The great sulfur depletion of Earth’s mantle is not a signature of mantle–core equilibration

The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.     

The sulfur isotope composition of basaltic rocks

The sulfur isotope composition of tholeiitic basalts, olivine alkali basalts and alkalirich undersaturated basalts were investigated. A method of preparation was devised

1. for the extraction of the small amounts of sulfur contained in the rock samples (about 100 ppm S),
2. for the separation of sulfide- and sulfate-sulfur.

Tholeiitic and olivine alkali basalts show a predominance of sulfide-sulfur. Alkali-rich undersaturated basalts show sulfide- and sulfate-sulfur. The oxidation potential of the magma is reflected in the proportions of sulfide- and sulfate-sulfur. Differences in the conditions of oxidation are also the cause of the sulfur isotope fractionation observed. The mean in the isotope composition of the sulfur in the olivine alkali basalts (with the exception of two samples which show extreme deviation) is δ ³⁴S= +1.3 per mil. The values for the olivine alkali basalts are concentrated around this mean in a remarkable way, showing only small deviation for the individual samples. When the tholeiitic basalts deviate from this mean, it is only with a relative enrichment in the ³²S isotope. With a pronounced variation of the individual values, the mean for the sulfide-sulfur is δ ³⁴S=?0.3 per mil. The few sulfate values of both types of basalt are without significance for the discussion of their origin. However, this does not apply to the alkali-rich undersaturated basalts. Due to the higher water content, this basaltic magma had a higher oxygen partial pressure which favoured the formation of SO₂ and SO ₄ ^2? besides H₂S while pressure was released during the ascent of the magma. The sulfur isotope fractionation connected with this oxidation led to a total enrichment of ³⁴S in the rock, (δ ³⁴S for total sulfur: +3.1 per mil) with particular favouring the sulfate (δ ³⁴S=+4.2 per mil). It is accepted that the sulfur of all three types of basalts derives directly from the mantle. The olivine alkali basalts show the least deviation from the mantle value, which, in the place of origin of the basalts from the region investigated, would probably have been δ ³⁴S=+1.3(±0.5) per mil. From this it may be concluded that the olivine alkali basalts — the most frequent type of basalt in this region — had their origin in the partial melting of the mantle without further differentiation. From the sulfur isotope data we concluded that the primary isotope composition of the continental tholeiitic basalts probably corresponds to that of the olivine-alkali basalts, and to that of the mantle. However, due to degasing in the layers near to the surface, some samples lost ³⁴S, which may be related to the formation of SO₂ during the release of pressure. There is no positive indication of a differentiation in shallow depths (<15 km — in the sense of Green and Ringwood, 1967). The reason for the obvious isotopic fractionation of the alkali-rich undersaturated basalts may be seen in their higher primary water content. This is a pronounced indication of the origin of this type of magma. Bultitude and Green (1968) proved by experiment, that the formation of alkali-rich undersaturated basaltic magma is possible in the mantle in the presence of water. Only a small amount of water is available for the formation of magma in the mantle. With a water content higher than normal for basalts, only small amounts of magma can be formed, but at lower temperatures this would allow the melting of a larger fraction of mantle material. By reaction with the wall rock, these magmas could be enriched in those components of mantle minerals which have the lowest melting point. This may help to explain their geochemical characteristics.     

