西藏努日白钨矿床微量和稀土元素地球化学特征——对成矿流体与矿床成因的指示

对努日矿床白钨矿中稀土元素、微量元素的地球化学特征研究表明:白钨矿亏损V、Cs、Hf、Ta等元素,并具有异常低的Rb/Sr、Zr/Hf、Nb/Ta的比值,以及Hf/Sm、Nb/La、Th/La值也都远远小于1,指示原始富钨成矿流体来源于深部壳源岩浆结晶分异,并总体以富CL热液为主;采自不同位置的白钨矿样品其稀土元素组成基本一致,其球粒陨石配分曲线表现为明显轻稀土富集的右倾模式,具有明显的Ce正异常(δCe=1.066~1.107)和弱Eu负异常(δEu=0.768~0.910),表明白钨矿与流体之间稀土元素发生了不太明显的分异;白钨矿与夕卡岩化有密切关系的黑云母花岗岩的REE球粒陨石标准化配分曲线均为明显的右倾模式,ΣREE、δCe、δEu值基本一致,暗示岩体对努日白钨矿成矿物质的贡献。努日矿床初始热液流体为一中高温、中低盐度的流体,其沿着构造裂隙运移过程中,与比马组地层发生接触交代反应,体系中CO2和Ca含量的增加,流体的初始平衡体系被破坏,最终导致大量Ca2+与WO42-结合形成了巨量的白钨矿。     

赣北石门寺钨多金属矿床成矿流体演化过程：白钨矿微区成分限定

大湖塘钨矿地处江南造山带中段,为一大型钨-钼-铜多金属矿田,由4个矿床组成,其中石门寺矿床规模最大.文章利用LA-ICP-MS对石门寺矿床石英脉型钨矿中的白钨矿进行单矿物原位微区分析,以揭示成矿流体演化过程.研究表明,石英脉中的白钨矿可划分为2期,其中,早期白钨矿与黑钨矿、黑云母及石英共生,而晚期白钨矿在石英大脉中仅与石英共生.前者表现为右倾型稀土元素配分模式,而后者则显示平坦型稀土元素配分模式,两者均具Eu正异常.此外,早期白钨矿较晚期白钨矿具有较高的ΣREE、Mo、Sn、Nb、Ta、Y含量,但Sr含量较低.早期白钨矿表现出LREE富集型和较高的ΣREE、Nb、Ta含量,说明成矿流体来源于岩浆热液,从早期到晚期成矿流体中Eu由Eu2+为主转变为Eu3+为主,表明流体演化过程中氧逸度升高,暗示成矿晚期有氧化性大气降水加入.早期高LREE、Sn、Nb、Ta含量的白钨矿的沉淀以及辉钼矿结晶显著改变成矿流体的组成,导致晚期白钨矿具平坦型REE配分模式和低Mo、Sn、Nb、Ta的特征.此外,在流体演化过程中,新元古代花岗闪长岩中斜长石因为蚀变分解持续为成矿热液提供Eu和Sr,造成白钨矿Eu正异常和晚期白钨矿中Sr含量的升高.     

赣东北朱溪超大型钨矿床中白钨矿的稀土、微量元素地球化学特征及其Sm-Nd定年

赣东北朱溪超大型钨矿床是目前世界上最大的夕卡岩型钨矿床,为确定其成矿物质来源及成矿时代,在详细钻孔岩心编录基础上,本文对白钨矿运用LA-ICP-MS法分析了其单矿物的微量元素、稀土元素,并进行Sm-Nd同位素定年研究。结果显示:白钨矿微量元素中Mo、Nb、Ta富集,而Rb/Sr0.04,Nb/Ta=1.69~8.46、Zr/Hf=3.06~6.75,显示成矿物质的壳源特征。白钨矿的∑REE变化大(∑REE=3.25×10~(-6)~229.95×10~(-6)),LREE与HREE之间分馏明显((La/Yb)N=36~19 984),属于轻稀土富集型。依据δEu值的特征,将白钨矿分为δEu正异常(δEu=1.44~9.06)的轻稀土富集型和δEu负异常(δEu=-0.25~-0.82)的轻稀土富集型;在空间上,由远到近接近花岗岩,白钨矿的∑REE逐渐升高,δEu由正异常逐渐转变为负异常,有与花岗岩稀土配分曲线趋于一致的趋势。白钨矿Sm-Nd等时线年龄为(144±5)Ma,143 Nd/144 Nd初始比值为0.512 020,其εNd(t)为-9.753,二阶段模式年龄为1 745 Ma,其年龄与物质来源与朱溪花岗岩的一致,表明朱溪钨矿床是朱溪矿区隐伏花岗岩进一步演化的产物。     

