Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

Extreme P-, Bi-, Nb-, Sc-, U- and F-rich zircon from fractionated perphosphorous granites: The peraluminous Podlesí granite system, Czech Republic

The strongly peraluminous and P-rich, protolithionite and zinnwaldite leucogranites from Podlesí, western Krušné 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⁺  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⁺  P⁵⁺ + Y³⁺), pretulite (Sc³⁺ + P⁵⁺  Zr⁴⁺ + Si⁴⁺), brabantite-type (Ca²⁺ + (U, Th)⁴⁺ + 2P⁵⁺  2Zr⁴⁺ + 2Si⁴⁺), and ximengite-type (Bi³⁺ + P⁵⁺  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 Podlesí, granitic zircon became unstable and completely dissolved during greisenization. Part of the mobilized elements was reprecipitated in newly grown, hydrothermal zircon.     

Composition of coexisting zircon and xenotime in rare-metal granites from the Krušné Hory/Erzgebirge Mts. (Saxothuringian Zone,Bohemian Massif)

Zircon and xenotime, from two mineralogically and chemically contrasting granite suites occurring in the Kru?né Hory/Erzgebirge Mts., display extended compositional variability with respect to abundances of Zr, Hf, REE, Y, P, Th, Ca, Al, Fe and As. According to their geochemical signatures, P-rich (S-type) and P-poor (A-type) granites could be distinguished here. Both granite suites display high Ga/Al ratios (>2.6) and according to FeO_tot./(FeO_tot. + MgO) ratio can be classified as ferrous granites. Consequently, the both ratios cannot be used for discrimination S- and A-type granites. Both minerals are characterized by a variety of complex zircon-xenotime textures. They are usually strong hydrated and enriched in F. Zircon from P-rich granites displays a significant enrichment in P (up 0.24 apfu P), whereas zircon from P-poor granites has lower P and higher Y (up to 0.15 apfu Y). The xenotime-type substitution is the most important mechanism of isomorphic substitution in zircon in both granite suites. Zircon from both granite suites is typically enriched in Hf, especially unaltered zircon from P-rich granites (up to 8.2 wt. % HfO₂). However in altered zircons the Hf/Zr ratio is higher in the P-poor granites. The Hf-rich zircon from unaltered P-rich granite crystallised from low temperature granite melt, whereas altered zircons crystallised during post-magmatic hydrothermal alteration (greisenization). Xenotime from P-poor granites displays a considerable enrichment in HREE (up to 40 mol. % HREEPO₄) compared to xenotime from P-rich granites (up to 20 mol. % HREEPO₄). Xenotime compositions from P-rich granites are influenced by brabantite-type substitution, whereas for xenotime from P-poor granites the huttonite-type substitution is dominant. Unusual enrichments in HREE is significant for xenotime from P-poor granites, especially in Yb (up to 0.17 apfu Yb) and Dy (up to 0.11 apfu).     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

Titanian clinohumite–garnet–pyroxene rock from the Su-Lu UHP metamorphic terrane, China: chemical evolution and tectonic implications

A garnet–pyroxene rock containing abundant Ti-clinohumite (ca. 40 vol.%) occurs along with eclogites as small blocks in quartzo-feldsparthic gneiss in the southern end of the Chinese Su-Lu ultrahigh-pressure (UHP) metamorphic terrane. It consists of three aggregates: (1) Ti-clinohumite-dominated aggregate with interstitial garnet and pyroxene, (2) garnet+pyroxene aggregate with Ti-clinohumite inclusions, and (3) Ti-clinohumite-free aggregate dominated by garnet. Apatite, phlogopite, zircon, hematite, pentlandite, and an unknown Ni-Fe-volatile-Si (NFVS) mineral, which is replaced by Ni-greenalite, occur as accessories. Serpentine is the major secondary mineral. Garnet (Prp_63.9–64.6Alm_25.8–26.9Grs_1.4–7.9Uva_0.5–7.6Sps_1.0) in all three aggregates is pyrope-rich with very low grossular component, with that in the aggregate (2) most enriched in Cr (Cr₂O₃=2.55 wt.%). Orthopyroxene is depleted in Al (Al₂O₃=0.16 wt.% in the cores) and Ca (CaO=0.06–0.09 wt.% in the cores), with X_Mg (Mg/(Mg+Fe)) values at ca. 0.900. Clinopyroxene is chromian diopside with Fe³⁺≥Fe²⁺. Matrix clinopyroxene has a lower X_Mg (0.862) than that (0.887) included in Ti-clinohumite. The rock contains modest amount of heavy rare earth elements (HREE) (10 to 12×C1 chondrite), with significant enrichment in Cr, Co, Ni, V, Sr, and light rare earth elements (LREE) (22 to 33×C1 chondrite). The clinopyroxene is very enriched in Cr (Cr₂O₃ is up to 2.09 wt.% in the cores) and Sr (ca. 350 ppm) and LREE (Ce_N/Yb_N=157.7). Ti-clinohumite is enriched in Ni (1981 ppm), Co (123 ppm), and Nb (85 ppm).

