Understanding volcanic processes using UV camera measurements of sulfur dioxide and coincident infrasound and seismicity

The exsolution of volatiles from magma maintains an important control on volcanic eruption styles. The nucleation, growth, and connectivity of bubbles during magma ascent provide the driving force behind eruptions, and the rate, volume, and ease of gas exsolution can affect eruptive activity. Volcanic plumes are the observable consequence of this magmatic degassing, and remote sensing techniques allow us to quantify changes in gas exsolution. However, until recently the methods used to measure volcanic plumes did not have the capability of detecting rapid changes in degassing on the scale of standard geophysical observations. The advent of the UV camera now makes high sample rate gas measurements possible. This type of dataset can then be compared to other volcanic observations to provide an in depth picture of degassing mechanisms in the shallow conduit. The goals of this research are to develop a robust methodology for UV camera field measurements of volcanic plumes, and utilize this data in conjunction with seismoacoustic records to illuminate degassing processes. Field and laboratory experiments were conducted to determine the effects of imaging conditions, vignetting, exposure time, calibration technique, and filter usage on the UV camera sulfur dioxide measurements. Using the best practices determined from these studies, a field campaign was undertaken at Volcán de Pacaya, Guatemala. Coincident plume sulfur dioxide measurements, acoustic recordings, and seismic observations were collected and analyzed jointly. The results provide insight into the small explosive features, variations in degassing rate, and plumbing system of this complex volcanic system. This research provides useful information for determining volcanic hazard at Pacaya, and demonstrates the potential of the UV camera in multiparameter studies.

Dynamics of settling charged particles in turbulence : theory and experiments

It has been proposed that inertial clustering may lead to an increased collision rate of water droplets in clouds. Atmospheric clouds and electrosprays contain electrically charged particles embedded in turbulent flows, often under the influence of an externally imposed, approximately uniform gravitational or electric force. In this thesis, we present the investigation of charged inertial particles embedded in turbulence. We have developed a theoretical description for the dynamics of such systems of charged, sedimenting particles in turbulence, allowing radial distribution functions to be predicted for both monodisperse and bidisperse particle size distributions. The governing parameters are the particle Stokes number (particle inertial time scale relative to turbulence dissipation time scale), the Coulomb-turbulence parameter (ratio of Coulomb ’terminalar speed to turbulence dissipation velocity scale), and the settling parameter (the ratio of the gravitational terminal speed to turbulence dissipation velocity scale). For the monodispersion particles, The peak in the radial distribution function is well predicted by the balance between the particle terminal velocity under Coulomb repulsion and a time-averaged ’drift’ velocity obtained from the nonuniform sampling of fluid strain and rotation due to finite particle inertia. The theory is compared to measured radial distribution functions for water particles in homogeneous, isotropic air turbulence. The radial distribution functions are obtained from particle positions measured in three dimensions using digital holography. The measurements support the general theoretical expression, consisting of a power law increase in particle clustering due to particle response to dissipative turbulent eddies, modulated by an exponential electrostatic interaction term. Both terms are modified as a result of the gravitational diffusion-like term, and the role of ’gravity’ is explored by imposing a macroscopic uniform electric field to create an enhanced, effective gravity. The relation between the radial distribution functions and inward mean radial relative velocity is established for charged particles.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.

Indole based antioxidants for the treatment of ischemia reperfusion injury

With the number of ischemia reperfusion (I/R) injuries on the rise, and a lack of pharmacological intervention aimed at reducing free radical damage associated with I/R, we have developed 30 indole phenolic antioxidants that were synthesized by click chemistry to couple our indole with a phenolic or anisole derivative. The total antioxidant activity of the analogues was tested in vitro using the ferric thiocyanate lipid emulsion method. Compounds containing hydroxyl or methoxy aromatics at the 3 or 4 position on the aromatic coupled to the indole exhibited increased antioxidant scavenging. 4-methoxyindole derivatives (8a-e) exhibited increased scavenging (p < 0.05) compared to the known antioxidant butylated hydroxyanisole (BHA).

