辉钼矿亚晶粒范围内Re和187Os的失耦现象

对于一些粗颗粒辉钼矿样品,取样量小时,不能产生准确且重现性好的结果;取样量大时,则重现性好。这是因为Re和187Os在辉钼矿亚晶粒(微米级)范围内出现了失耦现象,也就是由于放射性成因187Os的迁移使Re和187Os在空间上不再保持连接。失耦的程度随辉钼矿年龄的增加和颗粒度的增大而更加明显。地质年龄年轻的自然细颗粒样品的失耦现象不明显,使用1～3mg样品就有可能取得准确且重现性好的结果。而地质年龄老的粗颗粒样品,则可能需要大约100mg甚至更多的样品才能得到重现性好的数据。增大取样量以及将样品研磨至粒度<0.1mm,以增加样品的均匀性,可有效克服失耦现象对准确定年的影响。     

Re-Os同位素定年方法进展及ICP-MS精确定年测试关键技术

本文介绍了Re-Os同位素定年的基本原理、技术发展及应用现状;综述了样品分解和Re-Os分离富集的主要方法,重点对ICP-MS法进行Re-Os同位素定年做了较详尽的介绍,包括质量分馏校正、干扰校正、含量初测、取样量的确定、稀释剂的稀释比及稀释剂加入量等,以确保高精度测试;评述了ICP-MS最常见的测定对象-辉钼矿中Re-Os的失耦现象及降低其对Re-Os同位素定年影响的对策,文中描述了由测定同位素比值计算含量时的误差传递公式并重申了最佳稀释比。最后,指出了Re-Os同位素定年方法研究中应该关注的工作方向。     

新疆可可托海3号伟晶岩脉成岩时代的限定:来自辉钼矿Re-Os定年的证据

可可托海3号伟晶岩脉因其完美的岩浆结晶分异特征而闻名世界,但针对其年代学方面的认识仍存在较大分歧。本次工作采集到产于3号脉边部带中的6件辉钼矿样品。其产出地质特征显示属于3号伟晶岩脉边部带形成时与围岩的热液交代成因,形成时间应与边部带近于同时或稍晚。文章利用辉钼矿Re-Os测年技术进行的年代学研究结果表明,6件辉钼矿Re-Os等时线年龄为(208.8±2.4)Ma(MSWD=0.89)以及模式年龄为(209.9±1.3)Ma(MSWD=0.69),在误差范围内一致,可忽略辉钼矿Re-Os体系可能产生的失偶现象,代表了辉钼矿在流体中沉淀的时间。在研究前人年代学成果基础上,笔者认为3号伟晶岩脉的形成起始于209 Ma左右,即中三叠世晚期。     

安徽省金寨县沙坪沟钼矿辉钼矿Re-Os年龄——兼论东秦岭-大别山中生代钼成矿作用期次划分

安徽省金寨县沙坪沟钼矿是新发现的超大型斑岩型钼矿床.文章介绍了该矿床的基本地质特征,并对其进行了精确的辉钼矿Re-Os同位素年代学测定.结果表明,沙坪沟钼矿辉钼矿模式年龄为(112.2±1.7)～(113.9±1.7) Ma,加权平均年龄为(113.18±0.54) Ma,MSWD - 0.39;等时线年龄为(113....     

赣南樟东坑钨矿两类矿化中辉钼矿的Re-Os同位素定年及其地质意义

赣南樟东坑钨矿具有典型的"上脉(黑钨矿石英脉)下体(蚀变细粒花岗岩)"和"上钨下钼"矿化模式,为了弄清黑钨矿石英脉与蚀变细粒岩体型矿化之间在成矿时间上的关系,对产于该矿细粒花岗岩中的辉钼矿和石英脉中的辉钼矿分别进行了Re-Os同位素定年.测试结果为:细粒花岗岩中的3件辉钼矿样品Re-Os等时线年龄为155.4±2.1Ma(MSWD=1.12),模式年龄154.9±2.6Ma~156.5±2.6Ma,加权平均年龄155.5±1.4Ma(MSWD=0.44);而石英脉中5件辉钼矿样品的Re-Os等时线年龄为154.6±1.7Ma(MSWD=0.030),模式年龄变化范围为154.2±2.3Ma~154.7±2.7Ma,加权平均年龄为154.29±0.98Ma(MSWD=0.045).上述结果表明,花岗岩体型矿化与石英脉型矿化的年龄在误差范围内高度一致,从而证明了岩体中的钼钨矿化与石英脉中的钨钼矿化为同一次岩浆热液矿化事件的产物.     

