Age and origin of gem corundum and zircon megacrysts from the Mercaderes–Rio Mayo area, South-west Colombia, South America

Potential sources for alluvial gem corundum and zircon from the Rio Mayo area, near Mercaderes, Colombia are reviewed, based on U–Pb dating of syngenetic and protogenetic mineral inclusions in corundum samples and on a zircon megacryst. Corundum recovered from the region (approx. 99% sapphire, 1% ruby) commonly shows growth banding, includes colour change stones and exhibits overlaps in colour ranges and inclusion characteristics. This suggests a contiguous genetic suite. The U–Pb dating used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) techniques. Because of the young ages and low-U contents of the dated zircons, the acquired data required a special statistical treatment. The results from zircon, fluorapatite and allanite-(Ce) inclusions provide a corundum crystallization age of 8 to 11 Ma, in relation to northern Andean Miocene uplift and magmatism. The zircon megacryst gave a younger crystallization age of c. 0.6 Ma, unrelated to the corundum genesis. Geochemical parameters (trace element and O isotope ranges) for corundum samples suggest a metamorphic/metasomatic origin. The age data rules out corundum genesis during the Late Cretaceous ophiolitic generation, but leave open possible later metasomatic interactions with this substrate. The Cr/Ga and Ga/Mg ratios and O isotope range for the corundum fall within the known limits for metasomatic, desilicated felsic/ultramafic ‘plumasitic’ associations, suggesting a possible parental source. Allanite, extremely rare as an inclusion in corundum elsewhere, may prove a characteristic inclusion for Rio Mayo corundum.     

Advances in our understanding of the gem corundum deposits of the West Pacific continental margins intraplate basaltic fields

Recent discoveries over the last decade of new gemfields, exploitation of new and existing deposits, and application of relatively new techniques have greatly increased our knowledge of the basalt-derived gem sapphire–ruby–zircon deposits. In this paper we focus on the Late Mesozoic to Cenozoic intraplate basaltic fields of the West Pacific continental margins. We review advances made in understanding the genesis of these deposits, based on the application of newer techniques. We also critically review existing data on the gem corundum deposits, in order to further refine a model for their origin.In some of the intraplate basaltic fields, corundum-bearing xenoliths have been found showing a range of PT formation conditions from 790 °C at 0.85 GPa to as much as 1100 to 1200 °C at 1.0 to 2.5 GPa. Although most magmatic sapphires contain syngenetic inclusions of columbite-group phases, zircon, spinel and rutile, some contain additional nepheline and K-feldspar, suggesting crystallization from more undersaturated alkaline magma while the Weldborough field of NE Tasmania also contains molybdenite and beryl, suggesting at least some interaction with more fractionated ‘granitic-type’ magmas. There is a large range in PT conditions calculated for the metamorphic rubies (from 780 to 940 °C, through 800 to 1150 °C up to 1000 to 1300 °C). Fluid/melt inclusion studies on magmatic corundums generally suggest that they formed in a CO₂-rich environment from a ‘syenitic’ melt under a range of T conditions from 720 to 880 °C up to 1000 to 1200 °C. Oxygen isotope studies reveal that typical magmatic corundums have values of + 4.4 to 6.9‰, whereas metamorphic corundums from the same basaltic host have lower values of + 1.3 to 4.2‰.Geochronological studies have shown that some fields produced a simple eruptive and zircon/corundum crystallization event while others had multiple eruptive events but only one or two zircon crystallization events. For a few fields, some corundums/zircons crystallized in storage regions and then remained relatively inert for periods of 200 to 400 Ma without significant change before transport to the surface in the Cenozoic. Tectonic studies of the Australian region suggest that many of the corundums crystallized from magmas related to episodic basaltic volcanism in a tectonic regime of extension, associated with the opening of the Tasman and Coral Seas. For the Asian region, the magmatic–polygenetic corundums within the basaltic fields largely crystallized in a tectonic regime of distributed E–W extension, whereas the metamorphic-metasomatic corundums crystallised in a transpressional regime associated with the collision of the Indian Plate with the Eurasian Plate (e.g., [Garnier, V., Giuliani, G., Maluski, H., Ohnenstetter, D., Deloule, E., 2003. Ar–Ar and U–Pb ages of marble-hosted ruby deposits from Central and South-east Asia. Geophysical Research Abstracts 5, 03751; Garnier, V., Giuliani, G., Ohnenstetter, D., and Schwarz, D., 2004. Les gisements de corindon: classification et genese. Les placers a corindon gemme. Le Regne Mineral 55, 7-47; Garnier, V., Ohnenstetter, D., Giuliani, G., Maluski, H., Deloule, E., Phan Trong, T., Pham Van, L., Hoang Quang, V., 2005a. Age and significance of ruby-bearing marble from the Red River Shear Zone, Northern Vietnam. Canadian Mineralogist 43, 1315–1329]).     

