Abstract This study focuses on analyzing depth distributions of d18O and changes in mixed layer thickness in the South China Sea (SCS). The oxygen isotopic compositions of the samples collected were determined using the Epstein-Mayeda (1953). The overall precision of the d18OSMOW measurements is +0.1‰. Our data suggest that depth changes of average d18OSMOW of seawater in the SCS as follows: the average d18OSMOW values for the surface (0-100m) is 0.02‰; subsurface (100-400m) is 0.2‰; intermediate (400-1500m) is ¡V0.03‰ and deep waters (>1500m) is ¡V0.06‰. The effect of monsoon on the mixed layer in the SCS water is evident as the increases in the mixed layer is always coincident with the northeast monsoon in winter. Furthermore, the d18OSMOW values are correlated linearly with the mixed layer thickness. In other words, the lower d18OSMOW values of seawater are, the less the thickness of mixed layer is.

Approved for public release; distribution is unlimited / This study was conducted to examine the effects of discrete precipitation events on the short-term and seasonal evolution of ocean mixed layer temperature and salinity structure. This study was located at Ocean Station "P" (50°N, 145°W) in the Northeast Pacific Ocean. Two numerical modeling experiments were performed. The first was to simulate the response of the mixed layer to hypothetical discrete (isolated) precipitation events. This experiment showed that the effect of a single discrete rain event can van' with season, with the mixed layer depth (MLD) at onset of the rain event, and with the strength of wind stress forcing. A single rain event can have lasting effects on mixed layer depth and temperature for up to 55 days after the event, depending upon the season. The second experiment simulated quasi-realistic "complex" precipitation forcing, with a realistic distribution of synoptic events over a 13-month period. For this experiment, four different precipitation "intensities" were tested. The values of temperature, salinity, and MLD predicted by the model were compared with observed Conductivity Temperature Depth measurements and with the values predicted using constant precipitation forcing. In all experiments, the modelled MLD's approximated the observed MLD and temperature cycle. MLD's for all cases were too deep while temperature was estimated well in winter and was too cool in summer. Predicted salinity provided the greatest discrepancy between the modeled and the observed cycle. The 96 cm, 400-day quasi-realistic precipitation forced case best approximated the salinity observations though predicted salinity was fresher than observed in winter and saltier than observed in summer. Model results suggest that the amount of precipitation observed at Ocean Station "P" was too low to explain the observed and simulated ocean salinity and temperature structure for the year. / http://archive.org/details/discreteprecipit00live / Lieutenant, United States Navy

This thesis describes the preparation of surface-attached monolayer tethers from electroreduction of aryldiazonium ions using a protection-deprotection strategy. Monolayers of ethynylphenyl, carboxyphenyl, aminophenyl and aminomethylphenyl were prepared. Glassy carbon (GC) and pyrolysed photoresist film (PPF) surfaces were modified electrochemically and characterised by redox probe voltammetry. The monolayer tethers were coupled with electro-active ferrocenyl (Fc) and nitrophenyl (NP) groups for the indirect electrochemical estimation of the surface concentration. Film thickness measurement was carried out using an atomic force microscopy (AFM) depth profiling technique. The surface concentration and film thickness measurement results were consistent with the formation of monolayer films after removal of the protecting groups. Preparation of mixed monolayers was studied using three different modification strategies: i) grafting from a solution containing two different protected aryldiazonium ions, ii) sequential grafting of two different protected aryldiazonium ions, and iii) grafting of protected aryldiazonium ions followed by removal of the protecting group and reaction of an amine or carboxylic acid derivative directly with the GC surface. The composition of the mixed layer prepared using the first method is difficult to control, whereas the possibility of multilayer formation cannot be discounted using the second method. Multilayer formation is unlikely using the third method. The electrocatalysis of oxygen reduction at mixed monolayer films was investigated briefly. The origin of the two reduction peaks frequently observed for electroreduction of aryldiazonium ions at carbon surfaces was studied. Electroreduction was carried out at GC and HOPG surfaces. The reduction peak at the more positive potential is surface sensitive, while the peak at the more negative potential is not. However, both reduction peaks lead to deposition of films and it is tentatively proposed that the more positive peak corresponds to reduction at a ‘clean’ GC electrode, and the more negative peak corresponds to reduction at the already grafted layer.

