Re–Os isotope and platinum-group element geochemistry of the Pobei Ni–Cu sulfide-bearing mafic–ultramafic complex in the northeastern part of the Tarim Craton

A number of mafic–ultramafic intrusions that host Ni–Cu sulfide mineralization occur in the northeastern Tarim Craton and the eastern Tianshan Orogenic Belt (NW China). The sulfide-mineralized Pobei mafic–ultramafic complex is located in the northeastern part of the Tarim Craton. The complex is composed of gabbro and olivine gabbro, cut by dunite, wehrlite, and melatroctolite of the Poyi and Poshi intrusions. Disseminated Ni–Cu sulfide mineralization is present towards the base of the ultramafic bodies. The sulfide mineralization is typically low grade (<0.5 wt.% Ni and <2 wt.% S) with low platinum-group element (PGE) concentrations (<24.5 ppb Pt and <69 ppb Pd); the abundance of Cu in 100 % sulfide is 1–8 wt.%, and Ni abundance in 100 % sulfide is typically >4 wt.%. Samples from the Pobei complex have εNd (at 280 Ma) values up to +8.1, consistent with the derivation of the magma from an asthenospheric mantle source. Fo 89.5 mol.% olivine from the ultramafic bodies is consistent with a primitive parental magma. Sulfide-bearing dunite and wehrlite have high Cu/Pd ratios ranging from 24,000 to 218,000, indicating a magma that evolved under conditions of sulfide saturation. The grades of Ni, Cu, and PGE in 100 % sulfide show a strong positive correlation. A model for these variations is proposed where the mantle source of the Pobei magma retained ~0.033 wt.% sulfide during the production of a PGE-depleted parental magma. The parental magma migrated from the mantle to the crust and underwent further S saturation to generate the observed mineralization along with its high Cu/Pd ratio at an R-factor varying from 100 to 1,200. The mineralization at Poshi and Poyi has very high γOs (at 280 Ma) values (+30 to +292) that are negatively correlated with the abundance of Os in 100 % sulfide (5.81–271 ppb) and positively correlated with the Re/Os ratios; this indicates that sulfide saturation was triggered by the assimilation of crustal sulfide with both high γOs and Re/Os ratios. When compared to other Permian mafic–ultramafic intrusions with sulfide mineralization in the East Tianshan, the Poyi and Poshi ultramafic bodies were formed from more primitive magmas, and this helps to explain why the sulfide mineralization has high Ni tenor.     

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.     

Geochemistry of the Kalatongke Ni–Cu–(PGE) sulfide deposit,NW China: implications for the formation of magmatic sulfide mineralization in a postcollisional environment

The Kalatongke (also spelt as Karatungk) Ni–Cu–(platinum-group element, PGE) sulfide deposit, containing 33 Mt sulfide ore with a grade of 0.8 wt.% Ni and 1.3 wt.% Cu, is located in the Eastern Junggar terrane, Northern Xinjiang, NW China. The largest sulfide ore body, which occupies more than 50 vol.% of the intrusion Y1, is dominantly comprised of disseminated sulfide with a massive sulfide inner zone. Economic disseminated sulfides also occur at the base of the intrusions Y2 and Y3. The main host rock types are norite in the lower part and diorite in the upper part of each intrusion. Enrichment in large ion lithophile elements and depletion in heavy rare earth elements relative to mid-ocean ridge basalt indicate that the mafic intrusions were produced from magmas derived from a metasomatized garnet lherzolite mantle. The average grades of the disseminated ores are 0.6 wt.% Ni and 1.1 wt.% Cu, whereas those of the massive ores are 2 wt.% Ni and 8 wt.% Cu. The PGE contents of the disseminated ores (14–69 ppb Pt and 78–162 ppb Pd) are lower than those of the massive ores (120–505 ppb Pt and 30–827 ppb Pd). However, on the basis of 100% sulfide, PGE contents of the massive sulfides are lower than those of the disseminated sulfides. Very high Cu/Pd ratios (>4.5 × 10⁴) indicate that the Kalatongke sulfides segregated from PGE-depleted magma produced by prior sulfide saturation and separation. A negative correlation between the Cu/Pd ratio and the Pd content in 100% sulfide indicates that the PGE content of the sulfide is controlled by both the PGE concentrations in the parental silicate magma and the ratio of the amount of silicate to sulfide magma. The negative correlations between Ir and Pd indicate that the massive sulfides experienced fractionation.     

