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A system based on variation of the octahedrally coordinated cations is proposed for graphical presentation and subdivision of tri- and dioctahedral K micas, which makes use of elemental differences (in a.p.f.u.): (Mg - Li) [= mgli] and (Fe-tot + Mn + Ti - Al-VI) [= feal]. All common true tri- and dioctahedral K micas are shown in a single polygon outlined by seven main compositional points forming its vertices. Sequentially clockwise, starting from Mg-3 (phlogopite), these points are: Mg2.5Al0.5, Al(2.167)square(0.833), Al1.75Li1.25, Li2Al (polylithionite), Fe22+Li, and Fe-3(2+) (annite). Trilithionite (Li1.5Al1.5), Li1.5Fe2+Al0.5, Fe22+Mg, and Mg2Fe2+ are also located on the perimeter of the polygon. IMA-siderophyllite (Fe22+Al) and muscovite (Al(2)square) plot inside. The classification conforms with the IMA-approved mica nomenclature and differentiates among the following mica species according to their position in a diagram consisting of nigh and feal axes plotted orthogonally; trioctahedral: phlogopite, biotite, siderophyllite, annite, zinnwaldite, lepidolite and tainiolite: dioctahedral: muscovite, phengite and celadonite. Potassium micas with [Si] <2.5 a.p.f.u. including IMA-siderophyllite, KFe22+AlAl2Si2O10(OH)(2), and IMA-eastonite, KMg2AlAl2Si2O10(OH)(2) seem not to form in nature. The proposed subdivision has several advantages. All common true, trioctahedral and dioctahedral K micas, whether Li-bearing or Li-free, are shown within one diagram, which is easy to use and gives every mica composition an unambiguously defined name. Mica analyses with Fe2+, Fe3+, Fe2+ + Fe3+, or Fe-tot can be considered, which is particularly Valuable for microprobe analyses. It facilitates easy reconstruction of evolutionary pathways of mica compositions during crystallization, a feature having key importance in petrologically oriented research. Equally important, the subdivision has great potential for understanding many of the crystal-chemistry features of the K micas. In turn this may allow one to recognize and discriminate the extent to which crystal chemistry or bulk composition controls the occurrence of some seemingly possible or hypothetical K mica
Accessory minerals of the Caledonian Rumburk granite are investigated to gain insight into its magmatic and post-magmatic evolution history. Recent geothermometers calibrated for trace elements in rutile (Zr), zircon (Ti), and quartz (Ti) were used to determine mineral-formation temperatures, which are compared with T data obtained from melt and fluid-inclusion Studies on quartz. Improved electron-microprobe analytical conditions allowed distinguishing several generations of rutile. Submicron-sized rutile needles included in quartz crystallized at around 739 +/- 13 degrees C and, thus, are evidently magmatic. Simultaneous crystallization of the high-T rutile and quartz is the favoured concept compared with an exsolution model for the needles. Th-U-total Pb dating of xenotime-(Y) by electron microprobe yielded a bimodal age distribution of 494 +/- 8 Ma (2 sigma; n = 44) and 311 +/- 8 Ma (2 sigma; n = 48), which is missing in monazite-(Ce). The older age correlates with the early Ordovician granite emplacement age Suggested by earlier isotopic Studies. The younger Carboniferous age also may be geologically reasonable, because the granite experienced a minor tectonothermal overprint during the Variscan orogenesis. However, whether this event has caused the resetting of the isotopic system in the xenotime is uncertain. This also holds for the age of the partial breakdown of monazite and xenotime into reaction coronas composed of fluorapatite, allanite-(Ce), epidote +/- clinozoisite. This alteration assemblage was likely produced already during autometasomatic reworking of the solidifying magma in Ordovician time, but it cannot be excluded that it relates to a Carboniferous fluid imprint connected with late-Variscan processes.
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
Fault zones are the locations where motion of tectonic plates, often associated with earthquakes, is accommodated. Despite a rapid increase in the understanding of faults in the last decades, our knowledge of their geometry, petrophysical properties, and controlling processes remains incomplete. The central questions addressed here in our study of the Dead Sea Transform (DST) in the Middle East are as follows: (1) What are the structure and kinematics of a large fault zone? (2) What controls its structure and kinematics? (3) How does the DST compare to other plate boundary fault zones? The DST has accommodated a total of 105 km of left-lateral transform motion between the African and Arabian plates since early Miocene (similar to 20 Ma). The DST segment between the Dead Sea and the Red Sea, called the Arava/Araba Fault (AF), is studied here using a multidisciplinary and multiscale approach from the mu m to the plate tectonic scale. We observe that under the DST a narrow, subvertical zone cuts through crust and lithosphere. First, from west to east the crustal thickness increases smoothly from 26 to 39 km, and a subhorizontal lower crustal reflector is detected east of the AF. Second, several faults exist in the upper crust in a 40 km wide zone centered on the AF, but none have kilometer-size zones of decreased seismic velocities or zones of high electrical conductivities in the upper crust expected for large damage zones. Third, the AF is the main branch of the DST system, even though it has accommodated only a part (up to 60 km) of the overall 105 km of sinistral plate motion. Fourth, the AF acts as a barrier to fluids to a depth of 4 km, and the lithology changes abruptly across it. Fifth, in the top few hundred meters of the AF a locally transpressional regime is observed in a 100-300 m wide zone of deformed and displaced material, bordered by subparallel faults forming a positive flower structure. Other segments of the AF have a transtensional character with small pull-aparts along them. The damage zones of the individual faults are only 5-20 m wide at this depth range. Sixth, two areas on the AF show mesoscale to microscale faulting and veining in limestone sequences with faulting depths between 2 and 5 km. Seventh, fluids in the AF are carried downward into the fault zone. Only a minor fraction of fluids is derived from ascending hydrothermal fluids. However, we found that on the kilometer scale the AF does not act as an important fluid conduit. Most of these findings are corroborated using thermomechanical modeling where shear deformation in the upper crust is localized in one or two major faults; at larger depth, shear deformation occurs in a 20-40 km wide zone with a mechanically weak decoupling zone extending subvertically through the entire lithosphere.