Petrogenesis of alkaline basalt-hosted sapphire megacrysts. Petrological and geochemical investigations of in situ sapphire occurrences from the Siebengebirge Volcanic Field,Germany

Megacrystic sapphires are frequently associated with alkaline basalts, most notably in Asia and Australia, although basalt is not generally normative in corundum. Most of these sapphire occurrences are located in alluvial or eluvial deposits, making it difficult to study the enigmatic relationship between the sapphires and their host rocks. Here, we present detailed petrological and geochemical investigations of in situ megacrystic sapphires within alkaline basalts from the Cenozoic Siebengebirge Volcanic Field (SVF) in Germany. Markedly, the sapphires show several micrometer thick spinel coronas at the contact with the host basalt, indicating chemical disequilibrium between the sapphire and the basaltic melt, supporting a xenogenetic relationship. However, in situ U–Pb dating of a Columbite Group inclusion within one Siebengebirge sapphire using laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) indicates a close genetic relationship between sapphire crystallization and alkaline mafic volcanism in the SVF. The syngenetic mineral inclusion suite including carbonates, members of the Pyrochlore, Betafite and Columbite Groupe minerals, as well as a high abundance of HFSE and of gaseous low-density CO₂ inclusions support a parentage of a highly evolved, MgO and FeO deficient carbonatitic melt. We identified CO₂ to be the link between alkaline basaltic volcanism and the xenocrystic sapphires. Only alkaline volcanic suites can build up enough CO₂ in this magma chamber upon fractionation so that at high degrees of fractionation a carbonatitic melt exsolves which in turn can crystallize sapphires.     

Gem corundum deposits of Madagascar: A review

Madagascar is one of the most important gem-producing countries in the world, including ruby and sapphires. Gem corundum deposits formed at different stages in the geological evolution of the island and in contrasting environments. Four main settings are identified: (1) Gem corundum formed in the Precambrian basement within the Neoproterozoic terranes of southern Madagascar, and in the volcano-sedimentary series of Beforona, north of Antananarivo. In the south, high-temperature (700 to 800 °C) and low-pressure (4 to 5 kbar) granulites contain deposits formed during the Pan-African orogenesis between 565 and 490 Ma. They accompany mafic and ultramafic complexes (ruby deposits of the Vohibory group), skarns at the contact between Anosyan granites and the Proterozoic Tranomaro group (sapphire deposits of the Tranomaro–Andranondambo district), and shear-zone corridors cross-cutting feldspathic gneisses, cordieritites and clinopyroxenites in the Tranomaro, Vohimena and Androyan metamorphic series (biotite schist deposits of Sahambano and Zazafotsy, cordieritites of Iankaroka and Ambatomena). The circulation of fluids, especially along discontinuities, allowed in-situ alkaline metasomatism, forming corundum host rocks related to desilicified granites, biotitites, “sakenites” and “corundumites”. (2) Gem corundum also occurs in the Triassic detrital formations of the Isalo group, as giant palaeoplacers in the Ilakaka–Sakaraha area. Here, sapphires and rubies may come from the metamorphic granulitic terranes of southern Madagascar. (3) Gem corundum deposits occur within the Neogene-Quaternary alkali basalts from Ankaratra (Antsirabe–Antanifotsy area) and in the Ambohitra Province (Nosy Be, Ambato and Ambondromifehy districts). Primary deposits are rare, except at Soamiakatra where ruby in gabbroic and clinopyroxenite xenoliths within alkali-basalts probably derive from mantle garnet peridotites. The blue-green-yellow sapphires typical of basaltic fields are always recovered in palaeoplacer (in karst formed upon Jurassic limestones from the Montagne d'Ambre, Antsiranana Province) and alluvial and soil placers (Ankaratra volcanic massif). (4) Deposits occur within Quaternary eluvial, colluvial and alluvial concentrations, such as high-quality rubies from the Andilamena and Vatomandry deposits.     

The conditions of formation of sapphire and zircon in the areas of alkali-basaltoid volcanism in Central Vietnam

Study of the chemical composition of clinopyroxene and garnet megacrysts from the Dak Nong sapphire deposit and model calculations have shown that megacrysts originated from the crystallization of alkali basaltoid magma in a deep-seated intermediate chamber at 14–15 kbar, which is close to the Moho depth (50 km) in this part of southeastern Asia. The chamber was a source of heat and CO₂ fluids for the generation of crustal syenitic melts producing sapphires and zircons. The formation conditions of sapphires and zircons are significantly different. The presence of jadeite inclusions in placer zircons points to high pressures during their crystallization, which is confirmed by the ubiquitous decrepitation of CO₂-rich melt inclusions. Sapphires crystallized from iron-rich syenitic melt in the shallower Earth’s crust horizons with the participation of CO₂ and carbonate–H₂O–CO₂ fluids. The subsequent eruptions of alkali basalts favored the transportation of garnet and pyroxene megacrysts as well as sapphire and zircon xenocrysts to the surface. It is shown that sapphire deposits can be produced only during multistage basaltic volcanism with deep-seated intermediate chambers in the regions with thick continental crust. The widespread megacryst mineral assemblage (clinopyroxene, garnet, sanidine, ilmenite) and the presence of placer zircon megacrysts can be used as indicators for sapphire prospecting.     