While it is possible to enrich ultramafites in incompatible elements in a subducted slab, the high Al, Fe, Ti, and low Si, Ca, and Na contents in the Ti-clinohumite rock are difficult to account for by crustal metasomatism of an ultramafite. On the other hand, the similarity in major and trace element compositions and their systematic variations between the Ti-clinohumite-garnet-pyroxene rock of this study and those of Mg-metasomatised Fe–Ti gabbros reported in the literature suggest that crustal metasomatism occurred in a gabbroic protolith, which resulted in addition of Cr, Co, Ni, and Mg and removal of Si, Ca, Na, Al, and Fe. This implies that the rock was in contact with an ultramafite at low pressure. During subsequent subduction, the metagabbro was thrust into the country gneiss, where gneiss-derived hydrous fluids caused enrichment of Sr and LREE in recrystallised clinopyroxene. P–T estimates for the high-pressure assemblage are ca. 4.2 GPa and ca. 760 °C, compatible with those for the eclogites and gneisses in this terrane. It is possible that the Ti-clinohumite-garnet-pyroxene rock and associated eclogites represent remnants of former oceanic crust that was subducted to a great depth.     

Lower crustal melting and the role of open-system processes in the genesis of syn-orogenic quartz diorite–granite–leucogranite associations: constraints from Sr–Nd–O isotopes from the Bandombaai Complex, Namibia

The Bandombaai Complex (southern Kaoko Belt, Namibia) consists of three main intrusive rock types including metaluminous hornblende- and sphene-bearing quartz diorites, allanite-bearing granodiorites and granites, and peraluminous garnet- and muscovite-bearing leucogranites. Intrusion of the quartz diorites is constrained by a U–Pb zircon age of 540±3 Ma.

Quartz diorites, granodiorites and granites display heterogeneous initial Nd- and O isotope compositions (_{Nd (540 Ma)}=−6.3 to −19.8; δ¹⁸O=9.0–11.6‰) but rather low and uniform initial Sr isotope compositions (⁸⁷Sr/⁸⁶Sr_initial=0.70794–0.70982). Two leucogranites and one aplite have higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.70828–0.71559), but similar initial _Nd (−11.9 to −15.8) and oxygen isotope values (10.5–12.9‰). The geochemical and isotopic characteristics of the Bandombaai Complex are distinct from other granitoids of the Kaoko Belt and the Central Zone of the Damara orogen. Our study suggests that the quartz diorites of the Bandombaai Complex are generated by melting of heterogeneous mafic lower crust. Based on a comparison with results from amphibolite-dehydration melting experiments, a lower crustal garnet- and amphibole-bearing metabasalt, probably enriched in K₂O, is a likely source rock for the quartz diorites. The granodiorites/granites show low Rb/Sr (<0.6) ratios and are probably generated by partial melting of meta-igneous (intermediate) lower crustal sources by amphibole-dehydration melting. Most of the leucogranites display higher Rb/Sr ratios (>1) and are most likely generated by biotite-dehydration melting of heterogeneous felsic lower crust. All segments of the lower crust underwent partial melting during the Pan-African orogeny at a time (540 Ma) when the middle crust of the central Damara orogen also underwent high T, medium P regional metamorphism and melting. Geochemical and isotope data from the Bandombaai Complex suggest that the Pan-African orogeny in this part of the orogen was not a major crust-forming episode. Instead, even the most primitive rock types of the region, the quartz diorites, represent recycled lower crustal material.     

