Original estimates of phosphorus (P) concentrations in the Precambrian oceans before 1.9 Ga gave a budget of ~10-25% of modern day levels. This budget was challenged by accounting for high silica (Si) concentrations that were believed to have outcompeted P for binding sites on precipitating iron oxide-hydroxide particles during the chemical oxidation and burial of iron (Fe). Such iron oxide-hydroxide particles are considered as proxies of ancient iron-rich sedimentary rocks, such as banded iron formations, which are often used to infer the dissolved chemistry of trace elements in the ancient oceans. This study raises the question of wether arsenic (As) had an effect of the binding of P to precipitating iron minerals, during the co-precipitation of Iron oxide- hydroxide in elevated Fe and Si concentrations characteristic of the early oceans. This hypothesis is based on the chemical similarities seen between P and As. Results show a more pH dependent competition between P and AsIII, whereby P outcompetes AsIII at a pH <7. The effect decreases as the pH rises until pH ~8 at which the effect cancels out and AsIII becomes somewhat predominant over P. AsV on the other hand, an analogue to P, is outcompeted by P throughout pH 5-10. Distribution coefficients (Kd) of P on iron oxide-hydroxide particles were not affected by the concentration of Si in solution. Average Kd and standard error between concentrations of Si, across the sample pH of 5-10 revealed an average Kd of 0.072 (±0.01) μM-1. This is strikingly similar to another experimental Kd at 0.075 (±0.003) μM-1, when the effects of Si are excluded. The average Kd in this study is also consistent with the average Kd of 0.06 μM-1 from a range of As-rich hydrothermal systems reported in a previous study, supporting the original idea of Precambrian P levels being low. The average Kd between concentrations of Fe revealed a Kd of 0.12 (±0.03) μM-1 although this was not statistically significant from the average Kd between groups of Si. In addition to low levels of P, the Precambrian oceans likely also contained high levels of As, due to the high hydrothermal activity. This scavenging of P from oceanic waters would have become increasingly important as surface oceans became more oxygenated and the presence of AsV would have been greater. Because the availability of Si does not show any great effect on the uptake of P by precipitating iron oxide-hydroxides, Si concentration is likely not a proxy for oceanic P concentrations. It is proposed that low dissolved P levels are consistent with early oceans that w!ere a lot more hydrothermally influenced than the oceans of today. / Prekambriska fosfor (P) nivåer var ursprungligen estimerade till ca 10-25% utav koncentrationen funnen i dagens havsvatten. Denna budget blev motsagd i och med att kisel (Si) sades kunna ersätta bundet fosfor på järn oxid-hydroxid partiklar som precipiterade genom kemisk oxidation och sedimentering av järn (Fe). Dessa järn oxid-hydroxid partiklar anses användbara som proxy för formationen av uråldriga järn-rika sedimentära bergarter såsom banded iron formation (BIF), vilka används idag för att bestämma mängden spårämnen i de uråldriga haven. Denna studie ställer frågan huruvida arsenik (As) påverkar mängden P som binder till precipiterande järn mineral under procession av co-precipitering av järn oxid-hydroxid i lösning med förhöjda koncentrationer av Fe och Si, karakteristiska för the uråldriga haven. Denna hypotes är baserad på de kemiska likheter som finns mellan P och As. Resultaten påvisar en pH beroende konkurrens mellan P och AsIII där P utkonkurrerar AsIII vid låg pH. Effekten av denna konkurrans minskar med ökande pH tills effekten blir omvänd omkring pH 8 och P blir istället till viss del utkonkurrerad av AsIII. AsV å andra sedan, en verklig kemisk analog till P, är kontinuerligt utkonkurrerad av P genom alla utförda pH, pH 5-10. Distribueringskoefficienter (Kd) för P på järn oxid-hydroxid partiklar visade ingen påverkan av mängden Si tillgängligt. Medelvärdet av Kd och standard error mellan data av alls pH, grupperat av Si, gav ett värde av 0.072 (±0.01) μM-1. Detta är påfallande nära ett experimentellt framtaget Kd värde av 0.075 (±0.03) μM-1 då effekten av Si är borttagen. Medelvärdet i denna studie är också sammanfallande med det Kd medelvärde man finner idag från olika hydrotemala system av 0.063 (±0.01) μM-1. Detta ger support till den originala idén att de prekambriska haven troligen hade låga halter P tillgängligt. Medelvärdet av Kd mellan koncentrationer av Fe gav ett värde av 0.12 (±0.03) μM-1, dock var detta värde ej statistiskt significant från det Kd utifrån koncentrationer av Si. Förutom de låga nivåer av P i de Prekambriska haven så var det troligen även höga halter av As på grund av utbredd hydrotermal aktivitet. Detta uppfångande av P i de tidiga haven var troligen en alltmer viktigare process då ytvatten blev syrerikare och den oxiderade formen av As, det vill säga AsV hade varit mer vanligt förekommande. Framför allt då den konkurrerande effekten av Si kan bortses när P såväl som As inte påverkas av dess närvaro till den grad man hade trott. Detta gör även att mängden Si troligen inte är en tillförlitlig proxy för att estimera P nivåer i de uråldriga haven. Därmed föreslås det att de prekambriska haven var k!arakteriserade av låga P nivåer, jämfört med idag.

