湖南沃溪金-锑-钨矿床成因的稀土元素地球化学证据

沃溪金-锑-钨矿床的稀土元素地球化学组成良好地反映了成矿作用的条件和过程,并为示踪矿床成因提供了有用的信息.以流体包裹体为代表的成矿溶液,以较高的稀土总量、显著的轻稀土富集和缺乏明显的铕异常为特征,代表了一种通过在碎屑沉积物柱中循环而萃取矿质的演化的海水热液.矿石相对于成矿流体(母液)富集重稀土而轻微亏损铕,反映了矿石沉淀过程中来自于海水的稀土元素掺合.同一矿层内由下往上,重稀土相对富集的程度逐渐增大而稀土总量则逐渐降低,表明随着热液化学沉淀作用的进行,海水掺合的影响逐渐增强.矿石的稀土元素组成,无论在分布模式还是在轻重稀土之间的分馏程度上,均与其他许多 Sedex型多金属矿床十分相似,暗示了这些矿床具有相似的成因机制.稀土元素地球化学特征支持矿床同生沉积成因的观点.     

Ore-Forming Fluids of Vein-Type Fluorite Deposits of the Cerro Aspero Batholith,Southern Cordoba Province,Argentina

Vein-type fluorite deposits in the southern part of the Sierras Pampeanas, Córdoba Province, Argentina, occur mainly hosted by calc-alkaline porphyritic biotite granites, which belong to the Paleozoic, post-tectonic Cerro Aspero batholith. The fluorite veins, of Cretaceous age, occupy steeply dipping, strike-slip regional fault zones, and are composed of fluorite and chalcedony, locally with subordinate amounts of pyrite and, in some cases, coffinite and pitchblende. These veins show typical open-space-filling textures and are closely related to pervasive silicic and argillic alteration of the host granite.

Three successive stages of mineralization were distinguished on the basis of vein chronology, REE data, and fluid-inclusion study in fluorite ores. These stages generally display slightly fractionated REE patterns (La/Yb = 1.4 to 14), with REE behavior given by a relatively stronger LREE fractionation with respect to HREE. The REE composition of the fluids responsible for fluorite deposition was largely controlled by differential mobility of the REE during the silicic or argillic alteration of the host granite. Preferential leaching of HREE over LREE occurred during both alteration types, but in the argillic alteration the LREE were practically not removed. The total homogenization of primary-like aqueous inclusions took place invariably in the liquid phase at temperatures ranging from 187°C to 103°C, with concentrations of values around 160°C, 136°C, and 116°C (stages I, II, and III, respectively), defining a clear trend of fluid cooling. This cooling is accompanied by large changes in the fO₂ of the fluid, from oxidizing to reducing, as inferred from the Eu/Eu? ratios and the mineral assemblage (pyrite, pitchblende, and coffinite).

The three stages of fluorite deposition exhibit temperatures of ice melting within the interval from ?0.3°C to +0.4° C, indicating that the mineralizing fluids were exclusively aqueous and highly dilute. No evidence of fluid mixing or boiling was found. The fluid-inclusion data suggest that the proposed three stages of mineralization probably were the result of a single hydrothermal event, and strongly support a single, uniform fluid reservoir for the ore-forming solutions; evidently, the latter were heated meteoric waters rather than fluids generated in deep-seated environments within the crust.     

大冶-武山矿化夕卡岩的稀土元素地球化学研究

用ICP-MS分析了25个含矿夕卡岩样品的REE含量,其中对8个样品的石榴子石等矿物中的熔融包裹体进行了均一温度测定,还对5个夕卡岩样品石榴子石中的熔融包裹体进行了电子探针分析.在这些样品的石榴子石、辉石或方解石中都观察到熔融包裹体.夕卡岩的球粒陨石标准化REE分布模式具有两个突出特点:其一是以富集轻稀土元素(LREE)右倾为特征;其二是多数以具有Eu正异常为特征.夕卡岩球粒陨石标准化REE分布模式有三种类型:第一类型显示斜率不大的右倾直线;第二类型具有以Ce为峰值的折线的特征,即REE线段向上凸,在Ce处有一极大值(个别无峰值,LREE曲线向上凸,呈穹隆状);第三类型为过渡型REE分布模式.在当今REE资料有限的情况下,利用稀土元素地球化学特点鉴别夕卡岩成因是困难的.     

