Origin of zoned spinel by coupled dissolution–precipitation and inter-crystalline diffusion: evidence from serpentinized wehrlite, Bangriposi, Eastern India

Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe³⁺ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr₂O₃, Al₂O₃ and MgO and complementary increase in Fe₂O₃ at constant FeO. In diffusion profiles, Fe₂O₃–Cr₂O₃ crossover coincides with Al₂O₃ decrease to values <0.5 wt% in ferritchromite zone, with Cr₂O₃ continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O₂): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.     

Genesis of superimposed hypogene and supergene Fe orebodies in BIF at the Madoonga deposit, Yilgarn Craton, Western Australia

The Madoonga iron ore body hosted by banded iron formation (BIF) in the Weld Range greenstone belt of Western Australia is a blend of four genetically and compositionally distinct types of high-grade (>55 wt% Fe) iron ore that includes: (1) hypogene magnetite–talc veins, (2) hypogene specular hematite–quartz veins, (3) supergene goethite–hematite, and (4) supergene-modified, goethite–hematite-rich detrital ores. The spatial coincidence of these different ore types is a major factor controlling the overall size of the Madoonga ore body, but results in a compositionally heterogeneous ore deposit. Hypogene magnetite–talc veins that are up to 3 m thick and 50 m long formed within mylonite and shear zones located along the limbs of isoclinal, recumbent F₁ folds. Relative to least-altered BIF, the magnetite–talc veins are enriched in Fe₂O_3(total), P₂O₅, MgO, Sc, Ga, Al₂O₃, Cl, and Zr; and depleted in SiO₂ and MnO₂. Mafic igneous countryrocks located within 10 m of the northern contact of the mineralised BIF display the replacement of primary igneous amphibole and plagioclase, and metamorphic chlorite by hypogene ferroan chlorite, talc, and magnetite. Later-forming, hypogene specular hematite–quartz veins and their associated alteration halos partly replace magnetite–talc veins in BIF and formed during, to shortly after, the F₂-folding and tilting of the Weld Range tectono-stratigraphy. Supergene goethite–hematite ore zones that are up to 150 m wide, 400 m long, and extend to depths of 300 m replace least-altered BIF and existing hypogene alteration zones. The supergene ore zones formed as a result of the circulation of surface oxidised fluids through late NNW- to NNE-trending, subvertical brittle faults. Flat-lying, supergene goethite–hematite-altered, detrital sediments are concentrated in a paleo-topographic depression along the southern side of the main ENE-trending ridge at Madoonga. Iron ore deposits of the Weld Range greenstone belt record remarkably similar deformation histories, overprinting hypogene alteration events, and high-grade Fe ore types to other Fe ore deposits in the wider Yilgarn Craton (e.g. Koolyanobbing and Windarling deposits) despite these Fe camps being presently located more than 400 km apart and in different tectono-stratigraphic domains. Rather than the existence of a synchronous, Yilgarn-wide, Fe mineralisation event affecting BIF throughout the Yilgarn, it is more likely that these geographically isolated Fe ore districts experienced similar tectonic histories, whereby hypogene fluids were sourced from commonly available fluid reservoirs (e.g. metamorphic, magmatic, or both) and channelled along evolving structures during progressive deformation, resulting in several generations of Fe ore.     

The stability of hydrous phases beyond antigorite breakdown for a magnetite-bearing natural serpentinite between 6.5 and 11 GPa

