Alteration at the Olympic Dam IOCG–U deposit: insights into distal to proximal feldspar and phyllosilicate chemistry from infrared reflectance spectroscopy

Twenty thousand metres of diamond drill core representing a 14 km cross-section from weakly to intensely altered Roxby Downs Granite through the Olympic Dam Breccia Complex, host to the Olympic Dam iron-oxide–copper–gold–uranium deposit in South Australia, was analysed using the HyLogger-3 spectral scanner. Thermal and shortwave infrared spectroscopy results from 30 drill holes provide insight into the spatial relationships between quartz, orthoclase–microcline, albite–oligoclase and progressively changing sericite and chlorite compositions. The relative proportions of quartz, feldspars and phyllosilicates were mapped with thermal infrared spectroscopy. Variations in the chemistry of sericite and chlorite were extracted by proxy from their shortwave infrared spectral response, together with their relative spatial distribution. HyLogger scanning has revealed four deposit-scale mineralogical trends, progressing from least-altered Roxby Downs Granite into mineralisation where most of the feldspar has been replaced by sericite + hematite + quartz: (1) a progressive Al–OH wavelength shift of 2205 nm to 2210 nm for sericite, followed by a spatially rapid reversal corresponding to lower phengite/muscovite abundance ratios; (2) progressive Mg/Fe–OH wavelength shift of 2248 nm to 2252 nm reflecting an increase in the Fe:Mg ratio of chlorite; (3) increasing ratio of microcline to orthoclase followed by a rapid decrease; and (4) slightly decreasing ratio of albite to oligoclase followed by plagioclase destruction prior to albite replacement by sericite. The HyLogger feldspar results support recent petrographic evidence for hydrothermal albite and K-feldspar at the Olympic Dam deposit, not previously reported. The spectral results from continuous HyLogger scans also show that the microscopic observations and proposed feldspar replacement reactions are not locally isolated phenomena, but are applicable at the deposit and regional-scale. A modified quartz–K-feldspar–plagioclase ternary diagram utilising mineralogy interpreted from HyLogger thermal infrared spectra (QAP_TIR) diagram along with supporting data on the abundance ratios of orthoclase/microcline and albite/plagioclase, and the wavelength shifts in characteristic absorption features for sericite and chlorite, can be used as empirical vectors towards mineralisation within the Olympic Dam mineral system, with potential application to other IOCG ore-forming systems. Intrusion of Gairdner Dyke Swarm dolerite dykes into sericite ± hematite altered Roxby Downs Granite results in retrograde albite–chlorite–magnetite alteration envelopes (up to tens of metres thick) overprinting the original sericite ± hematite alteration zone and needs to be carefully evaluated to ensure that such areas are not falsely downgraded during exploration.     

Coupled alkali-feldspar dissolution and secondary mineral precipitation in batch systems: 1. New experiments at 200 °C and 300 bars

Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.     

Mantled feldspars from the Golden Horn batholith,Washington

Mantled feldspars that formed by resorption, development of skeletal plagioclase crystals, and filling with alkali feldspar are common in the Golden Horn batholith, Washington. Subhedral plagioclase mantles have weak normal zoning from An₁₇ to An₁₀. Plagioclase zoning and twinning are crosscut by resorption channels. Resorption cavities and channels are coated with albite (An₁₀). Anhedral, perthitic orthoclase within the plagioclase is optically continuous with orthoclase in channels and on the mantle exterior.This texture resulted from resorption of calcic cores of plagioclase as pressure decreased when water-undersaturated granite magma intruded to a shallow crustal level. At shallow level, only alkali feldspar and quartz crystallized and were available to fill the skeletal plagioclase.     

Retrograde metamorphic reactions in deforming granites and the origin of flame perthite

Abstract Microprobe analyses of feldspars in granite mylonites containing flame perthite give compositions that invariably plot as three distinct clusters on a ternary feldspar diagram: orthoclase (Or_92–97), albite and oligoclase-andesine. The albite occurs as grains in the matrix, as flame-shaped lamellae in orthoclase, and in patches within plagioclase grains. We present a metamorphic model for albite flame growth in the K-feldspar in these rocks that is related to reactions in plagioclase, rather than alkali feldspar exsolution. Flame growth is attributed to replacement and results from a combination of two retrograde reactions and one exchange reaction under greenschist facies conditions. Reaction 1 is a continuous or discontinuous (across the peristerite solvus) reaction in plagioclase, in which the An component forms epidote or zoisite. Most of the albite component liberated by Reaction 1 stays to form albite in the host plagioclase, but some Na migrates to form the flames within the K-feldspar. Reaction 2 is the exchange of K for Na in K-feldspar. Reaction 3 is the retrograde formation of muscovite (as ‘sericite’) and has all of the chemical components of a hydration reaction of K-feldspar. The Si and Al made available in the plagioclase from Reaction 1 are combined with the K liberated from the K-feldspar, to produce muscovite in Reaction 3. The muscovite forms in the plagioclase, rather than the K-feldspar, as a result of the greater mobility of K relative to Al. The composition of the albite flames is controlled by both the peristerite and the alkali feldspar miscibility gaps and depends on the position of these solvi at the pressure and temperature that existed during the reaction. Using an initial plagioclase composition of An₂₀, the total reaction can be summarized as: 20 oligoclase + 1 K-feldspar + 2 H₂O = 2 zoisite + muscovite + 2 quartz + 15 albite_plagioclase+ 1 albite_flame. This model does not require that any additional feldspar framework be accreted at replacement sites: Na and K are the only components that must migrate a significant distance (e.g. from one grain to the next), allowing Al to remain within the altering plagioclase grain. The resulting saussuritization is isovolumetric. The temperature and extent of replacement depends on when, and how much, water infiltrates the rock. The fugacity of the water, and therefore the pressure of the fluid, may have been significantly lower than lithostatic during flame growth.     

