Chemical composition of tourmaline from the Yunlong tin deposit, Yunnan, China: implications for ore genesis and mineral exploration

Summary ?The Yunlong tin deposit is located in the northern part of the Lancangjiang metamorphic zone of the Sanjiang Tethys orogen series in western Yunan province of China. It consists of vein-type cassiterite ores, which are mainly hosted in migmatites of Caledonian age. Abundant tourmaline is associated with the ores, quartz–tourmaline veins and barren migmatized gneiss and migmatites. A detailed electron microprobe study has been carried out to document the chemical compositions of tourmaline from this deposit. The results exhibit a systematic compositional change that might be used as tracer for ore genesis and in prospecting for tin mineralization. Tourmalines from the ore bodies are dravite with Fe/(Fe + Mg) ratios of 0.09 ∼ 0.31 and Ca/(Ca + Na) ratios of 0.03 ∼ 0.40. These tourmalines are also rich in chromium (up to 0.74 wt% Cr₂O₃) and tin (up to 0.42 wt% Sn). In contrast, tourmalines from the barren migmatites are mostly schorl with Fe/(Fe + Mg) ratios of 0.38 ∼ 0.94 and Ca/(Ca + Na) ratios of 0.00 ∼ 0.14. Tourmalines from quartz–tourmaline veins that occur between ore bodies and the migmatites show intermediate compositions, i.e., Fe/(Fe + Mg) = 0.09 ∼ 0.59, Ca/(Ca + Na) = 0.01 ∼ 0.22. It is suggested that the Mg-rich nature of the tourmaline can be used as an exploration tool in this region to target tin mineralization, because the tourmalines show increasing Mg contents and are more dravitic when approaching the ore bodies. It is likely that the formation of the Yunlong tin deposit was related to migmatitic-hydrothermal processes. The high Mg and Cr contents in tourmalines from the ore bodies were probably derived from the local meta-sedimentary and meta-volcanic rocks of the Precambian Chongshan Group rather than from the granites in the region. Received December 28, 2000; revised version accepted January 25, 2002     

Internally consistent gahnitic spinel-cordierite-garnet equilibria in the FMASHZn system: geothermobarometry and applications

The equilibrium (Mg, Fe, Zn)₃Al₂Si₃O₁₂+2Al₂SiO₅=3(Mg, Fe, Zn)Al₂O₄+5SiO₂ garnet + sillimanite/kyanitc = spinel + quartz was calibrated in the piston-cylinder apparatus between 11 and 30 kbar, and over the temperature range of 950 to 1200°C. Three experimental mixes of Mg no. [100^*MgO/(MgO+FeO)] 40, 47 and 60, in the FeO –MgO–Al₂O₃–SiO₂–ZnO (FMASZn) system were used under low oxygen fugacities and anhydrous conditions. We derive a ternary Fe–Mg–Zn symmetric mixing model for aluminous spinels in equilibrium with garnet, to quantify the increase in gahnitic end-member of spinel with increasing pressure and descreasing temperature. Further experiments in the spinel-cordieritequartz-sillimanite field were combined with garnet-cordierite data from the literature to produce a consistent set of equations describing the exchange reactions in FMASHZn relevant to quartz-sillimanite bearing rocks at granulite facies conditions. As spinel is an important mineral participating in many rocks of aluminous composition at granulite-facies conditions, and as zinc contributes to an enlargement of spinel's stability field towards higher pressures and lower temperatures, the thermobarometric calibrations presented here will be most significant in delineating the prograde and retrograde trajectory of P-T paths.     

Tourmaline in Proterozoic Massive Sulfide Deposits from Rajasthan, India

We have analyzed the chemical composition and boron isotope composition of tourmaline from tourmalinites, granite and a quartz-tourmaline vein from the Deri ore zone and from a pegmatitic band in the Rampura-Agucha ore body. These two Proterozoic massive sulfide deposits occur in the Aravalli-Delhi orogenic belt, Rajasthan, northwest India. Tourmaline from stratiform tourmalinites closely associated with the massive sulfides in the Deri deposit have preserved their original chemical compositions despite regional and thermal metamorphism in the area. These tourmalines have low Fe/(Fe + Mg) ratios (0.19–0.30; mean 0.26) that suggest formation close to the sediment-sea water interface. The δ¹¹B values (−15.5 and −16.4‰) are compatible with boron derived from leaching of argillaceous sediments and/or felsic volcanics underlying the original massive sulfide deposit during its formation. Boron isotope compositions measured in tourmaline from a post-ore granite and quartz-tourmaline vein in the Deri deposit indicate that boron in these tourmalines was derived from the tourmalinites produced during ore formation. The boron isotope systematics of a coarse brown tourmaline crystal from a pegmatitic band on the hanging wall contact of the Rampura-Agucha deposit indicate that 45 ± 25% of the boron within the original tourmaline was lost during upper amphibolite facies regional metamorphism. Received: 3 April 1996 / Accepted: 11 April 1996     

Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ¹⁸O, δD, δ¹¹B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (^X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ¹⁸O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ¹¹B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ¹⁸O = 12.4 ‰, δD = ?29.5 ‰, and δ¹¹B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ¹⁸O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ¹¹B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on ¹⁸O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ¹⁸O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ¹⁸O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ¹⁸O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.     

Loss of metals from pelites during regional metamorphism

In aluminous metapelites the ratio H₂O⁺/K₂O decreases with increasing metamorphic grade and degree of reaction. This ratio is a very practical indicator for the progress of the mineral reconstitution during progressive metamorphism. With decreasing values of the ratio H₂O⁺/ K₂O the Cu concentration and the following element ratios also decrease either continuously or in stepwise fashion: Tl/K₂O, Ba/K₂O, Pb/K₂O, Bi/K₂O, Hg/K₂O, Sr/Na₂O, Zn/(Fe²⁺+Mg), Cd/(Fe²⁺+Mg); Rb/K₂O remains approximately constant. In the aluminous metapelites of the Damara Orogen in Namibia the following losses occur between the biotite isograd and anatexis: 61% Cu, 20% Tl, 34% Ba, 59% Pb, 86% Bi, 46% Hg, 30% Sr, 25% Zn, 31% Cd. Thus the potential of regional metamorphism to form hydrothermal deposits in the low grade environment should not be neglected.     

Tourmaline in a low grade clastic metasedimentary rock: an example of the petrogenetic potential of tourmaline

Detrital tourmaline grains and their associated tourmaline overgrowths provide a means to unravel the provenance and petrogenetic history of low grade clastic metasedimentary rocks. Evidence derives from tourmaline grains found in a lithic wacke metamorphosed to chlorite zone conditions. The detrital tourmaline cores are diagnostic indicators of the source rocks of the sediment whereas the overgrowths record both diagenetic and metamorphic reactions in the rock. Tourmaline grains consist of a detrital core surrounded by asymmetric overgrowths comprised of inner and outer rims. Abrupt chemical discontinuities between each of these zones implies that volume diffusion within tourmaline was minor under the conditions of formation. Compositions of the detrital cores vary widely, yet can be correlated with source rock types that are consistent with lithic fragments recognizable in the metawacke. At either the analogous or antilogous pole, inner rim compositions proximal to the detrital cores converge, despite the substrate tourmaline composition, indicating an approach to chemical equilibrium. However, significant dufferences in Al and X-site vacancies at the expense of Mg, Na and Ti between the analogous and antilogous poles of the inner rims demonstrate the presence of significant amounts of compositional polarity. Outer rim compositions at either pole also converge but compositional polarity between the analogous and antilogous poles persists. The presence of the inner and outer rims separated by a compositional discontinuity suggests punctuated evolution of the overgrowth. This implies that boron was sporadically available during diagenesis and metamorphism. Based on boron contents of minerals, this may correspond to a mechanism such as boron release due to polytypic change of illite or consumption of illite and/or muscovite. As such, tourmaline growth stages may serve as a monitor of chemical reactions in low grade metamorphic rocks.     

