Two-feldspar geothermometry in granulite facies metamorphic rocks

A geothermometric technique based on equilibria between coexisting plagioclase and alkali feldspar was applied to quartzo-feldspathic granulites from Salvador, BA, Brazil. The conditions of metamorphism were determined to be in the range 750 ° C–800 ° C, 4–8 Kb, by comparison with experimental data on the stabilities of sapphirine, phlogopite and other minerals occurring in the associated rocks. Selected feldspar data gives temperatures near, but slightly below, this range. Several variants of the Wood and Banno model, as well as an empirical two-pyroxene geothermometer, were also tested and found to give temperatures which were apparently 50 °–100 ° high. The solubility of Al₂O₃ in orthopyroxene indicates temperatures which are about 200 ° to high, suggesting that Fe in the natural assemblages significantly changes relationships observed experimentally in MgO-Al₂O₃-SiO₂ systems.     

Restoration of the elemental and stable-isotopic compositions of diffusionally altered minerals in slowly cooled rocks

 In polymineralic plutonic igneous and metamorphic rocks, slowly cooled crystals seldom retain their initial chemical compositions. This paper introduces a new, simple and widely applicable material-balance method that recovers the former compositions of minerals – regenerating in many rock types their chemical memory of the environment in which they formed – without a priori knowledge of temperature or pressure or diffusion kinetics. Restored stable-isotopic, trace-element, and/or major-element compositions provide a basis for interpretations of petrogenetic processes and conditions, including recovery of peak temperature and pressure, depth, and average diffusion distance during re-equilibration. Case studies illustrate applications of the mineral-restoration technique to regional crustal dynamics, ore metallogeny, and igneous fluid dynamics and petrogenesis. The first illustrative case addresses the controversial origin of decimetre-thick, modally graded rock layers in the Skaergaard intrusion. Layer-wide mineral-chemistry gradients that previously were ascribed a primary origin are here shown to be due to sub-solidus diffusive re-equilibration amongst minerals that initially were chemically uniform. This finding redefines the constraints to be satisfied by fluid-dynamic models of chemical differentiation processes in the magma chamber, and eliminates the basis of prior interpretations of the modally graded layers as products of in situ crystallization on the magma chamber's floor. In another case, lower crustal olivine-chromite cumulates underwent a long two-stage history of mineral-composition readjustment spanning >500° C. The technique introduced here removes the effects of the second-stage solid-state diffusion, recovering mineral compositions that represent the igneous solidus temperature at the termination of the metasomatic stage. The third example removes effects of retrograde diffusive ion-exchange from garnet, hornblende, and clinopyroxene in order to restore the rock's chemical memory of its pressure and depth of crystallization. The depth corresponds to a measure of extreme Cenozoic uplift and erosion (∼58 km) along the Main Mantle Thrust, which juxtaposes the underthrusting Indian Plate and the over-riding Kohistan island-arc terrain in the Pakistani Himalayas. Received: 28 March 1995 / Accepted: 11 April 1996     

Two-feldspar geothermometry,geobarometry in mesozonal granitic intrusions: Three examples from the Piedmont of Georgia

The equilibrium temperatures for coexisting plagioclase and potassium feldspar pairs have been calculated for various textural varieties of feldspar from 3 post-metamorphic granites from the Georgia Piedmont; the Danburg, Siloam, and Stone Mountain plutons. Assuming an intermediate structural state for the feldspars at time of equilibration, crystallization temperatures match those expected from experimental data for quartz monzonite magmas (650 to 780° C). The variations in solidus temperature, recorded in the feldspars, may be used to estimate relative differences in depth of intrusion. Sharp reversals in plagioclase compositional trends may be caused by isothermal decreases in confining pressure associated with upward migration through the crust. In fine grained and slowly cooled intrusions, albite tends to be lost from the alkali feldspar grains, and recrystallizes as separate unzoned grains of oligoclase, thus erasing the previous thermal history. Perthite exsolution and re-equilibration within the alkali feldspar grains appears to continue down to temperatures of 400° C or so, although the zoned plagioclase does not homogenize. The recrystallization associated with changes in structural state may facilitate exsolution within alkali feldspar grains.     