碳酸盐(岩)的稀土元素特征及其古环境指示意义

稀土元素主要通过交代碳酸盐矿物的Ca^{2+0进入碳酸盐格架,所以沉积碳酸盐(岩}的稀土元素特征能够很好的指示沉积流体来源和古环境。常用的稀土元素指标包括稀土元素总量(ΣREE)、稀土元素配分型式、以及La、Ce、Eu、Gd和Y等元素的异常指数。碳酸盐(岩)的稀土元素含量可能受到硅酸盐矿物、Fe-Mn氧化物/氢氧化物和磷酸盐等非碳酸盐组分以及成岩蚀变作用的影响。因此,在分析过程中,我们只有排除这些影响因素,才能用碳酸盐(岩)的稀土元素指标来探讨流体来源和古环境。这要求我们采集新鲜剖面上的样品,并用适当浓度的弱酸进行分步溶样,提取适当的组分,避免样品中的非碳酸盐组分干扰原始沉积组分的稀土元素特征。不同的沉积水体和沉积相下形成的碳酸盐(岩)具有不同的稀土元素特征:从太古宙到全新世的海相碳酸盐(岩)记录了LREE亏损、La正异常和高Y/Ho值的稀土元素特征;海底孔隙水的稀土元素特征则受氧化-还原条件、离子络合形式、孔隙流体来源的制约;热液流体具有LREE富集、Eu正异常的稀土元素特征;河水和湖泊有相对平坦的稀土元素特征。因此,碳酸盐(岩)的稀土元素特征具有重要的古环境指示意义。     

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(–Fe) Deposits in Japan

Abstract: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(-Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits are of meteoric water origin whereas those for the Yoshiwara-Sannotake Cu(-Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively-coupled plasma mass spectrometry (ICP-MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase-clinopyroxene rock, called Inishi rock) from the Kamioka Zn-Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara-Sannotake Cu(-Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite-normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn-Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara-Sannotake Cu(-Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).     

新疆蒙库铁矿床稀土元素地球化学及对铁成矿作用的指示

新疆富蕴县蒙库大型铁矿呈层状、似层状、透镜状赋存于下泥盆统康布铁堡组变质火山-沉积岩系中.矿体中发育矽卡岩,但矽卡岩并不产在侵入岩接触带上.绿帘石、石榴石和矿石的稀土配分模式具有相似性,均为轻稀土富集,正铕异常,基本上无铈异常,暗示它们之间存在成因联系.石榴石稀土配分模式呈折线型,具有明显的正铕异常,石榴石流体包裹体中熔融包裹体、熔流包裹体和气液包裹体共存,表明石榴石矽卡岩具有岩浆成因和热液成因的特征,形成于晶体 熔体 流体三相共存的岩浆-热液过渡阶段.矿床地质特征、矽卡岩矿物和矿石稀土特征表明蒙库铁矿为矽卡岩型矿床.     

湘江悬浮物的稀土元素地球化学研究

在湘江及其支流采集了44件悬浮物样品进行稀土元素 ICP—MS分析。研究表明,湘江悬浮物中稀土总量(∑REE)、轻稀土(LREE) 和重稀土(HREE)含量分别为63～387 μg/g,58.2～353 μg/g和4.8～34μg/g。尽管湘江悬浮物中稀土分布不均匀,稀土含量相差很大,所有样品的球粒陨石标准化曲线均呈向右倾斜的富LREE的模式,北美页岩标准化模式为LREE稍富集的平坦型。湘江中下游河心与两岸水体悬浮物中稀土发生了明显分异。湘江悬浮颗粒物中REE受多方面因素控制,其源区控制了REE分配模式,而其稀土元素含量与颗粒中粘土矿物及重矿物有关。支流捞刀河悬浮物稀土的分布模式为Eu正异常型,与北美页岩有显著差别,捞刀河的悬浮物物源及成因有待进一步研究。     

