Late Magmatic Fluids Research Articles

What controls Sn-W mineralization in granite batholith: A case study from the world-class Dulong Sn-Zn polymetallic ore deposit of SW China

Magmatic-hydrothermal ore deposits hosted in granitic batholiths are an important source of tungsten (W) and tin (Sn). However, it remains enigmatic whether and how the Sn-W mineralization is triggered by the spatially associated batholith because the Sn-W-bearing granitic rocks are more likely to occur as small intrusions. Here we used a combination of LA-ICP-MS cassiterite U-Pb dates, published whole-rock geochemical, and high-precision exploration data to evaluate a genetic link between the world-class Dulong Sn-Zn polymetallic ore deposit and its spatially associated batholith in SW China. Our new cassiterite U-Pb dates indicate that the Sn-Zn and Sn-Cu mineralization events were temporally associated with the emplacement of concealed granites and porphyritic dykes respectively, consistent with the spatial pattern between Sn-Zn-Cu mineralized zones and granitic rocks in the Dulong ore district as revealed by the high-precision exploration data. The compiled data presented in this study show that these granitic rocks throughout the batholith are of S-type and highly fractionated affinities, and their parent magmas might experience similar degrees of fractionation. Importantly, the low Nb/Ta ratios (most < ∼5) in granites of the Dulong ore district are markedly differentiated from highly variable values (∼2.0 to ∼ 9.4) in the batholith, which may be caused by the extensive sub-solidus interaction with late magmatic fluids. Furthermore, the granites of the Dulong ore district are significantly poorer in Sn-Zn contents than those of the Laojunshan batholith, suggesting the extensive Sn-Zn-rich fluids exsolved from highly evolved granitic magmas could lead to a significant decrease in Sn-Zn contents in consolidated granites and the formation of Sn-Zn ore deposit, due to the relatively high fluid/melt partition coefficients of Sn and Zn. In conjunction with evidence from previous numerical and mineralogical models, and the spatial pattern between Sn-Zn mineralized zones and apical parts of concealed pluton in the Dulong ore district as revealed by high-precision drill data, we propose a model involving highly evolved granitic magmas that formed batholith, apical portions of which as the emanative centers of Sn-Zn-rich fluids played a crucial role in the formation of the world-class ore deposit.

Barium isotope compositions of altered oceanic crust from the IODP Site 1256 at the East Pacific rise

This study reports barium (Ba) isotope compositions of intact altered oceanic crust (AOC) recovered from Integrated Ocean Drilling Program (IODP) Site 1256, East Pacific Rise (EPR), to investigate the behavior of Ba isotopes during both low-temperature seawater alteration and high-temperature hydrothermal alteration processes in the oceanic crust. The Ba isotope compositions of the volcanic section and sheeted dike complex have large variations and are mostly heavier than those of the fresh EPR MORB, with δ138/134Ba ranging from −0.01‰ to +0.39‰, which may be attributed to the modification of Ba isotopes by seawater and hydrothermal fluid during low-temperature and high-temperature alteration. The samples from the plutonic complex display much lighter Ba isotope compositions than the fresh EPR MORB, having δ138/134Ba values of −0.22‰ to −0.06‰, which may reflect the influence of late magmatic fluids. Because of the large Ba isotope variation in the AOC and the obvious difference in Ba isotope compositions between the AOC and the upper mantle, the recycling of the AOC could result in Ba isotope heterogeneity in the mantle and further indicate the application of Ba isotopes for tracing crustal material recycling in the Earth's mantle.

The origin of fluorite deposits in the Bou-Izourane district (Central High Atlas of Morocco) and its relationships with the Tamazeght magmatic complex

Fluorite deposits in the Bou-Izourane district of the High Atlas in Morocco are distributed over seven known mineralized sites near the Middle Eocene Tamazeght magmatic complex and hosted in sedimentary rocks (limestones and marls) of the Lower Jurassic (Bou-Izourane, Takkat, Bou-Kharouba and Tabja deposits), magmatic rocks (Bou-Imetssene and Meghsan deposits) and skarns (Tamazeght and Bou-Imetssene deposits). This paper examines the origin of the mineralizing fluids and the relationship between the Tamazegth complex and fluorite deposits. Fluorspar occurs in veins oriented according to three families (N20, N50-80 and N120), in karst cavities and as stratabound deposits. Three stages are identified in the mineralization: (1) fluorite emplacement associated with the dissolution of the host rocks; (2) fracturing and sealing by calcite and finally (3) silicification associated with the partial dissolution of fluorite and calcite. Fluid inclusions in fluorite hosted in marls and carbonates of the Lower Jurassic have low salinities (1.5 to 3 wt% equiv. NaCl) and homogenization temperatures between 91 °C and 159 °C. Fluid inclusions in the Tabja, Tamazeght and Meghsan fluorites exhibit the same salinity range, but with increased homogenization temperatures, ranging from 99 °C to 241 °C, with a vapour phase containing CO2. Secondary solid daughter phases, such as nahcolite, calcite and strontianite are identified. Only Bou-Imtessene fluorite has high salinity fluid inclusions (∼18 wt% equiv. NaCl) and intermediate homogenization temperatures between 126 °C and 187 °C. These high local salinities and the presence of nahcolite and secondary carbonates in the fluid inclusions of the Tabja, Tamazeght and Meghsan fluorites may reflect the involvement of late-magmatic fluids. The δ18O isotopic composition of the fluid that precipitated calcites from Tabja (highest Th) and Bou-Izourane (lowest Th) indicates a meteoric origin. Fluorite has a broadly similar REE distribution to that of the Tamazeght carbonatites, suggesting that REE are derived from: i) carbonatites by hydrothermal alteration (e.g., Bou-Izourane, Bou-Kharouba and Takkat), and ii) carbonatitic (late-magmatic) fluids (e.g., Tabja, Tamazeght, Meghsan and Bou-Imtessene). Our data shows that fluorite mineralization in the Bou-Izourane district and the spatially associated middle Eocene Tamazeght magmatism have a direct genetic relationship through the contribution of late-magmatic F-rich fluids in close proximity to the complex. Fluorite mineralization farther from the complex is formed by per descensum circulation of meteoric waters along fractures resulting in fluorine leaching. The Tamazeght complex acts as a heat source and driving mechanism for fluid flows. The dissolution and recrystallization reactions are made possible by a strong geothermal gradient persisting after the complex was emplaced. The upwelling of these hydrothermal fluids into the calcium-rich host rocks (limestone and marl) leads to the precipitation of fluorite.

