Kokchetavite: a new potassium-feldspar polymorph from the Kokchetav ultrahigh-pressure terrane

Kokchetavite, a new polymorph of K-feldspar (KAlSi₃O₈), has been identified as micrometer-size inclusions in clinopyroxene and garnet in a garnet-pyroxene rock from the Kokchetav ultrahigh-pressure terrane, Kazakhstan. Kokchetavite has a hexagonal structure with a =5.27(1) Å, c=7.82(1) Å, V=188.09 ų, Z=1, and is found to be associated with phengite + /-cristobalite (or quartz) + siliceous glass ± phlogopite/titanite/calcite/zircon, occurring as multi-phase inclusions in clinopyroxene and garnet. It is concluded that kokchetavite could not be an exsolution phase in host minerals. Instead, it might be metastably precipitated from an infiltrated K-rich melt during rock exhumation. Alternatively, although less likely, kokchetavite might be derived from dehydration of K-cymrite, which, in turn, was formed at high pressures. In either case, kokchetavite is a metastable polymorph of K-feldspar.     

Oxidized sulfur-rich mafic magma at Mount Pinatubo,Philippines

Basaltic fragments enclosed in andesitic dome lavas and pyroclastic flows erupted during the early stages of the 1991 eruption of Mount Pinatubo, Philippines, contain amphiboles that crystallized during the injection of mafic magma into a dacitic magma body. The amphiboles contain abundant melt inclusions, which recorded the mixing of andesitic melt in the mafic magma and rhyolitic melt in the dacitic magma. The least evolved melt inclusions have high sulfur contents (up to 1,700 ppm) mostly as SO₄ ^2–, which suggests an oxidized state of the magma (NNO+1.4). The intrinsically oxidized nature of the mafic magma is confirmed by spinel–olivine oxygen barometry. The value is comparable to that of the dacitic magma (NNO+1.6). Hence, models invoking mixing as a means of releasing sulfur from the melt are not applicable to Pinatubo. Instead, the oxidized state of the dacitic magma likely reflects that of parental mafic magma and the source region in the sub-arc mantle. Our results fit a model in which long-lived SO₂ discharge from underplated mafic magma accumulated in the overlying dacitic magma and immiscible aqueous fluids. The fluids were the most likely source of sulfur that was released into the atmosphere during the cataclysmic eruption. The concurrence of highly oxidized basaltic magma and disproportionate sulfur output during the 1991 Mt. Pinatubo eruption suggests that oxidized mafic melt is an efficient medium for transferring sulfur from the mantle to shallow crustal levels and the atmosphere. As it can carry large amounts of sulfur, effectively scavenge sulfides from the source mantle and discharge SO₂ during ascent, oxidized mafic magma forms arc volcanoes with high sulfur fluxes, and potentially contributes to the formation of metallic sulfide deposits.Editorial responsibility: J. Hoefs

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U–Pb and Hf-isotope analysis of zircons in mafic xenoliths from Fuxian kimberlites: evolution of the lower crust beneath the North China craton

Mafic xenoliths from the Paleozoic Fuxian kimberlites in the North China craton include garnet granulite, and minor pyroxene amphibolite, metagabbro, anorthosite and pyroxenite. The formation conditions of the amphibolites are estimated at 745–820 °C and 7.6–8.8 Kb (25–30 km); the granulites probably are derived from greater depths in the lower crust. LAM-ICPMS U–Pb dating of zircons from four granulites reveals multiple age populations, recording episodes of magmatic intrusion and metamorphic recrystallisation. Concordant ages and upper intercept ages, interpreted as minimum estimates for the time of magmatic crystallisation, range from 2,620 to 2,430 Ma in three granulites, two amphibolites and two metagabbros. Lower intercept ages, represented by near-concordant zircons, are interpreted as reflecting metamorphic recrystallisation, and range from 1,927 to 1,852 Ma. One granulite contains two metamorphic zircon populations, dated at 1,927±55 Ma and 600–700 Ma. Separated minerals from one granulite and one amphibolite yield Sm–Nd isochron ages of 1,619±48 Ma (¹⁴³Nd/¹⁴⁴Nd)i=0.51078), and 1,716±120 Ma (¹⁴³Nd/¹⁴⁴Nd)i=0.51006), respectively. These ages are interpreted as recording cooling following metamorphic resetting; model ages for both samples are in the range 2.40–2.66 Ga. LAM-MC-ICPMS analyses of zircon show a range in ¹⁷⁶Hf/¹⁷⁷Hf from 0.28116 to 0.28214, corresponding to a range of _Hf from –34 to +12. The relationships between ²⁰⁷Pb/²⁰⁶Pb age and _Hf show that: (1) the granulites, amphibolites and metagabbro were derived from a depleted mantle source at 2.6–2.75 Ga; (2) zircons in most samples underwent recrystallisation and Pb loss for 100–200 Ma after magmatic crystallisation, consistent with a residence in the lower crust; (3) metamorphic zircons in several samples represent new zircon growth, incorporating Hf liberated from breakdown of silicates with high Lu/Hf; (4) in other samples metamorphic and magmatic zircons have identical ¹⁷⁶Hf/¹⁷⁷Hf, and the younger ages reflect complete resetting of U–Pb systems in older zircons. The Fuxian mafic xenoliths are interpreted as the products of basaltic underplating, derived from a depleted mantle source in Neoarchean time, an important period of continental growth in the North China craton. Paleoproterozoic metamorphic ages indicate an important tectonic thermal event in the lower crust at 1.8–1.9 Ga, corresponding to the timing of collision between the Eastern and Western Blocks that led to the final assembly of the North China craton. The growth of metamorphic zircon at 600–700 Ma may record an asthenospheric upwelling in Neoproterozoic time, related to uplift and a regional disconformity in the North China craton.     

