Eigenschaften von thermoresponsiven Bürstenpolymeren

In dieser Doktorarbeit werden die Eigenschaften von thermoresponsiven Bürstenpolymeren untersucht. Hierbei konnten erstmalig thermische Konformationsübergänge von zylindrischen Bürstenmolekülen auf Oberflächen beobachtet werden. Der Einfluss der Oberfläche auf die Umkehrbarkeit und die Kinetik der Übergänge wurde untersucht. Die dabei erhaltenen Erkenntnisse konnten verwendet werden, um das Verhalten der Polymere auf anderen Oberflächen vorherzusagen. Im zweiten Projekt wurde gezeigt, dass Einzelmolekül-Kraftspektroskopie eine gute Methode für die Untersuchung der mechanischen Eigenschaften von Bürstenpolymeren in guten Lösungsmitteln ist. Mit kleinen Substanzmengen kann die Persistenzlänge der Polymere bestimmt werden. Es ist möglich zu zeigen, dass die Persistenzlänge der Polymerbürsten von ihrer Seitenkettenlänge abhängt. Überraschenderweise funktioniert das Experiment nicht, wenn man die Bürsten aus einem Polymerfilm zieht anstatt ein Einzelmolekülexperiment durchzuführen. In diesem Fall zeigen die Kraft-Abstands-Kurven zu lange Kontur- und Persistenzlängen. Diese Beobachtung ist für lineare Polymere nicht gültig. Im dritten Teil der Doktorarbeit werden Kraft-Abstands-Experimente an einzelnen kollabierten Polymeren untersucht. In schlechten Lösungsmitteln zeigen die Bürsten ein moleküllängenabhängiges Kraft-Plateau, welches theoretisch vorausgesagt wurde und einen Phasenübergang von einem kollabierten zu einem entspannten Zustand der Polymerkette anzeigt. In Fly-Fishing-Experimenten kann man eine Hysterese zwischen den beiden Messkurven beobachten, welche bei mehrfachem Ziehen kleiner wird. Alle Experimente in schlechten Lösungsmitteln wurden mit linearen Polymeren reproduziert, um den Einfluss der Molekülarchitektur von den generellen Eigenschaften von Polymeren in schlechten Lösungsmitteln unterscheiden zu können. Zum Abschluss wird die Abhängigkeit der Polymerentfaltung von der Laderate des Experiments gemessen.

Thermal fluctuations and boundary conditions in the lattice Boltzmann method

The lattice Boltzmann method is a popular approach for simulating hydrodynamic interactions in soft matter and complex fluids. The solvent is represented on a discrete lattice whose nodes are populated by particle distributions that propagate on the discrete links between the nodes and undergo local collisions. On large length and time scales, the microdynamics leads to a hydrodynamic flow field that satisfies the Navier-Stokes equation. In this thesis, several extensions to the lattice Boltzmann method are developed. In complex fluids, for example suspensions, Brownian motion of the solutes is of paramount importance. However, it can not be simulated with the original lattice Boltzmann method because the dynamics is completely deterministic. It is possible, though, to introduce thermal fluctuations in order to reproduce the equations of fluctuating hydrodynamics. In this work, a generalized lattice gas model is used to systematically derive the fluctuating lattice Boltzmann equation from statistical mechanics principles. The stochastic part of the dynamics is interpreted as a Monte Carlo process, which is then required to satisfy the condition of detailed balance. This leads to an expression for the thermal fluctuations which implies that it is essential to thermalize all degrees of freedom of the system, including the kinetic modes. The new formalism guarantees that the fluctuating lattice Boltzmann equation is simultaneously consistent with both fluctuating hydrodynamics and statistical mechanics. This establishes a foundation for future extensions, such as the treatment of multi-phase and thermal flows. An important range of applications for the lattice Boltzmann method is formed by microfluidics. Fostered by the "lab-on-a-chip" paradigm, there is an increasing need for computer simulations which are able to complement the achievements of theory and experiment. Microfluidic systems are characterized by a large surface-to-volume ratio and, therefore, boundary conditions are of special relevance. On the microscale, the standard no-slip boundary condition used in hydrodynamics has to be replaced by a slip boundary condition. In this work, a boundary condition for lattice Boltzmann is constructed that allows the slip length to be tuned by a single model parameter. Furthermore, a conceptually new approach for constructing boundary conditions is explored, where the reduced symmetry at the boundary is explicitly incorporated into the lattice model. The lattice Boltzmann method is systematically extended to the reduced symmetry model. In the case of a Poiseuille flow in a plane channel, it is shown that a special choice of the collision operator is required to reproduce the correct flow profile. This systematic approach sheds light on the consequences of the reduced symmetry at the boundary and leads to a deeper understanding of boundary conditions in the lattice Boltzmann method. This can help to develop improved boundary conditions that lead to more accurate simulation results.