Geochemical significance of lithium and boron isotopic heterogeneity evolving during the crystallization of granitic melts

Abstract We present Li and B isotope data for muscovite, biotite, and feldspar + quartz separated from two-mica granite and biotite granite samples from the Huayang-Wulong granite suite (south Qinling, central China). Our data demonstrate systematic differences in the Li and B isotopic compositions among these minerals. Our results indicate that early-crystallizing minerals have lower δ7Li and δ11B values than the original melt and that residual melts and late magmatic fluids may acquire anomalously high δ7Li and δ11B values. Furthermore, our data imply that (1) late melts and magmatic fluids do not reflect the composition of their source melt, (2) minerals that crystallized over a large segment of magma evolution may be isotopically zoned, and (3) mineral-selective alteration by late magmatic fluids camouflages the source of the fluid, whose δ7Li and δ11B values reflect the isotopic compositions of the altered minerals rather than the composition of the remaining rock.

Alteration of Feldspathoids Changes pH of Late-Magmatic Fluids: A Case Study from the Lovozero Peralkaline Massif, Russia

The 360-370-Ma-old Lovozero peralkaline massif (NW Russia) is a layered nepheline syenitic–foidolitic pluton. In the rocks of the massif, late-stage (auto)metasomatic alterations of rock-forming minerals are quite intense. We studied the products of the alteration of nepheline and sodalite via microtextural, microprobe, and spectroscopic methods. We found that these minerals are extensively replaced by the association between natrolite + nordstrandite ± böhmite ± paranatrolite in accordance with the following reactions: 3Nph + 4H2O → Ntr + Nsd + NaOH; 6Nph + 9H2O → Ntr + Pntr + 2Nsd + 2NaOH; Sdl + 4H2O → Ntr + Nsd + NaOH + NaCl, where Nph is nepheline, Ntr is natrolite, Nsd is nordstrandite, Pntr is paranatrolite, and Sdl is sodalite. As a result, about one-third of the sodium from nepheline (and sodalite) is set free and passes into the fluid. This leads to an increase in the Na/Cl ratio and, hence, the pH of the fluid. An increase in pH stabilizes hyperagpaitic minerals (e.g., ussingite, villiaumite, thermonatrite, and trona), which can crystallize in close proximity to pseudomorphized nepheline and sodalite. Thus, the alteration of feldspathoids increases the pH of late-magmatic fluids, which in turn can lead to the crystallization of hyperagpaitic minerals.

Assessing the Radiological Risks Associated with High Natural Radioactivity of Microgranitic Rocks: A Case Study in a Northeastern Desert of Egypt

This study aimed to evaluate the radiological hazards of uranium (238U), thorium (232Th), and potassium (40K) in microgranitic rocks from the southeastern part of Wadi Baroud, a northeastern desert of Egypt. The activity concentrations of the measured radionuclides were determined by using a gamma-ray spectrometer (NaI-Tl-activated detector). The mean (238U), (232Th), and (40K) concentrations in the studied rocks were found to be 3680.3, 3635.2, and 822.76 Bq/kg, respectively. The contents in these rocks were elevated, reaching up to 6.3 wt%. This indicated the alkaline nature of these rocks. The high ratios of Th/U in the mineralized rocks could be related to late magmatic mineralization, suggesting the ascent of late magmatic fluids through weak planes such as faults and the contact of these rocks with older granites. The present data were higher than those of the United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR) guideline limits. All the radiological hazard results indicated high human health risks. This confirmed that this area is not radiologically safe, and care must be taken when working in this area. This study showed that the area under investigation had high U content suitable for uranium extraction that could be used in the nuclear fuel cycle.

