At surface behaviour of juvenile and female southern elephant seals from King George Island from expeditions JUB1996 and JUB1997

Between December 1996 and February 1997, weaned pups and postmoult female southern elephant seals (Mirounga leonina) were fitted with satellite transmitters at King George Island (South Shetlands). Of the nine adult females tracked for more than two months, three stayed in a localized area between the South Shetlands and the South Orkneys. The other six females travelled southwest along the coast of the Antarctic Peninsula up to the Bellingshausen Sea. Two of them then moved far northeast and hauled out on South Georgia in October. One female was last located north of the South Shetlands in March 1998. In total, eight females were again sighted on King George Island and six of the transmitters removed. The tracks of the weaners contrasted with those of the adults. In January, five juveniles left King George Island for the Pacific sector ranging about four weeks in the open sea west of the De Gerlache Seamounts. Three of them returned to the tip of the Antarctic Peninsula in June, of which one was last located on the Patagonian Shelf in November 1997. A computer animation was developed to visualize the animal movements in relation to the extent and concentration of sea ice. The juveniles avoided sea ice while the adults did not. The latter displayed behavioural differences in using the pack ice habitat during winter. Some females adjusted their movement patterns to the pulsating sea ice fringe in far-distant foraging areas while others ranged in closed pack ice of up to 100 %. The feeding grounds of adult female elephant seals are more closely associated with the pack ice zone than previously assumed.

Search for associations containing young stars (SACY). VII. New stellar and substellar candidate members in the young associations

Context. The young associations offer us one of the best opportunities to study the properties of young stellar and substellar objects and to directly image planets thanks to their proximity (<200 pc) and age (≈5−150 Myr). However, many previous works have been limited to identifying the brighter, more active members (≈1 M_⊙) owing to photometric survey sensitivities limiting the detections of lower mass objects. Aims. We search the field of view of 542 previously identified members of the young associations to identify wide or extremely wide (1000−100 000 au in physical separation) companions. Methods. We combined 2MASS near-infrared photometry (J, H, K) with proper motion values (from UCAC4, PPMXL, NOMAD) to identify companions in the field of view of known members. We collated further photometry and spectroscopy from the literature and conducted our own high-resolution spectroscopic observations for a subsample of candidate members. This complementary information allowed us to assess the efficiency of our method. Results. We identified 84 targets (45: 0.2−1.3 M_⊙, 17: 0.08−0.2 M_⊙, 22: <0.08 M_⊙) in our analysis, ten of which have been identified from spectroscopic analysis in previous young association works. For 33 of these 84, we were able to further assess their membership using a variety of properties (X-ray emission, UV excess, Hα, lithium and K I equivalent widths, radial velocities, and CaH indices). We derive a success rate of 76–88% for this technique based on the consistency of these properties. Conclusions. Once confirmed, the targets identified in this work would significantly improve our knowledge of the lower mass end of the young associations. Additionally, these targets would make an ideal new sample for the identification and study of planets around nearby young stars. Given the predicted substellar mass of the majority of these new candidate members and their proximity, high-contrast imaging techniques would facilitate the search for new low-mass planets.

Estrutura produtiva da agropecuária, ocupação e pobreza no estado de Minas Gerais no ano de 2010