Magma–host interactions during differentiation and emplacement of a shallow-level, zoned granitic pluton (Tarçouate pluton, Morocco): implications for magma emplacement

The Tarçouate pluton (Anti-Atlas, Morocco) is an inversely zoned laccolith emplaced 583 Ma ago into low-grade metasediments, with the following succession: leucocratic granites, biotite–granodiorites (±monzodiorites), hornblende–granodiorites (±monzodiorites) and monzodiorites syn-plutonic dykes. These rocks form two distinct, chemically coherent, units:

(1) A main unit consists of layered (572<59 wt.%) and homogeneous (632<67%) hornblende–granodiorites, biotite–granodiorites (672<72%) and aplites (702<76%). All these rocks are metaluminous to peraluminous and display fractionated HREE depleted patterns (La/Yb_N=14–61; Yb_N=0.7–6.8). Initial ⁸⁷Sr/⁸⁶Sr ratios (0.7072 to 0.7080) increase, whereas _Nd(t) values (−1.7 to −2.8) decrease from the hornblende– to the biotite–granodiorites. Monzodiorites occur as mafic microgranular enclaves or syn-plutonic dykes.

(2) A subordinate unit consists of leucocratic, distinctly peraluminous, muscovite-bearing granites (722<75%) occurring at the northern edge of the pluton and as dykes in the surrounding schists towards the top of the pluton. These rocks are free of monzodioritic enclaves. They display less fractionated patterns with higher HREE contents (La/Yb_N=2–19; Yb_N=11–18), a distinct _Nd(t) value (−11.8) and a ⁸⁷Sr/⁸⁶Sr initial ratio (0.7480) within those of the surrounding schists (0.7393–0.7819).

Magma–host interactions are closely related to differentiation and occurred at different levels, but mainly before emplacement. Field relationships and petrogenetic modelling show that the bt–granodiorites formed at levels deeper than the level of emplacement, by fractional crystallisation (0.65

These data preclude any significant material transfer process for the emplacement of the Tarçouate pluton, but rather suggest assembly of successive pulses of variably differentiated crystal-poor magmas. These shallow level granitic plutons can be considered as an end-member of magma emplacement with minimum interactions with the country rocks.     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part II: Evolving zircon and thorite trace element chemistry

The Sn–W mineralized Mole Granite in Eastern Australia hosts zircon populations that crystallized at several stages during a protracted magmatic to hydrothermal evolution. Thirty-four elements have been quantified by laser-ablation inductively-coupled-plasma mass-spectrometric microanalysis with the aim of relating the chemistry of zircon to its growth environment. Trace element contents are highly variable for all textural occurrences. Zircon inclusions in earliest quartz phenocryst suggest that zircon was a liquidus phase that crystallized probably deep in the crust. Trace element contents are conspicuously high, showing only a slight positive Ce anomaly but a pronounced negative Eu-anomaly. Successive crystallization stages of magmatic zircon are characterized by progressive depletion in trace element contents, notably the rare earth elements, with an increasingly important positive Ce-anomaly. This evolution reflects saturation of REE accepting minerals such as monazite, thorite, xenotime and possibly apatite and is affected little by the exsolution of a magmatic–hydrothermal fluid. Zircon that is interpreted to have precipitated from aqueous fluids in Sn–W-bearing quartz veins shows REE patterns indistinguishable from those of late magmatic zircon. When combined with experimental evidence on the fluid–melt partitioning of REE, it indicates that the REE distribution coefficients for zircon/melt and zircon/fluid are largely comparable.

The second example of hydrothermal zircon crystallized some 2 My after the host granite. These crystals reveal an intragranular zonation of increasing trace element concentrations from core to rim. Therefore, REE abundances and patterns alone are not conclusive indicators of the geological environment in which zircon crystallized. Nevertheless, variations in trace element contents of zircon that relate to the chemistry of the melt or fluid from which zircon crystallized, as measured in cogenetic melt and fluid inclusions, are promising for future petrogenetic modeling.

Lead and Cs are strongly incompatible in hydrothermal zircon, with estimated zircon–fluid distribution coefficients D ≤ 0.001, while Sn and Li are moderately incompatible, D_Sn  0.6 and D_Li  0.1, and Ce is compatible, D_Ce  14. Moreover, hydrothermal zircon has a more pronounced negative Eu-anomaly and higher Ta/Nb and U/Th ratios than the magmatic zircons of the Mole Granite.     

