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.     

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.     

Chalcophile element constraints on magma differentiation of Quaternary volcanoes in Tengchong,SW China

The Tengchong volcanic field comprises numerous Quaternary volcanoes in SW China. The volcanic rocks are grouped into Units 1–4 from the oldest to youngest. Units 1, 3 and 4 are composed of trachybasalt, basaltic trachyandesite and trachyandesite, respectively, and Unit 2 consists of hornblende-bearing dacite. This rock assemblage resembles those of arc volcanic sequences related to oceanic slab subduction. Rocks of Units 1 and 3 contain olivine phenocrysts with Fo contents ranging from 65 to 85 mole%, indicating early fractionation of olivine and chromite prior to the eruption of magma. All the rocks from Units 1, 3 and 4 have very low PGE concentrations, with <0.05 ppb Ru and Rh, <0.2 ppb Pt and Pd, and Ir that is commonly close to, or slightly higher than detection limits (0.001 ppb). The small variations of Pt/Pd ratios (0.4–2.2) are explained by fractionation of silicate and oxide minerals. The 5-fold variations in Cu/Pd ratios (200,000–1,000,000) for the lavas at Tengchong, which do not vary systematically with fractionation, likely reflect retention of variable amounts of residual sulfide in the mantle source. In addition, all the rocks from Units 1, 3 and 4 have primitive mantle-normalized chalcophile element patterns depleted in PGE relative to Cu. Together with very low Cu/Zr ratios (0.06–0.24), these rocks are considered to have undergone variable degrees of sulfide-saturated differentiation in shallow crustal staging magma chambers. Large amounts of olivine and chromite crystallization probably triggered sulfide saturation of magma at depth for Units 1 and 3, whereas crustal contamination was responsible for sulfide saturation during ascent of magma for Unit 4.     

Metal sources for the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation,South China

Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.     

The geochemistry of trace elements in geothermal fluids,Iceland

Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.     

Rhodium,gold and other highly siderophile elements in orogenic peridotites and peridotite xenoliths

The concentrations of Rh, Au and other highly siderophile elements (HSE: Re, Os, Ir, Ru, Pt, Rh, Pd and Au), and ¹⁸⁷Os/¹⁸⁸Os isotope ratios have been determined for samples from peridotite massifs and xenoliths in order to further constrain HSE abundances in the Earth's mantle and to place constraints on the distributions processes accounting for observed HSE variations between fertile and depleted mantle lithologies. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS. The monoisotopic elements Rh and Au were quantified by standardization relative to the concentrations of Ru and Ir, respectively, and were determined from the same digestion aliquot as other HSE. The measurement precision of the concentration data under intermediate precision conditions, as inferred from repeated analyses of 2 g test portions of powdered samples, is estimated to be better than 10% for Rh and better than 15% for Au (1 s).Fertile lherzolites display non-systematic variation of Rh concentrations and constant Rh/Ir of 0.34 ± 0.03 (1 s, n = 57), indicating a Rh abundance for the primitive mantle of 1.2 ± 0.2 ng/g. The data also suggest that Rh behaves as a compatible element during low to moderate degrees of partial melting in the mantle or melt–mantle interaction, but may be depleted at higher degrees of melting. In contrast, Au concentrations and Au/Ir correlate with peridotite fertility, indicating incompatible behaviour of Au during magmatic processes in the mantle. Fertile lherzolites display Au/Ir ranging from 0.20 to 0.65, whereas residual harzburgites have Au/Ir < 0.20. Concentrations of Au and Re are correlated with each other and suggest similar compatibility of both elements. The primitive mantle abundance of Au calculated from correlations displayed by Au/Ir with Al₂O₃ and Au with Re is 1.7 ± 0.5 ng/g (1 s).The depletion of Pt, Pd, Re and Au relative to Os, Ir, Ru and Rh displayed by residual harzburgites, suggests HSE fractionation during partial melting. However, the HSE abundance variations of fertile and depleted peridotites cannot be explained by a simple fractionation process. Correlations displayed by Pd/Ir, Re/Ir and Au/Ir with Al₂O₃ may reflect refertilization of previously melt depleted mantle rocks due to reactive infiltration of silicate melts.Relative concentrations of Rh and Au inferred for the primitive mantle model composition are similar to values of ordinary and enstatite chondrites, but distinct from carbonaceous chondrites. The HSE pattern of the primitive mantle is inconsistent with compositions of known chondrite groups. The primitive mantle composition may be explained by late accretion of a mixture of chondritic with slightly suprachondritic materials, or alternatively, by meteoritic materials mixed into mantle with a HSE signature inherited from core formation.     