This study applies Bayesian inversion to receiver functions (RF) to estimate local shear wave velocity (Vs) structure of the crust and upper mantle beneath two ocean bottom seismometers (OBS) offshore, and two land-based seismometers onshore Vancouver Island, British Columbia, Canada. We use passive seismic data recorded on NC89, a permanent NEPTUNE (North-east Pacific Time-series Undersea Networked Experiments) OBS located on the continental slope, and on a temporary autonomous KECK foundation OBS, KEBB, located at the Endeavour segment of the Juan de Fuca Ridge (JdFR). The two land based seismometers (OZB and PGC) are located on Vancouver Island and are part of the Canadian National Seismograph Network (CNSN). The introduction of NEPTUNE has helped to fill a gap in offshore seismic monitoring, however; due to high noise levels and a relatively short deployment time, few useful events have been recorded (to date) for RF analysis. In this study, we utilize three-component, broadband recordings of large (M6+), distant (30 -100 degrees) earthquakes to compute RFs due to locally generated P (compressional) to S (shear) converted waves. RFs are then inverted using a non-linear Bayesian approach which yields optimal profiles of Vs, Vp (compressional wave velocity), and strike and dip angles, as well as rigorous uncertainty estimates for these parameters. Near the JdFR a thin sediment layer (<1 km) is resolved overlying a 2 km thick oceanic crust. The crust contains a large velocity contrast at the depth of an expected axial magma chamber. The oceanic crust thickens to 10 km at the continental slope where it is overlain by 5 km of sediments. At the coastal station (OZB) a low velocity zone is imaged at 16 km depth dipping approximately 12 degrees NE. Evidence for this low velocity zone is also seen beneath southern Vancouver Island (PGC) at a depth consistent with previous studies. Determining such models at a number of locations (from the spreading ridge to the coast) provides new information regarding local structure and can aid in seismic hazard analysis. / Graduate

This thesis is concerned with a project to apply the method of pressure modulation radiometry to measurements of the temperature and water vapour distributions in the atmosphere of Mars. The technique has already been used successfully to measure temperature (and occasionally composition) in the atmospheres of Earth and Venus. Two pressure modulators, containing carbon dioxide and water vapour respectively, are used in the Pressure Modulator Infrared Radiometer (PMIRR), on the payload of Mars Observer, scheduled for launch in September 1992. The composition of the Martian atmosphere is almost pure CO2, so the emission lines are unusually broad, so that the mean pressure in the CO2 modulator has to be much larger than for previous modulators, thus increasing the power consumption. The limited power available in a Martian spacecraft requires that the power consumption of the pressure modulator and drive be minimized. As a result a high­efficiency drive circuit was designed and developed. Water vapour is of major importance to the Martian environment and there are several outstanding questions about its behaviour. Measurements using the pressure modulator technique for terrestrial water vapour measurements have had limited success, raising questions about its suitability for condensible, affinitive molecules. A new model of the thermodynamics of pressure modulators was developed to predict their mechanical and spectroscopic behaviour, and spectroscopic measurements of the pressure modulator cell transmission, with high spectral and temporal resolution, using a tunable diode laser spectrometer (TDLS), were performed. The measured transmission agrees well with the predictions of the model, indicating that pressure modulation radiometry can be applied to measurements of water vapour, giving confidence in the successful study of Martian climatology by the PMIRR instrument.

