Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

Elastic behaviour and structural evolution of topaz at high pressure

The elastic behaviour and the high-pressure structural evolution of a natural topaz, Al_2.00Si_1.05O_4.00(OH_0.26F_1.75), have been investigated by means of in situ single-crystal X-ray diffraction up to 10.55(5) GPa. No phase transition has been observed within the pressure range investigated. Unit-cell volume data were fitted with a third-order Birch-Murnaghan Equation of State (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are: V ₀=345.57(7) ų, K _T0=164(2) GPa and K′=2.9(4). The axial-EoS parameters are: a ₀=4.6634(3) Å, K _T0(a)=152(2) GPa, K′(a)=2.8(4) for the a-axis; b ₀=8.8349(5) Å, K _T0(b)=224(3) GPa, K′(b)=2.6(6) for the b-axis; c ₀=8.3875(7) Å, K _T0(c)=137(2) GPa, K′(c)=2.9(4) for the c-axis. The magnitude and the orientation of the principal Lagrangian unit-strain ellipsoid were determined. At P−P ₀=10.55 GPa, the ratios ε₁:ε₂:ε₃ are 1.00:1.42:1.56 (with ε₁||b, ε₂||a, ε₃||c and |ε₃| > |ε₂| > |ε₁|). Four structural refinements, performed at 0.0001, 3.14(5), 5.79(5) and 8.39(5) GPa describe the structural evolution in terms of polyhedral distortions.     

常温高压下石膏在水中的溶解度突变现象及其意义

我们在26℃和0.1~900MPa压力下进行了纯水中石膏的溶解实验。实验结果发现在低于608MPa的压力下石膏一直保持稳定,而在高于该压力下石膏才开始发生溶解。在其后的八次加压过程中,尽管体积在缩小,但压力却并不线性上升,且石膏也不发生进一步的溶解。当加压使体系压力增加,且压力超过668MPa时石膏才突然全部溶解完。这种现象一方面表明压力对矿物在水中的溶解具有某种控制作用,另一方面,也可能说明水在高压下具有完全不同于常压下的性质。这意味着地壳内在约18km深度处可能存在着一种物理化学界面。该界面将对矿物、岩石及其地球物理性质产生重要影响。     

Contribution of interstitial OH groups to the incorporation of water in forsterite

Water incorporation in forsterite samples synthesized under low to medium silica-activity conditions mostly occurs via a substitutional mechanism in which a Si vacancy is compensated by four protons. Corresponding IR absorption spectra display a cluster of narrow and weakly anharmonic OH-stretching bands at wavenumbers above 3,500 cm^?1. However, this diagnostic spectrum is often superimposed to one broader absorption band, rarely two, displaying pronounced temperature-dependent properties and tentatively assigned to H atoms in interstitial position (Ingrin et al. in Phys Chem Miner 40:499–510, 2013). Here, we investigate the structural and vibrational properties of selected interstitial H-bearing defects in forsterite using a first-principles modeling approach. We show that the broad bands discussed by Ingrin et al. (Phys Chem Miner 40:499–510, 2013) are most likely related to interstitial OH groups in the vacant octahedral sites alternating with the M2 sites along the c axis of the forsterite structure. The corresponding OH defects lead to the formation of fivefold coordinated Si species. Their peculiar thermal properties stem from the vibrational phase relaxation due to the anharmonic coupling of the high-energy local OH-stretching mode with a low-energy vibrational mode. This “exchange mode” corresponds to the hindered longitudinal translation of the OH group. These results suggest that at high pressure, hydrogen incorporation in forsterite is dominated by coexisting interstitial OH groups and (4H)_Si defects.     

Physical and numerical simulations of the presence of a forsterite transitional zone at high temperature and pressure: insight for scCO2 geological storage

Geological sequestration is one of the most effective ways to reduce greenhouse gases, such as carbon dioxide (CO₂). The deep oceanic crust dominated by ultrabasic rock could store CO₂ permanently. However, the storage mechanism has not been thoroughly understood because of the limited amount of research and experiments conducted. This study explored the reactive mechanisms of water–rock–gas in an ultrabasic system under different conditions. Forsterite, the most dominant mineral found in ultrabasic reservoirs, was used to conduct laboratory physical simulation experiments. Two experimental systems were designed including an scCO₂–forsterite–water system and an N₂–forsterite–water system. All experiments were performed for 1000 h at an experimental temperature of 150°C and a pressure of 150 bar, respectively, to mimic the geological conditions. The liquid products from the experiments were analysed by inductively coupled plasma-optical emission spectrometry, whereas the solid samples were analysed by scanning electron microscopy with energy disperse spectroscopy. Results showed that: (1) in the early stage during scCO₂/N₂–forsterite–water interaction, forsterite was dissolved with a reactive transitional zone forming on the surface, which caused H⁺ to enter into the silicate framework and accelerated the reaction; (2) in the N₂ system, the dissolution of forsterite was inhibited by the Mg²⁺ concentration after reaching its saturation in the late stage; and (3) in the scCO₂ system, magnesite was precipitated as a secondary mineral during the late stage, which promoted the dissolution of forsterite. As a result, the degree of dissolution of forsterite in the scCO₂ system was far higher than in the N₂ system. The experimental results are consistent with the numerical simulation using TOUGHREACT, a geochemical simulation procedure, which showed that CO₂ promotes the dissolution of forsterite greatly at high temperature and pressure.     

