Origins of Nd–Sr–Pb isotopic variations in single scheelite grains from Archaean gold deposits,Western Australia

Accessory gangue scheelite (CaWO₄) from the Archaean Mt. Charlotte lode Au deposit can be divided into two types with different rare earth element (REE) signatures. In some scheelite grains, specific REE signatures are reflected by different cathodoluminescence colours, which can be used to map their often complex oscillatory intergrowths. Domains with specific REE contents from two grains were sampled for Sm/Nd, Rb/Sr and Pb isotopic analyses using a micro-drilling technique.Type I scheelite is strongly enriched in middle REE (MREE) and Eu anomalies are either absent or slightly positive. Four fragments collected from Type I regions of two crystals have initial ⁸⁷Sr/⁸⁶Sr and ε_Nd values ranging from 0.70141 to 0.70163 and +2.5 to +3.5, respectively, and Pb isotope ratios reflecting the composition of greenstone sequence. This may indicate that Nd and Pb have their source, either locally or regionally, in the greenstones. Basic greenstone lithologies have ⁸⁷Sr/⁸⁶Sr<0.7015, and the radiogenic Sr signatures indicate that part of the Sr originated from felsic lithologies located either within or beneath the host greenstone pile. Alternatively, the Sr signature may have evolved from preferential leaching of a Rb-rich mineral during hydrothermal alteration of the greenstone.The REE patterns of Type II scheelite are either flat or MREE-depleted and have strong positive Eu anomalies. Three fragments collected from Type II regions of the same two crystals have initial ⁸⁷Sr/⁸⁶Sr ratios and ε_Nd values between 0.70130 and 0.70146, and +1.1 to +2.6, respectively, and Pb isotope signatures that are once again similar to that of the greenstone. This implies that ⁸⁷Sr/⁸⁶Sr ratios in Type II fluids were closer to those of the host dolerite (0.7008–0.7013), due to more extensive fluid interaction with the dolerite.A positive correlation between Na and REE suggests that REE³⁺ are accommodated by the coupled substitution REE³⁺+Na⁺=2 Ca²⁺ into both Type I and Type II scheelite. This is consistent with a fractional crystallisation model to explain the change in REE patterns from Type I to Type II, but not with a model involving different coupled substitutions and fluids from different origins. We propose that the complex REE and isotopic signatures of scheelite at Mt. Charlotte are related to small (<m) to medium (<km) scale processes involving mixing between “fresh” batches of hydrothermal fluid with fluids that had already been involved in extensive wall-rock alteration.The very high-ε_Nd values measured in some scheelites have been previously used to link gold mineralisation with komatiites containing unusually high Sm/Nd ratios. However, tiny (<20 μm) grains of secondary hydroxyl-bastnäsite were found within micro-fractures of one scheelite grain containing an extremely high-ε_Nd signature. The hydroxyl-bastnäsite probably formed during recent REE redistribution within the scheelite as a result of meteoric fluid circulation. The scale of this cryptic low-temperature alteration is sufficient to explain the anomalously high-ε_Ndi values observed in scheelite from Western Australia.     

REE Distribution in Scheelite from the Yubileinoe Porphyry Gold Deposit,South Urals: Evidence from LA-ICP-MS Data

Zoned scheelite crystals from the Yubileinoe porphyry gold deposit were studied by EMPA and LA-ICP-MS. The MoO₃ content decreases from 10–13 wt % in the crystal center to less than 2 wt % in the rim. Scheelite is enriched in LREE with respect to HREE and has negative Eu and Ce anomalies. Early scheelite has a flat REE distribution pattern with a negative slope, while the latter has asymmetrical convex REE spectra due to the lower La content and higher Nd, Sm, and Gd concentrations. The REE distribution in early scheelite has been established as inherited from ore-bearing granitic rocks, while this distribution in later generations of the mineral was determined by hydrothermal fluid.     

Multiple sources for mineralizing fluids in the Charmitan gold(-tungsten) mineralization (Uzbekistan)

