Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

An Appropriate Role for the Leadership: A Quantitative Analysis of the Effects of House Leadership on Open-Seat Races

This paper investigates the effects on open-seat races in the United States House of Representatives. This project focuses on the influence that the House leadership exerts on races. Generally, the leadership influences race through spending by party organizations and leadership visits. During each election cycle, national party organizations spend millions of dollars to get their candidates into office. I have developed a multiple regression model that measures different types of spending from the Democratic Congressional Campaign Committee, the National Republican Congressional Committee, and the Republican National Committee and the effects of these spending types on the election results. Also, the study examines the number of visits by each party’s leadership to each race. I introduced control variables that account for the year, the competitiveness of each race, and the individual candidate fundraising. In terms of statistical significance, the results were mixed showing one type of party spending to be highly influential in the outcome of the race. Competitiveness and individual candidate fundraising also achieved statistical significance. The study also includes a qualitative investigation of leadership visits and individual case studies in order to understand better the way in which the data interact in real campaigns.

A Su Salud Injury Prevention expansion: Analysis of injury prevention perceptions in a Hispanic community

Unintentional injury is the leading cause of death for American ages one to 44 and is ranked in the top ten causes of death for all age groups (CDC, 2006a). A Su Salud Injury Prevention was developed to address injury prevention awareness and education. The program is a mass media education campaign that uses role models, mass media, and community outreach to prevent injury. In 2009, University Health System (UHS) expanded the program. Baseline data were collected from 426 residents in targeted neighborhoods northwest of downtown San Antonio to support the expansion. The purpose of this study was to explore injury perceptions, knowledge, and behaviors of adults living in the expansion area, and define the predominant factors associated with these perceptions. A secondary aim was to assess community awareness and willingness to participate in the program.^ Survey results showed motor vehicle crashes (MVC), falls, drinking and driving, and guns and assaults were considered the most serious injures for adults. The most serious child injuries were MVC, abuse and neglect, falls, and head injuries. Residents were knowledgeable of state seatbelt policy, and over 90% responded as compliant for seatbelt and child car seat use. Most were knowledgeable about drinking and driving state policy and negative outcomes. However, 70% of those reporting driving under the influence of alcohol within the last year engaged in repeat high risk behavior. Men and residents under the age of 55 were more likely to engage in repeat drinking and driving (OR= 3.6, 7.0 respectively). Residents consider injury prevention an important issue, and have interest in a local injury prevention program. Younger women are the most likely to participate in a local program as potential role models and volunteers.^ Results from the study are summarized into an injury prevention and demographic profile of the community that will be used to develop tailored injury prevention messages to create a more effective program, and support program coordinators in effective community engagement. Results will also be used as a comparative basis for future evaluation of a behavioral injury prevention program focused on a predominantly Mexican-American community.^

Detailed analysis of the organic carbon content in sediment cores M0002 and M0004

During IODP Expedition 302 (Arctic Coring Expedition-ACEX), the first scientific drilling campaign in the permantly ice-covered central Arctic Ocean, a 430 m thick sequence of upper Cretaceaous to Quaternary sediments has been drilled. The lower half of this sequence is composed of organic-carbon-rich (black shale-type) sediments with total organic carbon contents of about 1-14%. Significant amounts of the organic matter preserved in these sediments is of algae-type origin and accumulated under anoxic/euxinic conditions. Here, for the first time detailed data on the source-rock potential of these black shales are presented, indicating that most of the Eocene sediments have a (fair to) good source-rock potential, prone to generate a gas/oil mixture. The source-rock potential of the Campanian and upper Paleocene sediments, on the other hand, is rather low. The presence of oil or gas already generated in situ, however, can be ruled out due to the immaturity of the ACEX sediments.

Physical and chemical analysis of firn cores from Ronne Ice Shelf, Antarctica

This data on the distribution of the accumulation rate and 18O content of near-surface layers in the eastern part of the Ronne Ice Shelf, Antarctica, were derived from an analysis of 16 firn cores. The firn cores were drilled along the traverse route of the Filchner-V-Campaign in 1995. The traverse followed an ice flowline of the Foundation Ice Stream and reached the margin of the inland ice, an area which has not yet been investigated. On the ice shelf the accumulation rates decrease with distance from the coast. Ascending to the inland ice the accumulation rates again reach almost coastal values. This regional distribution is in agreement with the temperature gradient along the traverse. The 18O content of the near-surface layers is closely related to the 10 m firn temperature. They strongly decrease from the grounding line towards the inland ice. At the southernmost site at 1100 m a.s.l., the mean d18O value of the firn decreases to -40?. Ice with that isotopic signature was found in cores from the central part of the Ronne Ice Shelf just above the marine ice layer, indicating that it originates from this area. All ice deposited as snow further south was melted beneath the ice shelf after passing the grounding-line area. The time series of accumulation rate and 18O content reveal no climatic trend during the last 30-50 years.