Mantle Pb paradoxes: the sulfide solution

There is growing evidence that the budget of Pb in mantle peridotites is largely contained in sulfide, and that Pb partitions strongly into sulfide relative to silicate melt. In addition, there is evidence to suggest that diffusion rates of Pb in sulfide (solid or melt) are very fast. Given the possibility that sulfide melt “wets” sub-solidus mantle silicates, and has very low viscosity, the implications for Pb behavior during mantle melting are profound. There is only sparse experimental data relating to Pb partitioning between sulfide and silicate, and no data on Pb diffusion rates in sulfides. A full understanding of Pb behavior in sulfide may hold the key to several long-standing and important Pb paradoxes and enigmas. The classical Pb isotope paradox arises from the fact that all known mantle reservoirs lie to the right of the Geochron, with no consensus as to the identity of the “balancing” reservoir. We propose that long-term segregation of sulfide (containing Pb) to the core may resolve this paradox. Another Pb paradox arises from the fact that the Ce/Pb ratio of both OIB and MORB is greater than bulk earth, and constant at a value of 25. The constancy of this “canonical ratio” implies similar partition coefficients for Ce and Pb during magmatic processes (Hofmann et al. in Earth Planet Sci Lett 79:33–45, 1986), whereas most experimental studies show that Pb is more incompatible in silicates than Ce. Retention of Pb in residual mantle sulfide during melting has the potential to bring the bulk partitioning of Ce into equality with Pb if the sulfide melt/silicate melt partition coefficient for Pb has a value of ∼ 14. Modeling shows that the Ce/Pb (or Nd/Pb) of such melts will still accurately reflect that of the source, thus enforcing the paradox that OIB and MORB mantles have markedly higher Ce/Pb (and Nd/Pb) than the bulk silicate earth. This implies large deficiencies of Pb in the mantle sources for these basalts. Sulfide may play other important roles during magmagenesis: (1) advective/diffusive sulfide networks may form potent metasomatic agents (in both introducing and obliterating Pb isotopic heterogeneities in the mantle); (2) silicate melt networks may easily exchange Pb with ambient mantle sulfides (by diffusion or assimilation), thus “sampling” Pb in isotopically heterogeneous mantle domains differently from the silicate-controlled isotope tracer systems (Sr, Nd, Hf), with an apparent “de-coupling” of these systems.     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

祁连造山带中部拉脊山古地幔特征及其归属: 来自基性火山岩的地球化学证据

拉脊山火山岩带位于祁连造山带中部, 通过对该区早古生代基性火山岩系统的地球化学研究, 揭示该区早古生代地幔的性质及其地幔域的构造归属.研究表明, 拉脊山基性火山岩可以分为两类: Ⅰ类为大陆板内碱性玄武岩, 其稀土元素组成模式为轻稀土富集型, 并具有明显的Nb、Ta负异常, 而Zr、Hf无明显的负异常; Ⅱ类为与地幔柱活动有关的拉斑玄武岩, 具有洋岛玄武岩(OIB) 特征.稀土元素组成模式同样表现为轻稀土富集型, 但其富集程度比Ⅰ类基性火山岩的富集程度弱, 无Nb、Ta、Zr和Hf负异常.基性火山岩的Sr、Nd、Pb同位素组成特征显示, 基性火山岩的地幔源区具有亏损地幔(DM) 和第二类富集地幔(EMⅡ) 混合的特点, 而第二类富集地幔端元(EMⅡ) 占主导地位, 亏损地幔(DM) 物质混入的程度较低; 并具有Dupal异常的同位素特征.通过与华北南缘、北秦岭和扬子北缘西段地幔的Pb同位素组成相比, 表明拉脊山造山带古地幔与北秦岭、南秦岭西段和扬子北缘西段地幔的Pb同位素组成相似.进而表明拉脊山造山带古地幔属于扬子型富放射性成因铅地幔, 而非华北型贫放射性成因铅地幔      

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano,Hawaii

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ³⁴S_Σs of $\text{0.7 ± 0.1 ‰}$. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is $\text{+7.5 ± 1.5‰}$. On the other hand, the concentration and δ³⁴S_Σs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and $\text{?0.8 ± 0.2‰}$, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the $\text{?o}{}_2$ and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO₂ from basalt thereby depleting sulfate and ³⁴S in basalt.The volcanic sulfur gases, predominantly SO₂, from the 1971 and 1974 fissures in Kilauea Crater have δ³⁴S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ³⁴S value of sulfur gases (largely SO₂) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ³⁴S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ³⁴S values (+5 to +6%._o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.     