Phase relations for a natural serpentinite containing 5 wt% of magnetite have been investigated using a multi-anvil apparatus between 6.5 and 11 GPa and 400–850 °C. Post-antigorite hydrous phase assemblages comprise the dense hydrous magnesium silicates (DHMSs) phase A (11.3 wt% H₂O) and the aluminous phase E (Al-PhE, 11.9 wt% H₂O). In addition, a ferromagnesian hydrous silicate (11.1 wt% H₂O) identified as balangeroite (Mg,Fe)₄₂Si₁₆O₅₄(OH)₄₀, typically described in low pressure natural serpentinite, was found coexisting with Al-PhE between 650 and 700 °C at 8 GPa. In the natural antigorite system, phase E stability is extended to lower pressures (8 GPa) than previously reported in simple chemical systems. The reaction Al-phase E?=?garnet?+?olivine?+?H₂O is constrained between 750 and 800 °C between 8 and 11 GPa as the terminal boundary between hydrous mineral assemblages and nominally anhydrous assemblages, hence restricting water transfer into the deep mantle to the coldest slabs. The water storage capacity of the assemblage Al-PhE?+?enstatite (high-clinoenstatite)?+?olivine, relevant for realistic hydrated slab composition along a relatively cold temperature path is estimated to be ca. 2 wt% H₂O. Attempts to mass balance run products emphasizes the role of magnetite in phase equilibria, and suggests the importance of ferric iron in the stabilization of hydrous phases such as balangeroite and aluminous phase E.     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

Primary petrology,mineralogy and age of the Letšeng-la-Terae kimberlite (Lesotho,Southern Africa) and parental magmas of Group-I kimberlites

The Let?eng-la-Terae kimberlite (Lesotho), famous for its large high-value diamonds, has five distinct phases that are mined in a Main and a Satellite pipe. These diatreme phases are heavily altered but parts of a directly adjacent kimberlite blow are exceptionally fresh. The blow groundmass consists of preserved primary olivine with Fo_86?88, chromite, magnesio-ulvöspinel and magnetite, perovskite, monticellite, occasional Sr-rich carbonate, phlogopite, apatite, calcite and serpentine. The bulk composition of the groundmass, extracted by micro-drilling, yields 24–26 wt% SiO₂, 20–21 wt% MgO, 16–19 wt% CaO and 1.9–2.1 wt% K₂O, the latter being retained in phlogopite. Without a proper mineral host, groundmass Na₂O is only 0.09–0.16 wt%. However, Na-rich K-richterite observed in orthopyroxene coronae allows to reconstruct a parent melt Na₂O content of 3.5–5 wt%, an amount similar to that of highly undersaturated primitive ocean island basanites. The groundmass contains 10–12 wt% CO₂, H₂O is estimated to 4–5 wt%, but volatiles and alkalis were considerably reduced by degassing. Mg# of 77.9 and 530 ppm Ni are in equilibrium with olivine phenocrysts, characterize the parent melt and are not due to olivine fractionation. ⁸⁷Sr/⁸⁶Sr_(i)?=?0.703602–0.703656, ¹⁴³Nd/¹⁴⁴Nd_(i)?=?0.512660 and ¹⁷⁶Hf/¹⁷⁷Hf_(i)?=?0.282677–0.282679 indicate that the Let?eng kimberlite originates from the convective upper mantle. U–Pb dating of groundmass perovskite reveals an emplacement age of 85.5?±?0.3 (2σ) Ma, which is significantly younger than previously proposed for the Let?eng kimberlite.     

Leaching of silica bands and concentration of magnetite in Archean BIF by hypogene fluids: Beebyn Fe ore deposit, Yilgarn Craton, Western Australia