The anisotropic properties of granites – effects of tectonic emplacement mode on potential crystalline host rocks for nuclear waste deposits in Germany

Abstract. For permanent nuclear waste disposal sites, crystalline rocks, especially granitic/granodioritic batholiths, are considered an appropriate host rock. Principally, three types of granitic plutons occur in the extra-alpine crystalline basement of Germany that were consolidated during the late Paleozoic Variscan orogeny of Central Europe: (i) Pre-Variscan voluminous granodiorites that are hardly affected by the subsequent continent–continent collision; (ii) voluminous granites in various tectonic settings intruded during the late orogenic stage of the Variscides; (iii) post-orogenic granites related to vast Permian intracontinental extension. Thus, in terms of the syn-intrusive tectonic setting and post-intrusive processes there are significant differences. Although it can be expected that different tectonic environments caused significant differences in the material properties, for Germany, however, there is no systematic study regarding the fabric of such plutonites. In order to find the most suitable “granite” we investigate the primary anisotropy of granites evolved during the emplacement and crystallization of the melt. For this we sample rocks of all three principal types and various syn-intrusive tectonic settings, i.e., compression, extension, strike-slip, transtension, and transpression. By means of combined measurements of the “Anisotropy of the Magnetic Susceptibility” and the “Shape Preferred Orientation” we characterize the syn-intrusive flow pattern, i.e., the magmatic foliation and lineation. The Crystallographic Preferred Orientation is analyzed by a combination of neutron time-of-flight experiments and electron backscatter diffraction measurements at the Frank Laboratory of Neutron Physics at JINR, Dubna, Russia, and the TU Bergakademie Freiberg respectively. Furthermore, special attention is given to the systematic mapping of annealed microcracks evolved during late magmatic fluid escape and/or post-crystallization hydrothermal activity. In a second step we compare the primary anisotropy with the post-magmatic fracture pattern of the particular granites. Those fractures constitute probable fluid pathways and, thus, the first-order risk for a potential permanent nuclear waste disposal. All datasets are organized in a Geological Information System allowing for a complete traceability of the different investigation steps. The results of this study will serve as a basis for a future detailed exploration.

PGE distribution in Merensky wide-reef facies of the Bushveld Complex, South Africa: Evidence for localized hydromagmatic control

ABSTRACT The wide-reef facies of the Merensky Reef in the eastern part of the western lobe of the Bushveld Complex was sampled in order to better resolve otherwise spatially constrained variation in highly siderophile elements across this geological unit. The platinum group element mineralogy and whole-rock highly siderophile element concentrations were measured across two vertical sections in close proximity. In one section, the Merensky Reef unit was bound by top and bottom platinum group elements-enriched horizons (reefs) with a well-developed pegmatoidal phase in the top third of the intrareef pyroxenite, but with neither a top nor a bottom chromitite present. The other drill core section featured a thin (&amp;lt;1 cm thick) chromitite layer associated with the highest platinum group element concentrations of any rock in this study as the bottom reef, but with a chromitite-absent top reef, and very poor development of the pegmatoid. Primitive mantle-normalized profiles of the main lithological units show relatively flat, primitive mantle-like highly siderophile element abundances (Cr, V, Co, Ni, platinum group elements, Au and Cu) in the Merensky pyroxenite, with modest depletion in Ir-affiliated platinum group elements. The platinum group element-rich top and bottom reefs, and the pegmatoidal upper pyroxenites, display characteristic enrichment in the Pt-affiliated platinum group elements and undepleted Ir-affiliated platinum group elements. The leuconoritic hanging wall and footwall rocks show comparable highly siderophile element profiles, distinguished from one another by relative depletion in the Pt-affiliated platinum group elements of the footwall samples. The vertical variation in highly siderophile element abundances through both sections is characterized by low platinum group element abundances through the lower reef pyroxenite, with platinum group element, Au, and Cu ± Ni concentrations increasing through the upper pegmatoidal pyroxenite, and main enrichment peaks at the top and bottom reefs. Significant localized (centimeter-scale) zones of chalcophile metal depletion are present immediately above the top reef and below the bottom reef. In addition, a wider zone of Pt-affiliated platinum group elements (with Pd more depleted than Pt)-depletion was identified within the pegmatoidal pyroxenite around one meter below the top reef. The platinum group element mineralogy of the bottom reef consists mainly of platinum group element sulfides, with minor arsenides and antimonides. In contrast, the platinum group element mineralogy of the top reef, and the small amount of data from the intrareef pyroxenite, mainly consist of Pt-affiliated platinum group elements-Bi-tellurides. The Pt-sulfides are mainly equant, relatively coarse crystals (many grains between 50 to 100 μm2 area), contrasting with the Pt-affiliated platinum group elements-Sb-As and -Bi-Te minerals that tend be high aspect-ratio grains, occurring in veinlets or as rims on earlier-forming platinum group element phases. These Te-As-Bi-Sb compounds are closely associated with chlorite, actinolite, quartz, and chalcopyrite, consistent with secondary deposition at lower temperatures and association with aqueous fluids. A model is proposed involving the emplacement of the Merensky unit as a magma pulse into at least semi-crystallized host rock, followed by aqueous fluid saturation and local migration, combined with concentration of late magmatic fluids around the top and bottom contacts of the magma pulse. Late remobilization of Pt-affiliated platinum group elements from the zones immediately (centimeter-scale) above the top reef, and from the underlying meter or two of pyroxenite, and from the centimeters underlying the bottom reef, have added additional platinum group elements to the reefs as late platinum group elements-Te-As-Bi-Sb minerals, independent of whether or not chromite is present in the reef initially.