Structural evolution of rutile-type and CaCl2-type germanium dioxide at high pressure

 Germanium dioxide was found to undergo a transition from the tetragonal rutile-type to the orthorhombic CaCl₂-type phase above 25 GPa. The detailed structural evolution of both phases at high pressure in a diamond anvil cell has been investigated by Rietveld refinement using angle-dispersive, X-ray powder-diffraction data. The square of the spontaneous strain (a−b)/(a+b) in the orthorhombic phase was found to be a linear function of pressure and no discontinuities in the cell constants and volume were observed, indicating that the transition is second-order and proper ferroelastic. Compression of the GeO₆ octahedra was found to be anisotropic, with the apical Ge-O distances decreasing to a greater extent than the equatorial distances and becoming shorter than the latter above 7 GPa. Above this pressure, the GeO₆ octahedron exhibits the common type of tetragonal distortion predicted by a simple ionic model and observed for most rutile-type structures such as those of the heavier group-14 dioxides and the metal difluorides. Above the phase transition, the columns of edge-sharing octahedra tilt about their two fold axes parallel to c and the rotation angle reaches 10.2(5)° by 36(1) GPa so as to yield a hexagonal close-packed oxygen sublattice. The compressibility increases at the phase change as is expected for a second-order transition at which an additional compression mechanism becomes available.     

Stability of the assemblage albite plus forsterite at high temperatures and pressures with petrologic implications

The maximum limits of the assemblage albiteforsterite have been determined experimentally at high pressures and temperatures. At subsolidus temperatures, albite plus forsterite is replaced at high pressures by jadeitic clinopyroxene and enstatitic orthopyroxene. The boundary for this reaction lies within experimental uncertainity of that for jadeite=albite+nepheline. Melting of albite+forsterite at high pressures produces enstatite+liquid, which is different from the low-pressure eutectic behavior. Melting rates are very slow and several hundred hours are required to establish equilibrium near the solidus. The subsolidus boundary for albite plus forsterite lies near that for sanidine plus forsterite, but with a shallower slope which more closely matches that of anorthite plus forsterite. Both albite plus forsterite and anorthite plus forsterite are replaced at high pressures by an assemblage containing clinopyroxene plus orthopyroxene, unlike sanidine plus forsterite, which is replaced by a feldspathoid plus orthopyroxene. The presence of sodium enlarges the depth region over which plagioclase lherzolite can stably exist; it may also stabilize alkali feldspar plus olivine in crustal rocks.     

The intensity of amphibole OH bands in the infrared absorption spectrum

Polarized IR spectra of single-crystals of amphiboles show that the molar absorptivity of the fundamental vibrational OH band is strongly wavenumber dependent. The intensity increases by a factor of 1.6 from 3674 cm^-1 (tremolite endmember; MgMgMg) to 3618 cm^-1 (grunerite endmember; FeFeFe). Spectra obtained from Ca and Fe-Mg amphiboles consist of sharp, well-resolved bands on a well-defined background. The high intensity of the OH bands in Ca and Fe-Mg amphiboles makes it sometimes necessary to thin the samples to under 2 μm thickness, whereas alkali amphiboles can be measured at 25–50 μm thickness.     