Thermal Casimir effect at fluid interfaces: Fluctuation-induced forces between anisotropic colloids

We study the effective interaction between two ellipsoidal particles at the interface of two fluid phases which are mediated by thermal fluctuations of the interface. Within a coarse-grained picture, the properties of fluid interfaces are very well described by an effective capillary wave Hamiltonian which governs both the equilibrium interface configuration and the thermal fluctuations (capillary waves) around this equilibrium (or mean-field) position. As postulated by the Goldstone theorem the capillary waves are long-range correlated. The interface breaks the continuous translational symmetry of the system, and in the limit of vanishing external fields - like gravity - it has to be accompanied by easily excitable long wavelength (Goldstone) modes – precisely the capillary waves. In this system the restriction of the long-ranged interface fluctuations by particles gives rise to fluctuation-induced forces which are equivalent to interactions of Casimir type and which are anisotropic in the interface plane. Since the position and the orientation of the colloids with respect to the interface normal may also fluctuate, this system is an example for the Casimir effect with fluctuating boundary conditions. In the approach taken here, the Casimir interaction is rewritten as the interaction between fluctuating multipole moments of an auxiliary charge density-like field defined on the area enclosed by the contact lines. These fluctuations are coupled to fluctuations of multipole moments of the contact line position (due to the possible position and orientational fluctuations of the colloids). We obtain explicit expressions for the behavior of the Casimir interaction at large distances for arbitrary ellipsoid aspect ratios. If colloid fluctuations are suppressed, the Casimir interaction at large distances is isotropic, attractive and long ranged (double-logarithmic in the distance). If, however, colloid fluctuations are included, the Casimir interaction at large distances changes to a power law in the inverse distance and becomes anisotropic. The leading power is 4 if only vertical fluctuations of the colloid center are allowed, and it becomes 8 if also orientational fluctuations are included.

Model predictive control in thermal management of multiprocessor systems-on-chip

MultiProcessor Systems-on-Chip (MPSoC) are the core of nowadays and next generation computing platforms. Their relevance in the global market continuously increase, occupying an important role both in everydaylife products (e.g. smartphones, tablets, laptops, cars) and in strategical market sectors as aviation, defense, robotics, medicine. Despite of the incredible performance improvements in the recent years processors manufacturers have had to deal with issues, commonly called “Walls”, that have hindered the processors development. After the famous “Power Wall”, that limited the maximum frequency of a single core and marked the birth of the modern multiprocessors system-on-chip, the “Thermal Wall” and the “Utilization Wall” are the actual key limiter for performance improvements. The former concerns the damaging effects of the high temperature on the chip caused by the large power densities dissipation, whereas the second refers to the impossibility of fully exploiting the computing power of the processor due to the limitations on power and temperature budgets. In this thesis we faced these challenges by developing efficient and reliable solutions able to maximize performance while limiting the maximum temperature below a fixed critical threshold and saving energy. This has been possible by exploiting the Model Predictive Controller (MPC) paradigm that solves an optimization problem subject to constraints in order to find the optimal control decisions for the future interval. A fully-distributedMPC-based thermal controller with a far lower complexity respect to a centralized one has been developed. The control feasibility and interesting properties for the simplification of the control design has been proved by studying a partial differential equation thermal model. Finally, the controller has been efficiently included in more complex control schemes able to minimize energy consumption and deal with mixed-criticalities tasks