Mineral assemblages present within the Charmitan gold(-tungsten) quartz-vein mineralization have been investigated for their cathodoluminescence behaviour, chemical composition and noble gas isotope systematics. This inventory of methods allows for the first time a systematic reconstruction of the paragenetic relationships of quartz, scheelite, sulphides and native gold within the gold mineralization at Charmitan and provides the basis to utilise noble gas data in the discussion of sources and evolution of ore-forming fluids. The vein quartz is classified into four generations based on microscopic and cathodoluminescence investigations. Quartz I shows intense brittle deformation as associated scheelite I. Undeformed scheelite II overgrows scheelite I and has lower light rare earth element and higher intermediate rare earth element contents as well as higher strontium concentrations. Scheelite II is associated with the economic gold mineralization and formed during re-crystallisation and re-precipitation of material which was partly re-mobilised from early scheelite I during infiltration of gold-bearing fluids. Early stage native gold inclusions are often associated with stage 2 sulphides, scheelite II and bismuth tellurides and contain Ag (3.6–24.4 wt.%), Hg (≤1.0 wt.%) and Bi (≤0.2 wt.%). Later stage electrum grains occur in association with stage 3 sulphides and sulphosalts and contain Hg (<0.8 wt.%) and elevated Sb concentrations (up to 3.0 wt.%). Noble gas isotope data (³He/⁴He: 0.2-0.4 Ra) for hydrothermal ore fluids trapped in the gold-related sulphides and sulphosalts (stage 2 pyrite and arsenopyrite; stage 3 pyrite, sphalerite, galena and lead sulphosalts) suggest that diverse fluid sources were involved in the formation of the Charmitan gold deposit. These data are indicative of a small, but significant input of fluids from external, deep-seated (mantle and possibly lower crust) sources. A decrease in the input of mantle helium and an increasing role of crustal helium from early to later stages of the mineralization is suggested by the measured ³He/⁴He and ⁴⁰Ar*/⁴He ratios. Sulphides from ore veins in meta-sedimentary rocks contain higher portions of meteoric fluids than those in intrusive rock types as indicated by their lower ³He/³⁶Ar ratios. The ³He/³⁶Ar ratios in the meta-sedimentary rocks agree well with ratios typical of gold mineralizations in the Tien Shan gold province completely hosted by meta-sedimentary sequences, indicating intense fluid-wall rock interaction.     

REE controls in ultramafic hosted MOR hydrothermal systems: An experimental study at elevated temperature and pressure

A hydrothermal experiment involving peridotite and a coexisting aqueous fluid was conducted to assess the role of dissolved Cl⁻ and redox on REE mobility at 400°C, 500 bars. Data show that the onset of reducing conditions enhances the stability of soluble Eu⁺² species. Moreover, Eu⁺² forms strong aqueous complexes with dissolved Cl⁻ at virtually all redox conditions. Thus, high Cl⁻ concentrations and reducing conditions can combine to reinforce Eu mobility. Except for La, trivalent REE are not greatly affected by fluid speciation under the chemical and physical condition considered, suggesting control by secondary mineral-fluid partitioning. LREE enrichment and positive Eu anomalies observed in fluids from the experiment are remarkably similar to patterns of REE mobility in vent fluids issuing from basalt- and peridotite-hosted hydrothermal systems. This suggests that the chondrite normalized REE patterns are influenced greatly by fluid speciation effects and secondary mineral formation processes. Accordingly, caution must be exercised when using REE in hydrothermal vent fluids to infer REE sources in subseafloor reaction zones from which the fluids are derived. Although vent fluid patterns having LREE enrichment and positive Eu anomalies are typically interpreted to suggest plagioclase recrystallization reactions, this need not always be the case.     

A Study on the Mineralization of the Woxi Au–Sb–W Deposit,Western Hunan,China

The Woxi Au–Sb–W deposit in the western Hunan Province, China, is of hydrothermal vein type characterized by a rare mineral assemblage of stibnite, scheelite and native gold, of which gold fineness ranges from 998.6 to 1000. The mineralization sequence observed in the deposit is, from early to late, coarse‐grained pyrite – scheelite – stibnite – Pb–Sb–S minerals – sphalerite (+ cubanite) – fine‐grained pyrite. Native gold may have precipitated with scheelte. Microthermometric and LA–ICP–MS analyses of fluid inclusions in scheelite, quartz associated with scheelite and stibnite and barren quartz clarified that there may be at least three types of hydrothermal fluids during the vein formation in the Woxi deposit. Scheelite and native gold precipitated from the fluid of high temperature and salinity with high concentrations of metal elements, followed by stibnite precipitation. The later fluid of the highest temperature and salinity with low concentrations of the elements yielded the sphalerite mineralization. The latest fluid of low temperature and salinity with low concentrations of the elements is observed mainly in barren quartz. The remarkably high Au/Ag concentration ratios determined in the fluid inclusions in scheelite might be the reason for the extremely high gold fineness of native gold.     