Phytoplankton, dissolved inorganic nutrients and hydrography during the ACEx/SIMTECO campaign in the southern Brazilian shelf in June 2012 (SW Atlantic - Winter 2012)

The response of phytoplankton assemblages to hydrographical forcing across the southern Brazilian shelf was studied based on data collected during wintertime (June/2012), complemented with MODIS-Aqua satellite imagery. The in situ data set was comprised by water column structure properties (derived from CTD casts), dissolved inorganic nutrients (ammonium, nitrite, nitrate, phosphate and silicate) and phytoplankton biomass [chlorophyll a (Chl a) concentration] and composition. Phytoplankton assemblages were assessed by both microscopy and HPLC-CHEMTAX approaches. A canonical correspondence analysis associating physical, chemical and phytoplankton composition data at surface evinced a tight coupling between the phytoplankton community and hydrographic conditions, with remarkable environmental gradients across three different domains: the pelagic, outer shelf Tropical Water (TW); the mid shelf domain under influence of Subtropical Shelf Water (STSW); and the inner shelf domain mainly under influence of riverine outflow of the Plata River Plume Water (PPW). Results showed that intrusion of low salinity and nutrient-rich PPW stimulated the phytoplankton growth and diversity within the inner shelf region, with enhanced Chl a levels (>1.3 mg/m**3) and a great abundance of diatoms, ciliates, dinoflagellates, raphidophyceans and cryptophytes. Conversely, other diatoms (e.g. Rhizosolenia clevei), tiny species of prochlorophytes and cyanobacteria and a noticeable contribution of dinoflagellates and other flagellates associated with lower Chl a levels (<0.93 mg/m**3), characterized the TW domain, where low nutrient concentrations and deep upper mixed layer were found. The transitional mid shelf domain showed intermediate levels of both nutrients and Chl a (ranging 1.06-1.59 mg/m**3), and phytoplankton was mainly composed by dinoflagellates, such as Dinophysis spp., and gymnodinioids. Results have shown considerable phytoplankton diversity in winter at that section of the southwestern Atlantic Ocean.

Instability Analysis of Incompressible Open Cavity Flows

El problema del flujo sobre una cavidad abierta ha sido estudiado en profundidad en la literatura, tanto por el interés académico del problema como por sus aplicaciones prácticas en gran variedad de problemas ingenieriles, como puede ser el alojamiento del tren de aterrizaje de aeronaves, o el depósito de agua de aviones contraincendios. Desde hace muchos a˜nos se estudian los distintos tipos de inestabilidades asociadas a este problema: los modos bidimensionales en la capa de cortadura, y los modos tridimensionales en el torbellino de recirculación principal dentro de la cavidad. En esta tesis se presenta un estudio paramétrico completo del límite incompresible del problema, empleando la herramienta de estabilidad lineal conocida como BiGlobal. Esta aproximación permite contemplar la estabilidad global del flujo, y obtener tanto la forma como las características de los modos propios del problema físico, sean estables o inestables. El estudio realizado permite caracterizar con gran detalle todos los modos relevantes, así como la envolvente de estabilidad en el espacio paramétrico del problema incompresible (Mach nulo, variación de Reynolds, espesor de capa límite incidente, relación altura/profundidad de la cavidad, y longitud característica de la perturbación en la dirección transversal). A la luz de los resultados obtenidos se proponen una serie de relaciones entre los parámetros y características de los modos principales, como por ejemplo entre el Reynolds crítico de un modo, y la longitud característica del mismo. Los resultados numéricos se contrastan con una campaña experimental, siendo la principal conclusión de dicha comparación que los modos lineales están presentes en el flujo real saturado, pero que existen diferencias notables en frecuencia entre las predicciones teóricas y los experimentos. Para intentar determinar la naturaleza de dichas diferencias se realiza una simulación numérica directa tridimensional, y se utiliza un algoritmo de DMD (descomposición dinámica de modos) para describir el proceso de saturación. ABSTRACT The problem of the flow over an open cavity has been studied in depth in the literature, both for being an interesting academical problem and due to the multitude of industrial applications, like the landing gear of aircraft, or the water deposit of firefighter airplanes. The different types of instabilities appearing in this flow studied in the literature are two: the two-dimensional shear layer modes, and the three-dimensional modes that appear in the main recirculating vortex inside the cavity. In this thesis a parametric study in the incompressible limit of the problem is presented, using the linear stability analysis known as BiGlobal. This approximation allows to obtain the global stability behaviour of the flow, and to capture both the morphological features and the characteristics of the eigenmodes of the physical problem, whether they are stable or unstable. The study presented here characterizes with great detail all the relevant eigenmodes, as well as the hypersurface of instability on the parameter space of the incompressible problem (Mach equal to zero, and variation of the Reynolds number, the incoming boundary layer thickness, the length to depth aspect ratio of the cavity and the spanwise length of the perturbation). The results allow to construct parametric relations between the characteristics of the leading eigenmodes and the parameters of the problem, like for example the one existing between the critical Reynolds number and its characteristic length. The numerical results presented here are compared with those of an experimental campaign, with the main conclusion of said comparison being that the linear eigenmode are present in the real saturated flow, albeit with some significant differences in the frequencies of the experiments and those predicted by the theory. To try to determine the nature of those differences a three-dimensional direct numerical simulation, analyzed with Dynamic Mode Decomposition algorithm, was used to describe the process of saturation.