Dissakisite-(Ce) chemical composition: some implications for its origins

Euhedral dissakisites from Trimouns dolomite mine, France, is compositionally zoned. Back-scattered electron (BSE) images reveal that each of the described dissakisite crystals has three distinct compositional zones: normal zoned core (Mg-rich), oscillatory zoned middle (Ca–Al-rich) and homogeneous rim (Fe–ΣREE-rich). The latter zone with Fe²⁺ > Mg corresponds to allanite-(Ce). Dissakisite-(Ce) also displays pronounced zoning in Fe/Mg which may suggest that the temperature of crystallization continuously decreased from core to rim. Despite a systematic increase in Fe/Mg of the dissakisite with an allanite rim, there is no monotonic decrease in the REE zoning: the normal zoned core and homogeneous rim are rich in La, Ce and Pr, but the relatively REE-poor oscillatory zoned middle is relatively abundant in Y, Sm and Gd. Discontinuous variation in REE content of the dissakisite, with the allanite rim may indicate a localized change in either the relative concentration of various ligands or pH of the crystallizing fluid. Observations under the polarizing microscope confirm that the different zones have simultaneous extinction. These chemical and optical observations suggest that epitaxial crystallization of dissakisite, from Trimouns, passes through three formation stages. The ternary Fe²⁺–Mg²⁺–(Al + Fe)³⁺ diagram illustrates that in general dissakisite can be classified into two groups, (Al + Fe)³⁺-rich and an Mg-rich; dissakisite from Trimouns belongs to the former group. Chondrite-normalized REE patterns of dissakisites from Trimouns are similar to those of allanites formed by hydrothermal fluids. In conclusion, it is clear from the above two geochemical characteristics that dissakisites from Trimouns are of (Al + Fe)³⁺-type, and were derived from hydrothermal fluids.     

High-pressure and ultrahigh-temperature metamorphism at Komateri, northern Madurai Block, southern India

We report for the first time the evidence for prograde high-pressure (HP) metamorphism preceding a peak ultrahigh-temperature (UHT) event in the northernmost part of the Madurai Block in southern India. Mg–Al-rich Grt–Ged rocks from Komateri in Karur district contain poikiloblastic garnet with numerous multi-phase inclusions. Although most of the inclusion assemblages are composed of gedrite, quartz, and secondary biotite, rare staurolite + sapphirine and spinel + quartz are also present. The X_Mg (=Mg/[Fe+Mg]) of staurolite (0.45–0.49) is almost consistent with that reported previously from Namakkal district in the Palghat–Cauvery Shear Zone system (X_Mg = 0.51–0.52), north of the Madurai Block. The HP event was followed by peak UHT metamorphism at T = 880–1040 °C and P = 9.8–12.5 kbar as indicated by thermobarometric computations in the Grt–Ged rock and associated mafic granulite. Symplectic intergrowth of spinel (X_Mg = 0.50–0.59, ZnO < 1.7 wt.%) and quartz, a diagnostic indicator of UHT metamorphism, probably formed by decompression at UHT conditions. The rocks subsequently underwent retrograde metamorphism at T = 720–760 °C and P = 4.2–5.1 kbar. The P–T conditions and clockwise exhumation trajectory of the Komateri rocks, comparable to similar features recorded from the Palghat–Cauvery Shear Zone system, suggest that the Madurai Block and the Palghat–Cauvery Shear Zone system underwent similar HP and UHT metamorphic history probably related to the continent–continent collision during the final stage of amalgamation of Gondwana supercontinent.     

Petrography and geochemistry of the iron-rich rocks in the banded iron formation of the Chilpi Group,Central India: Implications on the level of oxygen in the Paleoproterozoic atmosphere before the “Proterozoic iron ore gap”

The Chilpi Group (2050–1850 Ma) in the Bastar Craton contains Banded Iron Formation (BIF) deposited immediately after the Great Oxidation Event but before the “Proterozoic iron ore gap”. Baseline geochemical data generated from this crucial period of Earth's history representing the transition from an initial high productivity period followed by productivity collapse, thereby delaying the evolution of biota, are interpreted in terms of the redox state of the ocean and atmospheric oxygen content. Presence of chamosite, greenalite and siderite in the ironstones of the Chilpi Group, identified during present analysis, provide valuable information regarding the redox state of the shallow sea. Geochemical analyses reveal high concentrations of Fe₂O₃^total and SiO₂ (average ~ 87.85 wt%) in iron-rich bands. Trace elements commonly enriched in detrital phases (e.g. Sc, Hf, Nb, Th and Zr) show good correlation with total REE concentration, but these have concentration below the cut-off limit defined for detrital sediments (except 3 samples). Higher concentration of these elements in greenalite/chamosite-rich samples indicates accumulation of these elements in greenalite/chamosite during primary precipitation. Most of the samples have low concentrations of Al₂O₃ (<5 wt%) and TiO₂ (<0.5 wt%), but some chamosite-bearing samples show enrichments of Al₂O₃ (up to ~20 wt%). Post-Archean Australian Shale normalised rare earth elements with Y (REEY) patterns, showing a superchondritic Y/Ho ratio (average 32.15) and positive La, Gd and Y anomalies, indicate the preservation of seawater like signatures. Though a low positive Eu-anomaly, and Al/(Al + Fe + Mn) versus Fe/Ti plot suggest seawater signature with possible mixing of hydrothermal fluids and/or <10 % detrital components, preservation of seawater signatures and no involvement of high-temperature hydrothermal fluids are deduced from Eu/Sm versus Sm/Yb and Eu/Sm versus Y/Ho patterns. The Eu/Sm and Y/Ho ratios lower than the seawater and a mixing trend away from oceanic hydrothermal solution indicate possible mixing of freshwater with seawater for the observed REEY patterns. Redox-sensitive trace element ratios indicate a dysoxic to suboxic-anoxic condition in the depositional basin. Presence of oolitic textures and occurrence of chamosite support the shallow water (<60 m water depth) and anoxic condition in the depositional basin. The oxygen content of 10⁻³–10⁻⁵ times the present atmospheric level in the atmosphere is inferred for the period during the deposition of the BIF.     