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.     

中国西部典型铜镍矿床亲铜元素特征对比

通过对喀拉通克、黄山东、金川和白马寨4个铜镍矿床亲铜元素特征进行比较,结果发现所有矿床具有相似的左倾原始地幔标准化配分模式和铂族元素明显亏损的共同特点;其亲铜元素质量分数却明显不同,铂族元素质量分数最高的金川铜镍矿床以Ni为主,喀拉通克矿床则表现为Cu占优势;矿床的初始岩浆为铂族元素不亏损的玄武质岩浆,应是地幔岩石较高程度部分熔融的产物;少量硫化物预先熔离是造成中国铜镍矿床成矿母岩浆亏损铂族元素和w（Cu）/w（Pd）远大于原始地幔（w（Cu）/w（Pd））的控制因素;不同程度（量）的硫化物熔离导致母岩浆中亲铜元素质量分数不同,R值低不是主要原因;早期发生硫饱和可能是铜镍矿床成矿的必要条件,成矿的关键可能在于新鲜岩浆的不断补给;少量硫化物预先熔离结合不含矿岩石亏损铂族元素,暗示这些矿区深部具有找矿潜力。     

Genesis of the Permian Baimazhai magmatic Ni–Cu–(PGE) sulfide deposit, Yunnan, SW China

The ~260 Ma-old Baimazhai Ni–Cu–(PGE) sulfide deposit in the Jinping region, Yunnan, SW China, is hosted in a small mafic–ultramafic intrusion, which intruded Ordovician sandstone and slate. The intrusion is concentric with lens shape, about 530 m long, 190 m wide and 24 to 64 m thick, trends 296°, and dips 22°NE. The massive sulfide ore body forms the core of the intrusion and is surrounded by variably mineralized orthopyroxenite, websterite and barren gabbro. The proportion of gabbro, websterite, orthopyroxenite and massive ore is approximately 30, 30, 20 and 20 vol.%, respectively. Magmatic pyrrhotite, pentlandite and chalcopyrite make up more than 90% of the massive ores. The massive ores contain high Ni (1.6 to 4.2 wt%) and Cu (0.4 to 6.5 wt%) and low ∑PGE contents (85 to 524 ppb). They have Pd/Ir ratios ranging from 6.7 to 530, Pd/Pt ratios from 0.7 to 2.6 and Cu/(Pd×1,000) ratios from 31 to 400, which are comparable with those of the silicate rocks [Pd/Ir = 4 to 183, Pd/Pt = 0.7 to 3.5, and Cu/(Pd×1,000) = 100 to 400]. Similar Pd/Pt and Cu/Pd ratios of the silicate rocks and massive ores throughout the intrusion indicate a single sulfide segregation event. Excess sulfide melt segregation resulted from intensive crustal contamination that formed Si-rich and Mg-rich basaltic magmas in a deep-seated staging chamber before magma emplacement. The immiscible sulfide melts and the silicate melts were eventually evacuated from the staging magma chamber by compressive forces. Flow differentiation under high velocity concentrated the sulfide melts toward the middle of the magma flow, and consequently, formed a massive sulfide ore body in the central part of the intrusion. Low concentrations of PGEs and general absence of platinum-group minerals in the massive ores may have resulted from a relatively large mass fraction of the sulfide melts (e.g. R-factor = ~70) in Baimazhai compared with other intrusions elsewhere, such as Noril’sk-Talnakh with a R-factor of >10,000.     

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.     

