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In magmatic Nickel-Copper-Platinum-group elements (Ni-Cu-PGE) sulfide deposits, PGE occur as solid solution in base metal sulfides (BMS) or occur as platinum-group minerals (PGM). In different deposits, such as the world-class deposits at Jinchuan and Noril’sk district which formed from sulfide liquids with different oxygen fugacity (fO2), the proportion of PGE forming PGMs and entering BMS as solid solution are variable and the PGMs are different in mineral species and morphology. The early-cumulated massive ores from the two deposits were analyzed using Electron Probe Microanalysis (EPMA), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), Scanning Electron Microscope (SEM) and Focused Iron Beam and Transmission Electron Microscope (FIB-TEM). Combined with whole-rock PGE and semimetals data, this contribution discusses the effect of thermodynamic conditions (mostly fO2) and semimetals on the distribution of PGE and the mineral species and morphology of PGM in magmatic sulfide deposits. The Noril’sk massive ores commonly contain 5–12 vol% of magmatic magnetite whereas magnetite is absent in the Jinchuan massive ores, which suggests that the sulfide liquid at Noril’sk had a higher oxygen fugacity (fO2) compared to the sulfide liquid at Jinchuan. In the Jinchuan massive ores, only ∼ 39 % Ir and 37 % Rh are presented in solid solution within BMS. Meanwhile, many (Ir-Rh-Pt)AsS crystals with grain sizes of 200 nm to 2.5 μm were recognized enclosed in BMS grains and cobaltite-gersdorffite solid solution (CGSS) or rarely located at BMS grain boundaries. Microstructures of the (Ir-Rh-Pt)AsS minerals suggests that they probably crystallized from the sulfide liquid together with MSS. In contrast, more than 63 % Ir and 89 % Rh are presented in solid solution within BMS and no (Ir-Rh-Pt)AsS crystal was found in the Noril’sk massive ores. On the other hand, arsenides, stannide, antimonides, tellurides and bismuthides of Pd and/or Pt (Pt-Pd-semimetal minerals) were found in the Jinchuan and Noril’sk massive ores. This study suggests that thermodynamic conditions (especially fO2) control the valence states of semimetals (especially As) affecting the behavior of PGE in sulfide liquids. A relatively low fO2 of sulfide liquids leads to a relatively high Asn-/Asn+ ratio, which is atomical ratio of the anion to cation of As (n represents valence number), and results in relative more Ir-AsS, Rh-AsS and Pt-As pre-nucleation clusters. These pre-nucleation clusters were enriched in or near the migrating MSS grain boundaries and finally reaching oversaturation and nucleation of (Ir-Rh-Pt)AsS crystals occurred. In contrast, a relatively high oxygen fugacity (fO2) of sulfide liquids results in a low Asn-/Asn+ ratio and Ir-AsS, Rh-AsS and Pt-As pre-nucleation clusters forming a negligible amount of (Ir-Rh-Pt)AsS minerals and facilitating Ir and Rh to enter MSS crystal lattice. As for the deposits formed from sulfide liquids with a relatively low fO2, such as the deposits at Jinchuan, Yangliuping and Sudbury, the fractional crystallization of MSS together with (Ir-Rh-Pt)AsS minerals resulted in PGE differentiation.