Mineralogy and Geochemistry of Ocelli in the Damtjernite Dykes and Sills, Chadobets Uplift, Siberian Craton: Evidence of the Fluid–Lamprophyric Magma Interaction

The study reports petrography, mineralogy and carbonate geochemistry and stable isotopy of various types of ocelli (silicate-carbonate globules) observed in the lamprophyres from the Chadobets Uplift, southwestern Siberian craton. The Chadobets lamprophyres are related to the REE-bearing Chuktukon carbonatites. On the basis of their morphology, mineralogy and relation with the surrounding groundmass, we distinguish three types of ocelli: carbonate-silicate, containing carbonate, scapolite, sodalite, potassium feldspar, albite, apatite and minor quartz ocelli (K-Na-CSO); carbonate–silicate ocelli, containing natrolite and sodalite (Na-CSO); and silicate-carbonate, containing potassium feldspar and phlogopite (K-SCO). The K-Na-CSO present in the most evolved damtjernite with irregular and polygonal patches was distributed within the groundmass; the patches consist of minerals identical to minerals in ocelli. Carbonate in the K-Na-CSO are calcite, Fe-dolomite and ankerite with high Sr concentration and igneous-type REE patterns. The Na-CSO present in Na-rich damtjernite with geochemical signature indicates the loss of the carbonate component. Carbonate phases are calcite and Fe-dolomite, and they depleted in LREE. The K-SCO was present in the K-rich least-evolved damtjernite. Calcite in the K-SCO has the highest Ba and the lowest Sr concentration and U-shaped REE pattern. The textural, mineralogical and geochemical features of the ocelli and their host rock can be interpreted as follows: (i) the K-Na-CSO are droplets of an alkali–carbonate melt that separated from residual alkali and carbonate-rich melt in highly evolved damtjernite; (ii) the Na-CSO are droplets of late magmatic fluid that once exsolved from a melt and then began to dissolve; (iii) the K-SCO are bubbles of K-P-CO2 fluid liberated from an almost-crystallised magma during the magmatic–hydrothermal stage. The geochemical signature of the K-SCO carbonate shows that the late fluid could leach REE from the host lamprophyre and provide for REE mobility.

Ni-Cu sulfide mineralization and PGM from the Samapleu mafic-ultramafic intrusion, Yacouba complex, western Ivory Coast

ABSTRACT The mafic-ultramafic Samapleu deposits of the Yacouba complex, which host nickel, copper sulfides, and platinum-group minerals, are located in the Biankouma-Silipou region, western Ivory Coast. These intrusions originate from the mantle and would have been established during the Proterozoic (2.09 Ga) around 22 km deep within the Archean granulites (3.6–2.7 Ga) which at least partially contaminated them. Platinum-group and sulfide minerals from the Samapleu deposits were studied using optical microscopy, scanning electron microscopy, the electronic microprobe, X-ray fluorescence, fire assay, and a Thermo Fisher Scientific Delta S isotope ratio mass spectrometer system. The sulfide mineralization (mainly pyrrhotite, pentlandite, chalcopyrite ± pyrite) is mainly disseminated with, in places, semi-massive to massive sulfide veins. It is especially abundant in pyroxenite horizons with net or breccia textures. The isotopic ratios of sulfur measured from the sulfides (an average of 0.1‰), the R factor (between 1500 and 10,000), and the Cu/Pd ratios indicate a mantle source. Thus, the sulfides would have formed from sulfide liquids produced by immiscibility from the silicate mantle magma under mafic-ultramafic intrusion emplacement conditions and with possible geochemical modification of the magmas by assimilation of the surrounding continental crust. The platinum-group minerals (michenerite, merenskyite, moncheite, Co-rich gersdorffite, irarsite, and hollingworthite) are mainly associated with the sulfide phases. The nature of the platinum-group minerals is indicative of the probable role of late-magmatic hydrothermal fluids during the mineralizing process.

Banded Charnockite: The Result of Crustal Magma Generation, Piecemeal Emplacement, and Fluid-Driven Mineral Replacement in High-Grade Crust (Central Dronning Maud Land, Antarctica)

Our study of a banded charnockite complex of the Mühlig-Hofmannfjella in Dronning Maud Land, Antarctica, illustrates how the combination of high-temperature (re-)crystallization processes, melts, and volatile fluids leads to complex intrusive, metasomatic, and structural relationships. The igneous complex consists of gently dipping sets of charnockite interlayered with dolerite and leucogranite. The banded complex formed primarily by magmatic processes, but with superimposed modifications by metasomatism. The charnockite has a ferroan composition and contains both orthopyroxene (Fs80–84) and olivine (Fa94–96). Zircon U-Pb dates the emplacement of charnockite at 515 Ma, and inherited zircon cores and negative εNd values of −3 to −5 indicate that the age of the source of the magma was about 1100 Ma. Neodymium isotopes were not homogenized during the Cambrian magmatic event, which suggests that the generation and emplacement of the magma took place in separate batches during construction of the banded complex. By contrast, the Rb-Sr system in the charnockite was extensively homogenized, likely because of the superimposed late-magmatic fluid activity, which also produced the bands and networks of leucogranites. These events occurred during the late stages of the assembly of Gondwana, with postcollisional extension and mantle upwelling maintaining a high heat flow.