化学地球动力学中的铂族元素地球化学

对球粒陨石和地幔样品来讲,Ru,Rh,Pd,Os,Ir和Pt等贵金属元素的含量比值在一定程度上是相同的,但是在地幔样品中它们的含量实际上比球粒陨石低大约2个数量级,因此提出了核幔分离之后地球增生过程的“后增薄层”假说。数百公里尺度地幔橄榄岩的PEG分布的不均一性除被认为由于增生阶段的不均一造成外,更可能是由于地幔形成之后的地幔过程、核－幔及壳－幔相互作用造成。部分熔融、岩浆结晶分异（特别是硫化物、金属相析离）、流体（包括岩浆）／岩石相互作用等造成了大型俯冲带、造山带中地幔橄榄岩、蛇绿岩和杂岩体的PGE分异,也是形成铬铁矿,大型贵金属矿床的主要机制。     

On the elusive isotopic composition of lunar Pb

Highly radiogenic Pb isotope compositions determined for volcanic glass beads from the Apollo 14 soil sample 14163 are similar to those commonly determined for mare basalts and are correlated with chemical variations observed in the beads. This indicates that Pb unsupported by in-situ U decay has a similar origin in both glass beads and mare basalt samples and is likely to reflect variations of ²³⁸U/²⁰⁴Pb (μ) in the lunar mantle. An alternative explanation that this Pb is a result of late equilibration with the radiogenic Pb present in soil is less likely as it would imply that all other characteristics of glass beads such as their chemistry must also be a consequence of equilibration near the lunar surface. Regardless of the origin of unsupported Pb, observed variations of Pb isotope compositions in the glass beads and mare basalts appear to be a result of two component mixing between a primitive reservoir with a μ-value similar to the Earth’s mantle and KREEP with a μ-value in excess of several thousand. This range cannot be explained by the fractionation of major rock forming minerals from the crystallising Lunar Magma Ocean and instead requires substantial extraction of sulphide late in the crystallisation sequence. The proportion of sulphide required to produce the inferred range places limits on the starting μ of the Moon prior to differentiation, demanding a relatively high value of about 100-200. Low μ indicated by several basalt samples and previously analysed volcanic glass beads can be explained by the preservation of an early (but post Ferroan Anorthosite) sulphide rich reservoir in the lunar mantle, while a complete range of Pb isotope compositions observed in the glass beads and mare basalts can be interpreted as mixing between this sulphide rich reservoir and KREEP.     

东太平洋北部胡安·德富卡洋中脊Mothra热液场硫化物烟囱体成矿物质来源:铅和硫同位素组成

对采自Mothra热液场Faulty Towers硫化物烟囱体群(47°57.447,N,129°06.568W)的一个硫化物烟囱体进行了铅和硫同位素组成的研究工作.分析结果表明,铅同位素组成的分布范围为:206Pb/204Pb=18.665～18.828; 207Pb/204Pb=15.460～15.607; 208...     

Platinum-group element constraints on source composition and magma evolution of the Kerguelen Plateau using basalts from ODP Leg 183

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ∼0.1 (Ir, Ru) to ∼5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (∼30%) and fractional crystallization (∼45%).First order approximations of the fractionation required to produce the KP basalts from an ∼30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available K_d values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.     

Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ¹⁸O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO₂, Al₂O₃). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ⁵⁶Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ¹⁸O and δ⁵⁶Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ⁵⁶Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ¹⁸O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ¹⁸O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ¹⁸O and δ⁵⁶Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).     

Fractionation of the noble metals by physical processes

During partial melting in the earth’s mantle, the noble metals become fractionated. Os, Ir, Ru, and Rh tend to remain in the mantle residue whereas Pt, Pd, and Re behave mildly incompatible and are sequestered to the silicate melt. There is consensus that sulfide plays a role in the fractionation process; the major noble metal repository in the mantle is sulfide, and most primitive mantle melts are sulfide-saturated when they leave their mantle sources. However, with sulfide–silicate partitioning, the fractionation cannot be modeled properly. All sulfide–silicate partition coefficients are so extremely high that a silicate melt segregating from a mantle source with residual sulfide should be largely platinum-group elements free. We offer a physical alternative to sulfide–silicate chemical partitioning and provide a mechanism of generating a noble metal-rich melt from a sulfide-saturated source: Because sulfide is at least partially molten at asthenospheric temperature, it will behave physically incompatible during melt segregation, and a silicate melt segregating from a mantle residue will entrain molten residual sulfide in suspension and incorporate it in the basaltic pool melt. The noble metal abundances of a basalt then become independent of sulfide–silicate chemical partitioning. They reflect the noble metal abundances in the drained sulfide fraction as well as the total amount of sulfide entrained. Contrary to convention, we suggest that a fertile, sulfide-rich mantle source has more potential to generate a noble metal-enriched basaltic melt than a refractory mantle source depleted by previous partial melting events.     