The observation of less chaoticity and enhanced interannual periodicity of transient waves in the Martian atmosphere in comparison with that of the Earth suggests the hypothesis of a low-dimensional underlying atmospheric attractor. Grounded on this hypothesis, two questions can be asked: is there a small set of atmospheric modes, measured and classified by a suitable norm, capable of describing the atmosphere of Mars? If this set exists, are those atmospheric modes able to reproduce the dynamical behaviour of the atmosphere of Mars? The answer to these questions, constituting the central focus of this thesis, has led to the first application of POD-Galerkin methods to a state-of-the-art Mars general circulation model. The proper orthogonal decomposition (POD) as a method for extracting coherent structures, called empirical orthogonal functions (EOFs), provided a means to answer the first question in the positive. An important amount of atmospheric total energy (TE) was found to be concentrated in a few EOFs (e.g., 90% TE in 20 EOFs). The most energetic EOFs were identified with atmospheric motions such as thermal tides and transient waves. The Galerkin projection of the hydrostatic primitive equations onto the span of the EOFs provided a systematic method to establish physically plausible interactions between the most energetic EOFs. These interactions were complemented with closure schemes representing interactions with unresolved modes. This requirement proved to be essential in order to obtain bounded behaviour. In the diagnostic analysis, represented by the POD alone, increasing the number of EOFs directly leads to a better approximation of the atmospheric state. In contrast, the dynamic reconstruction of the atmospheric evolution does not depend only on the number of included EOFs. Other important factors to obtain realistic evolution are the inclusion of every mode involved in the description of a particular kind of motion (diurnal tide, semidiurnal tide or transients) and the retention of higher order modes that may interact strongly with the modes of interest. Once these conditions are satisfied the behaviour of the reduced models is greatly improved. Implications of these findings for future work are discussed.

Using a two-dimensional nonlinear numerical simulation of a (viscous) stratified shear layer, strong instabilities resulted from the resonant interaction of a long linearly neutrally stable wave and the corresponding fastest growing wave. This linearly fastest growing wave, with optimal initial conditions, grows initially at a rate five times that predicted by linear theory. With other initial conditions, the linearly fastest growing wave may actually decay. The possibility of this type of interaction is suggested by the weakly nonlinear theory (cf. Maslowe, 1977). This coupled system of fourth order nonl inear partial differential equations was solved using a modified pseudospectral scheme for the spatial variables, incorporating the use of fast Fourier transforms to calculate spatial derivatives, and a second order Adams-Bashforth scheme for the temporal derivatives . / Dans cette etude, en utilisant une simulation numerique nonlineaire a deux dimensions d'une couche stratifiee, decollee et visqueuse, on obtint des resultats interessants a partir des cas correspondant a l'interaction resonnante d'une onde longue a stabilite neutre et d'une onde courte qui croit la plus rapidement selon la theorie lineaire. En utilisant certaines conditions initiales, l'onde courte croit initialement a un taux cinq fois superieur a celui predit par la theorie lineaire. Avec d'autres conditions initiales l'onde courte decroit. La possibilite de ce genre d'interaction est predite par la theorie faiblement nonlineaire (voir Maslowe, 1977). Ce systeme couple aux equations nonlineaires du quatrieme ordre aux derivees partielles, est resolu par une methode pseudo-spectrale modifiee, pour les variables spatiales, et une methode Adams-Bashforth du second ordre pour les derivees temporelles. fr

Thesis (Ph. D.)--Case Western Reserve University, 2008. / Frances Payne Bolton [School of Nursing]. Includes bibliographical references.