亲铜元素的地球化学行为研究进展及其在岩浆硫化物矿床中的应用

亲铜元素在岩浆演化和硫化物熔离过程中的行为是解释岩浆硫化物矿床形成过程的一个窗口,通过实验研究来探讨亲铜元素的地球化学行为,并用于岩浆硫化物矿床的定量化研究是此类矿床今后的一个发展方向。本文总结了硫和亲铜元素在岩浆演化过程中的行为规律,并阐明了在岩浆硫化物矿床中的应用,在如下五个方面分别做了讨论：① 通过实验对玄武质岩浆中S溶解度的研究,总结出引起硫化物饱和的4个控制因素: 岩浆混合、温度迅速降低、壳源混染、快速的结晶分异作用;② 通过Ni在橄榄石和硅酸盐熔浆中的分配,定量模拟了岩浆演化过程中,橄榄石中的Ni含量随着橄榄石成分（Fo）变化的规律;③ 总结了Ni—Cu—PGE—Au在液态硫化物和硅酸盐岩浆中的分配系数,总结了控制分配系数的因素,并探讨了“R因素”对亲铜元素富集的控制机理;④ 橄榄石被硫化物包围时,与硫化物发生交换反应,通过交换反应系数（KD）可以定量估算硫化物熔浆中Ni的含量;⑤ 通过实验得出的亲铜元素在单硫化物固溶体（MSS）和液态硫化物之间的分配,总结了岩浆铜镍硫化物矿床中的分带现象。最后探讨了岩浆硫化物矿床存在的问题和发展方向。     

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.     

东天山黄山东铜镍矿床铂族元素地球化学特征及其意义

黄山东岩体位于东天山北部的土墩—黄山—镜儿泉—图拉尔根镁铁—超镁铁质岩带中段,受康古尔塔格—黄山深大断裂控制,是由二辉橄榄岩、橄榄辉长岩、辉长苏长岩和辉长闪长岩组成的复式岩体。黄山东铜镍硫化物矿床镁铁质岩石和矿石中的铂族元素(PGE)含量很低,其中IPGE(Os, Ir, Ru, Rh)与PPGE(Pt, Pd)含量相近,PPGE略高于IPGE。岩石平均2×10-9,矿石平均86×10-9。在矿石中,PGE含量与硫含量呈正相关关系。在原始地幔标准化图解上,岩石和矿石具有相似的分配模式,PPGE和IPGE之间分异很弱。Ni/Cu—Pd/Ir关系图以及岩石地球化学资料显示,形成黄山东岩体的原始岩浆为MgO含量较高的PGE不亏损的拉斑玄武质岩浆。岩浆在上升的过程中发生过早期硫化物深部熔离,带走了岩浆中大部分的PGE,可能是造成黄山东矿床母岩浆中PGE明显亏损的主要原因。矿石低的Pd/Ir比值（为4.22～17.24,平均值为849）及高的Ir含量（为2.04×10-9～21.45×10-9,平均值为8.79×10-9）显示黄山东矿床成矿过程中后期热液作用不明显。铂族元素地球化学特征和岩石地球化学资料显示了地壳物质的混染以及橄榄石、辉石等矿物的分离结晶是引起该矿床硫饱和并发生硫化物熔离作用而成矿的主要因素。     

