Using ecological niche modelling to infer past, present and future environmental suitability for Leiopelma hochstetteri, an endangered New Zealand native frog

Leiopelma hochstetteri is an endangered New Zealand frog now confined to isolated populations scattered across the North Island. A better understanding of its past, current and predicted future environmental suitability will contribute to its conservation which is in jeopardy due to human activities, feral predators, disease and climate change. Here we use ecological niche modelling with all known occurrence data (N = 1708) and six determinant environmental variables to elucidate current, pre-human and future environmental suitability of this species. Comparison among independent runs, subfossil records and a clamping method allow validation of models. Many areas identified as currently suitable do not host any known populations. This apparent discrepancy could be explained by several non exclusive hypotheses: the areas have not been adequately surveyed and undiscovered populations still remain, the model is over simplistic; the species` sensitivity to fragmentation and small population size; biotic interactions; historical events. An additional outcome is that apparently suitable, but frog-less areas could be targeted for future translocations. Surprisingly, pre-human conditions do not differ markedly highlighting the possibility that the range of the species was broadly fragmented before human arrival. Nevertheless, some populations, particularly on the west of the North Island may have disappeared as a result of human mediated habitat modification. Future conditions are marked with higher temperatures, which are predicted to be favourable to the species. However, such virtual gain in suitable range will probably not benefit the species given the highly fragmented nature of existing habitat and the low dispersal ability of this species. (C) 2010 Elsevier Ltd. All rights reserved.

Predicting new molecular species of potential interest to atmospheric chemistry: The isomers HSI and HIS

Structural, vibrational, and energetic properties of new molecular species, HSI and HIS are investigated for the first time using a state-of-the-art theoretical approach. These molecules can be easily differentiated by their geometric parameters and vibrational spectra. HSI is much more stable, and a direct unimolecular isomerization is very unlikely. Kinetics estimates predict that only at low temperatures there is a possibility of isolating HIS. For HS-I, we estimate a bond dissociation energy of 46.25 kcal/mol, and a heat of formation at 298.15 K of 12.84 kcal/mol. For the H(2)S + I(2) -> HSI + HI reaction enthalpy, we found 8.40 kcal/ mol. (C) 2008 Elsevier B.V. All rights reserved.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.