Geochemistry of stratabound scheelite mineralisation and associated calc-silicate rocks from Chitral,NE Hindu Kush,Pakistan

Tungsten mineralisation in the NE Hindu Kush terrain occurs 8 km NW of the Tirich Boundary Zone suture between Karakoram and Eastern Hindu Kush. Scheelite occurs mainly in calc-silicate rocks and subordinately in tourmalinites associated with metasediments at Miniki Gol, Chitral. The investigated area underwent two phases of deformation and was metamorphosed up to sillimanite grade, followed by the emplacement of leucogranite and hydrothermal activity. The mineral assemblages of the calc-silicate rocks, comprising clinozoisite, quartz, calcic-amphibole, plagioclase, chlorite, biotite, calcite, sphene, garnet and scheelite, clearly express a skarn type environment. The coexistence of the scheelite grains with clinozoisite and the occurrence of anomalous values of ZrO₂ and Ta₂O₅ in the scheelite grains imply a genetic link between the scheelite mineralisation and post-magmatic hydrothermal fluids. The enrichment of Zr, Hf, Be, Sn, W, Th, U, Ga, Nb, F and Y along with total REE in the scheelite-bearing calc-silicate rocks compared with the associated metasediments assigns that the rocks at Miniki Gol have undergone a pronounced hydrothermal activity. Strong positive correlations between Zr, Hf, Nb, Y, Ta, F and REE, and the mobility of REE are consistent with this consideration. Aqueous fluid inclusions in the scheelite-bearing calc-silicate rocks display very low salinity, suggesting a mixing of magmatic fluids with meteoric water. The formation of intergrown scheelite and clinozoisite indicates a high pH and CO₂-deficient fluid. The tungsten mineralization may be related to the Miniki Gol leucogranite which occurs at a distance of only 400 m.     

LA-ICP-MS原位分析白钨矿稀土元素

白钨矿是各类矿床中较为常见的副矿物,通过分析白钨矿的稀土元素质量分数及其标准化配分模式图,可为矿床成矿流体特征及演化提供重要的判别依据。本文对东北地区羊鼻山矽卡岩型矿床和杨金沟热液脉型矿床两个典型钨矿床的白钨矿样品中的稀土元素进行了激光剥蚀-电感耦合等离子体质谱（LA-ICP-MS）原位分析。其中：羊鼻山矽卡岩型矿床白钨矿LA-ICP-MS分析方法所获得的稀土元素配分曲线模式与前人用传统的溶液-ICP-MS分析方法所获得的结果完全吻合,表明采用剥蚀束斑44 μm和剥蚀频率7 Hz的193 nm ArF激光器,NIST 610作外部标样,Ca作内标元素,对基体效应影响最小,所获数据可靠,方法可行;而杨金沟热液脉型矿床白钨矿溶液-ICP-MS分析方法与LA-ICP-MS分析法所获得结果既具有相似性又具有差异性。原因在于羊鼻山白钨矿的成因类型为矽卡岩型、粒度较小且形成时间短,因此不同矿物颗粒间、同一矿物不同部位间稀土元素的配分模式一致;而杨金沟白钨矿的成因类型属于热液脉型、粒度较大、沉淀结晶时间长,因此同一矿物不同部位的稀土元素的配分模式因成矿流体早晚阶段不同而不同。基于以上对比研究发现,无论是在取样和测试过程方面,还是数据准确度方面,相比传统溶液-ICP-MS分析法,LA-ICP-MS原位分析法均具有明显的优势,主要表现在样品形式简单、粒度和质量分数要求低、测试周期短、费用低且结果精确度高;同时其可对不同成矿阶段或白钨矿不同部位成分进行精细测定,从而得出不同成矿阶段或白钨矿不同部位的稀土元素质量分数,以及在更高的空间分辨率下获得更详细准确的数据信息。此外,对白钨矿（尤其是无明显环带者）进行LA-ICP-MS原位分析时,既可采用电子探针微量分析（EPMA）准确测定Ca的质量分数,也可直接采用标准化学式计算Ca的质量分数,分析所得数据同样可以获得合理的地质解释。     

云南大坪金矿白钨矿微量元素、稀土元素和Sr-Nd同位素组成特征及其意义

利用ICP-MS和同位素质谱分析了大坪金矿含金石英脉中白钨矿的微量元素、稀土元素和Sm-Nd、Rb-Sr同位素组成,结果显示大坪白钨矿中富Sr、Ba,而亏损Mo、Bi、Sn、Nb、Ta等,指示原始成矿流体与岩浆的结晶分异作用无关,并非前人普遍认为的岩浆水和大气降水的混合流体;样品的REE球粒陨石标准化配分曲线为高度一致的右倾和MREE富集型,Eu出现正异常,表明白钨矿与流体之间REE元素发生了强烈分异,白钨矿中REE的配分行为主要表现为REE^3＋与Na^＋成化合价补偿形式替代Ca^2＋选择性进入白钨矿晶格中,成矿流体是相对封闭的高温、富Na^＋的还原性热液体系;Sr-Nd同位素组成显示本区原始成矿流体主要来自下地壳,但不排除有幔源物质加入.原始成矿流体的形成与区域性剪切带的活动有关,韧性剪切作用导致下地壳富CO2流体上升,并与闪长岩发生强烈的水岩反应,而剪切带中脆性断裂的形成是成矿流体迁移、集中、沸腾和矿质沉淀的触发因素.     