Argon retentivity of hornblendes: A field experiment in a slowly cooled metamorphic terrane

Hornblende from samples of amphibolite and granitic gneiss, collected within a single outcrop in the central Adirondacks, yield significantly different ⁴⁰Ar*/³⁹Ar_k dates of 948 ± 5 and 907 ± 5 Ma. Assuming that this terrane cooled slowly following high-grade metamorphism and that the samples have experienced the same thermal history, the difference in dates apparently reflects a corresponding difference in blocking temperature for diffusion of radiogenic argon in these hornblende samples.The Fe/(Fe + Mg + Mn) of the hornblende samples are 0.8 and 0.6, the higher ratio corresponding to the younger ⁴⁰Ar*/³⁹Ar_k date. Transmission electron microscopy observations indicate that both hornblende samples are homogeneous and devoid of any exsolution, but contain zones of fibrous phyllosilicates ~0.1 to 2 μm wide parallelling (100) and (110). These alteration zones probably formed during post-metamorphic cooling as a result of the migration of fluids through the hornblendes, and are obvious pathways for argon escape from hornblende. As these features are more abundant in the hornblende sample with the younger⁴⁰Ar*/³⁹Ar_k date and higher Fe/(Fe + Mg + Mn), they may influence the argon blocking temperature by effectively partitioning the hornblende grains into diffusion domains of varying size.Biotite from the granitic gneiss yields an ⁴⁰Ar*/³⁹Ar_k date of 853 ± 2 Ma, with a mildly discordant stepheating spectrum that in part reflects the degassing of submicroscopic inclusions precipitated during alteration of the host biotite. Plagioclase from the amphibolite yields a ⁴⁰Ar*/³⁹Ar_k integrated date of 734 ± 3 Ma. All the ⁴⁰Ar*/³⁹Ar_k data are consistent with postmetamorphic cooling rates of 1° to 5°C/Ma.     

Internally-consistent geothermometry and H2O barometry in metamorphic rocks: The example garnet-chlorite-quartz

Temperature and H₂O activity can be determined with high precision using metamorphic mineral assemblages that define both a dehydration equilibrium and a temperature-sensitive cation-exchange equilibrium. Such determinations are obtained by applying the Gibbs method and then integrating two resulting differential equations, as illustrated here for the assemblage garnet-chlorite-quartz. The first equation, a geothermometer that monitors temperature based upon Fe–Mg exchange between garnet and chlorite, was calibrated using rocks at Pecos Baldy, New Mexico: 0=0.05 P(bars)–19.02 T(K)+4607 ln K _D+24,156 with errors of ±8°C based upon analytical precision. The second equation monitors differences in the activity of water between specimens (1) and (2): 0=(0.1 X _{Mg–chl, 1} – 2.05)(P ₂ – P ₁) +[–33.02+5.96 ln(X _{Fe–chl, 1}/X _{alm, 1})][T ₂–T ₁ –2.67 RT ₁ln[a(H₂O)₂/a(H₂O)₁] +5.96 T ₁ln(X _{Fe–chl, 2} X _{alm, 1}/X _{Fe–chl, 1} X _{alm, 2}).For samples equilibrated at the same pressure and temperature, microprobe analytical errors of 1% limit precision to ±0.01 a(H₂O). For samples equilibrated at the same pressure but variable temperature, uncertainty of ±8°C limits precision to ±0.06 a(H₂O). Extreme presure sensitivity requires that the H₂O-barometer be applied only to rocks where pressure gradients are absent or well-constrained. The geothermometer gives temperatures in agreement with two other garnet-chlorite geothermometers (Dickenson and Hewitt 1986; Ghent et al. 1987) and with garnet-biotite geothermometry (ferry and Spear 1978) over the temperature range 350–520°C. Application of the relative H₂O barometer shows variations in the activity of water approaching 0.30 in several study areas. Either pelitic schists commonly equilibrate with a fluid that is not pure H₂O, or some pelitic rocks undergo metamorphism in the absence of a free fluid phase.     