The ~2,752-Ma Weld Range greenstone belt in the Yilgarn Craton of Western Australia hosts several Fe ore deposits that provide insights into the role of early hypogene fluids in the formation of high-grade (>55 wt% Fe) magnetite-rich ore in banded iron formation (BIF). The 1.5-km-long Beebyn orebody comprises a series of steeply dipping, discontinuous, <50-m-thick lenses of magnetite–(martite)-rich ore zones in BIF that extend from surface to vertical depths of at least 250 m. The ore zones are enveloped by a 3-km-long, 150-m-wide outer halo of hypogene siderite and ferroan dolomite in BIF and mafic igneous country rocks. Ferroan chlorite characterises 20-m-wide proximal alteration zones in mafic country rocks. The magnetite-rich Beebyn orebody is primarily the product of hypogene fluids that circulated through reverse shear zones during the formation of an Archean isoclinal fold-and-thrust belt. Two discrete stages of hypogene fluid flow caused the pseudomorphic replacement of silica-rich bands in BIF by Stage 1 siderite and magnetite and later by Stage 2 ferroan dolomite. The resulting carbonate-altered BIF is markedly depleted in SiO₂ and enriched in CaO, MgO, LOI, P₂O₅ and Fe₂O_3(total) compared with the least-altered BIF. Subsequent reactivation of these shear zones and circulation of hypogene fluids resulted in the leaching of existing hypogene carbonate minerals and the concentration of residual magnetite-rich bands. These Stage 3 magnetite-rich ore zones are depleted in SiO₂ and enriched in K₂O, CaO, MgO, P₂O₅ and Fe₂O_3(total) relative to the least-altered BIF. Proximal wall rock hypogene alteration zones in mafic igneous country rocks (up to 20 m from the BIF contact) are depleted in SiO₂, CaO, Na₂O, and K₂O and are enriched in Fe₂O_3(total), MgO and P₂O₅ compared with distal zones. Recent supergene alteration affects all rocks within about 100 m below the present surface, disturbing hypogene mineral and the geochemical zonation patterns associated with magnetite-rich ore zones. The key vectors for identifying hypogene magnetite-rich Fe ore in weathered outcrop include textural changes in BIF (from thickly to thinly banded), crenulated bands and collapse breccias that indicate volume reduction. Useful indicators of hypogene ore in less weathered rocks include an outer carbonate–magnetite alteration halo in BIF and ferroan chlorite in mafic country rocks.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Geochemistry of magmatic and hydrothermal zircon from the highly evolved Baerzhe alkaline granite: implications for Zr–REE–Nb mineralization

The Baerzhe alkaline granite pluton hosts one of the largest rare metal (Zr, rare earth elements, and Nb) deposits in Asia. It contains a geological resource of about 100 Mt at 1.84 % ZrO₂, 0.30 % Ce₂O₃, and 0.26 % Nb₂O₅. Zirconium, rare earth elements (REE), and Nb are primarily hosted by zircon, yttroceberysite, fergusonite, ferrocolumbite, and pyrochlore. Three types of zircon can be identified in the deposit: magmatic, metamict, and hydrothermal. Primary magmatic zircon grains occur in the barren hypersolvus granite and are commonly prismatic, with oscillatory zones and abundant melt and mineral inclusions. The occurrence of aegirine and fluorite in the recrystallized melt inclusions hosted in the magmatic zircon indicates that the parental magma of the Baerzhe pluton is alkali- and F-rich. Metamict zircon grains occur in the mineralized subsolvus granite and are commonly prismatic and murky with cracks, pores, and mineral inclusions. They commonly show dissolution textures, indicating a magmatic origin with later metamictization due to deuteric hydrothermal alteration. Hydrothermal zircon grains occur in mineralized subsolvus granite and are dipyramidal with quartz inclusions, with murky CL images. They have 608 to 2,502 ppm light REE and 787 to 2,521 ppm Nb, much higher than magmatic zircon. The texture and composition of the three types of zircon indicate that they experienced remobilization and recrystallization during the transition from a magmatic to a hydrothermal system. Large amounts of Zr, REE, and Nb were enriched and precipitated during the transitional period to form the giant low-grade Baerzhe Zr–REE–Nb deposit.     

Investigation on mineralogy,geochemistry and fluid inclusions of the Goushti hydrothermal magnetite deposit,Fars Province,SW Iran: A comparison with IOCGs