Potential minerals for determining U–Th–Pb chemical age using electron microprobe

After a decade of studies and development, it is now accepted that reliable U–Th–total Pb isochron ages can be calculated for monazite using an electron microprobe at μm scale, either directly on thin sections or on separated grains mounted in polished section. The potential for determining U–Th–Pb chemical ages from other U- and Th-enriched phases has been investigated compared to chemical monazite-dating results for which individual spot-age precisions of 20 to 100 Ma can be achieved from individual spot analyses. Using isochron plots for monazite, the age homogeneity of a given population of data can be assessed and, depending upon the number of analyses (n  50), a precision of 5 to 10 Ma can be obtained. The U content in xenotime widely varies from less than 0.1 wt.% up to 3 wt.%, but Th rarely exceeds 1 wt.%. As a consequence, the amount of radiogenic Pb produced during a given period remains significantly lower for xenotime than for monazite, leading to a lower precision (± 20 Ma) on the mean ages. Xenotime, however, appears to remain as a closed system, but common Pb must be carefully checked. Furthermore, the electron-microprobe technique (EPMA) allows controlling any age discrepancy on xenotime grains as small as 10–20 μm that cannot be dated by other isotopic methods. Such xenotime ages can be useful when studying the monazite–xenotime equilibrium. The electron microprobe is not the most reliable method for dating zircon since U and Th concentrations are generally low and common Pb is not negligible. Nevertheless, the spatial resolution of EPMA coupled with isotope methods allows conclusive in situ studies about radiogenic Pb mobility and metamictization. Thorite does not seem suitable for dating with either isotope methods or EPMA because of continuous radiogenic Pb loss. Conversely, the oxide phases, thorianite and baddeleyite are robust minerals with closed systems. They are rather rare and seem to incorporate negligible common Pb, making EPMA a method of choice for dating them. For thorianite, the precision on the mean age can be similar as that obtained for monazite, or even better, while the precision for baddeleyite cannot be significantly better than 20 to 50 Ma due to the limited amount of U ( 0.1%) and the lack of Th.     

Magma–carbonate interaction: An experimental study on ultrapotassic rocks from Alban Hills (Central Italy)

The Alban Hills ultrapotassic volcanic district is one of the main districts emplaced during Quaternary time along the Tyrrhenian margin of Italy. Alban Hills lava flows and scoria clasts are made up essentially of clinopyroxenes and leucites and their chemical composition is mostly K-foiditic. Differentiated products (MgO < 3 wt.%) are characterised by low SiO₂ concentration (< 50 wt.%) and geochemical features indicate that this unique differentiation trend is driven by crystal fractionation plus carbonate crust interaction. Notably, the Alban Hills Volcanic District was emplaced into thick limestone units. With the aim of constraining the magmatic differentiation, we performed experiments on the Alban Hills parental composition (plagioclase-free phono-tephrite) under anhydrous, hydrous, and hydrous-carbonated conditions. Experiments were carried out at 1 atm, 0.5 GPa and 1 GPa, temperatures ranging from 1050 to 1300 °C, and H₂O and CaCO₃ in the starting material up to 2 and 7 wt.%, respectively. The experiments performed at 0.5 GPa are the most representative of the Alban Hills plumbing system. Clinopyroxene and leucite are the main phases occurring under all the investigated conditions and the liquidus phases. Nevertheless, our experimental results demonstrate that the occurrence of CaCO₃ in the starting material strongly affects phase relations. Experiments performed under hydrous conditions crystallize magnetite and phlogopite at relatively high temperature. This early crystallization drives the glass composition towards a silica enrichment, resulting in a differentiation trend moving from phono-tephritic (Alban Hills parental composition) to phonolitic compositions. This is in contrast with micro-textural evidence showing late crystallization of magnetite and phlogopite in the natural products and with the composition of the juvenile products. On the contrary, in the CaCO₃-bearing experiments (i.e., simulating magma–carbonate interaction) the magnetite and phlogopite stability fields are strongly reduced. As a consequence, the melt differentiation is mainly controlled by the cotectic crystallization of clinopyroxene and leucite, resulting in a differentiation trend moving towards K-foiditic compositions. These experimental results are in agreement with micro-textural features and chemical compositions of Alban Hills natural products and with the magmatic differentiation model inferred by geochemical data. Magma–carbonate interaction is not a rare process and its occurrence has been demonstrated for different plumbing systems. However, the uniqueness of the Alban Hills liquid line of descent suggests that the efficacy of the carbonate contamination process is controlled by different factors, the dynamics of the plumbing system being one of the most important.     