Experimental silicate mineral/melt partition coefficients for beryllium and the crustal Be cycle from migmatite to pegmatite

Partition coefficients (D_Be^mineral/melt) for beryllium between hydrous granitic melt and alkali feldspars, plagioclase feldspars, quartz, dark mica, and white mica were determined by experiment at 200 MPa H₂O as a function of temperature (650-900°C), activity of Be in melt (trace levels to beryl saturation), bulk composition, and thermal run direction. At trace levels, Be is compatible in plagioclase of An₃₁ (1.84 at 700°C) and muscovite (1.35 at 700°C) but incompatible in biotite (0.39-0.54 from 650-800°C), alkali feldspar (0.38-0.19 from 680-850°C), quartz (0.24 at 800°C), and albite (0.10 at 750°C). The partition coefficients are different at saturation of the melt in beryl: lower in the case of plagioclase of An₃₁ (0.89 at 700°C), muscovite (0.87 at 700°C), biotite (0.18-0.08 from 675-800°C), alkali feldspar (0.18-0.14 from 680-700°C), and quartz (0.17-0.08 from 750-800°C), but higher in the case of albite (0.37 at 750°C).With other data sources, these new partition coefficients were utilized to track, first, the distribution of Be between aluminous quartzofeldspathic source rocks and their anatectic melts, and second, the dispersion or concentration of Be in melt through igneous crystal fractionation of different magma types (e.g., S-type, I-type) up to beryl-saturated granitic pegmatites and, finally, into their hydrothermal aureoles. Among the rock-forming minerals, cordierite, calcic oligoclase, and muscovite (in this order) control the fate of Be because of the compatibility of Be in these phases. In general, beryl-bearing pegmatites can arise only after extended crystal fractionation of large magma batches (to F, fraction of melt remaining, ≤0.05); granitic magmas that originate from cordierite-bearing protoliths or that contain large modal quantities of calcic oligoclase will not achieve beryl saturation at any point in their evolution.     

Hydrothermal alteration and mass exchange in the hornblende latite porphyry,Rico, Colorado

The Rico paleothermal anomaly, southwestern Colorado, records the effects of a large hydrothermal system that was active at 4 Ma. This hydrothermal system produced the deep Silver Creek stockwork Mo deposit, which formed above the anomaly's heat source, and shallower base and precious-metal vein and replacement deposits. A 65 Ma hornblende latite porphyry is present as widespread sills throughout the area and provided a homogenous material that recorded the effects of the hydrothermal system up to 8 km from the center. Hydrothermal alteration in the latite can be divided into a proximal facies which consists of two assemblages, quartz-illite-calcite and chlorite-epidote, and a distal facies which consists of a distinct propylitic assemblage. Temperatures were gradational vertically and laterally in the anomaly, and decreased away from the centra heat source. A convective hydrothermal plume, 3 km wide and at least 2 km high, was present above the stock-work molybdenum deposit and consisted of upwelling, high-temperature fluids that produced the proximal alteration facies. Distal facies alteration was produced by shallower cooler fluids. The most important shallow base and precious-metal vein deposits in the Rico district are at or close to the boundary of the thermal plume. Latite within the plume had a large loss of Na₂O, large addition of CaO, and variable SiO₂ exchante. Distal propylitized latite samples lost small amounts of Na₂O and CaO and exchanged minor variable amounts of SiO₂. The edge of the plume is marked by steep Na₂O exchange gradients. Na₂O exchange throughout the paleothermal anomaly was controlled by the reaction of the albite components in primary plagioclase and alkali feldspars. Initial feldspar alteration in the distal facies was dominated by reaction of the plagioclase, and the initial molar ratio of reactants (alkali feldspar albite component to plagioclase albite component) was 0.35. This ratio of the moles of plagioclase to alkali feldspar albite components that reacted evolved to 0.92 as the reaction progressed. Much of the alkali feldspar albite component in the proximal facies reacted while the, primary plagioclase was still unreacted, but the ratio for these assemblages increased to 1.51 when the plagioclase entered the reaction paragenesis. Plagioclase reaction during distal propylitic alteration resulted in pseudomorphic albite mixed with illite and a loss of Na₂O. CaO is lost in the distal facies as hornblende reacts to chlorite, although some calcium may be fixed in calcite. CaO is added to the proximal facies as the quantity of chlorite replacing hornblende increases and epidote and calcite are produced.     