The Goushti iron deposit from Dehbid area located in the Sanandaj-Sirjan metamorphic Belt (SSB), SW Iran is hosted by the Early Mesozoic silicified dolomite. Mineralized zones are lithostructurally controlled and oriented NW-SE parallel to the Zagros Orogenic Belt (ZOB). Magnetite, the major ore mineral, occurs as open space fillings and is accompanied by the secondary mineral phases hematite, goethite and martite. Gangue minerals mainly include quartz, dolomite and K-feldspar are associated with minor hydrosilicates. Calc-silicates such as wollastonite and diopside, minerals typical of skarns, are virtually absent from the ore zones. Fe₂O₃ content in the mineralized zones varies in the range of 38–75 wt%. The concentrations of Au, Cu, P, Ti, Cr and V as well as Co/Ni, Cr/V, (LREE)/(HREE), Eu/Sm and La/Lu values and Eu-Ce anomalies of the studied ores indicate that the Goushti deposit is a hydrothermal magnetite type. The subvolcanic rhyolite and basalt in this area are regarded as the source of iron and heat in the mineralizing system. The fluid inclusion data showed that magnetite deposited from the ore-bearing fluid with salinities 1–7 wt% NaCl equivalent at temperatures of 130–200 °C. A decrease in temperature and pressure, supplemented by fluid mixing, is the major controlling factor in iron oxide precipitation. The field relationships and mineralogical–geochemical characteristics of iron ores indicate that the Goushti hydrothermal deposit could not be classified as a member of the IOCG (Iron Oxide-Copper-Gold) deposits.     

Experimental study into the petrogenesis of crystal-rich basaltic to andesitic magmas at Arenal volcano

Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H₂O/(H₂O + CO₂) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5?wt% SiO₂) from a nearby scoria cone containing olivine (Fo₉₂), plagioclase (An₈₆), clinopyroxene (Mg# = 82) and magnetite (X_ulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO₂) with 5 wt% H₂O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H₂O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H₂O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al₂O₃ samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

Hydrothermal processes in partially serpentinized peridotites from Costa Rica: evidence from native copper and complex sulfide assemblages

Native metals and metal alloys are common in serpentinized ultramafic rocks, generally representing the redox and sulfur conditions during serpentinization. Variably serpentinized peridotites from the Santa Elena Ophiolite in Costa Rica contain an unusual assemblage of Cu-bearing sulfides and native copper. The opaque mineral assemblage consists of pentlandite, magnetite, awaruite, pyrrhotite, heazlewoodite, violarite, smythite and copper-bearing sulfides (Cu-pentlandite, sugakiite [Cu(Fe,Ni)₈S₈], samaniite [Cu₂(Fe,Ni)₇S₈], chalcopyrite, chalcocite, bornite and cubanite), native copper and copper–iron–nickel alloys. Using detailed mineralogical examination, electron microprobe analyses, bulk rock major and trace element geochemistry, and thermodynamic calculations, we discuss two models to explain the formation of the Cu-bearing mineral assemblages: (1) they formed through desulfurization of primary sulfides due to highly reducing and sulfur-depleted conditions during serpentinization or (2) they formed through interaction with a Cu-bearing, higher temperature fluid (350–400 °C) postdating serpentinization, similar to processes in active high-temperature peridotite-hosted hydrothermal systems such as Rainbow and Logatchev. As mass balance calculations cannot entirely explain the extent of the native copper by desulfurization of primary sulfides, we propose that the native copper and Cu sulfides formed by local addition of a hydrothermal fluid that likely interacted with adjacent mafic sequences. We suggest that the peridotites today exposed on Santa Elena preserve the lower section of an ancient hydrothermal system, where conditions were highly reducing and water–rock ratios very low. Thus, the preserved mineral textures and assemblages give a unique insight into hydrothermal processes occurring at depth in peridotite-hosted hydrothermal systems.     

