Simulating the effects of vegetation and landscape structure on fire behavior in northeastern Portugal: the case of holm oak (Quercus rotundifolia)

O fogo é um processo frequente nas paisagens do norte de Portugal. Estudos anteriores mostraram que os bosques de azinheira (Quercus rotundifolia) persistem após a passagem do fogo e ajudam a diminuir a sua intensidade e taxa de propagação. Os principais objetivos deste estudo foram compreender e modelar o efeito dos bosques de azinheira no comportamento do fogo ao nível da paisagem da bacia superior do rio Sabor, localizado no nordeste de Portugal. O impacto dos bosques de azinheira no comportamento do fogo foi testado em termos de área e configuração de acordo com cenários que simulam a possível distribuição destas unidades de vegetação na paisagem, considerando uma percentagem de ocupação da azinheira de 2.2% (Low), 18.1% (Moderate), 26.0% (High), e 39.8% (Rivers). Estes cenários tiveram como principal objetivo testar 1) o papel dos bosques de azinheira no comportamento do fogo e 2) de que forma a configuração das manchas de azinheira podem ajudar a diminuir a intensidade da linha de fogo e área ardida. Na modelação do comportamento do fogo foi usado o modelo FlamMap para simular a intensidade de linha do fogo e taxa de propagação do fogo com base em modelos de combustível associados a cada ocupação e uso do solo presente na área de estudo, e também com base em fatores topográficos (altitude, declive e orientação da encosta) e climáticos (humidade e velocidade do vento). Foram ainda usados dois modelos de combustível para a ocupação de azinheira (áreas interiores e de bordadura), desenvolvidos com base em dados reais obtidos na região. Usou-se o software FRAGSATS para a análise dos padrões espaciais das classes de intensidade de linha do fogo, usando-se as métricas Class Area (CA), Number of Patches (NP) e Large Patches Index (LPI). Os resultados obtidos indicaram que a intensidade da linha de fogo e a taxa de propagação do fogo variou entre cenários e entre modelos de combustível para o azinhal. A intensidade média da linha de fogo e a taxa média de propagação do fogo decresceu à medida que a percentagem de área de bosques de azinheira aumentou na paisagem. Também foi observado que as métricas CA, NP e LPI variaram entre cenários e modelos de combustível para o azinhal, decrescendo quando a percentagem de área de bosques de azinheira aumentou. Este estudo permitiu concluir que a variação da percentagem de ocupação e configuração espacial dos bosques de azinheira influenciam o comportamento do fogo, reduzindo, em termos médios, a intensidade da linha de fogo e a taxa de propagação, sugerindo que os bosques de azinhal podem ser usados como medidas silvícolas preventivas para diminuir o risco de incêndio nesta região.

Evaluation of the conductor-like screening model for real solvents for the prediction of the water activity coefficient at infinite dilution in ionic liquids

Ionic liquids (ILs) have attracted great attention, from both industry and academia, as alternative fluids for very different types of applications. The large number of cations and anions allow a wide range of physical and chemical characteristics to be designed. However, the exhaustive measurement of all these systems is impractical, thus requiring the use of a predictive model for their study. In this work, the predictive capability of the conductor-like screening model for real solvents (COSMO-RS), a model based on unimolecular quantum chemistry calculations, was evaluated for the prediction water activity coefficient at infinite dilution, gamma(infinity)(w), in several classes of ILs. A critical evaluation of the experimental and predicted data using COSMO-RS was carried out. The global average relative deviation was found to be 27.2%, indicating that the model presents a satisfactory prediction ability to estimate gamma(infinity)(w) in a broad range of ILs. The results also showed that the basicity of the ILs anions plays an important role in their interaction with water, and it considerably determines the enthalpic behavior of the binary mixtures composed by Its and water. Concerning the cation effect, it is possible to state that generally gamma(infinity)(w) increases with the cation size, but it is shown that the cation-anion interaction strength is also important and is strongly correlated to the anion ability to interact with water. The results here reported are relevant in the understanding of ILs-water interactions and the impact of the various structural features of its on the gamma(infinity)(w) as these allow the development of guidelines for the choice of the most suitable lLs with enhanced interaction with water.

Computational and experimental study of the behavior of cyano-based ionic liquids in aqueous solution

The solvation of cyano- (CN-) based ionic liquids (ILs) and their capacity to establish hydrogen bonds (H-bonds) with water was studied by means of experimental and computational approaches. Experimentally, water activity data were measured for aqueous solutions of ILs based on 1-butyl-3-methylimidazolium ([BMIM](+)) cation combined with one of the following anions: thiocyanate ([SCN](-)), dicyanamide ([DCA](-)), or tricyanomethanide ([TCM](-)), and of 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM][TCB]). From the latter data, water activity coefficients were estimated showing that [BMIM][SCN] and [BMIM][DCA], unlike [BMIM][TCM] and [EMIM][TCB], are able to establish favorable interactions with water. Computationally, the conductor like screening model for real solvents (COSMO-RS) was used to estimate the water activity coefficients which compare well with the experimental ones. From the COSMO-RS results, it is suggested that the polarity of each ion composing the ILs has a strong effect on the solvation phenomena. Furthermore, classical molecular dynamics (MD) simulations were performed for obtaining an atomic level picture of the local molecular neighborhood of the different species. From the experimental and computational data it is showed that increasing the number of CN groups in the ILs' anions does not enhance their ability to establish H-bonds with water but decreases their polarities, being [BMIM][DCA] and [BMIM][SCN] the ones presenting higher propensity to interact.