Platinum-Group Element Geochemical Characteristics of the Picrites and High-Ti Basalts in the Binchuan Area,Yunnan Province

The Binchuan area of Yunnan is located in the western part of the Emeishan large igneous province in the western margin of the Yangtze Block.In the present study,the Wuguiqing profile in thickness of about 1440 m is mainly composed of high-Ti basalts,with minor picrites in the lower part and andesites,trachytes,and rhyolites in the upper part.The picrites have relatively higher platinum-group element（PGE） contents（ΣPGE=16.3-28.2 ppb）,with high Cu/Zr and Pd/Zr ratios,and low S contents（5.03-16.9 ppm）,indicating the parental magma is S-unsaturated and generated by high degree of partial melting of the Emeishan large igneous province（ELIP） mantle source.The slightly high Cu/Pd ratios（11 000-24 000） relative to that of the primitive mantle suggest that 0.007%sulfides have been retained in the mantle source.The PGE contents of the high-Ti basalts exhibit a wider range（ΣPGE=0.517-30.8 ppb）.The samples in the middle and upper parts are depleted in PGE and haveε_Nd（260 Ma） ratios ranging from -2.8 to -2.2,suggesting that crustal contamination of the parental magma during ascent triggered sulfur saturation and segregation of about 0.446%-0.554% sulfides,and the sulfide segregation process may also provide the ore-forming material for the magmatic Cu-Ni-PGE sulfide deposits close to the studied basalts.The samples in this area show Pt-Pd type primitive mantle-normalized PGE patterns,and the Pd/Ir ratios are higher than that of the primitive mantle（Pd/Ir=1）,indicating that the obvious differentiation between Ir-group platinum-group elements（IPGE） and Pd-group platinum-group elements（PPGE） are mainly controlled by olivine or chromites fractionation during magma evolution.The Pd/Pt ratios of most samples are higher than the average ratio of mantle（Pd/Pt=0.55）,showing that the differentiation happened between Pt and Pd.The differentiation in picrites may be relevant to Pt hosted in discrete refractory Pt-alloy phase in the mantle;whereas the differentiation in the high-Ti basalts is probably associated with the fractionation of Fe-Pt alloys,coprecipitating with Ir-Ru-Os alloys.Some high-Ti basalt samples exhibit negative Ru anomalies,possibly due to removal of laurite collected by the early crystallized chromites.     

阜新中生代火山岩的铂族元素特征——以碱锅和乌拉哈达为例

采用镍锍火试金法结合ICP—MS分析了碱锅玄武岩和乌拉哈达高镁安山岩样品中的Ir．Ru、Rh、Pt和Pd的含量。原始地幔标准化后的PGE分布模式呈正斜率型，Pd／Ir值高于相应的地幔比值，表明铂族元素发生了分异，这是由于在部分熔融过程中，Ir存在于地幔矿物相尖晶石和合金中，而Pd赋存于硫化物中造成的，乌拉哈达高镁安山岩中的铂族元素还可能在结晶分异过程中受到先期结晶的矿物相和合金的影响。阜新火山岩Pt的负异常可能是包含Pt的金属合金残留在地幔中造成。     