Fractal models for the fragmentation of rocks and soils: a review

Fragmentation, the process of breaking apart into fragments, is caused by the propagation of multiple fractures at different length scales. Such fractures can be induced by dynamic crack growth during compressive/tensile loading or by stress waves during impact loading. Fragmentation of rocks occurs in resoonse to tectonic activity, percussive drilling, grinding and blasting. Soil fragmentation is the result of tillage and planting operations. Fractal theory, which deals with the scaling of hierarchical and irregur systems, offers new opportunities for modeling the fragmentation process. This paper reviews the literature on fractal models for the fragmentation of heterogeneous brittle earth materials. Fractal models are available for the fragmentation of: (1) classical aggregate; (2) aggregates with fractal pore space; and (3) aggregates with fractal surfaces. In each case, the aggregates are composed of building blocks of finite size. Structural failure is hierarchical in nature and takes place by multiple fracturing of the aggregated building blocks. The resulting number-size distribution of fragments depends on the probability of failure, P(1/bⁱ) at each level in the hierarchy. Models for both scale-invariant and scale-dependent are reviewed. In the case of scale-invariant P(1/bⁱ)< 1, theory predict: D_f = 3 + log [P(1/bⁱ)]/log[b] for classical aggregates; D_f=D_m+log[P(1/bⁱ)]/log[b] for aggregates with fractal pore space; and D_f=D_s for aggregates with fractal surfaces. where b is a scaling factor and D_f, D_m and D_s are the fragmentation, mass and surface fractal dimensions, respectively. The physical significance of these parameters is discussed, methods of estimating them are reviewed, and topics needing further research are identified.     

Geochemistry and geothermometry of volcanic rocks from Serra Branca,Iberian Pyrite Belt,Portugal

Volcanic rocks from Serra Branca, Iberian Pyrite Belt, Portugal, consist of calc-alkaline felsic and intermediate rocks. The latter are massive andesites, whereas the former include four dacitic to rhyolitic lithologies, distinguishable on spiderdiagrams and binary plots of immobile elements. Zircon thermometry indicates that two felsic suites may have formed from different magmas produced at distinct temperatures, with only limited fractionation within each suite. Alternatively, all the felsic rocks can be related through fractionation of a single magma if the lower zircon saturation temperature obtained for one suite merely results from Zr dilution, mostly reflecting silicification.The relatively high magma temperatures at Serra Branca ease the classification of felsic rocks based on their HFSE contents and also indicate volcanogenic massive sulfide deposit favorability. This contrasts with other areas of the Belt that register lower magma temperatures and are subsequently barren. However, magma temperatures may have not been high enough to cause complete melting of refractory phases in which HFSE reside during crustal fusion of an amphibolite protolith, implying difficult discrimination of tectonic environments for the felsic rocks. The intermediate rocks were possibly formed by mixing between basaltic magmas and crustal material, compatible with volcanism in an attenuated continental lithosphere setting.     

Geochemistry and geothermometry of volcanic rocks from Serra Branca, Iberian Pyrite Belt, Portugal

Volcanic rocks from Serra Branca, Iberian Pyrite Belt, Portugal, consist of calc-alkaline felsic and intermediate rocks. The latter are massive andesites, whereas the former include four dacitic to rhyolitic lithologies, distinguishable on spiderdiagrams and binary plots of immobile elements. Zircon thermometry indicates that two felsic suites may have formed from different magmas produced at distinct temperatures, with only limited fractionation within each suite. Alternatively, all the felsic rocks can be related through fractionation of a single magma if the lower zircon saturation temperature obtained for one suite merely results from Zr dilution, mostly reflecting silicification.