Marble-hosted ruby deposits from Central and Southeast Asia: Towards a new genetic model

Marble-hosted ruby deposits represent the most important source of colored gemstones from Central and South East Asia. These deposits are located in the Himalayan mountain belt which developed during Tertiary collision of the Indian plate northward into the Eurasian plate. They are spatially related to granitoid intrusions and are contained in platform carbonates series that underwent high-grade metamorphism. All occurrences are located close to major tectonic features formed during Himalayan orogenesis, directly in suture zones in the Himalayas, or in shear zones that guided extrusion of the Indochina block after the collision in South East Asia. Ar–Ar dating of micas syngenetic with ruby and U–Pb dating of zircon included in ruby gives evidence that these deposits formed during Himalayan orogenesis, and the ages document the extensional tectonics that were active, from Afghanistan to Vietnam, between the Oligocene and the Pliocene.The petrography shows that ruby-bearing marbles formed in the amphibolite facies (T = 610 to 790 °C and P ~ 6 kbar). A fluid inclusion study defines the conditions of gem ruby formation during the retrograde metamorphic path (620 < T < 670 °C and 2.6 < P < 3.3 kbar) for the deposits of Jegdalek, Hunza and northern Vietnam.Whole rock analyses of non-ruby-bearing marbles indicate that they contain enough aluminum and chromiferous elements to produce all the ruby crystals that they contain. In addition, (C, O)-isotopic analyses of carbonates from the marbles lead to the conclusion that the marbles acted as a metamorphic closed fluid system that were not infiltrated by externally-derived fluids. The carbon isotopic composition of graphite in marbles reveals that it is of organic origin and that it exchanged C-isotopes with the carbonates during metamorphism. Moreover, the O-isotopic composition of ruby was buffered by metamorphic CO₂ released during devolatilisation of marble and the H-isotopic composition of mica is consistent with a metamorphic origin for water in equilibrium with the micas. The (C, O, H)-isotopic compositions of minerals associated with marble-hosted ruby are all in agreement with the hypothesis, drawn from the unusual chemistry of CO₂–H₂S–COS–S₈–AlO(OH)-bearing fluids contained in fluid inclusions, that gem ruby formed at P ~ 3 kbar and 620 < T < 670 °C, during thermal reduction of evaporite by organic matter, at high temperature-medium pressure metamorphism of platform carbonates during the Tertiary India–Asia collision. The carbonates were enriched in Al- and chromiferous-bearing detrital minerals, such as clay minerals that were deposited on the platform with the carbonates, and in organic matter. Ruby formed during the retrograde metamorphic path, mainly by destabilization of muscovite or spinel. The metamorphic fluid system was rich in CO₂ released from devolatilisation of carbonates, and in fluorine, chlorine and boron released by molten salts (NaCl, KCl, CaSO₄). Evaporites are key to explaining the formation of these deposits. Molten salts mobilized in situ Al and metal transition elements contained in marbles, leading to crystallization of ruby.     

Alkaline-ultrabasic mantle-derived magmas, their sources, and crystallization features: Data of melt inclusion studies

To find out the reasons responsible for the diversity of igneous rocks forming the alkaline-ultrabasic carbonatite Krestovskiy massif (the Maimecha–Kotui province, Russia) we have studied melt inclusions in clinopyroxene of trachydolerites, porphyric melanephelinites, and tholeiites. It was established that the homogenization temperatures of inclusions in these rocks are rather close: 1140–1180 °C, 1190–1230 °C, and 1150–1210 °C, respectively. Compositions of melt inclusions in clinopyroxenes from different rocks are significantly different. The chemical composition of clinopyroxene of trachydolerites corresponds to that of trachybasalts and their derivatives. The inclusions are enriched in Sr, Ba, P, and S and their total sum of alkalies (at K ≥ Na) is never less than 5–6 wt.%. Inclusions from the rims of clinopyroxene phenocrysts in porphyric melanephelinites are similar in composition also to inclusions in trachydolerites. But in the cores of clinopyroxene phenocrysts the composition of inclusions corresponds to nephelinite melt. The composition of some melt inclusions in the intermediate and cores zones of clinopyroxene from porphyric melanephelinite has high SiO₂ (53–55 wt.%), MgO (8–9 wt.%) and a low (1–2 wt.%) total sum of alkalies (at Na ≥ K) and is depleted in Al₂O₃ (6–7 wt.%), which is similar to the composition of basaltic komatiites. The composition of inclusions in tholeiites is also basic, highly magnesian, and low-alkaline, Sr and Ba are rare to absent. Compared to the inclusions of basaltic komatiite composition, the inclusions in tholeiites are enriched in Al and depleted in Ca, Ti, and P. The melts trapped in clinopyroxenes from different rocks contain low (0.014–0.018 wt.%) water but they are enriched in F: from 0.37 wt.% in nephelinite melts to 0.1–0.06 wt.% in tholeiite and basaltic komatiite melts. Inclusions in all the rocks under study, host clinopyroxene, and the rocks themselves are significantly enriched in incompatible elements (1–2 orders of magnitude relative to the mantle norm). In tholeiites, the partitioning of these elements is rather uniform, while in trachydolerites and especially in melanephelinites it is contrasting with a drastic depletion in HREE relative to LREE, MREE, and HFSE. A conclusion is made that the Krestovskiy massif was formed by no less than three mantle-derived magmas: melanephelinite, tholeiite and basaltic komatiite. Magmas were generated in different magma sources at different depths with various degrees of enrichment in incompatible elements. These magmas were, most likely, dominated by melanephelinite magma. In intermediate chambers this magma differentiated to form derivative melts of nephelinite, trachydolerite–trachyandesite–trachyte compositions. Komatiite-basalt melts were, most likely, derivatives of primitive meimechite magmas.     