Permeability of the rocks from the Kola superdeep borehole at high temperature and pressure: implication to fluid dynamics in the continental crust

Permeability of the samples collected from the surface and from the depths of 8–11 km in the Kola SG-3 and from the depth of 3.8 in the KTB boreholes was studied at temperatures up to 600 °C and pressures up to 150 MPa. These PT correspond to in situ conditions of the deep parts of the superdeep boreholes and to the conditions of progressive and regressive metamorphism of the Kola series rocks. The experiments were carried out with fluid filtration parallel and normal to rock foliation and parallel to core axis. The temperature–permeability trend behavior depends on effective pressure and depth of sample collection. At low effective pressure, a temperature increase leads first to a permeability decrease and then to its increase. At higher effective pressure, inversions appear on all the temperature trends of the samples collected from great depths. In contrast, permeability of the samples selected at shallow depth (3.8 km) and on the surface decreases within the entire temperature range. As a rule, with flow parallel to foliation, the values of permeability are higher than with flow normal to foliation. The results of microstructure studies allow to conclude that microcrack initiation and closure, due to a competitive influence of temperature and pressure cause such permeability behavior. In the samples, there are two families of microcracks: with low aspect ratio and those with high aspect ratio. Their effect on rock permeability changes with temperature. On sample heating, the low aspect ratio microcracks close and, on the contrary, high aspect ratio ones open. The total effect is expressed by minima in the temperature–permeability trends. Permeability anisotropy increases with temperature, reaches a maximum at 200 °C and then decreases. Sample permeability decreases with different gradients at simultaneous increase of temperature and pressure, simulating in situ depth increase. Hence, the deep seat rocks can vary greatly in permeability and against the common background of permeability decrease with depth, local deep aquifers may occur. At PT of progressive metamorphism the permeability values were high enough to permit the fluid flow to penetrate the whole volume of rock massif. At PT of regressive metamorphism, the permeability values were a few decimal orders lower, so fluid flow could be concentrated in large disjunctive zones only.     

In-situ IR measurements of OH species in quartz at high temperatures

The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour. At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm^–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration. This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational frequency from 3396 to 3386 cm^–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al) begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs. Received: 18 February 1998/ Accepted: 10 July 1998     

单斜辉石中缺陷OH结合机理的变温红外光谱实验研究

利用变温红外光谱及偏振实验的结果,依据晶体化学理论及键长与振动频率的关系,从热膨胀速率这一新的角度探讨了单斜辉石中缺陷OH的结合机理。单斜辉石中OH的红外吸收峰主要有3组:3600~3620cm-1、3500~3540cm-1和3445~3465cm-1。第1组峰对应的的OH结合方式是Si4 O2- 1/2H2Al3 OH-,第3组峰对应的OH结合方式是H填充M2空位。第2组峰对应的OH结合方式复杂,可能和多个位置有关。第2和第3两组OH偶极的振动方向一致,都是M1和M2的共棱O2—O1,而第1组OH偶极的振动方向则是M2的O2—O3棱。     

Experimental deformation of a synthetic dunite at high temperature and pressure. II. Transmission electron microscopy

We have performed detailed transmission electron microscope on most of the deformed synthetic dunite specimens prepared in the study by Zeuch and Green (1984). We have identified three basic types of sub-boundaries, simple tilt walls in (100) and (001). composed by b = [100] and b = [001] edge dislocations, respectively, and twist boundaries in (010) composed of b = [100] and b = [001] screws. We have also observed more complex, asymmetric lilt boundaries in (100) and (001). Like the (010) twist boundaries, these asymmetric tilt walls are common only at the highest temperatures and lowest strain rates. Subgrain development is extensive at the higher temperatures and lower strain rates, and subgrains are composed of the above-mentioned three types of sub-boundaries; edge components in (100) and (001) ire “knitted” to screw components in (010) as described by Kirby and Wegner (1978) for naturally deformed olivine. In many areas of the samples which we studied, subgrain development is not observed, but parallel arrays of tilt boundaries of one type or the other are present. At higher temperatures and lower strain rates. “(100) organization” (Durham et al., 1977) is common; this structure consists of parallel arrays of (100) tilt boundaries with b = [100] screws connecting the sub-boundaries. At lower temperatures we have observed an analogous arrangement of (001) sub-boundaries and b = [001] screws, which we refer to as “(001) organization”. Under all experimental conditions, dislocations with b = [100] and b = [001] are present in approximately equal numbers. However, the two types of dislocations also have distinctly different geometries under all test conditions. We suggest that the transition from slip parallel to [001] to slip parallel to [100] with increasing temperature, which has been reported in earlier studies may also depend upon water content. The substructures which we observe are virtually identical to those seen in many naturally deformed peridolites. and we conclude that the mechanisms involved in both natural and laboratory deformation of olivine polycrystals are similar. On the other hand, the substructures reported here are very different from those observed in experimentally deformed olivine single crystals. It seems likely that these substructural differences reflect fundamental differences in the behavior oh single crystals and polycrystals. which are in turn reflected in different measured creep strengths.     