铜、镍、铂族元素地球化学性质及其在幔源岩浆起源、演化和岩浆硫化物矿床研究中的意义

Ni、Cu和PGE具有不同于其他微量元素的特殊的地球化学性质,这些特殊的性质使得它们在幔源岩浆起源和演化以及岩浆硫化物矿床的成因研究中具有不可替代的作用。在S不饱和的条件下,Ni、Os、Ir和Ru具有相容元素的特性,而Cu和Pd是强不相容元素,因此,它们在玄武岩浆分离结晶过程中常常发生分异。一旦体系达到S饱和,这些元素则会强烈地进入硫化物熔浆,特别是PGE具有极高的硫化物熔浆/硅酸盐熔浆分配系数,极微量的硫化物熔离便可导致残余岩浆中PGE的显著亏损,因此,PGE是玄武岩浆硫化物熔离作用最敏感的示踪元素。硫化物熔离和成矿实质上是幔源岩浆特殊演化过程的结果,所以,Ni,Cu和PGE的特殊性质可用来探讨岩浆硫化物成矿的关键控制因素。Ni、Cu和PGE具有不同的单硫化物固溶体/硫化物熔浆分配系数,因此,它们也是硫化物熔浆结晶分异的重要示踪元素。本文试图从Ni、Cu和PGE地球化学性质和行为入手,并借助一些研究实例,对它们在幔源岩浆起源和演化以及岩浆硫化物矿床成因研究中的示踪意义进行系统介绍。     

Geochemical Characteristics and Metallogenesis of the Qingkuangshan Ni‐Cu‐PGE Mineralized Mafic‐Ultramafic Intrusion in Huili County,Sichuan Province,SW China

The Qingkuangshan Ni-Cu-PGE deposit, located in the Xiaoguanhe region of Huili County, Sichuan Province, is one of several Ni-Cu-PGE deposits in the Emeishan Large Igneous Province (ELIP). The ore-bearing intrusion is a mafic-ultramafic body. This paper reports major elements, trace elements and platinum-group elements in different types of rocks and sulfide-mineralized samples in the intrusion. These data are used to evaluate the source mantle characteristics, the degree of mantle partial melting, the composition of parental magma and the ore-forming processes. The results show that Qingkuangshan intrusion is part of the ELIP. The rocks have trace element ratios similar to the coeval Emeishan basalts. The primitive mantle-normalized patterns of Ni-Cu-PGE have positive slopes, and the ratios of Pd/Ir are lower than 22. The PGE compositions of sulfide ores and associated rocks are characterized by Ru depletion. The PGE contents in bulk sulfides are slightly depleted relative to Ni and Cu, which is similar to the Yangliuping Ni-Cu-PGE deposit. The composition of the parental magma for the intrusion is estimated to contain about 14.65 wt% MgO, 48.66 wt% SiO2 and 15.48 wt% FeOt, and the degree of mantle partial melting is estimated to be about 20%. In comparison with other typical Ni-Cu-PGE deposits in the ELIP, the Qingkuangshan Ni-Cu-PGE deposit has lower PGE contents than the Jinbaoshan PGE deposit, but has higher PGE contents than the Limahe and Baimazhai Ni-Cu deposit, and has similar PGE contents to the Yangliuping Ni-Cu-PGE deposit. The moderate PGE depletions in the bulk sulfide of the Qingkuanghan deposit suggest that the parental magma of the host intrusion may have undergone minor sulfide segregation at depth. The mixing calculations suggests that an average of 10% crustal contamination in the magma, which may have been the main cause of sulfide saturation in the magma. We propose that sulfide segregation from a moderately PGE depleted magma took place prior to magma emplacement at Qingkuangshan, that small amounts of immiscible sulfide droplets and olivine and chromite crystals were suspended in the ascending magma, and that the suspended materials settled down when the magma passed trough the Qingkuangshan conduit. The Qingkuangshan sulfide-bearing intrusion is interpreted to a feeder of Emeishan flood basalts in the region.     

新疆北山红石山含铜镍镁铁-超镁铁质岩体PGE和Re-Os同位素地球化学特征及成矿意义

对新疆北山地区红石山镁铁-超镁铁质岩体中含铜镍的硫化物矿石和岩石进行了铂族元素和Re-Os同位素地球化学特征研究,结果表明,矿石及岩石的铂族元素(PGE)总量较低,变化于0.54×10-9~15.84×10-9之间。较低的Pd/Ir比值表明岩石主要受岩浆作用控制,后期热液作用影响不明显。较高的Cu/Pd和Ti/Pd比值表明岩浆在演化过程中发生了硫化物的熔离。岩体的母岩浆为有早期结晶橄榄石加入的高镁的玄武质岩浆。γOs(t)的变化较大,变化于-282~+282之间,表明有较多的地壳物质混入。地壳物质混染和橄榄石等矿物的分离结晶可能是引起岩浆中的S达到饱和进而熔离的重要因素。红石山岩体是经历了结晶分异和硫化物熔离后橄榄石的堆积体与残余岩浆演化的混合体。     

