No description available.

Mg/Ca and d18O derived from marine biogenic carbonates have been widely used as reliable paleoenvironmental proxy for seawater temperature, salinity and water mass circulation reconstructions. The use of Mg/Ca is based on long residence time in seawater and uniform distribution with habitat depth of planktonic foraminifera. Fluid Mg/Ca affects mineralogy of CaCO3, thus high seawater Mg/Ca favors precipitation of aragonite instead of calcite. The records of d18O in carbonates yield strong correlation with seawater temperature, salinity and d18O. Distribution of d18O in water is highly heterogeneous within longitude, latitude and depth. Therefore a combination of foraminieral d18O and Mg/Ca could resolve temperature, d118Owater, and hence salinity, which is linked to variability in fresh water balance and glacial ice volume throughout geologic history. In this work we study the effects of important seawater/fluid parameters on Mg/Ca in inorganic and d18O in natural samples and provide data for improving paleoceanographic reconstructions.

The Pliocene world c.5.3 Ma to c.2.58 Ma exhibited a relatively stable climate with a warmer global mean surface temperature than present-day by ~2 °C to 3 °C, and palaeoclimate analysis from this interval is used to understand climate drivers in ‘warmer world’. Previous oxygen isotope thermometry investigations of Pliocene southern North Sea Basin (SNSB) Aequipecten opercularis from the Coralline Crag Formation in Suffolk, UK repeatedly reveal evidence of a cold-temperate climate regime. Contrastingly, other biological proxies record a warm-temperate/sub-tropical regime. This investigation concentrated on oxygen, carbon and microgrowth increment widths (MIWS) of fossil shell material from Pliocene SNSB spanning an interval of~4.4 Ma to ~2.5 Ma. The study sites included shallow marine Pliocene formations from the western and eastern SNSB, the Ramsholt Member of the Coralline Crag Formation, Suffolk UK, and the Luchtbal Sands and Oorderen Sands Members of the Lillo Formation, Belgium, and the Oosterhout Formation in the Netherlands. Oxygen isotopic palaeotemperature results showed cooler summer temperatures than presently in the SNSB, which were reflective of a cool-temperate regime. There was no evidence of warm-temperate or sub-tropical summer palaeotemperatures in the Pliocene SNSB as suggested by other planktonic proxies. This investigation discussed the possible causal factors for the cooler – than- expected winter and summer palaeotemperatures in the ‘warmer’ Pliocene world as recorded by this proxy. Discrepancies between the cool summer benthic palaeotemperatures from the bivalves and the warmer sub-tropical or warm-temperate summer palaeotemperature estimations from planktonic biological proxies was rectified by the application of a theoretical summer stratification factor (SSF). However, rectifying the discrepancies between cooler (cold-temperate) benthic winter palaeotemperatures and the warmer winter palaeotemperatures from other proxies was difficult because stratification does not occur during the winter. Dormancy behaviours in the warm- temperate –sub-tropical organisms was proposed as a suitable mechanism to allow their coexistence with the cool-tolerant bivalves, which were able to grow and feed underneath the thermocline during the summer months. Therefore, the investigation showed how the Pliocene SNSB exhibited a greater seasonality than occurs presently in the SNSB. The driver for the cooler winter temperatures in the Pliocene SNSB was not identified. Localised explanations including continental wind effects, interannual variations in MOC strength, and increased storm activity in the winter bringing cooler water into the SNSB were all suggested as potential drivers. Global features of climate including interglacial/glacial cycles and orbital forcing effects were factors also proposed for the overall mixed palaeotemperature signal in the Pliocene SNSB.

Rhyolites of the Picabo volcanic field (10.4-6.6 Ma) of the Yellowstone hotspot in eastern Idaho are preserved as thick ignimbrites and lavas along the margins of the Snake River Plain. This study presents new O and Hf isotope data and U-Pb geochronology from individual zircons, O isotope data from major phenocrysts, whole rock Sr and Nd isotope data, whole rock geochemistry, and trace element and volatile analyses of quartz-hosted melt inclusions, which were used to characterize the evolution of rhyolite generation through the eruptive sequence. The chemical composition of the first eruption of the caldera complex, the Tuff of Arbon Valley, suggests magma generation through repeated magma injection into the crust, remelting, crystallization, mixing, and crustal assimilation. Subsequent eruptions have diverse and low δ18O signatures indicating rhyolite generation through the remelting of variably hydrothermally altered volcanics, followed by rapid batch assembly. This thesis includes co-authored material previously published.