Chemistry of magnetite-apatite from albitite and carbonate-hosted Bhukia Gold Deposit,Rajasthan, western India – An IOCG-IOA analogue from Paleoproterozoic Aravalli Supergroup: Evidence from petrographic,LA-ICP-MS and EPMA studies

The Bhukia gold (+copper) deposit hosted by albitite and carbonates that occur within the Paleoproterozoic Aravalli-Delhi Fold Belt (ADFB) in western India consists of magnetite, graphite, apatite and tourmaline along with sulfide mineralization. Ubiquitous presence of magnetite and apatite in gold-sulfide association, alteration patterns and shear controlled mineralization suggest it to be IOCG (Iron-oxide copper gold) type deposits. The detailed mineral chemistry of magnetite and apatite are generated and interpreted in terms of their genetic significance, hydrothermal and magmatic origin vis-à-vis their affiliation with IOCG deposition. The data suggest that the magnetite has hydrothermal affiliation. The Ni/Cr ratio is greater than 1, which is explained by differences in solubility and mobility of Ni and Cr in hydrothermal fluids and is corroborated with other key evidences including that of wide ranging Mg concentration further supports a strong hydrothermal input that is envisaged for the deposition of magnetite. Concentration of vanadium in magnetite is generally <1000 ppm in case of barren hydrothermal occurrences while in the study area, it is relatively higher as it is attributed to the gold-sulfide-Cu mineralization. Ti vs Ni/Cr, Ni/(Cr+Mn) vs Ti+V, Ca+Al+Mn vs Ti+V and Al+Mn vs Ti+V variations are interpreted in terms of magnetite genesis. EPMA data suggests that apatite present in Bhukia is of fluorapatite variety with F content >1 wt% and F/Cl >1. Higher concentration of F and moderate Mn along with lower concentration of Cl attests their magmatic hydrothermal character and its derivation from meta-volcano sedimentary source. REE patterns obtained from LA-ICP-MS analysis suggest enrichment of LREE relative to MREE and HREE with negative Eu anomaly. Y/∑REE, La/Sm, Ce/Th and Eu/Eu¹ vs Ce/Ce¹ values of apatite is indicative of their origin in a highly oxidized environment. Presence of magnetite along with apatite is a common feature in IOCG-IOA (Iron-Oxide Apatite) association. Bhukia Gold Deposit has many similarities with Kiruna type Iron-Oxide Apatite (IOA) deposits particularly with respect to their similar tectonic setting, alteration patterns, mineral assemblages such as abundance of magnetite, apatite and presence of late stage sulfides based on EPMA and Laser ablation ICP-MS (LA-ICP-MS) studies. Lithological, petro-mineralogical and geochemical signatures of magnetite and apatite infer that the Bhukia is a possible IOCG-IOA type gold deposit typically associated with sulfides and graphite which may be used as petrogenetic indicators and pathfinders for exploration.     

贵州泥堡金矿床热液方解石地球化学特征及地质意义

已有研究表明,右江盆地卡林型金矿成矿期方解石具有独特的中稀土元素富集特点,但其成因还存在诸多争议。贵州泥堡金矿存在成矿期和非成矿期2种热液方解石脉,其中成矿期方解石脉多出现在矿化凝灰质细砾岩与凝灰质（粉）砂岩中,矿物组合为含砷黄铁矿+毒砂+石英+方解石;非成矿期方解石脉在未蚀变灰岩、矿化凝灰质细砾岩与凝灰质（粉）砂岩中均发育,且常穿切成矿期含硫化物方解石脉。文章通过对2种类型方解石脉开展稀土元素与碳、氧同位素、成矿期方解石脉内金属硫化物电子探针与微区原位LA-ICP-MS元素分析,发现与成矿期方解石脉共生的黄铁矿具典型的环带结构,黄铁矿环带和毒砂富Au、As、Sb、Hg、Cu、Co、Ni等元素。成矿期方解石脉显示中稀土元素富集模式和Eu正异常特征,表明金成矿流体为还原性流体,明显不同于非成矿期方解石脉的轻稀土元素富集模式和Eu负异常特征。泥堡金矿成矿期热液方解石的中稀土元素富集模式,与中国西南低温Au-Sb矿床成矿期方解石、萤石、磷灰石等矿物的稀土元素组成特征一致,酸性成矿流体的稀土元素组成可能是导致该金矿区成矿期方解石富集中稀土元素的主要原因。该区热液方解石特有的地球化学特征,使其在低温热液金矿床成矿年代学研究及深部找矿应用方面具有重要前景。     

