A secondary precious and base metal mineralization in chromitites linked to the development of a Paleozoic accretionary complex in Central Chile

Platinum-group element (PGE) and gold inclusions are usually present in peridotites and chromitite deposits associated with ophiolites. Here, we present the first detailed study of the mineralogy of precious metals in ultramafic rocks hosted in the Paleozoic Coastal Accretionary Complex of Central Chile. In these ultramafic rocks the mineralization of precious metals is associated with small meter-size pods and veins of massive chromitite hosted in serpentinite-filled shear zones. Crystallographic orientation maps of single chromite grains, obtained using the Electron-Backscattered Secondary Diffraction technique, allow us to identify two types of chromite in the precious-metal bearing chromitites: (1) Type A chromite, characterized by an average misorientation per grain of ≤ 2° and chemically homogeneous cores surrounded by a porous rim with abundant inclusions of chlorite, and (2) Type B chromite, which exhibits higher degrees of misorientation (2–8°) and porosity, and abundant silicate inclusions, but a relatively homogeneous chemical composition. In situ analyses using EMPA and LA-ICP-MS for major, minor and trace elements indicate that composition of the magmatic chromite is only preserved in the cores of Type A chromite grains. Core to rim chemical trends in these Type A chromites are characterized by a progressive increase of the Cr# with a decrease of the Mg#, loss of Al and addition of Fe^2 + in the porous rim. The observed changes in the microstructure and chemistry of chromite are associated with the infiltration of external fluids through shear zones filled with antigorite (± talc) developed in partly serpentinized peridotites (i.e., olivine–lizardite dunites). Thermodynamic calculations using the phase equilibria relations in the system Cr₂O₃–MgO–FeO–Al₂O₃–SiO₂–H₂O (CrMFASH) indicate that Fe^2 +-rich porous chromite + chlorite replaced the original assemblage chromite + olivine in the chromitite while prograde antigorite was formed. According to our results this transformation occurred at ~ 510–560 °C when external fluids penetrated the ultramafic/chromitite bodies through shear zones. These temperatures are slightly higher than estimated for the metamorphic peak in the host metapelitic rocks (i.e., ~ 420 °C at 9.3 kbar), suggesting that a hotter ultramafic body was captured by the metasediments of the accretionary prism during their exhumation through subduction channel. Chlorite geothermometry yielded a wide range of lower temperature from 430 to 188 °C, for chlorite present in the porous chromite rims. These results are in agreement with the retrograde overprint under greenchist-facies metamorphism conditions recorded by metapelitic host rocks and minor volcanogenic massive sulphide deposits in the area (300–400 °C, ~ 3–4 kbar). We suggest that although initially decoupled, the chromitite-bearing ultramafic rocks and their metasedimentary host undergone a common metamorphic PT pathway of exhumation during the formation and evolution of the subduction-related accretionary complex.The chromitites contain appreciable amounts of the platinum-group elements (up to 347 ppb total) and gold (up to 24 ppb), present as inclusions of platinum-group minerals (PGM) and alloys as well as native gold. The PGM identified include native osmium, laurite (RuS₂), irarsite (IrAsS), osarsite (OsAsS), omeiite (OsAs₂), Pt–Fe alloy (possibly isoferroplatinum) and a suite of inadequately identified phases such as PtSb (possibly stumpflite), PdHg (possibly potarite), RhS, Ir–Ni and Ir–Ni–Ru compounds. Only a few grains of osmium and laurite were identified in unaltered cores of chromite and therefore considered as magmatic in origin formed during the high-T event of chomite crystallisation in the upper mantle. The other PGM were located in the porous chromite associated with chlorite or base-metal minerals (BMM) that often fill the pores of this altered chromite or are intergrowth with antigorite in the host serpentinized ultramafic rock. The assemblage of BMM identified in the studied rocks include sulphides [millerite (NiS), polydymite (Ni₃S₄), violarite (FeNi₂S₄), galena (PbS), sphalerite (ZnS), chalcocite (CuS)], arsenides [(orcelite (Ni_5 − xAs₂) and maucherite (Ni₁₁As₈)], the sulpharsenide gersdorfitte (NiAsS), and native bismuth. The irregular shape of several PGM grains observed in porous chromite suggest disequilibrium, whereas others exhibit perfectly developed crystal faces with the associated secondary silicate or base-metal mineral suggesting neoformation of PGMs in situ from metamorphic fluids. We suggest that the origin of these PGM inclusions is magmatic, but some grains were reworked in situ when metalloid (i.e., As, Sb, Pb, Zn and Hg)-rich fluids released from metasediments penetrated the ultramafic rocks through active shear zones, once the ultramafic bodies became tectonically mixed with the host metasedimentary host rocks. During this event, gold sourced from the (meta)sediments was also precipitated within chromitites and serpentinites.     

