Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

High-pressure granulites: formation, recovery of peak conditions and implications for tectonics

High‐pressure granulites are characterised by the key associations garnet‐clinopyroxene‐plagioclase‐quartz (in basic rocks) and kyanite‐K‐feldspar (metapelites and felsic rocks) and are typically orthopyroxene‐free in both basic and felsic bulk compositions. In regional metamorphic areas, two essential varieties exist: a high‐ to ultrahigh‐temperature group and a group representing overprinted eclogites. The high‐ to ultrahigh‐temperature type formerly contained high‐temperature ternary feldspar (now mesoperthite) coexisting with kyanite, is associated with garnet peridotites, and formed at conditions above 900 °C and 1.5 GPa. Clinopyroxene in subordinate basic rocks is Al‐rich and textural evidence points to a high‐pressure–high‐temperature melting history. The second variety contains symplectite‐like or poikilitic clinopyroxene‐plagioclase intergrowths indicating former plagioclase‐free, i.e. eclogite facies assemblages. This type of rock formed at conditions straddling the high‐pressure amphibolite/high‐pressure granulite field at around 700–850 °C, 1.0–1.4 GPa. Importantly, in the majority of high‐pressure granulites, orthopyroxene is secondary and is a product of reactions at pressures lower than the peak recorded pressure. In contrast to low‐ and medium‐pressure granulites, which form at conditions attainable in the mid to lower levels of normal continental crust, high‐pressure granulites (of nonxenolith origin) mostly represent rocks formed as a result of short‐lived tectonic events that led to crustal thickening or subduction of the crust into the mantle. Short times at high‐temperature conditions are reflected in the preservation of prograde zoning in garnet and pyroxene. High‐pressure granulites of both regional types, although rare, are known from both old and young metamorphic terranes (e.g. c. 45 Ma, Namche Barwa, E Himalaya; 400–340 Ma, European Variscides; 1.8 Ga Hengshan, China; 1.9 Ga, Snowbird, Saskatchewan and 2.5 Ga Jianping, China). This spread of ages supports proposals suggesting that thermal and tectonic processes in the lithosphere have not changed significantly since at least the end of the Archean.     

Layer parallel shortening in salt-detached folds: constraint on cross-section restoration

Cleavage-fissility perpendicular to bedding is a common feature in the external part of fold-and-thrust belts. Three techniques were used to determine the internal distortion in the frontal Southern Pyrenees: the analysis of strain markers such as burrows and rain drops, the measurement of fissility, and the measurement of anisotropy of magnetic susceptibility (AMS). The comparison of the three techniques showed a good fit although they differ in sensitivity to penetrative strain variations in the range of deformation values explored in the study case. On the regional scale, the values of layer parallel shortening (LPS) derived from the markers analysis are very constant and account for 16–23% of shortening. These values are two to three times larger than the shortening values calculated from the restoration of the macroscopic scale structures and indicate a good decoupling above the Cardona salt Formation. This study permitted an accurate restoration of the low-amplitude el Guix detached anticline.     

Neoproterozoic accretionary and collisional events on the western margin of the Siberian craton: new geological and geochronological evidence from the Yenisey Ridge

The geological, structural and tectonic evolutions of the Yenisey Ridge fold-and-thrust belt are discussed in the context of the western margin of the Siberian craton during the Neoproterozoic. Previous work in the Yenisey Ridge had led to the interpretation that the fold belt is composed of high-grade metamorphic and igneous rocks comprising an Archean and Paleoproterozoic basement with an unconformably overlying Mesoproterozoic–Neoproterozoic cover, which was mainly metamorphosed under greenschist-facies conditions. Based on the existing data and new geological and zircon U–Pb data, we recognize several terranes of different age and composition that were assembled during Neoproterozoic collisional–accretional processes on the western margin of the Siberian craton. We suggest that there were three main Neoproterozoic tectonic events involved in the formation of the Yenisey Ridge fold-and-thrust belt at 880–860 Ma, 760–720 Ma and 700–630 Ma. On the basis of new geochronological and petrological data, we propose that the Yeruda and Teya granites (880–860 Ma) were formed as a result of the first event, which could have occurred in the Central Angara terrane before it collided with Siberia. We also propose that the Cherimba, Ayakhta, Garevka and Glushikha granites (760–720 Ma) were formed as a result of this collision. The third event (700–630 Ma) is fixed by the age of island-arc and ophiolite complexes and their obduction onto the Siberian craton margin. We conclude by discussing correlation of these complexes with those in other belts on the margin of the Siberian craton.     