Paleoenvironmental reconstructions from cave sediments of the Moravian Karst, Czech Republic / by Pavel Sroubek.

This thesis presents a paleoclimatic/paleoenvironmental study conducted on clastic cave sediments of the Moravian Karst, Czech Republic. The study is based on environmental magnetic techniques, yet a wide range of other scientific methods was used to obtain a clearer picture of the Quaternary climate. My thesis also presents an overview of the significance of cave deposits for paleoclimatic reconstructions, explains basic environmental magnetic techniques and offers background information on the study area – a famous karst region in Central Europe with a rich history. In Kulna Cave magnetic susceptibility variations and in particular variations in pedogenic susceptibility yield a detailed record of the palaeoenvironmental conditions during the Last Glacial Stage. The Kulna long-term climatic trends agree with the deep-sea SPECMAP record, while the short-term oscillations correlate with rapid changes in the North Atlantic sea surface temperatures. Kulna Cave sediments reflect the intensity of pedogenesis controlled by short-term warmer events and precipitation over the mid-continent and provide a link between continental European climate and sea surface temperatures in the North Atlantic during the Last Glacial Stage. Given the number of independent climate proxies determined from the entrance facies of the cave and their high resolution, Kulna is an extremely important site for studying Late Pleistocene climate. In the interior of Spiralka Cave, a five meter high section of fine grained sediments deposited during floods yields information on the climatic and environmental conditions of the last millenium. In the upper 1.5 meters of this profile, mineral magnetic and other non-magnetic data indicate that susceptibility variations are controlled by the concentration of magnetite and its magnetic grain size. Comparison of our susceptibility record to the instrumental record of winter temperature anomalies shows a remarkable correlation. This correlation is explained by coupling of the flooding events, cultivation of land and pedogenetic processes in the cave catchment area. A combination of mineral magnetic and geochemical proxies yields a detail picture of the rapidly evolving climate of the near past and tracks both natural and human induced environmental changes taking place in the broader region.

Manual pumping test method for characterizing the productivity of drilled wells equipped with rope pumps

Since the introduction of the rope-pump in Nicaragua in the 1990s, the dependence on wells in rural areas has grown steadily. However, little or no attention is paid to rope-pump well performance after installation. Due to financial restraints, groundwater resource monitoring using conventional testing methods is too costly and out of reach of rural municipalities. Nonetheless, there is widespread agreement that without a way to quantify the changes in well performance over time, prioritizing regulatory actions is impossible. A manual pumping test method is presented, which at a fraction of the cost of a conventional pumping test, measures the specific capacity of rope-pump wells. The method requires only sight modifcations to the well and reasonable limitations on well useage prior to testing. The pumping test was performed a minimum of 33 times in three wells over an eight-month period in a small rural community in Chontales, Nicaragua. Data was used to measure seasonal variations in specific well capacity for three rope-pump wells completed in fractured crystalline basalt. Data collected from the tests were analyzed using four methods (equilibrium approximation, time-drawdown during pumping, time-drawdown during recovery, and time-drawdown during late-time recovery) to determine the best data-analyzing method. One conventional pumping test was performed to aid in evaluating the manual method. The equilibrim approximation can be performed while in the field with only a calculator and is the most technologically appropriate method for analyzing data. Results from this method overestimate specific capacity by 41% when compared to results from the conventional pumping test. The other analyes methods, requiring more sophisticated tools and higher-level interpretation skills, yielded results that agree to within 14% (pumping phase), 31% (recovery phase) and 133% (late-time recovery) of the conventional test productivity value. The wide variability in accuracy results principally from difficulties in achieving equilibrated pumping level and casing storage effects in the puping/recovery data. Decreases in well productivity resulting from naturally occuring seasonal water-table drops varied from insignificant in two wells to 80% in the third. Despite practical and theoretical limitations on the method, the collected data may be useful for municipal institutions to track changes in well behavior, eventually developing a database for planning future ground water development projects. Furthermore, the data could improve well-users’ abilities to self regulate well usage without expensive aquifer characterization.