Paleofluids circulation associated with the Gerês late-orogenic granitic massif,northern Portugal

The Hercynian late-orogenic granites from the Gerês massif, northern Portugal, underwent intense hydrothermal activity along tectonic structures striking N-S and NE-SW. The first hydrothermal stage is characterized by the albitization of feldspars (primary K-feldspar and plagioclase) followed by the dissolution of magmatic quartz, the chloritization of biotite, and the muscovitization of magmatic biotite and feldspars and occasionally of authigenic albite. Whole-rock geochemistry shows a decrease of SiO₂, K₂O and Rb and an increase of Na₂O, Al₂O₃ and Sr amounts during the albitization. The second hydrothermal stage is characterized by a mineral assemblage consisting of secondary quartz, albite, chlorite, hematite, apatite, muscovite, epidote, sphene and carbonates, which infilled the cavities produced by the early quartz leaching.Mass balance calculations demonstrate a noticeable element mobilization during the granite alteration. The average ∑REE of the Gerês granite is nearly constant at 154 ppm, but ranges from 91 to 163 ppm in the altered rocks. A relative LREE depletion and a slight HREE enrichment associated with a negative Eu anomaly characterize the feldspathization process of Gerês granite. The average ∑REE of the Carris granite is at 159 ppm but in the altered epidote + chlorite + hematite assemblage it reaches about 201 ppm with a slight HREE increase.Two different fluids were involved in the hydrothermal alteration. A first aqueous fluid (Lw₁), with a low to intermediate salinity (<10 wt.% eq. NaCl) circulated along the main structures (N-S, NE-SW and NW-SE), characterized by entrapment temperature lower than 350 °C and maximum pressure of 115 MPa followed by a later colder and more saline fluid (Lw₂) under a temperature of 220 °C and a pressure of about 27 MPa.Oxygen isotope data obtained on magmatic quartz indicate δ¹⁸O_quartz of + 9.3 and + 11.0‰, pointing to an interaction of magmatic fluids with others of meteoric origin. For the secondary quartz, δ¹⁸O_water of +0.5 and +0.7‰ were calculated for a temperature of 250 °C, suggesting a meteoric fluid with a possible seawater signature.The K-Ar data of K-feldspar from the altered rocks confirm an age of 273.6 ± 11.7 Ma, attributed to the first alteration process. Younger K-Ar ages between 155.8 ± 6.7 Ma and 124 ± 5.3 Ma were also obtained in the feldspathized rocks, confirming the late hydrothermal activity.Albitization and quartz dissolution of granitic rocks from the Gerês massif occurred at depths shallower than 5 km, induced by the circulation of fluids along brittle structures, during the orogenic uplift and extensional tectonics which affected the Iberian Massif in the Early Permian. A second major event is attributed to late hydrothermal circulations of aqueous brines until a depth of about 3 km, presumably derived from interaction with sub-surface evaporites throughout Late Jurassic to Early Cretaceous. These late hydrothermal events probably reflect the rifting episodes and the rising of geothermal gradient, associated with the opening of the Atlantic Ocean and Gulf of Biscay, respectively.     

Mesoproterozoic arc magmatism in SE India: Petrology,zircon U–Pb geochronology and Hf isotopes of the Bopudi felsic suite from Eastern Ghats Belt

The southern segment of the Eastern Ghats Mobile Belt (EGMB) in India was an active convergent margin during Mesoproterozoic, prior to the final collision in Neoproterozoic during the assembly of the Rodinia supercontinent. Here we present mineralogical, whole-rock geochemical, zircon U–Pb and Hf isotopic data from a granitoid suite in the Bopudi region in the EGGB. The granitoid complex comprises quartz monzodiorite with small stocks of rapakivi granites. The monzodiorite, locally porphyritic, contains K-feldspar megacrysts, plagioclase, quartz, biotite and ortho-amphibole. The presence of mantled ovoid megacrysts of alkali feldspar embaying early-formed quartz, and the presence of two generations of the phenocrystic phases in the rapakivi granites indicate features typical of rapakivi granites. The K-feldspar phenocrysts in the rapakivi granite are mantled by medium-grained aggregates of microcline (Ab₇ Or₉₃), which is compositionally equivalent to the rim of Kfs phenocryst and Pl (An_23–24 Ab₇₅). The geochemistry of both the granitoids shows arc-like features for REE and trace elements. LA-ICP-MS zircon analyses reveal ²⁰⁷Pb/²⁰⁶Pb ages of 1582 (MSWD = 1.4) for the rapakivi granite 1605 ± 3 Ma (MSWD = 3.9) for the monzodiorite. The zircons from all the granitoid samples show high REE contents, prominent HREE enrichment and a conspicuous negative Eu anomaly, suggesting a common melt source. The zircons from the monzodiorite have a limited variation in initial ¹⁷⁶Hf/¹⁷⁷Hf ratios of 0.28171–0.28188, with εHf(t) values of −2.2 to +2.8. Correspondingly, their two-stage Hf isotope model ages (T_DM2) ranging from 2.15 to 2.47 Ga probably suggest a mixed source for the magma involving melting of the Paleoproterozoic basement and injection of subduction-related juvenile magmas. The prominent Mesoproterozoic ages of these granitoids suggest subduction-related arc magmatism in a convergent margin setting associated with the amalgamation of the Columbia-derived fragments within the Neoproterozoic Rodinia assembly.     