New textural and mineralogical constraints on the origin of the Hongge Fe-Ti-V oxide deposit, SW China

The Hongge magmatic Fe-Ti-V oxide deposit in the Panxi region, SW China, is hosted in a layered mafic–ultramafic intrusion. This 2.7-km-thick, lopolith-like intrusion consists of the lower, middle, and upper zones, which are composed of olivine clinopyroxenite, clinopyroxenite, and gabbro, respectively. Abundant Fe-Ti oxide layers mainly occur in the middle zone and the lower part of the upper zone. Fe-Ti oxides include Cr-rich and Cr-poor titanomagnetite and granular ilmenite. Cr-rich titanomagnetite is commonly disseminated in the olivine clinopyroxenite of the lower parts of the lower and middle zones and contains 1.89 to 14.9 wt% Cr₂O₃ and 3.20 to 16.2 wt% TiO₂, whereas Cr-poor titanomagnetite typically occurs as net-textured and massive ores in the upper middle and upper zones and contains much lower Cr₂O₃ (<0.4 wt%) but more variable TiO₂ (0.11 to 18.2 wt%). Disseminated Cr-rich titanomagnetite in the ultramafic rocks is commonly enclosed in either olivine or clinopyroxene, whereas Cr-poor titanomangetite of the net-textured and massive ores is mainly interstitial to clinopyroxene and plagioclase. The lithology of the Hongge intrusion is consistent with multiple injections of magmas, the lower zone being derived from a single pulse of less differentiated ferrobasaltic magma and the middle and upper zones from multiple pulses of more differentiated magmas. Cr-rich titanomagnetite in the disseminated ores of the lower and middle zones is interpreted to represent an early crystallization phase whereas clusters of Cr-poor titanomagnetite, granular ilmenite, and apatite in the net-textured ores of the middle and upper zones are thought to have formed from an Fe-Ti-(P)-rich melt segregated from a differentiated ferrobasaltic magma as a result of liquid immiscibility. The dense Fe-Ti-(P)-rich melt percolated downward through the underlying silicate crystal mush to form net-textured and massive Fe-Ti oxide ores, whereas the coexisting Si-rich melt formed the overlying plagioclase-rich rocks in the intrusion.     

Fluid–rock reactions in the 1.3 Ga siderite carbonatite of the Grønnedal–Íka alkaline complex,Southwest Greenland

Petrogenetic studies of carbonatites are challenging, because carbonatite mineral assemblages and mineral chemistry typically reflect both variable pressure–temperature conditions during crystallization and fluid–rock interaction caused by magmatic–hydrothermal fluids. However, this complexity results in recognizable alteration textures and trace-element signatures in the mineral archive that can be used to reconstruct the magmatic evolution and fluid–rock interaction history of carbonatites. We present new LA–ICP–MS trace-element data for magnetite, calcite, siderite, and ankerite–dolomite–kutnohorite from the iron-rich carbonatites of the 1.3 Ga Grønnedal–Íka alkaline complex, Southwest Greenland. We use these data, in combination with detailed cathodoluminescence imaging, to identify magmatic and secondary geochemical fingerprints preserved in these minerals. The chemical and textural gradients show that a 55 m-thick basaltic dike that crosscuts the carbonatite intrusion has acted as the pathway for hydrothermal fluids enriched in F and CO₂, which have caused mobilization of the LREEs, Nb, Ta, Ba, Sr, Mn, and P. These fluids reacted with and altered the composition of the surrounding carbonatites up to a distance of 40 m from the dike contact and caused formation of magnetite through oxidation of siderite. Our results can be used for discrimination between primary magmatic minerals and later alteration-related assemblages in carbonatites in general, which can lead to a better understanding of how these rare rocks are formed. Our data provide evidence that siderite-bearing ferrocarbonatites can form during late stages of calciocarbonatitic magma evolution.     

Constraints on the mineralization processes of the Makeng iron deposit,eastern China: Fluid inclusion,H–O isotope and magnetite trace element analysis