Non-thermal emission in High Frequency Peaked blazars towards the Square Kilometer Array era

In this thesis work we will explore and discuss the properties of the gamma-ray sources included in the first Fermi-LAT catalog of sources above 10 GeV (1FHL), by considering both blazars and the non negligible fraction of still unassociated gamma-ray sources (UGS, 13%). We perform a statistical analysis of a complete sample of hard gamma-ray sources, included in the 1FHL catalog, mostly composed of HSP blazars, and we present new VLBI observations of the faintest members of the sample. The new VLBI data, complemented by an extensive search of the archives for brighter sources, are essential to gather a sample as large as possible for the assessment of the significance of the correlation between radio and very high energy (E>100 GeV) emission bands. After the characterization of the statistical properties of HSP blazars and UGS, we use a complementary approach, by focusing on an intensive multi-frequency observing VLBI and gamma-ray campaign carried out for one of the most remarkable and closest HSP blazar Markarian 421.

Thermal excitations of optical nanofibers measured with a fiber-integrated Fabry-Pérot cavity

Efficient coupling of light to quantum emitters, such as atoms, molecules or quantum dots, is one of the great challenges in current research. The interaction can be strongly enhanced by coupling the emitter to the eva-nescent field of subwavelength dielectric waveguides that offer strong lateral confinement of the guided light. In this context subwavelength diameter optical nanofibers as part of a tapered optical fiber (TOF) have proven to be powerful tool which also provide an efficient transfer of the light from the interaction region to an optical bus, that is to say, from the nanofiber to an optical fiber. rnAnother approach towards enhancing light–matter interaction is to employ an optical resonator in which the light is circulating and thus passes the emitters many times. Here, both approaches are combined by experi-mentally realizing a microresonator with an integrated nanofiber waist. This is achieved by building a fiber-integrated Fabry-Pérot type resonator from two fiber Bragg grating mirrors with a stop-band near the cesium D2-line wavelength. The characteristics of this resonator fulfill the requirements of nonlinear optics, optical sensing, and cavity quantum electrodynamics in the strong-coupling regime. Together with its advantageous features, such as a constant high coupling strength over a large volume, tunability, high transmission outside the mirror stop band, and a monolithic design, this resonator is a promising tool for experiments with nanofiber-coupled atomic ensembles in the strong-coupling regime. rnThe resonator's high sensitivity to the optical properties of the nanofiber provides a probe for changes of phys-ical parameters that affect the guided optical mode, e.g., the temperature via the thermo-optic effect of silica. Utilizing this detection scheme, the thermalization dynamics due to far-field heat radiation of a nanofiber is studied over a large temperature range. This investigation provides, for the first time, a measurement of the total radiated power of an object with a diameter smaller than all absorption lengths in the thermal spectrum at the level of a single object of deterministic shape and material. The results show excellent agreement with an ab initio thermodynamic model that considers heat radiation as a volumetric effect and that takes the emitter shape and size relative to the emission wavelength into account. Modeling and investigating the thermalization of microscopic objects with arbitrary shape from first principles is of fundamental interest and has important applications, such as heat management in nano-devices or radiative forcing of aerosols in Earth's climate system. rnUsing a similar method, the effect of the TOF's mechanical modes on the polarization and phase of the fiber-guided light is studied. The measurement results show that in typical TOFs these quantities exhibit high-frequency thermal fluctuations. They originate from high-Q torsional oscillations that couple to the nanofiber-guided light via the strain-optic effect. An ab-initio opto-mechanical model of the TOF is developed that provides an accurate quantitative prediction for the mode spectrum and the mechanically induced polarization and phase fluctuations. These high-frequency fluctuations may limit the ultimate ideality of fiber-coupling into photonic structures. Furthermore, first estimations show that they may currently limit the storage time of nanofiber-based atom traps. The model, on the other hand, provides a method to design TOFs with tailored mechanical properties in order to meet experimental requirements. rn