Eight-phase alkali feldspars: low-temperature cryptoperthite, peristerite and multiple replacement reactions in the Klokken intrusion

Eight feldspar phases have been distinguished within individual alkali feldspar primocrysts in laminated syenite members of the layered syenite series of the Klokken intrusion. The processes leading to the formation of the first four phases have been described previously. The feldspars crystallized as homogeneous sodian sanidine and exsolved by spinodal decomposition, between 750 and 600 °C, depending on bulk composition, to give fully coherent, strain-controlled braid cryptoperthites with sub-μm periodicities. Below ~500 °C, in the microcline field, these underwent a process of partial mutual replacement in a deuteric fluid, producing coarse (up to mm scale), turbid, incoherent patch perthites. We here describe exsolution and replacement processes that occurred after patch perthite formation. Both Or- and Ab-rich patches underwent a new phase of coherent exsolution by volume diffusion. Or-rich patches began to exsolve albite lamellae by coherent nucleation in the range 460–340 °C, depending on patch composition, leading to film perthite with ≤1 μm periodicities. Below ~300 °C, misfit dislocation loops formed, which were subsequently enlarged to nanotunnels. Ab-rich patches (bulk composition ~Ab₉₁Or₁An₈), in one sample, exsolved giving peristerite, with one strong modulation with a periodicity of ~17 nm and a pervasive tweed microtexture. The Ab-rich patches formed with metastable disorder below the peristerite solvus and intersected the peristerite conditional spinodal at ~450 °C. This is the first time peristerite has been imaged using TEM within any perthite, and the first time peristerite has been found in a relatively rapidly cooled geological environment. The lamellar periodicities of film perthite and peristerite are consistent with experimentally determined diffusion coefficients and a calculated cooling history of the intrusion. All the preceding textures were in places affected by a phase of replacement correlating with regions of extreme optical turbidity. We term this material ultra porous late feldspar (UPLF). It is composed predominantly of regions of microporous very Or-rich feldspar (mean Ab_2.5Or_97.4An_0.1) associated with very pure porous albite (Ab_97.0Or_1.6An_1.4) implying replacement below 170–90 °C, depending on degree of order. In TEM, UPLF has complex, irregular diffraction contrast similar to that previously associated with low-temperature albitization and diagenetic overgrowths. Replacement by UPLF seems to have been piecemeal in character. Ghost-like textural pseudomorphs of both braid and film parents occur. Formation of patch perthite, film perthite and peristerite occurred 10⁴–10⁵ year after emplacement, but there are no microtextural constraints on the age of UPLF formation.     

Geochemistry,Sr–Nd–Pb–Hf isotopes systematics and geochronological constrains on petrogenesis of the Xishan A-type granite and associated W–Sn mineralization in Guangdong Province,South China

The Xishan deposit, located in the western Guangdong Province in South China, is a quartz-vein type W-Sn deposit with an average Sn grade of 0.1–0.4 wt%. The deposit is temporally and spatially associated with Xishan alkali feldspar granite. The W–Sn mineralization is present mainly as veins that are hosted by the granite. In this paper we present new zircon U–Pb age, whole-rock geochemical data, Sr–Nd–Pb–Hf isotopic data and Re–Os age in order to constrain the nature and timing of magmatism and mineralization in the Xishan mining district with implications on geodynamic settings. LA–ICP–MS zircon U–Pb analyses yielded an age of 79.14 ± 0.31 Ma for the alkali feldspar granite, consistent with the molybdenite Re–Os age of 79.41 ± 1.11 Ma. The alkali feldspar granite shows high contents of SiO₂ (71.52–76.25 wt%), high total alkalis (Na₂O + K₂O = 9.35–13.51 wt%), high field strength elements (e.g. Zr = 95.4–116 ppm, Y = 97.1–138 ppm, Nb = 36.1–55.5 ppm, Ga = 97.1–138 ppm), and rare earth elements (total REE = 171.8–194.0 ppm) as well as high Ga/Al ratios (10,000 × Ga/Al = 3.23–3.82) suggesting that it has the geochemical characteristics of A-type granite and shows an A₂ subtype affinity. Sr–Nd isotopes of the alkali feldspar granite show that (⁸⁷Sr/⁸⁶Sr)_i values range from 0.7111 to 0.7183, and the ε_Nd(t) values and Nd model ages (T_2DM) vary from −6.8 to −6.5 and 1414 to 1433 Ma, respectively. The Pb isotopic compositions are variable, with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values ranging from 18.783 to 18.947, 15.709 to 15.722 and 38.969 to 39.244, respectively, indicating that the alkali feldspar granite was derived from a mantle-crust mixed source. In situ Hf isotopic analyses reveal that the alkali feldspar granite has ε_Hf(t) values ranging from −9.69 to −0.04 and two-stage Hf model ages from 1145 Ma to 1755 Ma, indicating that the alkali feldspar granite was formed by the partial melting of Mesoproterozoic crusts of the Cathaysia Block with additions of mantle-derived materials. These results, together with previously presented regional geological relationships, suggest that the formation of the Xishan granite and associated W–Sn mineralization is related to lithospheric extension and asthenospheric upwelling that are attributed to a directional change of Pacific plate motion.     

The Origin of Rapakivi Texture

The mantling of large ovoids of K-feldspar by a rim of plagioclasehas been investigated in the rapakivi granites from the Mid-ProterozoicWiborg batholith of SE Finland. The formation of rapakivi texture,in this the type area, was examined using a variety of techniquesincluding isotopic analyses of mineral separates from specifictextural sites. Cathodoluminescence combined with microprobeanalysis points to the pulsed development of the mantles involvinggrowth of successive plagioclases of composition An₃₀, An₂₅,and An₃, the last being in optical continuity with perthiticplagioclase exsolved from the K-feldspar. Plagioclase mantleshave high ¹⁸O and ⁸⁷Sr/⁸⁶ signatures relative to K-feldspar,which indicate the presence of a late, low-temperature componentthought to represent albite exsolved from the K-feldspar andredistributed onto the ovoid margin. Oligoclase components ofthe mantles are formed by a similar, although higher-temperaturemagmatic process. This involves the subsolvus re-equilibrationof alkali feldspar compositions with evolving melt conditions.Redistribution of the exsolved plagioclase from the alkali feldsparphenocrysts is linked to high fluorine contents of rapakivi-typemagmas, and this major reconstruction of the feldspar phenocrystsgenerates their distinctive ovoidal shape.     

