglian glacial limit, display a pattern of geographic 87Sr/86Sr biosphere variation (0.7080¿0.7105) controlled by solid geology, as demonstrated by high-density biosphere mapping. Data collected at a wider geographic scale, including above superficial deposits, indicate the dominant influence of re-worked local rocks on the biosphere. These methods have enabled a reclassification of the archaeologically important Cretaceous Chalk domain. Analysis of rainwater and other indicators of atmospheric deposition show that, in this setting, local biosphere variation is not significantly perturbed by atmospheric inputs. Time-related data from archaeological cattle and sheep/goat tooth enamel suggest that the modern biosphere data can be used to understand livestock management regimes and that these are more powerful than using an average value from the enamel. A more complete understanding of possible patterns of mobility in a group of humans has been achieved through analysis of material from Winchester and comparison with the Chalk biosphere domain. / British Geological Survey¿s British University Funding Initiative (BUFI) and the School of Life Sciences at the University of Bradford joint funding.

The exposed metamorphic core complexes in the Cyclades continental back-arc of southeast Greece host a range of base and precious metal deposits. Shallow crustal mineral deposits that formed since the late Miocene to active seafloor hydrothermal systems occur in the footwall and hanging wall of the major detachment systems and within all tectono-stratigraphic units. The carbonate-replacement, vein-type, intermediate-sulfidation epithermal, and skarn deposits tapped different sources of metals and fluids along the major low-angle detachment systems and steep normal faults. This study links the regional metallogenic diversity to fluid and crustal sources, within a framework of the evolving geodynamic context and complex basement structure. Over 30 mineral occurrences, from Lavrion of Attica on the Greek mainland across the Cycladic archipelago to Milos and Santorini on the active South Aegean volcanic arc, were investigated, encompassing ~40,000 km2 of the arc- to backarc system. Petrographic observations are combined with mineralogical, geochemical, and isotopic analyses (Pb, Sr, δ34S and δ18O) of galena (PbS) and ore-associated hydrothermal barite (BaSO4). New galena Pb isotope data complemented by Pb isotope data of galena from the literature exhibit a range of isotopic ratios, with a resolvable geologic pattern. Galena from deposits in the north-central Cyclades has low 206Pb/204Pb ≤18.84, while galena from the west Cyclades has higher 206Pb/204Pb ≥18.84. This distinct regional pattern is further supported by the Sr isotope signature of hydrothermal barite, with 87Sr/86Sr ≥0.711 in the north-central Cyclades and 87Sr/86Sr  ≤0.711 in the west Cyclades. When considered together with compiled Pb and Sr isotope data of potential source rocks, large-scale regional patterns in the isotopic signatures are recognized, suggesting two distinct sources of lead and strontium in the underlying basement of the core complexes. These two sources (Lower Cycladic Blueschist Nappe and Upper Cycladic Blueschist Nappe including the Cycladic Basement) correspond to known tectono-stratigraphic units of different provenance and age and help to correlate the basement over considerable distances, even where exposures are limited. Sulfur and oxygen isotope data of barite indicate variable contributions of sulfur from seawater and magmatic fluids among the range of deposit types. This indicates that different fluid generations evolved and tapped the basement, likely along the major detachment faults. The δ34S values of barite indicate that mineral deposits in the Cyclades can be clearly distinguished. Compiled whole-rock isotopic and geochemical data of the basement lithologies exhibit a broad dispersion. Miocene to recent mineralization in the Cyclades caused homogenization of the crustal sources and indicate regional lithological differences in the architecture of the exposed metamorphic core complexes. This thesis demonstrates that regional studies of the geochemical and isotopic composition of mineral deposits can provide additional constraints for the paleogeographic reconstruction of juxtaposed tectono-stratigraphic units across the Cyclades and other complex continental back-arc systems.

The quartz dioritic Quottoon Igneous Complex (QIC) is a major Paleogene (65-56 Ma) magmatic body in NW British Columbia and SE Alaska that was emplaced along the Coast shear zone (CSZ). The QIC contains two different igneous suites that provide information about source regions, magmatic processes and evolving tectonic regimes that changed from a dominantly convergent to a dominantly strike-slip regime between 65 to 55 Ma. Heterogeneous suite I rocks (e. g. along Steamer Passage) have a pervasive solid-state fabric, abundant mafic enclaves and dikes, metasedimentary screens, and variable color indices (25-50). The homogeneous suite II rocks (e. g. along Quottoon Inlet) have a weak (to absent) fabric developed in the magmatic state (aligned feldspars, melt filled shears), and more uniform color indices (24-34) than in suite I. Suite I rocks have Sr concentrations <750 ppm, avg. LaN/YbN = 10.4, and initial 87Sr/86Sr ratios that range from 0.70513 to 0.70717. The suite II rocks have Sr concentrations >750 ppm, avg. LaN/YbN = 23.1, and initial 87Sr/86Sr ratios that range from 0.70617 to 0.70686. This study proposes that the parental QIC magma (initial 87Sr/86Sr = 0.706) can be derived bypartial melting of an amphibolitic source reservoir at lower crustal conditions. Geochemical data (Rb, Sr, Ba and LaN/YbN) and initial 87Sr/86Sr ratios preclude linkages between the two suites by fractional crystallization or assimilation and fractional crystallization (AFC) processes. The suite I rocks are interpreted to be the result of magma mixing between the QIC parental magma and a mantle derived magma. The samples do not lie along a single mixing line due to continued evolution through fractional crystallization/AFC processes subsequent to magma mixing. The suite II rocks may be generated by AFC. Initial 87Sr/86Sr ratio data suggests that similar processes to those that affected the QIC may also have operated during the generation of other portions of the Great Tonalite Sill of southeast Alaska. / Master of Science

Global climate is controlled by two factors, the amount of heat energy received from the sun (solar insolation) and the way that heat is distributed Earth's surface. Solar insolation varies on timescales of 10s to 100s of thousands of years due to changes in the path of Earth's orbit about the sun (Milankovitch cycles). Earth's internal boundary conditions, such as paleogeography, the presence/absence of polar icecaps, atmospheric/oceanic chemistry and sea level, provide distribution and feedback mechanisms for the incoming heat. Variations in these internal boundary conditions may happen abruptly or, as in the case of plate tectonics, take millions of years. We use geochemical and sedimentological techniques to investigate the response of ocean chemistry, regional aridity and atmospheric and oceanic circulation patterns to climate change during both greenhouse and icehouse climates. To explore the connection between orbitally-forced changes in solar insolation, continental aridity and wind, we generated a high-resolution dust record for ~58 Myr old deep-sea sediments from Shatsky Rise. Our data provide the first evidence of a correlation between dust flux to the deep sea and orbital cycles during the Early Paleogene, indicating dust supply (regional aridity) responded to orbital forcing during the last major interval of greenhouse climate. The change in dust flux was comparable to that during icehouse climates implying subtle variations in solar insolation have a similar impact on climate during intervals of over-all warmth as they do during glacial-interglacial states. The Carboniferous Period (359-299 Ma) marks a critical time in Earth's history when a series of tectonic and biological events caused a shift in the mean climate state from a global "greenhouse" to an "icehouse". Geochemical records extracted from sedimentary rocks deposited in shallow epicontinental seaways are increasingly being used to infer relationships between tectonism, carbon cycling and climate and therefore are assumed to reflect global ocean processes. We analyzed radiogenic isotopes in biogenic apatite along a North American transect to constrain the degree of geochemical coupling between the epicontinental seas and the open ocean. Our results argue strongly for decoupling of North American seaways from the open ocean by latest Mississippian time.