流体在岩浆型铬铁矿和铂族元素成矿过程中的作用及意义

镁铁- 超镁铁岩是揭示地幔物质组成和壳幔相互作用的重要窗口，也是Ni- Cu- PGE- Cr等金属矿产资源的重要载体。不同的镁铁- 超镁铁岩体赋矿特征明显不同：蛇绿岩以产出铬铁矿床为特征，阿拉斯加型岩体主要赋含铂族元素(PGE)矿床，大型层状岩体则可同时产出铬铁矿床、PGE矿床和Cu- Ni硫化物矿床。这种成矿差异显然与赋矿岩体形成的构造背景、母岩浆经历的岩浆演化过程有关，但缺少关键控制因素的研究。前人对上述不同种类矿床的研究工作主要集中于地幔源区的部分熔融、上升过程中或岩浆房内的围岩混染和结晶分异等岩浆过程，而极少关注流体作用。近年来，实验岩石学和岩石地球化学的研究均表明幔源岩浆演化过程中的流体活动可能对成矿元素的富集迁移起到至关重要的作用，同时这些成矿元素的赋存状态和分配系数也在不断更新。厘清Cr和PGE在熔体演化——尤其是流体出溶过程中的地球化学行为，刻画并揭示其迁移富集、分离和再富集的成矿过程及控制因素，已成为当前岩浆矿床研究的热点。本文围绕富水流体与铬铁矿和PGE成矿关系的科学问题，总结了不同镁铁- 超镁铁岩体的成矿差异以及铬铁矿和PGE矿床成矿过程中的流体活动记录，提出流体性质和组分对铬铁矿和PGE迁移富集的控制作用，强调有必要开展蛇绿岩、大型层状镁铁- 超镁铁岩体和阿拉斯加型岩体的对比研究。     

浙东晚白垩世小雄破火山中火山-侵入杂岩的岩石成因

破火山内出露的火山岩与浅成侵入岩为硅质岩浆演化研究提供了一个重要窗口，从而备受关注。小雄破火山内的火山-侵入杂岩是中国东南沿海晚白垩世岩浆活动的典型代表，包括小雄组火山岩（K₂x）与两类侵入岩（花岗斑岩、正长斑岩）。本文以小雄火山-侵入杂岩为研究对象，开展了系统的锆石U-Pb年代学、岩石学和地球化学研究，旨在深入探讨破火山内火山岩与侵入岩之间的成因联系和岩浆演化过程。系统的LA-ICP-MS 锆石U-Pb年代学研究表明，小雄组火山岩形成于98~88Ma，并具有多期次喷发的特点，可分为下段、中段和上段，年龄分别为98~96Ma（K₂x¹）、95~92Ma（K₂x²）、~ 88Ma（K₂x³）。小雄花岗斑岩形成年龄为90Ma；正长斑岩形成稍晚，约88Ma。与下段流纹质玻屑凝灰岩的Nd-Hf同位素组成[ε_Nd（t）=-8.3~-7.2， ε_Hf（t）=-11.8~-7.2]相比，中段流纹岩要更为亏损[ε_Nd（t）=-5.84~-5.32， ε_Hf（t）=-10.1~-0.5]。研究表明，小雄组流纹质火山岩的母岩浆可能起源于发生在深部岩浆房中渐进的壳幔相互作用，中段流纹岩的源区混入了更多的亏损幔源组分。中段流纹岩与花岗斑岩具有相似的Nd-Hf同位素组成，以及 "互补"的微量元素地球化学特征，由发生在浅部岩浆房的分离结晶作用和堆晶作用所制约。值得注意的是，正长斑岩与花岗斑岩并不存在直接的成因演化关系，两者应是不同的起源。不同的正长斑岩岩株具有高度一致的结晶年龄、微量元素特征以及Nd-Hf同位素组成，以上特征均表明小雄破火山内的正长斑岩具有相同的起源。正长斑岩母岩浆起源于富集岩石圈地幔的部分熔融，岩浆源区混入了来自亏损的软流圈地幔组分，其地球化学成分变化主要受"普通辉石+磷灰石+钛铁矿"的分离结晶所控制。     

Chemical aspects of iron oxide coagulation in water: Laboratory studies and implications for natural systems

Initial coagulation rates of colloidal hematite (-Fe₂O₃) particles (diameter less than 0.1 µm) were measured experimentally in well-defined laboratory systems at constant temperature. The relative stability ratio,W, was obtained at various ionic strengths in NaCl medium and at pH values in the range from 3 to 12. ExperimentalW values ranged from 1 to 10⁴ in various systems. The results delineate the roles ofspecific andgeneralized coagulation mechanisms for iron oxides. Among the specifically-interacting species (G _ads ⁰ >G _coul ⁰ ) studied were phosphate, monomeric organic acids of various structures, and polymeric organic acids. The critical coagulation-restabilization concentrations of specifically-interacting anions (from 10^–7 to 10^–4 molar) can be compared with the general effects of non-specific electrolyte coagulants (10^–3 to 10^–1 molar). The laboratory results are interpreted with the help of a Surface Complex Formation/Diffuse Layer Model (SCF/DLM) which describes variations of interfacial charge and potential resulting from variations of coagulating species in solution. Comparison of these laboratory experiments with observations on iron behavior in estuarine and lake waters aids in understanding iron removal mechanisms and coagulation time scales in natural systems.     