The giant Bayan Obo REE deposit bears a large amount of iron resources as well. However, the genesis of iron mineralization is still highly controversial with limited research. In this study, new data of trace elements of magnetite from Bayan Obo ores, Eastern contact zone skarn and Heinaobao BIF are obtained by Laser ablation (LA) ICP-MS analyses, revealing the genesis of Bayan Obo iron resources through comparing study. The Bayan Obo deposit contains disseminated, banded and massive ores, and in which magnetite is associated with REE minerals, fluorite, aegirine, riebeckite, and biotite. Euhedral magnetite in the skarn of Eastern contact zone is usually associated with pyrite, biotite, fluorite, and bastnaesite. There are two types of magnetite in the Heinaobao BIF: (1) euhedral to subhedral magnetite associated with quartz and a small amount of amphibole; (2) anhedral magnetite associated with quartz, garnet, plagioclase, amphibole and biotite. Magnetite in the Bayan Obo is enriched in Ni, but depleted in Mg, Al, Ti, Ge, Mn, Ga and Zn, showing low and variable concentrations, which is similar to the hydrothermal magnetite. The contents of some trace elements (e.g. Ti, Mn, Sc, Zn, Nb and REE) of magnetite from the skarn ores are generally higher, indicating a relatively high formation temperature. Magnetite in the Heinaobao BIF is generally characterized by low and uniform trace element contents, except for the abnormal values of Ti, Al, Cr and Mn, suggesting the involvement of terrigenous clastic materials. Compared with Bayan Obo magnetite, the skarn magnetite has the highest Sn/Ga, Co/Ni, Nb/Ta, La/Yb, Ti/V and Ti/Al ratios, while magnetite in the BIF has the highest Al/Co and lowest Nb/Ta ratios. The significant difference in mineralogical and trace element characteristics among the three types of magnetite indicates that the iron resources in Bayan Obo deposit are unlikely to be a skarn Fe deposit nor a BIF deposit. However, the Bayan Obo magnetite shows similar geochemical characteristics to hydrothermal magnetite related to carbonatite, both of which are depleted in high field strength elements, such as Zr, Hf and Ta, and show strong positive anomalies of Mn and Zn and negative anomalies of Co and Ga. In addition, in the diagrams of Ti vs. Nb + Ta and Ti vs. Zr + Hf, the Bayan Obo magnetite falls into the field of hydrothermal magnetite associated with carbonatite. In conclusion, it is recommended that the Bayan Obo iron deposit is a typical hydrothermal deposit related to carbonatite. In this contribution, the skarn magnetite formed at high temperature and the BIF magnetite was contaminated by terrigenous materials deviating from the expected region in discriminant diagrams. It is therefore proposed that the validity of these diagrams depends on a full understanding of mineralogical characteristics of samples and magnetite precipitation environment, and that multiple discrimination diagrams should be used in combination.

The sediment-hosted Haerdaban Zn-Pb deposit is a newly discovered Zn-Pb deposit in the Sailimu terrane, Western Tianshan (NW China), containing ca. 0.64 Mt of ore at 6.19 wt% Zn and 1.09 wt% Pb. The mineralization consists mainly of veins, breccias and semi-massive sulfide ores within the dolomitic limestone and calcareous slate. Using LA-ICP-MS, this study investigates trace element and sulfur isotope composition of sulfide to constrain the genesis of the deposit. Four pyrite types were identified by variations in texture and composition. Porous pyrite (Py1) shows a significant enrichment in Mn, Ag, Sb, Tl, Ba, Pb, Cu, and Zn, whereas the pyrite overgrowth (Py2) and euhedral pyrite (Py3) are enriched in Co and As, but depleted in all other trace elements. This compositional trend is attributed to the release of trace elements from pyrite during recrystallization from a porous to massive texture. Pyrite (Py4) associated with sphalerite is inclusion-rich, but exhibits a depletion in most trace elements, except Ni and Sb. The underlying carbonaceous sediments are interpreted as a source of Ni, Sb and other metals for the ore-forming fluids. Sphalerite displays a wide variety of colors from dark brown to pale yellow, primarily related to variations in Fe contents. The overall Fe contents (0.25 to 6.12 wt%), Cd contents (524 to 1875 ppm) and Zn/Cd ratios (320 to 1258) in sphalerite are compatible with those of SEDEX Zn-Pb deposit. The contents of other elements in sphalerite are generally low. Calculated temperatures using trace element contents in sphalerite (GGIMFis geothermometer) range from 163 °C to 309 °C, indicating progressive cooling of ore-forming fluid. Pyrite, sphalerite and galena display a wide range of δ34S values from +3.9 to +18.3‰. The association of lower positive δ34S values (+3.9 to +8.8‰) and epithermal suite elements (Ni, As, Sb, and Tl) enrichment in porous pyrite indicate that sulfur in early sulfides was derived from thermochemical sulfate reduction (TSR) with a possible magmatic input. The dominant population of heavier δ34S values (+13.8 to +18.3‰) of massive sulfide support TSR as the main source of sulfur. The intermediate δ34S values (+7.0 to +13.0‰) of vein sulfide are likely a mixing of TSR-derived sulfur with light sulfur leached from diagenetic pyrite. The current data support the classification of Haerdaban as a metamorphosed SEDEX Zn-Pb deposit, where the main mineralization was the product of remobilization and upgrading of early exhalative ores during hydrothermal events.

