Origin of anomalously Ni-rich parental magmas and genesis of the Huangshannan Ni–Cu sulfide deposit,Central Asian Orogenic Belt,Northwestern China

The Huangshannan Ni–Cu sulfide deposit at the southern margin of the Central Asian Orogenic Belt (CAOB) is an important recent discovery in the Eastern Tianshan Region, Northwestern China. The Huangshannan Intrusion is composed of mafic and ultramafic rocks, and its websterite and lherzolite sequences host the sulfide orebodies. Olivine is the dominant mineral in the Huangshannan Intrusion, occurring as olivine inclusions hosted by pyroxene oikocrysts, as olivine crystals in magmatic sulfides, and as poikilitic crystals in the lherzolite. Small olivine inclusions always coexist with large poikilitic olivine crystals in the same sample, resulting in a heterogeneous texture on the scale of the oikocrysts. The Ni abundance ranges from 1540 to 3772 ppm in poikilitic olivine grains, from 2114 to 3740 ppm in olivine grains hosted by sulfide minerals, and from 2043 to 4023 ppm in olivine inclusions hosted by pyroxene oikocrysts. For the three types of olivine, the ranges in forsterite (Fo) content are 78.97–84.92 mol.%, 81.57–84.79 mol.%, and 80.33–84.68 mol.%, respectively. The Ni content of olivine in the lherzolite is anomalously high relative to the range found in most within plate olivine-bearing mafic-ultramafic rocks. The composition of olivine is controlled mainly by that of the parental magma, fractional crystallization and reactions with interstitial silicate and sulfide melts. Both fractional crystallization and reaction with interstitial silicate may cause a decrease in the Ni content of olivine. The possibility that Ni–Fe exchange causes the anomalously high Ni contents in olivine can be excluded because the olivine grains contained in sulfide have similar or lower Ni content than the olivine grains hosted in the silicate rock. Most of the olivine grains are unzoned, and they have anomalously high Ni contents throughout the crystal. Assuming a partition coefficient of Ni between olivine and silicate magma to be 7, the measured Ni content of olivine in the lherzolite (1540–4023 ppm with a mean of 2907 ppm) indicates that the parental magma contains 220–575 ppm (average of 415 ppm) Ni. This value is higher than that found in basaltic magmas that crystallized olivine with similar Fo contents compared to the Huangshannan Intrusion. As mentioned above, the symmetric and reproducible variations in both Fo and Ni contents from core to margin in most of the olivine grains cannot be explained by fractional crystallization and reactions with interstitial silicate or sulfide melts but may reflect the equilibration of the olivine with new fluxes of magma as the chamber was replenished. The anomalously Ni-rich composition of the parental magmas of the Huangshannan Intrusion, relative to those of many other mineralized olivine-bearing mafic-ultramafic intrusions, may be produced by upgrading and scavenging of metals from a previously formed sulfide melts by a moderately Ni-rich magma. The mass-balance calculations of PGE data indicate that the parental magma that formed lherzolite contains 0.04 ppb Os, 0.02 ppb Ir and 0.4 ppb Pd, whereas the parental magma that formed websterite has 0.02 ppb Os, 0.009 ppb Ir and 0.75 ppb Pd. Rayleigh modeling using PGE tenors indicates that the massive sulfides may be produced by monosulfide solid solution (MSS)-sulfide liquid fractionation from the magma that formed the websterite. Rayleigh modeling of Fo and Ni contents of olivine shows that the parental magma that formed the lherzolite has experienced previous sulfide segregation and olivine crystallization.     

Genesis of the Huangshannan high-Ni tenor magmatic sulfide deposit in the Eastern Tianshan,northwest China: Constraints from PGE geochemistry and Os–S isotopes