赣南樟东坑钨矿两类矿化中辉钼矿的Re-Os同位素定年及其地质意义

赣南樟东坑钨矿具有典型的"上脉(黑钨矿石英脉)下体(蚀变细粒花岗岩)"和"上钨下钼"矿化模式, 为了弄清黑钨矿石英脉与蚀变细粒岩体型矿化之间在成矿时间上的关系, 对产于该矿细粒花岗岩中的辉钼矿和石英脉中的辉钼矿分别进行了Re-Os同位素定年. 测试结果为: 细粒花岗岩中的3件辉钼矿样品Re-Os等时线年龄为155.4±2.1 Ma(MSWD=1.12), 模式年龄154.9±2.6 Ma~156.5 ± 2.6 Ma, 加权平均年龄155.5±1.4 Ma(MSWD=0.44);而石英脉中5件辉钼矿样品的Re-Os等时线年龄为154.6±1.7 Ma(MSWD=0.030), 模式年龄变化范围为154.2±2.3 Ma~154.7±2.7 Ma, 加权平均年龄为154.29±0.98 Ma(MSWD=0.045). 上述结果表明, 花岗岩体型矿化与石英脉型矿化的年龄在误差范围内高度一致, 从而证明了岩体中的钼钨矿化与石英脉中的钨钼矿化为同一次岩浆热液矿化事件的产物.      

东秦岭南泥湖钼（钨）矿田Re—Os同位素年龄及其地质意义

位于华北克拉通南缘东秦岭钼矿带的南泥湖为一超大型夕卡岩斑岩型钼(钨)矿田,本研究采用电感耦合等离子体质谱仪法对南泥湖钼矿田三个矿床6件辉钼矿进行了Re-Os同位素年龄测定,获得南泥湖矿床的辉钼矿Re-Os模式年龄为141.8±2.1 Ma;三道庄矿床的辉钼矿Re-Os模式年龄为144.5±2.2～145.0±2.2Ma,平均为145.0±2.2 Ma;上房沟矿床的辉钼矿Re-Os模式年龄为143.8士2.1～145.8±2.1 Ma,平均为144.8±2.1 Ma;6件样品的等时线年龄为141.5±7.8 Ma(2σ),准确厘定了成矿时间.Re-Os同位素还表明:南泥湖钼矿的成矿物质来源以下地壳成分为主,但混有少量地幔组分.南泥湖钼矿是在中国东部中生代构造体制大转换中形成,属于中国东部中生代大规模成矿作用的一部分.     

辉钼矿Re-Os同位素定年方法的改进与应用

公认的Re-Os同位素定年代表物辉钼矿,目前已在金属硫化物矿床年代学研究领域获得了广泛的应用。本研究采用浓HNO₃分解辉钼矿样品,大大地简化了Re和Os的化学制备过程,并根据辉钼矿中正常Os含量水平相对放射成因¹⁸⁷Os可以忽略的特点,以正常Os标准为稀释剂,实现了仪器测量过程中Os同位素质量分馏的在线校正,改善了分析数据的质量。该方法经辉钼矿国家标准物质进行验证,获得了满意的Re、Os含量及Re-Os年龄数据,并且在南岭地区与连阳复式岩体相关的姓坪夕卡岩型钼矿床成矿年龄研究中获得了成功应用。在实际应用中,为了获得有意义的能反映真实地质事件的年龄数据,辉钼矿样品不仅要有足够的取样量,而且还要保证粒度细、混合均匀。     