Origin of tourmaline and oxide minerals from the metamorphosed Rampura Agucha Zn-Pb-(Ag) deposit, Rajasthan, India

Summary The sediment-hosted exhalative Rampura Agucha Zn-Pb-(Ag) deposit in Rajasthan, India, contains a number of oxide minerals which have been formed as a result of high-grade metamorphism. Gahnite (Zn_0.66–0.75Fe_0.13–0.24Mg_0.06–0.13Al_1.98–2.01O₄) is a common minor phase in the ores and formed from breakdown of sphalerite and Al-rich silicates. Pyrophanite-ilmenite solid solution (Fe_0.42–0.68Mn_0.32–0.58Ti_0.99–1.01O₃) is very rare and occurs, intergrown with rutile, as a result of unmixing of a Ti-Fe-Mn bearing precursor mineral.Dravite-rich tourmaline with Fe/(Fe+Mg) ratios around 0.02 occurs at the hanging wall contact of the orebody with the paragneisses and is intergrown with the ore minerals. Tourmaline from the stratabound ores is distinguished from schorl-rich tourmaline of two pegmatite samples which show Fe/(Fe+Mg) ratios of 0.43 and 0.62, respectively. It is argued that dravite-rich tourmaline (or another B-rich precursor mineral) is of premetamorphic origin. This dravite-rich tourmaline recrystallized during high-grade metamorphism when the metamorphic fluid, represented by H₂O-CO₂±CH₄-N₂ inclusions, was trapped.Amphiboles, muscovites and biotites from metamorphic rocks of the deposit display radiometric³⁹Ar/⁴⁰Ar cooling ages between 788 and 909 Ma.

---

Dravit-reicher Turmalin und Oxide der metamorphen Zn-Pb-(Ag) Lagerstätte Rampura Agucha, Rajasthan, Indien

Zusammenfassung Die sedimentär-exhalative Zn-Pb-(Ag) Lagerstätte Rampura Agucha in Rajasthan, Indien, beinhaltet eine Reihe von Oxidmineralen, die infolge der hochgradigen Regional-metamorphose gebildet wurden. Gahnit (Zn_0.66–0.75Fe_0.13–0.24 Mg_0.06–0.13Al_1.98–2.01O₄) ist eine häufig anzutreffende Phase, die sich aus Sphalerit und Al-reichen Silikatphasen gebildet hat. Pyrophanit-Ilmenit (Fe_0.42–0.68Mn_0.32–0.58 T_0.99–1.01O₃) ist sehr selten und bildet, aufgrund der Entmischung eines Ti-Fe-Mn hältigen Vorläuferminerals, Verwachsungen mit Rutil.Dravit-reicher Turmalin mit einem Fe/(Fe+Mg) Verhältnis um 0.02 bildete sich gleichzeitig mit den Sulfidmineralen am Kontakt des Erzkörpers mit den hangenden Paragneisen der Lagerstätte. Dieser Turmalin unterscheidet sich klar von Schörlreichem Turmalin mit Fe/(Fe+Mg) Verhältnissen von 0.43 und 0.62 von zwei Pegmatiten. Die Herkunft dieses prämetamorphen Dravit-reichen Turmalins (oder dessen Vorgängerminerals) ist unklar. Dieser Turmalin rekristallisierte während der Metamorphose, wobei er das metamorphe H₂O-CO₂±CH₄-N₂-Fluid in Form von primären Einschlüssen einschloß.Amphibol, Muskowit und Biotit wurden mittels³⁹Ar/⁴⁰Ar-Methode datiert und liefern radiometrische Abkühlungsalter zwischen 788 und 909 Ma.

