Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment

Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the í2Ssulfide, í3Ssulfide, and Sthiolate ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe3+ and Fe2.5+ components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm-1 vs -360 cm-1, respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter ì2/k-, leads to an S ) 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe3+ center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

Alteration and alterability of the anorthosite from Angola

Siliceous rocks are widely used as dimension stone but the last decades have registered an increase rate of their alteration when exposed to polluted environments. Anorthosites were treated by acidified solutions of HCl, HN03 and H2S04 simulating acid rain and the response was recorded through different experiments such as on the surface of the polished rock and on the surface of uncovered thin sections. The main components, plagioclase and olivine, both responded in similar ways to each acid solution, although following different trends; while plagioclase develops a thin layer which acts as protection to the mineral, olivine at first undergoes alteration due to leaching of magnesium and iron and in a following stage, is mechanically removed from the rock. The action of warm water on the rock was tested through the use of the Soxhlet extractor which caused changes on the rock colour and leaching of several cations from its components.

Archaeological Remains Accounting for the Presence and Exploitation of the North Atlantic Right Whale Eubalaena glacialis on the Portuguese Coast (Peniche, West Iberia), 16th to 17th Century

The former occurrence of the North Atlantic right whale Eubalaena glacialis on the Portuguese coast may be inferred from the historical range of that species in Europe and in NW Africa. It is generally accepted that it was the main prey of coastal whaling in the Middle Ages and in the pre-modern period, but this assumption still needs firming up based on biological and archaeological evidence. We describe the skeletal remains of right whales excavated at Peniche in 2001-2002, in association with archaeological artefacts. The whale bones were covered by sandy sediments on the old seashore and they have been tentatively dated around the 16th to 17th centuries. This study contributes material evidence to the former occurrence of E. glacialis in Portugal (West Iberia). Some whale bones show unequivocal man-made scars. These are associated to wounds from instruments with a sharp-cutting blade. This evidence for past human interaction may suggest that whaling for that species was active at Peniche around the early 17th century.