含有普通锇的辉钼矿Re-Os同位素定年研究

通过大量数据统计,表明较高比例的辉钼矿中存在普通锇。普通锇可能以类质同像形式存在于辉钼矿样品中,理论上辉钼矿中可能含有较高含量普通锇。辉钼矿样品含有较高含量普通锇可能对Re-Os定年结果产生很大影响,从原理上并结合实例证实了普通锇含量对辉钼矿Re-Os年龄影响程度。对于一般辉钼矿样品来讲,如果187Os总量(放射成因187Os与非放射成因187Os之和)与普通锇比值小于20,需要考虑普通锇对Re-Os模式年龄的影响,并提出了对于含有普通锇辉钼矿模式年龄的计算方法。先做出187Os/188Os-187Re/188Os等时线,求得初始187Os/188Os值,再根据初始187Os/188Os值和单个样品的普Os含量求得非放射成因的普Os中187Os的量。最后根据Re含量以及放射成因187Os含量得到模式年龄。     

河南商城县汤家坪钼矿辉钼矿铼-锇同位素年龄及地质意义

为查明商城县汤家坪大型钼矿床形成的时代,建立钼多金属矿成矿模式,利用电感耦合等离子体质谱仪对汤家坪等3个钼矿床的7件辉钼矿样品进行了Re-Os同位素年龄测定,获得汤家坪钼矿床辉钼矿Re-Os等时线年龄为(113.1±7.9)Ma,准确厘定其成矿时代为早白垩世;测得天目沟钼矿床辉钼矿Re-Os同位素模式年龄为(121.6±2.1)Ma,大银尖钼矿床辉钼矿Re-Os同位素模式年龄为(122.1±2.4)Ma,初步确定大别山钼成矿带的成矿年龄大约在(122.1±2.4)～(113.1±7.9)Ma之间。结合前人研究成果,认为大别山北麓钼成矿作用的地球动力学背景为燕山晚期大别造山带在伸展机制下岩石圈减薄,中国中东部区域构造-动力体制由近EW向构造为主向近SN向构造为主的大转换时期。     

Macroscale NTIMS and microscale LA-MC-ICP-MS Re-Os isotopic analysis of molybdenite: Testing spatial restrictions for reliable Re-Os age determinations, and implications for the decoupling of Re and Os within molybdenite

We present a detailed study of Re-Os age determinations for eight natural molybdenite samples of like polytype (2H), spanning a range of age, natural grain size and deposit type. The focus of the study is to critically evaluate the effects of sampling, sample preparation and aliquant size on the accuracy and reproducibility of Re-Os ages for these molybdenite samples. We find that for some molybdenite samples, analysis of small sample aliquants (<20 mg) may not yield accurate or reproducible Re-Os ages, whereas analysis of larger aliquants from the same mineral separate do yield reproducible Re-Os dates. Such an observation is best explained if Re and ¹⁸⁷Os are internally decoupled within molybdenite grains. This finding is supported from spot analyses by laser ablation MC-ICP-MS analyses presented here and is consistent with previously published observations.The degree of decoupling between Re and ¹⁸⁷Os appears to increase both as a function of increasing grain size, and increasing age of molybdenite. From detailed dating of individual molybdenite mineral separates, we provide approximate minimum aliquant amounts required for reproducible Re-Os age dating, as a function of molybdenite age and grain size. Geologically younger, naturally fine-grained molybdenite samples appear to show little Re and ¹⁸⁷Os decoupling, and reproducible ages can be determined from some samples with as little as 1 mg of aliquant. Geologically old, and coarse-grained molybdenite samples may require as much as 40 mg of aliquant from a much larger mineral separate to overcome Re and ¹⁸⁷Os decoupling. The mechanism(s) of Re and ¹⁸⁷Os decoupling within molybdenite is not constrained by this results of this study, but the observation that the degree of decoupling increases with grain size (distance) and age (time/geologic history) may suggest primary diffusive control. Assuming that Re and ¹⁸⁷Os decoupling in molybdenite results primarily from diffusion of ¹⁸⁷Os, apparent diffusion coefficients are calculated (D = x²/t). Estimates of D for Os made in this way range from 2.8 × 10⁻²⁶ to 2.1 × 10⁻²¹ m²/s, which are broadly similar to experimentally derived diffusion coefficients for Os in Fe-sulfide minerals and for Re in molybdenite at temperatures <500°C.     