This thesis aimed to contribute to the discussion about the relationship between agricultural production structure, occupation and poverty in Brazil, specifically in the state of Minas Gerais, in 2010. The issue of employment is becoming increasingly challenging in the face of ongoing modernization process in agriculture, capital intensive and labor saver looking levels ever higher production and productivity. The productive inclusion can be an effective way to exit from poverty (the work is often the only asset of the poor). In this sense, we sought to investigate what activities or groups of activities occupied a larger number of people and generated higher yields and can potentially have contributed to a lower incidence of poverty. The basis for primary data was the 2010 Population Census (microdata). To achieve the objectives we used descriptive analysis, Pearson correlation coefficients and quantile regressions. Among the main findings highlight that agriculture occupied more and generated higher overall income than ranching presented more precarious, despite having lower average incomes and income percentile values, greater heterogeneity and instability, as well as higher proportions of poor. Overall, commodities showed greater formalization and lower poor proportions. In the case of agriculture, commodities activities occupied less, generated lower mass income and middle-income (although income percentiles slightly larger and more informality) and had lower poverty indicators than non-commodity (more heterogeneous rents). In livestock, commodities had higher percentages of occupation, income (although middle-income values and percentiles slightly smaller), and smaller proportions of poor than non-commodity (more heterogenous). In terms of occupation and income stood out the farming activities unspecified (non-commodity), the coffee growing and cattle (commodities). The cultivation of coffee and cattle had the lowest poverty indicators. agricultural production diversification indicators showed positive correlations with the occupation in activities not commodities (only), but also with the proportion of poor, indigent and concentration of income. In addition, the occupation in not commodities showed positive correlations with poverty indicators. It is noteworthy that the occupations in soybeans, coffee and fruit showed negative correlation coefficients with the indicators of poverty, indigence and gini. Finally, among the agricultural activities, there was to go to occupied in agricultural activities not commodities for commodity would be 'more equalizer' (decreasing coefficients over the distribution of income) than for cattle. The occupation in livestock (mostly non-commodity) would generate greater impact on the lower income deciles, but their coefficients grow back in the last deciles, which shows its most perverse character. Among the activities that would affect more strongly the lower deciles and less the higher deciles stand out pig farming, poultry, citrus cultivation, coffee and sugar cane. The cattle and the cultivation of soy, had the highest rates, but they grow back in the last deciles, which shows a more wicked character.

Bridging the Scale Gap from Leaf to Canopy in Biosphere-Atmosphere Gas and Particle Exchanges

Terrestrial ecosystems, occupying more than 25% of the Earth's surface, can serve as

`biological valves' in regulating the anthropogenic emissions of atmospheric aerosol

particles and greenhouse gases (GHGs) as responses to their surrounding environments.

While the signicance of quantifying the exchange rates of GHGs and atmospheric

aerosol particles between the terrestrial biosphere and the atmosphere is

hardly questioned in many scientic elds, the progress in improving model predictability,

data interpretation or the combination of the two remains impeded by

the lack of precise framework elucidating their dynamic transport processes over a

wide range of spatiotemporal scales. The diculty in developing prognostic modeling

tools to quantify the source or sink strength of these atmospheric substances

can be further magnied by the fact that the climate system is also sensitive to the

feedback from terrestrial ecosystems forming the so-called `feedback cycle'. Hence,

the emergent need is to reduce uncertainties when assessing this complex and dynamic

feedback cycle that is necessary to support the decisions of mitigation and

adaptation policies associated with human activities (e.g., anthropogenic emission

controls and land use managements) under current and future climate regimes.

With the goal to improve the predictions for the biosphere-atmosphere exchange

of biologically active gases and atmospheric aerosol particles, the main focus of this

dissertation is on revising and up-scaling the biotic and abiotic transport processes

from leaf to canopy scales. The validity of previous modeling studies in determining

iv

the exchange rate of gases and particles is evaluated with detailed descriptions of their

limitations. Mechanistic-based modeling approaches along with empirical studies

across dierent scales are employed to rene the mathematical descriptions of surface

conductance responsible for gas and particle exchanges as commonly adopted by all

operational models. Specically, how variation in horizontal leaf area density within

the vegetated medium, leaf size and leaf microroughness impact the aerodynamic attributes

and thereby the ultrane particle collection eciency at the leaf/branch scale

is explored using wind tunnel experiments with interpretations by a porous media

model and a scaling analysis. A multi-layered and size-resolved second-order closure

model combined with particle

uxes and concentration measurements within and

above a forest is used to explore the particle transport processes within the canopy

sub-layer and the partitioning of particle deposition onto canopy medium and forest

oor. For gases, a modeling framework accounting for the leaf-level boundary layer

eects on the stomatal pathway for gas exchange is proposed and combined with sap

ux measurements in a wind tunnel to assess how leaf-level transpiration varies with

increasing wind speed. How exogenous environmental conditions and endogenous

soil-root-stem-leaf hydraulic and eco-physiological properties impact the above- and

below-ground water dynamics in the soil-plant system and shape plant responses

to droughts is assessed by a porous media model that accommodates the transient

water

ow within the plant vascular system and is coupled with the aforementioned

leaf-level gas exchange model and soil-root interaction model. It should be noted

that tackling all aspects of potential issues causing uncertainties in forecasting the

feedback cycle between terrestrial ecosystem and the climate is unrealistic in a single

dissertation but further research questions and opportunities based on the foundation

derived from this dissertation are also brie

y discussed.