Enrichment of Rh,Ru, Ir and Os in Cr spinels from oxidized magmas: Evidence from the Ambae volcano,Vanuatu

Experimental studies, performed under oxidized conditions (fO₂ > QFM + 2, where QFM is quartz–fayalite–magnetite oxygen buffer), have shown that Rh, Ru, Ir and Os are strongly compatible with Cr spinel, whereas empirical studies of Cr spinels from ultramafic–mafic rocks suggest that the experimental results may overestimate the partition coefficients. We report laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of platinum-group elements (PGE), Au and Re abundances in Cr spinels from the Ambae volcano, Vanuatu (fO₂ = QFM + 2.5), the Jimberlana layered intrusion, western Australia, and the Bushveld complex, South Africa (fO₂ ～ QFM). The results show that Rh and IPGEs (Iridium-group PGE; Ru, Ir, Os) partition strongly into the Cr spinels that crystallized from the oxidized Ambae lavas whereas most of the Cr spinels from the more reduced Jimberlana layered intrusion and the Bushveld complex contain no detectable PGE, Au or Re, with exception of ～10 ppb of Ir in some Jimberlana Cr spinels. In the Ambae Cr spinels, Rh, Ru and, to lesser extent Os, are positively correlated with Fe³⁺, Ni and V. The homogeneous distribution of Rh and IPGEs in LA-ICP-MS time-resolved spectra indicates that these elements are in solid solution in Cr spinels. Pt–Fe alloys occur as inclusions within the Ambae Cr spinels, which indicate that the Ambae melt was saturated with Pt.Our results show that partitioning of Rh, Ru and Ir into Cr spinels increases with increasing oxygen fugacity, which suggests that the high concentrations of these elements in the Ambae Cr spinels are due to the high oxygen fugacity of the host magma. Therefore, Cr spinels may play an important role in controlling the concentrations of Rh and IPGEs during fractional crystallization of oxidized ultramafic–mafic magmas and during partial melting of oxidized arc mantle.     

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.     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

Petrology and geochemistry of Abyssal Peridotites from the Manipur Ophiolite Complex,Indo-Myanmar Orogenic Belt,Northeast India: Implication for melt generation in mid-oceanic ridge environment

The Manipur Ophiolite Complex (MOC) located in the Indo-Myanmar Orogenic Belt (IMOB) of Northeast India forms a section of the Tethyan Ophiolite Belt of the Alpine–Himalayan orogenic system. Whole rock compositions and mineral chemistry of mantle peridotites from the MOC show an affinity to the abyssal peridotites, characterized by high contents of Al₂O₃ (1.28–3.30 anhydrous wt.%); low Cr# of Cr-spinel (0.11–0.27); low Mg# of olivine (∼Fo₉₀) and high Al₂O₃ in pyroxenes (3.71–6.35 wt.%). They have very low REE concentrations (∑REE = 0.48–2.14 ppb). Lherzolites display LREE-depleted patterns (La_N/Sm_N = 0.14–0.45) with a flat to slightly fractionated HREE segments (Sm_N/Yb_N = 0.30–0.65) whereas Cpx-harburgites have flat to upward-inflected LREE patterns (La_N/Sm_N = 0.13–1.23) with more fractionated HREE patterns (Sm_N/Yb_N = 0.13–0.65) than the lherzolite samples. Their platinum group elements (PGE) contents (<50 ppb) and distinct mantle-normalised PGE patterns with the Pd/Ir values (1.8–11.9) and Pt/Pt^* values (0.2–1.1) show an affinity to the characteristic of the residual mantle material. Evaluation of mineralogical and petrological characteristics of these peridotites suggests that they represent the residues remaining after low degree of partial melting (∼2–12%) in the spinel stability field of a mid-oceanic ridge environment. The well-preserved mid-oceanic ridge characteristics of these peridotites further suggest that the mantle section was subsequently trapped in the forearc region of the subduction zone without undergoing significant modification in their chemistry by later subduction-related tectonic and petrological processes before its emplacement to the present crustal level.     