Combining trace-element compositions, U–Pb geochronology and Hf isotopes in zircons to unravel complex calcalkaline magma chambers in the Upper Cretaceous Srednogorie zone (Bulgaria)

Precise U–Pb geochronology and Hf isotope tracing of zircon is combined with whole-rock geochemical and Sr and Nd isotope data in order to unravel processes affecting mafic to felsic calcalkaline magmas prior to and during their crystallization in crustal magma chambers along the southern border of Central Srednogorie tectonic zone in Bulgaria (SE Europe). ID-TIMS U–Pb dating of single zircons from felsic and mixed/mingled dioritic to gabbroic horizons of single plutons define crystallization ages of around 86.5–86.0, 85.0–84.5 and 82 Ma. Concordia age uncertainties are generally less than 0.3 Ma (0.35%–2σ), and as good as 0.08 Ma (0.1%), when the weighted mean ²⁰⁶Pb/²³⁸U value is used. Such precision allows the distinction of magma replenishment processes if separated by more than 0.6–1.0 Ma and when they are marked by newly saturated zircons. We interpret zircon dates from a single sample that do not overlap to reflect new zircon growth during magma recharge in a long-lived crustal chamber. Mingling/mixing of the basaltic magma with colder granitoid mush at mid- to upper-crustal levels is proposed to explain zircon saturation and fast crystallization of U- and REE-rich zircons in the hybrid gabbro.Major and trace-element distribution and Sr and Nd whole-rock isotope chemistry define island arc affinities for the studied plutons. Slab derived fluids and a sediment component are constrained as enrichment sources for the mantle wedge-derived magma, though Hf isotopes in zircon suggest crustal assimilation was also important. Inherited zircons, and their corresponding ε-Hf, from the hybrid gabbroic rocks trace the lower crust as possible source for enrichment of the mantle magma. These inherited zircons are about 440 Ma old with ε-Hf of − 7 at 82 Ma, whereas newly saturated concordant Upper Cretaceous zircons reveal mantle ε-Hf values of + 7.2 to + 10.1. The upper and middle crusts contribute in the generation of the granitoid rocks. Their zircon inheritance is Lower Palaeozoic or significantly older and crustal dominated with 82–85 Ma corrected ε-Hf values of − 28. The Cretaceous concordant zircons in the granitoids are mantle dominated with a ε-Hf values spreading from + 3.9 to + 7.     

Metallogenesis of the Carajás Mineral Province, Southern Amazon Craton, Brazil: Varying styles of Archean through Paleoproterozoic to Neoproterozoic base- and precious-metal mineralisation