The role of inflammatory mediators in the overactive and bladder pain syndromes

The Overactive Bladder (OAB) and Bladder Pain Syndrome (BPS) are debilitating disorders for which the pathophysiological mechanisms are poorly understood. Injury or dysfunction of the protective urothelial barrier layer, specifically the proteoglycan composition and number, has been proposed as the primary pathological characteristic of BPS. For OAB, the myogenic theory with dysfunction of the muscarinic receptors is the most reiterated hypothesis. For both over activity of the inflammatory response has been posited to play a major role in these diseases. We hypothesise that BPS and OAB are peripheral sensory disorders, with an increase in inflammatory mediators, such as cytokines and chemokines, which are capable of activating, either directly or indirectly, sensory nerve activity causing the disease. The aim of the PhD is to identify potential new therapeutic targets for the treatment of BPS and OAB. We used medium throughput quantitative gene expression analysis of 96 inflammation associated mediators to measure gene expression levels in BPS and OAB bladder biopsies and compared them to control samples. Then we created a novel animal model of disease by specific proteoglycan deglycosylation of the bladder mucosal barrier, using the bacterial enzymes Chondroitinase ABC and Heparanase III. These enzymes specifically remove the glycosaminoglycan side chains from the urothelial proteoglycan molecules. We tested role of the identified mediators in this animal model. In addition, in order to determine on which patients peripheral treatment strategies may work, we assessed the effect of local anaesthetics on patients with bladder pain. Gene expression analysis did not reveal a difference in inflammatory genes in the OAB versus control biopsies. However, several genes were upregulated in BPS versus control samples, from which two genes, FGF7 and CLL21 were correlated with patient clinical phenotypes for ICS/PI symptom and problem indices respectively. In order to determine which patients are likely to respond to treatment, we sought to characterise the bladder pain in BPS patients. Using urodynamics and local anaesthetics, we differentiated patients with peripherally mediated pain and patients with central sensitisation of their pain. Finally to determine the role of these mediators in bladder pain, we created an animal model of disease, which specifically replicates the human pathology: namely disruption in the barrier proteoglycan molecules. CCL21 led to an increase in painrelated behaviour, while FGF7 attenuated this behaviour, as measured by cystometry, spinal c-fos expression and mechanical withdrawal threshold examination. In conclusion, we have identified CCL21 and FGF7 as potential targets for the treatment of BPS. Manipulation of these ligands or their receptors may prove to be valuable previously unexploited targets for the treatment of BPS.

Development of nanostructured hydrogel for spatial and temporal controlled release of active compounds

L’utilisation de nanovecteurs pour la livraison contrôlée de principes actifs est un concept commun de nous jours. Les systèmes de livraison actuels présentent encore cependant des limites au niveau du taux de relargage des principes actifs ainsi que de la stabilité des transporteurs. Les systèmes composés à la fois de nanovecteurs (liposomes, microgels et nanogels) et d’hydrogels peuvent cependant permettre de résoudre ces problèmes. Dans cette étude, nous avons développé un système de livraison contrôlé se basant sur l’incorporation d’un nanovecteur dans une matrice hydrogel dans le but de combler les lacunes des systèmes se basant sur un vecteur uniquement. Une telle combinaison pourrait permettre un contrôle accru du relargage par stabilisation réciproque. Plus spécifiquement, nous avons développé un hydrogel structuré intégrant des liposomes, microgels et nanogels séparément chargés en principes actifs modèles potentiellement relargués de manière contrôlé. Ce contrôle a été obtenu par la modification de différents paramètres tels que la température ainsi que la composition et la concentration en nanovecteurs. Nous avons comparé la capacité de chargement et la cinétique de relargage de la sulforhodamine B et de la rhodamine 6G en utilisant des liposomes de DOPC et DPPC à différents ratios, des nanogels de chitosan/acide hyaluronique et des microgels de N-isopropylacrylamide (NIPAM) à différents ratios d’acide méthacrylique, incorporés dans un hydrogel modèle d’acrylamide. Les liposomes présentaient des capacités de chargement modérés avec un relargage prolongé sur plus de dix jours alors que les nanogels présentaient des capacités de chargement plus élevées mais une cinétique de relargage plus rapide avec un épuisement de la cargaison en deux jours. Comparativement, les microgels relarguaient complétement leur contenu en un jour. Malgré une cinétique de relargage plus rapide, les microgels ont démontré la possibilité de contrôler finement le chargement en principe actif. Ce contrôle peut être atteint par la modification des propriétés structurelles ou en changeant le milieu d’incubation, comme l’a montré la corrélation avec les isothermes de Langmuir. Chaque système développé a démontré un potentiel contrôle du taux de relargage, ce qui en fait des candidats pour des investigations futures.

