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Thermal conductivity (lambda) is an essential physical property of minerals and rocks and fundamental in constraining the thermal field of the lithosphere. In case that adequate samples to measure lambda are not available, it could be indirectly inferred from calculation. One of the most widely applied indirect methods for rocks involve modal mineralogy and porosity as parameters that are incorporated into mathematical mean or mixing models. Robust inferences from these approaches for crystalline rocks were impeded by a small number of studied samples or restriction to certain rock types. We employ this method and examine its applicability to low-porosity plutonic rocks by calculating bulk thermal conductivity lambda(b) for 45 samples covering the entire range from gabbro/diorite to granite. We show that the use of the harmonic-mean model for both rock matrix and porosity provided a good match between lambda(b.meas) and lambda(b.calc) of <10% deviation (2 sigma), with relative and absolute errors amounting to 1.49.7% and 4.44.9%, respectively. The results of our study constitute a big step forward to a robust conclusion on the overall applicability of the harmonic-mean model for inferring lambda(b) of isotropic, low-porosity, mafic to silicic plutonic and metamorphic rocks with an acceptable magnitude of error. Drill cuttings and enclaves form particularly interesting objects for application of this method, as they are poorly suited for direct measurement. Well-derived lambda values for those rocks would permit to calculate heat flow and to model more profoundly the thermal state of the deeper lithosphere.
The mildly peraluminous granite of Seiffen, in the eastern Erzgebirge of Germany, is exposed by drillcores and associated with an abandoned Sri mine. The granite is of Stefanian age, with overlapping Th-U-total Pb monazite (302 +/- 4 Ma) and K-Ar siderophyllite ages (301 +/- 5 Ma). It is among the youngest granites in the Erzgebirge, emplaced in an extensional setting. The medium-grained, equigranular granite classifies as high-F, low-P Li-mica granite of A-type affinity. It is spatially associated with a high-Si rhyolitic microgranite, documenting the shallow intrusion level of this igneous association. Zircon, monazite-(Ce), and xenotime-(Y) constitute important radioactive accessory minerals in the granite, hosting the major proportions (> 80-90%) of the bulk-rock budgets of the REE, Y, and Th. A significant percentage of U (40-50%) may reside within unidentified phases or precipitated along grain boundaries. The most uncommon accessory phase is late-magmatic ytterbian xenotime-(Y) containing up to 11.2 wt% Yb2O3, in addition to 7.3 wt% Er2O3 and 7.9 wt% Dy2O3. The Seiffen granite (epsilon(Nd(300)) = -4.6) is geochemically evolved and rich in Sri (23-63 ppm) and W (11-14 ppm). It contains elevated to high concentrations of incompatible lithophile elements such as F, Li, Ga, Rb, Y, Nb, Cs, REE, Th, and U, thus having much in common chemically with subvolcanic ongonites. The most prominent compositional feature is the strong enrichment (in ppm) in Be (51-55) and Ta (23-28). The granite exhibits flat chondrite-normalized REE patterns (La-N/Lu-N = 1.35-1.48) and a moderate negative Eu anomaly (Eu/Eu* = 0.12-0.13). Indications for alteration-induced, postmagmatic disturbances of initial elemental abundances are weak and mainly relate to the ore-forming elements Sri and U.
Fractional crystallization of peraluminous F- and H(2)O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions. We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.
Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona, area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Otztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO4O) and Al-OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO4OH), are discussed in the light of fH(2)O- and fO(2)-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO-FeO/Fe2O3-TiO2-SiO2-H2O-O-2 (CFTSH) and CaO-FeO/Fe2O3-Al2O3- SiO2-H2O-O-2 (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite +quartz+ H2O = amphibole +titanite and oxidation reactions such as amphibole + ilmenite + O-2 = titanite + magnetite + quartz + H2O during amphibolite-facies metamorphism, or, as in the case of the Otztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH(2)O and fO(2) to be high for titanite formation, which is also in accordance with equilibria involving Al-OH titanite. This study shows that, in addition to P, T, bulk-rock composition and composition of the coexisting fluid, fO(2) and fH(2)O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.