The Huangshannan magmatic Ni-Cu sulfide deposit is one of a group of Permian magmatic Ni-Cu deposits located in the southern Central Asian Orogenic belt in the Eastern Tianshan, northwest China. It is characterized by elevated Ni tenor (concentrations in recalculated 100% sulfide) in sulfide within ultramafic rocks (9–19 wt%), with values much higher than other deposits in the region. Sulfides of the Huangshannan deposit are composed of pentlandite, chalcopyrite, and pyrrhotite and the host rock is relatively fresh, indicating that the high-Ni tenor is a primary magmatic feature rather than formed by alteration processes. It is shown that sulfides with high-Ni tenor can be generated by sulfide-olivine equilibrium at an oxygen fugacity of QFM +0.5, for magmas containing 450 ppm Ni and 20% olivine. Ores with >10 wt% sulfur have relatively low PGE and Ni tenors compared to other ores, R factor (mass ratio of silicate to sulfide liquid) modeling of Ni indicates that they formed at moderate R values (150–600). Based on this constraint on R values, ores with <10 wt% sulfides in the Huangshannan deposit can be segregated from a similar parental magma with 0.05 ppb Os, 0.023 ppb Ir, and 0.5 ppb Pd at R values between 600 and 3000. This, coupled with the supra-cotectic proportions of sulfide liquid to cumulus silicates in the Huangshannan ores imply mechanical transport and deposition of sulfide liquid in a magma pathway or conduit, in which sulfides must have interacted with large volumes of silicate magma. Platinum and Pd depletion relative to other platinum group elements (PGEs) are observed in fresh and sulfide-rich samples (S > 4.5 wt%). As sulfide-rich samples are also depleted in Cu, and as interstitial sulfides in those samples are physically interconnected at a scale of several cms, the low Pt and Pd anomalies are attributed to solid Pt and Pd phases crystallization and retention with the monosulfide solid solution (MSS) and Cu-rich sulfide liquid percolation during MSS fractionation. This finding indicates that Pt anomalies in sulfide-rich rocks from magmatic Ni-Cu deposits in the Eastern Tianshan are the result of sulfide fractionation rather than a hydrothermal effect. ¹⁸⁷Os/¹⁸⁸Os_(278Ma) values of the lherzolite samples vary from 0.27 to 0.37 and γOs_(278Ma) values vary from 110 to 189, indicating significant magma interaction with crustal sulfides, rich in radiogenic Os. Well constrained γOs values and δ³⁴S values (−0.4 to 0.8‰) indicate that crustal contamination occurred at depth before the arrival of the magma in the Huangshannan chamber. Regionally, deposits with high-Ni tenor have not been reported other than the Huangshannan deposit; however, many intrusions with high-Ni contents in olivine are present in NW China, such as the Erhongwa, Poyi and Poshi intrusions. Those intrusions are capable of forming high-Ni tenor sulfides due to olivine-sulfide-silicate equilibrium and relative high-Ni content in parent magma, making them attractive exploration targets.     

Major,trace and platinum group element (PGE) geochemistry of Archean Iron Ore Group and Proterozoic Malangtoli metavolcanic rocks of Singhbhum Craton,Eastern India: Inferences on mantle melting and sulphur saturation history

The geological and metallogenic history of the Singhbhum Craton of eastern India is marked by several episodes of volcanism, plutonism, sedimentation and mineralization spanning from Paleoarchean to Mesoproterozoic in a dynamic tectonic milieu. Distinct signatures of this Archean-Proterozoic geodynamic process are preserved in discrete crustal provinces that constitute the Singhbhum Craton. Here we report new major, trace and PGE geochemical data from the ~ 3.4 Ga Iron Ore Group (IOG) volcanic rocks of the Jamda-Koira basin, a part of the BIF-bearing volcano-sedimentary sequences of the Noamundi-Jamda-Koira iron ore basin in the western part of Singhbhum Granite (SBG), and ~ 2.25 Ga metavolcanic rocks of Malangtoli. The IOG and Malangtoli volcanic rocks are porphyritic basalts and despite belonging to different ages, they exhibit similar mineralogical composition marked by clinopyroxene, plagioclase (present as both phenocryst and groundmass), opaques and volcanic glass (restricted to groundmass). The igneous mineralogy of these rocks has been overprinted by greenschist to lower amphibolite grade of metamorphism. The Malangtoli samples show low and high MgO compositional varieties. Immobile trace element compositions classify the IOG samples as andesite having a calc-alkaline composition, whereas the Malangtoli rocks correspond to basalt and andesite displaying a tholeiitic to calc-alkaline trend. The IOG basalts show low to moderate PGE contents marked by 26.23–68.35 ppb of ΣPGE, whereas the Malangtoli basalts display a moderate to high concentration of PGE (ΣPGE = 43.01–190.43 ppb). The studied samples have relatively enriched ΣPPGE ranging from 24.1–63.3 ppb (IOG) and 34–227.3 ppb (Malangtoli) against 2.2–4.1 ppb and 1.9–8.9 ppb ΣIPGE contents respectively. PPGE/IPGE ratios for IOG and Malangtoli samples range from 7.7–17.6 and 4.8–59.9. HFSE, REE and PGE compositions suggest a low degree (< 1 to 1%) of partial melting in the garnet lherzolite domain for the generation of IOG volcanic rocks. The parental magma of the Malangtoli basalts were generated by lower to higher degrees (3–< 10%) of mantle melting at depths corresponding to spinel to garnet lherzolite regime. Trace element (Zr/Nb, Th/Ta, Th/Nb, Ni/Cu) and PGE (Pd/Ir, Pd/Pt, Cu/Pd, Ni/Pd, Cu/Ir) ratios corroborate a sulphide saturated and PGE depleted character of IOG volcanic rocks that underwent crustal assimilation. In contrast, the high MgO Malangtoli basalts exhibit sulphide undersaturated, PGE undepleted nature devoid of crustal contamination whereas the low MgO Malangtoli basalts are sulphide saturated, PGE depleted and crustally contaminated. The IOG volcanic rocks correspond to intraoceanic arc with polygenetic crustal signatures, and show affinity towards arc-generated calc-alkaline basalts. The low- and high MgO basalts of Malangtoli are affiliated to transitional arc to rift-controlled back arc tectonic setting in a basinal environment that developed proximal to an active convergent margin.     

