Ab initio quantum mechanical study of γ-AlOOH boehmite: structure and vibrational spectrum

The structure and vibrational spectrum of boehmite have been investigated at the quantum-mechanical level with the CRYSTAL code, using a Gaussian-type basis set and the B3LYP Hamiltonian. Three space groups are considered in this study: Cmcm, Cmc2₁, P2₁/c. Cmcm turns out to correspond to a transition state, whereas Cmc2₁ and P2₁/c are minimum energy structures. The difference among them is the position of H atoms only, the Al-O frame being essentially the same. Harmonic frequencies at the Γ point have been computed. The comparison between calculated and experimental frequencies shows a good agreement for the Al-O part of the spectrum (under 790 cm⁻¹). For the Al-OH bending modes (800–1,300 cm⁻¹) an absolute differences of 50–100 cm⁻¹ is observed; for the OH stretching modes (3,200–3,500 cm⁻¹) it increases to 120–200 cm⁻¹: anharmonicity is large because OH groups are involved in strong hydrogen bonds.     

An example of fingerprint detection of greenhouse climate change

As an example of the technique of fingerprint detection of greenhouse climate change, a multivariate signal or fingerprint of the enhanced greenhouse effect is defined using the zonal mean atmospheric temperature change as a function of height and latitude between equilibrium climate model simulations with control and doubled CO₂ concentrations. This signal is compared with observed atmospheric temperature variations over the period 1963 to 1988 from radiosonde-based global analyses. There is a significant increase of this greenhouse signal in the observational data over this period.These results must be treated with caution. Upper air data are available for a short period only, possibly too short to be able to resolve any real greenhouse climate change. The greenhouse fingerprint used in this study may not be unique to the enhanced greenhouse effect and may be due to other forcing mechanisms. However, it is shown that the patterns of atmospheric temperature change associated with uniform global increases of sea surface temperature, with El NinoSouthern Oscillation events and with decreases of stratospheric ozone concentrations individually are different from the greenhouse fingerprint used here.     

Integrated Futures for Europe’s Mountain Regions: Reconciling Biodiversity Conservation and Human Livelihoods

Introduction Europe's mountains cover nearly half of the continent's area (Price et al. 2004) and land cover varies significantly (European Commission 2004). In most massifs, except for Sicily, southern Greece, and the British Isles, forest cover is dominant. In northern Europe, grassland is proportionately more important, and much of the mountains of the British Isles is covered by moorland. In central and southern Europe, arable land is of far greater importance than grassland, with Med…     

Cambrian to Devonian Geologic Evolution of the Sierra de Comechingones, Eastern Sierras Pampeanas, Argentina: Evidence for the Development and Exhumation of Continental Crust on the Proto-Pacific Margin of Gondwana

Crystalline rocks from the Sierra de Comechingones, eastern Sierras Pampeanas, evolved through three distinct orogenic cycles during the Eopalaeozoic: (1) the first tectono-thermal event named Pampean orogeny (550 to 505 Ma), which peaked in the Early Cambrian, was responsible for extensive metamorphism, partial melting, juvenile magmatism, rapid decompression, and persistent tectonic activity. Large part of the crustal section that was residing at middle levels (c. 27 km) was heated above 800 °C during the thermal peak stage of the Pampean orogeny; decompression of the Pampean orogen's core took place at this high temperature. The exhumation mechanism that assisted rapid uplifting combined the effects of ongoing tectonic forces with a buoyant instability created by a large amount of anatectic magmas in the middle to lower crust. (2) Beginning at the Early Ordovician, the Famatinian orogeny produced an overall shortening, causing pervasive textural reworking of the Cambrian metamorphic sequences under a high-strain regime. By being adjacent to the Famatinian magmatic arc, the western border of the Cambrian crystalline package absorbed imposed deformation along a crustal scale ductile shear zone. Within this zone, the high-grade metamorphic rocks were reworked and re-hydrated to lower temperature assemblages (<600°C and 3–6 kbar). Early Ordovician subduction-related igneous activity, even though manifested as small plutons, intruded Cambrian crystalline sequences, and experienced textural reworking during Late Famatinian tectonic exhumation. Late Famatinian convergence resulted in west-vergent ductile shear zones that placed Cambrian onto Ordovician crystalline sequences. (3) During post-Famatinian times (360–400 Ma) enduring crustal perturbation produced intra-crustal-derived granitic magmatism. West- to northwest-directed thrusting was concentrated in belts nucleated along crustal-scale tectonic boundaries formed between older tectono-stratigraphic units. As a result, Devonian anatectic granites were formed and tectonically extruded among Pampean and Famatinian crystalline sequences. The post-Famatinian event is also characterised by the intrusion of batholith-scale monzogranites into Pampean and Famatinian crystalline sequences residing in the upper crust.

Crystalline rocks currently exposed in the Sierra de Comechingones show that they crystallised and were exhumed in a setting where tectono-thermal activity lasted, even though it might have waned, until the Middle Palaeozoic. From the latest Neoproterozoic (c. 550 Ma) until the Late Devonian (c. 360 Ma) tectonic activity was intermittently acting, indicating continuous convergence along the proto-Pacific margin of Gondwana.     

Amphibolite to granulite transition in aluminous greywackes from the Sierra de Comechingones, Córdoba, Argentina

We discuss upper-amphibolite to granulite facies, early Palaeozoic metamorphism and partial melting of aluminous greywackes from the Sierra de Comechingones, SE Sierras Pampeanas of Central Argentina. Consistent P–T estimates, obtained from equilibria involving Al and Ti exchange components in biotite and from more traditional thermobarometric equilibria, suggest that peak metamorphism of the exposed section took place at an essentially constant pressure of 7–8 kbar, and at temperatures ranging from 650 to 950 °C. Mineral compositions record an initial decompression, after peak metamorphism, of c. 1.5 kbar, which was accompanied by a cooling of c. 100 °C. Upper-amphibolite facies gneisses consist of the assemblage Qtz+Pl+Bt+Grt+Rt/Ilm. The transition to the granulite facies is marked by the simultaneous appearance of the assemblage Kfs+Sil and of migmatitic structures, suggesting that the amphibolite to granulite transition in the Sierra de Comechingones corresponds to the beginning of melting. Rocks with structural and/or chemical manifestations of partial melting range from metatexites, to diatexites, to melt-depleted granulites, consisting of the assemblage Grt+Crd+Pl+Qtz+Ilm±Ath. The melting stage overlapped at least partially with decompression, as suggested by the occurrence of cordierite, in both the migmatites and the residual granulites, of two distinct textural types: idiomorphic porphyroblasts (probably representing peritectic cordierite) and garnet-rimming coronas. Metapelitic rocks are unknown in the Sierra de Comechingones. Therefore, it appears most likely that the Al-rich residual assemblages found in the migmatites and residual granulites were formed by partial melting of muscovite- and sillimanite-undersaturated metagreywackes. We propose a mechanism for this that relies on the sub-solidus stabilization of garnet and the ensuing changes in the octahedral Al content of biotite with pressure and temperature.