Geology and genesis of the Debao Cu polymetallic skarn deposit, southwestern China

The Debao deposit, with stratiform orebodies in Middle-Upper Cambrian carbonate rocks, is a rare Early Paleozoic skarn copper deposit in the South China Block. Garnet U-Pb dating yielded a lower intercept 206Pb/238U date of 438.8 ± 7.3 Ma, which is coeval with the related granite (439 ~ 441 Ma). Skarns contain garnets with andraditic compositions (Ad53~93Gr4~46Py1~8) and clinopyroxene (Hd5~11Di89~94Jo0~1 and Hd52~85Di13~46Jo1~4) with low Mn/Fe ratios (<0.1), showing typical mineral compositions of Cu skarn deposits. The proximal garnet skarn mainly developed at the bottom and both sides of the orebody, while distal pyroxene skarn developed in its interior and upper parts. The garnets in the bottom of the orebodies contain more andraditic compositions than their upper parts. The prograde skarn minerals have a range of δ18Ofluid values from 8.81 to 9.53‰, and the sulfide minerals of the main ore stage have a range of δ34S values from −2.40 to 2.57‰, both suggesting a magmatic origin of the ores. In the Debao deposit, hydrothermal magnetite from different skarn zones contains substantial amounts of Al, Sn, Ga, Mn, Mg, Ti, Zn, Co, V, and Ni. The content of Al and Ti in the magnetite, which was considered to derive from the wall rock due to fluid-rock interaction, was positively correlated with temperature. Magnetite in the retrograde skarn stage from the proximal garnet skarn zone contains more Ti and V than that from the distal pyroxene skarn zone, indicating a gradual decrease in temperature and increase in oxygen fugacity of the ore-forming fluid in this stage. The magnetite has higher Sn content (mainly hundreds to thousands of ppm) than normal skarn deposits, implying that high oxygen fugacity occurs during the retrograde skarn stage. Subsequently, the formation of magnetite led to a decrease in the oxygen fugacity of the ore-forming fluid. The decrease of oxygen fugacity and temperature provided favorable conditions for subsequent precipitation of Cu sulfides. Minor vein-type Cu mineralization related to late magmatic fluid extraction of sulfur from the sedimentary strata was recognized. All geologic and geochemical data suggested that the deep skarn in the region transformed from Early Paleozoic carbonate has copper mineralization potential.

Contribution to the understanding of the Pinheiro Machado Complex (Dom Feliciano Belt, Brazil): A study of textures, mineral chemistry, and crystallization conditions

This article presents textures, mineral chemistry, and geothermobarometric data for the southeastern Pinheiro Machado Complex rocks (PMC), eastern domain of the Dom Feliciano Belt, Rio Grande do Sul, Brazil. The PMC is composed by comagmatic intrusions of quartz diorite, tonalite, and granodiorite with medium‐ to fine‐grained equigranular and medium‐grained inequigranular textures with subordinate alkali‐feldspar macrocrystals. Partial melting features are observed in the comagmatic as melt pools and melt films. Amphibolite xenoliths also occur, presenting sharp‐angled to rounded contacts with the intrusions and evidences of partial assimilation, marked by mafic schlierens. Electron probe microanalyzer punctual analyses were used to classify amphibole, plagioclase, biotite, epidote, and titanite, as well as for the calculations of the crystallization P–T conditions. Amphiboles consist of pargasite for the comagmatic intrusions, and Mg‐hornblende for the amphibolite. Plagioclase ranges from oligoclase to andesine (An15‐40) in both units. Biotite corresponds to annite, with Fe/(Fe + Mg) &gt; 0.3. The epidote has mostly magmatic characteristics in the comagmatic intrusions, with pistacite content 25–30%. Titanite has two distinct textures, titanite I is well formed, subhedral to euhedral, with up to 3 mm; while titanite II is anhedral with size &gt;1 mm and rounded shapes, being both chemically homogeneous. The estimated P–T conditions for the amphibolite crystallization, using plagioclase‐hornblende geothermometer are 650–850°C and 3.62–4.95 kbar, whereas the conditions from the comagmatic intrusions are 714–871°C and 4.44–6.10 kbar. In the mineral phases there is a prevalence in the recrystallization field between subgrain rotation (SGR) and grain boundary migration (GBM) in submagmatic flow. These new data indicate that possibly at the end of PMC crystallization, late magmatic fluids caused re‐equilibrium of mineral phases, mainly in biotite and feldspars. Finally, we suggest that the PMC is the result of continuous and repeated comagmatic intrusions in a continental magmatic arc setting at a depth of 20–30 km in an amphibolitic continental crust.