The evolution of spinel lherzolite xenoliths and the nature of the mantle at Kilbourne Hole,New Mexico

In peridotites, olivine, clinopyroxene, and orthopyroxene are complex solid solutions with wide stability fields. Depending mostly on bulk composition and pressure, these minerals may be accompanied by plagioclase (low pressure), spinel (moderate pressure), or garnet (high pressure), resulting in 4-phase and rarer 5-phase assemblages. Although a particular mineral assemblage is stable over a range of P–T, the compositions of the individual minerals vary with changing P–T conditions. Application of standard geothermobarometers to olivine–clinopyroxene–orthopyroxene–spinel peridotites is problematic. An alternative approach is to use a bulk rock composition to calculate equilibrium phase diagrams to determine the conditions under which a particular assemblage is stable. This requires consideration of the 7-component system SiO₂–Al₂O₃–Cr₂O₃–FeO–MgO–CaO–Na₂O, internally consistent thermodynamic data for end members, and reliable mixing models for all mineral solutions. Experimental studies in simpler systems, and solution models from the literature, permit derivation of multicomponent thermodynamic mixing models for the key minerals. The models, when applied to xenoliths from Kilbourne Hole, constrain P and T of equilibration and are less sensitive to mineral compositional variations, or uncertainty in activity models, than standard thermobarometry. Our modeling provides the first tightly constrained pressure estimates for Kilbourne Hole, placing the xenoliths in the spinel stability field at depths (30–45 km) that correspond to the uppermost mantle beneath the Rio Grande Rift. The fine-grained equigranular lherzolite, porphyroclastic lherzolite, and some harzburgite-dunite specimens equilibrated at average conditions of 11.5 Kbar-930°C, 12 Kbar-990°C, and 13 Kbar-1,080°C, respectively. The mantle beneath the Rio Grande Rift is layered; the fine-grained equigranular lherzolite derives from relatively shallow depth (35 km average), and the porphyroclastic lherzolite from slightly deeper levels. Lying 5–10 km beneath both lherzolites, the harzburgite-dunite represents a depth where melt extraction has significantly altered mantle chemistry and where local thermodynamic equilibrium has not been maintained.     

Neoproterozoic tectonic evolution of the Hongseong area, southwestern Gyeonggi Massif, South Korea; implication for the tectonic evolution of Northeast Asia

Two types of Neoproterozoic metabasites occur together with regionally intruded arc-related Neoproterozoic granitoids (ca. 850–830 Ma) in the Hongseong area, southwestern Gyeonggi Massif, South Korea, which is the extension of the Dabie–Sulu collision belt in China. The first type of metabasite (the Bibong and Baekdong metabasites) is a MORB-like back-arc basin basalt or gabbro formed at ca. 890–860 Ma. The Bibong and Baekdong metabasites may have formed during back-arc opening by diapiric upwelling of deep asthenospheric mantle which was metasomatized by large ion lithophile element (LILE) enriched melt or fluid derived from the subducted slab and/or subducted sediment beneath the arc axis. The second type of metabasite (the Gwangcheon metabasite) formed in a plume-related intra-continental rift setting at 763.5 ± 18.3 Ma and is geochemically similar to oceanic island basalt (OIB). These data indicate a transition in tectonic setting in the Hongseong area from arc to intra-continental rift between ca. 830 and 760 Ma. This transition is well correlated to the Neoproterozoic transition from arc to intra-continental rift tectonic setting at the margin of the Yangtze Craton and corresponds to the amalgamation and breakup of Rodinia Supercontinent.     

Experimental deformation of a synthetic dunite at high temperature and pressure. I. Mechanical behavior, optical microstructure and deformation mechanism

We have performed a series of 27 deformation experiments on a very dry synthetic dunite, using the Griggs solid medium apparatus. Strain rates ranged from 1 × 10 ⁴ to 1 × 10 ⁷ sec ¹, temperatures varied from 1100° to 1300 °C, and the confining pressure was maintained at 10 or (more usually) 15 kbar. MACOR^IM, a commercially available, anhydrous, machinable glass ceramic with a low melting point, was used in many of the experiments. We find that strength measurements performed using macor as a confining medium are similar to results obtained using sodium chloride as the confining solid. Tests performed in undried sample assemblies using air-dried dunite specimens resulted in creep strengths greater than those found in any earlier studies except those of Post (1973. 1977). A single test on a sample for which both sample and assembly were dried at a temperature sufficiently high to drive off any adsorbed water resulted in a creep strength comparable to that determined by Post (1973, 1977) for very dry Mt. Burnett dunite. Despite our experimental difficulties, we are led to believe that our synthetic dunite exhibits mechanical behavior consistent with that determined in other experimental studies in which natural dunites and peridotites were used. Furthermore, we conclude that dry dunite is very probably as strong as the oft-disputed results of Post earlier indicated. Finally, we show that the optical textures of our highly recrystallized experimental specimens are essentially identical to naturally produced porphyroclastic textures and that the deformation mechanism in both the experimental and natural specimens is probably dislocation creep with recovery by dynamic recrystallization.     