Geochemistry and Origin of Ananai Stratiform Manganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Major and trace element contents are reported for Permian manganese ore and associated greenstone from the Ananai manganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The manganese deposit occurs between greenstone and red chert, or among red chert beds. Chemical compositions of manganese ore are characterized by enrichments in Mn, Ca, P, Co, Ni, Zn, Sr and Ba, and negative Ce and positive Eu anomalies relative to post-Archean average Australian Shale (PAAS). Geochemical features of the manganese ore are similar to those of modern submarine hydrother-mal manganese deposits from volcanic arc or hotspot setting. In addition, geochemical characteristics of the greenstone closely associated with the Ananai manganese deposit are analogous to those of with-in plate alkaline basalt (WPA). Consequently, the Ananai manganese deposit was most likely formed by hydrothermal activity related to hotspot volcanism in the Panthalassa Ocean during the Middle Permian. This is the first report documenting the terrestrially-exposed manganese deposit that was a submarine precipitate at hotspot.     

Lermontovskoe Tungsten Skarn Deposit: the Oldest Mineralization in the Sikhote-Alin Orogen, Far East Russia

Abstract. Lermontovskoe tungsten skarn deposit in central Sikhote-Alin is concluded to have formed at 132 Ma in the Early Cretaceous, based on K-Ar age data for muscovite concentrates from high-grade scheelite ore and greisenized granite. Late Paleozoic limestone in Jurassic - early Early Cretaceous accretionary complexes was replaced during hydrothermal activity related to the Lermontovskoe granodiorite stock of reduced type. The ores, characterized by Mo-poor scheelite and Fe^3+- poor mineral assemblages, indicate that this deposit is a reduced-type tungsten skarn (Sato, 1980, 1982), in accordance with the reduced nature of the granodiorite stock.
The Lermontovskoe deposit, the oldest mineralization so far known in the Sikhote-Alin orogen, formed in the initial stage of Early Cretaceous felsic magmatism. The magmatism began shortly after the accretionary tectonics ceased, suggesting an abrupt change of subduction system. Style of the Early Cretaceous magmatism and mineralization is significantly different between central Sikhote-Alin and Northeast Japan; reduced-type and oxidized-type, respectively. The different styles may reflect different tectonic environments; compressional and extensional, respectively. These two areas, which were closer together before the opening of the Japan Sea in the Miocene, may have been juxtaposed under a transpressional tectonic regime after the magmatism.     

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H₂ which reacts with magmatically derived CO₂ to form CH₄ and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH₄ with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO₂-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450–550 °C at 2.8–4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. δ¹³C values for methane range from − 22.4‰ to − 5.4‰, confirming a largely abiogenic origin for the gas. The presence of primary CH₄-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in δ¹³C isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks.     

Application of the QUILF thermobarometer to the peralkaline trachytes and pantellerites of the Eburru volcanic complex, East African Rift, Kenya

The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO₂ > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.     

Petrology, geochemistry and the mechanisms determining the distribution of platinum-group element and base metal sulphide mineralisation in the Platreef at Overysel, northern Bushveld Complex, South Africa

Platinum-group element (PGE) mineralisation within the Platreef at Overysel is controlled by the presence of base metal sulphides (BMS). The floor rocks at Overysel are Archean basement gneisses, and unlike other localities along the strike of the Platreef where the floor is comprised of Transvaal Supergroup sediments, the intimate PGE–BMS relationship holds strong into the footwall rocks. Decoupling of PGE from BMS is rare and the BMS and platinum-group mineral assemblages in the Platreef and the footwall are almost identical. There is minimal overprinting by hydrothermal fluids; therefore, the mineralisation style present at Overysel may represent the most ‘primary’ style of Platreef mineralisation preserved anywhere along the strike. Chondrite-normalised PGE profiles reveal a progressive fractionation of the PGE with depth into the footwall, with Ir, Ru and Rh dramatically depleted with depth compared to Pt, Pd and Au. This feature is not observed at Sandsloot and Zwartfontein, to the south of Overysel, where the footwall rocks are carbonates. There is evidence from rare earth element abundances and the amount of interstitial quartz towards the base of the Platreef pyroxenites that contamination by a felsic melt derived from partial melting of the gneissic footwall has taken place. Textural evidence in the gneisses suggests that a sulphide liquid percolated down into the footwall through a permeable, inter-granular network that was produced by partial melting around grain boundaries in the gneisses that was induced by the intrusion of the Platreef magma. PGE were originally concentrated within a sulphide liquid in the Platreef magma, and the crystallisation of monosulphide solid solution from the sulphide liquid removed the majority of the IPGE and Rh from it whilst still within the mafic Platreef. Transport of PGE into the gneisses, via downward migration of the residual sulphide liquid, fractionated out the remaining IPGE and Rh in the upper parts of the gneisses leaving a ‘slick’ of disseminated sulphides in the gneiss, with the residual liquid becoming progressively more depleted in these elements relative to Pt, Pd and Au. Highly sulphide-rich zones with massive sulphides formed where ponding of the sulphide liquid occurred due to permeability contrasts in the footwall. This study highlights the fact that there is a fundamental floor rock control on the mechanism of distribution of PGE from the Platreef into the footwall rocks. Where the floor rocks are sediments, fluid activity related to metamorphism, assimilation and later serpentinisation has decoupled PGE from BMS in places, and transport of PGE into the footwall is via hydrothermal fluids. In contrast, where the floor is comprised of anhydrous gneiss, such as at Overysel, there is limited fluid activity and PGE behaviour is controlled by the behaviour of sulphide liquids, producing an intimate PGE–BMS association. Xenoliths and irregular bands of chromitite within the Platreef are described in detail for the first time. These are rich in the IPGE and Rh, and evidence from laurite inclusions indicates they must have crystallised from a PGE-saturated magma. The disturbed and xenolithic nature of the chromitites would suggest they are rip-up clasts, either disturbed by later pulses of Platreef magma in a multi-phase emplacement or transported into the Platreef from a pre-existing source in a deeper staging chamber or conduit.