---

---

With 8 Figures     

Boron in metapelites controlled by the breakdown of tourmaline and retrograde formation of borosilicates in the Yanai area,Ryoke metamorphic belt,SW Japan

Tourmaline-out isograd formed by the breakdown of tourmaline is defined in the upper amphibolite-facies metapelites in the Yanai area, Ryoke metamorphic belt, SW Japan. The rim composition of tourmaline progressively becomes aluminous with ascending metamorphic grade, and the chemical zoning of tourmaline is controlled by ^X□AlNa_–1Mg_–1 and MgTi^YAl_–2 vectors in low- to medium-grade zones where muscovite is stable, whereas it is controlled by Mg(OH)^YAl_–1O_–1, CaMgO^X□_–1 ^YAl_–1(OH)_–1 and MgTi^YAl_–2 vectors in further higher–grade, muscovite-unstable zones. The size of tourmaline increases drastically where breakdown of muscovite+quartz takes place, probably due to the growth of tourmaline during breakdown of muscovite. On the high-temperature side of the tourmaline-out isograd, depletion of whole-rock boron is observed. Escape of boron-bearing melt or the fluid evolved from the melt during its crystallization probably caused this depletion, although locally trapped, boron-bearing melt or fluid formed irregularly shaped tourmaline and dumortierite during retrograde metamorphism.     

The 1.90–1.88 Ga magmatism in the southernmost Guyana Shield, Amazonas, Brazil: Geology, geochemistry, zircon geochronology, and tectonic implications

The southernmost Guyana Shield-Uatumã subdomain, northeastern Amazonas State, Brazil is dominantly formed by granitoid and volcanic rocks from the Água Branca Suite (ABS), undivided Granite Stocks (GS) and São Gabriel volcano–plutonic system (SGS). The ABS is characterized by a granite series that exhibits comparatively low Fe/(Fe + Mg) ratio, low (Nb/Zr)_N, high Sr values and high Rb/Zr ratio. Its rocks display metaluminous to weakly peraluminous (A/CNK 0.94–1.06), high-K calc-alkaline, I normal-type character and have moderately to strongly fractionated rare earth elements (REE) pattern. The SG granites and SGS effusive–ignimbrite–granite association is metaluminous to weakly peraluminous (A/CNK 0.84–1.18), high-K calc-alkaline, has moderately to weakly fractionated REE trend, higher Fe/(Fe + Mg) ratio, lower Sr content and lower Rb/Zr ratio. The ABS geochemical signature is consistent with formation from volcanic arc rocks and small participation of collisional setting rocks, whereas the SG and SGS have post-collisional tectonic rocks-related geochemical signature. This model is in harmony with a post-collisional extensional regime, started with the 1.90–1.89 Ga Água Branca magmatism, and culminated with the 1.89–1.88 Ga São Gabriel system at an early stage of intracratonic reactivation, which included intrusion of mafic dikes. The Uatumã subdomain was related to mantle underplating with continental uplift and its origin involved contributions of 2.3–2.44 Ga Archean-contaminated Trans-Amazonian, 2.13–2.21 Ga Trans-Amazonian, 1.93–1.94/2.0 Ga Tapajós-Parima. Foliation styles point out that part of the Água Branca granitoids recorded later deformational effects, likely related to the Rio Negro Province formation.     

Hydrous peridotites with Ti-rich chromian spinel as a low-temperature forearc mantle facies: evidence from the Happo-O’ne metaperidotites (Japan)