Pseudoleucite syenites at Loch Borralan, Scotland: Petrology and a genetic model

ABSTRACT The alkaline Loch Borralan intrusion (Assynt Region, NW Highlands of Scotland) consists of a composite arrangement of several ultramafic to felsic plutonic rock bodies which were emplaced around 430 Ma into the Moine Thrust Zone during the Caledonian Orogeny. Some of the Loch Borralan rocks are ultrapotassic and contain pseudoleucite, i.e., a pseudomorph of alkali feldspar and nepheline after leucite. In total, 25 samples have been investigated, representing garnet-bearing pseudoleucite syenites and accompanying rock types such as nepheline-garnet-bearing syenites, alkali feldspar syenites, an amphibole syenite, a biotite-clinopyroxene syenite, and calcite-bearing glimmerites. Pseudoleucite is always associated with garnet, biotite, orthoclase, and minor clinopyroxene and titanite. Mineral chemical data indicate rather primitive magma compositions with no major differences between the various investigated main rock units. The abundant occurrence of up to 2 cm large, mostly euhedral pseudoleucite crystals and petrological phase considerations suggest that magmatic leucite physically separated from its host magma as a flotation cumulate. Based on our data and a comparison with previous field-based and experimental work, K-rich basanitic to tephriphonolitic melts that originated from a K-enriched mantle source may be parental to these rocks. The high liquidus temperatures at low pressures (e.g., ∼1100 °C at 1 bar PH2O) required to crystallize leucite could have resulted from the ascent of successive melt batches in a composite intrusion. Later melt batches would increase the temperature in earlier, already partially cooled batches, causing an increase in temperature and a decrease in pressure during ascent. The subsequent decomposition of leucite to pseudoleucite is interpreted to result from either dry breakdown or autometasomatism, i.e., involvement of late-magmatic fluids.

Arsenic in the rock-soil-plant system and related health risk in a magmatic-metamorphic belt, West of Iran.

Following earlier reports of water contamination and arsenic (As) toxicity symptoms in residents of Kurdistan Province, As was determined in rock, soil and plant samples to investigate its fate from rock to crops and its potential effects on human health. Total As content ranged from 4.9 to 10,000mg/kg, 7.7-430mg/kg and < 0.05-25,079µg/kg (dry weight) in rock, soil and plant samples, respectively. The Qorveh-Bijar region data indicated that magmatic differentiation has enriched late magmatic fluids in As. High rare earth elements concentration, dissociation coefficient, and positive Eu anomaly in volcanic rocks, indicated the prevalence of intermediate to felsic composition. The highest As concentration was measured in travertine. In soil, As average level in Qorveh and Bijar was 48.5 and 107mg/kg, respectively. Higher pollution index and geoaccumulation index (Igeo) were also calculated for Bijar County. The As concentration in crop samples was greater than the recommended maximum permissible concentration for foodstuff. Mann-Whitney U test revealed significant differences between As concentration in different plant species and no difference between plants in Bijar and Qorveh. Also, alfalfa displayed the highest biological accumulation coefficient among the investigated plants. The calculated chronic daily intake of As in Bijar County was higher than the recommended levels for wheat and barley grains. Moreover, the hazard quotient (HQ) and incremental lifetime cancer risk assessments revealed high non-cancer (HQ > 1 for both adults and children) and cancer (particularly for barley in Bijar) risks for inhabitants via consumption of As contaminated crops cultivated in the study area.

Genesis of the graphite orbicules in the Huangyangshan graphite deposit, Xinjiang, China: Evidence from geochemical, isotopic and fluid inclusion data

