VILLELA, FRANCO N. J. Análise decadal do fluxo de CO2 entre o oceano e a atmosfera na passagem de Drake, Oceano Austral. 2011. 148 f. Dissertação (mestrado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM), Universidade de São Paulo, São Paulo, 2011. Para a área delimitada pelos paralelos 60ºS e 62,5ºS e pelos meridianos 60ºW e 65ºW, localizada no sul da Passagem de Drake, no Oceano Austral, próximo à Península Antártica, foram calculadas as distribuições médias de 2000 a 2009, sazonais e anual, do fluxo de CO2 na interface oceano-atmosfera e de suas variáveis associadas: a pressão parcial de CO2 na superfície marinha (PCO2sw), a pressão parcial de CO2 na atmosfera (PCO2ar), a diferença da pressão parcial de CO2 entre o oceano e a atmosfera (PCO2) e a taxa de transferência gasosa (TR), que é produto do coeficiente solubilidade do CO2 na água do mar pela velocidade de transferência gasosa. A parametrização utilizada no cálculo dos fluxos foi a de Takahashi et al. (2009) com TR dependente da velocidade do vento ao quadrado multiplicada por um fator de escala 0,26. A área de estudo tem cerca de 75 mil km2 e foi dividida em uma grade espacial de 0,5º x 0,5º, resultando em 50 quadrículas. Foram utilizados mais de 46 mil medições de PCO2sw, que na média espacial variou de 362,7 ±11,2 a 371,9 ±17,5 µatm, no verão e primavera respectivamente. A PCO2 variou de -0,4 a 5,7 µatm no outono e primavera, respectivamente. A TR variou de 0,065 ±0,04 a 0,088 ±0,002 gC.mês-1.m-2.µatm-1, no verão e inverno, respectivamente. O fluxo líquido, se tomando a concentração de gelo como negligenciável, variou de -0,039 ±0,865 a 0,456 ±1,221 gC.m-2.mês-1, no outono e inverno, respectivamente. O fluxo total anual de carbono, estimado através da média espacial por quadrícula, foi de 95 GgC.ano-1. Dessa maneira, na estimativa anual, a superfície do mar se comporta como fonte de CO2 para a atmosfera, principalmente devido à região da plataforma continental com PCO2sw consideravelmente maior que o da atmosfera. Sazonalmente sugere-se que no verão a maior disponibilidade de radiação solar, a temperatura da superfície do mar (TSM) mais elevada e os ventos mais fracos favorecem a produção de biomassa fitoplanctônica, fazendo com que a bomba biológica seja o processo dominante na diminuição da PCO2sw e na absorção de CO2 atmosférico pela superfície marinha. Já no inverno, os ventos se intensificam e, associados com o forte resfriamento da TSM, promovem a mistura com águas profundas ricas em carbono inorgânico dissolvido, levando a superfície marinha a um estado de supersaturação de CO2 em relação à atmosfera. Ventos circumpolares de oeste mais intensos e deslocados para sul tem sido apontados como a causa do aumento da PCO2sw em igual ou maior taxa do que ocorre na atmosfera. Na área de estudo foi levantada uma tendência média da intensidade do vento de 0,23 ±0,03 m.s-1.década-1 e um aumento na freqüência da componente zonal de oeste (positiva) de 1,47 ± 1,13 % .década-1. Sugere-se que estas tendências estejam relacionadas com o Modo Anular Austral (SAM). Entretanto, a tendência decadal estimada para a PCO2sw foi menor que para a atmosfera, apesar de ambas indicarem tendência de aumento. Acredita-se que a grande variabilidade e distribuição esparsa de dados tenham mascarado a magnitude da estimativa da tendência de PCO2sw. / VILLELA, FRANCO N. J. Decadal analysis of the CO2 sea-air flux in the Drake Passage, Southern Ocean 2011. 148 f. Dissertação (mestrado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM), Universidade de São Paulo, São Paulo, 2011. For the area bounded by parallels 60°S and 62.5°S and meridians 60°W and 65°W, located in the southern Drake Passage in the Southern Ocean, near the Antarctic Peninsula, mean seasonal and annual distributions of CO2 flux at the ocean-atmosphere interface, from 2000 to 2009, have been computed, as well as their associated variables: the CO2 partial pressure at sea surface (PCO2sw), the CO2 partial pressure in atmosphere (PCO2ar), the CO2 pressure difference between ocean and atmosphere (PCO2), and the gas transfer rate (TR), which is the product of the CO2 solubility coefficient in sea water by the gas transfer velocity. The parameterization used to calculate fluxes was that of Takahashi et al. (2009) with TR depending on the squared wind speed multiplied by a scale factor 0.26. The study area has about 75,000 km2 and was divided into a grid of 0.5° x 0.5°, resulting in 50 area boxes. Over 46,000 PCO2sw measurements were used, which in the spatial mean varied from 362.7±11.2 to 371.9±17.5 µatm, in summer and spring, respectively. The PCO2 varied from 0.4 to 5.7 µatm in autumn and spring, respectively. TR varied from 0.065±0.04 to 0,088±0.002 gC.month-1.m-2.µatm-1, in summer and winter, respectively. The net flux, taking ice concentration as negligible, varied from 0.039±0.865 to 0.456±1.221 gC.month-1.m-2, in autumn and winter, respectively. The total annual carbon flux, estimated through the spatial mean per square, was 95 GgC.y-1. Thus, in the annual estimate the region acts as a source to the atmosphere, mainly due to the continental shelf having PCO2sw considerably greater than that of the atmosphere. Seasonally, it is suggested that in summer the greater availability of solar radiation, warmer sea surface temperature (SST), and weaker winds favor the production of phytoplanktonic mass, making the biological pump the dominating process in lowering the PCO2sw and the absorption of atmospheric CO2 by the sea surface. On the other hand, in winter winds intensify and, in association with the strong cooling of the SST, promote mixing with deep waters rich in dissolved inorganic carbon, leading the sea surface to a state of supersaturation in CO2 relative to the atmosphere. Stronger circumpolar west winds and displaced to the south have been pointed as the cause for the increase of PCO2sw at a rate equal to or greater than that occurring in the atmosphere. In the study area it has been detected a mean trend of wind intensity 0.23±0.03 m.s-1.decade-1 and an increase in the western zonal component of 1.47±1.3%.decade-1. It is suggested that these trends are related to the Southern Annular Mode (SAM). However, the decadal trend estimated for the PCO2sw was smaller than for the atmosphere, in spite of both indicating increasing tendencies. It is believed that the great variability and scatter distribution of the data have masked the magnitude of the PCO2SW trend estimate.