黔东北沿河大竹园萤石矿床成矿物质来源探讨:地球化学制约

黔东北沿河大竹园萤石矿赋存于下奥陶统桐梓组及红花园组碳酸盐岩内,受NW向断裂构造控制。该类萤石矿床在黔东北及渝东南一带广泛分布。本文对该萤石矿床的萤石单矿物及围岩进行了微量元素及稀土元素地球化学分析,结果显示萤石的微量元素仅Pb、Zn、Co、Ni等元素含量相对较高,Rb、Sr、Ta、Zr、Nb、V、Cr、U、Th、Hf等元素含量仅为地壳值的0.01~0.05倍。稀土元素含量很低(∑REE=2.35×10–6~4.80×10–6),相对富集轻稀土元素(LREE/HREE=3.12~6.33),具有Eu正、负异常(δEu=0.59~1.59)和Ce负异常(δCe=0.80~0.96)。萤石与赋矿围岩具有相近的微量元素配分型式,均明显亏损Nb、Zr、Hf等元素,富集Ba、U、Sr等元素。萤石与赋矿碳酸盐岩都具有轻稀土相对富集、重稀土相对亏损,明显右倾的REE配分型式。综合分析认为该萤石矿的成矿物质Ca主要来源于碳酸盐岩围岩;而碳酸盐岩围岩的F元素含量很低,结合萤石的微量元素及δEu、δCe值特征,暗示形成萤石的成矿流体经过了深部演化,成矿物质F可能主要来自深部富F地层。     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

江南古陆西段木瓜园钨矿床成矿流体演化过程研究

木瓜园白钨矿位于江南古陆钨矿带西段,矿体主要产于花岗闪长斑岩中,局部产于侵入围岩(岩性主要为粉砂质板岩、砂质板岩,局部绢云母板岩)的石英脉中,是揭示该区成矿规律的重要组成。本文利用显微测温和阴极发光图像技术对木瓜园钨矿床不同成矿阶段的流体包裹体及白钨矿原位微量元素特征进行了系统研究。结果显示:(1)钨矿床包裹体类型有富液相气液两相包裹体、含子晶包裹体和CO2包裹体,此外还有少量的富气相包裹体和液相包裹体;流体包裹体盐度范围为3.39%~12.18%Na Cleqv,均一温度范围为161~396℃,属于Na Cl-H_2O体系。(2)白钨矿微量元素研究显示以富集Mo、Nb、Sr、Ba为特征,白钨矿的铕异常(δEu)由早期的钾硅酸阶段(0.46)到晚期的硫化物阶段(2.98)逐渐由负异常到正异常,表明成矿流体氧逸度逐渐减弱。白钨矿的稀土元素配分模式与矿区的花岗闪长斑岩的稀土元素配分模式相似,白钨矿中正的Eu异常可能是短期相对还原条件造成的,推测形成木瓜园白钨矿的流体继承了母岩浆的稀土元素特征,白钨矿是在相对还原和微弱波动的氧化还原条件下沉淀。白钨矿Zr/Hf比值0.93~50.84,平均16.88,Y/Ho介于62.57~21.96,平均为33.34,变化幅动较大,指示成矿阶段存在不同程度的外来流体混合。白钨矿的Nb/Ta比值变化范围为1.75~42.72,平均为23.57,指示成矿物质可能来源为壳幔混合;白钨矿中LREE/HREE变化范围为0.12~11.37,具有斑岩型钨矿床的特征。     

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.     

福建李坊重晶石矿床形成环境及矿床成因

为了解福建李坊重晶石矿床成因和成矿物质来源,对重晶石单矿物的主量元素、稀土元素、微量元素和硫同位素进行了研究,研究结果显示:重晶石单矿物表现出富Al、Si、Fe的特征;ΣREE总量较低,富集轻稀土元素;δEu呈正异常,δCe呈负异常;微量元素富集Ba、Rb、Nb、Th、P等元素,亏损K、Zr等元素;各个中段δ34S均值大于32.6‰,且直方图中只显示一个主峰。重晶石单矿物成因判别图解、ΣREE-La/Yb图解,分别指示了重晶石单矿物形成于热水沉积区,成矿物质来源于沉积岩区;Si O2/Al2O3、MnO/TFe2O3、U/Th等比值指示了弱碱性—碱性的氧化环境;(La/Ce)N、Al/(Al+Fe)等比值指示大陆边缘环境。研究表明,李坊重晶石矿床形成于大陆边缘构造环境的热水沉积成矿作用,其Ba主要来源于沉积岩区,S主要来源于寒武纪海水,并且有较多陆源物质的输入。     

