石英、黄铁矿及其包裹体的稀土元素特征——以胶东焦家式金矿为例

本文采用ICP—MS测定了焦家、马塘、东季、红布等焦家式金矿床中黄铁矿、石英及其包裹体的稀土元素组成。结果表明：采用ICP—MS直接测定黄铁矿包裹体的稀土元素是可行的;包裹体爆裂丰度虽然对稀土总量有影响,但矿源稀土元素背景值的差异也是流体中稀土总量差别的主要原因之一。∑REE、δEu、δCe及LREE／HREE、(La/Yb)N、(Ce/Yb)N、(La／Lu)N都是有意义的稀土元素特征参数;焦家式金矿同一成矿阶段黄铁矿、石英及其包裹体的稀土元素特征相似,显示了它们的同源特征;不同成矿阶段黄铁矿、石英及其包裹体的稀土元素特征有差异,反映了其成矿流体特征的差异。     

不同类型热液金矿系统的流体包裹体特征

为使流体包裹体研究结果得到较好的解释,避免矿床地质描述与流体包裹体研究结果发生矛盾,本文试图以金矿床为例,建立科学而简便易行的矿床地质与包裹体特征之间的链接。为此,本文简单评述了现有金矿床成因分类方案,建议以主导成矿系统发育的地质作用特征划分5种类型：①浆控高温热液型,包括斑岩型、爆破角砾岩型、铁氧化物型、夕卡岩型等岩浆热液型矿床;②造山型,即变质热液型;③浅成低温热液型——陆相火山岩一次火山岩中的改造热液型;④微细粒浸染型（卡林型或／类卡林型）——沉积岩容矿的改造热液型;⑤热水沉积型（VMS型和SEDEX型）——水下喷出地表的改造热液型。然后,分别介绍了5类成矿系统的标志性地质和流体包裹体特征,找出了它们之间具有成因标志意义的关键性差异;将成矿流体分为改造、变质和岩浆3个端元性成分,发现多数热液矿床具有多阶段多因复成的特点,晚阶段流体均为改造热液或有大量改造热液注入,因此指出,晚阶段的流体、蚀变和矿化特征不能用于判别矿床成因和类型,只有早阶段的特征才能准确指示矿床成因和类型。改造热液以低温、低盐度、低CO2含量为特征,主要来自大气降水和／或海水;变质热液以中温、低盐度、高CO2含量为特征,而岩浆热液则以高温、高盐度、高CO2含量为特征;岩浆热液矿床发育含多种子晶包裹体和高盐度富CO2的包裹体,变质热液矿床发育低盐度富CO2包裹体,改造热液矿床总体缺乏含子晶包裹体和富／含CO2包裹体,大量发育水溶液包裹体。最后,讨论了各类成矿系统发育的岩石圈构造背景,如造山型矿床形成于地壳挤压造山．变质．隆升过程,热水沉积型矿床形成于地壳拉张成盆过程,古生代或更早的浅成低温热液型矿床只能保存在增生型造山带等,提出矿床及其包裹体是研究大陆动力学的理想探针。     

招平断裂带上盘金矿床石英流体包裹体同位素组成特征及地质意义

招-平断裂是胶东招掖金矿带的主要控矿断裂,其上盘金矿床受NE向断裂构造控制,赋矿围岩为胶东群变质岩,金矿化以含金硫化物石英脉为主。通过首次对招远灵雀山金矿床富金石英脉石英流体包襄体Rb-Sr等时线年龄的测定,获得116±23Ma成矿年龄。从而说明招-平断裂带上盘金矿大规模成矿期发生于早白垩世的构造体系转折期。对富金石英脉石英流体包襄体同位素特征研究表明。该地区成矿热液均以幔源为主,具有与招掖金矿带其它金矿类似的成矿热液系统。由此可以看出招．平断裂带上盘也具有良好的成矿条件。     

燕山地区金矿床包裹体成分特征

燕山地区金矿床主要有5种类型，并明显地分为南北两个成矿带，其流体包裹体的成分特征也存在明显差别。北矿带主要表现为高H2O、低CO2、K^ /Na^ 值低，K^ 、Na^ 含量高，盐度低等特征。南矿带则主要表现为低H2O，高CO2，K^ /Na^ 值稍高，Ca^2 含量高，盐度高等特征。阐述了产于变质岩和侵入岩中两类金矿床包裹体成分的差异和成矿流体成分的差异。     