Human activities such as mining and smelting of lead (Pb) ores and combustion of alkyllead additives in gasoline have resulted in extensive global Pb pollution. Since the late 1960's studies of polar ice and snow have been undertaken to evaluate the extent of anthropogenic Pb emissions in recent times as well as to investigate changes in anthropogenic Pb emissions in the more distant past. The polar ice sheets have been used to investigate Pb pollution as they offer a long-term record of human activity located far from pollution sources and sample aerosol emissions on a hemispheric scale. Lead isotopes have been previously used to identify sources of Pb in polar snow and ice, while new evaluations of Pb isotopic compositions in aerosols and Pb ore bodies allow more thorough evaluations of anthropogenic Pb emissions. Lead isotopic compositions and Pb and Barium (Ba) concentrations have been measured in snow and ice core samples from Law Dome, East Antarctica, to produce a detailed pollution history between 1530 AD and 1989 AD. Such a record has been produced to evaluate changes in anthropogenic Pb emission levels and sources over the past 500 years, to determine when industrial (anthropogenic) activities first began to influence Antarctica and also to investigate natural Pb fluxes to Antarctica. Additional samples were also collected from Law Dome snow and ice cores to respectively investigate seasonal variations in Pb and Ba deposition, and the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. All samples were measured by thermal ionisation mass spectrometry, for which techniques were developed to reliably analyse Pb isotopic compositions in Antarctic samples containing sub-picogram per gram concentrations of Pb. / Particular attention was given to the quantity of Pb added to the samples during the decontamination and sample storage stages of the sample preparation process. These stages, including the use of a stainless steel chisel for the decontamination, contributed ~5.2 pg to the total sample analysed, amounting to a concentration increase of ~13 fg g-1. In comparison, the mass spectrometer ion source contributed typically 89 +/- 19 fg to the blank, however its influence depended upon the amount of Pb available for analysis and so had the greatest impact when small volumes of samples with a very low concentration were analysed. As a consequence of these careful investigations of the Pb blank contributions to the samples, the corrections made to the Pb isotopic ratios and concentrations measured are smaller than previously reported evaluations of Pb in Antarctica by thermal ionisation mass spectrometry. The data indicate that East Antarctica was relatively pristine until -1884 AD, after which the first influence of anthropogenic Pb in Law Dome is observed. "Natural", pre-industrial, background concentrations of Pb and Ba were - 0.4 pg/g and - 1.3 pg/g, respectively, with Pb isotopic compositions within the range 206Pb/207Pb = 1.20 - 1.25 and 208Pb/207Pb = 2.46 - 2.50 and an average rock and soil dust Pb contribution of 8-12%. A major pollution event was observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration fourfold and changing 206Pb/207Pb ratios in the ice to ~1.12. Based on Pb isotopic systematics and Pb emissions statistics, this was attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia. / Anthropogenic Pb inputs to Law Dome were most significant from ~1900 to 1910 and from ~1960 to 1980. During the 20th century, Ba concentrations were consistently higher than "natural" levels. This was attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation. Law Dome ice dated from 1814 AD to 1819 AD was analysed for Pb isotopes and Pb, Ba and Bismuth (Bi) concentrations to investigate the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. The presence of volcanic debris in the core samples was observed from late-1816 AD to 1818 AD as an increase in sulphate concentrations and electrical conductivity of the ice. Barium concentrations were approximately three times higher than background levels from mid-1816 to mid1818, consistent with increased atmospheric loading of rock and soil dust, while enhanced Pb/Ba and Bi/Ba ratios, associated with deposition of volcanic debris, were observed at mid-1814 and from early-1817 to mid-1818. From the results, it appeared likely that Pb emitted from Tambora was removed from the atmosphere within the 1.6 year period required to transport aerosols to Antarctica. Increased Pb and Bi concentrations observed in Law Dome ice ~1818 AD were attributed to either increased heavy metal emissions from Mount Erebus, or increased fluxes of heavy metals to the Antarctic ice sheet resulting from climate and meteorological modifications following the Tambora eruption. / A non-continuous series of Law Dome snow core samples dating from 1980 to 9185 AD were analysed to investigate seasonal variations in the deposition of Pb and Ba. It was found that Pb and Ba at Law Dome do exhibit seasonal variations in deposition, with higher concentrations of Pb and Ba usually observed during Summer and lower concentrations of Pb and Ba usually observed during the Autumn and Spring seasons. At Law Dome, broad patterns of seasonal Pb and Ba deposition are evident however these appear to be punctuated by short-term deposition events or may even be composed of a continuum of short-term deposition events. This variability suggests that complex meteorological systems are responsible for the transport of Pb and Ba to Law Dome, and probably Antarctica in general.