The relatively high magma temperatures at Serra Branca ease the classification of felsic rocks based on their HFSE contents and also indicate volcanogenic massive sulfide deposit favorability. This contrasts with other areas of the Belt that register lower magma temperatures and are subsequently barren. However, magma temperatures may have not been high enough to cause complete melting of refractory phases in which HFSE reside during crustal fusion of an amphibolite protolith, implying difficult discrimination of tectonic environments for the felsic rocks. The intermediate rocks were possibly formed by mixing between basaltic magmas and crustal material, compatible with volcanism in an attenuated continental lithosphere setting.     

Exhumation of high-pressure rocks: a review of concepts and processes

The exhumation of high-pressure metamorphic rocks requires either the removal of the overburden that caused the high pressures, or the transport of the metamorphic rocks through the overburden. Exhumation cannot be achieved simply by thrusting or strike-slip faulting. It may be caused by erosion of shortened and thickened crust, but this is unlikely to be the only mechanism for exhuming rocks from depths greater than about 20 km. One or more of the following additional mechanisms may be involved. 1 Corner flow of low-viscosity material trapped between the upper and lower plates in a subduction zone can cause upward flow of deeply buried rock, and may explain some occurrences of high-pressure tectonic blocks in mélange. This process does not, however, appear to be adequate to explain the exhumation of regional high-pressure terrains. 2 Buoyancy forces acting directly on metamorphic rock bodies may cause them to rise relative to more dense surroundings. This is likely to be the most important mechanism of exhumation of crustal rocks subducted into the mantle, but cannot explain the emplacement of coherent tracts of high-density metamorphic rock into shallow crustal levels. Some high-pressure blocks emplaced at shallow levels in accretionary terrains may have been entrained in diapiric intrusions of low-density mud or serpentinite. 3 Extension driven by the forces associated with contrasts in surface elevation may explain the exhumation and structural setting of many high-pressure terrains. Extension may occur in the upper part of an accretionary wedge thickened by underplating; or it may affect the whole lithosphere in a region of intracontinental convergence, if surface elevation has been increased by the removal of a lithospheric root. In the second case extension may be accompanied by magmatism and an evolution towards higher temperature during decompression of the metamorphic terrain.     

LA-MC-ICPMS Pb-Pb dating of rutile from slowly cooled granulites: Confirmation of the high closure temperature for Pb diffusion in rutile

Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The ²⁰⁷Pb-²⁰⁶Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (T_c) for Pb diffusion in rutile that is less than the T_c of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the T_c for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher T_c than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current T_c estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.     

Zoning patterns in orthopyroxene and garnet in granulites: implications for geothermometry

Compositional maps of orthopyroxene and garnet of contrasting grain size and in contact with different minerals were made from two paragneiss granulites from the Minto terrane of northern Quebec. The compositional maps provide clear evidence of late exchange of Fe/(Fe + Mg) after Ca in garnet and Al in orthopyroxene had been quenched-in. The extent of late Fe-Mg exchange was controlled by neighbouring minerals, with negligible Fe-Mg gradients against plagioclase and quartz, and substantial gradients against exchangeable Fe-Mg minerals. Cores of grains in contact with exchangeable Fe-Mg neighbours are progressively more reset in Fe/(Fe + Mg) as grain size decreases, whereas cores of even small grains surrounded by only plagioclase and quartz are not significantly different in Fe/(Fe + Mg) than cores of the largest grains. Gradients of Ca in garnet and of Al in orthopyroxene in grains of uniform Fe/(Fe + Mg) preserve a high-temperature retrograde history during which intergranular exchange effected compositional uniformity of mineral rims and intragranular Fe-Mg diffusion in garnet and orthopyroxene was rapid enough to homogenize Fe/(Fe + Mg). The transition from efficient intergranular exchange at relatively high temperatures to local Fe-Mg exchange at lower temperatures may have been controlled by loss of an intergranular exchange medium in the rock, possibly an internally generated dehydration melt phase. Implications for geothermometry of granulites include the following (numerical values are particular to this study): (1) core compositions of garnet and orthopyroxene grains in contact with exchangeable neighbours may be reset in Fe/(Fe + Mg) relative to the most refractory compositions by an amount equivalent to 120d? C; (2) Fe-Mg exchange thermometry using even the most refractory Fe/(Fe + Mg) compositions may not record peak granulite conditions, possibly recording instead the temperature at which an intergranular exchange medium was lost from the rock; and (3) temperature-sensitive net transfer equilibria involving Al solubility in orthopyroxene yield temperatures up to 150d? C higher than maximum Fe-Mg exchange temperatures, even in grains with flat Fe/(Fe - Mg) compositional profiles, making them a better means of estimating peak granulite temperatures than Fe-Mg exchange thermometry.     