Phase transition of synthetic zinc ferrite spinel (ZnFe2O4) at high pressure, from synchrotron X-ray powder diffraction

 Synthetic Zn-ferrite (ideally ZnFe₂O₄; mineral name: franklinite) was studied up to 37 GPa, by X-ray powder diffraction at ESRF (Grenoble, France), on the ID9 beamline; high pressure was achieved by means of a DAC. The P-V equation of state of franklinite was investigated using the Birch-Murnaghan function, and the elastic properties thus inferred [K₀ = 166.4(±3.0) GPa K₀ ^′ = 9.3(±0.6) K₀ ^″ = −0.22 GPa⁻¹] are compared with earlier determinations for MgAl-spinel and magnetite. The structural behaviour of Zn-ferrite as a function of pressure was studied by Rietveld refinements, and interpreted in the light of a phase transition from spinel to either CaTi₂O₄- or MnFe₂O₄-like structure; this transformation occurs above 24 GPa. Received: 15 March 1999 / Accepted: 22 April 2000     

The nature and origin of sideritic ironstone bands in the Tertiary Lowmead and Duaringa Basins,Queensland

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %₀ δ¹⁸O (PDB) and ‐5.5‰ to +12.9‰ δ¹³C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ¹⁸O (PDB) and ‐18.6‰ to +16.4‰ δ¹³C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ¹⁸O values of many of the siderites. The carbon isotope data show that the carbonate for the formation of the siderite originated predominantly from methanogenic fermentation processes but there was also the varying influence of bacterial oxidation processes. The different petrological and isotopic characteristics of the ironstones broadly reflect variations in their depositional environments and the variable eogenetic conditions in which the siderite formed. There is no suitable single model to explain the genesis of all the different types of ironstones other than that a synsedimentary iron‐enrichment process is involved.     

Tectonometamorphic evolution of the Bohemian Massif: evidence from high pressure metamorphic rocks

The Variscan orogenic belt, of which the Bohemian Massif is a part, is typically recognized for its characteristic low pressure, high temperature metamorphism and a large volume of granites. However, there are also bodies of high pressure rocks (eclogites, garnet peridotites and high pressure granulites) which are small in size but widely distributed throughtout the Massif. Initially the high pressure rocks were considered to be relicts of a much older orogenic event, but the increasing data derived from isotopic and geochronological investigations show that many of these rocks have Palaeozoic protoliths. Metamorphic ages from the high pressure rocks define no single event. Instead, a number of discrete clusters of ages are found between about 430 Ma and the time of the dominant low pressure event at around 320–330 Ma.Most of the eclogite and granulite facies rocks are assigned to allochthonous nappes that arrived close to the end of the low pressure event, but before final granite intrusion. The nappes contain a mixture of different units and the relationship between rocks with high pressure relicts and host gneisses with no apparent signs of deep burial is still problematic. Some of the high pressure rocks retain evidence of multiple stages of partial re-equilibration during uplift. Moreover, it can be shown in certain instances that host gneisses also endured a multistage metamorphic development but with a peak event convergent with one of the breakdown stages in the enclosed rocks with high pressure relicts. It thus appears that the nappe units are composite bodies probably formed during episodic intracrustal thrusting. Fluids derived from prograde dehydration reactions in the newly under thrusting slab are taken to be the catalysts that drove the partial re-equilibrations.On the scale of the whole Massif it can be seen within the units with high pressure relicts that the temperature at the peak recorded pressure and that during the breakdown are variable in different locations. It is interpreted that regional metamorphic gradients are preserved for given stages in the history and thus the present day dismembered nappe relicts are not too far removed from their original spatial distribution in an original coherent unit. From the temperature information alone it is highly probable that the refrigerating underthrusting slab was situated in the north-west. However, this north-west to south-east underthrusting probably represents the major 380–370 Ma event and is no guide to the final thrusting that emplaced the much thinned nappe pile with high pressure relicts.Granite genesis is attributed to the late stage stacking, during the final Himalayan-type collision stage, of thinned crust covered by young, water-rich, sediments — erosion products of the earlier orogenic stages. Regional metamorphism at shallow depths above the voluminous granites was followed by final nappe emplacement which rejuvenated the granite ascent in places. Correspondence to: P. J. O'Brien