Esta memoria doctoral forma parte del proyecto financiado por el Ministerio de Ciencia e Innovación (CICYT, CTQ2010-21183-C02-01), el cual tiene entre sus objetivos la búsqueda de nuevas cepas con capacidad para producir emulsionantes naturales poliméricos. Existe un interés real en el aislamiento y caracterización estructural y funcional de nuevos exopolímeros (EPS) obtenidos a partir de microorganismos de ambientes extremos que pudieran ser utilizados con estos fines en diversas industrias. Para ello, se realizó en primer lugar el estudio de los EPS desde el punto de vista ultraestructural, de cepas antárticas adaptadas al frío, mediante técnicas de microscopía electrónica de transmisión (MET) después de procesar las muestras por criofijación a alta presión seguida de criosustitución (HPF-FS). Estas técnicas aportaron numerosos detalles sobre la ultraestructura de las distintas cepas y el material extracelular que producen, al lograr preservar el material biológico próximo a su estado natural. Se observó que este material polimérico extracelular es para la mayoría de las cepas complejo con la presencia de material capsular alrededor de las células y abundantes estructuras vesiculares dispersas en la matriz extracelular secretada por las bacterias. Es la primera vez que se describen y visualizan de manera tan clara y abundante las vesículas de membrana externa (VME) que producen bacterias no patógenas de ambientes naturales antárticos. De igual forma, es la primera vez que se reporta la presencia de estas estructuras en cepas de los géneros Marinobacter y Psychrobacter. Asimismo, se estudió el origen de las proteínas presentes en las VME mediante geles SDS-PAGE donde se mostraron los perfiles proteicos comparados con las proteínas de membrana externa. Esto evidenció el origen de estas VME formadas a partir de esta membrana, al presentar proteínas en la fracción de VME, que comigraron con proteínas que estaban presentes en la fracción de membrana externa, además en el perfil proteico de la membrana externa se detectaron proteínas adicionales que no estaban presentes en VME. Se estudió la influencia de la temperatura sobre la producción y morfología de VME producidas en la cepa S. livingstonensis NF22T Para esta bacteria psicrotolerante se demostró que la temperatura influye en la producción de VME. A bajas temperaturas la cantidad de VME que produce la cepa es mayor, su tamaño es menor y más regular y el perfil electroforético muestra la expresión diferencial de algunas proteínas, viéndose sobrexpresadas proteínas relacionadas con funciones de transporte a nivel de membrana. Se realizaron análisis proteómicos para identificar las proteínas presentes en las VME producidas a 4 y 16 ºC a partir de S. livingstonensis NF22T y S. vesiculosa M7T. Para ambas cepas se identificaron fundamentalmente proteínas de membrana externa y periplasmáticas con diferentes funciones fisiológicas, destacando por su abundancia las proteínas implicadas en el transporte y metabolismo de iones inorgánicos así como las relacionadas en la biogénesis de las envueltas celulares. El material extracelular (EPS) obtenido y purificado a partir de Shewanella vesiculosa M7T presentó mayor actividad emulsionante frente a aceites comestibles que los emulsionantes comercializados goma arábiga y xantano y su caracterización reveló que contiene abundantes VME y polímeros polisacarídicos, siendo sus componentes químicos mayoritarios azúcares neutros y aminados, lípidos de membrana y aminoácidos. / The present work is part of the research project (CICYT, CTQ2010-21183-C02-01), which has among its objectives the search for new strains capable to produce natural polymeric emulsifiers. There is a real interest in the isolation and structural and functional characterization of new exopolymers (EPS) derived from microorganisms of extreme environments that could be used for these purposes in various industries. Many Gram-negative, cold-adapted bacteria from the Antarctic environment produce large amounts of extracellular matter, which has potential biotechnology applications. We examined the ultrastructure of extracellular matter from Antarctic bacteria by transmission electronic microscopy after high pressure freezing and freeze substitution. All analyzed extracellular matter appeared as a netlike mesh composed of a capsular polymer around cells and large numbers of outer membrane vesicles (OMV), which have not been described for members of the genera Psychrobacter and Marinobacter so far. OMV showed the typical characteristics described for these structures, and seemed to be surrounded by the same capsular polymer as that found around cells. The analysis of OMV proteins from Antarctic strains by SDS-PAGE showed different banding profiles in OMV compared to the outer membrane, suggesting some kind of protein sorting during membrane vesicle formation. For the psychrotolerant bacterium, S. livingstonensis NF22T, the growth temperature seemed to influence the amount and morphology of OMV. In an initial attempt to elucidate the functions of OMV from S. livingstonensis NF22T and S. vesiculosa M7T we conducted a proteomic analysis on membrane vesicles obtained at 4 and 16°C. At both temperatures, OMV were highly enriched in outer membrane proteins and periplasmic proteins related to nutrient processing and transport in Gram-negative bacteria, suggesting that OMV could be related with nutrient sensing and bacterial survival. Differences were observed in the expression of some proteins depending on incubation temperature but further studies will be necessary to define their roles and implications in the survival of bacteria in the extreme Antarctic environment. The extracellular material (EPS) obtained and purified from Shewanella vesiculosa M7T had a higher emulsifying activity against edible oils than commercial emulsifiers like arabic and xanthan gums. Characterization of this EPS revealed that it contains abundant OMV and polysaccharides polymers, with neutral and amino sugars, membrane lipids and aminoacids as its major chemical components.