Hydrothermal hydrocarbon gases: 1, Genesis and geothermometry

Various sources for hydrothermal CH₄ have been proposed over the years. While C isotope studies have narrowed the possibilities, enough higher hydrocarbon gas data now exist both to supplement the isotopic data and to permit additional deductions regarding origins. Comparison of typical C₁–C₆ data for gases of various origins (from sedimentary and crystalline rocks, and hydrothermal systems) reveals certain characteristics. Apart from isotopic differences, hydrothermal hydrocarbons differ from sedimentary hydrocarbons mainly in possessing tendencies towards a relative excess of CH₄, higher normal/iso ratios for butane and pentane, and relatively high amounts of C₆ gases. Despite these differences, consideration of the evidence indicates that hydrothermal hydrocarbon gases in most cases originate like sedimentary basin gases by thermal degradation of organic matter in the relatively shallow subsurface. The principal characteristic of these hydrothermal gases, “excess” CH₄, appears to have a geothermometric function. The following empirical relationship has been derived: t°C=57.8 log(CH₄/C₂H₆)+96.8, which fits moderately well a range of geothermal fields worldwide. This gas geothermometer may be particularly applicable during geothermal exploration in areas where there is little direct knowledge of subsurface conditions.     

榴辉岩相高压-超高压变质岩的He同位素地球化学研究现状与问题

He同位素是区分地壳、地幔物质,研究壳-幔相互作用最灵敏的示踪剂之一,但其在高压-超高压变质作用过程中的地球化学行为目前仍不清楚,因而制约其在榴辉岩研究中的应用。中国作为高压-超高压榴辉岩带分布的重要地区,榴辉岩产出得天独厚,大洋、大陆两种俯冲成因榴辉岩均有分布。本文在归纳榴辉岩相高压-超高压变质岩研究进展的基础上,分析了He同位素示踪在榴辉岩研究中的应用现状。     