The Aue-Schwarzenberg Granite Zone (ASGZ), in the western Erzgebirge of Germany, is composed of small, late- Variscan F-poor biotite and two-mica granites. The biotite granites (Aue granite suite, Beierfeld, Bernsbach) are weakly to mildly peraluminous (A/CNK = 1.07-1.14; 70-76 wt% SiO2), display similar Sr-87/Sr-86 initial ratios (0.7065-0.7077; t = 325 Ma), and exhibit a narrow range in epsilon Nd-325 (-2.6 to -3.5). They are closely affiliated compositionally with the biotite granites in the distant, more voluminous Nejdek massif (Czech Republic). The two-mica granites (Schwarzenberg granite suite, Lauter) are Si-rich (74-77 wt% SiO2) and mildly to strongly peraluminous (A/CNK = 1.17- 1.26). The granites from Schwarzenberg Lire distinctly higher in their Sr(i)ratios (0.709-0.713; t = 325 Ma) and possess lower values of epsilon Nd-325 (-4.9 to -5.2) relative to the biotite granites. The Lauter granites have a Nd-isotopic composition between -3.6 and -4.0 (t = 325 Ma). Mean Th-U-total Pb uraninite ages (Ma +/- 2 sigma) obtained for the granites from the Aue Suite (324.3 +/- 3. 1), Beierfeld (323.7 +/- 3.1), Bernsbach (320.7 +/- 2.9), Schwarzenberg (323.3 +/- 2.4), and the Kirchberg granite al Burkersdorf (322.7 +/- 3.5) indicate that magmatism in the ASGZ commenced in the Namurian and took place early within the major episode of granite formation in the Erzgebirge-Vogtland zone (327-318 Ma). Geochemical and mineralogical patterns of variably altered samples imply that the ASGZ granites are unlikely to have significantly contributed to the formation of spatially associated metalliferous ore deposits (Sn, W, Mo, Ph, Zn, Bi, Co, Ni), except for uranium. In particular the Aue granite suite should have served as major Source for U accumulated in the economically important post-granitic deposits of Schneeberg and Schlema-Alberoda.
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.
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.
Annite and Fe-rich siderophyllite constitute the rock-forming micas in the late-Variscan composite granite pluton of Konigshain, Lausitz, Germany. This multiphase pluton is composed of three fractionated, but not chemically specialized monzogranite types, which contain lithophile elements such as Li, Rb, Cs, Sn, and F in average quantities. Abundant miarolitic pegmatites of the NYF family with a broad diversity of rare minerals occur in the apical part of the pluton. These pegmatitic cavities locally contain di- and trioctabedral micas as well as cation-deficient micas. Trioctahedral micas comprise F-rich manganoan lithian siderophyllite to manganoan zinnwaldite, zinnwaldite, and minor lepidolite. The formula [calculated on the basis of 22 anion valencies and 2 (F + OH + Cl)] of the most Mn-rich siderophyllite is (K0.85Rb0.08Na0.04)(0.97)(Al0.99Li0.91Fe0.51Mn0.42Ti0.01Zn0.01)(2.85) (Si3.21Al0.79)(4)O- 10(F1.80OH0.19Cl0.01)(2). This mica constitutes one of the most Mn-rich siderophyllite compositions reported to date. The lithium micas poorer in Mn are distinguished by elevated concentrations of Rb (up to 2.5 wt % Rb2O), CS (UP to 1.2 wt % Cs2O), and F (up to 9.6 wt %). This fluorine content is probably consistent with the maximum possible F occupation of 2 of the (F,OH,Cl)-site. The structural formula of the most Li-rich lepidolite is (K0.83Rb0.07Cs0.03)(0.93) (Li1.62Al1.00Fe0.38)(3.00)(Si3.62Al0.38)(4) O-10(F1.91OH0.09)(2). During hydrothermal alteration, lepidolite and zinnwaldite became partially depleted in K, Li, Rb, Cs, and F and gradually transformed into cation-deficient micas (lithian phengite to illite of phengitic affinity)
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.
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.