The inhabitants of marine benthos must combat the ecological pressure caused by predation, competition and fouling through a series of mechanisms, one of which is chemical defense. This type of protection is particularly extended among sessile and/or sluggish organisms, such as sponges, soft corals or ascidians. The strategies to prevent predation are related to bad taste rather than to toxicity. Moreover, they must be considered along with nutritional quality, since the more nutritious the prey, higher quantities or more potent repellents are needed to gain protection. The production of defensive secondary metabolites is energetically expensive. For this reason, the Optimal Defense Theory (ODT) predicts that defenses must be allocated in the most valuable or more exposed structures or body-regions. In Antarctic communities, the main predators are asteroids, and defensive agents are hence expected to accumulate in superficial layers of potential prey. But dense populations of amphipods, which associate opportunistically with biosubtrata, obtaining both refuge and direct or indirect sources of nutrition, are also very influencing on these bottoms. It has been reported that chemical defenses are very common in Antarctic organisms, in accordance with our results. However, the research effort has not been the same for all the groups, and there are still many aspects to learn on the chemical ecology, like the identification of the implicated products, their mode of functioning or their localization and origin. This PhD has focused on three relevant groups of the Antarctic benthos, quite understudied: hexactinellid sponges, soft corals and colonial ascidians. Two influencing sympatric predators were selected, the sea star Odontaster validus, which is a known model predator, and for the first time, the amphipod Cheirimedon femoratus, used to perform feeding experiments for the detection of repellent chemical defenses. We designed a new protocol which provided numerous methodological profits, as well as a remarkable discriminatory potential for unpalatable activities. In a survey with 31 species of Antarctic organisms, a larger incidence of unpalatable activities was recorded towards C. femoratus than against the asteroid, especially in algae and sponges, in which amphipods may particularly influence defenses distribution for representing potential host-preys. Some organisms instead, seemed to exploit alternative defensive strategies. The ecological success of the three studied groups is probably related to the presence of chemical defenses. In hexactinellid sponges these are weak, yet compensated with a low energetic content, and derive from primary metabolites, such as steroid derivates. Some glucosphingolipids instead, could have a chemotaxonomical value as chemical markers in rossellid sponges. In soft corals, chemical protection is obtained from products originating from both, primary (wax esters) and secondary metabolism (sesquiterpenoids), which seem to cooperate in an additive way, and are likely exuded within the coral mucus in living specimens. The use of primary metabolites for defense represents an effective energy saving strategy. In colonial ascidians, defensive secondary metabolites of terpenoid and alkaloid nature with potent bioactivities predominate, and in some species these are accumulated in internal tissues. Presumably, this distribution is related to the production of chemically defended lavae. Some bioactive secondary metabolites isolated from various sources, like the meridianins, may suggest a broad evolutionary retention, or a symbiotic origin. Regarding bacterial antifouling, ascidians exhibited poor activity, while some soft corals did display inhibition. With this work we provide the identification, localization, and possible origin of several defensive agents in three relevant groups of Antarctic benthic invertebrates. / Los habitantes del bentos antártico combaten la depredación, la competencia y el recubrimiento desarrollando mecanismos como la defensa química. Ésta estrategia está particularmente extendida entre organismos sésiles y organismos de cuerpo blando. Las defensas repelentes contra depredadores han de considerarse junto con la calidad nutricional, pues las dietas muy energéticas enmascaran la repelencia. La producción de metabolitos secundarios defensivos es costosa. Por ello, la Teoría de Defensa Optimizada (ODT) prevé que han de localizarse en las regiones corporales más valiosas o expuestas. En las comunidades antárticas los principales depredadores son las estrellas de mar y se postula la concentración de defensas en áreas superficiales en las presas. Pero también influyen las poblaciones de anfípodos asociados a los biosustratos, obteniendo en ellos refugio y fuente de alimentación. Esta tesis se centra en las defensas químicas de tres grupos relevantes del bentos antártico relativamente poco estudiados: esponjas hexactinélidas, corales blandos y ascidias coloniales. Se seleccionaron dos depredadores simpátricos, la estrella Odontaster validus y, por primera vez, fue utilizado el anfípodo Cheirimedon femoratus. Diseñamos un nuevo protocolo con numerosas ventajas metodológicas además de un gran potencial discriminatorio, y observamos que en 31 especies hubo mayor repelencia hacia el anfípodo que hacia la estrella, sobretodo en algas y esponjas, que podrían representar potenciales huéspedes-presa. A partir de aquí estudiamos muestras de los tres grupos seleccionados. En hexactinélidas, las defensas químicas son más débiles y derivadas del metabolismo primario, pero compensadas con un bajo valor nutricional. Algunos glucoesfingolípidos, podrían tener valor quimiotaxonómico como marcadores de la familia Rossellidae. En corales blandos existen metabolitos de defensa primarios y secundarios operando sinérgicamente, y probablemente forman parte del mucus superficial. En ascidias coloniales, los metabolitos defensivos son secundarios y muy potentes; además, en algunas especies éstos tienden a acumularse en tejidos internos, presumiblemente para producir larvas protegidas químicamente. Las ascidias mostraron poca actividad antibacteriana, pero algunos corales exhibieron respuestas inhibitorias. Esta Tesis proporciona la estructura, distribución y posible origen de los metabolitos responsables de las actividades defensivas en tres grupos relevantes de invertebrados antárticos.