Pb and Nd isotopic composition of the Jigongshan granite: constraints on crustal structure of Tongbaishan in the middle part of the Qinling–Tongbai–Dabie orogenic belt, Central China

The Qinling–Dabie–Sulu belt is the world's largest ultrahigh pressure (UHP) metamorphic belt. The UHP metamorphism is well dated at 220–245 Ma in the Dabie–Sulu belt but at 507 Ma in the Qinling belt. The Tongbaishan is located between the Qinling orogenic belt to the west and the Dabie–Sulu UHP metamorphic belt to the east. It is the key area for studying the tectonic relation between the Qinling and Dabie–Sulu belts and the diachronous UHP metamorphism. The Jigongshan granitic pluton (t=128 Ma) with a total area of 1200 km², composed of monzogranite, was mostly emplaced into the Tongbai complex, an exposed basement in the Tongbaishan. The Jigongshan granites have SiO₂=69.85–72.35%, K₂O/Na₂O=0.87–1.13, A/CNK=0.91–1.03, Rb/Sr=0.14–0.25 and Th/U=3.3–12. Their REE compositions show strongly fractionated patterns with (La/Yb)_N=14–58 and Eu*/Eu=0.79–1.05. The granites are characterized by low radiogenic Pb isotopic composition. The present-day whole-rock Pb isotopic ratios are ²⁰⁶Pb/²⁰⁴Pb=16.707–17.055, ²⁰⁷Pb/²⁰⁴Pb=15.239–15.326 and ²⁰⁸Pb/²⁰⁴Pb=37.587–37.853, which are similar to that of the continental lower crust. Their _Nd(t) values range from −16 to −20, and depleted-mantle Nd model ages (T_DM) from 1.8 to 2.2 Ga. The above evidence indicates that the magma of the Jigongshan granites was derived from the partial melting of the continental crust. The Pb and Nd isotopic compositions of the Jigongshan granites resemble those of the Dabie core complex in the Dabieshan but are distinct from those of the Tongbai complex in the Tongbaishan. Thus, the Dabie core complex would be the magma source of the Jigongshan granites. The result implies that the Dabie core complex is extended to the west and constitutes the unexposed basement underlaying the Tongbai complex in the Tongbaishan.     

邹家山铀矿床伴生重稀土元素的赋存特征

初步研究发现,相山矿田邹家山矿床中伴生有较高的重稀土元素,回收这些珍稀的资源和探索其成因具有重要的意义,而查明这些伴生稀土在铀矿床中的赋存特征是前期基础性工作。为此本文采用电子探针和激光剥蚀电感耦合等离子体质谱分析了邹家山铀矿床中稀土元素的赋存状态。结果显示：该矿床稀土矿物主要为独居石、氟碳钙铈矿和磷钇矿;独居石、氟碳钙铈矿的LREE/HREE>1,为轻稀土富集型;而磷钇矿的LREE/HREE<1,为重稀土富集型。沥青铀矿、钛铀矿、铀钍石、铀石、钍石、锆石等铀钍矿物的稀土特征为重稀土富集型;铀钍矿物稀土总量（∑REE+Y）较高,为（3 805.78~65 307.00）×10^-6,LREE/HREE<1,为0.01~0.80,平均为0.29。其他伴生矿物磷灰石、钾长石为轻稀土富集型,萤石为轻、重稀土富集型两类都有,而伊利石、黄铁矿的轻重稀土无明显相对富集。重稀土在磷钇矿和铀钍矿物中以类质同象形式存在,少量赋存于伴生矿物。     

Magmatic evolution of Li–F, rare-metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)