Recent episodes of extreme weather and the drastic consequences they can have for ecosystems, societies, and economies, emphasize the need for a better understanding of Earths climate. In order to gain a better understanding of modern and future climate, a more thorough knowledge of past climates at the highest resolution possible from different regions is necessary. To this end, a study of seasonal temperature variability in the waters off the northern coast of Iceland was undertaken. Twenty-six bivalves were selected from marine sediment cores recovered from the northern and northwestern coasts of Iceland. Bivalves were selected from intervals of climatic interest as determined from sedimentological characteristics. Shells were micromilled and the carbonate analysed for stable oxygen and carbon isotope values. Oxygen isotope values are driven principally by the temperature of the water from which the shell was precipitated. These data provide a time-series of discrete climate profiles of seasonal temperature variations from c. 360 cal yr BC to cal yr AD 1660, each recording 2 to 9 consecutive years of temperature variability. Several notable warm and cold periods were identified and characterized in terms of maximum and minimum temperatures. As this period overlaps the Viking Age (c. 790 to 1070) and the establishment of Norse colonies in Iceland and Greenland, the temperature record was compared with historical records and demonstrates the significant impact of variation in temperature seasonality on the establishment, development, and in some cases, collapse of societies in the North Atlantic.

Ecosystem metabolism is an important indicator of aquatic ecosystem function. This thesis concerns ecosystem metabolism as recorded by daily variation in dissolved oxygen (DO) and δ18O-DO in an impacted temperate river network, the Grand River, Ontario, Canada, and specifically addresses the effects of stream size and human disturbance including agriculture, deforestation, and wastewater treatment plants (WWTPs). A suite of 14 sites in the Grand River network was selected with stream sizes varying from 2nd to 7th order. A transient model of river ecosystem oxygen metabolism, ROM-TM, was developed in order to calculate river ecosystem metabolic rates and reaeration rates from field observation of changes in DO and δ18O-DO. ROM-TM is an inverse modeling approach programmed using MATLAB. Key parameters describing the main metabolic processes, gas exchange, and isotopic fractionation, such as maximum photosynthetic rate (Pm), photosynthetic efficiency (a), respiration rate at 20℃ (R20), gas exchange coefficient (k), respiration isotopic fractionation factor (aR), and photorespiration coefficient (βR), can be obtained by matching of model predictions with field data. Besides being capable of teasing apart metabolic processes and gas exchange to provide daily average estimates of metabolic parameters at the ecosystem level, ROM-TM can be used to address issues related to light including light saturation phenomena at the ecosystem level, the effect of cloud cover on metabolic balance and photorespiration. Primary production responses to light along a longitudinal gradient in the Grand River network were described by means of P-I curves. Both light-limited and light-saturated conditions were observed. Production parameters Pm and Ik in the Grand River network exhibited an increase with stream order, while a was independent of stream size. However, a did vary among and within sites. Higher light availability in small and middle-sized streams without riparian trees was associated with high Pm, Ik and Ec, but low a. Ecosystem-level Pm in both small periphyton-dominated streams and large macrophyte-dominated rivers in the Grand River basin were generally less than community-level Pm values from the literature. However, two Grand River sites had comparable Pm to literature-derived Pm due to the prolific growth of macrophytes supported by high nutrient effluents from upstream WWTPs. Ecosystem-level a in my study streams were also less than those at the community level, indicating there was a declining trend of this parameter with scale, from individual, community to ecosystem. Derived parameters (e.g., Ik, Ec, and saturation point) increased from the individual level to the community level, and then to the ecosystem level. From May to early October, metabolic rates in the Grand River network (gross primary production, GPP = 0.4 to 20 and ecosystem respiration, ER = 2 to 33 g O2 m-2 day-1) were within the broad range of metabolic rates occurring in the temperate region, regardless of stream size. The Grand River network is a net heterotrophic system. The total GPP and ER for whole basin was 3.3e+08 and 4.2e+08 g O2 day-1, respectively. Reach geomorphology controls the spatial patterns of stream metabolism in the Grand River network, although the spatial patterns may be modified by effects of human disturbance on riparian vegetation, nutrients and other factors. Stream order and channel width, as measures of stream size, are good predictors of metabolic rates and ratios of GPP: ER from small streams to the central Grand River. Ecosystem metabolic rates and ratios generally increase with stream size, but with site-specific variation. The Grand River network is experiencing effects of human disturbance, mostly downstream of the urban areas and least in small streams with remaining riparian forest. The small and middle-sized streams (2nd to 4th order) without riparian trees in agriculture regions in the Grand River basin did not exhibit significantly different GPP and ER than their counterparts with riparian trees. The stimulative effect of increased light availability due to open canopy on GPP in non-shaded streams may be offset by shading from stream banks and riparian grasses, and unstable sediments resulting from agricultural activities. Large river sites impacted by WWTPs had significantly increased metabolic rates, both GPP and ER, compared to two upstream sites impacted by agriculture only. This result suggests that urban areas cause impacts on the Grand River that are superimposed on the impacts of agriculture. Three aspects of metabolism of the Grand River differ from the general pattern for the temperate regions: (1) a increase trend of GPP: ER ratios with stream size from 2nd to 7th order; (2) overall, human activities in the Grand River watershed have stronger positive effects on the GPP than on the ER; (3) the middle-sized to large river sites (5th-7th order) had greater influence than small to middle-sized streams (2nd-5th order) in the Grand River on overall GPP and ER. The general trend of GPP: ER ratio in tropical, subtropical, temperate, and global data approximately conforms to the predictions of the River Continuum Concept (RCC). However, the maximum ratio of GPP: ER in mid-reaches of river networks is not usually >1 as proposed in the RCC. There is a latitude and stream size shift phenomenon regarding where the peak ratio of GPP: ER occurs in each climate zone. The maximum GPP: ER ratio is higher at higher latitudes and occurs at higher order streams. The study of stream ecosystem metabolism can benefit from the addition of the second oxygen budget, δ18O-DO, in four ways: (1) it is better to use both DO and δ18O-DO budgets, rather than DO only, in sampling protocols with low temporal frequency but high spatial frequency; (2) the δ18O-DO time series data can provide relatively independent constraints on parameter estimation; (3) the addition of δ18O-DO in using two oxygen budgets to quantify metabolic rates provides a way, the cross-plot of δ18O-DO against fraction of DO saturation, to indicate trophic status of an aquatic ecosystem; and (4) the addition of δ18O-DO can provide an estimate of aR at the ecosystem level that can be used to understand factors affecting respiration.

