Significance of selective crystal entrainment and differential crystal-melt separation in petrogenesis of granites from the Tongbai orogen

Partial melting has been shown to be an important mechanism for intracrustal differentiation and granite petrogenesis. However, a series of compositional differences between granitic melt from experiments and natural granites indicate that the processes of crustal differentiation are complex. To shed light on factors that control the processes of crustal differentiation, and then the compositions of granitic magma, a combined study of petrology and geochemistry was carried out for granites (in the forms of granitic veins and parautochthonous granite) from a granulite terrane in the Tongbai orogen, China. These granites are characterized by high SiO₂ (>72 wt%) and low FeO and MgO (<4 wt%) with low Na₂O/K₂O ratios (<0.7). Minerals in these granites show variable microstructures and compositions. Phase equilibrium modelling using P–T pseudosections shows that neither anatectic melts nor fractionated melts match the compositions of the target granites, challenging the conventional paradigm that granites are the crystallized product of pure granitic melts. Based on the microstructural features of minerals in the granites, and a comparison of their compositions with crystallized minerals from anatectic melts and minerals in granulites, the minerals in these granitoids are considered to have three origins. The first is entrained garnets, which show comparable compositions with those in host granulites. The second is early crystallized mineral from melts, which include large plagioclase and K-feldspar (with high Ca contents) crystals as well as a part of biotite whose compositions can be reproduced by crystallization of the anatectic melts. The compositions of other minerals such as small grained plagioclase, K-feldspar and anorthoclase in the granites with low Ca contents are not well reconstructed, so they are considered as the third origin of crystallized products of fractionated melts. The results of mass balance calculation show that the compositions of these granites can be produced by mixing between different proportions of crystallized minerals and fractionated melts with variable amounts of entrained minerals. However, the calculated modal proportions of different crystallized minerals (plagioclase, K-feldspar, biotite and quartz) in the granites are significantly different from those predicted by melt crystallization modelling. Specifically, some rocks have lower modes of biotite and plagioclase, whereas others show lower K-feldspar modes than those produced by melt crystallization. This indicates that the crystallized minerals would be differentially separated from the primary magmas to form the evolved magmas that produce these granites. Therefore, the crystal entrainment and differential melt-crystal separation make important contributions to the composition of the target granites. Compared with leucogranites worldwide, the target granites show comparable compositions. As such, the leucogranites may form through the crystal fractionation of primary granitic magmas at different extents in addition to variable degrees of partial melting.     

Experimental study of a biotite-bearing granitic system under water-saturated and water-undersaturated conditions

Phase relationships in haplogranitic melts containing ferromagnesian minerals were investigated in the temperature range 760–850°C, atP _total=2 kbar, =0.25 1.00, and at NNO buffer conditions. The compositions of coexisting biotite, orthopyroxene, magnetite and granitic melt were determined by electron microprobe. Biotite was the only Fe–Mg mineral in the starting material. It disappeared in water-undersaturated melts at temperatures above 830°C and in melts saturated with water above 810°C. Magnetite was present in all runs. Orthopyroxene became stable between 780 and 800°C. The Mg/(Mg+Fe) ratios of biotite (0,63–0,72) and orthopyroxene (0,63–0,71) are similar in water-saturated and undersaturated melts at comparable temperatures and increase slightly with increasing temperature. The solubility of Mg in haplogranitic melts is very low (0,07–0,24 wt% MgO). It increases slightly with temperature and is independent of the prevailing water activity. The solubility of Fe is low (0,91–1,37 wt% FeO); it also increases with increasing temperature, and it is higher in water-saturated than in water-undersaturated melts.     

Thermodynamic analysis of the system Na2O-K2O-CaO-Al2O3-SiO2-H2O-F2O?1: Stability of fluorine-bearing minerals in felsic igneous suites