新疆北山地区两个含铜镍镁铁—超镁铁质岩体铂族元素地球化学研究

对北山地区坡一和罗东含铜镍的镁铁-超镁铁质岩体铂族元素研究表明,两个岩体的铂族元素(PGE)总量较低,PPGE较IPGE富集,原始地幔标准化模式呈正斜率,均较原始地幔亏损,具Ir和Rh的弱负异常。较低的Pd/Ir比值表明岩石主要受岩浆作用控制,后期热液作用影响不明显。两个岩体的原生岩浆均为MgO 含量较高的PGE不亏损的拉斑玄武质岩浆,较高的Cu/Pd、Ti/Pd比值表明岩浆在演化过程中发生了硫化物的熔离。罗东岩体早期矿物相（橄榄石、铬铁矿）的分离结晶作用对岩浆中的硫达到饱和具有重要的贡献,而坡一岩体该作用对硫化物熔离的贡献不明显。坡一和罗东岩体的R值表明两岩体均具有达到中型Ni矿床的潜力。     

Platinum-group element geochemistry of the Zhuqing Fe-Ti-V oxide ore-bearing mafic intrusions in western Yangtze Block,SW China: control of platinum-group elements by magnetite

Platinum-group element (PGE) geochemistry combined with elemental geochemistry and magnetite compositions are reported for the Mesoproterozoic Zhuqing Fe–Ti–V oxide ore-bearing mafic intrusions in the western Yangtze Block, SW China. All the Zhuqing gabbros display extremely low concentrations of chalcophile elements and PGEs. The oxide-rich gabbros contain relatively higher contents of Cr, Ni, Ir, Ru, Rh, and lower contents of Pt and Pd than the oxide-poor gabbros. The abundances of whole-rock concentrations of Ni, Ir, Ru, and Rh correlate well with V contents in the Zhuqing gabbros, implying that the distributions of these elements are controlled by magnetite. The fractionation between Ir–Ru–Rh and Pt–Pd in the Zhuqing gabbros is mainly attributed to fractional crystallization of chromite and magnetite, whereas Ru anomalies are mainly due to variable degrees of compatibility of PGE in magnetite. The order of relative incompatibility of PGEs is calculated to be Pd?<?Pt?<?Rh?<?Ir?<?Ru. The very low PGE contents and Cu/Zr ratios and high Cu/Pd ratios suggest initially S-saturated magma parents that were highly depleted in PGE, which mainly formed due to low degrees of partial melting leaving sulfides concentrating PGEs behind in the mantle. Moreover, the low MgO, Ni, Ir and Ru contents and high Cu/Ni and Pd/Ir ratios for the gabbros suggest a highly evolved parental magma. Fe–Ti oxides fractionally crystallized from the highly evolved magma and subsequently settled in the lower sections of the magma chamber, where they concentrated and formed Fe–Ti–V oxide ore layers at the base of the lower and upper cycles. Multiple episodes of magma replenishment in the magma chamber may have been involved in the formation of the Zhuqing intrusions.     