Identification of ore extraction and metal working in ancient times: a case study of Sagalassos (SW Turkey)

The extensive territory of the ancient (Hellenistic to Byzantine) city of Sagalassos (SW Turkey) offered a rich variety in natural mineral resources. The frequent occurrence of iron slag in the excavations at the site proved the local working of metal. A geochemical prospection campaign was done in the territory of the ancient city in order to identify or discard the city and its territory as a self-sustaining metallurgical centre. Secondly, the geochemical impact of ancient metallurgy was investigated. Geochemical anomalies identified in stream sediments are explained by the presence of mineralised deposits and ancient metal working. Mg, Cr, Co and Ni anomalies point to chromite and chrysotile-magnetite deposits related to the basic rocks of the Lycian nappes in the area. Fe, V and Ti anomalies indicate the presence of iron mineralisations, which have been worked for iron production in ancient times. Finally, the association of P, Cu, Pb, Mn, As and Ag anomalies are an indicator of human activity at archaeological sites. Within the framework of this geochemical prospection, a metal working site apart from the city of Sagalassos was identified. Here, ore was both extracted and processed to workable iron.     

Predators of juvenile blue crabs outside of refuge habitats in lower Chesapeake Bay

Blue crabsCallinectes sapidus in lower Chesapeake Bay are subject to high rates of predation during the late summer of their first year of growth as they migrate out of vegetated nursery habitats. Predators, potentially contributing to this pattern, were identified in video-recorded field observations of tethered juvenile crabs (20–25 mm carapace width). Predators were also tested in large laboratory tanks containing similarly-sized untethered crabs as prey. Seven different predators attacked tethered crabs in the field. Only two predators, larger blue crabs and northern puffers,Sphoeroides maculatus, consistently succeeded in preying on crabs in both field and laboratory settings. These results confirm the importance of cannibalism on juvenile blue crabs and identify puffers as a potentially overlooked source of predation pressure.     

A method for precise measurement of argon 40/36 and krypton/argon ratios in trapped air in polar ice with applications to past firn thickness and abrupt climate change in Greenland and at Siple Dome, Antarctica

We describe a method for measuring the ⁴⁰Ar/³⁶Ar ratio and the ⁸⁴Kr/³⁶Ar ratio in air from bubbles trapped in ice cores. These ratios can provide constraints on the past thickness of the firn layer at the ice core site and on the magnitude of past rapid temperature variations when combined with measured ¹⁵N/¹⁴N. Both variables contribute to paleoclimatic studies and ultimately to the understanding of the controls on Earth’s climate. The overall precision of the ⁴⁰Ar/³⁶Ar method (1 standard error of the mean) is 0.012‰ for a sample analyzed in duplicate, corresponding to ±0.6 m in reconstructed firn thickness. We use conventional dynamic isotope ratio mass spectrometry with minor modifications and special gas handling techniques designed to avoid fractionation. About 100 g of ice is used for a duplicate pair of analyses. An example of the technique applied to the GISP2 ice core yields an estimate of 11 ± 3K of abrupt warming at the end of the last glacial period 15,000 years ago. The krypton/argon ratio can provide a diagnostic of argon leakage out of the bubbles, which may happen (naturally) during bubble close-off or (artifactually) if samples are warmed near the freezing point during core retrieval or storage. Argon leakage may fractionate the remaining ⁴⁰Ar/³⁶Ar ratio by +0.007‰ per ‰ change in ⁸⁴Kr/³⁶Ar, introducing a possible bias in reconstructed firn thickness of about +2 m if thermal diffusion is not accounted for or +6 m if thermal diffusion effects are quantified with measured ¹⁵N/¹⁴N. Reproducibility of ⁸⁴Kr/³⁶Ar measured in air is about ±0.2‰ (1 standard error of the mean) but is about ±1‰ for ice core samples. Ice core samples are systematically enriched in ⁸⁴Kr/³⁶Ar relative to atmosphere by ∼5‰, probably reflecting preferential size-dependent exclusion of the smaller argon atom during bubble entrapment. Recent results from the Siple Dome ice core reveal two climate events during the last deglaciation, including an 18-m reduction in firn thickness associated with an abrupt warming at sometime between 18 and 22 kyr BP and a partial or total removal of the firn during an ablation event at 15.3 kyr BP.     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal

 A Raman scattering and X-ray diffraction study of the thermal decomposition of a naturally occurring, ettringite-group crystal is presented. Raman spectra, recorded with increasing temperature, indicate that the thermal decomposition begins at ≈55 °C, accompanied by dehydration of water molecules from the mineral. This is in contrast to previous studies that reported higher temperature breakdown of ettringite. The dehydration is completed by 175 °C and this results in total collapse of the crystalline structure and the material becomes amorphous. The Raman scattering results are supported by X-ray diffraction results obtained at increasing temperatures. Received: 9 July 2001 / Accepted: 14 August 2002