<p>Enzymes are useful tools as specific analytical reagents. Two different analysis methods were developed for use in the separate fields of protein science and organic synthesis. Both methods rely on the substrate specificity of enzymes. Enzyme catalysis and substrate specificity is described and put in context with each of the two developed methods.</p><p>In <strong>paper I </strong>a method for C-terminal peptide sequencing was developed based on conventional Carboxypeptidase Y digestion combined with matrix assisted laser desorption/ionization mass spectrometry. An alternative nucleophile was used to obtain a stable peptide ladder and improve sequence coverage.</p><p>In paper<strong> II </strong>and <strong>III</strong>, three different enzymes were used for rapid analysis of enantiomeric excess and conversion of O-acylated cyanohydrins synthesized by a defined protocol. Horse liver alcohol dehydrogenase,<em> Candida antarctica</em> lipase<strong> </strong>B<strong> </strong>and pig liver esterase were sequentially added to a solution containing the O-acylated cyanohydrin. Each enzyme caused a drop in absorbance from oxidation of NADH to NAD⁺. The conversion and enantiomeric excess of the sample could be calculated from the relative differences in absorbance.</p>

The Darwin-Hatherton glacial system (DHGS) drains from the East Antarctic Ice Sheet (EAIS) and through the Transantarctic Mountains (TAM) before entering the Ross Embayment. Large ice-free areas covered in glacial sediments surround the DHGS, and at least five glacial drift sheets mark the limits of previous ice extent. The glacier belongs to a group of slow-moving EAIS outlet glaciers which are poorly understood. Despite this, an extrapolation of a glacial drift sheet boundary has been used to determine the thickness of the EAIS and the advanced West Antarctic Ice Sheet (WAIS) during the Last Glacial Maximum (LGM). In order to accurately determine the past and present contributions of the Antarctic ice sheets to sea level changes, these uncertainties should be reduced. This study aims to examine the present and LGM ice dynamics of the DHGS by combining newly acquired field measurements with a 3-D numerical ice sheet-shelf model. The fieldwork included a ground penetrating radar survey of ice thickness and surface velocity measurements by GPS. In addition, an extensive dataset of airborne radar measurements and meteorological recordings from automatic weather stations were made available. The model setup involved nesting a high-resolution (1 km) model of the DHGS within a lower resolution (20 km) all-Antarctic simulation. The nested 3-D modelling procedure enables an examination of the impact of changes of the EAIS and WAIS on the DHGS behaviour, and accounts for a complex glacier morphology and surface mass balance within the glacial system. The findings of this study illustrate the difference in ice dynamics between the Darwin and Hatherton Glaciers. The Darwin Glacier is up to 1500 m thick, partially warm-based, has high driving stresses (~150 kPa), and measured ice velocities increase from 20-30 m yr⁻¹ in the upper parts to ~180 m yr⁻¹ in the lowermost steepest regions, where modelled flow velocities peak at 330 m yr⁻¹. In comparison, the Hatherton Glacier is relatively thin (<900 m), completely cold-based, has low driving stresses (~85 kPa), and is likely to flow with velocities <10 m yr⁻¹ in most regions. It is inferred that the slow velocities with which the DHGS flows are a result of high subglacial mountains restricting ice flow from the EAIS, large regions of frozen basal conditions, low SMB and undulating bedrock topography. The model simulation of LGM ice conditions within the DHGS implies that the ice thickness of the WAIS has been significantly overestimated in previous reconstructions. Results show that the surface of the WAIS and EAIS away from the TAM would have been elevated 600-750 and 0-80 m above present-day levels, respectively, for the DHGS to reach what was inferred to represent the LGM drift sheet limit. Ultimately, this research contributes towards a better understanding of the dynamic behaviour of slow moving TAM outlet glaciers, and provides new insight into past changes of the EAIS and WAIS. This will facilitate more accurate quantifications of contributions of the WAIS and EAIS to changes in global sea level.