辽宁丹东五龙与四道沟金矿床成因对比—流体包裹体证据

对产于辽宁丹东三股流花岗闪长岩体外围的五龙与四道沟大型金矿床地质、流体包裹体岩相学及测温特征进行对比研究表明,五龙与四道沟金矿床成因存在一定差异。五龙金矿床含金石英脉与四道沟金矿床早期石英脉成矿流体主要来自于三股流岩浆活动,而四道沟矿区主矿化阶段成矿流体来源可能与矿区燕山晚期中酸性脉岩活动有关。     

山东省胶东地区焦家式金矿床中含金石英大脉流体包裹体的特征

著名的焦家式金矿以破碎蚀变岩型矿化为特征,但近年来也发现有含金石英大脉。含金石英大脉的流体包裹体以气液两相为主,含液相CO2包裹体次之;均一温度主峰在290℃附近,次峰在200℃附近;盐度主要为(2～10)%NaCl;估算压力为20～38MPa;包裹体气相成分以H2O为主,其次为CO2;黄铁矿包裹体离子组成一般Na+>K+>Ca2+,SO42->Cl->F-,石英包裹体离子组成一般K+>Na+>Ca2+(变形石英Na+>K+>Ca2+),SO42->Cl->F-。焦家式金矿含金石英大脉的上述特征与玲珑式金矿含金石英脉类似,但与处于同一矿床的破碎蚀变岩型矿化有一定差异。含金石英大脉以充填为特征,而破碎蚀变岩型矿化以交代为特征。     

Compositional re-equilibration of fluid inclusions in quartz

Compositional modifications to salt-water fluid inclusions in quartz were observed following exposure to disequilibrium conditions in a series of laboratory experiments in which samples containing inclusions of known composition were annealed at 3 kbar and 600≤T≤825°C in the presence of fluids having different compositions for time intervals ranging from a few days to one month. Changes in inclusion compositions following re-equilibration were monitored using salt crystal dissolution temperatures and/or IR (infra red) spectroscopy. The behaviors of both synthetic and natural fluid inclusions were studied. The synthetic samples were re-equilibrated under P _int=P _conf conditions to minimize stress in the crystal surrounding the inclusions, and were subjected to both f _H2O ^int f _H2O ^conf and f _H2O ^int f _H2O ^conf . After re-equilibration for four days at T≥600°C, most inclusions displayed significant compositional changes Without decrepitation. Salinity variations as large as ≈ 25 wt% were inferred for brine inclusions exposed to f _H2O ^int ≠f _H2O ^conf for 16 days at 825°C. The majority of our observations are consistent with the net diffusion of water toward the reservior having the lowest μH₂O; i.e., synthetic NaCl−H₂O fluid inclusions exhibited increased Tm(NaCl)s (implying lower relative H₂O contents) when re-equilibrated in the presence of fluids having lower μH₂O, whereas, similar (and, in some cases, the same) inclusions exhibited decreased Tm(NaCl)s (implying higher H₂O contents) after exposure to fluids having higher μH₂O. The behavior of natural salt-water fluid inclusions during re-equilibration was generally consistent with corresponding observations on synthetic samples verifying that compositional changes are not restricted to synthetic inclusions. Our results clearly show that there was chemical communication between fluids trapped as inclusions in quartz and the external fluid reservoir. Additionally, it is evident that although applied stress can significantly enhance the re-equilibration rate, strain in the crystal host around the inclusions resulting from large pressure differentials between the internal and confining fluids is not a necessary prerequisite for compositional change. Finally, because significant compositional changes can be induced in brine inclusions in quartz during shortterm exposure to non-equilibrium conditions at 600≤T≤825°C in the laboratory, it is likely that similar changes may result at much lower temperatures during exposure of natural rocks to non-equilibrium conditions over geologic time.     

黔东南石英脉型金矿床中铁白云石流体包裹体研究

铁白云石是黔东南石英脉型金矿主成矿阶段的主要脉石矿物之一,与金的矿化关系十分密切,在金的运移、沉淀等方面起着重要作用,其流体包裹体特征可以反映成矿流体性质.通过对铁白云石开展系统的流体包裹体岩相学观察、均一法测温和冰点测定,计算出包裹体盐度和密度等数据.结果表明:铁白云石包裹体较为发育,以含CO2的包裹体为主;均一温度集中在240~300℃范围内,平均均一温度为267.21℃;成矿流体的盐度为7.31%~21.40%(NaCl),平均为15.31%(NaCl);成矿流体的密度介于0.72~0.97 g/cm3之间,平均为0.89 g/cm3.认为黔东南石英脉型金矿床属于低盐度、高密度的中温热液矿床.     