The influence of sulfur on partitioning of siderophile elements

Sulfur is a potential light element in the liquid outer core of the Earth. Its presence in segregating metal may have had an influence in distribution of metal-loving (siderophile) elements during early accretion and core formation events in the Earth. The observed “excess” abundance of siderophile elements in the terrestrial mantle, relative to an abundance expected from simple core-mantle equilibrium at low temperature and pressure, may indicate a reduction in the iron-loving tendency of siderophile elements in the presence of sulfur in the metallic phase. The present experimental partitioning study between iron-carbon-sulfur-siderophile element bearing liquid metal and liquid silicate shows that for some siderophile elements this sulfur effect may be significant enough to even change their character to lithophile. Large and intricate variations in metal-silicate partition coefficients (D^met/sil) have been observed for many elements, e.g., Ni, Co, Ge, W, P, Au, and Re as a function of sulfur content. Moderately siderophile elements Ge, P, and W show the most significant response (sulfur-avoidance) by an enhanced segregation into the associated sulfur-deficient phases. Highly siderophile elements Ir, Pt, and Re show a different style of sulfur-avoidance (alloy-preference) by segregating as sulfur-poor, siderophile element-rich alloys. Both groups are chalcophobic. D^met/sil for Ni, Co, and Au moderately decreases with increasing sulfur-content in the liquid metal. D^met/sil for chalcophile element, Cr, in contrast, increases with sulfur. Irrespective of the sulfur-content, in the presence of a carbon-saturated liquid metal, P is always lithophile. The general nonmetal-avoidance tendency of siderophile elements (and acceptance of chalcophile elements) in the liquid metal, postulated by Jones and Malvin (1990) in the FeNiS(sulfur)M (siderophile) system is found to be present in the metal-silicate system as well. A sulfur-bearning liquid metal segregation can potentially reduce the metal-loving nature of many elements to explain the excess paradox. Sulfur-bearing core segregation, however, might require an efficient draining of exsolved immiscible sulfide liquids from the molten silicate, or an increasing siderophility of sulfur at high pressure to reduce the mantle sulfur content to the observed (<300 ppm) value. Moreover, the chondritic relative abundance pattern of many moderately or highly siderophile elements in the upper mantle is not explained by the presence of sulfur in the segregating metals. Core formation is more complex and intricate than equilibrium segregation.     

湘东北地区主要有色金属矿床成矿物质来源——来自硫、铅同位素的证据

湘东北地区有色金属矿床成矿物质来源综合研究相对缺乏。以桃林铅锌矿、栗山铅锌矿、井冲钴铜多金属矿为研究对象,分析矿床主成矿期矿石硫化物单矿物的硫、铅同位素地质特征,结合七宝山铜多金属矿等研究现状,综合研究湘东北地区有色金属矿床的成矿物质来源规律。硫同位素特征表明,4个矿床的成矿物质整体为深部岩浆硫源,其中,七宝山矿床为较典型的岩浆硫源,桃林、栗山、井冲等矿床混入了少量地层硫源,且桃林矿床比栗山、井冲矿床混入地层硫源的比例更高。铅同位素特征表明,4个矿床的成矿物质来源以上地壳为主,但混入了少部分幔源物质,且七宝山、井冲的幔源物质混入比例更高。     

The concentrations of the noble metals in Southern African flood-type basalts and MORB: implications for petrogenesis and magmatic sulphide exploration

Concentrations of the platinum-group elements have been determined in several suites of southern African flood-type basalts and mid-ocean ridge basalt (MORB), covering some 3 Ga of geologic evolution and including the Etendeka, Karoo, Soutpansberg, Machadodorp, Hekpoort, Ventersdorp and Dominion magmas. The magmas cover a compositional range from 3.7 to 18.7% MgO, 26–720 ppm Ni, 16–250 ppm Cu, and <1–255 ppb total platinum-group elements (PGE). The younger basalts (Etendeka, Karoo) tend to be depleted in PGE relative to Cu, while most of the older basalts (Hekpoort, Machadodorp, Ventersdorp, Dominion) show no PGE depletion relative to Cu. Further, the younger basalts tend to have lower average Pt/Pd ratios than the older basalts, and the MORBs have lower average Pt/Pd than the continental basalts within the broad groupings of "old" and "young" basalts. This may reflect (1) a decreasing degree of mantle melting through geologic time, and (2) source heterogeneity, in that the MORBs are derived from predominantly asthenospheric mantle, whereas the continental basalts also contain a lithospheric mantle component enriched in Pt. In addition to these factors, some PGE fractionation also occurred during differentiation of the magmas, with Pd showing incompatible behaviour and the other PGE variably compatible behaviour. The examined southern African flood-type basalts and MORB appear to offer limited prospects for magmatic sulfide ores, largely because they show little evidence for significant chalcophile metal depletion that could be the result of sulphide extraction during ascent and crystallization.Editorial responsibility: I. Parsons     

Petrology and Geochemistry of Intraplate Basalts in the South Auckland Volcanic Field, New Zealand: Evidence for Two Coeval Magma Suites from Distinct Sources