Terrigenous input and marine productivity for the Pacific sector of the Southern Ocean based on lipid biomarkers

In this study, we present a new multiproxy data set of terrigenous input, marine productivity and sea surface temperature (SST) from 52 surface sediment samples collected along E-W transects in the Pacific sector of the Southern Ocean. Allochtonous terrigenous input was characterized by the distribution of plant wax n-alkanes and soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs). 230Th-normalized burial rates of both compound groups were highest close to the potential sources in Australia and New Zealand and are strongly related to lithogenic contents, indicating common sources and transport. Detection of both long-chain n-alkanes and brGDGTs at the most remote sites in the open ocean strongly suggests a primarily eolian transport mechanism to at least 110°W, i.e. by prevailing westerly winds. Two independent organic SST proxies were used, the UK'37 based on long-chain alkenones, and the TEX86 based on isoprenoid GDGTs. Both, UK'37 and TEX86 indices show robust relationships with temperature over a temperature range between 0.5 and 20°C, likely implying different seasonal and regional imprints on the temperature signal. While alkenone-based temperature estimates reliably reflect modern SST even at the low temperature end, large temperature residuals are observed for the polar ocean using the TEX86 index. 230Th-normalized burial rates of alkenones are highest close to the Subtropical Front and are positively related to lithogenic fluxes throughout the study area. In contrast, highest isoGDGT burial south of the Antarctic Polar Front is not related with dust flux but may be largely controlled by diatom blooms, and thus high opal fluxes during austral summer.

Ground penetrating radar (GPR) and electrical resistivity tomography (ERT) survey on the neotectonic activity of the Padul-Nigüelas Fault Zone (PNFZ), Southern Spain

The Padul-Nigüelas Fault Zone (PNFZ) is situated at the south-western mountain front of the Sierra Nevada (Spain) in an extensive regime and belongs to the internal zone of the Betic Cordilleras. The aim of this study is a collection of new evidence for neotectonic activity of the fault zone with classical geological field work and modern geophysical methods, such as ground penetrating radar (GPR). Among an apparently existing bed rock fault scarp with triangular facets, other evidences, such as deeply incised valleys and faults in the colluvial wedges, are present in the PNFZ. The preliminary results of our recent field work have shown that the synsedimentary faults within the colluvial sediments seem to propagate basinwards and the bed rock fault is only exhumed due to erosion for the studied segment (west of Marchena). We will use further GPR data and geomorphologic indices to gather further evidences of neotectonic activity of the PNFZ.

(Table 1) Salinity, dissolved organic carbon and absorption characteristics of surface river waters around Hudson Bay

Composition and concentration of colored dissolved organic matter (CDOM) have been determined in Hudson Bay and Hudson Strait by excitation emission matrix spectroscopy (EEM) and parallel factor analysis (PARAFAC). Based on 63 surface samples, PARAFAC identified three fluorescent components, which were attributed to two humic- and one protein-like components. One humic-like component was identified as representing terrestrial organic matter and showed a conservative behaviour in Hudson Bay estuaries. The second humic-like component, traditionally identified as peak M, originated both from land and produced in the marine environment. Component 3 had spectra resembling protein-like material and thought to be plankton-derived. The distribution and composition of CDOM were largely controlled by water mass mixing with protein-like component being the least affected. Distinctive fluorescence patterns were also found between Hudson Bay and Hudson Strait, suggesting different sources of CDOM. The optically active fraction of DOC (both absorbing and fluorescing) was very high in the Hudson Bay (up to 89%) suggesting that fluorescence and absorbance can be used as proxies of the DOC concentration.