We report compositions of homogenized quartz-hosted melt inclusions from a layered sequence of Li-, F-rich granites in the Khangilay complex that document the range of melt evolution from barren biotite granites to Ta-rich, lepidolite–amazonite–albite granites. The melt inclusions are crystalline at room temperature and were homogenized in a rapid-quench hydrothermal apparatus at 200 MPa before analysis. Homogenization runs determined solidus temperatures near 550 °C and full homogenization between 650 and 750 °C. The compositions of inclusions, determined by electron microprobe and Raman spectroscopy (for H₂O), show regular overall trends of increasing differentiation from the least-evolved Khangilay units to apical units in the Orlovka intrusion. Total volatile contents in the most-evolved melts reach over 11 wt.% (H₂O: 8.6 wt.%, F: 1.6 wt.%, B₂O₃: 1.5 wt.%). Concentrations of Rb range from about 1000 to 3600 ppm but other trace elements could not be measured reliably by electron microprobe. The resulting trends of melt evolution are similar to those described by the whole-rock samples, despite petrographic evidence for albite- and mica-rich segregations previously taken as evidence for post-magmatic metasomatism.

Melt variation trends in most samples are consistent with fractional crystallization as the main process of magma evolution and residual melt compositions plot at the granite minimum in the normative Qz–Ab–Or system. However, melts trapped in the highly evolved pegmatitic samples from Orlovka deviate from the minimum melt composition and show compositional variations in Al, Na and K that requires a different explanation. We suggest that unmixing of the late-stage residual melt into an aluminosilicate melt and a salt-rich dense aqueous fluid (hydrosaline melt) occurred. Experimental data show the effectiveness of this process to separate K (aluminosilicate melt) from Na (hydrosaline melt) and high mobility of the latter due to its low viscosity and relatively low density may explain local zones of albitization in the upper parts of the granite.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

High and low temperature alteration of uranium and thorium minerals, Um Ara granites, south Eastern Desert, Egypt

The Um Ara area, in the south Eastern Desert of Egypt contains a number of uranium occurrences related to granitic rocks. U-rich thorite, thorite and zircon are the main primary uranium- and thorium-bearing minerals found in mineralized zones of the Um Ara alkali-feldspar granites; uranophane is the most common secondary uranium mineral. U-rich thorite contains blebs of galena, has rims of uranophane and contains inclusions of Zr-rich thorite. Electron probe microanalysis (EPMA) provides an indication of a range of solid solution between thorite and zircon, in which intermediate phases, such as Th-rich zircon and Zr-rich thorite, were formed. These phases have higher sum of all cations per formula (2.05 to 2.06 apfu, for 4 oxygen atoms) than that of ideal thorite and zircon. This is attributed to the presence of substantial amount of interstitial cations such as Ca, U and Al in these phases. Some zircon grains are stoichiometric in composition, other altered grains display lower SiO₂ and ZrO₂ contents. Enrichment of Th and U in altered zircon preferentially involves coupled substitution (Ca²⁺ + (Th,U)⁴⁺ ↔ 2Zr⁴⁺ + 2Si⁴⁺), implying that significant U and Th may enter the Zr and Si position in zircon. Negative correlation of Zr vs. Hf and Al may indicate that Hf and Al have been introduced to the zircon during later fluid alteration rather than during the primary magmatic event. A two-stage metallogenetic model is proposed for the alteration processes and origin of U- and Th-bearing minerals in the Um Ara alkali-feldspar granite: 1) the first stage was dominated by hydrothermal alteration and accompanied by albitization, k-feldspathization, desilicification, chloritization, hematitization, silicification, argillization, fluoritization and corrosion of primary U-bearing minerals. Solid-solution between thorite and zircon occurred during this stage. The second stage occurred at the near-surface profile where circulating meteoric water played an important role in mobilizing the early formed primary U-bearing minerals. Uranium was likely transported as a calcium uranyl carbonate complexes. When these complexes lost their stabilities by precipitation of calcite, they decomposed in the presence of silica to form uranophane.     