Metasomatism and melting history of a Variscan lithospheric mantle domain: evidence from the Puy Beaunit xenoliths (French Massif Central)

Mantle xenoliths from Puy Beaunit (French Massif Central) are compositionally varied, ranging from relatively fertile spinel lherzolites to refractory spinel dunites. Fertile peridotites have registered a modal (amphibole-bearing lherzolites) and cryptic metasomatic event that took place before the last Permian (257 Ma) melting episode. Depletion processes have been constrained by chemical modelling: the depletion is related to different degrees of partial melting, but two major melt extraction episodes are needed to explain the range of major element composition. The second event was responsible for the local large-scale dunitification of former residues. The first melting event (F25%) and metasomatic enrichment are attributed to an ancient fluid and/or liquid infiltration that could be related to a pre-Variscan regional subduction (located to the north of the Beaunit area). Texture acquisition and major deformation of the mantle xenoliths were sub-contemporaneous of the subduction and would result from lithospheric delamination. The second melting event (F17%) produced high-Mg basalts with calc-alkaline trace element signature that gave rise to the Permian underplating episode recognised in western Europe.     

Geological and SHRIMP II U-Pb constraints on the age and origin of the Breves Cu-Au-(W-Bi-Sn) deposit,Carajás,Brazil

The Breves deposit in the Carajás Copper-Gold Belt, Brazil, a member of the Cu-Au-(W-Bi-Sn) group of deposits, contains about 50 Mt of 1.22% Cu, 0.75 g/t Au, 2.4 g/t Ag, 1,200 g/t W, 70 g/t Sn, 175 g/t Mo and 75 g/t Bi. It is hosted by sandstones and siltstones of the Águas Claras Formation (minimum age of 2,681±5 Ma) in the roof zone of a complex, highly altered granite intrusion. The mineralisation is disseminated in a greisenized zone, resulting from alteration of probable monzogranites and syenogranites. The ore-bearing greisen contains abundant xenomorphic quartz in association with Fe-chlorite and muscovite. The gangue assemblage also includes fluorite, tourmaline, and minor amounts of monazite, xenotime, chlorapatite, thorite, zircon, calcite, siderite and bastnäesite. Copper mineralisation is dominated by chalcopyrite associated with pyrite, arsenopyrite, pyrrhotite and molybdenite. Gold particles, in equilibrium with native bismuth, are common as inclusions in chalcopyrite. The greisen contains sub-economic concentrations of tungsten and niobium that are related to the presence of ferberite, qitianlingite and Nb-rutile. SHRIMP II zircon dating of the host granites gives ²⁰⁷Pb/²⁰⁶Pb ages of 1,878±8 and 1,880±9 Ma for two phases, and a combined age of 1,879±6 Ma. SHRIMP II dating of monazite and xenotime grains in late- to post-mineralisation veins gives a combined ²⁰⁷Pb/²⁰⁶Pb age of 1,872±7 Ma, indistinguishable from the ages of the granites. This provides a genetic connection between the Breves deposit and the ca. 1.88 Ga A-type granite magmatism that typifies the Carajás Belt as part of a much larger, intracratonic magmatic province that extends over much of the Amazonian Craton. The recognition of this association has exploration implications, not only for the geophysical signature of the granite roof zones, but also for likely geochemical dispersion around the deposits of this type.Editorial handling: G. Beaudoin     