A comparative study: long and short term effect of a nutrition sensitive approach to delay the progression of HIV to AIDS among people living with HIV (PLWH) in Nigeria

Background: Malnutrition has a negative impact on optimal immune function, thus increasing susceptibility to morbidity and mortality among HIV positive patients. Evidence indicates that the prevalence of macro and micronutrient deficiencies (particularly magnesium, selenium, zinc, and vitamin C) has a negative impact on optimal immune function, through the progressive depletion of CD4 T-lymphocyte cells, which thereby increases susceptibility to morbidity and mortality among PLWH. Objective: To assess the short and long term effects of a nutrition sensitive intervention to delay the progression of human immune-deficiency virus (HIV) to AIDS among people living with HIV in Abuja, Nigeria. Methods: A randomized control trial was carried out on 400 PLWH (adult, male and female of different religious background) in Nigeria between January and December 2012. Out of these 400 participants, 100 were randomly selected for the pilot study, which took place over six months (January to June, 2012). The participants in the pilot study overlapped to form part of the scale-up participants (n 400) monitored from June to December 2012. The comparative effect of daily 354.92 kcal/d optimized meals consumed for six and twelve months was ascertained through the nutritional status and biochemical indices of the study participants (n=100 pilot interventions), who were and were not taking the intervention meal. The meal consisted of: Glycine max 50g (Soya bean); Pennisetum americanum 20g (Millet); Moringa oleifera 15g (Moringa); Daucus carota spp. sativa 15g (Carrot). Results: At the end of sixth month intervention, mean CD4 cell count (cell/mm3) for Pre-ART and ART Test groups increased by 6.31% and 12.12% respectively. Mean mid upper arm circumference (MUAC) for Pre-ART and ART Test groups increased by 2.72% and 2.52% within the same period (n 400). Comparatively, participants who overlapped from pilot to scale-up intervention (long term use, n 100) were assessed for 12 months. Mean CD4 cell count (cell/mm3) for Pre-ART and ART test groups increased by 2.21% and 12.14%. Mean MUAC for Pre-ART and ART test groups increased by 2.08% and 3.95% respectively. Moreover, student’s t-test analysis suggests a strong association between the intervention meal, MUAC, and CD4 count on long term use of optimized meal in the group of participants being treated with antiretroviral therapy (ART) (P<0.05). Conclusion: Although the achieved results take the form of specific technology, it suggests that a prolong consumption of the intervention meal will be suitable to sustain the gained improvements in the anthropometric and biochemical indices of PLWHIV in Nigeria.

The Responsiveness, Content Validity, and Convergent Validity of the Measure Yourself Concerns and Wellbeing (MYCaW) Patient-Reported Outcome Measure

Objective Measure Yourself Concerns and Wellbeing (MYCaW) is a patient-centred questionnaire that allows cancer patients to identify and quantify the severity of their ‘Concerns’ and Wellbeing, as opposed to using a pre-determined list. MYCaW administration is brief and aids in prioritising treatment approaches. Our goal was to assess the convergent validity and responsiveness of MYCaW scores over time, the generalisability of the existing qualitative coding framework in different complementary and integrative healthcare settings and content validity. Methods Baseline and 6-week follow-up data (n=82) from MYCaW and FACIT-SpEx questionnaires were collected for a service evaluation of the ‘Living Well With The Impact of Cancer’ course at Penny Brohn Cancer Care. MYCaW construct validity was determined using Spearman's Rank Correlation test, and responsiveness indices assessed score changes over time. The existing qualitative coding framework was reviewed using a new dataset (n=158) and coverage of concern categories compared to items of existing outcome measures. Results Good correlation between MYCaW and FACIT-SpEx score changes were achieved (r= -0.57, p≥0.01). MYCaW Profile and Concern scores were highly responsive to change: SRM=1.02 and 1.08; effect size=1.26 and 1.22. MYCaW change scores showed the anticipated gradient of change according to clinically relevant degrees of change. Categories including ‘Spirituality’, ‘weight change’ and ‘practical concerns’ were added to the coding framework to improve generalisability. Conclusions MYCaW scores were highly responsive to change, allowing personalized patient outcomes to be quantified; the qualitative coding framework is generalisable across different oncology settings and has broader coverage of patient-identified concerns compared with existing cancer-related patient-reported outcome measures.