REE constraints on fractionation processes of massive-type anorthosites on the Lofoten Islands, Norway

Summary Rare Earth Element (REE) data of 34 samples of magmatic rocks from the Lofoten Islands in Norway lend support to the derivation of anorthosites, ferrodiorites and jotunites by fractionation and cumulus processes from typical basaltic magma. Both REE concentration and Eu anomalies (expressed as Eu/Eu^*) form continuous linear trends from anorthosite towards gabbro, ferrodiorite and jotunite in discrimination diagrams against molar CaO/Al₂O₃ ratios indicating the predominant accumulation of plagioclase. Eu/Eu^* decreases from about 4 in the cumulates (anorthosites) to around 1 in the fine-grained gabbroic dikes and to below 1 in some ferrodiorites and the jotunite. The various types of ferrodiorites and the jotunite are regarded as residual liquids, in some cases with variable amounts of cumulus plagioclase. The whole fractionation series from gabbro towards anorthosites and ferrodiorites can be observed in a single intrusion. With increasing fractionation, the REE patterns generally change from flat, slightly LREE-enriched or LREE-depleted to steep and strongly LREE-enriched. These changes and the REE abundances are mainly controlled by the abundance of apatite. Temporally and spatially related mangerites and charnockites form a trend from low-SiO₂ mangerites with Eu/Eu^* > 1 to intermediate-SiO₂ acidic mangerites with Eu/Eu^* ≈ 1 and charnockites with Eu/Eu^* < 1. Accordingly, the low-SiO₂ mangerites are interpreted as alkali feldspar-rich cumulates and the charnockites as residual liquids derived from the acidic mangerites. The mangerites with Eu/Eu^* around 1 have patterns similar to those of some highly evolved ferrodiorites possibly indicating a genetic link. Received December 12, 1999; revised version accepted November 15, 2000     

Hydrocarbon- and ore-bearing basinal fluids: a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin,South China

The Youjiang basin, which flanks the southwest edge of the Yangtze craton in South China, contains many Carlin-type gold deposits and abundant paleo-oil reservoirs. The gold deposits and paleo-oil reservoirs are restricted to the same tectonic units, commonly at the basinal margins and within the intrabasinal isolated platforms and/or bioherms. The gold deposits are hosted by Permian to Triassic carbonate and siliciclastic rocks that typically contain high contents of organic carbon. Paragenetic relationships indicate that most of the deposits exhibit an early stage of barren quartz ± pyrite (stage I), a main stage of auriferous quartz + arsenian pyrite + arsenopyrite + marcasite (stage II), and a late stage of quartz + calcite + realgar ± orpiment ± native arsenic ± stibnite ± cinnabar ± dolomite (stage III). Bitumen in the gold deposits is commonly present as a migrated hydrocarbon product in mineralized host rocks, particularly close to high grade ores, but is absent in barren sedimentary rocks. Bitumen dispersed in the mineralized rocks is closely associated and/or intergrown with the main stage jasperoidal quartz, arsenian pyrite, and arsenopyrite. Bitumen occurring in hydrothermal veins and veinlets is paragenetically associated with stages II and III mineral assemblages. These observations suggest an intimate relationship between bitumen precipitation and gold mineralization. In the paleo-petroleum reservoirs that typically occur in Permian reef limestones, bitumen is most commonly observed in open spaces, either alone or associated with calcite. Where bitumen occurs with calcite, it is typically concentrated along pore/vein centers as well as along the wall of pores and fractures, indicating approximately coeval precipitation. In the gold deposits, aqueous fluid inclusions are dominant in the early stage barren quartz veins (stage I), with a homogenization temperature range typically of 230°C to 270°C and a salinity range of 2.6 to 7.2 wt% NaCl eq. Fluid inclusions in the main and late-stage quartz and calcite are dominated by aqueous inclusions as well as hydrocarbon- and CO₂-rich inclusions. The presence of abundant hydrocarbon fluid inclusions in the gold deposits provides evidence that at least during main periods of the hydrothermal activity responsible for gold mineralization, the ore fluids consisted of an aqueous solution and an immiscible hydrocarbon phase. Aqueous inclusions in the main stage quartz associated with gold mineralization (stage II) typically have a homogenization temperature range of 200–230°C and a modal salinity around 5.3 wt% NaCl eq. Homogenization temperatures and salinities of aqueous inclusions in the late-stage drusy quartz and calcite (stage III) typically range from 120°C to 160°C and from 2.0 to 5.6 wt% NaCl eq., respectively. In the paleo-oil reservoirs, aqueous fluid inclusions with an average homogenization temperature of 80°C are dominant in early diagenetic calcite. Fluid inclusions in late diagenetic pore- and fissure-filling calcite associated with bitumen are dominated by liquid C₂H₆, vapor CH₄, CH₄–H₂O, and aqueous inclusions, with a typical homogenization temperature range of 90°C to 180°C and a salinity range of 2–8 wt% NaCl eq. It is suggested that the hydrocarbons may have been trapped at relatively low temperatures, while the formation of gold deposits could have occurred under a wider and higher range of temperatures. The timing of gold mineralization in the Youjiang basin is still in dispute and a wide range of ages has been reported for individual deposits. Among the limited isotopic data, the Rb–Sr date of 206 ± 12 Ma for Au-bearing hydrothermal sericite at Jinya as well as the Re–Os date of 193 ± 13 Ma on auriferous arsenian pyrite and ⁴⁰Ar/³⁹Ar date of 194.6 ± 2 Ma on vein-filling sericite at Lannigou may provide the most reliable age constraints on gold mineralization. This age range is comparable with the estimated petroleum charging age range of 238–185 Ma and the Sm–Nd date of 182 ± 21 Ma for the pore- and fissure-filling calcite associated with bitumen at the Shitouzhai paleo-oil reservoir, corresponding to the late Indosinian to early Yanshanian orogenies in South China. The close association of Carlin-type gold deposits and paleo-oil reservoirs, the paragenetic coexistence of bitumens with ore-stage minerals, the presence of abundant hydrocarbons in the ore fluids, and the temporal coincidence of gold mineralization and hydrocarbon accumulation all support a coeval model in which the gold originated, migrated, and precipitated along with the hydrocarbons in an immiscible, gold- and hydrocarbon-bearing, basinal fluid system.     