Platinum mineralization of the Svetly Bor and Nizhny Tagil intrusions,Ural Platinum Belt

This paper presents the results of a detailed mineralogical and micro analytical study of two Ural-Alaskan type intrusions in the Ural Platinum Belt: (1) the dunite-hosted mineralization of the Svetly Bor intrusion, and (2) the chromitite mineralization of the Nizhny Tagil intrusion. Two generations of platinum minerals are typical of both intrusions: magmatic Pt–Fe(Ni) alloys, and post-magmatic Pt(Fe,Ni,Cu) alloys. A trend from ferroan platinum to isoferroplatinum (Pt,Fe → Pt₃Fe) is shown for magmatic alloys of the Svetly Bor intrusion. Magmatic alloys of the Nizhny Tagil intrusion are represented by ferroan platinum (with Ni) only, varying in Fe. The magmatic Pt–Fe alloys of both intrusions were depleted in Fe during the evolution of ore-forming systems and crystallized during the entire magmatic process, generally as fine cubic crystals and anhedral grains hosted by dunite at the magmatic stage during and after the crystallization of dunite (platinum–dunite type of the Svetly Bor intrusion). The evolution of mineral paragenesis was accompanied by a temperature drop, as well as increases in fO₂ and fS₂.Most of the platinum was concentrated in the residual melts together with chromium, and crystallized in the final stage of the magmatic process (platinum–chromite ore of the Nizhny Tagil intrusion). Post-magmatic Pt(Fe,Cu,Ni) alloys formed during the serpentinization of dunite evolved according to a general compositional trend from tetraferroplatinum and ferronickelplatinum to tulameenite and later to Pt–Cu alloy and Pt-oxide (PtFe) → Pt(Fe,Cu,Ni) → Cu₃Pt → Pt–O. Platinum-rich mineralization of both intrusions was formed in the late magmatic stage from a melt rich in volatiles, regardless of their location in dunite or chromitites. Most probably, the rock structure (fracture systems) was the determining factor in the migration of PGE-rich residual melts and ore accumulation.     

Mineral chemistry and geochemical behavior of hydrothermal alterations associated with mafic intrusive-related Au deposits at the Atud area,Central Eastern Desert,Egypt

Vein-type gold deposits in the Atud area are related to the metagabbro–diorite complex that occurred in Gabal Atud in the Central Eastern Desert of Egypt. This gold mineralization is located within quartz veins and intense hydrothermal alteration haloes along the NW–SE brittle–ductile shear zone, as well as along the contacts between them. By using the mass balance calculations, this work is to determine the mass/volume gains and losses of the chemical components during the hydrothermal alteration processes in the studied deposits. In addition, we report new data on the mineral chemistry of the alteration minerals to define the condition of the gold deposition and the mineralizing fluid based on the convenient geothermometers. Two generations of quartz veins include the mineralized grayish-to-white old vein (trending NW–SE), and the younger, non-mineralized milky white vein (trending NE–SW). The ore minerals associated with gold are essentially arsenopyrite and pyrite, with chalcopyrite, sphalerite, enargite, and goethite forming during three phases of mineralization; first, second (main ore), and third (supergene) phases. Three main hydrothermal alteration zones of mineral assemblages were identified (zones 1–3), placed around mineralized and non-mineralized quartz veins in the underground levels. The concentrations of Au, Ag, and Cu are different from zone to zone having 25–790 ppb, 0.7–69.6 ppm, and 6–93.8 ppm; 48.6–176.1 ppb, 0.9–12.3 ppm, and 39.6–118.2 ppm; and 53.9–155.4 ppb, 0.7–3.4 ppm, and 0.2–79 ppm for zones 1, 2, and 3, respectively.The mass balance calculations and isocon diagrams (calculated using the GEOISO-Windows program) revealed the gold to be highly associated with the main mineralized zone as well as sericitization/kaolinitization and muscovitization in zone 1 more than in zones 2 and 3. The sericite had a higher muscovite component in all analyzed flakes (average X_Ms = 0.89), with 0.10%–0.55% phengite content in wall rocks and 0.13%–0.29% phengite content in mineralized quartz veins. Wall rocks had higher calcite (CaCO₃) contents and lower MgCO₃ and FeCO₃ contents than the quartz veins. The chlorite flakes in the altered wall rocks were composed of pycnochlorite and ripidolite, with estimated formation temperatures of 289–295 °C and 301–312 °C, respectively. Albite has higher albite content (95.08%–99.20%) which occurs with chlorite in zone 3.     

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.     