Measuring energy spectra of TeV gamma-ray emission from the Cygnus region of our galaxy with Milagro

High energy gamma rays can provide fundamental clues to the origins of cosmic rays. In this thesis, TeV gamma-ray emission from the Cygnus region is studied. Previously the Milagro experiment detected five TeV gamma-ray sources in this region and a significant excess of TeV gamma rays whose origin is still unclear. To better understand the diffuse excess the separation of sources and diffuse emission is studied using the latest and most sensitive data set of the Milagro experiment. In addition, a newly developed technique is applied that allows the energy spectrum of the TeV gamma rays to be reconstructed using Milagro data. No conclusive statement can be made about the spectrum of the diffuse emission from the Cygnus region because of its low significance of 2.2 σ above the background in the studied data sample. The entire Cygnus region emission is best fit with a power law with a spectral index of α=2.40 (68% confidence interval: 1.35-2.92) and a exponential cutoff energy of 31.6 TeV (10.0-251.2 TeV). In the case of a simple power law assumption without a cutoff energy the best fit yields a spectral index of α=2.97 (68% confidence interval: 2.83-3.10). Neither of these best fits are in good agreement with the data. The best spectral fit to the TeV emission from MGRO J2019+37, the brightest source in the Cygnus region, yields a spectral index of α=2.30 (68% confidence interval: 1.40-2.70) with a cutoff energy of 50.1 TeV (68% confidence interval: 17.8-251.2 TeV) and a spectral index of α=2.75 (68% confidence interval: 2.65-2.85) when no exponential cutoff energy is assumed. According to the present analysis, MGRO J2019+37 contributes 25% to the differential flux from the entire Cygnus at 15 TeV.

La Yeguada volcanic complex, western Panama : an assessment of the geologic hazards using new 40AR/39Ar Ages

La Yeguada volcanic complex is one of three Quaternary volcanic centers in Panama, and is located on the southern slope of the Cordillera Central mountain range in western Panama, province of Veraguas. To assess potential geologic hazards, this study focused on the main dome complex near the village of La Laguna and also examined a cinder cone 10 km to the northwest next to the village of Media Luna. Based on newly obtained 40Ar/39Ar ages, the most recent eruption occurred approximately 32 000 years ago at the Media Luna cinder cone, while the youngest dated eruption at the main dome complex occurred 0.357 ± 0.019 Ma, producing the Castillo dome unit. Cerro Picacho is a separate dome located 1.5 km east of the main complex with a date of 4.47 ± 0.23 Ma, and the El Satro Pyroclastic Flow unit surrounds the northern portion of the volcanic complex and has an age of 11.26 ± 0.17 Ma. No Holocene (10 000 years ago to present) activity is recorded at the La Yeguada volcanic complex and therefore, it is unlikely to produce another eruption. The emergence of a new cinder cone is a possibility, but the associated hazards tend to be low and localized, and this does not pose a significant threat to the small communities scattered throughout the area. The main geologic hazard at the La Yeguada volcanic complex is from landslides coming off the many steep slopes.

Parallel algorithm for solving integer linear programs

Linear programs, or LPs, are often used in optimization problems, such as improving manufacturing efficiency of maximizing the yield from limited resources. The most common method for solving LPs is the Simplex Method, which will yield a solution, if one exists, but over the real numbers. From a purely numerical standpoint, it will be an optimal solution, but quite often we desire an optimal integer solution. A linear program in which the variables are also constrained to be integers is called an integer linear program or ILP. It is the focus of this report to present a parallel algorithm for solving ILPs. We discuss a serial algorithm using a breadth-first branch-and-bound search to check the feasible solution space, and then extend it into a parallel algorithm using a client-server model. In the parallel mode, the search may not be truly breadth-first, depending on the solution time for each node in the solution tree. Our search takes advantage of pruning, often resulting in super-linear improvements in solution time. Finally, we present results from sample ILPs, describe a few modifications to enhance the algorithm and improve solution time, and offer suggestions for future work.