Chalcophile element geochemistry and petrogenesis of high-Ti and low-Ti magmas in the Permian Emeishan large igneous province,SW China

Sulfide-poor mafic layered intrusions, sills/dykes and lava flows in the Funing region, SW China, are part of the ~260 Ma Emeishan large igneous province. They belong to either a high-Ti group (TiO₂ = 1.6–4.4 wt%) with elevated Ti/Y ratios (351–1,018), or a low-Ti group (TiO₂ < 1.2 wt%) with low Ti/Y ratios (133–223). This study investigates the role of fractionation of olivine, chromite and sulfide on the distributions of chalcophile elements, Ni, Cu and PGE, of the high-Ti and low-Ti group rocks at Funing. The high-Ti group rocks contain 1.6–5.3 ppb Pt + Pd, 0.06–0.43 ppb Ir and 0.01–0.13 ppb Ru, and show relative constant (Cu/Pd)_PM ratios (4.0–9.7) and a negative correlation between Ni/Pd and Cu/Ir ratios. Fractionated IPGE/PPGE patterns and very negative Ru anomalies of the high-Ti group rocks, together with low Fo values (59–62 mol%) of olivine, indicate that the high-Ti magmas may have experienced fractionation of olivine and chromite under S-undersaturated condition. Based on the PGE concentrations, the low-Ti group rocks can be further divided into two subgroups; a high-PGE low-Ti subgroup and a low-PGE low-Ti subgroup. The high-PGE low-Ti group rocks are rich in MgO (10–20 wt%), but Fo values of olivine from the rocks are low (74–76 mol%). The rocks contain highly variable PGE (Pt + Pd = 1.7–88 ppb, Ir = 0.05–1.3 ppb), Ni (179 –1,380 ppm) and Cu (59–568 ppm). They have Cu/Zr ratios >1, low (Y/Pd)_PM ratios (0.2–7.1) and nearly constant (Cu/Pd)_PM ratios (1.5–3.8). The even and parallel chalcophile element patterns of the high-PGE low-Ti subgroup rocks are likely a result of olivine-dominated fractionation under S-undersaturated condition. The low-PGE low-Ti group rocks have low MgO (4.5–8.9 wt%) and very poor PGE (Pt + Pd 0.5–1.6 ppb, Ir 0.004–0.02 ppb) with low Cu/Zr ratios (0.1–0.5), high (Y/Pd)_PM (26–70) and variable (Cu/Pd)_PM ratios (2.8–14). The trough-like chalcophile element patterns of the low-PGE low-Ti subgroup rocks indicate that the magmas were sulfide saturation and sulfide melts were extracted from the magmas. The extracted sulfide melts might be potential Ni–Cu sulfide ores at depth in the Funing region.     

Chalcophile elemental compositions and origin of the Tuwu porphyry Cu deposit,NW China

The Tuwu porphyry Cu deposit in the eastern Tianshan Orogenic Belt of southern Central Oceanic Orogen Belt contains 557 Mt ores at an average grade of 0.58 wt.% Cu and 0.2 g/t Au, being the largest porphyry Cu deposit in NW China. The deposit is genetically related to dioritic and plagiogranitic porphyries that intruded the Carboniferous Qieshan Group. Ore minerals are dominantly chalcopyrite, pyrite and enargite. Porphyric diorites have Sr/Y and La/Yb_N ratios lower but Y and Yb contents higher than plagiogranites. Diorites have highly variable Cu but nearly constant PGE contents (most Pd = 0.50–1.98 ppb) with Cu/Pd ratios ranging from 10,900 to 8,900,000. Plagiogranites have PGEs that are positively correlated with Cu and have nearly uniform Cu/Pd ratios (5,100,000 to 7,800,000). Diorites have concentrations of Re (0.73–15.18 ppb), and ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios lower but common Os contents (0.006–0.097 ppb) higher than plagiogranites. However, both the diorites and plagiogranites have similar normalized patterns of rare earth elements (REE), trace element and platinum-group elements (PGEs). All the samples are characterized by the enrichments of LREE relative to HREE and display positive anomalies of Pb and Sr but negative anomalies of Nb and Ta in primitive-mantle normalized patterns. In the primitive mantle-normalized siderophile element diagrams, they are similarly depleted in all PGEs but slightly enriched in Au relative to Cu.Our new dataset suggests that both the diorite and plagiogranite porphyries were likely evolved from magmas derived from partial melting of a wet mantle wedge. Their parental magmas may have had different water contents and redox states, possibly due to different retaining time in staging magma chambers at the depth, and thus different histories of magma differentiation. Parental magmas of the diorite porphyries are relatively reduced with less water contents so that they have experienced sulfide saturation before fractional crystallization of silicate minerals, whereas the relatively more oxidized parental magmas with higher water contents of the plagiogranite porphyries did not reach sulfide saturation until the magmatic-hydrothermal stage. Our PGE data also indicates that the Cu mineralization in the Tuwu deposit involved an early stage with the enrichments of Au, Mo and Re and a late stage with the enrichment of As but depletion of Au–Mo. After the formation of the Cu mineralization, meteoric water heated by magmas penetrated into and interacted with porphyritic rocks at Tuwu, which was responsible for leaching Re from hosting rocks.     