Fractional crystallization and the formation of thick Fe–Ti–V oxide layers in the Baima layered intrusion,SW China

The Baima layered intrusion is located in the central part of the Emeishan Large Igneous Province (ELIP). The N–S striking intrusion is ~ 24 km long and ~ 2 km thick and dips to the west. Based on variations in modal proportions and cumulus mineral assemblages, the intrusion from the base to the top is simply subdivided into a lower zone (LZ) with most of the economic magnetite layers, and an upper zone (UZ) with apatite-bearing troctolite and gabbro. The rock textures suggest crystallization of the Fe–Ti oxide slightly later than plagioclase (An_67-54) but relatively earlier than olivine (Fo_74-55), followed by clinopyroxene and finally apatite.Relatively low olivine forsterite content and abundant ilmenite exsolution lamellae in clinopyroxene indicate that the Baima parental magma is a highly evolved Fe–Ti-rich magma. Via MELTS model, it demonstrates that under a closed oxygen system, extensive silicate mineral fractionation of a picritic magma might lead to Fe and Ti enrichment and oxygen fugacity elevation in the residual magma. When such Fe–Ti-rich magma ascends to the shallower Baima intrusion, the Fe–Ti oxides may become an early liquidus phase. Well-matched olivine and plagioclase microprobe data with the results of MELTS calculation, combined with relatively low CaO content in olivine (0.02–0.08 wt.%) indicate that wall-rock contamination probably plays a weak role on oxygen fugacity elevation and the early crystallization of Fe–Ti oxides. Several reversals in whole-rock chromium and plagioclase anorthite contents illustrate that multiple recharges of such Fe–Ti-rich magma mainly occurred along the lower part of the Baima magma chamber. Frequent Fe–Ti-rich magma replenishment and gravitational sorting and settling are crucial for the development of thick Fe–Ti oxide layers at the base of the Baima layered intrusion.     

Geochemistry and petrogenesis of the Gallego Volcanic Field,Solomon Islands,SW Pacific and geotectonic implications

The Upper Miocene to present day Gallego Volcanic Field (GVF) is located in northwest Guadalcanal, Solomon Islands, SW Pacific, and potentially includes the offshore Savo volcano. The GVF is a multi-centred complex covering an area of ~ 800 km² on Guadalcanal and a further ~ 30 km² on the island of Savo, north of west Guadalcanal. GVF volcanism is characterised by effusive eruptions of lava, intrusion of sub-volcanic plutons, as well as pyroclastic flow and fall deposits dominated by block and ash flow deposits. Geochemical analysis of a representative suite of samples from the GVF demonstrates that the GVF comprise largely a ‘main suite’ of basalts to andesites and minor trachyandesites. The predominant mineralogy of the GVF comprises plagioclase, amphibole, clinopyroxene and magnetite-ilmenite. Associated with the ‘main suite’ are cognate nodules composed of hornblendite, gabbros, and clinopyroxenite. Interpretation of major and trace element geochemistry and petrographic studies suggests that fractionation was dominated by early clinopyroxene, and later amphibole + clinopyroxene + minor plagioclase. Geochemical features such as the incompatibility of Sr suggest that plagioclase largely crystallised en-masse late in the fractionation sequence. The presence of amphibole and late fractionation of plagioclase is suggestive of derivation from initially water-rich magmas. The region is characterised by strong geographically-related geochemical variations as evidenced by the Woodlark (and Manus) basins: basalts become more arc-like within the ocean basins with decreasing distance to the subducting trench. The GVF-Savo volcanoes are spatially and geochemically affected by deep N-S fractures that show some evidence of sympathetic geochemical variations with distance from the trench (e.g. Sr/Y ratios). Comparison with a range of international data for Th/Nb vs Pb/Nb and Dy/Yb vs SiO₂ indicate that: amphibole was indeed a strong controlling phase on magmatic evolution; garnet had no obvious role; there was little sediment input into the source region; that relative Pb/Nb enrichments may be linked to similar enrichments within the subducting Woodlark basin (and by analogy with the Manus basin and its abundant hydrothermal Pb-rich sulphide deposits); and the predominant influence on the source region for GVF-Savo was from metasomatic fluids and/or melts from the slab subducting at the southern trench.     