The newly discovered Huangtan Au-Cu deposit is located in the central Dananhu - Tousuquan arc of Eastern Tianshan, southern Central Asian Orogenic Belt (CAOB). It is the first Au-dominated volcanogenic massive sulfide (VMS) polymetallic deposit in the Eastern Tianshan. Veinlet-disseminated and massive orebodies are hosted within Early Silurian pyritic phyllic tuff and volcanic breccia and controlled by a secondary fracture zone of the Kalatag fault with extensive hydrothermal alteration. Four primary alteration/mineralization stages have been recognized as follows: (1) Early ore stage (S1), forming mainly ore-barren fine quartz veins with minor gold-bearing sulfides; (2) main ore stage (S2), forming mainly thick quartz veins with abundant coarse-grained subhedral pyrite (S2-1), and plentiful chalcopyrite, sphalerite, barite and Au-bearing sulfide veins (S2-2); (3) late ore stage (S3), which is characterized by plenty of barren quartz–calcite veins with few sulfides; and (4) supergene stage (S4), accompanied by abundant oxide mineralization, including malachite, jarosite and other supergene minerals. From S1 to S3, microthermometric data of fluid inclusions show homogenization temperatures of 263–379 °C (mean = 308 °C), 188-292 °C (mean = 240 °C), and 118-198 °C (mean = 158 °C), respectively, and salinities of 5.3–14.2 (mean = 10.8) wt.% NaCl equiv., 2.8–10.7 (mean = 7.6) wt.% NaCl equiv., and 0.3–14.1 (mean = 2.6) wt.% NaCl equiv., respectively. The ore-forming fluids are characterized by middle-low temperature, low salinity, relatively reduced condition, and an H2O-NaCl ± CO2 ± CH4 system. The δ34S values (−5.25‰ to 0.50‰) and Pb isotopic ratios (206Pb/204Pb = 17.868–19.495, 207Pb/204Pb = 15.446–15.575, and 208Pb/204Pb = 37.350–38.491) suggest that the ore-forming materials came predominantly from a deep-seated magma source with a minor contribution of lower continental crust. The δ18OH2O and δDV-SMOW values of fluid inclusions in each metallogenic stage range from −6.1 to 5.6‰ and −66.8 to −53.9‰, respectively, suggesting the dominant role of magmatic water mixed with convectively circulating heated seawater during fluid evolution. Fluid cooling dilution, local boiling, and fluid mixing were considered as the main mechanisms of metal precipitation. The 40Ar-39Ar plateau age of hydrothermal muscovite from the late ore stage (S3) is 414.4 ± 0.4 Ma, which represents the upper limit age of shallow hydrothermal alteration and Au-Cu mineralization. It is also consistent with the Early Silurian polymetallic metallogenic event in the Kalatag district. The auriferous Huangtan and adjacent Cu-Zn-rich Huangtupo VMS deposits show obvious ore-forming element differences, and constitute a unique VMS metallogenic system in the Eastern Tianshan Orogenic Belt (ETOB), which provides an important research object and new insight for ore prospecting in the peripheral Gobi Desert area.

Nelsonite and Fe–Ti oxides ore are common in Proterozoic massif-type anorthosites and layered intrusions. Their geneses have long been controversial, with existing hypotheses including liquid immiscibility between Si-rich and Fe–Ti–P-rich melts and gravitational fractionation among apatite, magnetite, ilmenite and silicates. In this paper, we report detailed field geology and mineral geochemical studies of the nelsonite and Fe–Ti oxides ore from the Damiao anorthosite complex, NE China. Geological observations indicate that the nelsonite and Fe–Ti oxides ore occur as irregularly inclined stratiform-like or lensoid or veins, and are in sharp contact with the anorthosite and gabbronorite. The widespread veins and lenses structure of the Damiao nelsonite and Fe–Ti oxides ore in the anorthosite indicates their immiscibility-derived origin. The apatite in the nelsonite and gabbronorite shows evolution trends different from that in the gabbronorite in the diagrams of Sr versus REEs and Eu/Eu*, suggesting that petrogenesis of the nelsonite and gabbronorite is different from the gabbronorite. Compared with the gabbronorite, the nelsonite and Fe–Ti oxides ore have magnetite high in Cr, plagioclase high in Sr and low in An, and apatite high in Sr, low in REEs with negative Eu anomaly. The evidence permits us to propose that the Damiao Fe–Ti oxides ore/nelsonite and gabbronorite were derived from different parental magmas. The gabbronorite was formed by solidification of the interstitial ferrodioritic magma in the anorthosite, which was the residual magma after extensive plagioclase and pyroxene crystallization and was carried upward by the plagioclase crystal mesh. In contrast, the Fe–Ti oxides ore and nelsonites and mangerite were produced by crystallization of the Fe–Ti–P-rich and SiO2-rich magmas, respectively, due to the liquid immiscibility that occurred when the highly evolved ferrodioritic magma mixed with newly replenished magmas. The variation from Fe–Ti oxides ore to nelsonite and gabbro-nelsonite upwards (as apatite content increases with height) in the steeply inclined Fe–Ti oxides orebodies suggest that gravity fractionation may have played important roles during the crystallization of the Fe–Ti–P-rich magma.