The Happo-O’ne peridotite complex is situated in the northeastern part of the Hida Marginal Tectonic Zone, central Japan, characterized by the high-P/T Renge metamorphism, and is considered as a serpentinite mélange of Paleozoic age. Peridotitic rocks, being massive or foliated, have been subjected to hydration and metamorphism. Their protoliths are mostly lherzolites to harzburgites with subordinate dunites. We found a characteristic mineral assemblage, olivine + orthopyroxene + tremolite + chlorite + chromian spinel, being stable at low-T, from 650 to 750°C, and high-P, from 16 to 20 kbar, tremolite–chlorite peridotites of the tremolite zone. Olivines are Fo₈₈–Fo_91, and orthopyroxenes (Mg# = 0.91) show low and homogenous distributions of Al₂O₃ (up to 0.25 wt%), Cr₂O₃ (up to 0.25 wt%), CaO (up to 0.36 wt%) and TiO₂ (up to 0.06 wt%) due to the low equilibration temperature. Chromian spinels, which are euhedral and enclosed mainly in the orthopyroxenes, have high TiO_2, 3.1 wt% (up to 5.7 wt%) on average, and high Cr# [=Cr/(Cr + Al) atomic ratio], 0.95 on average but low Fe³⁺ [=Fe³⁺/(Cr + Al + Fe³⁺) atomic ratio, <0.3]. The bulk-rock chemistry shows that the Happo-O’ne metaperidotites with this peculiar spinel are low in TiO₂ (0.01–0.02 wt%), indicating no addition of TiO₂ from the outside source during the metamorphism; the high TiO₂ of the peculiar spinel has been accomplished by Ti release from Ti-bearing high-T pyroxenes during the formation of low-T, low-Ti silicates (<0.1 wt% TiO₂) during cooling. Some dunites are intact from hydration: their olivine is Fo₉₂ and spinel shows high Cr#, 0.72. The Happo-O’ne metaperidotites (tremolite–chlorite peridotites), being in the corner of the mantle wedge, are representative of a hydrous low-T, high-P mantle peridotite facies transitional from a higher T anhydrous peridotite facies (spinel peridotites) formed by in situ retrograde metamorphism influenced by fluids from the subducting slab. They have suffered from low-T (<600°C) retrogressive metamorphism to form antigorite and diopside during exhumation of the Renge metamorphic belt.     

Chemical and boron isotopic compositions of tourmaline from the Paleoproterozoic Houxianyu borate deposit,NE China: Implications for the origin of borate deposit

The Houxianyu borate deposit in northeastern China is one of the largest boron sources of China, hosted mainly in the Paleoproterozoic meta-volcanic and sedimentary rocks (known as the Liaohe Group) that are characterized by high boron concentrations. The borate ore-body has intimate spatial relationship with the Mg-rich carbonates/silicates of the Group, with fine-grained gneisses (meta-felsic volcanic rocks) as main country rocks. The presence of abundant tourmalinites and tourmaline-rich quartz veins in the borate orebody provides an opportunity to study the origin of boron, the nature of ore-forming fluids, and possible mineralization mechanism. We report the chemical and boron isotopic compositions of tourmalines from the tourmaline-rich rocks in the borate deposit and from the tourmaline-bearing fine-grained gneisses.Tourmalines from the fine-grained gneisses are chemically homogeneous, showing relatively high Fe and Na and low Mg, with δ¹¹B values in a narrow range from +1.22‰ to +2.63‰. Tourmalines from the tourmaline-rich rocks, however, commonly show compositional zoning, with an irregular detrital core and a euhedral overgrowth, and have significantly higher Mg, REE (and more pronounced positive Eu anomalies), V (229–1852 ppm) and Sr (208–1191 ppm) than those from the fine-grained gneisses. They show varied B isotope values ranging from +4.51‰ to +12.43‰, which plot intermediate between those of the terrigenous sediments and arc rocks with low boron isotope values (as represented by the δ¹¹B = +1.22‰ to +2.63‰ of the fine-grained gneisses of this study) and those of marine carbonates and evaporates with high boron isotope values. In addition, the rim of the zoned tourmaline shows notably higher Mg, Ti, V, Sn, and Pb, and REE (particularly LREEs), but lower Fe, Co, Cr, Ni, Zn, Mn, and lower δ¹¹B values than the core. These data suggest that (1) the sources of boron of the borate ore-body are mainly the Paleoproterozoic meta-volcanic and sedimentary rocks, and (2) the ore-forming fluids should be the high temperature metamorphic fluids related to the amphibolite-facies metamorphism of the Paleoproterozoic foldbelt, which leach boron from the boron-rich meta-volcanic and sedimentary rocks of the Liaohe Group, and the boron-rich metamorphic fluids subsequently interacted with the marine Mg-rich carbonates and evaporates, forming borate deposit, the tourmaline overgrowth in the rim and the tourmaline-rich rocks.     

