Calcium carbonate preservation in the equatorial Pacific

The Pliocene-Pleistocene history of CaCO3 preservation in the central equatorial Pacific is reconstructed from a suite of deep-sea cores and is compared to fluctuations in global ice volume inferred from delta18O records. The results are highlighted by: (1) a strong covariation between CaCO3 preservation and ice volume over 104 to 106 year time scales; (2) a long-term increase in ice volume and CaCO3 preservation since 3.9 Ma demonstrated by a deepening of the lysocline and the carbonate critical depth; (3) a dramatic shift to greater CaCO3 preservation at 2.9 Ma; (4) distinctive ice-volume growth and CaCO3 preservation events at 2.4 Ma, which are associated with the significant intensification of northern hemisphere glaciation; (5) a mid-Pleistocene transition to 100-kyr cyclicity in both CaCO3 preservation and ice volume; and (6) a 600-kyr Brunhes dissolution cycle superimposed on the late Pleistocene glacial/interglacial 100-kyr cycles. CaCO3 preservation primarily reflects the carbonate chemistry of abyssal waters and is controlled by long-term (106 year) and short-term (104 to 105 year) biogeochemical cycling and by distinct paleoclimatic events. We attribute the long-term increase in CaCO3 preservation primarily to a fractionation of CaCO3 deposition from continental shelf to ocean basin, and secondarily to a gradual rise in the riverine and glaciofluvial flux of Ca++. On shorter time scales, the fluctuations in CaCO3 preservation slightly lag ice volume fluctuations and are attributed to climatically induced changes in the circulation and chemistry of Pacific deep water.

UVB radiation generates sunburn pain and affects skin by activating epidermal TRPV4 ion channels and triggering endothelin-1 signaling.

At our body surface, the epidermis absorbs UV radiation. UV overexposure leads to sunburn with tissue injury and pain. To understand how, we focus on TRPV4, a nonselective cation channel highly expressed in epithelial skin cells and known to function in sensory transduction, a property shared with other transient receptor potential channels. We show that following UVB exposure mice with induced Trpv4 deletions, specifically in keratinocytes, are less sensitive to noxious thermal and mechanical stimuli than control animals. Exploring the mechanism, we find that epidermal TRPV4 orchestrates UVB-evoked skin tissue damage and increased expression of the proalgesic/algogenic mediator endothelin-1. In culture, UVB causes a direct, TRPV4-dependent Ca(2+) response in keratinocytes. In mice, topical treatment with a TRPV4-selective inhibitor decreases UVB-evoked pain behavior, epidermal tissue damage, and endothelin-1 expression. In humans, sunburn enhances epidermal expression of TRPV4 and endothelin-1, underscoring the potential of keratinocyte-derived TRPV4 as a therapeutic target for UVB-induced sunburn, in particular pain.

Stable isotope and Mg/Ca ratios of Globigerinoides ruber from core-top sediment samples

Seasonal changes in surface ocean temperature are increasingly recognized as an important parameter of the climate system. Here we assess the potential of analyzing single-specimen planktonic foraminifera as proxy for the seasonal temperature contrast (seasonality). Oxygen isotopes and Mg/Ca ratios were measured on single specimens of Globigerinoides ruber, extracted from surface sediment samples of the Mediterranean Sea and the adjacent Atlantic Ocean. Variability in d18O and Mg/Ca was then compared to established modern seasonal changes in temperature and salinity for both regions. The results show that (1) average d18O-derived temperatures correlate with modern annual average temperatures for most sites, (2) the range in d18O- and Mg/Ca-derived temperature estimates from single-specimen analysis resembles the range in seasonal temperature values at the sea surface (0-50 m) in the Mediterranean Sea and the Atlantic Ocean, and (3) there is no strong correlation between Mg/Ca- and d18O-derived temperatures from the same specimens in the current data set, indicating that other parameters (salinity, carbonate ion concentration, symbiont activity, ontogenesis, and natural variability) potentially affect these proxies.

Mg/Ca ratio, Sr/Ca ratio and stable isotopes of the foraminifera Oridorsalis umbonatus in surface sediment samples

We investigate the influence of carbonate system parameters (carbonate ion concentration, [CO3**2-]; carbonate ion saturation, Delta [CO3**2-]) on the trace element and stable isotope ratios in the endobenthic foraminifera Oridorsalis umbonatus. Data from modern core top samples from the Namibian continental slope suggest that the shell composition of this species is influenced by the chemistry of the pore-water. For these organic-rich sediments, the impact of ocean bottom water properties on both pore-water and shell chemistry is surprisingly small. Sr/Ca correlates positively with [CO3**2-] and to a lesser extent with Delta [CO3**2-], which is opposed to previous results. A [CO3**2-] decrease of 10 µmol/kg leads to an increase of 0.05 mmol/mol in Sr/Ca. We observe a correlation between shell d18O (corrected for temperature and d18O seawater) and [CO3**2-], however, the variability of the corrected d18O is close to the analytical limit. No clear dependences were observed for d13C and Mg/Ca.

Foraminifera Mg/Ca, test weight and XDX for sediment core WIND28K

A record of deep-sea calcite saturation (D[CO3**-2]), derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (~15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ~4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ~4°C colder in MIS 3 compared to the Holocene (8 ka B.P.).