Chromitites from the Luanga Complex,Carajás,Brazil: Stratigraphic distribution and clues to processes leading to post-magmatic alteration

The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe³⁺)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al₂O₃ activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe³⁺ and Fe²⁺ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe²⁺) cations and minor to none exchange between trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe²⁺ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe²⁺)) and Al# (100Al/(Cr + Al + Fe³⁺)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.     

Genesis and tectonic setting of ophiolitic chromitites from the Dehsheikh ultramafic complex (Kerman,southeastern Iran): Inferences from platinum-group elements and chromite compositions

Chromitite bodies of various sizes associated with dunite envelopes have been found in the Dehsheikh ultramafic massif, in the southeastern part of the outer Zagros ophiolite belt. The chromitites occur as layered and lenticular bodies, and show both magmatic and deformational textures, including massive, disseminated, banded and nodular types. The Dehsheikh chromitites display a variation in Cr# [100 × Cr / (Cr + Al)] from 69 to 78, which is typical of high-Cr chromitites. The Al₂O₃ and TiO₂ contents of chromites range from 10.3 wt.% to 16.9 wt.% and 0.12 wt.% to 0.35 wt.%, respectively. The Al₂O₃, TiO₂, and FeO/MgO values calculated for parental melts of Dehsheikh chromitites are within the range of boninitic melts. Chondrite-normalized distribution patterns of platinum-group elements show relative enrichments in Ru, Ir, and Os, and depletions in Rh, Pd, and Pt that are typical of chromitites associated with ophiolites formed by high degrees of mantle partial melting. The presence of Na-rich amphibole inclusions in chromite grains, together with the mineralogical and chemical composition of the chromitites and estimates of their parental melt compositions are used to help establish the tectono-magmatic setting. It is shown that the Dehsheikh massif is an ophiolite formed in a suprasubduction zone setting. We suggest that the composition of the rocks in this section was influenced by hydrous partial melts which might be formed in the subduction zone. Variable melt/rock interaction produced melt channel networks in the dunite which allowed the parental melt of the chromitite to percolate through them. Similar characteristics have been observed in other ophiolite complexes from the outer Zagros Iranian ophiolitic belt; these are believed to be the product of magmatism in a fore-arc environment.     

Electron probe microanalysis and microscopy: Principles and applications in characterization of mineral inclusions in chromite from diamond deposit

Electron probe microanalysis and microscopy is a widely used modern analytical technique primarily for quantifying chemical compositions of solid materials and for mapping or imaging elemental distributions or surface morphology of samples at micrometer or nanometer-scale. This technique uses an electromagnetic lens-focused electron beam, generated from an electron gun, to bombard a sample. When the electron beam interacts with the sample, signals such as secondary electron, backscattered electron and characteristic X-ray are generated from the interaction volume. These signals are then examined by detectors to acquire chemical and imaging information of the sample. A unique part of an electron probe is that it is equipped with multiple WDS spectrometers of X-ray and each spectrometer with multiple diffracting crystals in order to analyze multiple elements simultaneously. An electron probe is capable of analyzing almost all elements (from Be to U) with a spatial resolution at or below micrometer scale and a detection limit down to a few ppm.Mineral inclusions in chromite from the Wafangdian kimberlite, Liaoning Province, China were used to demonstrate the applications of electron probe microanalysis and microscopy technique in characterizing minerals associated with ore deposits, specifically, in this paper, minerals associated with diamond deposit. Chemical analysis and SE and BSE imaging show that mineral inclusions in chromite include anhydrous silicates, hydrous silicates, carbonates, and sulfides, occurring as discrete or single mineral inclusions or composite multiple mineral inclusions. The chromite–olivine pair poses a serious problem in analysis of Cr in olivine using electron probe. Secondary fluorescence of Cr in chromite by Fe in olivine drastically increases the apparent Cr₂O₃ content of an olivine inclusion in a chromite. From the chemical compositions obtained using electron probe, formation temperatures and pressures of chromite and its mineral inclusions calculated using applicable geothermobarometers are from 46 kbar and 980 °C to 53 kbar and 1130 °C, which are within the stability field of diamond, thus Cr-rich chromite is a useful indication mineral for exploration of kimberlite and diamond deposit. A composite inclusion in chromite composed of silicate and carbonate minerals has a bulk composition of 33.2 wt.% SiO₂, 2.5 wt.% Al₂O₃, 22.0 wt.% MgO, 7.5 wt.% CaO, 2.5 wt.% BaO, 0.8 wt.% K₂O, 25.5 wt.% CO₂, and 0.8 wt.% H₂O, similar to the chemical composition of the Wafangdian kimberlite, suggesting that it is trapped kimberlitic magma.     