This thesis examines the utility of the Rényi entropy (RE), a measure of the complexity of probability density functions, as a tool for finding physically meaningful patterns in geophysical data. Initially, the RE is applied to observational data of long-lived atmospheric tracers in order to analyse the dynamics of stratospheric transitions regions associated with barriers to horizontal mixing. Its wider applicability is investigated by testing the RE as a method for highlighting internal boundaries in snow and ice from ground penetrating radar (GPR) recordings. High-resolution 500 MHz GPR soundings of dry snow were acquired at several sites near Scott Base, Antarctica, in 2008 and 2009, with the aim of using the RE to facilitate the identification and tracking of subsurface layers to extrapolate point measurements of accumulation from snow pits and firn cores to larger areas. The atmospheric analysis focuses on applying the RE to observational tracer data from the EOS-MLS satellite instrument. Nitrous oxide (N2O) is shown to exhibit subtropical RE maxima in both hemispheres. These peaks are a measure of the tracer gradients that mark the transition between the tropics and the mid-latitudes in the stratosphere, also referred to as the edges of the tropical pipe. The RE maxima are shown to be located closer to the equator in winter than in summer. This agrees well with the expected behaviour of the tropical pipe edges and is similar to results reported by other studies. Compared to other stratospheric mixing metrics, the RE has the advantage that it is easy to calculate as it does not, for example, require conversion to equivalent latitude and does not rely on dynamical information such as wind fields. The RE analysis also reveals occasional sudden poleward shifts of the southern hemisphere tropical pipe edge during austral winter which are accompanied by increased mid-latitude N2O levels. These events are investigated in more detail by creating daily high-resolution N2O maps using a two-dimensional trajectory model and MERRA reanalysis winds to advect N2O observations forwards and backwards in time on isentropic surfaces. With the aid of this ‘domain filling’ technique it is illustrated that the increase in southern hemisphere mid-latitude N2O during austral winter is probably the result of the cumulative effect of several large-scale, episodic leaks of N2O-rich air from the tropical pipe. A comparison with the global distribution of potential vorticity strongly suggests that irreversible mixing related to planetary wave breaking is the cause of the leak events. Between 2004 and 2011 the large-scale leaks are shown to occur approximately every second year and a connection to the equatorial quasi-biennial oscillation is found to be likely, though this cannot be established conclusively due to the relatively short data set. Identification and tracking of subsurface boundaries, such as ice layers in snow or the bedrock of a glacier, is the focus of the cryospheric part of this project. The utility of the RE for detecting amplitude gradients associated with reflections in GPR recordings is initially tested on a 25 MHz sounding of an Antarctic glacier. The results show distinct regions of increased RE values that allow identification of the glacial bedrock along large parts of the profile. Due to the low computational requirements, the RE is found to be an effective pseudo gain function for initial analysis of GPR data in the field. While other gain functions often have to be tuned to give a good contrast between reflections and background noise over the whole vertical range of a profile, the RE tends to assign all detectable amplitude gradients a similar (high) value, resulting in a clear contrast between reflections and background scattering. Additionally, theoretical considerations allow the definition of a ‘standard’ data window size with which the RE can be applied to recordings made by most pulsed GPR systems and centre frequencies. This is confirmed by tests with higher frequency recordings (50 and 500 MHz) acquired on the McMurdo Ice Shelf. However, these also reveal that the RE processing is less reliable for identifying more closely spaced reflections from internal layers in dry snow. In order to complete the intended high-resolution analysis of accumulation patterns by tracking internal snow layers in the 500 MHz data from two test sites, a different processing approach is developed. Using an estimate of the emitted waveform from direct measurement, deterministic deconvolution via the Fourier domain is applied to the high-resolution GPR data. This reveals unambiguous reflection horizons which can be observed in repeat measurements made one year apart. Point measurements of average accumulation from snow pits and firn cores are extrapolated to larger areas by identifying and tracking a dateable dust layer horizon in the radargrams. Furthermore, it is shown that annual compaction rates of snow can be estimated by tracking several internal reflection horizons along the deconvolved radar profiles and calculating the average change in separation of horizon pairs from one year to the next. The technique is complementary to point measurements from other studies and the derived compaction rates agree well with published values and theoretical estimates.