Platinum-group elemental chemistry of the Baima and Taihe Fe–Ti oxide bearing gabbroic intrusions of the Emeishan large igneous province,SW China

Nickel-, copper-, and platinum group element (PGE)-enriched sulphide mineralization in large igneous provinces has attracted numerous PGE studies. However, the distribution and behavior of PGEs as well as the history of sulphide saturation are less clear in oxide-dominated mineralization. Platinum group elements of oxide-bearing layered mafic intrusions from the Emeishan large igneous province are examined in this study. Samples collected from the Baima and Taihe oxide-bearing layered gabbroic intrusions reveal contrasting results. The samples from Baima gabbroic rocks have low total PGE abundances (ΣPGE < 4 ppb) whereas the Taihe gabbroic rocks, on average, have more than double the concentration but are variable ranging from ΣPGE < 2 ppb to ΣPGE ∼300 ppb. The Baima gabbro is platinum-subgroup PGE (PPGE = Rh, Pt and Pd) enriched and iridium-subgroup PGE (IPGE = Os, Ir and Ru) depleted, with a distinct positive Ru anomaly on a primitive mantle normalized multi-element plot. The Taihe gabbros are also PPGE enriched but with negative Ru and Pd anomalies on a primitive mantle normalized multi-element plot. The PGE concentrations of Baima rocks are indicative of fractionation of a relatively evolved, mafic, S-undersaturated parental magma that was affected by earlier sulphide segregation. In contrast, the Taihe rocks record evidence of both S-saturated and S-undersaturated conditions and that the parental magma was likely emplaced very close to S-saturation. Comparisons of the platinum group element contents in the Emeishan flood basalts and the Emeishan oxide-bearing intrusions suggest that the PGE budget in a magma is not controlled by magma series (high-Ti vs. low-Ti), but very much by crustal contamination. The unlikelihood of substantial crustal contamination in the Taihe magma allowed the magma to remain S-undersaturated for a longer duration. PGE and sulphide mineralization was not identified in the Taihe intrusion but the presence of one PGE-enriched sample (Pt + Pd = ∼300 ppb) suggests that the parental magma likely did not experience sulphide segregation and is a potential target for further prospecting.     

Petrogenesis of Miocene alkaline volcanic suites from western Bohemia: whole rock geochemistry and Sr–Nd–Pb isotopic signatures

The Mid to Late Miocene intraplate alkaline volcanic suites of western Bohemia are relict of the intensive voluminous volcanism accompanied by large-scale uplift and doming. The association with the uplift of the NE flank of the Cheb–Domažlice Graben (CDG) is uncertain in view of the mostly transpressional tectonics of the graben. The volcanism is most probably of the Ohře/Eger Rift off-rift settings. Two cogenetic volcanic suites have been recognised: (i) silica-saturated to oversaturated consisting of olivine basalt–trachybasalt-(basaltic) trachyandesite–trachyte–rhyolite (13.5 to 10.2 Ma) and (ii) silica-undersaturated (significantly Ne-normative) (melilite-bearing) olivine nephelinite–basanite–tephrite (18.3 to 6.25 Ma). A common mantle source is suggested by similar primitive mantle-normalised incompatible element patterns and Sr–Nd–Pb isotopic compositions for the assumed near-primary mantle-derived compositions of both suites, i.e., olivine basalt and olivine nephelinite. Apparently, they were generated by different degrees of partial melting of a common mantle source, with garnet, olivine and clinopyroxene in the residuum. Negative Rb and K anomalies indicate a residual K-phase (amphibole/phlogopite) and melting of partly metasomatised mantle lithosphere. The evolution of the basanite–olivine basalt–trachybasalt-(basaltic) trachyandesite–trachyte–rhyolite suite suggests the presence of an assimilation–fractional crystallization process (AFC). Substantial fractionation of olivine, clinopyroxene, Fe–Ti oxide, plagioclase/alkali feldspar and apatite accompanied by a significant assimilation of magma en route by crustal material is most evident in evolved member, namely, trachytes and rhyolites. The magmas were probably sourced by both sub-lithospheric and lithospheric partly metasomatised mantle. The evolution of the (melilite-bearing) olivine nephelinite–basanite–tephrite suite is less clear because of its limited extent. Parental magma of both these rock suites is inferred to have originated by low-degree melting of the mantle source initiated at ca. 18 Ma and reflects mixing of asthenosphere-derived melts with isotopically enriched lithospheric melts. The older Oligocene alkaline rocks (29–26 Ma) occur within the Cheb–Domažlice Graben (CDG) locally but are significant in the closely adjacent neighbouring western Ohře Rift. The Sr–Nd–Pb isotopic composition of primitive volcanic rocks of both suites is similar to that of the European Asthenospheric Reservoir (EAR). Initial Pb isotopic data plot partly above the northern hemisphere reference line at radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios of ∼19 to 20, and indicate the presence of a Variscan crustal component in the source.     