Using platinum-group elements and Au geochemistry to constrain the genesis of podiform chromitites and associated peridotites from the Soghan mafic–ultramafic complex,Kerman, Southeastern Iran

The podiform chromite deposit of the Soghan mafic–ultramafic complex is one of the largest chromite deposits in south-east Iran (Esfandagheh area). The Soghan complex is composed mainly of dunite, harzburgite, lherzolite, pyroxenite, chromitite, wehrlite and gabbro. Olivine, orthopyroxene, and to a lesser extent clinopyroxene with highly refractory nature, are the primary silicates found in the harzburgites and dunites. The forsterite content of olivine is slightly higher in dunites (Fo₉₄) than those in harzburgites (Fo₉₂) and lherzolites (Fo₈₉). Chromian spinel mainly occurs as massive chromitite pods and as thin massive chromitite bands together with minor disseminations in dunites and harzburgites. Chromian spinels in massive chromitites show very high Cr-numbers (80–83.6), Mg-numbers (62–69) and very low TiO₂ content (averaging 0.17 wt.%) for which may reflect the crystallization of chromite from a boninitic magma. The Fe^3 +-number is very low, down to < 0.04 wt.%, in the chromian spinel of chromitites and associated peridotites of the Soghan complex.PGE contents are variable and range from 80 to 153 pbb. Chromitites have strongly fractionated chondrite-normalized PGE patterns, which are characterized by enrichments in Os, Ir and Rh relative to Pt and Pd. Moreover, the Pd/Ir value which is an indicator of PGE fractionation ranges from < 0.08 to 0.24 in chromitite of the Soghan complex. These patterns and the low PGE abundances are typical of ophiolitic chromitites and indicating a high degree of partial melting (about 20–24%) of the mantle source. Moreover, the Pd_N/Ir_N ratios in dunites are unfractionated, averaging 1.2, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru and Pd anomaly, and their Pd_N/Ir_N ratio averages 1.98 and 2.15 respectively.The mineral chemistry data and PGE geochemistry, along with the calculated parental melts in equilibrium with chromian spinel of the Soghan chromitites indicate that the Soghan complex was generated from an arc-related magma with boninitic affinity above a supra-subduction zone setting.     

Triassic volcanism in eastern Heilongjiang and Jilin provinces,NE China: Chronology,geochemistry, and tectonic implications

With the aim of constraining the Early Mesozoic tectonic evolution of the eastern section of the Central Asian Orogenic Belt (CAOB), we undertook zircon U–Pb dating and geochemical analyses (major and trace elements, Sr–Nd isotopes) of volcanic rocks of the Luoquanzhan Formation and Daxinggou Group in eastern Heilongjiang and Jilin provinces, China. The analyzed rocks consist mainly of dacite and rhyolite, with SiO₂ contents of 68.52–76.65 wt%. Three samples from the Luoquanzhan Formation and one from the Daxinggou Group were analyzed using laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U–Pb zircon techniques. Three zircons with well-defined oscillatory zoning yielded weighted mean ²⁰⁶Pb/²³⁸U ages of 217 ± 1, 214 ± 2, and 208 ± 1 Ma, and one zircon with oscillatory zoning yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 201 ± 1 Ma. These ages are interpreted to represent the timing of eruption of the volcanic rocks. The Triassic volcanic rocks are characterized by high SiO₂ and low MgO concentrations, enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs), (⁸⁷Sr/⁸⁶Sr)_i = 0.7040–0.7050 (Luoquanzhan Formation) and 0.7163–0.7381 (Daxinggou Group), and ε_Nd (t) = 1.89–3.94 (Luoquanzhan Formation) and 3.42–3.68 (Daxinggou Group). These geochemical features indicate an origin involving the partial melting of juvenile lower crust (Nd model ages (T_DM2) of 651–821 Ma) and that compositional variation among the volcanic rocks arose from mineral fractionation and minor assimilation. These volcanic rocks formed within an extensional environment following collision of the NCC and Jiamusi-Khanka Massif during the Late Paleozoic–Early Triassic.     