Evolution of Moldanubian rocks in Austria: review and synthesis

The Moldanubian zone in Austria comprises three major lithological units. Despite general agreement that nappe tectonics contributed to its current structure, the number and position of tectonic boundaries, or continental pieces that were involved in its evolution, as well as the age, extent and position of oceanic sutures are disputed. Recent models ascribe the Moldanubian tectonostratigraphic structure to its oblique, N- to NE-directed collision with Moravia only. The rocks of the Moldanubian Bunte series and Gföhl unit experienced a common, intensive overprint in the range 700–800 °C and 8–11 kbar. Textural evidence suggests that this overprint was attained during nearly isothermal decompression, so the rocks experienced higher pressures prior to this overprint. These conditions constrain a continent–continent collision environment that contributed to the formation of the Moldanubian granulites. The estimated metamorphic temperatures are close to T_max. During this Hercynian, high-T overprint, the minerals underwent extensive diffusion-controlled homogenization of elements. The early stages of retrogression of these units were characterized by isobaric cooling at c. 6 kbar in the range 650–500 °C that is related to the oblique collision of the Moldanubian and Moravian zones. Cooling to c. 400 °C is demonstrated by unstrained, diasporized corundum inclusions in garnet of common Moldanubian granulites. The available age data (including cooling ages) from metamorphic rocks show a very wide variation between 490 and 280 Ma that depends on sample characteristics and the dating method used. They demonstrate clearly, however, that the metamorphic overprint is Hercynian. The possibility that the large variation in ages reflects homogenization, resetting and closure of the isotopic systems attained at different, sample- and method-specific times is discussed. Age data varying between c. 370 and c. 346 Ma tentatively date different stages during the Hercynian, high-T decompression. The majority of zircon and monazite U/Pb ages as well as the hornblende and muscovite Ar/Ar cooling ages cluster between c. 345 and c. 326 Ma and date the effective closure conditions and the onset of rapid, nearly isobaric cooling. The continent–continent collision that formed the granulites pre-dates c. 370 Ma. The intra-Moldanubian nappe-stacking pre-dates thrusting of the Moldanubian zone over the Moravian zone. The range c. 340–335 Ma is the lower limit for completion of tectonic activity in the Moldanubian zone. The Moldanubian series are post-tectonically intruded by granitoids of the Southern Bohemian Pluton. Recent age determinations and geochemical evidence suggest that the formation of the early granitoid types took place in the lower crust in connection with the Hercynian high-grade overprint. The Moldanubian Monotone series in Austria is separated from the other Moldanubian units by a conspicuous tectonic horizon. It also differs from them by its characteristic high-T , low-P overprint, which is best demonstrated by a widespread cordierite gneiss.     

Reactive monazite and robust zircon growth in diatexites and leucogranites from a hot,slowly cooled orogen: implications for the Palaeoproterozoic tectonic evolution of the central Fennoscandian Shield,Sweden

Monazite in melt-producing, poly-metamorphic terranes can grow, dissolve or reprecipitate at different stages during orogenic evolution particularly in hot, slowly cooling orogens such as the Svecofennian. Owing to the high heat flow in such orogens, small variations in pressure, temperature or deformation intensity may promote a mineral reaction. Monazite in diatexites and leucogranites from two Svecofennian domains yields older, coeval and younger U–Pb SIMS and EMP ages than zircon from the same rock. As zircon precipitated during the melt-bearing stage, its U–Pb ages reflect the timing of peak metamorphism, which is associated with partial melting and leucogranite formation. In one of the domains, the Granite and Diatexite Belt, zircon ages range between 1.87 and 1.86 Ga, whereas monazite yields two distinct double peaks at 1.87–1.86 and 1.82–1.80 Ga. The younger double peak is related to monazite growth or reprecipitation during subsolidus conditions associated with deformation along late-orogenic shear zones. Magmatic monazite in leucogranite records systematic variations in composition and age during growth that can be directly linked to Th/U ratios and preferential growth sites of zircon, reflecting the transition from melt to melt crystallisation of the magma. In the adjacent Ljusdal Domain, peak metamorphism in amphibolite facies occurred at 1.83–1.82 Ga as given by both zircon and monazite chronology. Pre-partial melting, 1.85 Ga contact metamorphic monazite is preserved, in spite of the high-grade overprint. By combining structural analysis, petrography and monazite and zircon geochronology, a metamorphic terrane boundary has been identified. It is concluded that the boundary formed by crustal shortening accommodated by major thrusting.     