Discontinuity spacing analysis in rock masses using 3D point clouds

The complete characterization of rock masses implies the acquisition of information of both, the materials which compose the rock mass and the discontinuities which divide the outcrop. Recent advances in the use of remote sensing techniques – such as Light Detection and Ranging (LiDAR) – allow the accurate and dense acquisition of 3D information that can be used for the characterization of discontinuities. This work presents a novel methodology which allows the calculation of the normal spacing of persistent and non-persistent discontinuity sets using 3D point cloud datasets considering the three dimensional relationships between clusters. This approach requires that the 3D dataset has been previously classified. This implies that discontinuity sets are previously extracted, every single point is labeled with its corresponding discontinuity set and every exposed planar surface is analytically calculated. Then, for each discontinuity set the method calculates the normal spacing between an exposed plane and its nearest one considering 3D space relationship. This link between planes is obtained calculating for every point its nearest point member of the same discontinuity set, which provides its nearest plane. This allows calculating the normal spacing for every plane. Finally, the normal spacing is calculated as the mean value of all the normal spacings for each discontinuity set. The methodology is validated through three cases of study using synthetic data and 3D laser scanning datasets. The first case illustrates the fundamentals and the performance of the proposed methodology. The second and the third cases of study correspond to two rock slopes for which datasets were acquired using a 3D laser scanner. The second case study has shown that results obtained from the traditional and the proposed approaches are reasonably similar. Nevertheless, a discrepancy between both approaches has been found when the exposed planes members of a discontinuity set were hard to identify and when the planes pairing was difficult to establish during the fieldwork campaign. The third case study also has evidenced that when the number of identified exposed planes is high, the calculated normal spacing using the proposed approach is minor than those using the traditional approach.

Involvement and detachment in David Cameron and Ed Miliband’s political discourse. An analysis of deictic shields on the pronoun ‘I’ in UK 2015 General Election news interviews

The goal of my study is to investigate the relationship between selected deictic shields on the pronoun ‘I’ and the involvement/detachment dichotomy in a sample of television news interviews. I focus on the use of personal pronouns in political discourse. Drawing upon Caffi’s (2007) classification of mitigating devices into bushes, hedges and shields, I focus on deictic shields on the pronoun ‘I’: I examine the way a selection of ‘I’-related deictic shields is employed in a collection of news interviews broadcast during the electoral campaign prior to the UK 2015 General Election. My purpose is to uncover the frequencies of each of the linguistic items selected and the pragmatic functions of those linguistic items in the involvement/detachment dichotomy. The research is structured as follows. Chapter 1 provides an account of previous studies on the three main areas of research: speech event analysis, institutional interaction and the news interview, and the UK 2015 General Election television programmes. Chapter 2 is centred on the involvement/detachment dichotomy: I provide an overview of nonlinguistic and linguistic features of involvement and detachment at all levels of sentence structure. Chapter 3 contains a detailed account of the data collection and data analysis process. Chapter 4 provides an accurate description of results in three steps: quantitative analysis, qualitative analysis and discussion of the pragmatic functions of the selected linguistic features of involvement and detachment. Chapter 5 includes a brief summary of the investigation, reviews the main findings, and indicates limitations of the study and possible inputs for further research. The results of the analysis confirm that, while some of the linguistic items examined point toward involvement, others have a detaching effect. I therefore conclude that deictic shields on the pronoun ‘I’ permit the realisation of the involvement/detachment dichotomy in the speech genre of the news interview.

Navigation and meteorological data during campaign TARA_20090926Z of the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) sampled the world oceans on board a 36 m long schooner, collecting environmental data and organisms from viruses to planktonic metazoans for later analyses using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present dataset contains navigation and meteorological data measured during one campaign of the Tara Oceans Expedition. Latitude and Longitude were obtained from TSG data.

Navigation and meteorological data during campaign TARA_20091019Z of the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) sampled the world oceans on board a 36 m long schooner, collecting environmental data and organisms from viruses to planktonic metazoans for later analyses using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present dataset contains navigation and meteorological data measured during one campaign of the Tara Oceans Expedition. Latitude and Longitude were obtained from TSG data.