A comprehensive survey of the accessory-mineral assemblages in Variscan granites of the German Erzgebirge and Pan-African granites from Jordan revealed the occurrence of intermediate solid solutions of the tetragonal thorite- xenotime-zircon-coffinite mineral group with partially novel compositions. These solid solutions preferentially formed in evolved and metasomatically altered, P-poor leucogranites of either I- or A-type affinity. Thorite from the Erzgebirge contained up to 18-8 Wt-% Y2O3, 16.1 wt.% ZrO2, and 23.3 Wt-% UO2. Xenotime and zircon have incorporated Th in abundances up to 36.3 wt.% and 41.8 wt.% ThO2, respectively. Extended compositional gradation with only minor gaps is confined to hydrated members of this mineral group, and is observed to exist between thorite and xenotime, thorite and coffinite, and Y-HREE-bearing thorite and zircon. Complex, hydrous solid solutions containing elevated abundances of three or more of the endmembers are subordinate. Previously reported intermediate solid solutions between anhydrous zircon and xenotime, and anhydrous zircon and thorite, are not observed and are in conflict with experimental work demonstrating very limited miscibility between anhydrous species of endmember composition. The majority of hydrous intermediate solid solutions in the Th-Y-Zr-U system are likely thermodynamically unstable. Instead, they are probably metastable responses to unusual physico-chemical conditions involving various parameters and conditions, the relative importance of which is incompletely known. Leaching and dissolution of preexisting accessory phases during interaction with F-bearing hydrous fluids enriched in Th, Y(HREE), Zr, and/or U, and common deposition of the various elements at disequilibrium (supersaturation) seems to play a key role, but other processes may be of similar importance. Experimental work involving hydrous conditions and complex systems composed of more than two endmembers are needed to shed light into the stability relations of the chemically uncommon compositions treated in this study.
The strongly peraluminous and P-rich, protolithionite and zinnwaldite leucogranites from Podlesi, western Krusne Hory Mts., Czech Republic, contain accessory zircon with extraordinary enrichment of several elements, which constitute trace elements in common zircon. Elements showing a not yet reported anomalous enrichment include P (up to 20.2 wt.% P2O5; equivalent to 0.60 apfu, formula calculated on the basis of 4 oxygen atoms), Bi (up to 9.0 wt.% Bi2O3; 0.086 apfu), Nb (up to 6.7 wt.% Nb2O5, 0.12 apfu), Sc (up to 3.45 wt.% Sc2O3; 0.10 apfu), U (up to 14.8 wt.% UO2; 0.12 apfu) and F (up to 3.81 wt.% F; 0.42 apfu). Strong enrichment of P preferentially involved the berlinite-type substitution (2 Si4+ double left right arrow P5+ + Al3+) implying that significant Al may enter the Si position in zircon. Incorporation of other exotic elements is primarily governed by the xenotime (Si4++Zr4+ double left right arrow P5++Y3+), pretulite (Sc3++P5+ double left right arrow Zr4++Si4+), brabantite-type (Ca2++(U, Th)(4+)+2P(5+) double left right arrow 2Zr(4+)+2Si(4+)), and ximengite-type (Bi3++P5+double left right arrow Zr4++Si4+) substitution reactions. One part of the anomalous zircons formed late-magmatically, from a strongly peraluminous, P-F-U-rich hydrous residual melt that gave rise to the zinnwaldite granite. Interaction with aggressive residual fluids and metamictization have further aided in element enrichment or depletion, particularly in altered parts of zircon contained in the protolithionite granite. Most of the zircon from F-rich greisens have a composition close to endmember ZrSiO4 and are chemically distinct from zircon in its granite parent. This discrepancy implies that at Podlesi, granitic zircon became unstable and completely dissolved during greisenization. Part of the mobilized elements was reprecipitated in newly grown, hydrothermal zircon.