Time-dependent cracking and brittle creep in crustal rocks: A review

Rock fracture under upper crustal conditions is driven not only by applied stresses, but also by time-dependent, chemically activated subcritical cracking processes. These subcritical processes are of great importance for the understanding of the mechanical behaviour of rocks over geological timescales. A macroscopic manifestation of time-dependency in the brittle field is the observation that rocks can deform and fail at constant applied stresses, a phenomenon known as brittle creep. Here, we review the available experimental evidence for brittle creep in crustal rocks, and the various models developed to explain the observations. Laboratory experiments have shown that brittle creep occurs in all major rock types, and that creep strain rates are extremely sensitive to the environmental conditions: differential stress, confining pressure, temperature and pore fluid composition. Even small changes in any of these parameters produce order of magnitude changes in creep strain rates (and times-to-failure). Three main classes of brittle creep model have been proposed to explain these observations: phenomenological, statistical, and micromechanical. Statistical and micromechanical models explain qualitatively how the increasing influence of microcrack interactions and/or the increasing accumulated damage produces the observed evolution of macroscopic deformation during brittle creep. However, no current model can predict quantitatively all of the observed features of brittle creep. Experimental data are limited by the timescale over which experiments are realistically feasible. Clearly, an extension of the range of available laboratory data to lower strain rates, and the development of new modelling approaches are needed to further improve our current understanding of time-dependent brittle deformation in rocks.     

Influence of sedimentary environments on sulfur isotope ratios in clastic rocks: a review

Strata-bound sulfide deposits associated with clastic, marine sedimentary rocks, and not associated with volcanic rocks, display distributions of S³⁴ values gradational between two extreme types: 1. a flat distribution ranging from S³⁴ of seawater sulfate to values about 25 lower; and 2. a narrow distribution around value S³⁴ (sulfide)=S³⁴ (seawater sulfate) –50, and skewed to heavier values. S³⁴ (seawater sulfate) is estimated from contemporaneous evaporites. There is a systematic relation between the type of S³⁴ distribution and the type of depositional environment. Type 1 occurs in shallow marine or brackish-water environments; type 2 occurs characteristically in deep, euxinic basins. These distributions can be accounted for by a model involving bacterial reduction of seawater sulfate in systems which range from fully-closed batches of sulfate (type 1) to fully open systems in which fresh sulfate is introduced as reduction proceeds (type 2). The difference in the characteristic distributions requires that the magnitude of the sulfate-sulfide kinetic isotope effect on reduction be different in the two cases. This difference has already been suggested by the conflict between S³⁴ data for modern marine sediments and laboratory experiments. The difference in isotope effects can be accounted for by Rees' (1973) model of steady-state sulfate reduction: low nutrient supply and undisturbed, stationary bacterial populations in the open system settings tend to generate larger fractionations.

---

Zusammenfassung Schichtgebundene Sulfid-Lagerstätten in Begleitung von klastischen, marinen Sedimentgesteinen ohne Beteiligung vulkanischer Gesteine zeigen kontinuierliche Verteilungen der S³⁴-Werte zwischen zwei Extremtypen: 1. Eine flache Verteilung im Bereich von S³⁴-Werten des Seewasser-Sulfats bis zu Werten, die etwa 25 niedriger liegen. 2. Eine eng begrenzte Verteilung um den S³⁴ (Sulfid)-Wert=S³⁴ (Seewasser-Sulfat) –50 und asymmetrischer Verteilungskurve mit stärkerer Besetzung bei den schwereren Werten. Das S³⁴ (Seewasser-Sulfat) wird von gleichaltrigen Evaporiten abgeleitet. Es besteht eine systematische Beziehung zwischen der Art der S³⁴-Verteilung und dem Milieu des Ablagerungsraumes. Typ 1 tritt im marinen Flachwasser oder in brackischer Umgebung auf. Typ 2 ist charakteristisch für tiefe euxinische Becken. Diese Verteilungen können erklärt werden mit Hilfe eines Modells mit bakterieller Reduktion von Meerwasser-Sulfat in Systemen, die von völlig abgeschlossenen Sulfat-Mengen (Typ 1) bis zu völlig offenen Systemen reichen, in die bei fortschreitender Reduktion frisches Sulfat zugeführt wird (Typ 2). Der Unterschied in den charakteristischen Verteilungen setzt voraus, daß die Stärke der kinetischen Sulfat-Sulfid-Isotopen-Wirkung auf die Reduktion in beiden Fällen verschieden ist. Dieser Unterschied wurde bereits wegen der Widersprüche zwischen den verschiedenen S³⁴-Werten heutiger mariner Sedimente und Laborexperimente vermutet. Der Unterschied in der Isotopen-Wirkung kann durch das Modell von Rees (1973) für kontinuierlich ablaufende Sulfat-Reduktion erklärt werden. Geringes Nahrungsangebot und ungestörte, gleichbleibende Bakterien-Populationen in offenen Systemen neigen zur Erzeugung stärkerer Fraktionierungen.