Metasomatic alteration of chromite from parts of the late Archaean Sittampundi Layered Magmatic Complex (SLC), Tamil Nadu,India

Chromite deposits associated with layered anorthosite complexes in the Archaean high-grade terranes are rare in the world. The late Archaean Sittampundi Layered Magmatic Complex, Tamil Nadu, India is one of the few such deposits in the world where layers of Fe-Al rich chromites are associated with extremely calcic (An>95) anorthosite. ‘Frozen in’ magmatic mineralogy of the chromitite and the enclosing anorthosite suggest successive crystallization of chromite + clinopyroxene and chromite + clinopyroxene + anorthite from a hydrous Al-rich basaltic melt that was emplaced in a suprasubduction zone setting. Intense deformation and upper amphibolite facies metamorphism at ∼2.45 Ga converted the magmatic assemblages to hitherto unreported hornblende + gedrite + Mg-Al rich spinel ± chlorite bearing assemblages. During metamorphic reconstitution, chromite was pseudomorphically replaced by green spinel in the domains rich in secondary amphiboles. Mass-balance calculation and algebraic analyses of the observed mineralogy suggest that a number of chemical species including chromium became mobile during the formation of spinel pseudomorph in response to infiltration driven metamorphism. Aluminium became mobile in the length scale of chromite grain but remained immobile in the length scale of a thin section.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Geochemistry of platinum-group elements and mineral composition in chromitites and associated rocks from the Abdasht ultramafic complex,Kerman, Southeastern Iran

The Abdasht complex is a major ultramafic complex in south-east Iran (Esfandagheh area). It is composed mainly of dunite, harzburgite, podiform chromitites, and subordinate lherzolite and wehrlite. The podiform chromitites display massive, disseminated, banded and nodular textures. Chromian spinels in massive chromitites exhibit a uniform and restricted composition and are characterized by Cr# [= Cr / (Cr + Al)] ranging from 0.76 to 0.77, Mg# [= Mg/(Mg + Fe^2 +)] from 0.63 to 0.65 and TiO₂ < 0.2 wt.%. These values may reflect crystallization of the chromian spinels from boninitic magmas. Chromian spinels in peridotites exhibit a wide range of Cr# from 0.48 to 0.86, Mg# from 0.26 to 0.56 and very low TiO₂ contents (averaging 0.07 wt.%). The Fe^3 +# is very low, (< 0.08 wt.%) in the chromian spinel of chromitites and peridotites of the Abdasht complex which reflects crystallization under low oxygen fugacities.The distribution of platinum group elements (PGE) in Abdasht chromitites displays a high (Os + Ir + Ru)/(Rh + Pt + Pd) ratio with strongly fractionated chondrite-normalized PGE patterns typical of ophiolitic chromitites. Moreover, the Pd/Ir value, which is an indicator of PGE fractionation, is very low (< 0.1) in the chromitites.The harzburgite, dunite and lherzolite samples are highly depleted in PGE contents relative to chondrites. The Pd_N/Ir_N ratios in dunites are unfractionated, averaging 0.72, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru anomaly, and their Pd_N/Ir_N ratio averages 2.4 and 2.3 respectively. Moreover, the PGE chondrite and primitive mantle normalized patterns of harzburgite, dunite and lherzolite are relatively flat which are comparable to the highly depleted mantle peridotites.The mineral chemistry data and PGE geochemistry indicate that the Abdasht chromitites and peridotites were generated from a melt with boninitic affinity under low oxygen fugacity in a supra-subduction zone setting. The composition of calculated parental melts of the Abdasht chromitites is consistent with the differentiation of arc-related magmas.     

Contrasting Ordovician high- and low-pressure metamorphism related to a microcontinent-arc collision in the Eastern Cordillera of Perú (Tarma province)

High-pressure conditions of 11–13 kbar/500–540 °C during maximum burial were derived for garnet amphibolite in the Tapo Ultramafic Massif in the Eastern Cordillera of Peru using a PT pseudosection approach. A Sm–Nd mineral-whole rock isochron at 465 ± 24 Ma dates fluid influx at peak temperatures of ∼600 °C and the peak of high pressure metamorphism in a rodingite of this ultramafic complex. The Tapo Ultramafic Complex is interpreted as a relic of oceanic crust which was subducted and exhumed in a collision zone along a suture. It was buried under a metamorphic geotherm of 12–13 °C/km during collision of the Paracas microcontinent with an Ordovician arc in the Peruvian Eastern Cordillera. The Ordovician arc is represented by the western Marañon Complex. Here, low PT conditions at 2.4–2.6 kbar, 300–330 °C were estimated for a phyllite–greenschist assemblage representing a contrasting metamorphic geotherm of 32–40 °C/km characteristic for a magmatic arc environment.     