Thesis (M.S.)--University of Southern California, 2007. / Includes bibliographical references (leaves 92-96).

Thesis (Ph. D.)--Ludwig-Maximilians-Universität München, 2005.. / Title from PDF title page (viewed on May 13, 2006). Includes three articles co-authored with Sebastian Diehl. Vita. Includes bibliographical references.

Oceanic lithosphere constitutes the upper boundary layer of the Earth’s convecting mantle. Its structure and evolution provide a vital window on the dynamics of the mantle and important clues to how the motions of Earth’s surface plates are coupled to convection in the mantle below. The three-dimensional shear-velocity structure of the upper mantle beneath the Atlantic Ocean is investigated to gain insight into processes that drive formation of oceanic lithosphere. Travel times are measured for approximately 10,000 fundamental-mode Rayleigh waves, in the period range 30-130 seconds, traversing the Atlantic basin. Paths with >30% of their length through continental upper mantle are excluded to maximize sensitivity to the oceanic upper mantle. The lateral distribution of Rayleigh wave phase velocity in the Atlantic upper mantle is explored with two approaches. One, phase velocity is allowed to vary only as a function of seafloor age. Two, a general two-dimensional parameterization is utilized in order to capture perturbations to age-dependent structure. Phase velocity shows a strong dependence on seafloor age, and removing age-dependent velocity from the 2-D maps highlights areas of anomalously low velocity, almost all of which are proximal to locations of hotspot volcanism. Depth-dependent variations in vertically-polarized shear velocity (Vsv) are determined with two sets of 3-D models: a layered model that requires constant VSV in each depth layer, and a splined model that allows VSV to vary continuously with depth. At shallow depths (~75 km) the seismic structure shows the expected dependence on seafloor age. At greater depths (~200 km) high-velocity lithosphere is found only beneath the oldest seafloor; velocity variations beneath younger seafloor may result from temperature or compositional variations within the asthenosphere. The age-dependent phase velocities are used to constrain temperature in the mantle and show that, in contrast to previous results for the Pacific, phase velocities for the Atlantic are not consistent with a half-space cooling model but are best explained by a plate-cooling model with thickness of 75 km and mantle temperature of 1400oC. Comparison with data such as basalt chemistry and seafloor elevation helps to separate thermal and compositional effects on shear velocity.

abstract: Seismic observations have revealed two large low shear velocity provinces (LLSVPs) in the lowermost mantle beneath Pacific and Africa. One hypothesis for the origin of LLSVPs is that they are caused by accumulation of subducted oceanic crust on the core-mantle boundary (CMB). Here, I perform high resolution geodynamical calculations to test this hypothesis. The result shows that it is difficult for a thin (~ 6 km) subducted oceanic crust to accumulate on the CMB, and the major part of it is viscously stirred into the surrounding mantle. Another hypothesis for the origin of LLSVPs is that they are caused by thermochemical piles of more-primitive material which is remnant of Earth's early differentiation. In such case, a significant part of the subducted oceanic crust would enter the more-primitive reservoir, while other parts are either directly entrained into mantle plumes forming on top of the more-primitive reservoir or stirred into the background mantle. As a result, mantle plumes entrain a variable combination of compositional components including more-primitive material, old oceanic crust which first enters the more-primitive reservoir and is later entrained into mantle plumes with the more-primitive material, young oceanic crust which is directly entrained into mantle plumes without contacting the more-primitive reservoir, and depleted background mantle material. The result reconciles geochemical observation of multiple compositional components and varying ages of oceanic crust in the source of ocean-island basalts. Seismic studies have detected ultra-low velocity zones (ULVZs) in some localized regions on the CMB. Here, I present 3D thermochemical calculations to show that the distribution of ULVZs provides important information about their origin. ULVZs with a distinct composition tend to be located at the edges of LLSVPs, while ULVZs solely caused by partial melting tend to be located inboard from the edges of LLSVPs. This indicates that ULVZs at the edges of LLSVPs are best explained by distinct compositional heterogeneity, while ULVZs located insider of LLSVPs are better explained by partial melting. The results provide additional constraints for the origin of ULVZs. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2015