Thermodynamic analysis of the system Na₂O-K₂O-CaO-Al₂O₃-SiO₂-H₂O-F₂O_–1 provides phase equilibria and solidus compatibilities of rock-forming silicates and fluorides in evolved granitic systems and associated hydrothermal processes. The interaction of fluorine with aluminosilicate melts and solids corresponds to progressive fluorination of their constituent oxides by the thermodynamic component F₂O_–1. The chemical potential (F₂O_–1) buffered by reaction of the type: MO_n/2 (s)+n/2 [F₂O_–1]=MF_n (s, g) where M=K, Na, Ca, Al, Si, explains the sequential formation of fluorides: carobbiite, villiaumite, fluorite, AlF₃, SiF₄ as well as the common coexistence of alkali- and alkali-earth fluorides with rock-forming aluminosilicates. Formation of fluorine-bearing minerals first starts in peralkaline silica-undersaturated, proceeds in peraluminous silica-oversaturated compositions and causes progressive destabilization of nepheline, albite and quartz, in favour of villiaumite, cryolite, topaz, chiolite. Additionally, it implies the increase of buffered fluorine solubilities in silicate melts or aqueous fluids from peralkaline silica-undersaturated to peraluminous silica-oversaturated environments. Subsolidus equilibria reveal several incompatibilities: (i) topaz is unstable with nepheline or villiaumite; (ii) chiolite is not compatible with albite because it only occurs only at very high F₂O_–1 levels. The stability of topaz, fluorite, cryolite and villiaumite in natural felsic systems is related to their peralkalinity (peraluminosity), calcia and silica activity, and linked by corresponding chemical potentials to rock-forming mineral buffers. Villiaumite is stable in strongly peralkaline and Ca-poor compositions (An_<0.001). Similarly, cryolite stability requires coexistence with nearly-pure albite (An_<2). Granitic rocks with Ca-bearing plagioclase (An_>5) saturate with topaz or fluorite. Crystallization of topaz is restricted to peraluminous conditions, consistent with the presence of Li-micas or anhydrous aluminosilicates (cordierite, garnet, andalusite). Fluorite is predicted to be stable in peraluminous biotite granites, amphibole-, clinopyroxene- or titanite-bearing calc-alkaline suites as well as in peralkaline granitic and syenitic rocks. Fluorine concentrations in felsic melts buffered by the coexistence of F-bearing minerals and feldspars increase from peralkaline through metaluminous to mildly peraluminous compositions. At low-temperature conditions, the hydrothermal evolution of peraluminous granitic and greisen systems is controlled by white mica-feldspar-fluoride equilibria. With decreasing temperature, topaz gradually breaks down via: (i) (OH)F_–1 substitution and fluorine transfer to fluorite by decalcification of plagioclase below 600 °C, (ii) formation of muscovite and additional fluorite at 475–315 °C, and (iii) formation of paragonite and cryolite, consuming F-rich topaz and albite below 315 °C. These equilibria explain the absence of magmatic fluorite in Ca-bearing topaz granitic rocks; its abundance in hydrothermal rocks is due to: (i) closed-system defluorination of topaz, (ii) open-system decalcification of plagioclase or (iii) hydrolytic alteration. These results provide a complete framework for the investigation of fluorine-bearing mineral stabilities in felsic igneous suites.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.Editorial responsibility: T.L. Grove     

The generation and crystallization conditions of the Proterozoic Harney Peak Leucogranite,Black Hills,South Dakota,USA: Petrologic and geochemical constraints

The mineralogy, petrology and geochemistry of the Proterozoic Harney Peak Granite, Black Hills, South Dakota, were examined in view of experimentally determined phase equilibria applicable to granitic systems in order to place constraints on the progenesis of peraluminous leucogranites and commonly associated rare-element pegmatites. The granite was emplaced at 3–4 kbar as multiple sills and dikes into quartz-mica schists at the culmination of a regional high-temperature, low-pressure metamorphic event. Principally along the periphery of the main pluton and in satellite intrusions, the sills segregated into granite-pegmatite couplets. The major minerals include quartz, K-feldspar, sodic plagioclase and muscovite. Biotite-{Mg No. [Molar MgO/(MgO+FeO)]=0.32-0.38} is the predominant ferromagnesian mineral in the granite's core, whereas at the periphery of the main pluton and in the satellite intrusions tourmaline (Mg No.=0.18–0.48) is the dominant ferromagnesian phase. Almandine-spessartine garnet is also found in the outer intrusions. There is virtually a complete overlap in the wide concentration ranges of SiO₂, CaO, MgO, FeO, Sr, Zr, W of the biotite- and tourmaline-bearing granite suites with no discernable differentiation trends on Harker diagrams, precluding the derivation of one suite from the other by differentiation following emplacement. This is consistent with the oxygen isotope compositions which are 11.5 ± 0.6 for the biotite granites and 13.2 ± 0.8 for the tourmaline granites, suggesting derivation from different sources. The concentrations of TiO₂ and possibly Ba are higher and of MnO and B are lower in the biotite granites. The normative Orthoclase/Albite ratio is extremely variable ranging from 0.26 to 1.65 in the biotite granites to 0.01–1.75 in the tourmaline granites. Very few sample compositions fall near the high-pressure, watersaturated haplogranite minima-eutectic trend, indicating that the granites for the most part are not minimum melts generated under conditions with =1. Instead, most biotite granites are more potassic than the water-saturated minima and eutectics and in analogy with experimentally produced granitic melts, they are best explained by melting at 6 kbar, <1 and temperatures 800°C. Such high temperatures are also indicated by oxygen isotope equilibration among the constituent minerals (Nabelek et al. 1992). Several of the tourmaline granite samples contain virtually no K-feldspar and have oxygen isotope equilibration temperatures 716–775°C. Therefore, they must represent high-temperature accumulations of liquidus minerals crystallized under equilibrium conditions from melts more sodic than the water-saturated haplogranite minima or during fractionation of intruded melts into granite-pegmatite couplets accompanied by volatile-aided differentiation of the alkali elements. The indicated high temperatures, <1, the relatively high TiO₂ and Ba concentrations and the relatively low values of the biotite granites suggest that they were generated by high-extent, biotite-dehydration melting of an immature Archean metasedimentary source. The ascent of the hot melts may have triggered low-extent, muscovite-dehydration melting of schists higher in the crust producing the high-B, low-Ti melts comprising the periphery of the main pluton and the satellite intrusions. Alternatively, the different granite types may be the result of melting of a vertical section of the crust in response to the ascent of a thermal pulse, with the low- biotite granites generated at a deeper, hotter region and the high- tourmaline granites at a higher, cooler region of the crust. The low-Ti and high-B concentrations in the high- melts resulted in the crystallization of tourmaline rather than biotite, which promoted the observed differentiation of the melts into the granitic and pegmatitic layers found along the periphery of the main pluton and the satellite intrusions.     