Insights into the extreme PGE enrichment of the W Horizon,Marathon Cu-Pd deposit,Coldwell Alkaline Complex,Canada: Platinum-group mineralogy,compositions and genetic implications

The W Horizon, Marathon Cu-Pd deposit in the Mesoproterozoic Midcontinent rift is one of the highest grade PGE repositories in magmatic ore deposits world-wide. The textural relationships and compositions of diverse platinum-group mineral (PGM) and sulfide assemblages in the extremely enriched ores (>100 ppm Pd-Pt-Au over 2 m) of the W Horizon have been investigated in mineral concentrates with ∼10,000 PGM grains and in situ using scanning electron microprobe and microprobe analyses.Here we show, from ore samples with concentrations up to 23.1 Pd ppm, 8.9 Pt ppm, 1.4 Au ppm and 0.73 Rh ppm, the diversity of minerals (n = 52) including several significant unknown minerals and three new mineral species marathonite (Pd₂₅Ge₉; McDonald et al., 2016), palladogermanide (Pd₂Ge; IMA 2016-086, McDonald et al., 2017), kravtsovite (PdAg₂S, IMA No 2016-092, Vymazalová et al., 2017). The PGM are distributed as PG-, sulfides (52 vol%), -arsenides (34 vol%), -intermetallics of Au-Ag-Pd-Cu and Pd-Ge(10 vol%) and -bismuthides and tellurides (4 vol%). The discovery of abundant (>330 grains) large unknown sulfide minerals with Rh allows us to present analyses three significant potentially new minerals (WUK-1, WUK-2, WUK-3) that are all clearly enriched in Rh (averaging 4.2, 8.5 and 28.21 wt% Rh respectively). Several examples of paragenetic sequences and mineral chemical changes for enrichment of Cu, Pd and Rh with time are revealed in the PGM and base-metal sulfides. We suggest this enhanced metal enrichment formed in response to increasing fO₂ causing the oxidation of Fe²⁺ to Fe³⁺ and to a lesser extent, S.Phase relations in the Ag-Pd-S, Rh-Ni-Fe-S, Pd-Ge, Au-Pd-Cu-Ag, Pd-Ag-Te systems help constrain the crystallization temperatures of the majority of ore minerals in the W Horizon at ∼500 °C or moderate to high subsolidus temperatures (400–600 °C). Local transport by aqueous fluids becomes evident as minerals recrystallize down to <300 °C. The PGE-enriched W Horizon ores exhibit a complex post-magmatic history dominated by the effects of oxidation during cooling of a Cu-PGE enriched magma source from a deep reservoir.     

Water content in minerals of mantle xenoliths from the Udachnaya pipe kimberlites (Yakutia)

Distribution of water among the main rock-forming nominally anhydrous minerals of mantle xenoliths of peridotitic and eclogitic parageneses from the Udachnaya kimberlite pipe, Yakutia, has been studied by IR spectroscopy. The spectra of all minerals exhibit vibrations attributed to hydroxyl structural defects. The content of H₂O (ppm) in minerals of peridotites is as follows: 23–75 in olivine, 52–317 in orthopyroxene, 29–126 in clinopyroxene, and 0–95 in garnet. In eclogites, garnet contains up to 833 ppm H₂O, and clinopyroxene, up to 1898 ppm (~ 0.19 wt.%). The obtained data and the results of previous studies of minerals of mantle xenoliths show wide variations in H₂O contents both within different kimberlite provinces and within the Udachnaya kimberlite pipe. Judging from the volume ratios of mineral phases in the studied xenoliths, the water content varies over narrow ranges of values, 38–126 ppm. At the same time, the water content in the studied eclogite xenoliths is much higher and varies widely, 391–1112 ppm.     

Platinum-group elements in ores from the Kalmakyr porphyry Cu–Au–Mo deposit, Uzbekistan: bulk geochemical and laser ablation ICP-MS data

We studied primary ore samples from Kalmakyr, a giant Cu–Au–Mo porphyry deposit in eastern Uzbekistan. Disseminated and stockwork-type high-grade Cu–Au–Mo mineralization showed average concentrations of 55 ppb Pd, 5.5 ppb Pt, 0.95 ppb Rh, 0.49 ppb Ir, and 4.1 ppm Au (n = 8). This type of mineralization is characterized by the presence of pyrite, chalcopyrite, molybdenite, and gold. A peak Pd content of 292 ppb was determined in a base-metal-rich quartz vein in granodiorite porphyry, which contains galena, sphalerite, chalcopyrite, tetrahedrite, and gold. Palladium correlates with Cu, Ag, Se, and S. Mineralogical and laser ablation ICP-MS study confirmed that Pd is homogeneously distributed in chalcopyrite, which contains up to 110 ppm Pd, and tetrahedrite, containing up to 20 ppm Pd. An assessment of the Pd and Pt budget at Kalmakyr showed the potential of approximately 17 t of Pd and 1.7 t of Pt.     