Non-thermal properties of two galaxy filament candidates from JVLA observations

Large-scale structures can be considered an interesting and useful "laboratory" to better investigate the Universe; in particular the filaments connecting clusters and superclusters of galaxies can be a powerful tool for this intent, since they are not virialised systems yet. The large structures in the Universe have been studied in different bands, in particular the present work takes into consideration the emission in the radio band. In the last years both compact and diffuse radio emission have been detected, revealing to be associated to single objects and clusters of galaxies respectively. The detection of these sources is important, because the radiation process is the synchrotron emission, which in turn is linked to the presence of a magnetic field: therefore studying these radio sources can help in investigating the magnetic field which permeates different portions of space. Furthermore, radio emission in optical filaments have been detected recently, opening new chances to further improve the understanding of structure formation. Filaments can be seen as the net which links clusters and superclusters. This work was made with the aim of investigating non-thermal properties in low-density regions, looking for possible filaments associated to the diffuse emission. The analysed sources are 0917+75, which is located at a redshift z = 0.125, and the double cluster system A399-A401, positioned at z = 0.071806 and z = 0.073664 respectively. Data were taken from VLA/JVLA observations, and reduced and calibrated with the package AIPS, following the standard procedure. Isocountour and polarisation maps were yielded, allowing to derive the main physical properties. Unfortunately, because of a low quality data for A399-A401, it was not possible to see any radio halo or bridge.

Device-less patent foramen ovale closure by radiofrequency thermal energy

The goal of this study was to assess the feasibility, safety and success of a system which uses radiofrequency energy (RFE) rather than a device for percutaneous closure of patent foramen ovale (PFO). METHODS: Sixteen patients (10 men, 6 women, mean age 50 years) were included in the study. All of them had a proven PFO with documented right-to-left shunt (RLS) after Valsalva manoeuvre (VM) during transoesophageal echocardiography (TEE). The patients had an average PFO diameter of 6 +/- 2 mm at TEE and an average of 23 +/- 4 microembolic signals (MES) in power M-mode transcranial Doppler sonography (pm-TCD), measured over the middle cerebral artery. An atrial septal aneurysm (ASA) was present in 7 patients (44%). Balloon measurement, performed in all patients, revealed a stretched PFO diameter of 8 +/- 3 mm. In 2 patients (stretched diameter 11 and 14 mm respectively, both with ASA >10 mm), radiofrequency was not applied (PFO too large) and the PFO was closed with an Amplatzer PFO occluder instead. A 6-month follow-up TEE was performed in all patients. RESULTS: There were no serious adverse events during the procedure or at follow-up (12 months average). TEE 6 months after the first RFE procedure showed complete closure of the PFO in 50% of the patients (7/14). Closure appeared to be influenced by PFO diameter, complete closure being achieved in 89% (7/8) with a balloon-stretched diameter < or =7 mm but in none of the patients >7 mm. Only one of the complete closure patients had an ASA. Of the remainder, 4 (29%) had an ASA. Although the PFO was not completely closed in this group, some reduction in the diameter of the PFO and in MES was documented by TEE and pm-TCD with VM. Five of the 7 residual shunt patients received an Amplatzer PFO occluder. Except for one patient with a minimal residual shunt, all showed complete closure of PFO at 6-month follow-up TEE and pm-TCD with VM. The other two refused a closure device. CONCLUSIONS: The results confirm that radiofrequency closure of the PFO is safe albeit less efficacious and more complex than device closure. The technique in its current state should not be attempted in patients with a balloon-stretched PFO diameter >7 mm and an ASA.