Clays and clay mineral distribution studies are important for understanding the geological history of the Gulf of Mexico Basin, but few studies document any subsurface clay mineral distribution in the Gulf of Mexico. Shale samples from nine wells (30 samples) in the South Timbalier protraction were selected near known paleontological markers identifying the Miocene, Pliocene, and Pleistocene boundaries. Bulk mineralogy of each sample, determined by XRD, is primarily mixed-layer smectite and illite with a minor amount of kaolinite. The mixed-layer mineralogies are end-member smectite, mixed-layer smectite, mixed-layer illite, and end-member illite. These clay mineral fractions do not correlate with age. The illite mixed layer percentage correlates with depth, but the correlation decreases when depth is converted to temperature. However, the illite mixed layer fraction does not exhibit a strong correlation in this multiwell study when compared to a single well study in Ship Shoal using identical methods (Totten et al., 2002).

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The subject of this thesis is the application of optical backscatter measurements to locate a special property of the lowest part of the atmosphere -- the mixing height. Mixing height is the altitude of the top of the layer where all the fluxes emitted at the ground become well mixed. Since Holzworth in 1967, the knowledge of this altitude is considered relevant when modeling transport of pollutants or general fluxes originating at the ground. Indirect estimations of the mixing height are possible using atmospheric models, but its accuracy is quite low. Since several institutions are attempting to estimate precise ground fluxes, networks of measurement stations are being created. The correct use of the measured fluxes, in order to estimate the evolution of the air masses, is limited by the accuracy of the localization of this layer. It can be detected in several different ways. Most are related to a direct sounding, performed with meteorological balloons. Remote sensing techniques are also attempted with acoustical or optical instruments. Both optical and acoustical methods have advantages and disadvantages. This work is focused on optical instruments like lidar and ceilometers, which are basically small cost-effective lidar systems.

High-resolution physical and biogeochemical field data in central Lake Erie during the summers of 2008-2009 along with a three-dimensional numerical model were used to investigate the dynamics of basin scale waves and sediment resuspension mechanisms. In Chapter 2, the modal response of the Poincaré waves in the lake is assessed. The vertical mode-one Poincaré wave was found to be mostly dominant during the seasonal stratified period. The horizontal modal structure was also investigated in a sensitivity analysis, using the numerical model forced with real and idealized wind events. In Chapter 3, dynamics of bottom mixed layer (BML), primarily forced in the outer layer by surface seiches and Poincaré waves is studied for two 10-days representative intervals of weak and strong stratification. Shear velocity was calculated by least square fitting the well-known law-of-the-wall equation to observed near-bed velocity in a region of constant shear stress. Height of the BML is computed using water density (from water temperature) and compared with heights of logarithmic layer approximated using the law-of-the-wall equation and its modified form with buoyancy length scale term. Published equations for estimating BML heights are evaluated and modified for the lake. In Chapter 4, we investigate physical processes leading to sediment resuspension in the lake including surface waves (periods of 4-8s), up/downwelling events (periods of 3-4 day), and high frequency internal waves (periods of 5-45min). Temporal changes in near-bottom sediment resuspension are illustrated using changes in acoustic backscatter signals from current profilers and time series of turbidity measurements to identify the mechanism responsible for sediment resuspension. Resuspension is parameterized as a function of the critical velocity ~0.25ms-1 and from surface waves using linear wave theory. Finally, based on the critical velocity and sediment grain size analysis (from in-site field data), critical shear stress and Shields parameter are calculated and compared with previous observations in Lake Erie and in other locations suggesting a modified Shields diagram for silty bed materials. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2012-12-19 20:54:15.832