Roles of xenomelts,xenoliths, xenocrysts,xenovolatiles, residues,and skarns in the genesis,transport, and localization of magmatic Fe-Ni-Cu-PGE sulfides and chromite

Most sulfide-rich magmatic Ni-Cu-(PGE) deposits form in dynamic magmatic systems by partial melting S-bearing wall rocks with variable degrees of assimilation of miscible silicate and volatile components, and generation of barren to weakly-mineralized immiscible Fe sulfide xenomelts into which Ni-Cu-Co-PGE partition from the magma. Some exceptionally-thick magmatic Cr deposits may form by partial melting oxide-bearing wall rocks with variable degrees of assimilation of the miscible silicate and volatile components, and generation of barren Fe ± Ti oxide xenocrysts into which Cr-Mg-V ± Ti partition from the magma. The products of these processes are variably preserved as skarns, residues, xenoliths, xenocrysts, xenomelts, and xenovolatiles, which play important to critical roles in ore genesis, transport, localization, and/or modification. Incorporation of barren xenoliths/autoliths may induce small amounts of sulfide/chromite to segregate, but incorporation of sulfide xenomelts or oxide xenocrysts with dynamic upgrading of metal tenors (PGE > Cu > Ni > Co and Cr > V > Ti, respectively) is required to make significant ore deposits. Silicate xenomelts are only rarely preserved, but will be variably depleted in chalcophile and ferrous metals. Less dense felsic xenoliths may aid upward sulfide transport by increasing the effective viscosity and decreasing the bulk density of the magma. Denser mafic or metamorphosed xenoliths may also increase the effective viscosity of the magma, but may aid downward sulfide transport by increasing the bulk density of the magma. Sulfide wets olivine, so olivine xenocrysts may act as filter beds to collect advected finely dispersed sulfide droplets, but other silicates and xenoliths may not be wetted by sulfides. Xenovolatiles may retard settling of – or in some cases float – dense sulfide droplets. Reactions of sulfide melts with felsic country rocks may generate Fe-rich skarns that may allow sulfide melts to fractionate to more extreme Cu-Ni-rich compositions. Xenoliths, xenocrysts, xenomelts, and xenovolatiles are more likely to be preserved in cooler basaltic magmas than in hotter komatiitic magmas, and are more likely to be preserved in less dynamic (less turbulent) systems/domain/phases than in more dynamic (more turbulent) systems/domains/phases. Massive to semi-massive Ni-Cu-PGE and Cr mineralization and xenoliths are often localized within footwall embayments, dilations/jogs in dikes, throats of magma conduits, and the horizontal segments of dike-chonolith and dike-sill complexes, which represent fluid dynamic traps for both ascending and descending sulfides/oxides. If skarns, residues, xenoliths, xenocrysts, xenomelts, and/or xenovolatiles are present, they provide important constraints on ore genesis and they are valuable exploration indicators, but they must be included in elemental and isotopic mass balance calculations.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

U–Pb (zircon) and geochemical constraints on the age,origin, and evolution of Paleozoic arc magmas in the Oyu Tolgoi porphyry Cu–Au district,southern Mongolia