Geochemical Behaviors of REE and Other Trace Elements during the Formation of Strata-bound Skarns and Related Deposits: A Case Study of the Dongguashan Cu (Au) Deposit, Anhui Province, China

REE and other trace elements in the altered marbles, massive skarns and ores, as well as garnet and quartz were determined in order to examine the behaviors of trace elements during hydrothermal alteration. It is demonstrated that the high-field-strength (HFS) elements Zr, Hf, Th and Nb were immobile while other trace elements were mobile during the formation of skarns and related deposits. REE and ore-forming elements such as Cu and Ag in hydrothermally-altered marbles and skarns were provided primarily by hydrothermal fluids. In the direction transverse of the strata, the more deeply the marbles were altered, the higher the total REE abundance and the larger the negative Eu anomalies would be. The chondrite-normalized REE patterns of skarns are similar to those of the marbles, but the former are distinguished by much higher REE contents and more remarkable negative Eu anomalies. Those patterns were apparently not inherited from the marble protolith, but were controlled by garnets, which were determine     

The Rare Earth Elements and Uranium in Garnets from the Beinn an Dubhaich Aureole, Skye, Scotland, UK: Constraints on Processes in a Dynamic Hydrothermal System

Garnets from skarns in the Beinn an Dubhaich granite aureole,Isle of Skye, Scotland, have a large range of concentrationsof uranium (0·2–358 ppm) and the rare earth elements(REE) (23–4724 ppm). Variations in these concentrationscorrelate with major element zonation within the garnets, andwith changes in the shape of REE patterns. Typical patternsin most garnets display light REE (LREE) enrichment, flat heavyREE (HREE) distribution and a negative Eu anomaly. These patternsare interpreted to represent equilibrium trace element exchangebetween pre-existing pyroxene, hydrothermal fluid and calcicgarnets. Iron-rich zones are characterized by positive Eu anomaliesand an increase in the abundance of the LREE relative to theHREE. These patterns are interpreted as resulting from changesin REE speciation related to the introduction of externallybuffered fluid to the skarn system. Relatively Fe-poor zonesshow strongly HREE-enriched patterns with negative Eu anomaliesand in some instances depletions in Y relative to Ho and Dy,which are interpreted as resulting from surface sorption ofthe REE during rapid, disequilibrium garnet growth. Strong correlationsbetween U abundance and the REE patterns indicate that the sameprocesses have affected U distribution. Both types of patterncan be modified by the effects of closed-system crystallizationon REE abundance in the fluid, and changes in fluid major elementchemistry. KEY WORDS: fractionation; garnet; hydrothermal; rare earth elements; skarn     

川西呷村黑矿型多金属矿床热液体系稀土元素组成特征

本文首次测定了呷村黑矿矿石中流体包裹体的ＲＥＥ组成,计算了与含矿流纹岩系熔体平衡的岩浆热液ＲＥＥ含量。主成矿期流体具有轻稀土富集、Ｅｕ明显正异常的特点,但岩浆热液却具有明显的Ｅｕ负异常特征,结合热液体系氧同位素及稀土元素交换反应模拟,表明岩浆热液不是直接的成矿热液。蚀变围岩具显著的Ｅｕ正异常,其它稀土元素出现亏损。蚀变反应水／岩比值较大,蚀变岩中的ＲＥＥ组成反映了成矿热液ＲＥＥ的特点,且ＲＥＥ亏损     

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.     

The world-class Natalka gold deposit, northeast Russia: REE patterns, fluid inclusions, stable oxygen isotopes, and formation conditions of ore

REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)^2? complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by $ \delta ^{18} O_{H_2 O} REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)²⁻ complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by = +6.3 to +8.8‰ at 350°C and +3.6 to +5.9‰ at 280°C, respectively. The narrow interval of oxygen isotopic compositions shows that this source was homogeneous. The data obtained allow us to suggest that the deposit formation was related to magmatic activity, including the direct supply of ore components from a magma chamber and mobilization of these components in the processes of dehydration and decarbonation during contact and regional metamorphism. Original Russian Text ? N.A. Goryachev, O.V. Vikent’eva, N.S. Bortnikov, V.Yu. Prokof’ev, V.A. Alpatov, V.V. Golub, 2008, published in Geologiya Rudnykh Mestorozhdenii, 2008, Vol. 50, No. 5, pp. 414–444.     