"The need obliged us" : culture as capacity during the Hurricane Stan emergency response. A case study from Tectitan, Huehuetenango, Guatemala

A major deficiency in disaster management plans is the assumption that pre-disaster civil-society does not have the capacity to respond effectively during crises. Following from this assumption a dominant emergency management strategy is to replace weak civil-society organizations with specialized disaster organizations that are often either military or Para-military and seek to centralize decision-making. Many criticisms have been made of this approach, but few specifically addresses disasters in the developing world. Disasters in the developing world present unique problems not seen in the developed world because they often occur in the context of compromised governments, and marginalized populations. In this context it is often community members themselves who possess the greatest capacity to respond to disasters. This paper focuses on the capacity of community groups to respond to disaster in a small town in rural Guatemala. Key informant interviews and ethnographic observations are used to reconstruct the community response to the disaster instigated by Hurricane Stan (2005) in the municipality of Tectitán in the Huehuetenango department. The interviews were analyzed using techniques adapted from grounded theory to construct a narrative of the events, and identify themes in the community’s disaster behavior. These themes are used to critique the emergency management plans advocated by the Guatemalan National Coordination for the Reduction of Disasters (CONRED). This paper argues that CONRED uncritically adopts emergency management strategies that do not account for the local realities in communities throughout Guatemala. The response in Tectitán was characterized by the formation of new organizations, whose actions and leadership structure were derived from “normal” or routine life. It was found that pre-existing social networks were resilient and easily re-oriented meet the novel needs of a crisis. New or emergent groups that formed during the disaster utilized social capital accrued by routine collective behavior, and employed organizational strategies derived from “normal” community relations. Based on the effectiveness of this response CONRED could improve its emergency planning on the local-level by utilizing the pre-existing community organizations rather than insisting that new disaster-specific organizations be formed.

Structural characterization of water-soluble atmospheric organic matter by ultrahigh-resolution mass spectrometry

Isolated water-soluble analytes extracted from fog water collected during a radiation fog event near Fresno, CA were analyzed using collision induced dissociation and ultrahigh-resolution mass spectrometry. Tandem mass analysis was performed on scan ranges between 100-400 u to characterize the structures of nitrogen and/or sulfur containing species. CHNO, CHOS, and CHNOS compounds were targeted specifically because of the high number of oxygen atoms contained in their molecular formulas. The presence of 22 neutral losses corresponding to fragment ions was evaluated for each of the 1308 precursors. Priority neutral losses represent specific polar functional groups (H2O, CO2, CH3OH, HNO3, SO3, etc., and several combinations of these). Additional neutral losses represent non-specific functional groups (CO, CH2O, C3H8, etc.) Five distinct monoterpene derived organonitrates, organosulfates, and nitroxy-organosulfates were observed in this study, including C10H16O7S, C10H17NO7S, C10H17 NO8S, C10H17NO9S, and C10H17NO10S. Nitrophenols and linear alkyl benzene sulfonates were present in high abundance. Liquid chromatography/mass spectrometery methodology was developed to isolate and quantify nitrophenols based on their fragmentation behavior.

Game-theoretic view on intermediated exchange

Intermediaries permeate modern economic exchange. Most classical models on intermediated exchange are driven by information asymmetry and inventory management. These two factors are of reduced significance in modern economies. This makes it necessary to develop models that correspond more closely to modern financial marketplaces. The goal of this dissertation is to propose and examine such models in a game theoretical context. The proposed models are driven by asymmetries in the goals of different market participants. Hedging pressure as one of the most critical aspects in the behavior of commercial entities plays a crucial role. The first market model shows that no equilibrium solution can exist in a market consisting of a commercial buyer, a commercial seller and a non-commercial intermediary. This indicates a clear economic need for non-commercial trading intermediaries: a direct trade from seller to buyer does not result in an equilibrium solution. The second market model has two distinct intermediaries between buyer and seller: a spread trader/market maker and a risk-neutral intermediary. In this model a unique, natural equilibrium solution is identified in which the supply-demand surplus is traded by the risk-neutral intermediary, whilst the market maker trades the remainder from seller to buyer. Since the market maker’s payoff for trading at the identified equilibrium price is zero, this second model does not provide any motivation for the market maker to enter the market. The third market model introduces an explicit transaction fee that enables the market maker to secure a positive payoff. Under certain assumptions on this transaction fee the equilibrium solution of the previous model applies and now also provides a financial motivation for the market maker to enter the market. If the transaction fee violates an upper bound that depends on supply, demand and riskaversity of buyer and seller, the market will be in disequilibrium.