A reappraisal of the metamorphic history of the Tehuitzingo chromitite,Puebla state,Mexico

ABSTRACT

The Tehuitzingo ultramafic body (Acatlán Complex, southern Mexico) is a strongly serpentinized harburgitic body that encloses chromitite bodies and blocks of eclogitic rocks. Hydrous retrograde metamorphism on chromitite bodies resulted in the formation of: i) partly altered chromite characterized by unaltered cores surrounded by Fe²⁺-rich and Al-depleted porous chromite containing chlorite; ii) porous chromite corresponding to a chromite that was entirely transformed to Fe²⁺-rich and Al-depleted porous chromite; and iii) zoned chromite formed by modified cores surrounded by Fe³⁺-rich non-porous chromite and magnetite rims. The content of minor and trace elements (Ga, Ti, Ni, Zn, Co, Mn, V, Sc) in the cores of partly altered chromite preserves the magmatic fingerprint of back-arc-bearing chromitites, while the cores of zoned chromite are enriched in Zn, Co and Mn but depleted in Ga, Ti, Ni and Sc, and display a metamorphic signature. P-T pseudosections performed in the system CrMFASH allow us to constrain the temperature of formation of Fe²⁺-rich chromite by reaction of magmatic chromite with olivine between 584 and 449 °C; while the new thermodynamic calculations performed in the FMASH system shows that the Fe³⁺-rich non-porous chromite and magnetite rims in zoned chromites were formed at lower temperatures (i.e. 270–340 ºC and < 20 kbar). Temperatures of alteration obtained using our new thermodynamic model are in agreement with the qualitative estimation that use minor and trace elements in Fe²⁺-rich chromite (i.e. 560–700 ºC). These temperatures are more restricted than those estimated for chlorite hosted in partly altered (193–481 ºC) and porous chromite (158–255 ºC), and those reported in host serpentinite and associated eclogitic rocks (210–399 ºC). A comparison of P-T conditions estimated by our new thermodynamic models and the distribution of minor and trace elements in the different zones of chromites allow us to infer that the alteration took place during the hydrous retrograde metamorphism, and that the high-pressure metamorphism did not modify the composition of chromites. Thus, the microstructural zoning displayed by chromite grains was formed during the exhumation of a segment of a back-arc-related oceanic lithosphere, at similar temperature conditions than the Tehuitzingo serpentinite.     

Dissolution–reprecipitation process of magnetite from the Chengchao iron deposit: Insights into ore genesis and implication for in-situ chemical analysis of magnetite

Magnetite formed in different environments commonly has distinct assemblages and concentrations of trace elements that can potentially be used as a genetic indicator of this mineral and associated ore deposits. In this paper, we present textural and compositional data of magnetite from the Chengchao iron deposit, Daye district, China to provide a better understanding in the formation mechanism and genesis of the deposit and shed light on analytical protocols for in-situ chemical analysis of hydrothermal magnetite. Magnetite grains from the ore-related granitoid pluton, mineralized endoskarn, magnetite-dominated exoskarn, and vein-type iron ores hosted in marine carbonate intruded by the pluton were examined using scanning electron microscopy and analyzed for major and trace elements using electron microprobe. Back-scattered electron images reveal that primary magnetite from the mineralized skarns and vein-type ores were all partly reequilibrated with late-stage hydrothermal fluids, forming secondary magnetite domains that are featured by abundant porosity and have sharp contact with the primary magnetite. These textures are interpreted as resulting from a dissolution–reprecipitation process of magnetite, which, however, are mostly obscure under optically.Primary magnetite grains from the mineralized endoskarn and vein-type ores contain high SiO₂ (0.92–3.21 wt.%), Al₂O₃ (0.51–2.83 wt.%), and low MgO (0.15–0.67 wt.%), whereas varieties from the exoskarn ores have high MgO (2.76–3.07 wt.%) and low SiO₂ (0.03–0.23 wt.%) and Al₂O₃ (0.54–1.05 wt.%). This compositional contrast indicates that trace-element geochemical composition of magnetite is largely controlled by the compositions of magmatic fluids and host rocks of the ores that have reacted with the fluids. Compared to its precursor mineral, secondary magnetite is significantly depleted in most trace elements, with SiO₂ deceasing from 1.87 to 0.47 wt.% (on average) and Al₂O₃ from 0.89 to 0.08 wt.% in mineralized endoskarn and vein type ores, and MgO from 2.87 to 0.60 wt.% in exoskarn ores. On the contrary, average content of iron is notably increased from 69.2 wt.% to 71.9 wt.% in the secondary magnetite grains. The results suggest that the dissolution–reprecipitation process has been important in significantly removing trace elements from early-stage magnetite to form high-grade, high-quality iron ores in hydrothermal environments. The textural and compositional data confirm that the Chengchao iron deposit is of hydrothermal origin, rather than being crystallized from immiscible iron oxide melts as previously suggested. This study also highlights the importance of textural characterization using various imaging techniques before in-situ chemical analysis of magnetite, as is the case for texturally complicated UTh-bearing accessory minerals that have been widely used for UPb geochronology study.     