The Itacaiúnas Belt of the highly mineralised Carajás Mineral Province comprises ca. 2.75 Ga volcanic rocks overlain by sedimentary sequences of ca. 2.68 Ga age, that represent an intracratonic basin rather than a greenstone belt. Rocks are generally at low strain and low metamorphic grade, but are often highly deformed and at amphibolite facies grade adjacent to the Cinzento Strike Slip System. The Province has been long recognised for its giant enriched iron and manganese deposits, but over the past 20 years has been increasingly acknowledged as one of the most important Cu–Au and Au–PGE provinces globally, with deposits extending along an approximately 150 km long WNW-trending zone about 60 km wide centred on the Carajás Fault. The larger deposits (approx. 200–1000 Mt @ 0.95–1.4% Cu and 0.3–0.85 g/t Au) are classic Fe-oxide Cu–Au deposits that include Salobo, Igarapé Bahia–Alemão, Cristalino and Sossego. They are largely hosted in the lower volcanic sequences and basement gneisses as pipe- or ring-like mineralised, generally breccia bodies that are strongly Fe- and LREE-enriched, commonly with anomalous Co and U, and quartz- and sulfur-deficient. Iron oxides and Fe-rich carbonates and/or silicates are invariably present. Rhenium–Os dating of molybdenite at Salobo and SHRIMP Pb–Pb dating of hydrothermal monazite at Igarapé-Bahia indicate ages of ca. 2.57 Ga for mineralisation, indistinguishable from ages of poorly-exposed Archean alkalic and A-type intrusions in the Itacaiúnas Belt, strongly implicating a deep magmatic connection.A group of smaller, commonly supergene-enriched Cu–Au deposits (generally < 50 Mt @ < 2% Cu and < 1 g/t Au in hypogene ore), with enrichment in granitophile elements such as W, Sn and Bi, spatially overlap the Archean Fe-oxide Cu–Au deposits. These include the Breves, Águas Claras, Gameleira and Estrela deposits which are largely hosted by the upper sedimentary sequence as greisen-to ring-like or stockwork bodies. They generally lack abundant Fe-oxides, are quartz-bearing and contain more S-rich Cu–Fe sulfides than the Fe-oxide Cu–Au deposits, although Cento e Dezoito (118) appears to be a transitional type of deposit. Precise Pb–Pb in hydrothermal phosphate dating of the Breves and Cento e Dezoito deposits indicate ages of 1872 ± 7 Ma and 1868 ± 7 Ma, respectively, indistinguishable from Pb–Pb ages of zircons from adjacent A-type granites and associated dykes which range from 1874 ± 2 Ma to 1883 ± 2 Ma, with 1878 ± 8 Ma the age of intrusions at Breves. An unpublished Ar/Ar age for hydrothermal biotite at Estrela is indistinguishable, and a Sm–Nd isochron age for Gameleira is also similar, although somewhat younger. The geochronological data, combined with geological constraints and ore-element associations, strongly implicate a magmatic connection for these deposits.The highly anomalous, hydrothermal Serra Pelada Au–PGE deposit lies at the north-eastern edge of the Province within the same fault corridor as the Archean and Paleoproterozoic Cu–Au deposits, and like the Cu–Au deposits is LREE enriched. It appears to have formed from highly oxidising ore fluids that were neutralised by dolomites and reduced by carbonaceous shales in the upper sedimentary succession within the hinge of a reclined synform. The imprecise Pb–Pb in hydrothermal phosphate age of 1861 ± 45 Ma, combined with an Ar/Ar age of hydrothermal biotite of 1882 ± 3 Ma, are indistinguishable from a Pb–Pb in zircon age of 1883 ± 2 Ma for the adjacent Cigano A-type granite and indistinguishable from the age of the Paleoproterozoic Cu–Au deposits. Again a magmatic connection is indicated, particularly as there is no other credible heat or fluid source at that time.Finally, there is minor Au–(Cu) mineralisation associated with the Formiga Granite whose age is probably ca. 600 Ma, although there is little new zircon growth during crystallisation of the granite. This granite is probably related to the adjacent Neoproterozoic (900–600 Ma) Araguaia Fold Belt, formed as part of the Brasiliano Orogeny.Thus, there are two major and one minor period of Cu–Au mineralisation in the Carajás Mineral Province. The two major events display strong REE enrichment and strongly enhanced LREE. There is a trend from strongly Fe-rich, low-SiO₂ and low-S deposits to quartz-bearing and more S-rich systems with time. There cannot be significant connate or basinal fluid (commonly invoked in the genesis of Fe-oxide Cu–Au deposits) involved as all host rocks were metamorphosed well before mineralisation: some host rocks are at mid- to high-amphibolite facies. The two major periods of mineralisation correspond to two periods of alkalic to A-type magmatism at ca. 2.57 Ga and ca. 1.88 Ga, and a magmatic association is compelling.The giant to world-class late Archean Fe-oxide Cu–Au deposits show the least obvious association with deep-seated alkaline bodies as shown at Palabora, South Africa, and implied at Olympic Dam, South Australia. The smaller Paleoproterozoic Cu–Au–W–Sn–Bi deposits and Au–PGE deposit show a more obvious relationship to more fractionated A-type granites, and the Neoproterozoic Au–(Cu) deposit to crustally-derived magmas. The available data suggest that magmas and ore fluids were derived from long-lived metasomatised lithosphere and lower crust beneath the eastern margin of the Amazon Craton in a tectonic setting similar to that of other large Precambrian Fe-oxide Cu–Au deposits.     

Mineral and fluid inclusions in zircon of UHP metamorphic rocks from the CCSD-main drill hole: A record of metamorphism and fluid activity

The Chinese Continental Scientific Drilling (CCSD) main drill hole (0–3000 m) in Donghai, southern Sulu orogen, consists of eclogite, paragneiss, orthogneiss, schist and garnet peridotite. Detailed investigations of Raman, cathodoluminescence, and microprobe analyses show that zircons from most eclogites, gneisses and schists have oscillatory zoned magmatic cores with low-pressure mineral inclusions of Qtz, Pl, Kf and Ap, and a metamorphic rim with relatively uniform luminescence and eclogite-facies mineral inclusions of Grt, Omp, Phn, Coe and Rt. The chemical compositions of the UHP metamorphic mineral inclusions in zircon are similar to those from the matrix of the host rocks. Similar UHP metamorphic P–T conditions of about 770 °C and 32 kbar were estimated from coexisting minerals in zircon and in the matrix. These observations suggest that all investigated lithologies experienced a joint in situ UHP metamorphism during continental deep subduction. In rare cases, magmatic cores of zircon contain coesite and omphacite inclusions and show patchy and irregular luminescence, implying that the cores have been largely altered possibly by fluid–mineral interaction during UHP metamorphism.

Abundant H₂O–CO₂, H₂O- or CO₂-dominated fluid inclusions with low to medium salinities occur isolated or clustered in the magmatic cores of some zircons, coexisting with low-P mineral inclusions. These fluid inclusions should have been trapped during magmatic crystallization and thus as primary. Only few H₂O- and/or CO₂-dominated fluid inclusions were found to occur together with UHP mineral inclusions in zircons of metamorphic origin, indicating that UHP metamorphism occurred under relatively dry conditions. The diversity in fluid inclusion populations in UHP rocks from different depths suggests a closed fluid system, without large-scale fluid migration during subduction and exhumation.     