     

Trace-element heterogeneity in rutile linked to dislocation structures: Implications for Zr-in-rutile geothermometry

The trace-element composition of rutile is commonly used to constrain P–T–t conditions for a wide range of metamorphic systems. However, recent studies have demonstrated the redistribution of trace elements in rutile via high-diffusivity pathways and dislocation-impurity associations related to the formation and evolution of microstructures. Here, we investigate trace-element migration in low-angle boundaries formed by dislocation creep in rutile within an omphacite vein of the Lago di Cignana unit (Western Alps, Italy). Zr-in-rutile thermometry and inclusions of quartz in rutile and of coesite in omphacite constrain the conditions of rutile deformation to around the prograde boundary from high pressure to ultra-high pressure (~2.7 GPa) at temperatures of 500–565°C. Crystal-plastic deformation of a large rutile grain results in low-angle boundaries that generate a total misorientation of ~25°. Dislocations constituting one of these low-angle boundaries are enriched in common and uncommon trace elements, including Fe and Ca, providing evidence for the diffusion and trapping of trace elements along the dislocation cores. The role of dislocation microstructures as fast-diffusion pathways must be evaluated when applying high-resolution analytical procedures as compositional disturbances might lead to erroneous interpretations for Ca and Fe. In contrast, our results indicate a trapping mechanism for Zr.     

Trace element systematics in granulite facies rutile: implications for Zr geothermometry and provenance studies

Metamorphic rutile from granulite facies metapelitic rocks of the Archean Pikwitonei Granulite Domain (PGD; Manitoba, Canada) provides constraints on the systematics of trace elements in rutile during high‐temperature conditions and subsequent slow cooling. Compositional profiles and maps of the Zr concentrations in rutile grains (120–600 μm) from three metapelitic gneisses were acquired by electron probe micro‐analysis, using a spatial resolution of down to 2 μm. Simultaneously, profiles were analysed for Nb, Cr and V, which have significantly different diffusion characteristics in rutile. The profiles of all elements show relatively homogeneous concentrations within most grains, but significant inter‐grain differences even within a single thin section. Some rutile grains display a slight concentration decrease from a neighbouring garnet towards the matrix for all measured elements. The lack of diffusion profiles for all analysed elements shows that these are highly immobile in rutile and that distributions of these elements are primary and preserve prograde information. The Nb and Cr concentrations overlap with ranges that are ascribed to different provenances indicating that source discrimination based on these elements is not possible in all cases. High retentiveness for Zr implies that the Zr‐in‐rutile geothermometer is highly robust to diffusive re‐equilibration, even during very slow cooling (<2 °C Ma^?1) from granulite facies conditions. Most grains have high Zr contents (3000–4600 ppm). Differences between high Zr contents suggest that during growth under vapour‐absent conditions there may not be saturation of Zr in rutile, even if zircon is present. Therefore, several rutile grains need to be analysed in a sample to obtain a useful minimum peak temperature. The highest Zr concentrations correspond to ～900 °C. This is significantly higher than previous peak temperature estimates of 820 °C based on two‐feldspar thermometry. On a regional scale this implies that part of the PGD was affected by ultra‐high temperature (UHT) metamorphism. It also implies that rutile is able to preserve primary compositions even to UHT conditions. This study shows that, if combined with textural information, Zr‐in‐rutile has the potential to be a very useful tool for estimating rutile crystallization temperatures and peak metamorphic conditions. For granulite facies rocks, Zr‐in‐rutile yields more reliable peak metamorphic temperatures than most other exchange geothermometers, which tend to partially re‐equilibrate by diffusion during cooling.