Reaction mechanisms,physical conditions,and mass transfer during hydrothermal alteration of mica and feldspar in granitic rocks from south-central Maine,USA

Samples of granitic rock from south-central Maine contain primary igneous minerals altered by hydrothermal fluids. The reaction mechanisms (by which the over-all mineralogical change during the alteration was accomplished) involve several different mineral-fluid reactions at different reaction sites in the rock. The reactions involve both molecular and charged species in solution. The different reaction sites correspond to alteration of different primary igneous minerals. Biotite is partially converted to chlorite+sphene; microcline to muscovite; plagioclase to various combinations of muscovite, epidote, and calcite. The different reaction sites are linked by exchange of ions: some reaction sites produce ions consumed at other sites and vice versa. Physical conditions during the hydrothermal event are estimated from mineralogical and thermochemical data: P = 3,500 (±300) bars; T =425 ° (± 25 °)C. The fluid was characterized by X _{CO 2} = 0–0.13; ln([K⁺]/[H⁺ ]) = 10.0; ln([Ca²⁺]/[H⁺]²)=9.1; ln([Na⁺]/[H⁺]) = 10.5; Fe/(Fe+Mg) = 0.95. Amounts of secondary minerals in altered rock, when compared to the inferred mineral reactions that formed them, indicate that small but significant amounts (0.01–0.3mol/ 1,000cm³ altered rock) of CO₂, H₂O, H⁺, and K⁺ were added to the granites by fluids during the alteration, as well as lesser amounts (< 0.01–0.03 mol/1,000cm³ altered rock) of Mg²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Na⁺, and Ti⁴⁺. The sole element leached from the granitic rocks during alteration was Ca in amounts 0.1–0.3 mol/1,000 cm³ rock. By estimating the composition of the hydrothermal fluids before and after reaction with the granites and by measuring the amount of material added to or subtracted from the granites during the alteration, the amount and volume of hydrothermal fluid involved can be calculated. Two independent calculations require minimum volumes in the range 100–1,000 cm³ fluid/1,000cm³ altered rock to participate in the hydrothermal event.     

Melt composition control of Zr/Hf fractionation in magmatic processes

Zircon (ZrSiO₄) and hafnon (HfSiO₄) solubilities in water-saturated granitic melts have been determined as a function of melt composition at 800° and 1035°C at 200 MPa. The solubilities of zircon and hafnon in metaluminous or peraluminous melts are orders of magnitude lower than in strongly peralkaline melt. Moreover, the molar ratio of zircon and hafnon solubility is a function of melt composition. Although the solubilities are nearly identical in peralkaline melts, zircon on a molar basis is up to five times more soluble than hafnon in peraluminous melts. Accordingly, calculated partition coefficients of Zr and Hf between zircon and melt are nearly equal for the peralkaline melts, whereas for metaluminous and peraluminous melts D_Hf/D_Zr for zircon is 0.5 to 0.2. Consequently, zircon fractionation will strongly decrease Zr/Hf in some granites, whereas it has little effect on the Zr/Hf ratio in alkaline melts or similar depolymerized melt compositions.The ratio of the molar solubilities of zircon and hafnon for a given melt composition, temperature, and pressure is proportional to the Hf/Zr activity coefficient ratio in the melt. The data imply that this ratio is nearly constant and probably close to unity for a wide range of peralkaline and similar depolymerized melts. However, it changes by a factor of two to five over a relatively small interval of melt compositions when a nearly fully polymerized melt structure is approached. For most ferromagnesian minerals in equilibrium with a depolymerized melt, D_Hf > D_Zr. Typical values of D_Hf/D_Zr range from 1.5 to 2.5 for clinopyroxene, amphibole, and titanite. Because of the change in the Hf/Zr activity ratio in the melt, the relative fractionation of Zr and Hf by these minerals will disappear or even be reversed when the melt composition approaches that of a metaluminous or peraluminous granite. It is thus not surprising that fractional crystallization of such granitic magmas leads to a decrease in Zr/Hf, whereas fractional crystallization of depolymerized melts tends to increase Zr/Hf. There is no need to invoke fluid metasomatism to explain these effects. Results demonstrate that for ions with identical charge and nearly identical radius, crystal chemistry does not alone determine relative compatibilities. Rather, the effect of changing activity coefficients in the melt may be comparable to or even larger than elastic strain effects in the crystal lattice.     

A Jurassic garnet-bearing granitic pluton from NE China showing tetrad REE patterns