Solid inclusions of magmatic halite and sylvite in felsic granitoids, Sierra Norte, Córdoba, Argentina

This study provides evidence for the existence of halite and sylvite solid inclusions in igneous quartz and feldspars, the first to be reported in intrusive rocks, and to partially constrain the physicochemical environment that lets halides crystallize under magmatic conditions.Halite and sylvite solid inclusions were found included in quartz and feldspars from a micrographic–granophyric assemblage in a miarolitic aplite and, rarer, in alkali-feldspar from a miarolitic monzogranite. Monzogranite and aplite represent I-type, K-enriched postcollisional rocks of the Late Cambrian–Early Ordovician Sierra Norte–Ambargasta batholith in the Eastern Sierras Pampeanas. Both granitoids fall among the most evolved felsic rocks of the batholith, with aplite approaching haplogranitic compositions. Halite is far more common than sylvite and the presence and distribution of one or both halides are erratic within the felsic intrusive bodies. Halides occur as small skeletal grains, commonly in cross-shaped aggregates of less than 50 μm. No K or Na was found at the detection limits of EDS in either halite or sylvite respectively. Textural relationships suggest that the alkali-chlorides separated from the melt near the minima along the quartz–feldspar cotectics of P_H2O > 160 < 200 MPa in a silica-, and potassium-rich magmatic system at approximately 750–700 °C, prior to the H₂O-vapor saturated miarole-forming stage.Computed ratios for the magmatic volatile phase (MVP) coexisting with melt at the early stage of aplite crystallization are: NaCl/HCl = 0.11–0.97 and KCl/HCl = 0.24–1.62, being the highest range of values (0.79–0.97 and 1.45–1.62, respectively) found in those alkali-chloride-bearing samples. Maximum HCl/ΣCl_(MVP) (0.28 to 0.31) indicates higher total Cl concentration in the MVP of alkali-chloride-bearing aplites, which is much higher in the halite-free aplite samples (HCl/ΣCl_(MVP) = 0.59 to 0.74). One miarolitic monzogranite sample, where halite solid inclusions are present, also yielded the highest ratios for NaCl/HCl_(MVP) (0.91) and KCl/HCl_(MVP) (1.46), and the HCl/ΣCl_(MVP) is 0.30. A high HCl concentration in the fluid phase is suggested by the log f(HF)/f(H₂O) = − 4.75 to − 4.95, log f(HCl)/f(H₂O) = − 3.73 to − 3.86, and log f(HF)/f(HCl) = − 0.88 to − 1.22, computed at 750 °C after biotite composition. The Cl concentrations at 800 °C, computed with a D^v/l_Cl = 0.84 + 26.6P (P at 200 MPa), yielded values within the range of  70 to 700 ppm Cl in the melt and  4000 to 40 000 ppm Cl in the coexisting MVP. The preferential partitioning of Cl in the vapor phase is controlled by the D^v/l_Cl; however, the low concentration of Cl in the melt suggests that high concentrations of Cl are not necessary to saturate the melt in NaCl or KCl.Cl-saturation of the melt and coexisting MVP might have been produced by a drop in Cl solubility due to the near-haplogranitic composition of the granitoids after extreme fractionation, probably enhanced by fluctuating reductions of the emplacement pressure in the brittle monzogranite host. Liquid immiscibility, based in the differential viscosity and density among alkali-chloride saturated hydrosaline melt, aluminosilicate felsic melt, and H₂O-rich volatiles is likely to have crystallized halite and sylvite from exsolved hydrosaline melt. High degrees of undercooling might have been important at the time of alkali-chloride exsolution. The effectiveness of alkali-chloride separation from the melt at magmatic temperatures is in line with the interpretation of “halite subtraction” as a necessary process to understand the origin of the “halite trend” in highly saline fluid inclusions from porphyry copper and other hydrothermal mineralizations, despite the absence of the latter in the Cerro Baritina aplites, where this process preceded the exsolution of halite-undersaturated fluids.Pervasive alteration of the monzogranite country rock as alkali-metasomatic mineral assemblages, the mineral chemistry of some species, and the association of weak molybdenite mineralization are compatible with the activity of alkaline hypersaline fluids, most likely exsolved during the earliest stages of aplite consolidation.     

山东蓝宝石的包裹体研究

运用激光拉曼光谱、电子探针、包裹体测温等方法,对山东蓝宝石中的包裹体进行分析和测试。发现山东蓝宝石中包裹体数量巨大,裂隙、色带、针状包裹体以及多相包裹体是其主要的特征。其中主要的固体包裹体有锆石、刚玉、黑云母、尖晶石等,而多相包裹体的成分主要为H2O、CO2及玻璃相。电子探针结果显示,Fe的含量对于蓝宝石的颜色及色带的发育有制约作用。     

Porphyry Cu–Au and associated polymetallic Fe–Cu–Au deposits in the Beiya Area, western Yunnan Province, south China