The ocean mixed layer response to a tropical cyclone within, and immediately adjacent to, the Gulf of Mexico Loop Current is examined using a combination of ocean profiles and a numerical model. A comprehensive set of temperature, salinity, and current profiles acquired from aircraft-deployed expendable probes is utilized to analyze the three-dimensional oceanic energy and circulation evolution in response to Hurricane Lili's (2002) passage. Mixed-layer temperature analyses show that the Loop Current cooled <1 degree C in response to the storm, in contrast to typically observed larger decreases of 3-5 degrees C. Correspondingly, vertical current shears, which are partly responsible for entrainment mixing, were found to be up to 50% weaker, on average, than observed in previous studies within the directly-forced region. The Loop Current, which separates the warmer, lighter Caribbean Subtropical water from the cooler, heavier Gulf Common water, was found to decrease in intensity by -0.18 plus/minus 0.25 m/s over an approximately 10-day period within the mixed layer. Contrary to previous tropical cyclone ocean response studies which have assumed approximately horizontally homogeneous ocean strucutre prior to storm passage, a kinetic energy loss of 5.8 plus/minus 6.3 kJ/m^2, or approximately -1 wind stress-scaled energy unit, was observed. Using near-surface currents derived from satellite alimetery data, the Loop Current is found to vary similarly in magnitude, suggesting storm-generated energy is rapidly removed by the pre-exiting Loop Current. Further examination of the energy response using an idealized numerical model reveal that due to: 1) favorable coupling between the wind stress and pre-existing current vectors; and 2) wind-driven currents flowing across the large horizontal pressure gradient; wind energy transfer to mixed-layer kinetic energy can be more efficient in these regimes as compared to the case of an initially horizontally homogeneous ocean. However, nearly all of this energy is removed by advection by 2 local inertial periods after storm passage, and little evidence of the storm's impact remains. Mixed-layer vorticity within the idealized current also shows a strong direct response, but little evidence of an near-inertial wave wake results.

Vertical mixing is an important process that relates surface fluxes to concentrations of pollutants and other chemical species in the atmosphere. Errors in vertical mixing have been identified as a major source of uncertainties in various atmospheric modeling efforts including tracer transport, weather forecasting, and regional climate simulation. This thesis aims to quantify uncertainties in model-derived mixed layer heights (zi) over North America through direct comparisons between radiosonde observations and four models at different months of the year 2004 through the bulk Richardson number method. Results of this study suggest that considerable errors in zi exist throughout the region with the spatial and temporal variations of the errors differ significantly among the selected models. Over all, errors in zi were larger in global models than in the limited area mesoscale models, and the magnitude of the random error was two times larger than the bias. Notably, spatial regions of with extremely large positive biases correspond to those with especially large random errors. The biases and random errors, however, were not correlated linearly nor can be easily used to predict each other. Uncertainties in model-derived zi were attributed, through errors in the bulk Richardson number, to temperature and horizontal winds. Errors in both horizontal winds and temperatures were found contributing more or less the same to uncertainties in zi, with relative errors in both variables being the greatest in the lowest part of the troposphere. Lastly, independent observations from the cooperative profiler network suggest that data assimilation did not add qualitative advantages for the comparisons presented in this study. The mixed layer height uncertainties demonstrated in this study may provide a guide for selecting a model to simulate regional scale atmospheric transport and for interpreting flux estimation and inversions studies.

Commonly the thermal maturity of the Late Devonian to Early Mississippian Woodford shale found on the flanks of the Arbuckle Mountains of Oklahoma is determined by vitrinite reflectance, values ranging from 0.3-1.5%. Using phyllosilicate minerals, specifically diagenetic mixed layer illite/smectite and diagenetic illite, an understanding of the extent and processes leading to the thermal maturation may be developed. Analysis by XRD of the clay mineralogy of the Woodford shale found kaolinite and mixed layer illite/smectite with <5% smectite and R≥3 stacking order. Modeling of the Woodford shale also suggests the percentage of smectite present in mixed layer illite/smectite to be <5% and commonly <2.5%. Deconvolution of the illite (001) peak supports the low smectite content and high illite crystallinity. The long range ordered illite, R≥3, and high illite crystallinity values are indicative of diagenesis to anchizone conditions suggesting a higher thermal maturity relative to previously measured values of vitrinite reflectance.