U–Pb zircon chronology,geochemistry and isotopes of the Changyi banded iron formation in the eastern Shandong Province: Constraints on BIF genesis and implications for Paleoproterozoic tectonic evolution of the North China Craton

The Changyi banded iron formation (BIF) in the eastern North China Craton (NCC) occurs within the Paleoproterozoic Fenzishan Group. The BIF shows alternating quartz-rich light and magnetite-rich dark bands with magnetite (15–65 vol.%), quartz (25–65 vol.%) and amphibole (15–30 vol.%) constituting the major minerals. Minor garnet, epidote, chlorite, calcite, biotite and pyrite occur locally. The BIF bands are interlayered with amphibolite, hornblende gneiss, biotite quartz schist, garnet biotite schist, biotite gneiss and leptynite, and are intruded by granites. LA-ICP-MS U–Pb dating on zircons separated from the BIF bands and the wallrocks constrains the depositional age as 2240–2193 Ma and metamorphic age as ~ 1864 Ma. The dominant composition of SiO₂ + Fe₂O₃^T (average value of 92.3 wt.%) of the BIF bands suggests their formation mainly through chemical precipitation. However, the widely varying contents of major elements such as Al₂O₃ (0.58–6.99 wt.%), MgO (1.00–3.86 wt.%), CaO (0.22–4.19 wt.%) and trace elements such as Rb (2.06–40.4 ppm), Sr (9.36–42.5 ppm), Zr (0.91–23.6 ppm), Hf (0.04–0.75 ppm), Cr (89.1–341 ppm), Co (2.94–30.4 ppm), and Ni (1.43–52.0 ppm) clearly indicate the incorporation of clastics, especially continental felsic clastics, as also confirmed by the presence of ancient detrital zircons in the BIF bands. When normalized against Post Archean Average Shale (PAAS), the seawater-like signatures of REE distribution patterns, such as LREE depletion, positive La and Y anomalies, and superchondritic Y/Ho ratios (average value of 36.3), support the deposition in seawater. Strong positive Eu anomalies (Eu/Eu*_PAAS = 1.14–2.86) also suggest the participation of hydrothermal fluids. In addition, the sympathetic correlation between Cr, Co and Ni as well as the Co + Ni + Cu vs. ∑ REE and the Al₂O₃ vs. SiO₂ relations further indicates that the iron and silica mainly originated from hydrothermal fluids. Combined with regional geological investigation and protolith restoration of the wallrocks, a continental rift environment is suggested for the Changyi BIF deposition. The appearance of negative Ce_PAAS anomalies might suggest the influence of the Great Oxidation Event at the time of deposition. The Changyi BIF witnessed the major Paleoproterozoic rifting–collision events in the NCC and their unique distribution in the NCC contrasts with other examples elsewhere in the world.     