The Alkaline porphyries in the Beiya area are located east of the Jinshajiang suture, as part of a Cenozoic alkali-rich porphyry belt in western Yunnan. The main rock types include quartz-albite porphyry, quartz-K-feldspar porphyry and biotite–K-feldspar porphyry. These porphyries are characterised by high alkalinity [(K₂O + Na₂O)% > 10%], high silica (SiO₂% > 65%), high Sr (> 400 ppm) and ⁸⁷Sr/⁸⁶Sr (> 0.706)] ratio and were intruded at 65.5 Ma, between 25.5 to 32.5 Ma, and about 3.8 Ma, respectively. There are five main types of mineral deposits in the Beiya area: (1) porphyry Cu–Au deposits, (2) magmatic Fe–Au deposits, (3) sedimentary polymetallic deposits, (4) polymetallic skarn deposits, and (5) palaeoplacers associated with karsts. The porphyry Cu–Au and polymetallic skarn deposits are associated with quartz–albite porphyry bodies. The Fe–Au and polymetallic sedimentary deposits are part of an ore-forming system that produced considerable Au in the Beiya area, and are characterised by low concentrations of La, Ti, and Co, and high concentrations of Y, Yb, and Sc.The Cenozoic porphyries in western Yunnan display increased alkalinity away from the Triassic Jinshajiang suture. Distribution of both the porphyries and sedimentary deposits in the Beiya area are interpreted to be related to partial melting in a disjointed region between upper mantle lithosphere of the Yangtze Plate and Gondwana continent, and lie within a shear zone between buried Palaeo-Tethyan oceanic lithosphere and upper mantle lithosphere, caused by the subduction and collision of India and Asia.     

Evaluation of the uncertainty in estimation of metal resources of skarn tin in Southern China

This study is concerned with the problem of how many undiscovered mineral deposits can be expected to occur in the vicinity of any known deposit, especially if the deposit is nearly mined out. Skarn tin deposits in southern China were chosen to demonstrate that fractal modeling can be a useful tool to characterize the spatial–temporal distribution of mineral deposits, and to quantify their grades and tonnages. The results show that the spatial–temporal distribution of skarn tin deposits as well as their grades and tonnages satisfy fractal statistic, and suggest that 14 skarn tin deposits could be found around a known skarn tin deposit within a radius of 80 km. Monte Carlo simulation was used to combine the number of deposits and the frequency distributions of grade and tonnage and to capture the uncertainty in estimation of metal resources. At the 90%, 50% and 10% confidence levels, tin metal resources amount to 6 ton, 200 ton, and 1.0 × 10⁴ ton around a known tin deposit within a radius of 80, respectively.     

Contrasting ages between isotopic chronometers in granulites: monazite dating and metamorphism in the Higo Complex, Japan

The Higo Complex of west-central Kyushu, western Japan is a 25 km long body of metasedimentary and metabasic lithologies that increase in metamorphic grade from schist in the north to migmatitic granulite in the south, where granitoids are emplaced along the southern margin. The timing of granulite metamorphism has been extensively investigated and debated. Previously published Sm–Nd mineral isochrons for garnet-bearing metapelite yielded ca.220–280 Ma ages, suggesting high-grade equilibration older than the lower grade schist to the north, which yielded ca.180 Ma K–Ar muscovite ages. Ion and electron microprobe analyses on zircon have yielded detrital grains with rim ages of ca.250 Ma and ca.110 Ma. Electron microprobe ages from monazite and xenotime are consistently 110–130 Ma. Two models have been proposed: 1) high-grade metamorphism and tectonism at ca.115 Ma, with older ages attributed to inheritance; and 2) high-grade metamorphism at ca.250 Ma, with resetting of isotopic systems by contact metamorphism at ca.105 Ma during the intrusion of granodiorite. These models are evaluated through petrographic investigation and electron microprobe Th–U–total Pb dating of monazite in metapelitic migmatites and associated lithologies. In-situ investigation of monazite reveals growth and dissolution features associated with prograde and retrograde stages of progressive metamorphism and deformation. Monazite Th–U–Pb isochrons from metapelite, diatexite and late-deformational felsic dykes consistently yield ca.110–120 Ma ages. Earlier and later stages of monazite growth cannot be temporally resolved. The preservation of petrogenetic relationships, coupled with the low diffusion rate of Pb at < 900 °C in monazite, is strong evidence for timing high-temperature metamorphism and deformation at ca.115 Ma. Older ages from a variety of chronometers are attributed to isotopic disequilibrium between mineral phases and the preservation of inherited and detrital age components. Tentative support is given to tectonic models that correlate the Higo terrane with exotic terranes between the Inner and Outer tectonic Zones of southwest Japan, possibly derived from the active continental margin of the South China Block. These terranes were dismembered and translated northeastwards by transcurrent shearing and faulting from the beginning to the end of the Cretaceous Period.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.     

Composition and conditions of crystallization of zircon from the rare-metal ores of the Gremyakha–Vyrmes Massif,Kola Peninsula

The first data on the composition and inner structure of zircon, one of the main ore minerals of the rare-metal metasomatites of the Gremyakha–Vyrmes alkaline-ultramafic massif, are reported. Early zircon generations are enriched in Y and REE and contain numerous inclusions of rock-forming and accessory minerals of metasomatites, as well as syngenetic fluid inclusions of calcite, thorite and thorianite. Late generations differ in the elevated Hf content and contain no inclusions. The elevated concentrations of Ca and Th in the central zones of crystals are related to the presence of numerous micron-sized inclusions of calcite and thorium phases. All zircon varieties have extremely low U and Pb contents. Concentrations and distribution patterns of incompatible and rare-earth elements in zircon from the metasomatites of the Gremyakha–Vyrmes Massif are similar to those of syenite pegmatites and magmatic carbonatites around the world. Mineral from these associations shows a positive Ce anomaly and elevated HREE contents. According to the compositions of zircon and thorite inclusion in it and experimental data on the simultaneous synthesis of these minerals, the crystallization temperature of zircon was 700–750°С. Using Ti-in-zircon temperature dependence, late zurcon was formed at temperature of 700–750°С. The rare-metal metasomatites are formed at the final stages of the massif formation, presumably after foidolites. Carbonatites could initiate metasomatic reworking of foidolites and accumulation of trace metals in them. The evolution of the primary alkaline–ultramafic melt toward the enrichment in trace elements was mainly controlled by crystallization differentiation.     