NE China is characterized by the massive distribution of Phanerozoic granitoids. Most of them are of I- and A-type granites, whereas S-type granites are rarely documented. The present work deals with the Dongqing pluton, a small granitic body emplaced in the southern Zhangguangcai Range. The pluton comprises a two-mica (±garnet) granite and a garnet-bearing muscovite granite; the latter occurs as veins in the former. The pluton shows a gradational contact with the surrounding host granites. Rb–Sr and Sm–Nd isotope analyses on whole-rocks and minerals reveal that the two types of granites were emplaced synchronously at about 160 Ma. The pluton was emplaced coeval with the surrounding I-type granitic pluton, and had a rapid cooling history. It is characterized by an initial Sr isotopic ratio of 0.706, slightly negative _Nd(T) values (−0.5 to −1.9) and young depleted-mantle model ages (970–1090 Ma). This suggests that the parent magma originated from partial melting of relatively juvenile crust, which is largely compatible with the general scenario for much of the Phanerozoic granitoids emplaced in the Central Asian Orogenic Belt.Geochemically, the granites of the Dongqing pluton are peraluminous, with a Shand Index (molar ratio A/CNK) of 1.0–1.1 for the two-mica granites and 1.2–1.3 for the garnet-bearing granites. All the garnet-bearing granites and some of the two-mica granites show tetrad REE patterns (=tetrad group), whereas most two-mica granites show normal granitic REE patterns (=normal group). The normal group granites exhibit depletion in Nb, Ta, P and Ti in spidergrams, and generally weak positive Eu anomalies in REE patterns. By contrast, the tetrad group granites manifest depletion in Ba, Nb, Ta, Sr, P, and Ti and significant negative Eu anomalies. The trace element data constrain the parental magmas to having undergone extensive magmatic differentiation. During their late stage magmatic evolution, intense interaction of residual melts with aqueous hydrothermal fluids resulted in the non-CHARAC (charge and radius controlled) trace element behavior and the tetrad effect in REE distribution patterns. This, in turn, leads to the invalidation of the commonly used tectonic discrimination criteria derived from trace element abundances of normal granites. In view of this and previous studies, we conclude that there were probably no S-type granites produced in NE China during the Phanerozoic. Consequently, weathered sedimentary material did not play an important role in the genesis of the strongly peraluminous granites in the Zhangguangcai Range.     

Hydrothermal alteration of Variscan granites,southern Schwarzwald,Federal Republic of Germany

Hercynian S-type granites from the southeastern Schwarzwald granite series represent cogenetic biotite-and two-mica granites. Oxygen- and hydrogen-isotope data show that hydrothermal alteration invoking isotopically light surface waters resulted in a drastic reduction in ¹⁸O and D and pronounced disequilibrium between the minerals. Effective water-rock ratios are calculated to be high, about 0.8 vol units. A shift in the¹⁸O/¹⁶O and the chemical composition of the fluid due to water-rock interaction is continuously traced from pure H₂O with meteoric isotopic character in the deep-seated biotite granites to slightly saline water with rock-equilibrated isotopic composition in the two-mica granites at a shallower level. Substantial retrograde hydrometamorphism in the temperature range 500° to 200° C resulted mineralogically in high-temperature chloritization of biotite, and low-temperature muscovitization as well as feldspar alteration, respectively. Another result of the re-equilibration of cations is strong disturbance of the Rb–Sr system which affects measured ages and initial⁸⁷Sr/⁸⁶Sr values. Hydrothermal differentiation and alteration probably overlap to a very large extent magmatic differentiation processes.     

Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt

Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H₂O and H₂O+CO₂ at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H₂O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H₂O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, D_F (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of D_F in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that D_F is greater than one for water-saturated, peraluminous granitic melts containing 8 wt% F at 800° C and 2 kbar. D_F increases as temperature and as (H₂O/H₂O+CO₂) of the fluid increase. For topaz rhyolite melts containing 1 wt% F and with H₂O-rich fluids, D_F is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing 1 wt% F and in equilibrium with CO₂-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, D_F is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.     

Wetting behavior of partial melts during crustal anatexis: the distribution of hydrous silicic melts in polycrystalline aggregates of quartz

The equilibrium distribution of hydrous silicic melts in polycrystalline aggregates of quartz was characterized in a series of partial melting and melt distribution experiments in the systems quartz-albite-orthoclase-H₂O and quartz-anorthite-H₂O, at 650 to 1000 MPa and 800 to 900° C. Near-equilibrium textures in these experiments are characterized by very low quartz-quartz-melt wetting angles, and by a substantial number of thin melt films along grain boundaries. Wetting angles in the H₂O-saturated experiments are as follows: 18° at 800° C-1000 MPa, and 12° at 900° C-1000 MPa in the granitic system; 18° at 850° C-650 MPa, 15° at 900° C-650 MPa, and 15° at 900° C-1000 MPa in the quartzanorthite system. In the granitic system at 900° C-1000 MPa, a decrease of H₂O content in melt from 17 wt% (at saturation) to 6 wt%, results in a slight increase of wetting angle from 12° to 16°. These low wetting angles — and the observation that many grain boundaries are wetted by melt films-indicate that the ratio of quartz-quartz to quartz-melt interfacial energies (_ss/_s1) is high: 2. Secondary electron imaging of fracture surfaces of melt-poor samples provided a three-dimensional insight into the geometry of melt; at low melt fraction, melt forms an interconnected network of channels along grain edges, as predicted for isotropic systems with wetting angles below 60°. This high-permeability geometry suggests that the segregation of granitic melts is not as sluggish as previously anticipated; simple compaction calculations for a permeability range of 10^-12 to 10^-9 m² indicate that segregation may operate at low to moderate melt fractions (below 30 vol. %), within relatively short time-scales, i.e., 10⁵ to 10⁶ years. Quartzmelt textures show significant deviations from the equilibrium geometries predicted for isotropic partially molten systems. The most consistent deviation is the pervasive development of crystallographically-controlled, planar faces of quartz; these faces provide definitive evidence for non-isotropic quartz-melt surface energy. For most silicates other than quartz, the grain-scale distribution of partial melts deviates even more significantly from equilibrium distributions in isotropic systems; accordingly, in order to describe adequately melt distributions in most natural source regions, the equilibrium model should be modified to account for anisotropy of solid-liquid interfacial energy.Contribution CNRS-INSU-DBT n^o 651     

Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks

The solubilities of zircon, rutile, manganocolumbite (MnNb₂O₆), manganotantalite (MnTa₂O₆), and the rare earth phosphates LaPO₄, GdPO₄, and YbPO₄ in water-saturated haplogranitic melts containing 0–6 wt.% F were measured at 800° C and 2 kbar. The melt compositions investigated differ only in their F content, the proportions of Na, K, Al, and Si are identical in all experiments. While the solubilities of the rare earth phosphates are independent of F, the solubilities of all other minerals studied strongly increase with F. The TiO₂ content of haplogranitic melt in equilibrium with rutile increases linearly from 0.26 wt.% without F to 0.47 wt.% for melts containing 6 wt.% F. Over the same range of F concentrations, the ZrO₂ content of the melt in equilibrium with zircon increases with the square of the F content from less than 0.01 wt.% to 0.25 wt.%. The linear increase for rutile and the quadratic relationship for zircon suggest a complexing mechanism. Probably nonbridging oxygen atoms (NBO) expelled from coordination with Al by reaction with F form complexes with Ti and Zr, the ratio of NBO: metal cation being 1:1 for Ti, and 2:1 for Zr. Direct complexing by F is also a possibility. As titanium oxide phases and zircon are major sinks for HFS elements such as Ti, Nb, Ta, Zr, Hf, Th and REE in granites, their increased solubility in the presence of F favors the enrichment of these elements in residual mels. The Nb and Ta content of rutile in granitic pegmatites is due to extended solid solution of rutile with columbite group minerals, such as manganocolumbite and manganotantalite. The solubility of these components also increases with F, MnTa₂O₆ being more soluble than MnNb₂O₆. Rutile fractionation could therefore account for the increase in Ta/Nb frequently observed in highly differentiated granites. The solubility of the rare earth phosphates increases strongly from LaPO₄ to GdPO₄ to YbPO₄, which explains the enrichment of heavy rare earth elements in highly evolved granites. In the presence of F, many HFS elements will be highly incompatible in granitic systems. Therefore, in a suite of granitic rocks generated by differentiation from the same source magma, a strong correlation should exist between HFS elements and F. However, because of the influence of F on the solubility of refractory phases such as zircon, a similar correlation could also result from different batches of magma containing different amounts of F equilibrating with the same refractory phase.     

Petrogenesis and significance of late Caledonian granitoid magmatism in western Norway

Obduction of the late Ordovician Solund-Stavfjord Ophiolite Complex (443±3 Ma), west Norwegian Caledonides, involved generation and high-level emplacement of granitic and granodioritic dikes and plutons. Initial ⁸⁷Sr/⁸⁶Sr ratios in the granites are low (0.7042–0.7059), suggesting either a mantle component or a Rb-poor crustal source. Initial Nd (Nd(t)) ranges from-0.8 to-8.8, indicating that the granites represent recycling of old crustal rocks, which is supported by Precambrian inheritance in zircons from two of the studied granites. I argue that the Rb-Sr and the Sm-Nd isotope systems are decoupled in the sense that the Sr-and the Nd-isotopes derive their dominant signals from two different sources, a mantle source and a crustal source respectively. The granites are metaluminous to peraluminous and typically have high Sr, Ba and Na₂O/K₂O ratios. SiO₂ contents range from 66 to 74 wt%. REE abundances are highly variable; the La contents range from 80 to 200 times chondrite, and are inversely correlated with the contents of SiO₂. The concentration of Nd in the granites decreases asymptotically with decreasing Nd(t) suggesting fractional crystallization of accessory phases and assimilation of continental crust. This argument is supported by the presence of partly dismembered xenoliths in the granites with Nd(t)-values that are significantly lower than Nd(t)-values in the host granite. The following models are suggested for the granites. When the ophiolite complex obducted, an outboard subduction zone approached the continental margin, and subduction-related magmas accumulated beneath the continental margin, and probably intruded the overlying eugeosynclinal deposits. The mantle-derived magmas most likely evolved to granitoid composition by assimilation of these eugeosynclinal sediments and by fractional crystallization of amphibole, feldspar, sphene, and allanite. Alternatively, but less likely, the heat content of the mantle-derived magmas caused extensive melting of immature graywackes and calc-alkaline volcaniclastic rocks in the deepest portions of the eugeosyncline. Either way, during ascent, the compositions of the granitic melts were modified by fractional crystallization of LREE-rich phases and by assimilation of continental metasediments.     