湘西沃溪金锑钨矿床中白钨矿的稀土元素地球化学

对湘西沃溪金锑钨矿床进行了研究,结果表明,该矿床中自钨矿的稀土元素(REE)含量相对较高,为40.5～123.6 μg/g;且有明显的空间变化趋势,随矿区标高的增加而减少,这可能与流体运移过程中流体的REE浓度不断降低有关.不同产状的白钨矿均以轻稀土元素(LREE)亏损、中稀土元素(MREE)和重稀土元素(HREE)富集为特征;白钨矿样品的REE分布模式均存在着明显的M型四分组效应,暗示白钨矿的形成与流体作用或水/岩反应有关.进一步的研究表明,在沃溪白钨矿的沉淀过程中,成矿流体中的REE发生了明显分异,白钨矿对HREE,特别是MREE,具有明显的优先选择性;REE这种分配行为主要是受晶体化学因素的控制,与白钨矿晶体中Ca位置的大小密切相关,而与成矿流体中REE相对浓度、REE络合物的稳定性关系不大.     

兰坪白秧坪铜银多金属矿集区西矿带矿床成因

西矿带受瞎眼山断裂和四十里箐-上下庄断裂控制,矿体产于近NS向断裂旁侧次级断裂中,发育典型的中低温热液矿物组合,成矿流体来源于深部的热卤水.硫、铅同位素反映成矿物质具深源特征,稀土元素组成具有极明显的δEu负异常和δCe负异常,构造热流体为成矿的主导因素.成因类型属于推覆构造有关的中低温浅成热液矿床.     

渣滓溪大型脉状锑矿中钨矿化产出地质特征及找矿远景

渣滓溪大型脉状锑矿中异体共生有白钨矿化,受同一层位(岩性)、不同构造期次(类型)控制。矿区位于2条NE向区域性逆冲断层所挟持的抬升断块内,岀露地层为新元古界板溪群五强溪组浅变质的碎屑-火山碎屑沉积岩;已发现含钨矿化(体)层28层,层控(岩控)特征明显;白钨矿化主要呈细脉状产于岩石节理裂隙中。锑矿化富集段亦为钨矿脉富集段,钨与锑为同源不同期的产物。构造应力是完成元素活化、迁移和沉淀富集的主要成矿机制,矿床属于动力变质热液成因。区内含钨(体)层众多,成矿空间较大,具有侧伏延深、分段富集的特点,其找矿前景较好。     

Fluid inclusion studies of the Felbertal scheelite deposit

Fluid inclusion measurements on quartz, scheelite, beryl, fluorite and calcite in the metamorphosed Felbertal scheelite deposit display two main types of fluid inclusions:

1. H₂O-CO₂ fluid inclusions are characterized by variable amounts of CO₂ up to 18 wt.%. They show two or three phases at room temperature. The bulk homogenization temperatures for the inclusions range between +269 °C and +357 °C. The calculated salinities are between 2.2 and 7.8 wt.% NaCl equivalent. For the late CO₂-bearing fluid inclusions a methane component is evident from microthermometrical data (T_mclath >10.0 °C combined with T_mCO₂
2. Aqueous, two-phase fluid inclusions with salinities in the range between 0 and 11 wt.% NaCl equivalent. Their homogenization temperatures are scattered between 100 °C and 360 °C.

Both types of fluid inclusions are of Alpine origin. They do not record the conditions of the original tungsten ore formation in pre-Alpine (Upper Proterozoic) time. However, it was possible to deduce a path for the fluid evolution and the combined ore redeposition during the retrograde Alpine metamorphism and tectonism from microthermometrical and petrographical studies.     

新田岭白钨矿床稳定同位索地质学研究

本文以新田岭钙矽卡岩型白钨矿床为例,通过硫、碳、氢、氧稳定同位素研究所获得的成矿信息,探讨了矽卡岩白钨矿床的成因和物质来源。矿区氢氧同位素组成表明成矿深溶液属以岩浆水为主的混合岩浆水,后期变为大气降水;碳主要来源于地层碳,混有岩浆碳;硫源为深源硫与地层硫的混合。稳定同位素结合地质年代学研究,表明该矿床系与燕山早期黑云母花岗岩有关的接触交代型矿床,钨主要来源于大陆地壳重熔化岗岩浆热液。     