Der regionalen Schwerefeldmodellierung in polaren Gebieten kommt in vielerlei Hinsicht eine besondere und wachsende Bedeutung zu. Einerseits sind hochauflösende und präzise Geoidmodelle eine wichtige Eingangsgröße bei der Untersuchung und Quantifizierung geophysikalischer, ozeanographischer bzw. glaziologischer Phänomene, z. B. bei der Bestimmung der mittleren dynamischen Ozeantopographie oder der Anwendung des Schwimmgleichgewichts im Bereich von Schelfeisen, Meereis oder subglazialen Seen. Zudem werden sie allgemein zur Referenzierung von Höhenmodellen benötigt. Andererseits sind, aufgrund der unvermeidbaren polaren Datenlücken von Satellitenbeobachtungen jenseits der Grenzbreite (sog. „Polloch“), terrestrische Schweredaten auch für die globale Schwerefeldmodellierung unerlässlich. Jedoch sind die verfügbaren terrestrischen (bodennahen) Schwerebeobachtungen insbesondere im Gebiet der Antarktis äußerst lückenhaft und heterogen. So entspricht das tatsächliche Auflösungsvermögen selbst aktueller kombinierter Schwerefeldmodelle wie EGM2008 oder EIGEN-6C über dem antarktischen Kontinent lediglich dem der reinen Satellitenmodelle aus GRACE bzw. GOCE. Des Weiteren sind Standardverfahren der regionalen Geoidmodellierung hier nicht ohne Weiteres anwendbar. Neben der Heterogenität der Daten als praktischer Herausforderung muss aus theoretischer Sicht dem zusätzlichen Dichtekontrast durch das Eis Rechnung getragen werden. Die vorliegende kumulative Dissertation greift diese Problematik auf. Während die einzelnen Publikationen die Ergebnisse ausgewählter regionaler Fallstudien präsentieren, soll die folgende zusammenfassende Abhandlung einen doppelten Bogen spannen, indem die geophysikalischen Phänomene gleichzeitig als zu untersuchende Anwendungsgebiete und als Einflussfaktoren im Kontext der regionalen Geoidmodellierung beschrieben werden. So wird am Beispiel der Weddellsee gezeigt, wie die Meereisbedeckung die Qualität und Zuverlässigkeit der mithilfe der Satellitenaltimetrie abgeleiteten Schwerefeldmodelle beeinträchtigt. Diese Modelle bilden derzeit die alleinige Datengrundlage für die hochauflösenden globalen Modelle im Gebiet des Antarktischen Ozeans. Zugleich wird anhand des verfeinerten regionalen Modells und daraus abgeleiteter geostrophischer Geschwindigkeiten demonstriert, dass selbst lückenhafte und heterogene terrestrische Daten hier einen wesentlichen Beitrag zur simultanen Kalibrierung und Vereinheitlichung des Datenbestandes leisten können. Im Ergebnis konnten in den küstennahen Gewässern Differenzen von mehreren Dezimetern gegenüber Geoidhöhen aus EGM2008 festgestellt werden, welche teils auf systematische Abweichungen und teils auf Rauschen im globalen Modell zurückzuführen sind. Über dem Festland erreicht dessen Vernachlässigungsfehler im quadratischen Mittel sogar 0,75 m und Maxima von über 3 m. Ein weiteres verfeinertes und, dank geeigneter Eingangsdaten, sehr genaues und hochauflösendes Geoidmodell wird für die Region um den Vostoksee in der Ostantarktis abgeleitet. In Kombination mit Eisoberflächenhöhen und Eisdicken gelingt es, das Schwimmgleichgewicht des subglazialen Sees nachzuweisen. Das gegenüber GOCE zusätzlich gewonnene Geoidsignal ist hier mit 0,56 m Standardabweichung zwar etwas kleiner, jedoch wird im Vergleich mit der residualen Auslenkung des Seespiegels (0,26 m Standardabweichung) auch für diese Anwendung der signifikante und gegenüber dem Auflösungsvermögen von GOCE auch notwendige Beitrag eines regionalen Geoidmodells deutlich. Für das hydrostatische Gleichgewicht eines subglazialen Sees ist streng genommen das tatsächliche Schwerepotential in Höhe des Seespiegels maßgeblich. Dessen Berechnung erfordert eine Fortsetzung des Störpotentials nach unten innerhalb der Topographie, welche konzeptionell in engem Zusammenhang mit dem bekannten Geoid-Quasigeoid-Separationsterm steht. Dessen oft angenommene Approximation mithilfe der Bougueranomalie kann, angesichts der heutigen Anforderungen an ein modernes zentimetergenaues Geoid, gerade in rauem Gelände zu ungenau sein. In Anlehnung an aktuelle Arbeiten auf diesem Gebiet wird ein verallgemeinerter und zugleich verfeinerter Ansatz zur praktischen Berechnung des Terms erarbeitet. Am Beispiel des Himalaya werden die einzelnen Anteile im Rahmen einer Simulationsstudie quantifiziert und insbesondere ihre Sensitivität gegenüber dem Integrationsradius der Topographie untersucht. Besonderes Augenmerk liegt ebenso auf dem indirekten Effekt der Topographie in Bezug auf das Potential, welcher, im Gegensatz zur Anwendung eines planaren Modells, in sphärischer Betrachtungsweise nicht verschwindet. / In many respects, regional gravity field modeling in polar areas is of special, and growing, interest. On the one hand, high-resolution and precise geoid models are an important input parameter to investigate and quantify manifold geophysical, oceanographical and glaciological phenomena, e.g., the determination of the mean dynamic ocean topography, or the application of the hydrostatic equilibrium condition in the areas of ice shelves, sea ice, or subglacial lakes. Moreover, geoid models are in general needed as a reference for height models. On the other hand, because of the unavoidable polar data gaps in satellite measurements due to the inclination (the so-called “polar gap”), terrestrial gravity data are indispensable also for global gravity field modeling. However, the available terrestrial (ground-based) gravity datasets, in particular of Antarctica, are very sparse and heterogeneous. For example, over the Antarctic continent the true resolution of even the most recent combined global geopotential models such as EGM2008 or EIGEN-6C only corresponds to that of the satellite-only models derived from GRACE and GOCE, respectively. Furthermore, standard techniques of regional geoid modeling cannot be readily used in this area. Apart from the heterogeneity of the data as a practical challenge the additional density contrast implied by the covering sheet needs to be accounted for from the theoretical point of view. This complex situation is the starting point for the present cumulative dissertation. Whereas the individual publications present the results of selected regional case studies, the intention of the following summary is to draw an integrated picture aiming at explaining the