Subgrain-scale decoupling of Re and Os and assessment of laser ablation ICP-MS spot dating in molybdenite

Reproducibility of Re-Os molybdenite ages depends on sample size and homogeneity, suggesting that Re and Os are decoupled within individual molybdenite crystals and do not remain spatially linked over time. In order to investigate the Re-Os systematics of molybdenite at the subgrain (micron) scale, we report LA-ICP-MS Re-Os ages for an Archean molybdenite crystal from Aittojärvi, Finland, analyzed in situ in a white aplite matrix. A related Aittojärvi molybdenite (A996D), in the form of a very fine-grained mineral separate, is used as one of our in-house NTIMS standards, and thus its age of 2760 ± 9 Ma is well established. Measurements of (¹⁸⁷Re + ¹⁸⁷Os)/¹⁸⁵Re on micron scale spots along 200 μm traverses across the crystal yield a wide range of ages demonstrating that, in this case, microsampling of molybdenite does not produce geologically meaningful ages. Experimentation with mineral separations and sample size over a 7-yr period predicted that this would be the outcome. We suggest that ¹⁸⁷Os is more likely to be the mobile species, based on its charge and ionic radius, and that ¹⁸⁷Os becomes decoupled from parent ¹⁸⁷Re with time on the micron and larger scale. Incompatible charge and ionic radius for Os ions formed during reduction of molybdenite-forming fluids may explain the widely observed absence of common (initial) Os in molybdenite. Geologically accurate ages for molybdenite can only be obtained for fully homogenized crystals (or crystal aggregates) so that any post-crystallization ¹⁸⁷Re-¹⁸⁷Os decoupling is overcome.A growing number of geologically accurate ID-NTIMS ¹⁸⁷Re-¹⁸⁷Os ages for homogenized molybdenite suggest that postcrystallization mobility of radiogenic ¹⁸⁷Os must be limited to within the molybdenite mineral phase. We suggest that radiogenic ¹⁸⁷Os may be stored in micron scale dislocations, kink bands, and delamination cracks produced by deformation, and that the unusual structure and deformation response of molybdenite results in an increased chemical stability in this mineral. Migration of ¹⁸⁷Os into adjacent silicate phases is highly unlikely, but other contacting sulfides may take in Os. In an example from a Proterozoic skarn deposit at Pitkäranta (western Russia), we demonstrate minor loss of radiogenic ¹⁸⁷Os from molybdenite and a corresponding gain in adjacent chalcopyrite such that the molybdenite age is not perceptibly disturbed, whereas the resulting chalcopyrite ages are impossibly old. Therefore, it is unadvisable to perform Re-Os analytical work on any sulfide in contact or intimate association with molybdenite. In addition to large errors in the age, if the isochron method is employed, initial ¹⁸⁷Os/¹⁸⁸Os ratios could be erroneously high, leading to seriously errant genetic interpretations.     

半封闭硝酸溶解体系ICP-MS快速测定辉钼矿的Re-Os年龄及Re含量

Re-Os法能够直接厘定内生金属矿床成矿时代,但是封闭Carius管法化学流程复杂,且有一定的危险性。本文建立了一种简便快速测定辉钼矿Re-Os年龄及其Re含量的方法。用3 mL浓硝酸在10 mL比色管中溶解5~15 mg辉钼矿样品,将溶液中的钼酸沉淀分离后稀释定容,直接采用质谱测量187和185质量数比值(M187/M185)。利用辉钼矿Re-Os年龄标准物质JDC和HLP的M187/M185值与其年龄的正相关线性关系计算未知辉钼矿样品的Re-Os年龄,并通过¹⁸⁵Re计数利用相对法计算Re含量。本方法应用于测量13.26~2130 Ma的辉钼矿,Re-Os年龄的测定值与推荐值的相对偏差多数在0.36%~7.42%之间,由于放射性积累较多,长年龄样品测量的准确度较高。与传统Carius管法相比,该方法不需要加入稀释剂,省去了封闭和打开Carius管环节以及Re-Os分离纯化流程,适合于辉钼矿Re-Os年龄的初步分析。     