Siderophile and chalcophile elemental constraints on the origin of the Jinchuan Ni-Cu-(PGE) sulfide deposit, NW China

The Jinchuan deposit, NW China, is one of the world’s most important Ni-Cu-(PGE) sulfide deposits related to a magma conduit system and is hosted in an ultramafic intrusion. The intrusion is composed of lherzolite and dunite with the two largest sulfide ore bodies (named as ore body 1 and 2) in its middle portion. The sulfide ores may be disseminated, net-textured, or massive. The disseminated and net-textured sulfide ores are characterized by variable but generally low PGE concentrations: 10-3200 ppb Pt, 240-9800 ppb Pd, 17-800 ppb Ir, 25-1500 ppb Ru, and 15-400 ppb Rh in 100% sulfides. The massive sulfide ores are extremely low in Pt (<30 ppb) on a 100% sulfides and have very high Cu/Pd ratios, ranging from 10⁴ to 4.5 × 10⁵. The low PGE contents suggest that the sulfide ores formed from the silicate magmas that had already experienced prior-sulfide separation.Our calculations indicate that if the first stage basaltic magmas had contained 6.3 ppb Pt, 6.2 ppb Pd, and 0.1 ppb Ir, 0.008% sulfide removal would result in PGE-depletion in the residual magma with 0.57 ppb Pt, 0.25 ppb Pd, and 0.009 ppb Ir. The Jinchuan sulfides were formed by a second stage of sulfide segregation from a PGE-depleted magma under silicate/sulfide liquid ratios (R-factor) ranging from 10³ to 10⁴ in a deep-seated staging chamber. The massive sulfide ores and some of the net-textured sulfide ores exhibit strong negative Pt-anomalies that cannot be explained by sulfide segregation under variable R-factors. Instead, the sulfide melts that formed the massive ores were segregated from magmas experienced prior fractionation of Pt-Fe alloy. Alternatively, the Pt may have been selectively leached by hydrothermal fluids during remobilization of the sulfide melts that produced the massive sulfides, which occur in cross-cutting veins. We propose that the Jinchuan intrusion and ore bodies were formed by injections of sulfide-free and sulfide-bearing olivine mushes from a deep-seated staging chamber.     

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35 years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9 wt.%, with temperatures prior to quench ranging from 1140 °C to ambient (110 °C). Five eruption samples were also analyzed.Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006–1.40 ppb for Os and 0.0006–2.01 ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF₆ in some of the most magnesian samples.Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials.Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27 wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar.Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained.     

Origin of ultra-nickeliferous olivine in the Kevitsa Ni–Cu–PGE-mineralized intrusion, northern Finland

The 2,058 ± 4 Ma mafic–ultramafic Kevitsa intrusion is located in the Central Lapland greenstone belt, northern Finland. It is hosted by a Paleoproterozoic volcano–sedimentary sequence that contains komatiitic volcanic rocks and sulfide- and graphite-rich black schists. Economic Ni–Cu–(PGE) sulfide mineralization occurs in the middle part of the ultramafic lower unit of the intrusion. Two main types of ore are distinguished, “normal” and “Ni–PGE” ores. The normal ore is characterized by ~2 to 6 vol% disseminated sulfides and average Ni and Cu grades of 0.3 and 0.42 wt %, respectively (Ni/Cu < 1). The Ni–PGE ore has broadly similar sulfide contents, but a higher Ni grade and lower Cu grade. As a result, the Ni/Cu ratio reaches 15, much higher than in the normal ore. The Ni–PGE ores occur as irregular, discontinuous, lense-like bodies in the ultramafic rocks. Notably, the olivines in the Ni–PGE ore contain extremely high Ni contents of up to 14,000 ppm, which is significantly higher than the Ni content of olivine in other mafic–ultramafic igneous rocks globally (up to ~5,000 ppm) and in harmony with the associated Ni-rich sulfide assemblage containing pentlandite, millerite and pyrite. Microprobe mapping of olivine from the Ni–PGE ore suggests relatively low and homogeneous S contents and homogeneous distribution of Ni, Mg, Fe, which is inconsistent with the presence of sulfide inclusions in the olivine grains, or diffusion of Ni from interstitial sulfides into the olivine grains. We therefore conclude that Ni substitutes for Mg in the olivine lattice. The clinopyroxenes from the Ni–PGE ore also have unusually high Ni concentrations reaching 1,500 ppm and show a positive correlation with the nickel content of the associated olivine. The Ni_cpx/Ni_olivine is ~0.1 to 0.2 corresponding to high T partitioning of Ni between clinopyroxene and olivine. K _D of 20 can account for the partitioning of nickel between olivine and the sulfide phase, consistent with magmatic equilibration. These data suggest that the olivine, clinopyroxene, and sulfides all crystallized from a basaltic magma with an unexceptionally high Ni content ranging from 300 to 1,100 ppm. The Ni–PGE ores are spatially associated with ultramafic xenoliths. Olivine in these ultramafic xenoliths have relatively high Fo contents (up to 90 mol %) and high Ni contents (up to 5,200 ppm) suggesting that the xenoliths formed from a komatiitic parental magma. It is proposed that assimilation by the Kevitsa magma of massive or semi-massive sulfides associated with komatiitic rocks elevated the Ni content of the magma and resulted in the formation of Ni–PGE ores and related extremely Ni-rich olivines.     