Petrogenesis and mineralization of the Hulu Ni-Cu sulphide deposit in Xinjiang,NW China: constraints from Sr-Nd isotopic and PGE compositions

The Permian Hulu intrusion is one of several sulphide-bearing Permian mafic–ultramafic intrusions in the eastern part of the eastern Tianshan located at the southern margin of the Central Asian Orogenic Belt (CAOB) in Xinjiang, NW China. The intrusion is composed of lherzolite, olivine websterite, gabbro, and gabbro-diorite. Disseminated and net-textured Ni-Cu sulphide ores are located at the bottom of the lopolith complex. Negative Zr, Hf, Nb, and Ta anomalies, whole-rock εNd(t) values of +5.7 to +8.8, and variable (Th/Nb)_PM values (from 1.06 to 8.13) suggest that the source of the Hulu complexes is depleted mantle metasomatized by subducted slab-derived fluid and/or melt (~5% global subducted sediment and 15% slab fluid) that has experienced approximately 3% lower crustal and 10% upper crustal contamination. The Hulu intrusion is characterized by low PGE abundances i.e. 0.03–1.08 ppb Ir, 0.04–0.69 ppb Ru, 0.02–2.15 ppb Rh, 0.30–48.71 ppb Pt, and 0.21–344 ppb Pd. Our calculations indicate that if the Pd, Os, Ir, and Cu contents of the primary magma were 2.1 ppb, 0.03 ppb, 0.05 ppb, and 200 ppm, respectively, a variable R-factor between 200 and 1600 with residual magma that had experienced 0.01% early-sulphide segregation can explain the variation in Pd, Os, and Ir contents of sulphide-poor and disseminated sulphide samples of the Hulu deposit. Basaltic magma fractionation and assimilation and/or contamination of sulphur-bearing crustal materials might have triggered sulphur saturation to form Cu-Ni sulphide ores. Tarim basaltic PGE contents cannot be used as the mineralized parent magma for the Hulu intrusion because of the differing evolutionary trends of the Ni/Pd and Cu/Ir values. However, similar Cu/Ni and Pd/Ir values in Tarim basalts and Hulu Cu-Ni sulphide ores, as well as the same early sulphide segregation process, show that certain genetic relationships between them and magma sources are probably similar to each other.     

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.     

Field and geochemical characteristics of Mesoarchean to Neoarchean volcanic rocks in the Storø greenstone belt,SW Greenland: Evidence for accretion of intra-oceanic volcanic arcs

The Storø greenstone belt, southern West Greenland, consists of thrust-imbricated slices of Mesoarchean (>3060 Ma) and Neoarchean (ca. 2800 Ma) mafic to ultramafic volcanic rocks, volcaniclastic sediments, and gabbro–anorthosite associations. The belt underwent polyphase metamorphism at upper amphibolite facies conditions between 2650 and 2600 Ma. The contacts between the Mesoarchean and Neoarchean volcanic rocks, and surrounding Eoarchean to Neoarchean tonalite–trondhjemite–granodiorite (TTG) gneisses are tectonic and typically bounded by high-grade mylonites. Regardless of age, the volcanic rocks are dominated by mafic amphibolites with a tholeiitic basalt composition, near-flat to slightly enriched light rare earth element (LREE) patterns (La/Sm_cn = 0.91–1.48), relatively flat to slightly depleted heavy-REE (HREE) (Gd/Yb_cn = 1.0–1.28), and pronounced negative Nb–Ta anomalies (Nb/Nb* = 0.34–0.73) on chondrite- and primitive mantle-normalized diagrams. These geochemical characteristics are consistent with subduction zone geochemical signatures and partial melting of a shallow (<80 km) mantle source free of residual garnet. There is no geochemical evidence for contamination by older continental crust. The overall field and geochemical characteristics suggest that the thrust-imbricated basaltic rocks were erupted in intra-oceanic subduction zone settings. Sedimentary rocks are represented by garnet–biotite and quartzitic gneisses. They are characterized by relatively high contents of transition metal (Ni = 10–154 ppm; Cr = 7–166 ppm) and enriched LREE patterns (La/Sm_cn = 1.38–3.79). These geochemical characteristics suggest that the sedimentary rocks were derived from erosion of felsic to mafic igneous source rocks. Collectively, the structural and lithogeochemical characteristics of the Storø greenstone belt are consistent with collision (accretion) of unrelated Archean volcanic rocks formed in supra-subduction zone geodynamic settings. Accordingly, the Mesoarchean and Neoarchean rock record of the Storø greenstone belt may well be explained in terms of modern-style plate tectonic processes.