Uranium–Pb (zircon) ages are linked with geochemical data for porphyry intrusions associated with giant porphyry Cu–Au systems at Oyu Tolgoi to place those rocks within the petrochemical framework of Devonian and Carboniferous rocks of southern Mongolia. In this part of the Gurvansayhan terrane within the Central Asian Orogenic Belt, the transition from Devonian tholeiitic marine rocks to unconformably overlying Carboniferous calc-alkaline subaerial to shallow marine volcanic rocks reflects volcanic arc thickening and maturation. Radiogenic Nd and Pb isotopic compositions (ε_Nd(t) range from + 3.1 to + 7.5 and ²⁰⁶Pb/²⁰⁴Pb values for feldspars range from 17.97 to 18.72), as well as low high-field strength element (HFSE) contents of most rocks (mafic rocks typically have < 1.5% TiO₂) are consistent with magma derivation from depleted mantle in an intra-oceanic volcanic arc. The Late Devonian and Carboniferous felsic rocks are dominantly medium- to high-K calc-alkaline and characterized by a decrease in Sr/Y ratios through time, with the Carboniferous rocks being more felsic than those of Devonian age. Porphyry Cu–Au related intrusions were emplaced in the Late Devonian during the transition from tholeiitic to calc-alkaline arc magmatism. Uranium–Pb (zircon) geochronology indicates that the Late Devonian pre- to syn-mineral quartz monzodiorite intrusions associated with the porphyry Cu–Au deposits are ~ 372 Ma, whereas granodiorite intrusions that post-date major shortening and are associated with less well-developed porphyry Cu–Au mineralization are ~ 366 Ma. Trace element geochemistry of zircons in the Late Devonian intrusions associated with the porphyry Cu–Au systems contain distinct Th/U and Yb/Gd ratios, as well as Hf and Y concentrations that reflect mixing of magma of distinct compositions. These characteristics are missing in the unmineralized Carboniferous intrusions. High Sr/Y and evidence for magma mixing in syn- to late-mineral intrusions distinguish the Late Devonian rocks associated with giant Cu–Au deposits from younger magmatic suites in the district.     

Geological,geochronological, and H–O isotopic constraints on the genesis of the Tongjing Cu–Au deposit in the Ningwu basin,east China

The Tongjing Cu–Au deposit is a medium-sized deposit within the Ningwu volcanic basin, east China, and is hosted by Cretaceous volcanic rocks of the Dawangshan and Niangniangshan Formations. The veined and lenticular Cu–Au orebodies are spatially and temporally related to the volcanic and subvolcanic rocks of the Niangniangshan Formation in the ore district. The wall-rock alteration is dominated by silicification, siderite alteration, carbonation, sericitization, chloritization, and kaolinization. On the basis of field evidence and petrographic observations, two stages of mineralization are recognized: (1) a siderite–quartz–sulfide stage (Stage 1) associated with the formation of chalcopyrite and pyrite in a quartz and siderite gangue; and (2) a quartz–bornite stage (Stage 2) cutting the Stage 1 phases. Stage 1 is the main mineralization stage. Quartz that formed in Stage 1 has δ¹⁸O_H2O values of − 4.3‰ to 3.5‰ with δD values of fluid inclusion waters of − 97.1‰ to − 49.9‰, indicating that the ore-forming fluids were derived from early magmatic fluids and may have experienced oxygen isotopic exchange with meteoric water during Stage 1 mineralization.LA–MC–ICP–MS zircon U–Pb dating of the mineralization-related nosean-bearing phonolite and nosean-bearing phonolitic brecciated tuff at Tongjing yields ages of 129.8 ± 0.5 Ma and 128.9 ± 1.1 Ma, respectively. These results are interpreted as the crystallization age of the volcanic rocks of the Niangniangshan Formation. A hydrothermal sericite sample associated with Cu–Au mineralization at Tongjing yields a plateau ⁴⁰Ar–³⁹Ar age of 131.3 ± 1.3 Ma. These results confirm a genetic link between the volcanism and associated Cu–Au mineralization. The Tongjing Cu–Au deposit in the Ningwu basin is genetically and possibly tectonically similar to alkaline intrusion-related gold deposits elsewhere in the world.     

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.     

Mineral chemical constraints on the petrogenesis of mafic and intermediate volcanic rocks from the Erciyes and Hasandağ volcanoes,Central Turkey

Hasandağ and Erciyes stratovolcanoes, which produced both calc-alkaline and alkaline eruptive products, are the two important volcanic complexes in Central Anatolia. There are three geochemical evolution stages in the history of the Hasandağ strato volcanic complex: (1) Keçikalesi tholeiitic, (2) Hasandağ calc-alkaline and (3) Hasandağ alkaline. Volcanologic and petrologic characteristics of the Hasandağ and Erciyes calc-alkaline series show that water played an important role on the genesis of these rocks. These rocks are phenocryst-rich with vesicular texture, and contain hydrous mineral phases. The approximate pressure and temperature estimates obtained from the mineral chemistry studies of the Hasandağ strato volcanic complex indicate crystallization temperature of 1100 °C with 2.5–3.4 kbar pressure interval for the first stage of Keçikalesi tholeiitic volcanism, and about 850 °C temperatures with 4.3–9.6 kbar pressure intervals for the second stage of Hasandağ calc-alkaline volcanism.The geochemical evolution of Erciyes volcanic complex also exhibits three distinct evolutionary stages: (1) Koçdağ alkaline, (2) Koçdağ calc-alkaline and (3) Erciyes calc-alkaline. The temperature of Koçdağ alkaline volcanism is 1097–1181 °C and in a range of 5.1–6.7 kbar pressure, for Koçdağ calc-alkaline volcanism 850–1050 °C temperature to 2.0–6.6 kbar pressure interval, and for Erciyes calc-alkaline volcanism about 950 °C temperature, to 3.2–7.9 kbar pressure intervals were calculated. Polybaric origin of magma chambers for calc-alkaline and alkaline rocks and disequilibrium parameters observed in phenocrysts indicate that the rocks were affected by magma mixing processes in crustal magma chambers. The disequilibrium features of amphibole and plagioclase phenocrysts in these rocks point the latent heat in magma chambers and periodic recharging with mafic magma chambers and also show that magmas reequilibrate before the eruption.     