The Makeng iron deposit is located in the Yong’an-Meizhou depression belt in Fujian Province, eastern China. Both skarn alteration and iron mineralization are mainly hosted within middle Carboniferous-lower Permian limestone. Five paragenetic stages of skarn formation and ore deposition have been recognized: Stage 1, early skarn (andradite–grossular assemblage); Stage 2, magnetite mineralization (diopside–magnetite assemblage); Stage 3, late skarn (amphibole–chlorite–epidote–johannsenite–hedenbergite–magnetite assemblage); Stage 4, sulfide mineralization (quartz–calcite–fluorite–chlorite–pyrite–galena–sphalerite assemblage); and Stage 5, carbonate (quartz–calcite assemblage). Fluid inclusion studies were carried out on inclusions in diopside from Stage 2 and in quartz, calcite, and fluorite from Stage 4.Halite-bearing (Type 1) and coexisting two-phase vapor-rich aqueous (Type 3) inclusions in the magnetite stage display homogenization temperatures of 448–564 °C and 501–594 °C, respectively. Salinities range from 26.5 to 48.4 and 2.4 to 6.9 wt% NaCl equivalent, respectively. Two-phase liquid-rich aqueous (Type 2b) inclusions in the sulfide stage yield homogenization temperatures and salinities of 182–343 °C and 1.9–20.1 wt% NaCl equivalent. These fluid inclusion data indicate that fluid boiling occurred during the magnetite stage and that fluid mixing took place during the sulfide stage. The former triggered the precipitation of magnetite, and the latter resulted in the deposition of Pb, Zn, and Fe sulfides. The fluids related to magnetite mineralization have δ¹⁸O_fluid-VSMOW of 6.7–9.6‰ and δD of −96 to −128‰, which are interpreted to indicate residual magmatic water from magma degassing. In contrast, the fluids related to the sulfide mineralization show δ¹⁸O_fluid-VSMOW of −0.85 to −1.04‰ and δD of −110 to −124‰, indicating that they were generated by the mixing of magmatic water with meteoric water. Magnetite grains from Stage 2 exhibit oscillatory zoning with compositional variations in major elements (e.g., SiO₂, Al₂O₃, CaO, MgO, and MnO) from core to rim, which is interpreted as a self-organizing process rather than a dissolution-reprecipitation process. Magnetite from Stage 3 replaces or crosscuts early magnetite, suggesting that later hydrothermal fluid overprinted and caused dissolution and reprecipitation of Stage 2 magnetite. Trace element data (e.g., Ti, V, Ca, Al, and Mn) of magnetite from Stages 2 and 3 indicate a typical skarn origin.     

Differentiation of nelsonitic magmas in the formation of the ~1.74 Ga Damiao Fe–Ti–P ore deposit, North China

The ~1.74 Ga Damiao anorthosite complex, North China, is composed of anorthosite and leuconorite with subordinate melanorite, mangerite, oxide-apatite gabbronorite, perthite noritic (i.e., jotunitic) and ferrodioritic dykes. The complex hosts abundant vein-, pod- and lens-like Fe–Ti–P ores containing variable amounts of apatite (10–60 modal%) and Fe–Ti oxides. In addition to Fe–Ti–P ores, there are also abundant Fe–Ti ores which are closely associated with Fe–Ti–P ores in the deposit. Most of Fe–Ti–P ores are dominated by Fe–Ti oxides and apatite, devoid of silicate minerals, mineralogically similar to the common nelsonites elsewhere. In contrast, Fe–Ti ores are dominated by Fe–Ti oxides with minor apatite (<5 modal %). The parental magma of these ores, estimated from olivine and apatite compositions using mineral-melt partition coefficients, has composition similar to the ferrodioritic dykes. Fe–Ti–P ores have variable Fe–Ti oxides and apatite proportions, indicating that they are cumulates. Their simple assemblage of Fe–Ti oxides and apatite and local net-texture suggest that the Fe–Ti–P ores in Damiao have formed from nelsonitic melts immiscibly separated from the ferrodioritic magma during late-stage differentiation. Fe–Ti ores are also cumulates and have mineral compositions similar to Fe–Ti–P ores. The close association between Fe–Ti and Fe–Ti–P ores indicates that the Fe–Ti ores may have also formed from the nelsonitic melts. We proposed that differentiation of nelsonitic melts accompanied by gravity settling is responsible for the formation of Fe–Ti and Fe–Ti–P ores. Such a differentiation process in nelsonitic melts is well supported by variations of Sr, Y, Th, U, REE and Eu/Eu* of apatite in Fe–Ti–P ores. Using oxides/apatite ratio of 2:1 and compositions of apatite and calculated primary oxides, we estimate the composition of the nelsonitic melt as ~52.0 wt% Fe₂O₃t, ~18.5 wt% CaO, ~14.2 wt% P₂O₅, ~8.7 wt% TiO₂, ~4.0 wt% Al₂O₃ and ~1.1 wt% MgO with minor SiO₂, K₂O, Na₂O and F. Such a nelsonitic melt is suggested to be possibly conjugated with Si-rich melts compositionally similar to the Damiao jotunitic dykes (~50 wt% SiO₂ and ~15 wt% Fe₂O₃t) which may subsequently evolve to mangeritic rocks in Damiao. Our modeling also indicates that the onset of immiscibility occurs at a time when the evolved melt has ~44 wt% SiO₂, ~21 wt% Fe₂O₃t, ~3.0 wt% TiO₂ and ~2.6 wt% P₂O₅. High oxygen fugacity and phosphorous content in magmas may play important roles in the immiscibility of nelsonitic magmas, including promoting iron enrichments and widening the two-liquid field.     