A Cretaceous dike swarm provides evidence of a spreading axis in the back-arc basin of the Kohistan paleo-island arc,northwestern Himalaya,Pakistan

A 100–4000 m wide and 15 km long dike swarm, consisting of basalt and dolerite, occurs at the base of the Thelichi Formation in the Kohistan paleo-island arc terrane, north Pakistan. The dikes contain hornblende (altered from diopsidic-augite), diopsidic-augite (relics; ophitic to subophitic texture), chlorite, epidote, sphene, apatite, zircon, ilmenite, titanomagnetite and magnetite. The geochemistry reveals two groups of dikes: (1) Higher TiO₂ (2.74–3.50 wt%), Na₂O, Fe₂O₃ and lower Al₂O₃ (12.65–14.16 wt%) and MgO (3.73–5.04 wt%); (2) Lower TiO₂ (1.24–2.05 wt%), Na₂O, Fe₂O₃ and higher Al₂O₃ (14.02–16.52 wt%) and MgO (3.98–7.52 wt%). The MgO contents (3.73–7.52-wt%) show a variation in the dikes from relatively primitive to more evolved compositions. The dikes contain high amounts of both LILE and HFSE. The major, trace and rare-earth elements data confirm the MORB affinity and the back-arc basin origin of the dike swarm. The NW–SE orientation of the dike swarm and its 134 ± 3 Ma K–Ar age suggest the spreading axis of the back-arc basin in the Early Cretaceous.     

Rare greenockite (CdS) within the chromite–PGE association in the Bangur Gabbro,Baula-Nuasahi Complex,Eastern India

We report the presence of greenockite from the chromite–PGE–base metal sulfide association in the Bangur Gabbro, Baula-Nuasahi mafic–ultramafic complex. The CdS phase occurs, sans any precursor Cd-bearing phase, as minute grains within siderite micro-veins in close proximity to chlorite in the chalcopyrite + pyrrhotite + pentlandite + violarite assemblage. Using various calibrations, chlorite compositions yielded temperature ranges of 245 to 325 °C. The associated siderite might have formed at or little below the above temperature. Electron probe micro-analyses (EPMA) of greenockite reveal small amounts of Fe (1.01–1.61 wt.%), Zn (1.89–4.54 wt.%), and substitution of Zn for Cd. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of chalcopyrite nearer to and away from siderite micro-veins that host greenockite confirms maximum Cd concentrations of 78 and 144 ppm, respectively, entailing possible derivation of Cd from chalcopyrite. We propose the transport of Cd as bisulfide complex in a low temperature alkaline and reducing fluid and the simultaneous precipitation of greenockite and siderite by reaction with Fe-rich minerals, aided by decrease in pH and/or increase in f_O2.     

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.     

Triassic volcanism along the eastern margin of the Xing'an Massif,NE China: Constraints on the spatial–temporal extent of the Mongol–Okhotsk tectonic regime

We present new zircon U–Pb–Hf and whole-rock geochemical data for volcanic rocks along the eastern margin of the Xing'an Massif of NE China in order to further our understanding of the history of subduction towards the SE and the spatial extent of the Mongol–Okhotsk tectonic regime. Zircon U–Pb dating indicates that the Triassic volcanism in the Xing'an Massif occurred in two stages during the Middle (ca. 242 Ma) and Late (ca. 223–228 Ma) Triassic. Middle Triassic basaltic andesites in the Heihe area have an affinity to arc-type volcanic rocks. The zircon ε_Hf(t) values (+ 8.5 to + 12.7) suggest that the primary magma was generated by the partial melting of a relatively depleted mantle wedge that had been metasomatized by subduction-related fluids. The Late Triassic andesites in the Handaqi area exhibit geochemical affinities to high-Mg adakitic andesites. Their zircon ε_Hf(t) values (+ 11.5 to + 14.5) and T_DM2 ages (313–484 Ma) indicate that their primary magma was derived from the partial melting of a young subducted oceanic crust, followed by interaction with melts derived from mantle peridotite. The Late Triassic basaltic andesites, andesites, and dacites in the Zhalantun–Moguqi area have features similar to those of igneous rocks formed in subduction zones. Their zircon ε_Hf(t) values (+ 8.4 to + 15.4) and T_DM1 ages (260–542 Ma) indicate that their primary magma was derived from the partial melting of a depleted mantle wedge that had been metasomatized by subduction-related fluids. These data suggest that the Triassic volcanic rocks of the Xing'an Massif formed in an active continental margin setting associated with the southward subduction of the Mongol–Okhotsk oceanic plate towards the SE. We conclude that the Mongol–Okhotsk tectonic regime extended at least as far as the eastern margin of the Xing'an Massif, and that the tectonism spanned the period from the late Permian to early Early-Cretaceous.     