含辉钼矿全岩样品Re-Os同位素定年研究:在北京大庄科钼矿床中的应用

采用硝酸在比色管中对辉钼矿样品中Re含量进行初测的方法,测得辉钼矿标准样品JDC Re含量与推荐值在误差范围内基本一致,与传统的Carius管法相比,该方法具有简便快速的特点。传统的辉钼矿Re-Os同位素定年分析对象为辉钼矿单矿物,根据所测得的187Re/187Os值获得辉钼矿的Re-Os年龄,Re、Os在辉钼矿中大量富集,而在硅酸盐矿物中几乎没有,探索性地对含有辉钼矿的全岩样品进行Re-Os同位素定年,虽然所得Re、Os含量偏低,但187Re/187Os值不会变。该方法省去了选样过程花费的大量时间,避免了选样过程中可能造成的交叉污染。采用同位素稀释Carius管逆王水法探索性地对北京大庄科钼矿床中含辉钼矿全岩样品进行Re-Os同位素年龄测定,获得了(137.6±3.7)Ma精确的等时线年龄,与挑选出辉钼矿单矿物样品的Re-Os同位素等时线年龄(136.8±2.6)Ma吻合较好,直接厘定了大庄科钼矿的成矿时代。该年龄与矿区汉家川石英二长岩锆石U-Pb年龄一致,表明大庄科钼矿的形成与汉家川石英二长岩关系较为密切,为中国东部第二期大规模成矿作用的产物,形成于中国东部岩石圈伸展环境。     

小秦岭北缘马家洼石英脉型金钼矿床的辉钼矿Re-Os年龄及其意义

马家洼金钼矿床位于小秦岭北缘,矿体发育在由近东西向脆韧性断裂构造带控制的石英脉中。对该矿床辉钼矿样品进行的Re-Os同位素年代学研究表明:模式年龄范围是232.5～268.4 Ma,等时线年龄为(232±11)Ma,即钼成矿作用时代为早、中三叠世。辉钼矿样品的Re含量范围是(0.474～0.791)×10~(-6),初始~(187)Os/~(188)Os比值为2.4±6.4,Re-Os同位素组成特征指示了成矿物质主要来源于地壳。马家洼石英脉型金钼矿床是区域伸展体制下构造-流体成矿事件的产物。在华北板块南缘太古宙基底岩系中的脆韧性断裂构造带中寻找印支期和燕山期石英脉型金钼矿床和钼矿床是一个新的找矿方向。     

The remarkable Re–Os chronometer in molybdenite: how and why it works

The Re–Os (rhenium–osmium) chronometer applied to molybdenite (MoS₂) is now demonstrated to be remarkably robust, surviving intense deformation and high‐grade thermal metamorphism. Successful dating of molybdenite is dependent on proper preparation of the mineral separate and analysis of a critical quantity of molybdenite, unique to each sample, such that recognized spatial decoupling of ¹⁸⁷Re parent and ¹⁸⁷Os daughter within individual molybdenite crystals is overcome. Highly precise, accurate and reproducible age results are derived through isotope dilution and negative thermal ion mass spectrometry (ID‐NTIMS). Spatial decoupling of parent–daughter precludes use of the laser ablation ICP‐MS microanalytical technique for Re–Os dating of molybdenite. The use of a reference or control sample is necessary to establish laboratory credibility and for interlaboratory comparisons. The Rb–Sr, K–Ar and ⁴⁰Ar/³⁹Ar chronometers are susceptible to chemical and thermal disturbance, particularly in terranes that have experienced subsequent episodes of hydrothermal/magmatic activity, and therefore should not be used as a basis for establishing accuracy in Re–Os dating of molybdenite, as has been done in the past. Re–Os ages for molybdenite are almost always in agreement with observed geological relationships and, when available, with zircon and titanite U–Pb ages. For terranes experiencing multiple episodes of metamorphism and deformation, molybdenite is not complicated by overgrowths as is common for some minerals used in U–Pb dating (e.g. zircon, monazite, xenotime), nor are Re and Os mobilized beyond the margins of individual crystals during solid‐state recrystallization. Moreover, inheritance of older molybdenite cores, incorporation of common Os, and radiogenic Os loss are exceedingly rare, whereas inheritance, common Pb and Pb loss are common complications in U–Pb dating techniques. Therefore, molybdenite ages may serve as point‐in‐time markers for age comparisons.     