Types of anion-cation packing of mineral surfaces and their manifestation in various processes

Possible types of anion-cation packing of mineral surface were evaluated. Their role was estimated for the decoration of minerals with gold under vacuum (process simulating crystallization on a surface), mineral growth and intergrowth, adsorption, surface diffusion, and other surface processes. It was shown that there are two distinct types (I and II) of mineral surfaces differing in the character of crystallization of gold nanoparticles during decoration. Type I includes surfaces showing predominant formation of gold nanoparticles (5–15 nm) on growth (dissolution, evaporation) steps, dislocations, and point defects. These surfaces are represented by packed layers of O⁻² anions, alternating anions and cations, and identical atoms. Type II includes surfaces with the statistical distribution (10^9–12 cm⁻²) of gold nanoparticles (5–30 nm). Such patterns are characteristic of surfaces with packing of OH⁻ groups, OH⁻ in combination with O⁻², and with the statistical distribution of anions and cations. Type I surfaces show low adsorption capacity and a large extent of diffusion on them (∼10^3–4 nm). In contrast, type II surfaces have high adsorption capacity and low (∼50 nm) surface diffusion. Minerals dominated by type I surfaces grow by the layer and spiral mechanisms, and those dominated by type II surfaces grow by the normal mechanism. Original Russian Text ? N.D. Samotoin, L.O. Magazina, 2006, published in Geokhimiya, 2006, No. 10, pp. 1068–1084.     

Partitioning of rare earth elements between an aqueous chloride fluid phase and melt during the decompression-driven degassing of granite magmas

This paper reports the results of numerical simulation for the behavior of rare earth elements (REE) during decompression degassing of H₂O- and Cl-bearing granite melts at pressures decreasing from 3 to 0.5–0.3 kbar under near isothermal conditions (800 ± 25°C). Fluid phase in equilibrium with the melt contains mainly chloride REE complexes, and their behavior during magma degassing is, therefore, intimately related to the behavior of chlorine. It was shown that the contents and distribution patterns of REE in the aqueous chloride fluid phase formed during decompression vary considerably depending on (1) the contents of volatiles (Cl and H₂O) in the initial melt, (2) the redox state of the magma, and (3) the dynamics of fluid phase separation from magmas during their ascent toward the Earth’s surface. During decompressiondriven degassing, the contents of both Cl and REE in the fluid decrease, especially dramatically under opensystem conditions. The REE patterns of the fluid phase compared with those of the melt are characterized by a higher degree of light to heavy REE fractionation. A weak negative Eu anomaly may be present in the REE patterns of Cl-rich fluids formed during the early stages of degassing at relatively high pressures. At a further decrease in pressure and Cl content in the fluid, it is transformed into a positive Eu anomaly increasing during decompression degassing. Such an anomalous behavior of Eu during degassing is related to its occurrence in magmatic melts in two valence states, Eu³⁺ and Eu²⁺, whereas the other REE occur in melts mainly as (REE)³⁺. The Eu³⁺/Eu²⁺ ratio of melt is controlled by the redox state of the magmatic system. The higher the degree of melt reduction, the more pronounced the anomalous behavior of Eu during decompression degassing. The amount of REE extracted by fluid from melt during various stages of degassing does not significantly influence the content and distribution patterns of REE in the melt.     