Ecology of larval fishes and large zooplankton in the Keweenaw Current region of Lake Superior, with special focus on lake herring, Coregonus artedi

I assessed the influence of the Keweenaw Current and spring thermal bar on the distribution of larval fishes and large zooplankton in Lake Superior. In 1998 and 1999, samples were collected from inshore (0.2 – 3.0 km from shore) and offshore (5.0 – 9.0 km from shore) locations on three transects off the western coast of the Keweenaw Peninsula, Michigan. For larval fishes, density and size distribution patterns of lake herring (Coregonus artedi), rainbow smelt (Osmerus mordax), burbot (Lota lota), deepwater sculpin (Myoxocephalus thompsoni), and spoonhead sculpin (Cottus ricei) suggest a seasonal inshore to offshore movement. For zooplankton, seasonal warming appeared to be the major factor that limited planktonic catches of the primarily benthic Mysisrelicta and Diporeia spp., while simultaneously stimulated growth and reproduction of the cladocerans Daphnia spp., Holopedium gibberum, and Bythotrephes cederstroemi. In contrast, calanoid copepods as a group were abundant throughout the entire sampling season. The greatest abundances of zooplankton were generally encountered offshore, even for the cladocerans, which apparently expanded from inshore to offshore locations with seasonal warming. In 2000, sampling efforts focused on lake herring. Samples were collected from surface waters at 0.1 – 17.0 km from shore on two transects. Lake herring larvae were also reared in the laboratory from eggs in order to validate the use of otolith microstructure for aging. Increment deposition was not statistically different from a daily rate starting from 28 days after hatching, near the time of yolk-sac absorption, but larvae with lower growth rates could not be aged as accurately. In Lake Superior, lake herring tended to be slightly more abundant, larger, and older at inshore locations, but a dense patch of younger larvae was also encountered 7 – 13 km from shore. The distribution iiipatterns suggest that larvae were transported by prevailing currents into the study region, possibly from the more productive spawning regions in western Lake Superior. Growth rates were suppressed at offshore locations where temperatures were less than 8°C. These results indicate that lake herring larvae may be transported far distances from spawning concentrations by longshore currents, and water temperatures may largely control their growth.

Optical hysteresis of ridge waveguide magnetic garnet films and cavities in two-dimensional magneto-photonic crystal slabs

Magnetic iron garnets as well as magnetic photonic crystals are of great interests in magneto-optic applications such as isolators, current captors, circulators, TE-TM mode conversion, wavelength accordable filters, optical sensors and switches, all of which provide a promising platform for future integrated optical circuits. In the present work, two topics are studied based on magnetic iron garnet films. In the first part, the characteristics of the magnetization are investigated for ridge waveguides fabricated on (100) oriented iron garnet thin films. The magnetic response in magneto-optic waveguides patterned on epitaxial magnetic garnet films depends on the crystallographic orientation of the waveguides and the magnetic anisotropy of the material. These can be studied by polarization rotation hysteresis loops, which are related to the component of magnetization parallel to the light propagation direction and the linear birefringence. Polarization rotation hysteresis loops for low birefringence waveguides with different orientations are experimentally investigated. Asymmetric stepped curves are obtained from waveguides along, due to the large magnetocrystalline anisotropy in the plane. A model based on the free energy density is developed to demonstrate the motion of the magnetization and can be used in the design of magneto-optic devices. The second part of this thesis focuses on the design and fabrication of high-Q cavities in two-dimensional magneto-photonic crystal slabs. The device consists of a layer of silicon and a layer of iron garnet thin film. Triangular lattice elliptical air holes are patterned in the slab. The fundamental TM band gap overlaps with the first-order TE band gap from 0374~0.431(a/λ) showing that both TE and TM polarization light can be confined in the photonic crystals. A nanocavity is designed to obtain both TE and TM defect modes in the band gaps. Additional work is needed to overlap the TE and TM defect modes and obtain a high-Q cavity so as to develop miniaturized Faraday rotators.