The Huangyangshan graphite deposit in the East Junggar Orogen (China) contains intriguing graphite orbicules. This contribution is designed to present reasonably comprehensive assessment of their origin. In this deposit, the intrusive orebodies are mechanically juxtaposed against contacts with granitic wall rocks. The orbicules are typically concentrically zoned in texture with a notable binary configuration involving a central core and an outer shell. The orbicule cores possess mineralogical and compositional variations that are more or less similar to those of the granitic wall rocks. The orbicule shells are composed of various ferromagnesian minerals (clinopyroxene + hornblende) in stark contrast to the matrix, where hornblende, sanidine and albite have higher Mg#, Ab and An values, respectively. The replacement of silicates by graphite and sulfides (pyrrhotite + chalcopyrite + pyrite) is common. The graphite throughout the matrix and orbicules features a patchy distribution of major elements (C) and dispersed elements (Cr, Ni, Co, S, Cu, Zn, As, Pb, etc.). The carbon isotopic compositions of the orbicular ore are −20.9 to −20.5‰, analogous to those of the surrounding strata, i.e., −25.6 to −19.3‰. The sulfur isotopic compositions of sulfides in the orbicular ore are −4.8 to −2.6‰, which differ from those of the surrounding strata, i.e., 16.0–23.0‰. Fluid inclusions principally comprise the volatile component CH4 and solid daughter minerals (graphite + chalcopyrite) with Tm > 450 °C. Vapor-liquid two-phase fluid inclusions formed under conditions of Th = 143.6–367.5 °C, P = 3–194 bar, and fO2 = −52.76 to −31.15. The hydrogen and oxygen isotopic values of the orbicular ore are δD = −110.3 to −107.0‰ and δ18Owater = 10.1–11.7‰. Zircons from the orbicular ore have 206Pb/238U ages of 304–359 Ma, with a weighted average of 319.0 ± 6.4 Ma, overlapping the geochronological age of the granitic host rocks (305.1–321.4 Ma). The orbicular ore has SiO2 concentrations ranging from 53.30 to 72.61 wt%, falling within the compositional fields of granite, quartz monzonite, granodiorite, diorite, and monzodiorite in the TAS classification diagram. The Sr-Nd and Hf isotopic data from the orbicular ore indicate mixing between materials derived from the depleted mantle and materials derived from the crust, with a dominant mantle contribution. The petrographic, geochemical, isotopic and fluid inclusion characteristics indicate that the processes of incorporation of H2O and wall rock fragments, liquid immiscibility and exsolution of a late magmatic fluid were responsible for orbicule formation in the Huangyangshan deposit. The following genetic model is proposed: (1) In the late Carboniferous, a new orbicular magma containing organic matter-derived CH4 and deep-mantle SO2 emplaced within the Huangyangshan pluton. Contemporaneously, crystal fragments and H2O were incorporated into the orbicular magma from the granitic host rocks. (2) H2O saturation was reached in the orbicular magma and fostered segregation of a hydrous ferromagnesian melt (orbicules) with a silicic residual melt (matrix). (3) At approximately 630 °C, 2000 bar and −18 lgfO2, graphite and sulfides formed en masse through deuteric alteration: 3CH4 + 2SO2 + 2(Fe2+)7[Si4O11]2(OH)2 (hornblende) = 3C (graphite) + 2FeS (pyrrhotite) + 8SiO2 (quartz) + 2(Fe3Si4O10(OH)2 + Fe3(OH)6) (chlorite), following the expulsion of a late magmatic fluid from the ferromagnesian melt.

Composition and origin of Ti–Nb–Ta–Zr bearing minerals in the Abu Diab highly evolved granite from the Central Eastern Desert of Egypt

The central Eastern Desert (CED) of Egypt is well-known for its granite-related Nb–Ta mineralization. The garnet-bearing muscovite granite (GMG) of the Abu-Diab composite pluton in the CED consists mainly of quartz, K-feldspar (Or88–98), albite (An0-4) and muscovite, with accessory minerals including garnet, zircon, columbite, ilmenite, Ti-rich hematite, rutile, ilmenorutile, thorite, apatite, xenotime and chlorite. The GMG is weakly peraluminous and has low Nb/Ta (9.6–15.4) and Zr/Hf (16–31) with discernible REEs tetrad effect (TE1-3 = 1.11–1.35), typical of highly evolved granites. Zircon contains high concentrations of U and Th typical of late-magmatic zircon and similar to zircon type from highly evolved granite. The homogenous and weak zoned columbites are classified as manganocolumbite. The formation of Ta-rich rim in the columbite may indicate that later fluids were from the GMG granite itself at advanced fractionation into exsolving fluids, and not from an external source. Ilmenite is greatly enriched in MnO, which indicates the significant pyrophanite (up to 29 mol %) molecules in ilmenite through simple substitution of Mn for Fe2+ with increasing oxygen fugacity under magmatic-hydrothermal conditions. Xenotimes show low analytical totals, suggesting probably hydration during their post-magmatic alteration, while apatite is small-grained associated with tiny zircons, suggesting late-crystalized phases. During late magmatic differentiation stage, the interaction of granitic melt with F-rich late magmatic fluids could be resulted in the formation of Ti–Nb–Ta–Zr minerals. Overall, the Abu Diab GMG possesses mineralogical and geochemical features that make it a potential target for Ti–Nb–Ta–Zr minerals.

REE concentration processes in ion adsorption deposits: Evidence from the Ambohimirahavavy alkaline complex in Madagascar