Origin of the giant Allard Lake ilmenite ore deposit (Canada) by fractional crystallization,multiple magma pulses and mixing

The late-Proterozoic Allard Lake ilmenite deposit is located in the Havre-Saint-Pierre anorthosite complex, part of the allochtonous polycyclic belt of the Grenville Province. Presently the world's largest Fe–Ti oxide deposit, it had a pre-mining amount in excess of 200 Mt at grades over 60 wt.% hemo-ilmenite. The main ore body is a funnel-shaped intrusion, measuring 1.03 × 1.10 km and 100–300 m-thick. Two smaller bodies are separated by faults and anorthosite. The ore is an ilmenite-rich norite (or ilmenitite) made up of hemo-ilmenite (Hem_22.6–29.4, 66.2 wt.% on average), andesine plagioclase (An_45–50), aluminous spinel and locally orthopyroxene. Whole-rock chemical compositions are controlled by the proportions of ilmenite and plagioclase ± orthopyroxene which supports the cumulate origin of the deposit. Ore-forming processes are further constrained by normal and reverse fractionation trends of Cr concentration in cumulus ilmenite that reveal multiple magma emplacements and alternating periods of fractional crystallization and magma mixing. Mixing of magmas produced hybrids located in the stability field of ilmenite resulted in periodic crystallization of ilmenite alone. The unsystematic differentiation trends in the Allard Lake deposit, arising from a succession of magma pulses, hybridisation, and the fractionation of hemo-ilmenite alone or together with plagioclase suggest that the deposit formed within a magma conduit. This dynamic emplacement mechanism associated with continuous gravity driven accumulation of Fe–Ti oxides and possibly plagioclase buoyancy in a fractionating ferrobasalt explains the huge concentration of hemo-ilmenite. The occurrence of sapphirine associated with aluminous spinel and high-alumina orthopyroxene (7.6–9.1 wt.% Al₂O₃) lacking exsolved plagioclase supports the involvement of a metamorphic overprint during the synchronous Ottawan orogeny, which is also responsible for strong textural equilibration and external granule of exsolved aluminous spinel due to slow cooling.     

Compositions of biotite,amphibole, apatite and silicate melt inclusions from the Tongchang mine,Dexing porphyry deposit,SE China: Implications for the behavior of halogens in mineralized porphyry systems

The Dexing deposit, located in the Circum-Pacific ore belt, is the largest porphyry copper deposit in eastern China. It is composed of 3 separate plutons, which host three mines: Tongchang, Fujiawu and Zhushahong mines. The porphyritic granodiorite samples studied in this investigation were collected from the Tongchang ore-forming pluton of this giant deposit. This paper presents electron microprobe analyses of biotite, apatite, amphibole, plagioclase, potassium feldspar and rehomogenized glassy melt inclusions from the Tongchang porphyritic granodiorites. Petrographic observations of the samples are consistent with portions of the granodioritic magma represented by our samples being overprinted by potassic hydrothermal fluid which variably altered these minerals.All of the studied micas are Mg-rich biotites. The biotites are separated into altered magmatic and secondary types based on their petrographic and geochemical characteristics. The phlogopite components of the secondary biotites are typically higher than those of the altered magmatic biotites, and the X_Mg values of all biotites correlate negatively with Cl contents, consistent with the Mg–Cl avoidance principle. The X_Mg values also correlate negatively with (K₂O + Na₂O + BaO), FeO and TiO₂ for both generations of biotites. The calculated log (fH₂O/fHCl) values (for 690 K) of the coexisting potassic fluids, which are determined from the altered magmatic biotite compositions, range from 4.43 to 4.67, and are very similar to those of other major porphyry deposits. However, the log(fH₂O/fHF) and log(fHF/fHCl) values for the same batch of hydrothermal fluids are significant higher and lower than those of these other porphyry deposits, respectively.The Cl concentrations of amphiboles and melt inclusions range from 0.18 to 0.32 wt.% and 0.15 to 0.44 wt.%, respectively. Most apatites trapped in biotite and plagioclase phenocrysts display a bimodal Cl distribution: 0.19 to 1.35 wt.% and 1.48 to 3.73 wt.%. Similarly, the S contents of the apatite also show a distinct bimodal distribution reflecting the effects of variable anhydrite saturation during evolution of the Tongchang melt and variable dissolution of anhydrite by saline aqueous fluids. The Cl contents of the apatites from the Tongchang system are typically higher than those of other studied porphyry deposits. Furthermore, the Cl contents of the melt inclusions are at or very near the Cl saturation levels (0.36 to 0.46 wt.% at 850 °C and 50 MPa and 0.42 to 0.54 wt.% at 850 °C and 200 MPa) for these melt compositions at shallow crustal pressures. These findings suggest that the area of the granodioritic magma represented by our samples, and perhaps the bulk of the Tongchang granodioritic magma was rich in Cl. The melt inclusion compositions are consistent with a high-salinity, hydrosaline liquid being exsolved directly from the granodioritic melt directly. This high-salinity hydrosaline liquid was likely very efficient at dissolving, transporting and precipitating ore metals in the mineralizing magmatic–hydrothermal system.     