Experimental determination of the spinel peridotite to garnet peridotite inversion at 900° C and 1,000° C in the system CaO-MgO-Al2O3-SiO2, and at 900° C with natural garnet and olivine

Hydrothermal experiments were carried out at 2 kbar water pressure, 700 °–800 ° C, with the objective of determining the level of dissolved Zr required for precipitation of zircon from melts in the system SiO₂-Al₂O₃-Na₂O-K₂O. The saturation level depends strongly upon molar (Na₂O + K₂O)/Al₂O₃ of the melts, with remarkably little sensitivity to temperature, SiO₂ concentration, or melt Na₂O/ K₂O. For peraluminous melts and melts lying in the quartz-orthoclase-albite composition plane, less than 100 ppm Zr is required for zircon saturation. In peralkaline melts, however, zircon solubility shows pronounced, apparently linear, dependence upon (Na₂O + K₂O)/Al₂O₃, with the amount of dissolvable Zr ranging up to 3.9 wt.% at (Na₂O + K₂O)/Al₂O₃ = 2.0. Small amounts (1 wt.% each) of dissolved CaO and Fe₂O₃ cause a 25% relative reduction of zircon solubility in peralkaline melts.The main conclusion regarding zirconium/zircon behavior in nature is that any felsic, non-peralkaline magma is likely to contain zircon crystals, because the saturation level is so low for these compositions. Zircon fractionation, and its consequences to REE, Th, and Ta abundances must, therefore, be considered in modelling the evolution of these magmas. Partial melting in any region of the Earth's crust that contains more than 100 ppm Zr will produce granitic magmas whose Zr contents are buffered at constant low (< 100 ppm) values; unmelted zircon in the residual rock of such a melting event will impart to the residue a characteristic U- or V-shaped REE abundance pattern. In peralkaline, felsic magmas such as those that form pantellerites and comendites, extreme Zr (and REE, Ta) enrichment is possible because the feldspar fractionation that produces these magmas from non-peralkaline predecessors does not drive the melt toward saturation in zircon.Zircon solubility in felsic melts appears to be controlled by the formation of alkali-zirconosilicate complexes of simple (2:1) alkali oxide: ZrO₂ stoichiometry.     

The solubility of water in NaAlSi3O8 melts: a re-examination of Ab−H2O phase relationships and critical behaviour at high pressures

The solubility of water in melts in the NaAlSi₃O₈–H₂O system at high P and T was deduced from the appearance of quenched products and from water concentrations in the quenched glasses measured by ion probe, calibrated by hydrogen manometry. Starting materials were gels with sufficient water added to ensure saturation of the melts under the run conditions. Experiments were carried out for 10–30 h in an internally heated argon pressure vessel (eight at 1400° C and 0.2–0.73 GPa and three at 0.5 GPa and 900–1200° C) and for 1 h in a piston-cylinder apparatus (three at 1200° C, 1–1.3 GPa). No bubbles were observed in the glasses quenched at P<0.5 GPa or from T<1300° C at 0.5 GPa. Bubble concentration in glasses quenched from 1400° C was low at 0.5, moderate at 0.55 GPa and very high at 0.73 GPa and still higher in glasses quenched in the piston cylinder. Water concentration was measured in all glasses, except for the one at 0.55 GPa, for which it was only estimated, and for those at 0.73 GPa because bubble concentration was too high. Inferred water solubilities in the melt increase strongly with increasing P at 1400° C (from 6.0 wt% at 0.2 GPa to 15 at 0.55 GPa) and also with increasing T at 0.5 GPa (from 9.0 wt% at 900° C to 12.9 at 1400° C). The T variation of water solubility is fundamental for understanding the behaviour of melts on quenching. If the solubility decreases with T at constant P (retrograde solubility), bubbles cannot form by exsolution on isobaric quenching, whereas if the solubility is prograde they may do so if the cooling rate is not too fast. It is inferred from observed bubble concentrations and from our and previous solubility data that water solubility is retrograde at low P and prograde at and above 0.45 GPa; it probably changes with T from retrograde below to prograde above 900° C at 0.5 GPa. Moreover, the solubility is very large at higher pressures (possibly>30 wt% at 1.3 GPa and 1200° C) and critical behaviour is approached at 1.3 GPa and 1200° C. The critical curve rises to slightly higher P at lower T and intersects the three-phase or melting curve at a critical end point near 670° C and 1.5 GPa, above which albite coexists only with a supercritical fluid.     

Solubility and solution mechanisms of C-O-H volatiles in silicate melt with variable redox conditions and melt composition at upper mantle temperatures and pressures

Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, f_H2, was controlled in the range between that of the iron-wüstite-H₂O (IW) and the magnetite-hematite-H₂O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH₃-groups forming bonds with Si⁴⁺ together with molecular CH₄. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle.     

Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier,central Australia

Tourmaline rocks of previously unclear genesis and spatially associated with W- (Cu)-bearing calc-silicate rocks occur in Palaeoproterozoic supracrustal and felsic intrusive rocks in the Bonya Hills in the eastern Arunta Inlier, central Australia. Tourmalinisation of metapelitic host rocks postdates the peak of regional low-pressure metamorphism (M₁/D₁, ~500 °C, ~0.2 GPa), and occurred synkinematically between the two main deformation events D₁ and D₂, coeval with emplacement of Late Strangways (~1.73 Ga) tourmaline-bearing leucogranites and pegmatites. Tourmaline is classified as schorl to dravite in tourmaline–quartz rocks and surrounding tourmaline-rich alteration zones, and as Fe-rich schorl to foitite in the leucogranites. Boron metasomatism resulted in systematic depletion of K, Li, Rb, Cs, Mn and enrichment of B, and in some samples of Na and Ca, in the tourmaline rocks compared to unaltered metasedimentary host rocks. Whole-rock REE concentrations and patterns of unaltered schist, tourmalinised schist and tourmaline–quartz veins—the latter were the zones of influx of the boron-rich hydrothermal fluid—are comparable to those of post-Archaean shales. Thus, the whole-rock REE patterns of these rocks are mostly controlled by the metapelitic precursor. In contrast, REE concentrations of leucogranitic rocks are low (10 times chondritic), and their flat REE patterns with pronounced negative Eu anomalies are typical for fractionated granitic melts coexisting with a fluid phase. REE patterns for tourmalines separated from metapelite-hosted tourmaline–quartz veins and tourmaline-bearing granites are very different from one another but each tourmaline pattern mirrors the REE distribution of its immediate host rock. Tourmalines occurring in tourmaline–quartz veins within tourmalinised metasediments have LREE-enriched (La_N/Yb_N=6.3–55), shale-like patterns with higher REE (54–108 ppm). In contrast, those formed in evolved leucogranites exhibit flat REE patterns (La_N/Yb_N=1.0–5.6) with pronounced negative Eu anomalies and are lower in REE (5.6–30 ppm). We therefore conclude that REE concentrations and patterns of tourmaline from the different tourmaline rocks studied are controlled by the host rock and not by the hydrothermal fluid causing boron metasomatism. From the similarity of the REE pattern of separated tourmaline with the host rock, we further conclude that incorporation of REEs in tourmaline is not intrinsically controlled (i.e. by crystal chemical factors). Tourmaline does not preferentially fractionate specific REEs or groups of REEs during crystallisation from evolved boron- and fluid-rich granitic melts or during alteration of clastic metasediments by boron-rich magmatic-hydrothermal fluids.Editorial responsibility: J. Hoefs     

Mineralogy,geochemistry, radioactivity and environmental impacts of Gabal Marwa granites,southeastern Sinai,Egypt

The Gabal Marwa area is located in the southeastern part of Sinai,Egypt.It comprises gneisses and migmatites,granodiorites and monzogranites.Field,petrographic,mineralogic and chemical investigations indicated that the Gabal Marwa granites are classified as granodiorites and monzogranites.The monzogranites constitute the most predominant rock unit exposed in the study area.They have been subjected to hydrothermal alterations,especially along the shear zones.Sericitization,desilicification,nametasomatism and development of spotty or dendritic manganese oxides are the most pronounced alteration features.These alterations resulted in the increase of TiO2,Al2O3,FeOt,MnO,CaO,MgO,Na2O,K2O and Cr,Zr,Rb,Y and Sr and the decrease of SiO2,P2O5,Ni,Zn,Ba and Nb.Radiometric studies indicated that the altered granites belong to high thorium,high uranium granites.The U,Th,U and Th,Th/U,Th and U-K variation diagrams suggested that magmatic processes controlled the distribution of these elements but the effect of hydrothermal alteration processes were clearly distinct.The Scanning Electron Microscope and X-ray Diffraction analyses indicated that the most important radioactive minerals include uranothorite,thorite,zircon,monazite and samarskite.Cinnabar and Mn minerals were also found.From the U,Th,Ra and K activity concentrations obtained for all the studied granitic samples,radium equivalent activity(Raeq),external hazard index(Hex),and internal hazard index(Hin),were calculated to assess the radiation hazard to human beings living in dwellings made of the studied granites.Altered monzogranites have radioactivity above the proposed acceptable level and,therefore,caution must be taken when these granites are used as building materials.     

Iron and titanium solution properties in peraluminous and peralkaline rhyolitic liquids

The saturation surface of pseudobrookite (Fe₂TiO₅) was determined for melts in the system SiO₂-Al₂O₃-K₂O-FeO-Fe₂O₃-TiO₂ at 1400° C and 1 atm. The variation in concentrations of Fe₂O₃, TiO₂ and Fe₂TiO₅ in liquids can be used to infer relative changes in activity coefficients of these components with changing K₂O/(K₂O+Al₂O₃) of the melts. Saturation concentrations of these components are low and relatively constant in the peraluminous melts and increase with increasing K₂O/(K₂O+Al₂O₃) in peralkaline liquids. The activity coefficients of Fe₂O₃ and TiO₂ and Fe₂TiO₅, therefore, are higher in peraluminous liquids than in peralkaline liquids in this system. In addition, the iron redox ratio was measured as a function of K₂O/(K₂O+Al₂O₃) for liquids just below the saturation surface; was fixed so all variations in redox ratio are entirely due to changes in melt composition. The redox ratio from unsaturated liquids was applied to saturated liquids where redox analysis of the glass is impossible. The homogeneous equilibrium experiments indicate that the activity coefficient of Fe₂O₃ relative to that of FeO is significantly greater in peraluminous melts than peralkaline melts. Both the heterogeneous and homogeneous equilibria suggest that in peralkaline liquids K⁺in excess of that required to charge balance tetrahedral Al⁺³ is used to stabilize both Fe⁺³ and Ti⁺⁴. Calculations show that ferric iron and titanium compete equally effectively for charge-balancing potassium but neither can outcompete aluminum. The observed changes in solution properties of Fe₂O₃ and TiO₂ in the synthetic melts are used to explain variations in Fe-Ti oxide stabilities in natural peraluminous and peralkaline rhyolites and granites. Since the activity coefficients of both ferric iron and titanium are significantly higher in peraluminous liquids than in peralkaline liquids, Fe-Ti oxides should occur earlier in the crystallization sequence in peraluminous rhyolites than in peralkaline rhyolites. In addition, iron will be reduced in peraluminous granites and rhyolites relative to peralkaline ones under comparable P, T, and . Finally, observed crystallization patterns for minerals containing highly charged cations other than ferric iron and titanium are evaluated in the context of this and other experimental studies.     