贵州锦丰(烂泥沟)金矿床含砷黄铁矿和脉石英及其包裹体的稀土元素特征

贵州锦丰(烂泥沟)金矿是滇黔桂"金三角"目前已探明的最大的卡林型金矿床.含砷黄铁矿是该矿床最主要的载金矿物,脉石英是最显著的热液蚀变作用产物.含砷黄铁矿、脉石英及其包裹体具有相同的稀土元素特征,表现为轻重稀土分馏明显(LREE/HREE7.95～31.77,(La/Yb)N8.97～40.49);轻稀土有一定的分异((La/Sm)n3.20～5.29),曲线右倾程度大;重稀土分异不明显((Gd/Yb)n1.41～3.35),曲线平坦;负铕异常明显(δEu 0.59～0.71);微弱的铈负异常(δCe 0.97～0.98).代表成矿流体特征的脉石英包裹体稀土配分型式及特征值与区域上不同时代的幔源基性-超基性岩差别较大,而与矿床围岩、矿石、含砷黄铁矿及其包裹体稀土配分型式及特征值十分相似,具上部地壳普通沉积岩的特点,反映成矿流体主要不是来源于地幔,而是以壳源为主.Eu负异常反映了偏酸性(富CO2)、还原性的成矿环境;微弱的Ce负异常表明成矿流体来源于以沉积水和热脱水为主的盆地流体.     

Trace Elements in Fluid Inclusions in the Carlin—Type Gold Deposits,Southwestern Guizhou Province

Fluid inclusions in quartz from the Lannigou and Yata Carlin-type gold deposits in southwestern Guizhou were analyzed by inductively coupled plasma-mass spectrometry for their trace elements(Co,Ni,Cu,Pb,Zn,Pt,etc.).The results show that quartz fluid inclusions entrapped at different ore-forming stages contain higher Co,Ni,Cu,Pb and Zn.It has been found for the first time that the ore-forming fluids responsible for the Carlin-type gold deposits are rich in Pt.From this it can be concluded that basic volcanic rocks seem to be one of the important sources of ore-forming materials for the Carlin-type gold deposits.     

青海滩间山金矿的复合金成矿作用——来自流体包裹体方面的证据

流体包裹体研究表明,滩间山矿区的金矿体是2次热液-矿化事件的叠加产物。第一次热液-矿化作用与区域上加里东碰撞造山作用有关,形成的流体属于中低温(186～250℃)、低盐度〔w(NaCleq)1.4%～7.9%〕的H2O-CO2-CH4-NaCl体系,压力变化于(4900～1800)×105Pa之间,其主要沿NW向剪切带迁移和沉淀形成金矿化。第二次热液-矿化作用与晚古生代—早中生代碰撞造山作用密切相关,产生两种不混溶流体。第一种不混溶流体属于高温的H2O-NaCl体系,可能与岩浆侵入活动有关,第二种不混溶流体为温度274～289℃,盐度w(NaCleq)1.8%～7.9%,x(CO2)=0.19～0.27,x(H2O)=0.81～0.73,压力为(2300～1100)×105Pa的H2O-CO2-NaCl体系的流体,其沿NW向剪切带内的近NS向褶皱两翼的层间破碎带流动和沉淀,并最终导致滩间山矿床内金矿体的定位。按岩压估算,第一次热液-矿化事件发生于上地壳下部,第二次热液-矿化事件发生于浅成环境,这也进一步证实了滩间山矿床的金成矿于区域晚华力西时期的隆升造山过程中。与晚加里东碰撞造山期间相比,本区晚华力西期-印支期碰撞造山过程中的最大隆升幅度达9km左右。     

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.     

The origin of Kibaran (late Mid-Proterozoic) tin,tungsten and gold quartz vein deposits in Central Africa: a fluid inclusions study

Composition and evolution of fluids depositing tin and tungsten ores in Kibaran quartz vein deposits allow the modelling of devolatizing evolved granites as their source at depth. Fluids forming gold quartz veins and breccias are different from the first, especially by showing characteristics of a high-pressure environment. All deposits are controlled by compressional deformation whose fading phases affect earlier formed veins. These findings lead to the conclusion that both anatectic melting resulting in intrusion of fertile granites, and the generation of fluids forming gold deposits are the final consequence of deep crustal metamorphism. The latter was caused by crustal thickening immediately preceding the metallogenetic climax.     