Cyclic automorphic graph decompositions

Chapter 1 introduces the tools and mechanics necessary for this report. Basic definitions and topics of graph theory which pertain to the report and discussion of automorphic decompositions will be covered in brief detail. An automorphic decomposition D of a graph H by a graph G is a G-decomposition of H such that the intersection of graph (D) @H. H is called the automorhpic host, and G is the automorphic divisor. We seek to find classes of graphs that are automorphic divisors, specifically ones generated cyclically. Chapter 2 discusses the previous work done mainly by Beeler. It also discusses and gives in more detail examples of automorphic decompositions of graphs. Chapter 2 also discusses labelings and their direct relation to cyclic automorphic decompositions. We show basic classes of graphs, such as cycles, that are known to have certain labelings, and show that they also are automorphic divisors. In Chapter 3, we are concerned with 2-regular graphs, in particular rCm, r copies of the m-cycle. We seek to show that rCm has a ρ-labeling, and thus is an automorphic divisor for all r and m. we discuss methods including Skolem type difference sets to create cycle systems and their correlation to automorphic decompositions. In the Appendix, we give classes of graphs known to be graceful and our java code to generate ρ-labelings on rCm.

Performance evaluation of a novel asymmetric capacitor using a light-weight, carbon foam supported nickel electrode

Electrochemical capacitors have been an important development in recent years in the field of energy storage. Capacitors can be developed by utilizing either double layer capacitance at the electrode/solution interfaces alone or in combination with a battery electrode associated with a faradic redox process in one electrode. An asymmetric capacitor consisting of electrochemically deposited nickel hydroxide, supported on carbon foam as a positive electrode and carbon sheet as a negative electrode has been successfully assembled and cycled. One objective of this study has been to demonstrate the viability of the nickel carbon foam positive electrode, especially in terms of cycle life. Electrochemical characterization shows stable, high cycle performance in 26 wt. % KOH electrolyte with a maximum energy density of 4.1 Wh/Kg and a relaxation time constant of 6.24 s. This cell has demonstrated high cycle life, 14,500 cycles, with efficiency better than 98%. In addition, the cell failure mechanism and self-discharge behavior of the aforesaid capacitor are analyzed.

Recurrent voluminous sector collapses at Volcán Barú, Panama

Two volcanic debris avalanche deposits (VDADs), both attributed to sector collapse at Volcán Barú, Panama, have been identified after an investigation of deposits that covered more than a thousand square kilometers. The younger Barriles Deposit is constrained by two radiocarbon ages that are ~9 ka; the older Caisán Deposit is at or beyond the radiocarbon range, >43,500 ybp. The total runout length of the Caisán Deposit was ~50 km and it covers 1190 km2. The Barriles Deposit extended to about 45 km and covered an area of 966 km2, overlapping most of the Caisán. The VDADs are blanketed by pyroclastic deposits and contain a predominance of andesitic material likely representing volcanic dome rock which accumulated above the active vent at Barú before collapsing. Despite heavy vegetation in the field area, over 4000 individual hummocks were digitized from aerial photography. Statistical analysis of hummock locations and geometries depict flow patterns of highly- fragmented material reflecting the effects of underlying topography and also help to define the limit of Barriles’ shorter termination. Barriles and Caisán are primarily unconfined, subaerial volcanic deposits that are among the world’s most voluminous. Calculated through two different geospatial processes, thickness values from field measurements and inferences yield volumes >30 km23 for both deposits. VDADs of comparable scale come from Mount Shasta, USA; Socompa, Chile/Argentina; and Shiveluch, Russia. Currently, the modern edifice is 200-400m lower than the pre-collapse Barriles and Caisán summits and only 16-25% of the former edifice has been replaced since the last failure.