A combined fluid inclusion and S–Pb isotope study of the Neoproterozoic Pingshui volcanogenic massive sulfide Cu–Zn deposit,Southeast China

The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ³⁴S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.     

Geochemistry of S,Cu, Ni,Cr and Au-PGE in the garnet amphibolites from the Akom II area in the Archaean Congo Craton,Southern Cameroon

The fresh and weathered garnet amphibolites, from the Akom II area in the Archaean Congo Craton, were investigated to determine the S, Cu, Ni, Cr, and Au-PGE values. The garnet amphibolites are composed of amphibole, plagioclase, garnet, quartz, and accessory apatite, spinel, sericite, pyrite, chalcopyrite and non-identified opaque minerals. The presence of apatite, sericite, and two generations of opaque minerals suggests that they might be affected by hydrothermal alteration. They are characterized by moderate Al₂O₃, Fe₂O₃, CaO, V, Zn, and Co contents with negative Eu- and Ce-anomalies. The sulfur concentrations are variable (380–1710 ppm). According to the sulfur contents, amphibolites can be grouped into two: amphibolites with low contents, ranging between 380 and 520 ppm (av. = 457 ppm); and amphibolites with elevated contents, varying from 1140 to 1710 ppm (av. = 1370 ppm). Amphibolites contain contrast amounts of Cu (∼ 1800 to 5350 ppm) while nickel contents attain 121 ppm. Chromium contents vary from 43 to 194 ppm. Sulfur correlates positively with Cu and Cr, but negatively with Ni and Ni/Cr ratio. The total Au-PGE contents attain 59 ppb.The presence of amphibole and feldspars confirms the low degree of amphibolite weathering. The secondary minerals are constituted of kaolinite, gibbsite, goethite and hematite. Despite the accumulation of some elements, the major and trace element distribution is quite similar to that of fresh amphibolites. Nevertheless, the weathering processes lead to the depletion of several elements such as S (239–902 ppm), Cu (520–2082 ppm), and Ni (20–114 ppm). Chromium and Au-PGE show an opposite trend marked by a slight enrichment in the weathered amphibolites. Amidst the Au-PGE, Pd (60 ppb) and Pt (23 ppb) have elevated contents in the fresh rocks as well as in the weathered materials. The PPGE contents are much higher than IPGE contents in both types of materials. The Pd/Pt, Pd/Rh, Pd/Ru, Pd/Ir, Pd/Os, and Pd/Au values indicate that Pt, Rh, Ru, Ir, Os and Au are more mobile than Pd. Chondrite-normalized base metal patterns confirm the abundance of Pd and the slight enrichment of Au-PGE in weathered rocks. Palladium, Rh and Ir are positively correlated with S. Conversely Pt and Ru are negatively correlated with S and Au is not correlated with S. Despite the high and variable S and Cu contents, the garnet amphibolites possess low Au-PGE and other base metals contents.     

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.     

Melt impregnation phases in the mantle section of the Ślęża ophiolite (SW Poland)