Ion adsorption deposits, in which the rare earth elements (REE) occur adsorbed onto clay mineral surfaces, currently provide the world’s dominant supply of heavy REE (Gd-Lu). Concentration of REE within ion adsorption deposits has been proposed to be a dominantly supergene process, where easily degradable REE-minerals (e.g. REE-fluorcarbonates) break down and release REE that are then adsorbed onto clay mineral surfaces in the weathered material. Here we present data from the Cenozoic Ambohimirahavavy alkaline complex in Madagascar, with the aim of further constraining controls on the formation and HREE enrichment processes in ion adsorption deposits.The laterite weathering profiles described here are developed on alkaline igneous rocks, including both SiO2-undersaturated and oversaturated lithologies. The latter group includes REE mineralised peralkaline granitic pegmatites and granitic dykelets. The weathering mineralogy includes gibbsite, clay minerals and minor Fe and Mn oxyhydroxides. X-ray diffraction and infrared spectroscopy show that the clay fraction in all sites is dominated by kaolinite and halloysite (7 Å and 10 Å). Extraction with ammonium sulfate (0.5 M (NH4)2SO4, pH = 4; removes weakly adsorbed metals retained on the solid surface and dissolves carbonates) indicates that, in the different profiles and along the same profile, the leachable REE content is heterogeneous, ranging from 5 to 2300 mg/kg total REE, with 1 to 32% heavy REE. Leaching with magnesium chloride (0.5 M MgCl2, pH = 6; removes only weakly adsorbed REE) releases similar total REE concentrations, suggesting that most of the leachable REE are adsorbed onto mineral surfaces. In most of the laterite profiles, the amount of leachable REE continuously increases with depth up to the saprock. Recovery rates depend on the REE atomic number, generally decreasing from La to Lu except for Ce which is invariably low.In the Ambohimirahavavy complex, the nature of the protolith is the main factor controlling the amount of easily leachable REE in the laterite weathering profile. Hydrology and topography are secondary factors. The most favourable protoliths include SiO2-undersaturated volcanic lithologies and altered mudstone with granitic dykelets. The main primary REE minerals include agpaitic minerals (eudialyte) and allanite-(Ce). Locally in granitic pegmatite dykes, autometasomatism by late magmatic fluids inhibits formation of ion adsorption ore by transforming easily weathered agpaitic minerals into unweatherable zircon.

Mineral assemblages and temperature associated with Cu enrichment in the Seival area (Neoproterozoic Camaquã Basin of Southern Brazil)

The Neoproterozoic sequence of volcanic rocks in the Camaquã Basin included in the Lavras do Sul Shoshonitic Association hosts disseminated Cu deposits. The volcanic sequence in the Seival Mine area includes andesitic lava flows, lapilli tuff, volcanic agglomerate and andesitic dikes with pervasive alteration. The hydrothermal alteration is interpreted to be a product of late–magmatic fluids or the mixing of magmatic with meteoric fluids or basinal brines. The late–magmatic hydrothermal system started after volatile oversaturation and degassing in a magmatic system, which was partially segregated into vesicles. The similar REE contents in the andesine–labradorite and albite indicate that the fluid temperatures ranged from 600 to 250 °C. The crystallization of titanite and Fe–clinochlore to Mg–chamosite followed the albitization process. The temperature range associated with the chloritization process was estimated using a chlorite geothermometer and varied from 251 ± 56 to 183 ± 39 °C. The precipitation of Mg–saponite and smectite–rich chlorite/smectite mixed–layers in some andesitic lava flows and the precipitation of quartz, calcite, barite and hematite in fractures suggest fluid circulation with temperatures lower than the chloritization process. The alteration minerals are represented by chlorite and albite associated with pyrite–chalcopyrite, while chlorite/smectite mixed–layers and barite or hematite are associated with bornite–chalcocite–covellite. Thermodynamic calculations confirm the potential coprecipitation of pyrite–chalcopyrite with chlorite and albite. The occurrence of bornite–chalcocite–covellite and barite seems to be favored by low–temperature chlorite/smectite with neutral to mildly acidic water influx. Consequently, albitization and the process of chloritization at high temperatures (>ca. 251 ± 56 °C) can be used as an exploration guide for primary pyrite–chalcopyrite enrichment, and chlorite/smectite at low temperatures (ca. 250 to 50 °C) can be related to bornite–chalcocite–covellite or the process of Cu enrichment.

Petrogenesis and evolution of the Nuweibi rare-metal granite, Central Eastern Desert, Egypt

The Nuweibi rare-metal granite in the Central Eastern Desert of Egypt is highly evolved fine- to medium-grained leucogranite affected by pervasive albitization and greisenization. The intrusion holds an important tin–tantalum resource in the Egyptian Eastern Desert. Columbite–tantalite and cassiterite disseminations occur within the granite body, while the quartz ± feldspar veins cutting across the Nuweibi granite host only cassiterite disseminations. Microscopically, quartz and alkali-feldspar are the essential mineral constituents of Nuweibi granite, with minor mica (muscovite + rare biotite), while cassiterite, columbite–tantalite, zircon, allanite, beryl, tourmaline, titanite, and fluorite are accessories. Whole-rock geochemistry and micoanalytical data together with laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) dating of zircon and columbite have been used to constrain the evolution of the granite intrusion and associated mineralization. The Nuweibi granite is weakly peraluminous with extremely low MgO, CaO, TiO2, P2O5, Ba, and Sr contents and elevated Sn, Ta, Nb, and Rb contents. The REE patterns exhibit distinct tetrad effects, as well as negative Eu and Y anomalies. Also, the bulk rock Zr/Hf ratios are consistently < 10. The Nd isotopic system is disturbed and eNd values suggest a juvenile mantle and/or Neoproterozoic crustal source. The U–Pb system in zircon is disturbed and leaked continuously, while the U–Pb age of columbite is ~ 620 Ma. The geochemical and isotopic systematics of the Nuweibi intrusion reflect very advanced degree of fractionation combined with late magmatic fluid overprint which redistributed Sn and other mobile elements, while Ta still characterizes the igneous system.