Oxidized, magnetite-series, rapakivi-type granites of Carajás, Brazil: Implications for classification and petrogenesis of A-type granites

The varying geochemical and petrogenetic nature of A-type granites is a controversial issue. The oxidized, magnetite-series A-type granites, defined by Anderson and Bender [Anderson, J.L., Bender, E.E., 1989. Nature and origin of Proterozoic A-type granitic magmatism in the southwestern United States of America. Lithos 23, 19–52.], are the most problematic as they do not strictly follow the original definition of A-type granites, and approach calc-alkaline and I-type granites in some aspects. The oxidized Jamon suite A-type granites of the Carajás province of the Amazonian craton are compared with the magnetite-series granites of Laurentia, and other representative A-type granites, including Finnish rapakivi and Lachlan Fold Belt A-type granites, as well as with calc-alkaline, I-type orogenic granites. The geochemistry and petrogenesis of different groups of A-types granites are discussed with an emphasis on oxidized A-type granites in order to define their geochemical signatures and to clarify the processes involved in their petrogenesis. Oxidized A-type granites are clearly distinguished from calc-alkaline Cordilleran granites not only regarding trace element composition, as previously demonstrated, but also in their major element geochemistry. Oxidized A-type granites have high whole-rock FeO_t/(FeO_t + MgO), TiO₂/MgO, and K₂O/Na₂O and low Al₂O₃ and CaO compared to calc-alkaline granites. The contrast of Al₂O₃ contents in these two granite groups is remarkable. The CaO/(FeO_t + MgO + TiO₂) vs. CaO + Al₂O₃ and CaO/(FeO_t + MgO + TiO₂) vs. Al₂O₃ diagrams are proposed to distinguish A-type and calc-alkaline granites. Whole-rock FeO_t/(FeO_t + MgO) and the FeO_t/(FeO_t + MgO) vs. Al₂O₃ and FeO_t/(FeO_t + MgO) vs. Al₂O₃/(K₂O/Na₂O) diagrams are suggested for discrimination of oxidized and reduced A-type granites. Experimental data indicate that, besides pressure, the nature of A-type granites is dependent of ƒO₂ conditions and the water content of magma sources. Oxidized A-type magmas are considered to be derived from melts with appreciable water contents (≥ 4 wt.%), originating from lower crustal quartz-feldspathic igneous sources under oxidizing conditions, and which had clinopyroxene as an important residual phase. Reduced A-type granites may be derived from quartz-feldspathic igneous sources with a metasedimentary component or, alternatively, from differentiated tholeiitic sources. The imprint of the different magma sources is largely responsible for the geochemical and petrological contrasts between distinct A-type granite groups. Assuming conditions near the NNO buffer as a minimum for oxidized granites, magnetite-bearing granites formed near FMQ buffer conditions are not stricto sensu oxidized granites and a correspondence between oxidized and reduced A-type granites and, respectively, magnetite-series and ilmenite-series granites is not always observed.     

Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

豆乍山地区产铀与非产铀岩体黑云母成分及赋存副矿物特征

豆乍山岩体和香草坪岩体成岩时代相近,空间关系密切,为苗儿山中段豆乍山地区产铀与非产铀岩体。文章选择豆乍山和香草坪新鲜花岗岩中黑云母为研究对象,结合诸广、贵东地区产铀与非产铀岩体中黑云母的电子探针数据开展综合分析,并在此基础上进行了黑云母中包裹副矿物种类的对比研究。结果表明:产铀岩体黑云母基本以铁叶云母为主,非产铀岩体黑云母为铁质黑云母,且前者具有相对富铝、铁、锰,贫镁、钛特征;产铀豆乍山岩体黑云母中副矿物为锆石-磷钇矿-独居石-钛铁矿-金红石-方钍石-晶质铀矿,非产铀香草坪岩体黑云母中副矿物为锆石-磷灰石-褐帘石-独居石,缺少钍石和晶质铀矿。不同亚种黑云母具有不同的成岩成矿环境,与各矿化类型往往具有直接对应关系,铁叶云母的出现有可能可以作为产铀与非产铀岩体(铀成矿潜力)的间接判别标志,对于后期找矿具有较大指导意义。     

Geochronological, geochemical and geothermal constraints on petrogenesis of the Indosinian peraluminous granites in the South China Block: A case study in the Hunan Province