40Ar/39Ar ages of detrital muscovite and whole-rock slate/phyllite,Narragansett Basin,RI-MA,USA: implications for rejuvenation during very low-grade metamorphism

Late Pennsylvanian sedimentary rocks in the Narragansett basin were metamorphosed (lower anchizone to sillimanite grade) during late Paleozoic regional metamorphism at ca. 275–280 Ma. Twenty-five variably sized concentrates of detrital muscovite were prepared from samples collected within contrasting low-grade areas (diagenesis — lower greenschist facies). Microprobe analyses suggest that the constituent detrital grains are not chemically internally zoned; however, some grains within several concentrates display very narrow (<25 m), compositionally distinct, low-grade, epitaxial peripheral overgrowths. Detrital muscovite concentrates from the lower anchizone are characterized by internally concordant ⁴⁰Ar/³⁹Ar age spectra which define plateau ages of ca. 350–360 Ma. These are interpreted to date post-Devonian (Acadian) cooling within proximal source areas. Concentrates from lower grade sectors of the middle anchizone display slightly discordant spectra in which apparent ages systematically increase from ca. 250–275 Ma to define intermediate- and high-temperature plateaus of ca. 360–400 Ma. Detrital muscovite within samples from higher grade sectors of the middle anchizone and the upper anchizone are characterized by systematic low age discordance throughout both low-and intermediate-temperature increments. High-temperature ages only range up to ca. 330 Ma. Six size fractions of detrital muscovite from a sample collected within the lower greenschist facies have similarly discordant spectra, in which, apparent ages increase slightly throughout the analyses from ca. 250 Ma to 275 Ma. The detrital muscovite results are interpreted to reflect variable affects of late Paleozoic regional metamorphism. However, it is uncertain to what extent the systematic low age spectra discordance reflects intracrystalline gradients in the concentration of ⁴⁰Ar and/or experimental evolution of gas from relatively non-retentive epitaxial overgrowths. However, low age discordance occurs regardless of the extent of epitaxial overgrowth. Intermediate-temperature increments evolved during ⁴⁰Ar/³⁹Ar whole-rock analyses of five slate/phyllite samples are characterized by internally consistent apparent K/Ca ratios. These are attributed to gas evolved from constituent, very fine-grained white mica. Samples from lower grade portions of the middle anchizone are characterized by intermediate-temperature apparent ages which systematically increase from ca. 275–300 Ma to ca. 360–375 Ma before evolution of a high-temperature contribution from detrital plagioclase feldspar. This age variation may reflect partial late Paleozoic rejuvenation of very fine-grained detrital material with a source age similar to that for the detrital muscovites. Slate/phyllite samples from upper sectors of the middle anchizone and from the upper anchizone were completely rejuvenated during late Paleozoic metamorphism and record intermediate-and high-temperature plateau ages of ca. 270–290 Ma. These data document that metamorphic conditions of the lower to middle biotite zone (ca. 325–350 °C) are required to completely rejuvenate intracrystalline argon systems of detrital muscovite. Therefore, the ⁴⁰Ar/³⁹Ar dating method may be useful in determination of detrital muscovite provenance and in resolution of the metamorphic evolution of low-grade terranes.     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

The stability and origin of sodicgedrite in ultrahigh-temperature Mg-Al granulites: a case study from the Gondwana suture in southern India

Mg-Al-rich rocks from the Palghat-Cauvery Shear Zone System (PCSZ) within the Gondwana suture zone in southern India contain sodicgedrite as one of the prograde to peak phases, stable during T = 900–990°C ultrahigh-temperature metamorphism. Gedrite in these samples is Mg-rich (Mg/[Fe + Mg] = X _Mg = 0.69–0.80) and shows wide variation in Na₂O content (1.4–2.3 wt.%, Na^A = 0.33–0.61 pfu). Gedrite adjacent to kyanite pseudomorph is in part mantled by garnet and cordierite. The gedrite proximal to garnet shows an increase in Na^A and Al^IV from the core (Na^A = 0.40–0.51 pfu, Al^IV = 1.6–1.9 pfu) to the rim (Na^A = 0.49–0.61 pfu, Al^IV = 2.0–2.2 pfu), suggesting the progress of the following dehydration reaction: Ged + Ky → Na-Ged + Grt + Crd + H₂O. This reaction suggests that, as the reactants broke down during the prograde stage, the remaining gedrite became enriched in Na to form sodicgedrite, which is regarded as a unique feature of high-grade rocks with Mg-Al-rich and K–Si-poor bulk chemistry. We carried out high-P-T experimental studies on natural sodicgedrite and the results indicate that gedrite and melt are stable phases at 12 kbar and 1,000°C. However, the product gedrite is Na-poor with only <0.13 wt.% Na₂O (Na^A = 0.015–0.034 pfu). In contrast, the matrix glass contains up to 8.5 wt.% Na₂O, suggesting that, with the progressive melting of the starting material, Na was partitioned into the melt rather than gedrite. The results therefore imply that the occurrence of sodicgedrite in the UHT rocks of the PCSZ is probably due to the low H₂O activity during peak P-T conditions that restricted extensive partial melting in these rocks, leaving Na partitioned into the solid phase (gedrite). The occurrence of abundant primary CO₂-rich fluid inclusions in this rock, which possibly infiltrated along the collisional suture during the final amalgamation of the Gondwana supercontinent, strengthens the inference of low water activity.     