Is the Russell Cycle a true cycle? Multidecadal zooplankton and climate trends in the western English Channel

The Russell Cycle is one of the classical examples of climate influence on biological oceanography, represented as shifts in the marine plankton over several decades with warm and cool conditions. While the time-series data associated with the phenomenon indicate cyclical patterns, the question remains whether or not the Russell Cycle should be considered a “true cycle”. Zooplankton time-series data from 1924 to 2011 from the western English Channel were analysed with principal component (PC), correlation and spectral analyses to determine the dominant trends, and cyclic frequencies of the Russell Cycle indicators in relation to long-term hydroclimatic indices. PC1 accounted for 37.4% of the variability in the zooplankton data with the main contributions from non-clupeid fish larvae, southwestern zooplankton, and overall zooplankton biovolume. For PC2 (14.6% of data variance), the dominant groups were northern fish larvae, non-sardine eggs, and southern fish larvae. Sardine eggs were the major contributors to PC3 (representing 12.1% of data variance). No significant correlations were observed between the above three components and climate indices: Atlantic Multidecadal Oscillation, North Atlantic Oscillation, and local seawater temperature. Significant 44- and 29-year frequencies were observed for PC3, but the physical mechanisms driving the cycles are unclear. Harmonic analysis did not reveal any significant frequencies in the physical variables or in PCs 1 and 2. To a large extent, this is due to the dominant cycles in all datasets generally being long term (>50 years or so) and not readily resolved in the examined time frame of 88 years, hence restricting the ability to draw firm conclusions on the multidecadal relationship between zooplankton community dynamics in the western English Channel and environmental indices. Thus, the zooplankton time-series often associated and represented as the Russell Cycle cannot be concluded as being truly cyclical.

Is the Russell Cycle a true cycle? Multidecadal zooplankton and climate trends in the western English Channel

The Russell Cycle is one of the classical examples of climate influence on biological oceanography, represented as shifts in the marine plankton over several decades with warm and cool conditions. While the time-series data associated with the phenomenon indicate cyclical patterns, the question remains whether or not the Russell Cycle should be considered a “true cycle”. Zooplankton time-series data from 1924 to 2011 from the western English Channel were analysed with principal component (PC), correlation and spectral analyses to determine the dominant trends, and cyclic frequencies of the Russell Cycle indicators in relation to long-term hydroclimatic indices. PC1 accounted for 37.4% of the variability in the zooplankton data with the main contributions from non-clupeid fish larvae, southwestern zooplankton, and overall zooplankton biovolume. For PC2 (14.6% of data variance), the dominant groups were northern fish larvae, non-sardine eggs, and southern fish larvae. Sardine eggs were the major contributors to PC3 (representing 12.1% of data variance). No significant correlations were observed between the above three components and climate indices: Atlantic Multidecadal Oscillation, North Atlantic Oscillation, and local seawater temperature. Significant 44- and 29-year frequencies were observed for PC3, but the physical mechanisms driving the cycles are unclear. Harmonic analysis did not reveal any significant frequencies in the physical variables or in PCs 1 and 2. To a large extent, this is due to the dominant cycles in all datasets generally being long term (>50 years or so) and not readily resolved in the examined time frame of 88 years, hence restricting the ability to draw firm conclusions on the multidecadal relationship between zooplankton community dynamics in the western English Channel and environmental indices. Thus, the zooplankton time-series often associated and represented as the Russell Cycle cannot be concluded as being truly cyclical.

Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.