Pink manganian phengite in a high P/T meta-conglomerate from northern Syros (Cyclades, Greece)

A new occurrence of Mn-rich rocks was discovered within the high-pressure/low-temperature metamorphic rocks on the Palos peninsula of Syros (Greece). Near the summit of Mount Príonas, a meta-conglomerate consists of calcite (~63 wt%), pink manganian phengite, blue–purple manganian aegirine–jadeite, microcline, albite and quartz. In addition, it contains abundant braunite-rich aggregates (up to ~1.5 cm in diameter) that include hollandite [(Ba_0.98–1.02K_<0.01Na_<0.02Ca_<0.03) (Mn _1.02–1.52 ³⁺ Fe _0.38–0.88 ³⁺ Ti_0.29–0.92Mn _5.11–5.76 ⁴⁺ )O₁₆], barite and manganian hematite. Due to metamorphic recrystallization and deformation, the contacts between clasts and matrix are blurred and most clasts have lost their identity. In back-scattered electron images, many aegirine–jadeite grains appear patchy and show variable jadeite contents (Jd_10–67). These pyroxenes occur in contact with either quartz or albite. Manganian phengite (3.41–3.49 Si per 11 oxygen anions) is of the 3T type and contains 1.4–2.2 wt% of Mn₂O₃. At the known P–T conditions of high-pressure metamorphism on Syros (~1.4 GPa/ 470 °C), the mineral sub-assemblage braunite + quartz + calcite (former aragonite) suggests high oxygen fugacities relative to the HM buffer (+7 ≤ ?f_O2 ≤ + 17) and relatively high CO₂ fugacities. The exact origin of the conglomerate is not known, but it is assumed that the Fe–Mn-rich and the calcite-rich particles originated from different sources. Braunite has rather low contents of Cu (~0.19 wt%) and the concentrations of Co, Ni and Zn are less than 0.09 wt%. Hollandite shows even lower concentrations of these elements. Furthermore, the bulk-rock compositions of two samples are characterized by low contents of Cu, Co and Ni, suggesting a hydrothermal origin of the manganese ore. Most likely, these Fe–Mn–Si oxyhydroxide deposits consisted of ferrihydrite, todorokite, birnessite, amorphous silica (opal-A) and nontronite. Al/(Al + Fe + Mn) ratios of 0.355 and 0.600 suggest the presence of an aluminosilicate detrital component.     