Hydrogeochemistry in the Vouga River basin (central Portugal): Pollution and chemical weathering

To quantify and explain the contributions by pollution and chemical weathering to their composition, we studied the chemistries of springs and surface waters in the mountainous part of the Vouga River basin. Water samples were collected during a number of consecutive summer campaigns. Recharge rates were derived from monitored discharge rates within the basin. Very large contributions by meteoric, agricultural and domestic sources to the water chemistries were found, identified by the chloride, sulfate and nitrate concentrations: on average only 1/4 to 1/3 of the solutes could be attributed to chemical weathering. Two petrologic units characterize the river basin: granites and metasediments. The waters collected within metasediment units are distinct from those in granite terrain by a higher magnesium concentration. On that basis, it could be estimated that the Rio Vouga, when leaving the mountainous part of the basin, has for some 2/5 a signature determined by chemical weathering in the metasediments. The dominant primary minerals subject to chemical weathering are plagioclase (Pl) and biotite (in granite) or Pl and chlorite (in metasediment). Kaolinite, gibbsite and vermiculite are the major weathering products where annual precipitation (P) > 1000 mm y⁻¹, and kaolinite, vermiculite and smectite where P was lower. Using an algorithm based on the ratio of dissolved silica to bicarbonate, the contributions of chemical weathering of primary minerals could be unraveled. The results show that in granite the export rate (as mol ha⁻¹ y⁻¹ wt%mineral⁻¹) of oligoclase (Pl with An_10–30) was 5.0 ± 2.6 and of biotite 3.2 ± 2.6, while in metasediment these rates for albite (Pl with An_0–10) are 16.5 ± 8.9 and for chlorite are 0.5 ± 0.5. The observed decrease of dissolved silica in surface waters relative to springs was ascribed to (summer) uptake by aquatic biota.     

An unusual occurrence of an exploitable K-feldspar deposit hosted in the Ordovician Porphyroids (Southern Sardinia): Geology,mineralogy, geochemical features and economic potential

An atypical potassium feldspar deposit of real economic potential has been found at Arcu de su Bentu, Southern Sardinia, Italy. The massive mineralization occurs in the Middle Ordovician Porphyroids' metavolcanic complex, which consists of dominant metarhyolite and minor metarhyodacite lavas and/or ignimbritic flows, erupted in a sub-aerial environment. During Variscan orogenesis, the mineralized area was affected by low-grade (anchizone to greenschist facies) metamorphism.The deposit generally shows uniform macroscopic textural features over the entire outcrop, the significant presence of K-feldspar (sanidine) and quartz megacrystals, the latter being generally smaller than the former. Mafic minerals do not occur in significant proportions although minor amounts of biotite and muscovite occur locally. Besides the uncommon lithological type, the typical feature of this deposit is the unusual coarseness (10 to 20 cm in diameter) of the potassium feldspar crystals.The favourable geomorphological conditions of the area, high K₂O contents (6 to 8 wt.%), high proportion of K-feldspar in the mineralized rock (35 to 51 vol.%), and large reserves (estimated at 4,368,000 t in just one restricted part of the deposit), are all favourable conditions for future economic exploitation. In spite of this, mineralogical and chemical impurities may adversely affect the possible use of K-feldspar from Arcu de su Bentu in some conventional applications (e.g., manufacture of high-quality products such as ceramics). To assess the real future economic development of the deposit, market-specific beneficiation is required, although it is important to note that the bulk raw materials, even if they have a lower market value, could be still be targeted to specific industrial sectors (e.g., red grès).     

In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit,Western Junggar,NW China

Titanite (sphene, CaTiSiO₅) is sensitive to changes in temperature, oxygen and water fugacity, and fluid composition. In order to understand formation processes and the nature of hydrothermal fluids, various types of titanite from Cu ores at the Baogutu reduced porphyry Cu deposit were chosen for detailed study. Magmatic titanite is associated with biotite, plagioclase and K-feldspar, whereas hydrothermal titanite occurs with K-feldspar, chlorite, actinolite and calcite. The formation of hydrothermal titanite was related to hydration of igneous minerals under high fH₂O, whereas the widespread replacement of ilmenite by titanite (without magnetite) indicates a relatively low oxygen fugacity. Magmatic titanite has low Al, high Fe, Y, Sn, Zr, Nb and REE contents, relative to hydrothermal titanite. On the basis of the Zr-in-titanite and Al-in-chlorite geothermometers, formation temperatures for magmatic and hydrothermal titanite are estimated to be 687–739 °C and 250–670 °C, respectively. The gradual decrease in REE, Y and Sn contents from magmatic to late hydrothermal titanite was probably caused by precipitation of REE-bearing minerals. Magmatic and hydrothermal titanites have similar chondrite-normalized REE patterns with negative Eu anomalies and relatively flat HREE. Randomly selected titanites have Nd isotopic compositions similar to the host rocks. Thus, both magmatic and hydrothermal titanite are believed to have been predominantly derived from a mantle source.     

High-Ti muscovite as a prograde relict in high pressure granulites with metamorphic Devonian zircon ages (Běstvina granulite body,Bohemian Massif): Consequences for the relamination model of subducted crust