Tourmalinites from the Eastern Sierras Pampeanas, Argentina

In the eastern Sierras Pampeanas, Central Argentina, tourmalinites and coticules are found in close association with stratabound scheelite deposits in metamorphic terranes. In Sierra Grande (Agua de Ramón and Ambul districts) and Sierra de Altautina, tourmalinites are associated with stratabound scheelite deposits related to orthoamphibolites. In the Pampa del Tamboreo area, tourmalinites are located in biotite schists stratigraphically related to acid to intermediate metavolcanic rocks and scheelite-bearing quartzites.The mineral chemistry and boron isotopic compositions of tourmalinite-hosted and vein-hosted tourmalines are investigated. Overall, the tourmalines belong to the dravite-schorl series and are generally aluminous; Fe/(Fe+Mg) ranges from 0.33 to 0.85, Al/(Al+Fe+Mg) from 0.66 to 0.76 and the amount of X-site vacancy (0.12–0.48) indicates significant foitite components. Their boron isotopic compositions (δ¹¹B) are from −24.0‰ to−15.0‰.Similar mineral chemistries and boron isotopic values for tourmaline in tourmalinites related to stratabound scheelite mineralisation and in tungsten-bearing quartz veins suggest a common source for the boron and probably the tungsten. The field, chemical and isotopic relationships are consistent with tungsten and boron in quartz-vein deposits being remobilised from stratabound scheelite and tourmalinite, dominantly by liquid-state transfer associated with regional shear zones. Tungsten and boron in the original sedimentary sequence (now meta-exhalites) are ascribed to volcanogenic exhalations.     

Field setting,mineralogy, chemistry,and genesis of arc picrites,New Georgia,Solomon Islands

The field setting, petrography, mineralogy, and geochemistry of a suite of picrite basalts and related magnesian olivine tholeiites (New Georgia arc picrites) from the New Georgia Volcanics, Kolo caldera in the active ensimatic Solomon Islands arc are presented. These lavas, with an areal extent in the order of 100² km and almost 1 km thick in places, are located close to the intersection of the Woodlark spreading zone with the Pacific plate margin. They contain abundant olivine (Fo_94-75) and diopside (Cr₂O₃ 1.1-0.4%, Al₂O₃ 1–3%), and spinels characterised by a large range in Cr/(Cr+Al) (0.85–0.46) and Mg/(Mg+ Fe⁺⁺) (0.65–0.1). The spinels are Fe⁺⁺⁺ rich, with Fe⁺⁺⁺/ (Fe⁺⁺⁺+Cr+Al) varying from 0.06 to 1.0. A discrete group of spinels with the highest Cr/(Cr+Al) (0.83–0.86) and lowest Fe⁺⁺⁺ contents are included in the most Mg-rich olivine (Fo_91–94) and both may be xenocrystal in origin.The lavas, which range between 10–28% MgO, define linear trends on oxide (element) — MgO diagrams and these trends are interpreted as olivine (0.9) clinopyroxene (0.1) control lines. For the reconstructed parent magma composition of these arc picrites, ratios involving CaO, Al₂O₃, TiO₂, Zr, V and Sc are very close to chondritic. REE patterns are slightly LREE — enriched ((La/Sm)^N 1.3–1.43) and HREE are flat. All lavas show marked enrichments in K, Rb, Sr, Ba, and LREE relative to MORB with similar MgO contents, but the TiO₂ content of the proposed parent magma is close to those of postulated primary MORB liquids. It is proposed that the arc parent magma was produced by partial melting of sub-oceanic upper mantle induced by the introduction of LILE — enriched hydrous fluids derived by dehydration and/or partial melting of subducted ocean crust and possibly minor sediments.