A localized dehydration zone, Sondrum stone quarry, Halmstad, SW Sweden, consists of a central, 1 m wide granitic pegmatoid dyke, on either side of which extends a 2.5-3 m wide dehydration zone (650-700 degrees C; 800 MPa; orthopyroxene-clinopyroxene-biotite-amphibole-garnet) overprinting a local migmatized granitic gneiss (amphibole-biotite- garnet). Whole-rock chemistry indicates that dehydration of the granitic gneiss was predominantly isochemical. Exceptions include [Y + heavy rare earth elements (HREE)], Ba, Sr, and F, which are markedly depleted throughout the dehydration zone. Systematic trends in the silicate and fluorapatite mineral chemistry across the dehydration zone include depletion in Fe, (Y + HREE), Na, K, F, and Cl, and enrichment in Mg, Mn, Ca, and Ti. Fluid inclusion chemistry is similar in all three zones and indicates the presence of a fluid containing CO2, NaCl, and H2O components. Water activities in the dehydration zone average 0.36, or XH2O = 0.25. All lines of evidence suggest that the formation of the dehydration zone was due to advective transport of a CO2-rich fluid with a minor NaCl brine component originating from a tectonic fracture. Fluid infiltration resulted in the localized partial breakdown of biotite and amphiboles to pyroxenes releasing Ti and Ca, which were partitioned into the remaining biotite and amphibole, as well as uniform depletion in (Y + HREE), Ba, Sr, Cl, and F. At some later stage, H2O-rich fluids (H2O activity > 0.8) gave rise to localized partial melting and the probable injection of a granitic melt into the tectonic fracture, which resulted in the biotite and amphibole recording a diffusion profile for F across the dehydration zone into the granitic gneiss as well as a diffusion profile in Fe, Mn, and Mg for all Fe-Mg silicate minerals within 100 cm of the pegmatoid dyke
In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H2SO4 solutions at temperatures of 300, 600, and 900 degrees C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H2SO4 experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H2SO4 experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600 degrees C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10-20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H2SO4 experiment at 900 degrees C and 1,000 MPa indicates a pervasive nano- porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution-reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions
Quartz crystals from topaz-zinnwaldite-albite granites from Zinnwald (Erzgebirge, Germany) contain, in addition to primary and secondary fluid inclusions (FIs), abundant crystalline silicate-melt inclusions (MIs) with diameters up to 200 mum. These MIs represent various stages of evolution of a highly evolved melt system that finally gave rise to granite-related Sn-W mineralization. The combination of special experimental techniques with confocal laser Raman- microprobe spectroscopy and EMPA permits precise measurement of elevated contents of H2O, F, and B in re-homogenized MIs. The contents of H2O and F were observed to increase from 3 to 30 and 1.9 to 6.4 wt%, respectively, during magma differentiation. However, there is a second MI group, very rich in H2O, with values up to 55 wt% H2O and an F concentration of approximately 3 wt%. Ongoing enrichment of volatiles H2O, F, B, and Cl and of Cs and Rb can be explained in terms of magma differentiation triggered by fractional crystallization and thus, is suggested to reflect elemental abundances in natural magmas, and not boundary-layer melts. Partitioning between melt and cogenetic fluids has further modified the magmatic concentrations of some elements, particularly Sn. The coexistence of two types of MIs with primary FIs indicates fluid saturation early in the history of magma crystallization, connected with a continuous sequestration of Sn, F, and B. The results of this study provide additional evidence for the extraordinary importance of the interplay of H2O, F, and B in the enrichment of Sn during magma differentiation by decreasing the viscosity of and increasing the diffusivity in the melts as well as by the formation of various stable fluoride complexes in the melt and coexisting fluid