THERMAL CHARACTERIZATION OF COMBUSTION CHAMBER COMPONENTS IN A GASOLINE TURBOCHARGED DIRECT INJECTION (GTDI) ENGINE

This report is a PhD dissertation proposal to study the in-cylinder temperature and heat flux distributions within a gasoline turbocharged direct injection (GTDI) engine. Recent regulations requiring automotive manufacturers to increase the fuel efficiency of their vehicles has led to great technological achievements in internal combustion engines. These achievements have increased the power density of gasoline engines dramatically in the last two decades. Engine technologies such as variable valve timing (VVT), direct injection (DI), and turbocharging have significantly improved engine power-to-weight and power-to-displacement ratios. A popular trend for increasing vehicle fuel economy in recent years has been to downsize the engine and add VVT, DI, and turbocharging technologies so that a lighter more efficient engine can replace a larger, heavier one. With the added power density, thermal management of the engine becomes a more important issue. Engine components are being pushed to their temperature limits. Therefore it has become increasingly important to have a greater understanding of the parameters that affect in-cylinder temperatures and heat transfer. The proposed research will analyze the effects of engine speed, load, relative air-fuel ratio (AFR), and exhaust gas recirculation (EGR) on both in-cylinder and global temperature and heat transfer distributions. Additionally, the effect of knocking combustion and fuel spray impingement will be investigated. The proposed research will be conducted on a 3.5 L six cylinder GTDI engine. The research engine will be instrumented with a large number of sensors to measure in-cylinder temperatures and pressures, as well as, the temperature, pressure, and flow rates of energy streams into and out of the engine. One of the goals of this research is to create a model that will predict the energy distribution to the crankshaft, exhaust, and cooling system based on normalized values for engine speed, load, AFR, and EGR. The results could be used to aid in the engine design phase for turbocharger and cooling system sizing. Additionally, the data collected can be used for validation of engine simulation models, since in-cylinder temperature and heat flux data is not readily available in the literature..

SOLUTE-DERIVED THERMAL STABILITY OF NANOCRYSTALLINE ALUMINUM AND PROCESSING FACTOR INFLUENCE ON THE FORMATION OF AL6MN QUASICRYSTALS IN MELT-SPINNING

Thermal stability of nanograined metals can be difficult to attain due to the large driving force for grain growth that arises from the significant boundary area constituted by the nanostructure. Kinetic approaches for stabilization of the nanostructure effective at low homologous temperatures often fail at higher homologous temperatures. Thermodynamic approaches for thermal stabilization may offer higher temperature stability. In this research, modest alloying of aluminum with solute (1 at.% Sc, Yb, or Sr) was examined as a means to thermodynamically stabilize a bulk nanostructure at elevated temperatures. After using melt-spinning and ball-milling to create an extended solid-solution and nanostructure with average grain size on the order of 30-45 nm, 1 h annealing treatments at 673 K (0.72 Tm) , 773 K (0.83 Tm) , and 873 K (0.94 Tm) were applied. The alloys remain nanocrystalline (<100 nm) as measured by Warren-Averbach Fourier analysis of x-ray diffraction peaks and direct observation of TEM dark field micrographs, with the efficacy of stabilization: Sr>Yb>Sc. Disappearance of intermetallic phases in the Sr and Yb alloys in the x-ray diffraction spectra are observed to occur coincident with the stabilization after annealing, suggesting that precipitates dissolve and the boundaries are enriched with solute. Melt-spinning has also been shown to be an effective process to produce a class of ordered, but non-periodic crystals called quasicrystals. However, many of the factors related to the creation of the quasicrystals through melt-spinning are not optimized for specific chemistries and alloy systems. In a related but separate aspect of this research, meltspinning was utilized to create metastable quasicrystalline Al6Mn in an α-Al matrix through rapid solidification of Al-8Mn (by mol) and Al-10Mn (by mol) alloys. Wheel speed of the melt-spinning wheel and orifice diameter of the tube reservoir were varied to determine their effect on the resulting volume proportions of the resultant phases using integrated areas of collected x-ray diffraction spectra. The data were then used to extrapolate parameters for the Al-10Mn alloy which consistently produced Al6Mn quasicrystal with almost complete suppression of the equilibrium Al6Mn orthorhombic phase.