Zircon in gabbroids from the axial zone of the Mid-Atlantic ridge, Markov Deep, 6° N: Correlation of geochemical features with petrogenetic processes

This paper reports the results of detailed petrological-geochemical study of zircons and host rocks that were dredged from the Markov Deep area in the slow-spreading Mid-Atlantic ridge. The rocks are represented by variably cataclased gabbronorite with veinlets of oceanic plagiogranite (OPG) as well as leucocratic gabbro (primitive gabbro) and hornblende Fe-Ti oxide gabbronorite (ferrogabbro) without OPG. The studied zircons differ in morphology, inner structure, set of mineral inclusions (ingrowths), and content of trace elements. Compositional heterogeneity is also observed within individual grains. The REE distribution patterns in zircons are characterized by gentle growth from LREE to HREE, with prominent positive Ce anomaly and negative Eu anomaly, and in general fall in the range of zircons from magmatic rocks. Oceanic zircons clearly differ from continental populations in the U/Yb-Y and U/Yb-Hf discrimination diagrams, primarily, due to their lower U/Yb ratio at wide variations of Y and Hf contents. Zircons that contain inclusions of acid glass and hence, crystallized from OPG melt are relatively depleted in REE, especially HREE. This indicates that OPG was formed by partial melting of gabbro in the presence of concentrated water-salt fluid, which extracted REE from the plagiogranite melt. Zircons from gabbroids devoid of OPG inclusions have higher total REE contents than zircons from OPG. Late hydrothermal alterations of zircon are distinctly established by the formation of neogenic collomorphic (porous) texture and/or by composition of mineral inclusions and accompanied by significant enrichment in La. Heterogeneous distribution of Ti in zircon may be caused not only by a change in its crystallization temperature, but also variations in silica to titanium oxide activity ratios in the rocks during interaction with hydrothermal solution of variable acidity. A complex study of structural-morphological and geochemical features of oceanic zircons and phase composition of host rocks and inclusions provides insight into processes leading to the crystallization and subsequent evolution of this mineral in the rocks of oceanic lithosphere.     

贵州天桥铅锌矿床地球化学特征及其地质意义

通过对天桥铅锌矿床常量元素、稀土元素、同位素及微量元素等地球化学特征的分析,研究了天桥铅锌矿床的成矿物质流体来源及成矿过程。研究结果表明：（1）矿石、围岩等的稀土元素组成特点相似。∑REE相对较低,LREE/HREE比值较大,稀土配分曲线呈富轻稀土的右倾型曲线。Eu负异常明显,Ce具弱负异常特征。（2）矿床成矿物质流体多来源。受陆源影响较大,主要来自上地壳,且可能主要来自赋矿地层及围岩;无大洋地壳和原始地幔来源。（3）成矿作用为热液改造成矿。     

四川盆地南部寒武系白云石地球化学特征与形成机制

以四川盆地南部范店、岩孔、三汇场三个野外露头剖面的寒武系白云岩样品为研究对象,通过对白云石有序度、碳氧同位素、稀土元素、包裹体等地球化学特征的分析,认为研究区主要发育同生期微晶白云石(岩)、细-粉晶白云石、浅埋藏细晶白云石、以及鞍状白云石等四种类型,其中:微晶白云石(岩)、细-粉晶白云石的有序度较低,具有与同时期正常海相碳酸盐岩相近似的δ18O值,稀土元素配分模式近似一致,表现为具有LREE弱富集、HREE弱亏损的特征,这揭示了白云石化流体主要来源于高盐度海水,为蒸发泵白云石化、渗透回流白云石化作用的产物;而细晶白云石的有序度相对较高,稀土元素出现贫化迁移现象,∑REE值有所减少,推断为埋藏白云石化作用的产物;鞍状白云石的有序度高、δ18O值低,稀土元素富集,Eu具有正、负异常,包裹体均一化温度呈异常高值,呈双区间分布,表征白云石化流体来源于深部热液流体,可能为热液白云石化作用的产物。     