Geochronological and geochemical constraints on the petrogenesis of the early Paleoproterozoic potassic granite in the Lushan area,southern margin of the North China Craton

We conducted a geochronological and geochemical study on the Paleoproterozoic potassic granites in the Lushan area, southern margin of the North China Craton (NCC) to understand the tectonic regime of the NCC at 2.2–2.1 Ga. This rock suite formed at 2194 ± 29 Ma. The rocks are rich in SiO₂ (76.10–77.73 wt.%), and K₂O (5.94–6.90 wt.%) with high K₂O + Na₂O contents from 7.56 wt.% to 8.48 wt.%, but poor in CaO (0.10–0.28 wt.%), P₂O₅ (0.02–0.05 wt.%) and MgO (0.01–0.30 wt.%, Mg# = 1.08–27.3), indicating they experienced fractional crystallization. Major element compositions suggest the potassic granites share an affinity with high K calc-alkaline granite. Even though the Lushan potassic granitic rocks have high A/CNK ratios (1.11–1.25), which can reach peraluminous feature, the very low P₂O₅ contents and negative correlation of P₂O₅ and SiO₂ ruling out they are S-type granites. Different from peralkaline A-type granites, the Lushan potassic granites have variable Zr concentrations (160–344 ppm, 226 ppm on average) and 10,000 Ga/Al ratios (1.76–3.00), together with high zircon saturation temperatures (T_Zr = 826–885 °C), indicating they are fractionated aluminous A-type granites. Enriched LREE ((La/Yb)_N = 9.72–81.8), negative Eu anomalies, and low Sr/Y with no correlations in Sr/Y and Sr/Zr versus CaO suggest the possible presence of Ca-rich plagioclase and absence of garnet in the residual. Magmatic zircon grains have variable ε_Hf(t) values (−2.4 to +7.3) with zircon two-stage Hf model ages (T_DM^C) varying from 2848 Ma to 2306 Ma (mostly around ca. 2.5 Ga), and are plotted in the evolution line of crustal felsic rock. We propose that the rocks mainly formed by partial melting of ca. 2.50 Ga tonalitic–granodioritic crust as a result of upwelling mantle-derived magmas which provided thermal flux and source materials in an intra-continent rifting. The ca. 2.2 Ga magmatism suggests that intra-continental rifting occurred at 2.35–1.97 Ga at least in the southern margin of the NCC after its final cratonization in the late Neoarchean.     

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.     

Fault controlled Carboniferous A-type magmatism in the proto-Andean foreland (Sierras Pampeanas,Argentina): Geochemical constraints and petrogenesis

The intrusion of granitoids into the Eastern Sierras Pampeanas in the Early Carboniferous took place after a long period of mainly compressional deformation that included the Famatinian (Ordovician) and Achalian (Devonian) orogenies. These granitoids occur as small scattered plutons emplaced in a dominant extensional setting, within older metamorphic and igneous rocks, and many of them are arranged along a reactivated large shear zone. A set of 46 samples from different granitic rocks: Huaco granitic complex, San Blas pluton, and the La Chinchilla stock from the Sierra de Velasco, Zapata granitic complex from Sierra de Zapata, and the Los Árboles pluton from Sierra de Fiambalá, display high and restricted SiO₂ contents between 69.2 and 76.4 wt.%. On both FeO/(FeO + MgO) vs. SiO₂ and [(Na₂O + K₂O) ? CaO] vs. SiO₂ plots the samples plot in the ferroan and alkaline-calcic to calco-alkaline fields (FeO/(FeO + MgO) = 0.88–1.0%;[(Na₂O + K₂O) ? CaO] = 6.3–8.3%), thus showing an A-type granitoid signature. The high concentrations for the High Field Strength Elements (HSFE), such as Y, Nb, Ga, Ta, U, Th, etc. and flat REE patterns showing significant negative Eu anomalies are also typical features of A-type granites. Our petrogenetic model supports progressive fractional crystallization with dominant fractionation of feldspar and a source mineral assemblage enriched in plagioclase. Biotites have distinctive compositions with high FeO/MgO ratios (7.8–61.5), F (360–5610 ppm), and Cl (120–1050 ppm). The FeO/MgO ratios together with the F and Cl content of igneous biotites seem to reflect the nature of their parental host magmas and may be useful in identifying A-type granitoids. The isotopic data (Rb–Sr and Sm–Nd) confirm that the A-type granites represent variable mixtures of asthenospheric mantle and continental crust and different mixtures lead to different subtypes of A-type granite (illustrating the lack of consensus about A-type magma origin). We conclude that prominent shear zones play an important role in providing suitable conduits for ascending asthenospheric material and heat influx in the crust, a hypothesis that is in accord with other recent work on A-type granites.