The Indosinian granites in the South China Block (SCB) have important tectonic significance for the evolution of East Asia. Samples collected from Hunan Province can be geochemically classified into two groups. Group 1 is strongly peraluminous (A/CNK > 1.1), similar to S-type granites, and Group 2 has A/CNK = 1.0–1.1, with an affinity to I-type granites. Group 1 has lower FeOt, Al₂O₃, MgO, CaO, TiO₂ and ε_Nd(t) values but higher K₂O + Na₂O, Rb/Sr, Rb/Ba and ⁸⁷Sr/⁸⁶Sr(t) than those of Group 2. Samples of both groups have similar LREE enriched pattern, with (Eu/Eu) = 0.19–0.69, and strongly negative Ba, Sr, Nb, P and Ti anomalies. Geothermobarometry study indicates that the precursor magmas were emplaced at high-level depth with relatively low temperature (734–827 °C). Geochemical data suggest that Group 1 was originated from a source dominated by pelitic composition and Group 2 was from a mixing source of pelitic and basaltic rocks with insignificant addition of newly mantle-derived magma. Eight granitic samples in Hunan Province are dated at the cluster of 243–235 and 218–210 Ma by zircon U–Pb geochronology. Together with recent zircon U–Pb ages for other areas in the SCB, two age-clusters, including 243–228 Ma just after peak-metamorphism ( 246–252 Ma) and 220–206 Ma shortly after magma underplating event (224 Ma), are observed. It is proposed that in-situ radiogenic heating from the over-thickened crust induced dehydrated reaction of muscovite and epidote/zoisite to form the early Indosinian granites in response to the isostatic readjustments of tectonically thickened crust. Conductive heating from the underplating magma in the postcollisional setting triggered the formation of late Indosinian granites. Such a consideration is supported by the results from FLAC numerical simulation.     

Origin and evolution of Pliocene–Pleistocene granites from the Larderello geothermal field (Tuscan Magmatic Province, Italy)

Extensive, mainly acidic peraluminous magmatism affected the Tuscan Archipelago and the Tuscan mainland since late Miocene, building up the Tuscan Magmatic Province (TMP) as the Northern Apennine fold belt was progressively thinned, heated and intruded by mafic magmas. Between 3.8 and 1.3 Ma an intrusive complex was built on Larderello area (Tuscan mainland) by emplacement of multiple intrusions of isotopically and geochemically distinct granite magmas. Geochemical and isotopic investigations were carried out on granites cored during drilling exploration activity on the Larderello geothermal field. With respect to the other TMP granites the Larderello intrusives can be classified as two-mica granites due to the ubiquitous presence of small to moderate amounts of F-rich magmatic muscovite. They closely resemble the almost pure crustal TMP acidic rocks and do not show any of the typical petrographic features commonly observed in the TMP hybrid granites (enclaves, patchy zoning of plagioclase, amphibole clots). On the basis of major and trace elements, as well as REE patterns, two groups of granites were proposed: LAR-1 granites (3.8–2.3 Ma) originated by biotite-muscovite breakdown, and LAR-2 granites (2.3–1.3 Ma) generated by muscovite breakdown. At least three main crustal sources (at 14–23 km depth), characterized by distinct ε_Nd(t) and ⁸⁷Sr/⁸⁶Sr values, were involved at different times, and the magmas produced were randomly emplaced at shallow levels (3–6 km depth) throughout the entire field. The partial melting of a biotite-muscovite-rich source with low ε_Nd(t) value (about −10.5) produced the oldest intrusions (about 3.8–2.5 Ma). Afterwards (2.5–2.3 Ma), new magmas were generated by another biotite-rich source having a distinctly higher ε_Nd(t) value (−7.9). Finally, a muscovite-rich source with high ε_Nd(t) (about −8.9) gave origin to the younger group of granites (2.3–1.0 Ma). The significant Sr isotope disequilibrium recorded by granites belonging to the same intrusion is interpreted, as due to the short residence time of magmas in the source region followed by their rapid transfer to the emplacement level. Partial melting was probably triggered by multiple, small-sized mafic intrusions, distributed over the last 3.8 Ma that allowed temporary overstepping of biotite- and muscovite-dehydration melting reactions into an already pre-heated crust. Dilution in time of the magmatic activity probably prevented melt mingling and homogenization at depth, as well as the formation of a single, homogeneous, hybrid pluton at the emplacement level. Moreover the high concentrations of fluxing elements (B, F, Li) estimated for the LAR granites modified melt properties by reducing solidus temperatures, decreasing viscosity and increasing H₂O solubility in granite melts. The consequences were a more efficient, fast, magma extraction and transfer from the source, and a prolonged time of crystallization at the emplacement level. These key factors explain the long-lived hydrothermal activity recorded in this area by both fossil (Plio-Quaternary ore deposits) and active (Larderello geothermal field) systems.