芙蓉锡矿方解石稀土元素地球化学特征及其对成矿流体来源的指示

方解石是芙蓉锡矿田重要的脉石矿物。根据芙蓉矿田白蜡水矿区和狗头岭矿区不同产状(云英岩型、蚀变岩体型和构造蚀变带-矽卡岩型)矿石中方解石稀土元素地球化学特征研究表明:两矿区成矿期热液方解石具有两种稀土模式,LREE(轻稀土元素)富集型和相对平坦型。其中,蚀变岩体型方解石所具有的相对平坦型稀土模式代表了LREE带出后残余热液的稀土模式特征,而云英岩型和构造蚀变带—矽卡岩型方解石的LREE富集型稀土模式与骑田岭新鲜花岗岩类似,表明成矿过程中没有LREE明显带出的迹象,残余热液继承了岩浆期后热液的特征。成矿流体来源于骑田岭花岗岩岩浆期后热液。     

Inhomogeneous distribution of REE in scheelite and dynamics of Archaean hydrothermal systems (Mt. Charlotte and Drysdale gold deposits, Western Australia)

Scheelite is a widespread accessory mineral in hydrothermal gold deposits, and its rare earth element (REE) patterns and Nd and Sr isotopic compositions can be used to constrain the path and origin of the mineralising fluids and the age of the hydrothermal activity. Micro-analyses by laser ablation high resolution inductively coupled mass spectroscopy and cathodoluminescence imaging reveal a very inhomogeneous distribution of the REE in single scheelite grains from the Mt. Charlotte and Drysdale Archaean gold deposits in Western Australia. Two end-member REE patterns are distinguished: type I is middle REE (MREE)-enriched, with no or minor positive Eu-anomaly, whereas type II is flat or MREE-depleted with a strong positive Eu-anomaly. The chemical inhomogeneity of these scheelites is related to oscillatory zoning involving type I and type II patterns, with zone widths varying from below 1 to 200 μm. Intra-sectorial growth discontinuities, syn-crystallisation brittle deformation, and variations in the relative growth velocities of crystallographically equivalent faces suggest a complex crystallisation history under dynamic hydraulic conditions. The co-existence of MREE-enriched and MREE-depleted patterns within single scheelite crystals can be explained by the precipitation of a mineral which strongly partitions MREE relative to light and heavy REE. Scheelite itself has such characteristics, as does fluorapatite, which is locally abundant and has REE contents similar to that of scheelite. In this context, the systematic increase of the Eu-anomaly between type I and type II patterns is produced by the difference between the partition coefficients of Eu²⁺ and Eu³⁺, and not by fluid mixing or redox reactions. Consequently, the high positive Eu-anomaly typical of scheelite from gold ores may not necessarily be inherited from the hydrothermal fluid, but may reflect processes occurring during ore deposition. This case study demonstrates that in hydrothermal systems characterised by low REE concentrations in the fluid, and by the precipitation of a REE-rich mineral which strongly fractionates the REE, the REE patterns of such a mineral will be highly sensitive to the dynamics of the hydrothermal system. Received: 1 November 1999 / Accepted: 4 February 2000     

Metavolcanic host rocks,mineralization, and gossans of the Shaib al Tair and Rabathan volcanogenic massive sulphide deposits of the Wadi Bidah Mineral District,Saudi Arabia