The South Auckland Volcanic Field is a Pleistocene (1·59–0·51Ma) basaltic intraplate, monogenetic field situated south ofAuckland City, North Island, New Zealand. Two groups of basaltsare distinguished based on mineralogy and geochemical compositions,but no temporal or spatial patterns exist in the distributionof various lava types forming each group within the field: GroupA basalts are silica-undersaturated transitional to quartz-tholeiiticbasalts with relatively low total alkalis (3·0–4·6wt %), Nb (7–29 ppm), and (La/Yb)_N (3·4–7·6);Group B basalts are strongly silica-undersaturated basanitesto nepheline-hawaiites with high total alkalis (3·3–7·9wt %), Nb (32–102 ppm), and (La/Yb)_N (12–47). GroupA has slightly higher ⁸⁷Sr/⁸⁶Sr, similar _Nd, and lower ²⁰⁶Pb/²⁰⁴Pbvalues compared with Group B. Contrasting geochemical trendsand incompatible element ratios (e.g. K/Nb, Zr/Nb, Ce/Pb) areconsistent with separate evolution of Groups A and B from dissimilarparental magmas derived from distinct sub-continental lithosphericmantle sources. Differentiation within each group was controlledby olivine and clinopyroxene fractionation. Group B magmas weregenerated by <8% melting of an ocean island basalt (OIB)-likegarnet peridotite source with high ²³⁸U/²⁰⁴Pb mantle (HIMU)and enriched mantle (EMII) characteristics possibly inheritedfrom recycled oceanic crust. Group A magmas were generated by<12% melting of a spinel peridotite source also with HIMUand EMII signatures. This source type may have resulted fromsubduction-related metasomatism of the sub-continental lithospheremodified by a HIMU plume. These events were associated withMesozoic or earlier subduction- and plume-related magmatismwhen New Zealand was at the eastern margin of the Gondwana supercontinent. KEY WORDS: continental intraplate basalts; geochemistry; HIMU, EMII; Sr, Nd, and Pb isotopes; South Auckland; sub-continental lithospheric sources     

东秦岭中段板厂铜钼矿床S、Pb同位素对成矿物质来源的示踪作用

东秦岭钼矿带是我国最重要的钼多金属成矿带,近年来在东秦岭板厂地区取得了新的找矿突破。本文利用区域成矿动力学、硫化物的硫、铅同位素组成研究,结合成矿地质特征,对板厂铜钼多金属矿床成矿物质来源进行示踪,并以板厂矿床为基点总结东秦岭钼矿带的稳定同位素时空分布特征。板厂矿床12件硫化物样品δ(34S)范围为1.2×10-3~5.7×10-3,平均值0.6×10-3,与地幔(0±3×10-3)硫同位素值相近;东秦岭钼矿床δ(34S)位素值有随成矿时代渐新而逐渐升高的趋势,印支期钼矿床(221~226Ma)δ(34S)同位素值偏负,燕山期第一阶段钼矿床(138~151Ma)δ(34S)值由"0"值向正值变化,燕山期第二阶段钼矿床(113~131 Ma)δ(34S)值较高(平均4.93‰)。板厂矿床深部硫化物206Pb/204Pb值为17.121~17.798,207Pb/204Pb值为15.369~15.433,208Pb/204Pb值为36.867~37.485,具有明显的低放射性成因铅特征,其铅同位素组成与华北克拉通南缘的类熊耳群和太华群相似,幔源特征明显;浅部硫化物铅同位素值相对较高,206Pb/204Pb值为18.266~18.392,207Pb/204Pb值为15.560~15.622,208Pb/204Pb值为37.611~38.438,反映了造山带混合铅特征。板厂矿床形成于中国东部构造体制转折阶段,深部构造体制重新调整导致地幔物质上侵以及壳幔混合物的重新熔融,岩浆沿着深大断裂上涌,并将一定规模的含矿流体运移至浅部,由于物理化学条件的变化以及浅部流体的混合,成矿流体在最终构造薄弱带沉淀Cu、Mo等金属,形成板厂铜钼多金属矿床。综上,在晚侏罗世-早白垩世,东秦岭地区地幔熔体活动强烈,板厂铜钼多金属矿床成矿物质来源以幔源为主,有少量壳源物质混入。