The Toba caldera located in north Sumatra, Indonesia, is the source of the largest volcanic eruption in the Quaternary (Rose & Chesner 1987). Its enormous volume of 2800 km3 has been a matter of debate for decades and it is still unclear where and how the Toba magma was assembled. This study documents oxygen isotope data for a suite of whole rocks and minerals erupted as part of the Young Toba Tuff (YTT), some 74 ka ago (cf. Chesner et al. 1991). Oxygen isotope data has been obtained in-situ from quartz crystals (SIMS), whole rocks (conventional), as well as quartz, feldspar, amphibole and biotite (laser fluorination). In combination with cathodoluminescence (CL) imaging on the quartzes, the data are used to test the relative roles of shallow magmatic processes such as crystal fractionation, magma-crust interaction and crystal recycling within the Toba magmatic system. In addition, thermobarometric calculations have been performed on plagioclase and amphibole phenocrysts from the YTT to help unravel the magma storage and plumbing system that gave rise to the YTT. The combined evidence will be used to derive a model for shallow magma evolution and storage at Toba some 74 ka ago. The CL images of quartz crystals exhibit defined patterns of magmatic zoning, which broadly coincide with fluctuations in δ18O values in the quartz crystals, allowing correlation of textural and compositional data. Measured δ18Oquartz values range from 6.7 ‰ to 9.4 ‰, independent of position on crystal core or rim. Values for δ18Omagma have been calculated from quartz phenocrysts (assuming Δquartz-magma is 0.7 ‰ at magmatic temperatures). The lowest magma value is 6.0 ‰, apparently reflecting a primitive isotopic signal (Taylor & Sheppard 1986). The maximum calculated magma value is 8.7 ‰, indicating a significant crustal component and thus multiple sources to the Toba magmatic system. Several crystals, however, show internal zoning with gradually lower values towards the rims, pointing to a late-stage low-δ18O input, most probably from the shallow volcanic edifice. The crystals therefore record a complex and heterogeneous origin of the YTT magma, comprising a primitive and an evolved magmatic component topped up with several substantial crustal contributions to finally assemble the massive volume of the 74 ka Toba eruption.