Fluid inclusion and stable isotope evidence for the genesis of quartz-scheelite veins, Metaggitsi area, central Chalkidiki Peninsula, N. Greece

Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H₂O-CO₂ inclusions with highly variable (20–90 vol.%) CO₂ contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH₄. Type 2 inclusions are nearly 100 vol.% liquid CO_2, with traces of CH₄, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H₂O gas infrequently containing also small amounts of CO₂ (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH₄ and CO₂, into gas-rich (CO₂-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H₂O, or to the CO₂ phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10⁻³⁵ to 10⁻³¹ bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ¹⁸O water values of 3 to 6 per mil (SMOW) and δ¹³C CO₂₋ fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997     

Laser-induced time-resolved luminescence as a tool for rare-earth element identification in minerals

 We have determined and distinguished a number of rare-earth elements in several minerals by use of laser-induced time-resolved luminescence spectroscopy. Unlike the conventional measurement of steady-state luminescence, the method allows discrimination between ions that emit in the same spectral range but have different decay times. The main new results are the following: decay time data for all REE luminescence centers; Tm³⁺, Pr³⁺, Er³⁺, Ho³⁺ luminescence in apatite, scheelite, zircon, calcite, and fluorite; Eu³⁺ luminescence in apatite, zircon, fluorite, calcite, danburite, and datolite. Received: 17 April 2000 / Accepted: 4 January 2001     

Coexistence of a Fluid Phase with Granitic Magma: Geochemical Characteristics of REE and Cu in Miyako Granite and in Scheelite-bearing Aplitic Veins at the Yamaguchi Cu-W Skarn Deposit, Iwate, Japan

Abstract: The North granitic body of the Miyako pluton is located in the Northern Kitakami belt, Northeast Japan. The formation of the scheelite–chalcopyrite–magnetite–bearing aplitic veins and scheelite–chalcopyrite–magnetite–bearing Yamaguchi skarn deposit was closely associated with the formation of the Miyako plutons. Petrographic facies of the North granitic body vary from quartz diorite in marginal zone (zone A), to tonalite and granodiorite (zone B), and to granite (zone C) in the central. The large numbers of aplitic veins distributed around the Yamaguchi mining area are divided into two groups: barren and scheelite–mag–netite–chalcopyrite–bearing aplitic veins. The latter cut massive clinopyroxene skarns of the Yamaguchi deposit, and are composed of plagioclase, K‐feldspar and titanite. Some plagioclase crystals have dusty cores with irregularly shaped K‐feldspar flakes, and clear rims of albite. Textures of plagioclase in the mineralized aplitic veins are different from the idiomorphic textures with sharp plagioclase crystal boundaries that occur in the North granitic body and barren aplitic veins. These textural data suggest that the mineralized aplitic veins were formed from hydrothermal fluid. Changes in the contents of major and minor (Rb, Sr, Sc, Co, Th, U) elements in the North Miyako granitic body are similar to those of zoned plutons formed by typical magmatic differentiation processes. On the other hand, concentrations of REE, especially middle to heavy REE, of granitic rocks in zone C and barren aplitic veins are significantly lower than those of granitic rocks in zones A and B. The hypothetical chondrite‐normalized REE patterns, calculated assuming fractional crystallization from zone B granitic melt, suggest that REE concentrations of the residual melt increased with the degree of fractional crystallization, and changed into a pattern with enriched LREE and strongly negative Eu anomaly. However, the REE patterns of granitic rocks in zone C are different from the hypothetical patterns. Moreover, the REE patterns of magnetite–scheelite–chalcopyrite aplitic veins are quite different from those of granitic rocks. The Cu contents of granitic rocks in the North Miyako body increase from zone A (5–26 ppm) to zone B (10–26 ppm), and then clearly decrease to zone C (5–7 ppm) and drastically increase to the barren aplitic veins (39–235 ppm). Concentrations of Cu in the mineralized aplitic veins are also higher than those of the granitic rocks in zone C. The decrease in REE and Cu contents of granitic rocks from zone B to zone C is not a result of simple magmatic fractional differentiation. Fluid inclusions in quartz from mineralized aplitic veins contain 3.3 wt% NaCl equivalent and 5.8 wt% CO₂. It was also demonstrated experimentally that the removal of MREE and HREE by fluid from melt enabled the formation of complexes of REE and ligands of OH^‐ and CO₃^2‐. Based on the possibility that the melt of the granitic rocks of zone C and the mineralized aplitic veins coexisted with CO₂‐bearing fluid, it is thought that REE were extracted from the melt to the CO₂‐bearing fluid, and that the REE in the mineralized aplitic veins were transported by the CO₂‐bearing fluid. It is likely that the low HREE and Cu contents of the granitic rocks in zone C could have been caused by the removal of those elements from the granitic melt by the fluid coexisting with the melt. The expelled materials could have been the sources of scheelite–magnetite–chalcopyrite–bearing aplitic veins and copper mineralization of the Yamaguchi Cu‐W skarn deposit.     