Petrology and structure of the Palaeoproterozoic (1.9 Ga) Rytky nickel sulphide deposit,Central Finland: a comparison with the Kotalahti nickel deposit

The Palaeoproterozoic (1.9 Ga) Rytky and Kotalahti mafic-ultramafic intrusions are located in the contact zone between the Archaean craton and Proterozoic supracrustal rocks. During the second deformation event (D₂) the surrounding country rocks were subjected to intensive metamorphism and deformation associated with the Svecofennian orogeny; the Archaean/Proterozoic boundary controlled both D₂ thrusting and magma ascent. Emplacement of the Rytky and Kotalahti intrusions took place at the culmination of D₂, as shown by the gneiss inclusions with S₂ schistosity within the intrusions. Overthrusting continued after emplacement, with detached fragments of the bodies incorporated into the Archaean gneisses. During the third deformation event (D₃) the originally subhorizontal intrusions were rotated into a subvertical position, so that they now have their stratigraphic top towards the west. The Rytky intrusion is composed mainly of medium- and coarse-grained lherzolite, websterite and gabbronorite. The nickel deposit with pentlandite as the main nickel mineral is associated with the lherzolite and websterite. The coarse-grained lherzolite, websterite and melagabbro represent the first rocks to form, and they contain the nickel sulphide mineralisation. Country rock contamination, as indicated by high TiO₂, P₂O₅, Rb, Zr and light rare earth element contents (LREE), is most pronounced in the marginal part of the intrusion, which was the first to form. The variation in olivine composition (Fo 78.6-84.77 mole %; Ni 630–2386 ppm) and the metal ratio of the sulphide (Ni/Co 19.3 – 50.3) along with the internal stratigraphy of the intrusion indicate an in-situ process of sulphide ore formation.Editorial handling: P. LightfootAn erratum to this article can be found at     

Fine-Grained Aluminosiliciclastic Rocks of the Middle Riphean Stratotype Section in the Southern Urals: Formation Conditions,Composition and Provenance Evolution

General trends of the formation of Middle Riphean fine-grained aluminosiliciclastic rocks in the Bashkir Meganticlinorium are considered. It is shown that Yurmatinian shales do not contain any significant pyroclastic admixture. Judging from the relatively constant Th/Cr ratio throughout the Yurmatinian section, the tectonic regime in the study territory during the early Middle Riphean is suggested to be rather stable. The main paleoclimatic indices and indicators of the pelitic material maturity (CIA, CIW, IVC, PIA, and Ce/Y) suggest that paleodrainage systems in the early Middle Riphean were dominated by humid climate that gave way to the arid or semiarid type in the middle Yurmatinian. The low Mo/Mn ratio and some other indicators of redox conditions in shales from all Yurmatinian lithostratigraphic units show that no explicit reducing conditions existed in the basin during the early Middle Riphean. The shales were characterized by the increase in K₂O/Al₂O₃ ratio, gradual enrichment in REE, and growth of LREE/HREE and La_N/Yb_N ratios toward the middle Yurmatinian, indicating the gain of an appreciable amount of slightly weathered arkosic aluminosiliciclastic material in the sedimentary basin about 1220–1200 Ma ago. The REE distribution and the UCC- and AUC-normalized shale compositions suggest that the eroded upper crust was compositionally close to the UCC. The occurrence of mafic and ultramafic rocks is also inferred. Data points of Yurmatinian shales plotted in the Cr–Ni, Eu/Eu*–Gd_N/Yb_N, and (La/YB)_N–Yb_N diagrams are localized between the fields of Upper Archean and post-Archean rocks or within the latter field. Hence, post-Archean igneous and metamorphic complexes prevailed in paleodrainage systems of the early Middle Riphean. This is also confirmed by the model Nd ages.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Mn distribution in sphalerite: an EPR study

A study on Zn replacement in sphalerite by divalent Mn has been performed by using EPR spectroscopy. Twelve natural and synthetic samples with different Mn-contents were selected for the spectroscopic investigation. The EPR spectra vary from an hyperfine sextet to a single broad line according to their Mn-content. Three components, attributed to Mn(II) in different chemical coordination (namely isolated ions, interacting ions, clusters) have been determined by means of spectral simulation. The variations of the EPR signals among the different spectra are due only to the mixing of these components, without any variation of each spectral parameter. Differing distribution of Mn(II) was, therefore, observed at a local scale. Consequently, the specific interactions driving the coalescence of Mn(II) ions to form clusters may be responsible for the banded pattern in sphalerite crystals.