The reaction MgCr2O4 + SiO2 = Cr2O3 + MgSiO3 and the free energy of formation of magnesiochromite (MgCr2O4)

Low-temperature heat capacity measurements for MgCr₂O₄ have only been performed down to 52 K, and the commonly quoted third-law entropy at 298 K (106 J K⁻¹ mol⁻¹) was obtained by empirical extrapolation of these measurements to 0 K without considering the magnetic or electronic ordering contributions to the entropy. Subsequent magnetic measurements at low temperature reveal that the Néel temperature, at which magnetic ordering of the Cr³⁺ ions in MgCr₂O₄ occurs, is at ∼15 K. Hence a substantial contribution to the entropy of MgCr₂O₄ has been missed. We have determined the position of the near-univariant reaction MgCr₂O₄+SiO₂=MgSiO₃+Cr₂O₃. The reaction, which has a small positive slope in P-T space, has been bracketed at 100 K intervals between 1273 and 1773 K by reversal experiments. The reaction is extremely sluggish, and lengthy run times with a flux (H₂O, BaO-B₂O₃ or K₂O-B₂O₃) are needed to produce tight reversal brackets. The results, combined with assessed thermodynamic data for Cr₂O₃, MgSiO₃ and SiO₂, give the entropy and enthalpy of formation of MgCr₂O₄ spinel. As expected, our experimental results are not in good agreement with the presently available thermodynamic data. We obtain Δ _f H ^∘ ₂₉₈=−1759.2±1.5 kJ mol⁻¹ and S ^∘ ₂₉₈=122.1±1.0 J K⁻¹ mol⁻¹ for MgCr₂O₄. This entropy is some 16 J K⁻¹ mol⁻¹ more than the calorimetrically determined value, and implies a value for the magnetic entropy of MgCr₂O₄ consistent with an effective spin quantum number (S') for Cr³⁺ of 1/2 rather than the theoretical 3/2, indicating, as in other spinels, spin quenching. Received: 9 May 1997 / Accepted: 28 July 1997     

Seismic image of the deep crust at the eastern margin of the Alps (Austria): indications for crustal extension in a convergent orogen

A 39-km-long deep seismic reflection profile recorded during two field campaigns in 1996 and 2002 provides a first detailed image of the deep crust at the eastern margin of the Eastern Alps (Austria). The ESE–WNW-trending, low-fold seismic line crosses Austroalpine basement units and extends approximately from 20 km west of the Penninic window group of Rechnitz to 60 km SSE of the Alpine thrust front.The explosive-source seismic data reveals a transparent shallow crust down to 5 km depth, a complexly reflective upper crust and a highly reflective lowermost crust. The upper crust is dominated by three prominent west-dipping packages of high-amplitude subparallel reflections. The upper two of these prominent packages commence at the eastern end of the profile at about 5 and 10 km depth and are interpreted as low-angle normal shear zones related to the Miocene exhumation of the Rechnitz metamorphic core complex. In the western portion of the upper crust, east-dipping and less significant reflections prevail. The lowermost package of these reflections is suggested to represent the overall top of the European crystalline basement.Along the western portion of the line, the lower crust is characterised by a 6–8-km-thick band of high-amplitude reflection lamellae, typically observed in extensional provinces. The Moho can be clearly defined at the base of this band, at approximately 32.5 km depth. Due to insufficient signal penetration, outstanding reflections are missing in the central and eastern portion of the lower crust. We speculate that the result of accompanying gravity measurements and lower crustal sporadic reflections can be interpreted as an indication for a shallower Moho in the east, preferable at about 30.5 km depth.The high reflectivity of the lowermost part of the lower crust and prominent reflection packages in the upper crust, the latter interpreted to represent broad extensional mylonite zones, emphasises the latest extensional processes in accordance with eastward extrusion.     

Sediment Distribution Around Glacially Abraded Bedrock Landforms (Whalebacks) at Lago Tranquilo, Chile

Whalebacks are convex landforms created by the smoothing of bedrock by glacial processes. Their formation is attributed to glacial abrasion either by bodies of subglacial sediment sliding over bedrock or by individual clasts contained within ice. This paper reports field measurements of sediment depth around two whaleback landforms in order to investigate the relationship between glacigenic deposits and whaleback formation. The study site, at Lago Tranquilo in Chilean Patagonia, is situated within the Last Glacial Maximum (LGM) ice limits. The two whalebacks are separated by intervening depressions in which sediment depths are generally 0.2 to 0.3 m. Two facies occur on and around the whalebacks. These facies are: (1) angular gravel found only on the surface of the whalebacks, interpreted as bedrock fracturing in response to unloading of the rock following pressure release after ice recession, and (2) sandy boulder‐gravel in the sediment‐filled depressions between the two whalebacks, interpreted as an ice‐marginal deposit, with a mixture of sediment types including basal glacial and glaciofluvial sediment. Since the whalebacks have heavily abraded and striated surfaces but are surrounded by only a patchy and discontinuous layer of sediment, the implication is that surface abrasion of the whalebacks was achieved primarily by clasts entrained in basal ice, not by subglacial till sliding.     

Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.