The Wadi Bidah Mineral District of Saudi Arabia contains more than 16 small outcropping stratabound volcanogenic Cu–Zn–(Pb) ± Au-bearing massive sulphide deposits and associated zones of hydrothermal alteration. Here, we use major and trace element analyses of massive sulphides, gossans, and hydrothermally altered and least altered metamorphosed host rock (schist) from two of the deposits (Shaib al Tair and Rabathan) to interpret the geochemical and petrological evolution of the host rocks and gossanization of the mineralization. Tectonic interpretations utilize high-field-strength elements, including the rare earth elements (REE), because they are relatively immobile during hydrothermal alteration, low-grade metamorphism, and supergene weathering and therefore are useful in constraining the source, composition, and physicochemical parameters of the primary igneous rocks, the mineralizing hydrothermal fluid and subsequent supergene weathering processes. Positive Eu anomalies in some of the massive sulphide samples are consistent with a high temperature (>250°C) hydrothermal origin, consistent with the Cu contents (up to 2 wt.%) of the massive sulphides. The REE profiles of the gossans are topologically similar to nearby hydrothermally altered felsic schists (light REE (LREE)-enriched to concave-up REE profiles, with or without positive Eu anomalies) suggesting that the REE experienced little fractionation during metamorphism or supergene weathering. Hydrothermally altered rocks (now schists) close to the massive sulphide deposits have high base metals and Ba contents and have concave-up REE patterns, in contrast to the least altered host rocks, consistent with greater mobility of the middle REE compared to the light and heavy REE during hydrothermal alteration. The gossans are interpreted to represent relict massive sulphides that have undergone supergene weathering; ‘chert’ beds within these massive sulphide deposits may be leached wall-rock gossans that experienced silicification and Pb–Ba–Fe enrichment from acidic groundwaters generated during gossan formation.     

碳酸岩型稀土矿床成矿流体演化机制研究现状及展望

与碱性岩有关的碳酸岩型内生稀土矿床在中国乃至世界上轻稀土资源储量中占有极为重要的地位,诸如我国内蒙古的白云鄂博稀土矿床、川西冕宁—德昌稀土成矿带中的牦牛坪、大陆槽等稀土矿床、山东微山县郗山稀土矿床以及美国的Mountain Pass稀土矿床等都属于这种类型的稀土矿床。当前,对于这类稀土矿床的成矿流体演化机制,学界主要存在结晶分异作用、不混溶作用(熔体-熔体不混溶、熔体-流体不混溶以及流体-流体不混溶)以及热液交代蚀变作用之间的分歧。结晶分异作用可以使具有不相容性的稀土元素在残余熔体相中逐渐富集,直至形成稀土矿物。不混溶作用能够使稀土元素在不混溶后形成的两相或多相中的某一相中发生选择性富集,形成稀土矿化。成矿流体演化晚阶段的热液流体对早期生成的矿物或围岩进行交代蚀变,使其释放出能与稀土元素在热液中形成络合物的F-、(CO_3)~(2-)以及(SO_4)~(2-)等阴离子(团),并最终在合适的构造控矿部位和外界环境条件下,重结晶或沉淀出稀土矿物。上述3种观点各有其理论依据,但是在解释一些碳酸岩型稀土矿床地质现象或实验地球化学模拟结果的时候都或多或少存在一定程度上的不足。前人的研究结果表明,碳酸岩型稀土矿床中发育了大量的熔体包裹体、熔体-流体包裹体以及富CO_2的流体包裹体,以往在利用Linkam TS1400XY以及Linkam THMS600等这类常规高温热台,在101325 Pa条件下对其进行热力学测温时,这些包裹体大多在尚未达到完全均一状态前就已发生爆裂或泄露,极大制约了人们对这类稀土矿床在高温岩浆阶段和中高温岩浆-热液阶段成矿流体演化过程的认知。另外,对于稀土元素在成矿流体演化过程中的含量变化特征及其地球化学行为的研究,目前主要是通过包裹体成分组成的拉曼光谱分析,以及对矿体和围岩进行的全岩地球化学分析,尚缺乏单个包裹体中元素含量的原位微区分析方面的数据。未来,对碳酸岩型稀土矿床中发育的熔体包裹体、熔体-流体包裹体和富CO_2的流体包裹体,利用热液金刚石压腔开展高温高压原位均一实验模拟研究,以及对单个包裹体中微量元素的含量利用LA-ICP-MS进行原位微区分析,将是揭示该类稀土矿床成矿流体演化机制的关键。