Recent episodes of extreme weather and the drastic consequences they can have for ecosystems, societies, and economies, emphasize the need for a better understanding of Earths climate. In order to gain a better understanding of modern and future climate, a more thorough knowledge of past climates at the highest resolution possible from different regions is necessary. To this end, a study of seasonal temperature variability in the waters off the northern coast of Iceland was undertaken. Twenty-six bivalves were selected from marine sediment cores recovered from the northern and northwestern coasts of Iceland. Bivalves were selected from intervals of climatic interest as determined from sedimentological characteristics. Shells were micromilled and the carbonate analysed for stable oxygen and carbon isotope values. Oxygen isotope values are driven principally by the temperature of the water from which the shell was precipitated. These data provide a time-series of discrete climate profiles of seasonal temperature variations from c. 360 cal yr BC to cal yr AD 1660, each recording 2 to 9 consecutive years of temperature variability. Several notable warm and cold periods were identified and characterized in terms of maximum and minimum temperatures. As this period overlaps the Viking Age (c. 790 to 1070) and the establishment of Norse colonies in Iceland and Greenland, the temperature record was compared with historical records and demonstrates the significant impact of variation in temperature seasonality on the establishment, development, and in some cases, collapse of societies in the North Atlantic.

Oxygen and hydrogen isotopes (δ18O, δD) are increasingly powerful tools for reconstructing past hydroclimate variability. The utility of δ18O- and δD-based paleoclimate records, however, depends on our understanding of how well these tracers reflect past climate conditions. The dynamics controlling the relationship between climate and water isotope variability are highly complex and often poorly constrained, especially in the tropics, where many key high-resolution paleoclimate records rely on past rainfall isotopes as proxies for hydroclimate. In this dissertation, I use multi-year timeseries of daily rainfall and biweekly dripwater δ18O from northern Borneo – a site for stalagmite δ18O-based paleoclimate reconstruction in the heart of the West Pacific Warm Pool – to track the cloud-to-calcite transformation of δ18O and its relationship to large-scale climate variability. Chapter 2 investigates the variability of rainfall δ18O variability from northern Borneo on diurnal to interannual timescales and its relationship with local and regional climate. Chapter 3 investigates the rainfall-to-dripwater transformation of climate-related isotopic signals following water transit through the Borneo cave system. Overall, this dissertation provides empirical support for the interpretation of northern Borneo stalagmite δ18O as a robust indicator of regional-scale hydroclimate variability, where higher δ18O reflects regional drying. More generally, this research provides a roadmap for obtaining more nuanced interpretations of speleothem δ18O records from multi-year, high-resolution, paired timeseries of rainfall and dripwater δ18O.

Oxygen isotopes and major and trace element geochemistry have been used to evaluate the geochemical and tectonic history of a Franciscan hornblende-amphibolite and a eclogite block from Ring Mountain, Tiburon and three eclogite/blueschist blocks from Jenner Beach, California, all blocks have experienced varying amounts of retrogression. Relative to the presumed basaltic protolith, enrichments in large ion lithophile elements (LILEs) indicate interaction with sediment derived fluids in the retrograde eclogite and retrograde blueschist samples and high Mg, Cr, and Ni in actinolite rind indicate interaction with ultramafic rock. The [delta]¹⁸O values of chlorite from the Ring Mountain hornblende-amphibolite and the eclogite block have a narrow range of [delta]¹⁸O values (+7.7-8.2%₀, n=8) and actinolite from actinolite rind on the eclogite block from Ring Mountain and the blueschist/eclogite blocks from Jenner Beach are (+7.8-8.5%₀, n=5). Chlorite-actinolite geothermometry yields temperatures of 200-280°C for actinolite rind formation. Additionally, the [delta]¹⁸O values of both chlorite and actinolite at these temperatures indicates equilibrium with the measured value of Tiburon serpentinites, (7.6 to 8.1%₀, n = 3 Wenner and Taylor, 1974). Oxygen isotope analyses of garnet mineral separates from the eclogite and hornblende-amphibolite from Ring Mountain have [delta]¹⁸O values of +6.8±0.3%₀ (n=7), and +8.2±0.2%₀ (n=7), respectively. Garnets from the three eclogite/blueschist blocks at Jenner Beach have a [delta]¹⁸O value of +9.8±0.7%₀, (n=23). The difference in [delta]¹⁸O values of garnets between the high-grade blocks is likely due to in situ hydrothermal alteration of the seafloor basalt prior to subduction. The geochemical trends can be explained by a model in which during the early stages of subduction pieces of altered oceanic crust are detached from the downgoing slab and incorporated into the mantle wedge soon after reaching peak eclogite or amphibolite facies conditions. As subduction continues, the hanging wall cools and fluids released from subducted sediments infiltrate the overlying mantle wedge. As the blocks cool they develop a retrograde blueschist facies overprint under relatively static conditions. With cooling of the hanging wall and infiltration of sedimentary fluids, serpentinization induces reaction between the blocks and surrounding mantle wedge and Mg-rich actinolite rind is formed. The blocks are then plucked from the mantle wedge and incorporated into the subduction channel where they flow back to the surface via corner flow. / text