A rare earth element-rich carbonatite dyke at Bayan Obo, Inner Mongolia, North China

Summary ?A carbonatite dyke, extremely enriched in rare earth elements (REE), is reported from Bayan Obo, Inner Mongolia, North China. The REE content in the dyke varies from 1 wt% to up to 20 wt%. The light REEs are enriched and highly fractionated relative to the heavy REEs, and there is no Eu anomaly. Although carbon isotope δ¹³C (PDB) values of the carbonatites (−7.3 to −4.7‰) are within the range of normal mantle (−5±2‰), oxygen isotope δ¹⁸O (SMOW) (11.9 to 17.7‰) ratios apparently are higher than those of the mantle (5.7±1.0‰), indicating varying degrees of exchange with hydrothermal fluids during or after magmatic crystallization. The carbonatite is the result of partial melting followed by fractional crystallization. Primary carbonatite melt was formed by less than 1% partial melting of enriched mantle, leaving a garnet-bearing residue. The melt then rose to a crustal magma chamber and underwent fractional crystallization, producing further REE enrichment. The REE and trace element distribution patterns of the carbonatites are similar to those of fine-grained dolomite marble, the ore-host rock of the Bayan Obo REE–Nb–Fe giant mineral deposit. This fact may indicate a petrogenetic link between the dykes described here and the Bayan Obo mineral deposit. Received November 1, 2001; revised version accepted June 16, 2002     

Trace element distribution in Central Dabie eclogites

Coesite-bearing eclogites from Dabieshan (central China) have been studied by ion microprobe to provide information on trace element distributions in meta-basaltic mineral assemblages during high-pressure metamorphism. The primary mineralogy (eclogite facies) appears to have been garnet and omphacite, usually with coesite, phengite and dolomite, together with high-alumina titanite or rutile, or both titanite and rutile; kyanite also occurs occasionally as an apparently primary phase. It is probable that there was some development of quartz, epidote and apatite whilst the rock remained in the eclogite facies. A later amphibolite facies overprint led to partial replacement of some minerals and particularly symplectitic development after omphacite. They vary from very fine-grained dusty-looking to coarser grained Am + Di + Pl symplectites. The eclogite facies minerals show consistent trace element compositions and partition coefficients indicative of mutual equilibrium. Titanite, epidote and apatite all show high concentrations of REE relative to clinopyroxene. The compositions of secondary (amphibolite facies) minerals are clearly controlled by local rather than whole-rock equilibrium, with the composition of amphibole in particular depending on whether it is replacing clinopyroxene or garnet. REE partition coefficients for Cpx/Grt show a dependence on the Ca content of the host phases, with D _REE ^Cpx/Grt decreasing with decreasing D _Ca . This behaviour is very similar to that seen in mantle eclogites, despite differences in estimated temperatures of formation of 650–850 °C (Dabieshan) and 1000–1200 °C (mantle eclogites). With the exception of HREE in garnet, trace elements in the eclogites are strongly distributed in favour of minor or accessory phases. In particular, titanite and rutile strongly concentrate Nb and Zr, whilst LREE–MREE go largely into epidote, titanite and apatite. If these minor/accessory minerals behave in a refractory manner during melting or fluid mobilisation events and do not contribute to the melt/fluid, then the resultant melts and fluids will be strongly depleted in LREE–MREE. Received: 11 February 1999 / Accepted: 31 January 2000