Re－Os同位素体系及其在岩浆Cu－Ni－PGE矿床研究中的应用

Ｒｅ－Ｏｓ同位素由于其较高的半衰期特点，近年来国外广泛用于前寒武纪含Ｃｕ－Ｎｉ－ＰＧＥ镁铁—超镁铁岩成岩年龄测定，并结合其他地球化学数据，对壳幔岩浆源及作用进行解释研究。特别是由于Ｏｓ是６个ＰＧＥ的其中之一，而多用于岩浆Ｃｕ－Ｎｉ－ＰＧＥ矿床贵金属来源的判别。中国岩浆Ｃｕ－Ｎｉ－ＰＧＥ矿床以金川矿床为代表，已有的研究表明，可能存在岩浆混合成矿作用，开展Ｒｅ－Ｏｓ同位素体系的研究将会提供进一步判断的证据     

Geochemical Constraints on the Origin of the Ni–Cu Sulfide Ores in the Tejadillas Prospect (Cortegana Igneous Complex,SW Spain)

After the discovery of the Aguablanca ore deposit (the unique Ni–Cu mine operating in SW Europe), a number of mafic‐ultramafic intrusions bearing Ni–Cu magmatic sulfides have been found in the Ossa–Morena Zone of the Iberian Massif (SW Iberian Peninsula). The Tejadillas prospect is one of these intrusions, situated close to the border between the Ossa–Morena Zone and the South Portuguese Zone of the Iberian Massif. This prospect contains an average grade of 0.16 wt % Ni and 0.08 wt % Cu with peaks of 1.2 wt % Ni and 0.2 wt % Cu. It forms part of the Cortegana Igneous Complex, a group of small mafic‐ultramafic igneous bodies located 65 km west of the Aguablanca deposit. In spite of good initial results, exploration work has revealed that sulfide mineralization is much less abundant than in Aguablanca. A comparative study using whole‐rock geochemical data between Aguablanca and Tejadillas shows that the Tejadillas igneous rocks present a lower degree of crustal contamination than those of Aguablanca. The low crustal contamination of the Tejadillas magmas inhibited the assimilation of significant amounts of crustal sulfur to the silicate magmas, resulting in the sparse formation of sulfides. In addition, Tejadillas sulfides are strongly depleted in PGE, with total PGE contents ranging from 14 to 81 ppb, the sum of Pd and Pt, since Os, Ir, Ru and Rh are usually below or close to the detection limit (2 ppb). High Cu/Pd ratios (9700–146,000) and depleted mantle‐normalized PGE patterns suggest that the Tejadillas sulfides formed from PGE‐depleted silicate magmas. Modeling has led us to establish that these sulfides segregated under R‐factors between 1000 and 10,000 from a silicate melt that previously experienced 0.015% of sulfide extraction. All these results highlight the importance of contamination processes with S‐rich crustal rocks and multiple episodes of sulfide segregations in the genesis of high‐tenor Ni–Cu–PGE ore deposits in mafic‐ultramafic intrusions of the region.