Opx–Cpx exsolution textures in lherzolites of the Cretaceous Purang Ophiolite (S. Tibet,China), and the deep mantle origin of Neotethyan abyssal peridotites

ABSTRACT

We investigated lherzolitic peridotites in the Cretaceous Purang ophiolite along the Yarlung Zhangbo suture zone (YZSZ) in SW Tibet to constrain their mantle–melt evolution history. Coarse-grained Purang lherzolites contain orthopyroxene (Opx) and olivine (Ol) porphyroclasts with embayments filled by small olivine (Ol) neoblasts. Both clinopyroxene (Cpx) and Opx display exsolution textures represented by lamellae structures. Opx exsolution (Opx1) in clinopyroxene (Cpx1) is made of enstatite, whose compositions (Al₂O₃ = 3.85–4.90 wt%, CaO = <3.77 wt%, Cr₂O₃ = 0.85–3.82 wt%) are characteristic of abyssal peridotites. Host clinopyroxenes (Cpx1) have higher Mg#s and Na₂O, with lower TiO₂ and Al₂O₃ contents than Cpx2 exsolution lamellae in Opx, and show variable LREE patterns. Pyroxene compositions of the lherzolites indicate 10–15% partial melting of a fertile mantle protolith. P–T estimates (1.3–2.3 GPa, 745–1067°C) and the trace element chemistry of pyroxenes with exsolution textures suggest crystallization depths of ~75 km in the upper mantle, where the original pyroxenes became decomposed, forming exsolved structures. Further upwelling of lherzolites into shallow depths in the mantle resulted in crystal–plastic deformation of the exsolved pyroxenes. Combined with the occurrence of microdiamond and ultrahigh-pressure (UHP) mineral inclusions in chromites of the Purang peridotites, the pyroxene exsolution textures reported here confirm a multi-stage partial melting history of the Purang lherzolites and at least three discrete stages of P-T conditions in the course of their upwelling through the mantle during their intra-oceanic evolution.     

Stability of phengite and biotite in eclogites and characteristics of biotite- or orthopyroxene-bearing eclogites

Stability of phengite and biotite in eclogite is discussed using petrological data of natural eclogites, and the observational data are examined by thermodynamic calculations. Generally, phengite is a major K phase in natural eclogite and is stable in wide range of bulk composition. However, in eclogites from several localities of the Caledonides, biotite occurs as a stable eclogite-facies mineral, and is often associated with orthopyroxene. Bulk compositions of such biotite- or orthopyroxene-bearing eclogites are compared with those of eclogites from the Dabie–Sulu region, China, where phengite is a major K phase in eclogite. The biotite- or orthopyroxene-bearing eclogites from the Western Gneiss Region of the Caledonides are rich in MgO (10–15 wt%) and relatively poor in CaO (7–8 wt%) and Al₂O₃ (12–16 wt%). The CaO/MgO ratios of the biotite- or orthopyroxene-bearing eclogites are clearly lower than those of eclogites from the Dabie–Sulu region, indicating that MgO-rich and CaO-poor environments should be important for stabilizing of biotite and orthopyroxene in eclogite. Biotite-bearing eclogite from the North-East Greenland Eclogite Province is rich in MgO (≈16 wt%) and CaO (≈15.5 wt%) and extremely poor in Al₂O₃ (≈8 wt%). To stabilize biotite in eclogite, Al₂O₃-poor environments are also important. Bulk compositions of these biotite- or orthopyroxene-bearing eclogites are similar to picrite basaltic compositions. To examine these observational data, thermodynamic calculations were carried out in a seven-component system KH₂O_1.5–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂, which includes garnet, kyanite, phengite, biotite, quartz, omphacite, orthopyroxene and olivine in conjunction with mass-balance calculations. Firstly, calculations were performed on the average bulk composition of eclogites from the Dabie–Sulu region to lherzolite (KLB-1). The calculation results confirmed that phengite should be stable in eclogite with 'ordinary' basaltic composition, whereas biotite and orthopyroxene should be stable in picrite basaltic compositions (e.g. MgO >11.0 wt%, CaO <9.8 wt%, Al₂O₃ <15.2 wt% at 700 °C, 2.5 GPa). Further calculations in basaltic system confirmed that increase of MgO content and decrease of CaO and Al₂O₃ contents were important to stabilize biotite and orthopyroxene in eclogite. Thus, mineral assemblage in picrite basalt system should be completely different from that in normal basaltic system.