Kristallisation granitischer schmelzen

To elucidate the problem regarding the genesis of granites and migmatites, the influence of a) anorthite component, b) mafic components, and c) composition of the fluid phase on the crystallization of, granitic melts has been experimentally studied. As starting material, an obsidian with an average granitic composition has been selected and mixtures of this obsidian with anorthite or biotite have been made. H₂O or diluted solutions of NH₃, HF or HCl have been used as a fluid phase. The experiments were conducted under 2000 bars gas pressure and under isochemical conditions. At the outset of each experiment obsidian and the mixtures have been melted under 2000 bars pressure and then the temperature has been brought down stepwise, in order, to study the sequence and temperature of crystallization directly from the melt. The results of these experiments are plotted on a series of quartz-orthoclase-albite (Q-Ab-Or) melt diagrams, so that a better comparison with the different granitic systems and with the simple Q-Ab-Or-H₂0 system ofTuttle andBowen, (1958) can be achieved. The melt or crystallization diagrams of these complex granitic systems under study, represent projections of the Q-Ab-Or-An (An= anorthite) tetrahedron on to the base Q-Ab-Or. In all these triangular diagrams, there are three regions of crystallization: quartz, plagioclase and alkalifelspar. These three regions of crystallization are separated from each other by three cotectic lines; which meet at a point: the eutectic point. The sequence of crystallization of the leucocratic minerals; observed in the different granitic systems investigated experimentally here, can be understood with the help of such diagrams easily. From these experiments the following petrogenetically interesting results have been obtained:

1. 1.
   The order of crystallization of granitic melts is to a great extent influenced: by the normative proportion of the Ab/An components and the composition of the fluid phase. (It is not the variation in the An content directly but the variation in the relative proportions of Ab/An, that causes a change in the order of crystallization.) In general, with decreasing Ab/An proportion in a rock or a melt, the amount of albite component in the.eutectic melt decrease,. while at the same time- the amount of quartz and orthoclase components increase. When the Ab/An proportion of a rock is more than 3.5, then the corresponding eutectic melt is of granitic composition; and when the proportion is lesser than 3.5 the eutectic melt is quartz and orthoclase rich and has aplitic composition. Calc-alkaligranites and alkaligranites have an average Ab/An proportion of 4.7 and 10.5, respectively.     
   
   

Crustal xenoliths from Tertiary volcanics of the Northern Hessian Depression

A suite of crustal xenoliths from Tertiary basaltic tuffs of the Northern Hessian Depression (NHD) volcanic field comprises abundant meta-igneous pyroxene granulites of mafic, noritic to anorthositic, IAT and tonalitic composition. Less abundant are granitic, tonalitic and leucogranitic gneisses and metasedimentary xenoliths. A total of 49 samples were analyzed for modal compositions, for major and trace elements (including Li, Rb, Sr, Ba, Cs, V, Sc, Cr, Co, Ni, Y, Zr, Nb, Ta, Hf, Th and REE) and oxygen isotopes. Two-pyroxene thermometry yields temperatures between 700 and 900° C for mafic and noritic granulites. Feldspar thermometry indicates temperatures of 660°–710° C for tonalitic granulites and 470°–520° C for granitic and tonalitic gneisses. One highly depleted sillimanite-rich metasediment contains cordierite and garnet which have equilibrated at temperatures of 780° C. The general lack of garnet in the mafic and noritic granulites and the presence of sillimanite in felsic xenoliths indicates that metamorphic pressures have not exceeded 10 kb. Major and trace element data and oxygen isotope compositions of the mafic granulites are compatible with an origin from spilitized enriched-type MORB rocks (enrichment in ¹⁸O to 11 and in Li to 34 ppm at average SiO₂ contents of 44.1 wt%). These low-T spilites were transformed into amphibolites and then pyroxene granulites during subsequent high temperature metamorphic events. Low Si, Al, K, and Rb concentrations along with An contents in plagioclase ranging from near 50 to 98 mole percent suggest that amphibolite facies protoliths have generated tonalitic melts during partial melting at temperatures above 700° C. The mafic granulite xenoliths are interpreted as restites whereas the tonalitic samples probably represent the extracted partial melts derived by 20 to 30 percent degree of melting. Metasedimentary xenoliths strongly depleted in granitic component could represent restites from which granitic S-type partial melts have been extracted. Tonalitic and leucogranitic gneisses including one trondhjemite xenolith have many chemical characteristics (e.g. REE distribution) in common with tonalite-trondhjemite-granodiorite suites of the North Atlantic region but cannot be accounted for a more specific origin. Estimated elastic properties of the main types of NHD xenoliths yield P-wave velocities of 6.0–6.4 km^-1 for granitic, tonalitic and trondhjemite gneisses including tonalitic granulites and 6.5–7.0 for the more mafic xenoliths. When compared with two seismic depths-V_p profiles these data are in accordance with a model where the mafic, andesitic, noritic and tonalitic granulites comprise abundant rock types at depths between 29 km (Moho) and 20 km which mainly consists of old oceanic crust including subduction related volcanic products. The more felsic xenoliths probably represent material from depths between 12 and 20 km.