The ultramafic member of the Variscan Ślęża Ophiolite (SW Poland) consists of heavily serpentinised, refractory harzburgites. Those located down to 1.5 km below paleo-Moho contain scarce grains or aggregates of olivine, clinopyroxene and spinel. Non-serpentine phases occur in various assemblages: M1—olivine (Fo 90.2–91.0%, NiO 0.38–0.47 wt.%) and rounded or amaeboidal aluminous chromite, rimmed by Al poor chromite and magnetite; M2—olivine (Fo 90.5–91.5, NiO 0.32–0.44 wt.%), olivine with magnetite inclusions (Fo 87.1–92.5, NiO 0.01–0.68 wt.%), rounded, cleavaged clinopyroxene I (Mg# 91.1–93.2, Al₂O₃ 3.00–4.00 wt.%, Cr₂O₃ 1.00–1.40 wt.%) and elongated clinopyroxene II and clinopyroxene from symplectites with magnetite (Mg# = 92.2–94.1, Al₂O₃ 2.20–3.20 wt.% and Cr₂O₃ 0.80–1.20 wt.%). Clinopyroxene is depleted in REEs relative to chondrite. The M3 assemblage consists of intergrown olivine (Fo 90.8–92.7, NiO 0.20–0.38 wt.%) and clinopyroxene (Mg# = 96.0–98.1, Al₂O₃ 0.00–1.00 wt.% and Cr₂O₃ 0.20–0.60 wt.%).The M1 assemblage contains chromite which records greenschist-facies metamorphism. Textural relationships and chemical composition of clinopyroxene occurring in the M2 assemblage are similar to those formed in oceanic spreading centres by LREE depleted basaltic melt percolation. Olivine occurring in M1 assemblage and part of that from M2 have composition typical of residual olivine from the abyssal harzburgites and of olivine formed in those rocks by melt percolation. The olivine with magnetite inclusions (M2 assemblage) and that from M3 record later deserpentinization event, which supposedly produced also M3 clinopyroxene. The non-serpentine phases from the Ślęża ophiolite mantle member, albeit very poorly preserved, document depleted basaltic melt percolation in the Variscan oceanic spreading centre.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

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.     

Stratiform platinum-group element mineralization in the layered Northern Ultramafic Center of the Lac des Iles Intrusive Complex,Ontario, Canada

The Northern Ultramafic Centre (NUC) of the Lac des Iles Complex, Northwest Ontario hosts several platinum group element (PGE) occurrences, including the Sutcliffe Zone, which consists of four subparallel, stratiform PGE-enriched intervals exposed within the cyclically layered eastern flank of the NUC. Field relationships, mineral paragenesis and lithogeochemistry allowed for the identification of 14 cyclic cumulate sequences of two distinct types – Cyclic unit type A (CUA) and Cyclic unit type B (CUB). CUA-type and CUB-type units are interpreted to have formed from a Si-enriched and Si-poor parent magmas, respectively. PGE-enriched intervals occur in four of the CUA-type cyclic units (CUA-5, -6, -8 and -11). PGE enriched intervals are commonly associated with websterite, olivine websterite and gabbronorite containing primary disseminated sulfide (0.2–2 vol%) which are dominated by pyrrhotite, chalcopyrite, and pentlandite with minor cubanite, and troilite. In hydrothermally altered rocks enriched in PGE, primary sulfides are locally partially replaced by secondary chalcopyrite, sphalerite, heazlewoodite, and chalcocite. Palladium occurs either in solid solution with primary pentlandite or is associated with platinum group minerals (PGM) such as Pd-plumbide, Pd-telluride, and Pt-bismuthotelluride. PGMs commonly occur within primary sulfides, at contacts between primary sulfide–silicate minerals, or in association with secondary serpentine and actinolite. Gold and silver typically occur as electrum that exhibits similar textural characteristics and mineralogical associations as the PGMs.Two different chemostratigraphic patterns of PGE, Cu and S enrichment can be recognized among the mineralized CUA cycles: The first (top-loaded) occurs near the top of CUA cycles (CUA-6, -8 and -11) in websterite and/or gabbronorite, just below the levels at which CUB magmas were emplaced. The second (middle-loaded), occurs midway through the lower cycle (CUA-5) in the olivine websterite, which is overlain by CUA-6. Within the four mineralized intervals, PGE tenors average 643 ppm Pd + Pt (in 100% sulfide), Pd/Pt and Pd/Ir ratios range from 0.9 to 3.5 and 35 to 537, respectively, and S/Se ratios range between 500 and 6000. The highest PGE tenors (4377 ppm Pd + Pt) are found in the lowermost interval in serpentinized olivine websterite and have an average Pd/Pt ratio of 3.5 and a S/Se ratio of approximately 2000.It is proposed that orthomagmatic processes of fractional crystallization and dynamic magma recharge were the dominant mineralization processes triggering sulfide-saturation and PGE concentration at the Sutcliffe Zone. Textural relationships between PGM, sulfide minerals, and primary and secondary hydrous silicates suggest that late magmatic to postcumulus hydrothermal fluid infiltration occurred locally during and after sulfide mineralization of the PGE-enriched intervals. However, these fluids had a minimal effect on the distribution of PGE in the Sutcliffe Zone. The Sutcliffe Zone shares many similarities with classic stratiform PGE deposits in terms of Pd/Pt ratio, high PGE tenors, low abundance of sulfide, and PGM assemblages. However, it is distinguished from most stratiform PGE deposits by its tectonic environment and lithostratigraphic position and by the intimate spatial association of the two parental magmas that are interpreted to have been responsible for the observed chemostratigraphy and PGE enrichment.