Isotopic ratios and ion composition of massive ground ice on Herschel Island

Herschel Island in the southern Beaufort Sea is a push moraine at the northwestern-most limit of the Laurentide Ice Sheet. Stable water isotope (d18O, dD) and hydrochemical studies were applied to two tabular massive ground ice bodies to unravel their genetic origin. Buried glacier ice or basal regelation ice was encountered beneath an ice-rich diamicton with strong glaciotectonic deformation structures. The massive ice isotopic composition was highly depleted in heavy isotopes (mean d18O: -33 per mil; mean dD: -258 per mil), suggesting full-glacial conditions during ice formation. Other massive ice of unknown origin with a very large d18O range (from -39 to -21 per mil) was found adjacent to large, striated boulders. A clear freezing slope was present with progressive depletion in heavy isotopes towards the centre of the ice body. Fractionation must have taken place during closed-system freezing, possibly of a glacial meltwater pond. Both massive ground ice bodies exhibited a mixed ion composition suggestive of terrestrial waters with a marine influence. Hydrochemical signatures resemble the Herschel Island sediments that are derived from nearshore marine deposits upthrust by the Laurentide ice. A prolonged contact between water feeding the ice bodies and the surrounding sediment is therefore inferred.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Boron isotope and B/Ca ratios of planktonic foraminifera

Here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This new approach is fast (~10 samples analysed in duplicate per analytical session) and accurate (to better than 0.25 per mil at 95% confidence) with acceptable sample size requirements (1-3 mg of carbonate). A core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by MC-ICPMS and the isotopic composition of B(OH)-4 in seawater (as predicted using the recently measured isotopic equilibrium factor of 1.0272) at the depth of habitat. A down core and core top investigation of boron concentration (B/Ca ratio) shows that the partition coefficient is influenced by [CO2-3] complicating the application of this proxy. Nevertheless, it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the Caribbean Sea (ODP Site 999A) over the last 130 kyr. This reconstruction shows that during much of the Holocene and the last interglacial period surface water at Site 999A was in equilibrium with the atmosphere with respect to CO2. During the intervening colder periods although the surface water pCO2 was lower than the Holocene, it was a minor to significant source of CO2 to the atmosphere possibly due to either an expansion of the eastern equatorial Atlantic upwelling zone, or a more local expansion of coastal upwelling in the southern Caribbean. Such reorganisation of the oceanic carbonate system in favour of a larger source of CO2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric CO2 during glacial periods to be more efficient than previously supposed.

Seawater carbonate chemistry, Mg/Ca, Sr/Ca, oxygen production and calcification rate during experiments with coral Pocillopora damicornis, 2011

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca2+ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by 42Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr2+ and Ca2+ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca2+ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Rôle de la MAP3K DLK dans la réponse des neurones à l'ion calcium, un médiateur de dégénérescence et régénérescence

Le corps humain est composé de plusieurs milliards de cellules neuronales, lesquelles ont un impact primordial sur les systèmes vitaux. En effet, le système nerveux, étant lui-même un système vital du corps humain, effectue de nombreuses fonctions afin de voir au bon fonctionnement des autres systèmes du corps, tels que le système cardiovasculaire, le système digestif, le système musculaire et bien d’autres. Plusieurs maladies neurodégénératives telles que l’Alzheimer et la maladie de Creutzfeldt-Jakob, affectent les cellules nerveuses du corps et occasionnent la perte de différentes fonctions causant une diminution du bien-être et pouvant mener à la mort. La hausse du nombre d’individus atteint de maladies neurodégénératives observée au fils des ans nous montre l’importance de comprendre les phénomènes moléculaires qui se produisent lors des mécanismes de dégénérescence axonale dans les neurones. Lors de ma maîtrise dans le laboratoire du professeur Richard Blouin, j’ai étudié l’impact d’une augmentation intracellulaire de calcium sur la protéine dual leucine zipper kinase (DLK) en utilisant un modèle cellulaire humain, les SH-SY5Y. J’ai pu démontrer que l’entrée de calcium dans la cellule avait un impact sur la quantité de protéine DLK présente dans celles-ci. En effet, j’ai pu observer une diminution de la quantité de DLK dans les cellules suite à une entrée de calcium, un phénomène exclusivement calcium-dépendant. À l’aide d’inhibiteurs pharmacologiques, j’ai pu montrer l’implication, des calpaïnes, des protéases calcium-dépendantes reconnues pour leur rôle dans la dégénérescence axonale. Les essais in vitro montrent que DLK est une cible spécifique des calpaïnes.

CO-ELECTROPHORETIC DEPOSITION OF LIQUID METAL AND SILICON FOR LITHIUM-ION BATTERY APPLICATION

A low cost electrophoretic deposition (EPD) process was successfully used for liquid metal thin film deposition with a high depositing rate of 0.6 µ/min. Furthermore, silicon nano-powder and liquid metal were then simultaneously deposited as the negative electrode of lithium-ion battery by a technology called co-EPD. The liquid metal was hoping to act as the matrix for silicon particles during lithium ion insertion and distraction. Half-cell testing was performed using as prepared co-EPD sample. An initial discharge capacity of 1500 mAh/g was reported for nano-silicon and galinstan electrode, although the capacity fading issue of these samples was also observed.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.