Hallimond tube flotation of scheelite and calcite with amines

Hallimond tube flotation experiments have been carried out on the two calcium minerals scheelite and calcite using dodecylammonium chloride as collector. The main variables studied were the calcium ion concentration and the pH.In the case of scheelite, addition of calcium chloride markedly lowered the flotation recovery. Recovery was also lowered when the pH was reduced below about 10. Since it is known that the zeta potential of scheelite is almost independent of pH this confirms that co-adsorption of un-ionized amine is necessary for good flotation. Other un-ionized long-chain molecules can replace the amine; thus it was shown that excellent flotation can be obtained event at about pH 7 by adding dodecanol together with dodecylammonium chloride. With the completely ionic trimethyldodecylammonium chloride recoveries were poor and were independent of pH.In the case of calcite, calcium chloride had no immediate effect on flotation recovery, but at low collector concentrations marked depression occurred after many hours standing in the presence of calcium ions. The effect of pH on flotation of calcite was anomalous and there appear to be two pH regions in which recoveries are high.The results are discussed and attention is drawn to the need for more thorough studies of the calcium carbonate/water interface.     

吉林杨金沟白钨矿床地质特征及成因探讨

杨金沟白钨矿床赋存于下古生界五道沟群中上段,矿化类型主要为石英脉型。根据该矿床含矿石英脉流体包裹体均一温度,H、O、C同位素组成及白钨矿床中硫化物单矿物的硫同位素组成的研究与分析,进而认为,该矿床成因类型为中高温岩浆-热液叠加改造型。     

白钨矿床的地质特征及在吉林省的找矿方向

独立的白钨矿矿床和以白钨矿为主要组分的白钨矿矿床是一类重要的矿床。本文研究了这类矿床的实例,总结了这类矿床的成矿特征,提出了吉林省这类矿床的找矿方向。     

Trace element geochemistry of scheelite and rutile from metaturbidite-hosted quartz vein gold deposits, Meguma Terrane, Nova Scotia, Canada: genetic implications

Scheelite and rutile from several metaturbidite-hosted gold-bearing quartz vein deposits of the Meguma Terrane of Nova Scotia were analyzed for trace elements including rare earth elements, niobium and tantalum. Scheelites have high concentrations of Sr, Nb, Y and rare earth elements (REE) with bell-shaped chondrite-normalized REE patterns accompanied by both positive and negative Eu anomalies. They also have high Nb/Ta ratios (80–300). Three distinct trace element types of the scheelites are interpreted to reflect chemical differences in the pulses of hydrothermal fluids. Hydrothermal rutiles have high contents of W (up to 4.2 wt.% WO₃), are rich in Ta compared to Nb and have a very low Nb/Ta ratio (~0.3). Hydrothermal fluids which produced both scheelite with a high Nb/Ta and rutile with a low Nb/Ta ratio are an efficient medium for fractionation of this ratio although these two minerals play an important role during the process.     

The association of tourmalinite with stratiform scheelite deposits

Three types of stratiform scheelite deposits are recognised. They all commonly have a close spatial association with tourmalinite. Regional prograde calc-silicate rocks in Precambrian rift settings commonly contain >100 ppm WO₃ with enrichment to 0.5–1% WO₃ in retrograde metamorphic assemblages at fold hinges, joints, faults, shears and granite and pegmatite dyke contacts. The calc-silicate progenitor was probably a impure dolomitic carbonate sediment. Amphibolite-hosted scheelite deposits occur in metamorphosed altered mafic volcanics formed in a narrow rift graben. Scheelite occurs both as stratiform and stratabound footwall stringer ore which has undergone minor remobilization during tectonism. Tourmalinites are rarely the host for stratabound quartz-scheelite±wolframite veins remobilized from the host tourmalinite and associated metavolcanics during tectonism.Tourmaline associated with stratiform scheelite deposits comprise zoned schorl-dravite and are no different from other tourmalines associated with submarine exhalative ores. Tourmalinites are characterized by high SiO₂, Al₂O₃, B₂O₃ and Fe₂O₃ and, although they are commonly stratigraphically equivalent to submarine exhalative base metal deposits, they are depleted in P₂O₅, BaO and MnO.It is suggested that soft base-soft acid ligand complexes transported W from the mantle or leached crust for surficial submarine hot spring deposition. Enrichment during tectonism, especially in calc-silicate hosted deposits, took place at the sites of fluid focussing where , and pH were high. This enrichment by up to 10² derives from dissolution of scheelite by chloride solutions resulting in redeposition of scheelite in retrograde metamorphic assemblages.