High-pressure kyanite–K-feldspar granulites in the Běstvina granulite body, which belongs to the Variscan orogenic root in the Bohemian Massif, preserve muscovite, rutile and kyanite inclusions in garnet. High-Ti muscovite (Ti = 0.09–0.20 p.f.u., Si = 0.21–3.24 p.f.u.) included in garnet is associated with quartz and is in crystallographic continuity with biotite, interpreted in terms of exsolution from an original less-dioctahedral higher-Ti muscovite. The assemblage garnet–kyanite–antiperthite–perthite–quartz–rutile and the mineral compositions indicate a peak of metamorphism at about 900 °C and 17–21 kbar, based on P–T pseudosection modeling, ternary-feldspar and Zr-in-rutile thermometry. The matrix assemblage garnet–kyanite–plagioclase-K-feldspar–quartz–rutile–ilmenite and garnet rim compositions at contact with feldspars and quartz indicate the end of overall equilibration in the presence of melt at 12–14 kbar and 820–840 °C. Embayments of biotite and plagioclase locally replacing garnet, and connected with modification of garnet composition, may indicate sites of last isolated melt or diffusion of H₂O from that melt down to 10 kbar and 800 °C. Zircon with uniform cathodoluminescence (CL) pattern is present as rims around cores with faint oscillatory zoning, or as entire rounded grains. These zircons gave a cluster of ages at 359 ± 4 Ma, interpreted as the age of metamorphism. Zircon ages from the cores with common faint oscillatory zoning range from 500 to 398 Ma, and are interpreted as magmatic grains variably reset during metamorphism. Two older ages obtained on cores of 620 ± 18 Ma probably represent an inherited zircon component. Molar isopleths of zircon along the P–T path in pseudosections suggest that crystallization of metamorphic zircon occurred during decompression and cooling from 17 to 21 kbar and 900 °C to 12–14 kbar and 820–840 °C. The inferred P–T path and the age of metamorphism are discussed in the framework of a geodynamic model that considers the granulites to be a part of a subducted plate that failed to continue to subduct and was spread below the upper plate.     

Neoproterozoic arc magmatism in the southern Madurai Block,India: Subduction,relamination, continental outbuilding,and the growth of Gondwana

The Madurai Block in southern India is a composite collage of at least three sub-blocks, with Neoarchean–Paleoproterozoic segments in the north and central domains, and a Neoproterozoic segment in the south. Here we investigate a suite of rocks with magmatic protoliths that constitute the basement in the southern margin of the Madurai Block including alkali granites, charnockites, enderbites and gabbros. The alkali granites are dominantly composed of perthitic K-feldspar, minor plagioclase and quartz, with hornblende as the main mafic mineral suggesting a calc-alkaline nature. The enderbites and charnockites have a broadly similar mineralogical constitution except for the variation in the modal content of plagioclase, K-feldspar and quartz, as well as the additional presence of clinopyroxene in some of the enderbites. The high modal content of hornblende in the gabbros suggests crystallization from hydrous basaltic melts. The geochemical features of this suite are identical to those of arc magmatic rocks, with distinct Nb, Ta, and Ti depletion suggesting magmatism in a subduction-related environment. We envisage that the underplating of basaltic magmas within a convergent margin setting provided the heat input for lower crustal melting generating the charnockitic suite of rocks. The intrusion of the underplated mafic melts as gabbroic dykes and sills into the crystallizing felsic magmas resulted in magma mixing and mingling generating the widespread enclaves of gabbroic rocks. The alkali granites were derived from the differentiation of lower crustal melts. Zircon U–Pb data from the alkali granites yield weighted mean ²⁰⁶Pb/²³⁸U ages of 786 ± 10 to 772 ± 11 Ma for the oldest and the most dominant group of magmatic grains, with a 662 ± 20 Ma subordinate group. The oldest group of magmatic zircons in the charnockite samples shows ages of 938 ± 27 Ma, 896 ± 12 Ma, and 786 ± 9 Ma, suggesting multiple magmatic pulses during early and mid-Neoproterozoic. A subordinate population of magmatic zircons with ages of 661 ± 9 Ma and 632 ± 7 Ma is also present. In the enderbites, the magmatic zircon population yields weighted mean ages of 926 ± 22 Ma, 923 ± 36 Ma, 889 ± 13 Ma, 803 ± 10 Ma, 787 ± 23 Ma, 786 ± 10 Ma, 748 ± 27 Ma, 742 ± 11 Ma, 717 ± 8 Ma and 692 ± 10 Ma suggesting continuous and multiple pulses of magmas emplaced throughout early to mid-Neoproterozoic. Magmatic zircons from the gabbros show weighted mean ²⁰⁶Pb/²³⁸U ages of 903 ± 13 Ma, 777 ± 10 Ma, 729 ± 10 Ma and 639 ± 27 Ma. Metamorphic zircons from all the rock types show latest Neoproterozoic-Cambrian ages in the range of 567 ± 19 Ma to 510 ± 8 Ma suggesting prolonged heating. Zircon Lu–Hf data show that the alkali granite-charnockite-enderbite suite has depleted mantle ages (T_DM) in the range of 1164–2172 Ma and crustal residence ages (T_DM^C) of 1227–3023 Ma. These spots show both negative εHf(t) and positive εHf(t) values (− 22.1 to 10.6), suggesting magma derivation from mixed juvenile mid- to late-Mesoproterozoic components and reworked Mesoarchean to mid-Mesoproterozoic components. Zircon grains from the gabbroic rocks show depleted mantle ages and (T_DM) in the range of 1112–2046 Ma, crustal residence ages (T_DM^C) of 1306–2816 Ma, and both negative and positive εHf(t) values (− 17.8 to 7.9), suggesting that the magmas were dominantly derived from juvenile mid-Mesoproterozoic to Neoproterozoic components as well as reworked Mesoarchean to mid-Mesoproterozoic sources.Our data clearly reveal multiple arc magmatism along the southern Madurai Block during distinct pulses throughout early to late Neoproterozoic, suggesting an active convergent margin along this zone at this time. Crustal thickening occurred through relamination by mafic magmas associated with slab melting. Continental outbuilding and southward growth of the Madurai Block were associated with the lateral accretion of the vast sedimentary belt of Trivandrum Block, culminating in collisional metamorphism during latest Neoproterozoic–Cambrian associated with Gondwana assembly.