geophysical phenomena as both applications and influencing factors in the context of regional geoid modeling. Using the example of the Weddell Sea it is shown how sea-ice coverage affects the quality and reliability of marine gravity field models derived from radar satellite altimetry. At present, these models are the only input data to the high-resolution global geopotential models. At the same time, the refined regional model and geostrophic velocities derived thereof are employed to demonstrate how even sparse and heterogeneous terrestrial gravity data may provide a contribution to simultaneously calibrate and unify the available datasets. As a result, near the coast differences at the order of some decimeters could be observed in comparison with EGM2008, originating partly from systematic effects and noise in the global model. In the continental areas, its omission error even yields a standard deviation of 0.75 m and attains a maximum of more than 3 m. Another refined and, owing to appropriate input data, very precise and highly resolving geoid model is derived for the region around subglacial Lake Vostok. In combination with ice-surface heights and ice thickness data it is used to provide observational evidence that the lake is in a state of hydrostatic equilibrium. There, the additional geoid signal w.r.t. GOCE is a bit smaller (0.56 m standard deviation). However, considering the residual deviations of the apparent lake level (0.26 m standard deviation) the significant and necessary, as compared to the resolution of GOCE, contribution of a regional geoid model to this application is shown. In a strict sense, the relevant quantity to evaluate the hydrostatic equilibrium condition of a subglacial lake is the actual geopotential at the anticipated lake level. Its computation requires a downward continuation of the disturbing potential inside the topography, which is closely related to the concept of the well-known geoid-quasigeoid separation term. In the past, this term was frequently described as an approximation by means of the Bouguer anomaly. However, considering the modern requirements of the “one-centimeter geoid” this approximation may be too coarse over rough terrain. Following recent works in this field, a generalized yet refined approach for practical implementation of the term is developed. The individual constituents of the term are quantified. In particular, their sensitivity against the radius up to which topography is taken into account is investigated. For this simulation study, the Himalaya mountain region served as test area. Furthermore, special focus is given to the indirect of topography on the potential which, contrary to applying a planar model, does not vanish in the spherical approach.

This dissertation aims to develop an ethical system that can properly frame such questions as the morality of large-scale efforts to transform inanimate parts of nature, for example, proposals to terraform Mars. Such an ethics diverges from traditional approaches to ethics because it expands the class of entities regarded as morally considerable to include inanimate entities. I approach the task by building on the environmental ethical theory of Paul W. Taylor, as developed in his 1986 book Respect for Nature: A Theory of Environmental Ethics. I discuss various criticisms of Taylor and propose two extensions to his theory: an expansion of the scope of moral considerability to include all concrete material objects and the introduction of the concept of variable moral significance (the notion that all entities have inherent worth but some have more than others). Using Taylor’s modified and extended theory as a foundation, I develop something I call universal ethics. This is an ethical framework whose key elements are a fundamental ethical attitude of respect for the world and a principle of minimal harm. Universal ethics regards all concrete material entities, whether living or not, and whether natural or artefactual, as inherently valuable, and therefore as entitled to the respect of moral agents. I offer a defence of this ethical framework and discuss a number of practical applications, including criticism of proposals for the terraforming of Mars. I conclude that terraforming Mars or any other celestial body at this point in our history would be morally wrong. I also suggest that universal ethics provides an ethical foundation for efforts to protect Antarctica, and that it has implications for our relations to other inanimate parts of our world, including artefacts.

This dissertation aims to develop an ethical system that can properly frame such questions as the morality of large-scale efforts to transform inanimate parts of nature, for example, proposals to terraform Mars. Such an ethics diverges from traditional approaches to ethics because it expands the class of entities regarded as morally considerable to include inanimate entities. I approach the task by building on the environmental ethical theory of Paul W. Taylor, as developed in his 1986 book Respect for Nature: A Theory of Environmental Ethics. I discuss various criticisms of Taylor and propose two extensions to his theory: an expansion of the scope of moral considerability to include all concrete material objects and the introduction of the concept of variable moral significance (the notion that all entities have inherent worth but some have more than others). Using Taylor’s modified and extended theory as a foundation, I develop something I call universal ethics. This is an ethical framework whose key elements are a fundamental ethical attitude of respect for the world and a principle of minimal harm. Universal ethics regards all concrete material entities, whether living or not, and whether natural or artefactual, as inherently valuable, and therefore as entitled to the respect of moral agents. I offer a defence of this ethical framework and discuss a number of practical applications, including criticism of proposals for the terraforming of Mars. I conclude that terraforming Mars or any other celestial body at this point in our history would be morally wrong. I also suggest that universal ethics provides an ethical foundation for efforts to protect Antarctica, and that it has implications for our relations to other inanimate parts of our world, including artefacts.