The concentrations of platinum-group elements (PGE) and semimetal elements (As, Sb, Se, Te and Bi) in the base metal sulfides from the Yangliuping deposit were determined using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). Mass balance calculation reveals that the base metal sulfides only contain Cu-(PGE) sulfide deposits. Euhedral shape and similar chemical composition of the nanometer-size PGE-arsenides and sulfarsenides in the base-metal sulfides suggest that they crystallized from the sulfide melt before the crystallization of monosulfide solid solution (MSS) and intermediate solid solution (ISS). It is proposed that the nanometer-size PGE-arsenides and sulfarsenides formed from PGE-As molecular or polymolecular clusters in the sulfide liquid at high temperature. The PGE-As molecular or polymolecular clusters prevent As and PGE from partitioning into the base metal sulfide lattice and tend to form discrete nanometer-size PGE-arsenides and sulfarsenides. Thus, semimetal elements, particularly As, play an important role on behaviour of PGE during solidification of magmatic sulfide liquids.

The Fenghuangshan deposit is a typical Cu–Fe–Au skarn deposit in the Tongling area, Anhui province, Eastern China. The deposit has a paragenetic sequence of a prograde skarn stage, followed by a retrograde skarn stage, and a final quartz–sulfide and carbonate stages. Magnetite in the Fenghuangshan deposit mainly formed in the retrograde and carbonate stages. According to the morphology of magnetite and mineral assemblage of ores, we divided magnetite-bearing ores into three groups. Group 1 (early retrograde skarn stage) is represented by a mineral assemblage of magnetite and chalcopyrite. Group 2 (late retrograde skarn stage) has a mineral assemblage of magnetite, chalcopyrite, and wollastonite with characteristic ring-like magnetite. Group 3 (carbonate stage) is characterized by large amounts of calcite veins crosscut or associated with magnetite and intensive hematization of magnetite crosscut by the veins. Laser ablation (LA)–ICP–MS was used to determine trace element concentrations of magnetite from the three mineralization stages. Positive correlations among Mg, Al, Ca, and Si in magnetite indicate that these lithophile elements have similar behavior during the skarn formation process. Calcium is an important discriminant element for magnetite in skarn deposits. Positive correlations are also evident for Pb, Sn and W in magnetite, which also indicates their similar behavior. In general, magnetite grains of different stages have similar normalized trace element patterns, indicating that they share a common source. However, some elements such as Co and Mn in magnetite decrease from early retrograde skarn stage, late retrograde skarn stage to carbonate stage, which may be attributed to the precipitation of coexisting minerals (sulfides and carbonates) or the decreasing temperature. Magnetite grains of the retrograde stage have higher Mg + Mn and Si + Al contents than those of the carbonate stage, indicating a decreasing degree of fluid–rock interaction during the skarn formation process. Trace element data of skarn magnetite indicate a more widely compositional variation than previously suggested. Magnetite from the Fenghuangshan Cu–Fe–Au deposit has similar composition to those from other Cu, Cu–Fe or Cu polymetallic skarn deposits, but different from those from Fe skarn deposits, such that magnetite composition is very powerful in establishing the origin of skarn deposits.

The factors and processes that control trace-element partitioning among co-crystallizing cumulus minerals in layered intrusions have long been controversial. Here we address this issue using new laser ablation ICP-MS trace element data for magnetite, ilmenite, and clinopyroxene from the Panzhihua layered intrusion in the Emeishan large igneous province, SW China. The cumulus minerals display strong Ni, Co, and Cr depletions, indicative of parental magmas low in concentration of these elements probably due to prior sulfide removal and the fractionation of chromite or Cr-magnetite in a staging magma chamber at depth. Both magnetite and clinopyroxene show cyclical variations in some transition elements (e.g., Cr, V, and Ni) along the stratigraphic section. The average concentrations of these transition elements in magnetite are positively correlated with those in clinopyroxene, likely resulting from co-crystallization of magnetite and clinopyroxene. The incompatible element (e.g., Zr, Hf, and Nb) concentrations of the cumulus minerals from the Lower Zone are highly variable compared to those of the Middle and Upper Zones. These large variations in trace element compositions are attributed to a “trapped liquid shift” in the Lower Zone. Ilmenite crystals from the Panzhihua intrusion may have undergone extensive modification of transition elements during subsolidus re-equilibration with magnetite, leading to the decoupled variations of transition elements in ilmenite across the Lower Zone stratigraphy. Our study indicates that systematic trace element variations of the main cumulus mineral assemblage, rather than a single mineral, need to be considered to better constrain the magmatic differentiation and elemental fractionation of layered intrusions.