Provenance and Magmatic-Metamorphic Evolution of a Variscan Island-Arc Complex: Constraints from U-Pb Dating, Petrology, and Geospeedometry of the Kyffhauser Crystalline Complex, Central Germany

The Kyffhäuser Crystalline Complex, Central Germany, formspart of the Mid-German Crystalline Rise, which is assumed torepresent the Variscan collision zone between the East Avalonianterrane and the Armorican terrane assemblage. High-precisionU–Pb zircon and monazite dating indicates that sedimentaryrocks of the Kyffhäuser Crystalline Complex are youngerthan c. 470 Ma and were intruded by gabbros and diorites between345 ± 4 and 340 ± 1 Ma. These intrusions had magmatictemperatures between 850 and 900°C, and caused a contactmetamorphic overprint of the sediments at P–T conditionsof 690–750°C and 5–7 kbar, corresponding toan intrusion depth of 19–25 km. At 337 ± 1 Ma themagmatic–metamorphic suite was intruded by granites, syenitesand diorites at a shallow crustal level of some 7–11 km.This is inferred from a diorite, and conforms to P–T pathsobtained from the metasediments, indicating a nearly isothermaldecompression from 5–7 to 2–4 kbar at 690–750°C.Subsequently, the metamorphic–magmatic sequence underwentaccelerated cooling to below 400°C, as constrained by garnetgeospeedometry and a previously published K–Ar muscoviteage of 333 ± 7 Ma. With respect to P–T–D–tdata from surrounding units, rapid exhumation of the KCC canbe interpreted to result from NW-directed crustal shorteningduring the Viséan. KEY WORDS: contact metamorphism; U–Pb dating; hornblende; garnet; Mid-German Crystalline Rise; P–T pseudosection     

Polymetamorphism in garnet micaschists of the Saualpe Eclogite Unit (Eastern Alps,Austria), resolved by automated SEM methods and EMP–Th–U–Pb monazite dating

Polymetamorphic garnet micaschists from the Austroalpine Saualpe Eclogite Unit (Kärnten, Austria, Eastern Alps) display complex microstructural and mineral–chemical relationships. Automated scanning electron microscopy routines with energy dispersive X‐ray (EDX) spectral mapping were applied for monazite detection and garnet mineral–chemical characterization. When the Fe, Mg, Mn and Ca element wt% compositions are used as generic labels for garnet EDX spectra, complex zonations and porphyroblast generations can be resolved in complete thin sections for selective electron‐microprobe analyses. Two garnet porphyroblast generations and diverse monazite age populations have been revealed in low‐Ca and high‐Al‐metapelites. Garnet 1 has decreasing Mn, constant Ca and significantly increasing Mg from cores to rims. Geothermobarometry of garnet 1 assemblages signals a crystallization along a M1 prograde metamorphism at ~650 °C/6–8 kbar. Sporadic monazite 1 crystallization started at c. 320 Ma. Subsequent pervasive 300–250 Ma high‐Y and high‐Gd monazite 1 formation during decompression coincided with the intrusion of Permian and Early Triassic pegmatites. Monazite 1 crystallized along the margin of garnet 1. Coronas of apatite and allanite around the large 320–250 Ma monazite signal a retrogressive stage. These microstructures suggest a Carboniferous‐to‐Early‐Permian age for the prograde M1 event with garnet 1. Such a M1 event at an intermediate‐P/T gradient has not yet been described from the Saualpe, and preceded a Permo‐Triassic low‐P stage. The M2 event with garnet 2 postdates the corona formation around Permian monazite. Garnet 2 displays first increasing X_Ca at decreasing X_Mg, then increasing X_Ca and X_Mg, and finally decreasing X_Ca with increasing X_Mg, always at high Ca and Mg, and low Mn. This records a P–T evolution which passed through eclogite facies conditions and reached maximum temperatures at ~750 °C/14 kbar during decompression‐heating. A monazite 2 population (94–86 Ma) with lower Y and Gd contents crystallized at decreasing pressure during the Cretaceous (Eo‐Alpine) metamorphism M2 at a high‐P/T gradient. The Saualpe Eclogite Unit underwent two distinct clockwise metamorphic cycles at different P–T conditions, related to continental collisions under different thermal regimes. This led to a characteristic distribution pattern of monazite ages in this unit which is different from other Austroalpine basement areas.     

Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

Intergranular diffusion rates from the analysis of garnet surfaces: Implications for metamorphic equilibration

Novel approaches to garnet analysis have been used to assess rates of intergranular diffusion between different matrix phases and garnet porphyroblasts in a regionally metamorphosed staurolite‐mica‐schist from the Barrovian‐type area in Scotland. X‐ray maps and chemical traverses of planar porphyroblast surfaces reveal chemical heterogeneity of the garnet grain boundary linked to the nature of the adjacent matrix phase. The garnet preserves evidence of low temperature retrograde exchange with matrix minerals and diffusion profiles documenting cation movement along the garnet boundaries. Garnet–quartz and garnet–plagioclase boundaries preserve evidence of sluggish Mg, Mn and Fe diffusion at comparable rates to volume diffusion in garnet, whereas diffusion along garnet–biotite interfaces is much more effective. Evidence of particularly slow Al transport, probably coupled to Fe³⁺ exchange, is locally preserved on garnet surfaces adjacent to Fe‐oxide phases. The Ca distribution on the garnet surface shows the most complex behaviour, with long‐wavelength heterogeneities apparently unrelated to the matrix grain boundaries. This implies that the Ca content of garnet is controlled by local availability and is thought likely to reflect disequilibrium established during garnet growth. Geochemical anomalies on the garnet surfaces are also linked to the location of triple junctions between the porphyroblasts and the matrix phases, and imply enhanced transport along these channels. The slow rates of intergranular diffusion and the characteristics of different boundary types may explain many features associated with the prograde growth of garnet porphyroblasts. Thus, minerals such as quartz, Fe‐oxides and plagioclase whose boundaries with garnet are characterized by slow intergranular diffusion rates appear to be preferentially trapped as inclusions within porphyroblasts. As such grain boundary diffusion rates may be a significant kinetic impediment to metamorphic equilibrium and garnet may struggle to maintain chemical and textural equilibrium during growth in pelites.     

Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

Oxygen isotope speedometry in granulite facies garnet recording fluid/melt–rock interaction (Sør Rondane Mountains,East Antarctica)

In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ¹⁸O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ¹⁸O = ~15‰) to the rim (δ¹⁸O = ~11‰) suggests that the ¹⁸O/¹⁶O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the ¹⁸O/¹⁶O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ¹⁸O value of the garnet rim, together with the previously reported low δ¹⁸O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ¹⁸O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.     

Intragrain oxygen isotope zoning in titanite by SIMS: Cooling rates and fluid infiltration along the Carthage‐Colton Mylonite Zone,Adirondack Mountains,NY, USA

Oxygen isotopes are an attractive target for zoning studies because of the ubiquity of oxygen‐bearing minerals and the dependence of mineral ¹⁸O/¹⁶O ratios on temperature and fluid composition. In this study, subtle intragrain oxygen isotope zoning in titanite is resolved at the 10‐μm scale by secondary ion mass spectrometry. The patterns of δ¹⁸O zoning differ depending on microstructural context of individual grains and reflect multiple processes, including diffusive oxygen exchange, partial recrystallization, grain‐size reduction, and grain growth. Using the chronological framework provided by structural relations, these processes can be related to specific events during the Grenville orogeny. Titanite was sampled from two outcrops within the Carthage‐Colton Mylonite Zone (CCMZ), a long‐lived shear zone that ultimately accommodated exhumation of the Adirondack Highlands from beneath the Adirondack Lowlands during the Ottawan phase (1090–1020 Ma) of the Grenville orogeny. Titanite is hosted in the Diana metasyenite complex, which preserves three sequentially developed fabrics: an early NW‐dipping protomylonitic fabric (S₁) is crosscut by near‐vertical ultramylonitic shear zones (S₂), which are locally reoriented by a NNW‐dipping mylonitic fabric (S₃). Texturally early titanite (pre‐S₂) shows diffusion‐dominated δ¹⁸O zoning that records cooling from peak Ottawan, granulite‐facies conditions. Numerical diffusion models in the program Fast Grain Boundary yield good fits to observed δ¹⁸O profiles for cooling rates of 50 ± 20 °C Ma^?1, which are considerably faster than the 1–5 °C Ma^?1 cooling rates previously inferred for the Adirondack Highlands from regional thermochronology. High cooling rates are consistent with an episode of rapid shearing and exhumation along the CCMZ during gravitational collapse of the Ottawan orogen at c. 1050 Ma. Texturally later titanite (syn‐S₂) has higher overall δ¹⁸O and shows a transition from diffusion‐dominated to recrystallization‐dominated δ¹⁸O zoning, indicating infiltration of elevated‐δ¹⁸O fluids along S₂ shear zones and continued shearing below the blocking temperature for oxygen (~≤500 °C for grain sizes at the study site). The texturally latest titanite (post‐S₃) has growth‐dominated δ¹⁸O zoning, consistent with porphyroblastic grain growth following cessation of shearing along the Harrisville segment of the CCMZ.     

我国砂岩型铀矿分带特征研究现状及存在问题

作为一种重要的国家战略资源,砂岩型铀矿床是当今世界上最重要的铀矿床类型之一。本文详细地介绍了砂岩型铀矿在国内外的分布特征及占比情况,并对外生地质作用矿床类型中表生流体作用形成的层间渗透砂岩型和潜水渗透砂岩型铀矿床进行了讨论,发现层间渗透砂岩型铀矿床在外表颜色、矿物组合以及地球化学等方面均具有明显的氧化-还原分带现象,此外,矿床内部还具有细菌分带现象。颜色分带在氧化带、氧化-还原过渡带以及还原带之间具有明显不同的特征;矿物组合在不同分带之间各不相同;地球化学分带表现为U、TOC含量以及Fe~(2+)/Fe~(3+)、Th/U比值在各分带之间差异较大。此外,硫酸盐还原菌、硫杆菌、铁细菌及硝化菌等细菌在不同分带之间的数量相差悬殊,而且硫酸盐还原菌数量与TOC呈明显正相关性。通过矿化带内的碳、硫同位素分析,发现硫酸盐还原菌参与了成矿过程,推测其可能是导致碳、硫同位素分馏的主要因素。总体来看,颜色分带、矿物分带、地球化学分带以及细菌分带均与氧化-还原分带呈耦合关系。本文通过总结层间渗透砂岩型和潜水渗透砂岩型铀矿床的成矿模式和当前分带研究中存在的问题,提出了由细菌、地球化学反应参与的砂岩型铀矿床成矿机理,以及未来亟需解决的若干关键科学问题。典型砂岩型铀矿床的分带现象在物、化、探、遥等领域的异常响应对寻找砂岩型铀矿床具有重要的指导意义。