黔西南卡林型金矿床流体包裹体中微量元素研究

用ICP－MS测定了黔西南烂泥沟和丫他卡林型金矿床石英流体包裹体中的Co、Ni、Cu、Pb、Zn和Pt等元素的含量。结果显示，不同成矿阶段石英流体包裹体中均有较高的Co、Ni、Cu、Pb和Zn含量，并首次发现卡林型金矿床成矿流体中富含Pt。据此认为基性火山岩可能是卡林金矿床成矿物质的重要来源之一。     

Mixing of H2O-CO2 in fluid inclusions; geobarometry and Archean gold deposits

A modified Redlich-Kwong (MRK) equation of state for H₂O and CO₂ was used to calculate bulk molar volumes, mole fractions and CO₂ densities for mixed volatile fluid inclusions. The results allow very useful P-T diagrams to be constructed (for fixed CO₂ density) and contoured with volume percent CO₂ observed in the laboratory. These diagrams permit rapid qualitative or quantitative determination of the P-T path for a bulk inclusion isochore above the solvus in the system H₂O-CO₂ (±NaCl). The calculations suggest peak metamorphic pressures of 3–5 kb for some Archean greenstone gold deposits. Insights gained from this work may require reinterpretation of pressure estimates in published fluid inclusion studies.     

Salinity of the Archaean oceans from analysis of fluid inclusions in quartz

Fluids trapped in inclusions in well-characterized Archaean hydrothermal quartz crystals were analyzed by the extended argon–argon method, which permits the simultaneous measurement of chlorine and potassium concentrations. Argon and nitrogen isotopic compositions of the trapped fluids were also determined by static mass spectrometry. Fluids were extracted by stepwise crushing of quartz samples from North Pole (NW Australia) and Barberton (South Africa) 3.5–3.0-Ga-old greenstone belts. The data indicate that fluids are a mixture of a low salinity end-member, regarded as the Archaean oceanic water, and several hydrothermal end-members rich in Cl, K, N, and radiogenic parentless ⁴⁰Ar. The low Cl–K end-member suggests that the salinity of the Archaean oceans was comparable to the modern one, and that the potassium content of the Archaean oceans was lower than at present by about 40%. A constant salinity of the oceans through time has important implications for the stabilization of the continental crust and for the habitability of the ancient Earth.     

西准噶尔哈图成矿带主要金矿床流体包裹体特征及其意义

哈图成矿带位于西准噶尔地区达拉布特大断裂的西北侧,是新疆北部最重要的金成矿带之一。哈图成矿带从西南至北东依次分布着哈图、齐Ⅱ、齐Ⅲ、齐Ⅳ以及齐Ⅴ等金矿床,这些金矿床均受NEE向的安齐断裂及其次级断裂控制,矿体工业类型分石英脉型和蚀变岩型。笔者重点研究了哈图、齐Ⅱ和齐Ⅴ金矿床。根据脉体穿切关系和矿物交代关系,将哈图、齐Ⅱ和齐Ⅴ金矿床分为早、中、晚3个成矿阶段。流体包裹体研究表明,哈图金矿床流体包裹体主要有3种类型:富液相包裹体、富气相包裹体、CO2-H2O包裹体,齐Ⅱ、齐Ⅴ金矿床发育富液相包裹体和富气相包裹体。从早阶段至晚阶段,哈图、齐Ⅱ、齐Ⅴ金矿床主成矿阶段均一温度分别集中在213~285℃、240~306℃、225~319℃;w(Na Cleq)分别为0.53%~4.14%、1.91%~7.99%、0.88%~3.23%;密度分别为0.574~0.948 g/cm3、0.730~0.934 g/cm3、0.536~0.918 g/cm3,成矿压力分别为52.1~69.5 MPa、62.9~68.8 MPa、49.9~80.7 MPa,均属中-低温、低盐度、低密度流体,三者的成矿深度平均值均为2 km左右。哈图、齐Ⅱ和齐Ⅴ金矿床成矿流体分别属于Na Cl-H2O±CH4±CO2±N2、Na Cl-H2O±CH4、Na Cl-H2O±CH4±CO2体系。水-岩反应作用及流体的不混溶作用是导致金沉淀成矿的主要因素。     

流体包裹体在矿床研究中的作用

流体包裹体分析是现代矿床学研究的一个重要手段,对矿床类型的划分及成矿流体成分、温度、压力的研究有着重要的作用.在矿质沉淀的主要机制中,流体相分离及流体混合的主要证据来自流体包裹体;对金属在气相中的搬运的认识,也主要来自包裹体研究.成矿流体成分对认识金属在热液中的搬运方式起着重要作用,流体温度和压力数据是成矿流体动力学模式的重要制约.