Corundum inclusions in diamonds—discriminatory criteria and a corundum compositional dataset

Mineral inclusions of corundum are reported from diamonds from alluvial deposits of tributaries of the Rio Aripuanã, Juina, Brazil. We present the first recorded occurrence of sapphire as an inclusion in diamond and expand on the database of ruby and white corundum inclusions. Ruby inclusions are found to occur both as isolated and touching grains with aluminous pyroxene and associated with ferropericlase. Mineral chemistry and phase relations place the origin of such ruby-bearing diamonds within the lower mantle at 770 km. Mineral associations indaving other corundum inclusions were not observed; hence, their depth of origin is less certain.

Compositions of corundum samples were characterised by electron and ion microprobe. Given the scarcity of literature data, corundum samples from a variety of other geological settings were also analysed. Samples comprised corundums associated with granitic emplacement, metasomatism, amphibolite-facies and granulite-facies rocks, gem and industrial synthetic origins and carmine-coloured corundums recovered from kimberlite drill cores.

In addition to variable amounts of Cr, Fe, Ti, Mg and Si, measurable quantities of other transition elements and high field strength elements were also detected. Corundums from similar geological settings show very similar compositions and are easily distinguishable from other settings. Irrespective of locality, rubies from Norwegian, Tanzanian and Kenyan amphibolite-facies rocks are compositionally indistinguishable. Additionally, corundums from metasomatised zones associated with contact metamorphism from Arizona and Japan were very similar, particularly characterised by unusually high abundance of mobile Zr and Nb (tens of ppm). All Juina inclusions are particularly distinguishable from other corundums by high concentrations of Ni (18–171 ppm weight), typically at least an order of magnitude enriched over the same corundum varietal types from elsewhere. Furthermore, the sapphire inclusion exhibited much larger ratios of Ga and Ge to HFSE elements compared to otherwise similar samples, and ruby inclusions are distinguished by high Mg/Fe ratios (0.27–1.56 by weight). Compositional differences between inclusions in diamonds and corundums from other settings in addition to corundum's physical and chemical durability suggest that with the employment of rapid identification tools such as energy dispersive spectrometry (EDS) and laser-ICPMS, corundum has promise as an indicator of diamond prospectivity.     

Mineral inclusions in sapphire from the basalt-related deposit in Bo Phloi,Kanchanaburi, western Thailand: indication of their genesis

The Bo Phloi gem field in Kanchanaburi Province, Western Thailand, is closely associated with Cenozoic basalts. Blue and yellow sapphire, black spinel, and minor zircon have been mined for over three decades. The mineral inclusions observed in sapphire samples are alkali feldspar, nepheline, hercynitic spinel, zircon, manganiferous ilmenite, silica-rich enstatite, almandine–pyrope garnet, monazite, calcite, sapphirine, biotite–phlogopite mica, and staurolite. Based on their geochemical affinity, these mineral inclusions can be categorized into two main groups: felsic alkaline and contact-metamorphic, which appear to have originated from different processes. These inclusions provide new evidence for proposing a bimodal genetic model. Felsic alkaline origin is evidenced by the occurrence of a felsic alkaline inclusion suite and the REE geochemistry of sapphire-associated zircon, which indicates that most of the sapphires crystallized from a high-alkali felsic melt (probably, in the lower crust). Contact-metamorphic origin is evidenced by the presence of a contact-metamorphic inclusion suite, suggesting that some of these sapphires might also have originated from metasomatized crustal rocks and a contaminated melt along the contact zone of a basaltic intrusion (probably, in the upper mantle or lower crust).     

Significance of ~ 1.5 Ga zircon and monazite ages from charnockites in southern Lithuania and NE Poland

The presence of 1.52–1.50 Ga charnockites from the anorthosite–mangerite–charnockite–granite (AMCG) Mazury complex in southern Lithuania and NE Poland, in the western East European Craton (EEC) is revealed by secondary ion mass-spectrometry (SIMS) and EPMA geochronology. Early 1.85–1.82 Ga charnockites are related to major orogeny in the region whereas the newly studied charnockites intrude the already consolidated crust. The 1.52–1.50 Ga charnockite magmatism (SIMS data on zircon) was followed by high-grade metamorphism (EPMA data on monazite), which strongly affected the surrounding rocks. The 1.85–1.81 Ga zircon cores in Lazdijai and 1.81 Ga monazite domains in the Lanowicze charnockites represent the protolith age of a volcanic island arc. The 1.52–1.50 Ga charnockite magmatism and metamorphism are likely related to the distal, Danopolonian, orogeny further to the west, at the margin of Baltica. The c.1.52–1.50 Ga AMCG magmatism and metamorphism in the western EEC as well as the paired accretionary-rapakivi suites in Amazonia, may be the inboard manifestations of the same early Mesoproterozoic orogeny associated with the juxtaposition of Amazonia and Baltica during the amalgamation of the supercontinent Columbia.