Noble gas, CFC and other geochemical evidence for the age and origin of the Bath thermal waters, UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of 39Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved 85Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O2 into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.

Sr/Ca ratios of coccoliths from the Paleocene-Eocene Thermal Maximum

During the Paleocene-Eocene Thermal Maximum (PETM), rapid release of isotopically light C to the ocean-atmosphere system elevated the greenhouse effect and warmed temperatures by 5-7 °C for 105 yr. The response of the planktic ecosystems and productivity to the dramatic climate changes of the PETM may represent a significant feedback to the carbon cycle changes, but has been difficult to document. We examine Sr/Ca ratios in calcareous nannofossils in sediments spanning the PETM in three open ocean sites as a new approach to examine productivity and ecological shifts in calcifying plankton. The large heterogeneity in Sr/Ca among different nannofossil genera indicates that nannofossil Sr/Ca reflects primary productivity-driven geochemical signals and not diagenetic overprinting. Elevated Sr/Ca ratios in several genera and constant ratios in other genera suggest increased overall productivity in the Atlantic sector of the Southern Ocean during the PETM. Dominant nannofossil genera in tropical Atlantic and Pacific sites show Sr/Ca variations during the PETM which are comparable to background variability prior to the PETM. Despite acidification of the ocean there was not a productivity crisis among calcifying phytoplankton. We use the Pandora ocean box model to explore possible mechanisms for PETM productivity change. If independent proxy evidence for more stratified conditions in the Southern Ocean during the PETM is robust, then maintenance of stable or increased productivity there likely reflects increased nutrient inventories of the ocean. Increased nutrient inventories could have resulted from climatically enhanced weathering and would have important implications for burial rates of organic carbon and stabilization of climate and the carbon cycle.

Planktonic foraminifera, nannofossils and stable isotope record across tghe Paleocene-Eocene thermal maximum of ODP Hole 113-690B

The carbonate saturation profile of the oceans shoaled markedly during a transient global warming event known as the Paleocene-Eocene thermal maximum (PETM) (circa 55 Ma). The rapid release of large quantities of carbon into the ocean-atmosphere system is believed to have triggered this intense episode of dissolution along with a negative carbon isotope excursion (CIE). The brevity (120-220 kyr) of the PETM reflects the rapid enhancement of negative feedback mechanisms within Earth's exogenic carbon cycle that served the dual function of buffering ocean pH and reducing atmospheric greenhouse gas levels. Detailed study of the PETM stratigraphy from Ocean Drilling Program Site 690 (Weddell Sea) reveals that the CIE recovery period, which postdates the CIE onset by ~80 kyr, is represented by an expanded (~2.5 m thick) interval containing a unique planktic foraminiferal assemblage strongly diluted by coccolithophore carbonate. Collectively, the micropaleontological and sedimentological changes preserved within the CIE recovery interval reflect a transient state when ocean-atmosphere chemistry fostered prolific coccolithophore blooms that suppressed the local lysocline to relatively deeper depths. A prominent peak in the abundance of the clay mineral kaolinite is associated with the CIE recovery interval, indicating that continental weathering/runoff intensified at this time as well (Robert and Kennett, 1994). Such parallel stratigraphic changes are generally consonant with the hypothesis that enhanced continental weathering/runoff and carbonate precipitation helped sequester carbon during the PETM recovery period (e.g., Dickens et al., 1997, doi:10.1130/0091-7613(1997)025<0259:ABOGIT>2.3.CO;2 ; Zachos et al., 2005, doi:10.1126/science.1109004).