西秦岭西成矿集区厂坝岩体的钼矿化特征及其Re-Os年龄

甘肃西成矿集区是西秦岭最重要的多金属成矿区之一,以铅锌矿床为主,其次发育有金、铜、钼等矿床(点)。厂坝黑云母二长花岗岩体位于西成矿集区中东部,岩体南缘接触带部位发育石英脉型钼矿,辉钼矿呈中粗粒半自形团块状产于粗粒石英脉内。Re-Os同位素年代学研究表明,其模式年龄范围为207.7±3.0~209.8±2.8Ma,加权平均年龄为208.9±1.1 Ma,等时线年龄为209±15 Ma,指示钼矿化发生于晚三叠世。辉钼矿的铼含量介于18.82×10~(-6)~21.97×10~(-6)之间,平均19.65×10~(-6),表明成矿物质主要为壳幔混合来源,可能以壳源为主。钼矿化与区域岩浆活动以及金、铅锌成矿作用时代相近,是印支期区域构造-岩浆-流体活动的产物。钼矿化年龄的厘定为区内找矿提供了新的思路。     

Re-Os ages for Archean molybdenite and pyrite, Kuittila-Kivisuo, Finland and Proterozoic molybdenite, Kabeliai, Lithuania: testing the chronometer in a metamorphic and metasomatic setting

Seven ¹⁸⁷Re-¹⁸⁷Os ages were determined for molybdenite and pyrite samples from two well-dated Precambrian intrusions in Fennoscandia to examine the sustainability of the Re-Os chronometer in a metamorphic and metasomatic setting. Using a new ¹⁸⁷Re decay constant (1.666 × 10⁻¹¹y⁻¹) with a much improved uncertainty (±0.31%), we determined replicate Re-Os ages for molybdenite and pyrite from the Kuittila and Kivisuo prospects in easternmost Finland and for molybdenite from the Kabeliai prospect in southernmost Lithuania. These two localities contain some of the oldest and youngest plutonic activity in Fennoscandia and are associated with newly discovered economic Au mineralization (Ilomantsi, Finland) and a Cu-Mo prospect (Kabeliai, Lithuania). Two Re-Os ages for vein-hosted Kabeliai molybdenite average 1486 ± 5 Ma, in excellent agreement with a 1505 ± 11 Ma U-Pb zircon age for the hosting Kabeliai granite pluton. The slightly younger age suggests the introduction of Cu-Mo mineralization by a later phase of the Kabeliai magmatic system. Mean Re-Os ages of 2778 ± 8 Ma and 2781 ± 8 Ma for Kuittila and Kivisuo molybdenites, respectively, are in reasonable agreement with a 2753 ± 5 Ma weighted mean U-Pb zircon age for hosting Kuittila tonalite. These Re-Os ages agree well with less precise ages of 2789 ± 290 Ma for a Rb-Sr whole-rock isochron and 2771 ± 75 Ma for the average of six Sm-Nd T_DM model ages for Kuittila tonalite. Three Re-Os analyses of a single pyrite mineral separate, from the same sample of Kuittila pluton that yielded a molybdenite separate, provide individual model ages of 2710 ± 27, 2777 ± 28, and 2830 ± 28 Ma (Re = 17.4, 12.1, and 8.4 ppb, respectively), with a mean value of 2770 ± 120 Ma in agreement with the Kuittila molybdenite age. The Re and ¹⁸⁷Os abundances in these three pyrite splits are highly correlated (r = 0.9994), and provide a ¹⁸⁷Re-¹⁸⁷Os isochron age of 2607 ± 47 Ma with an intercept of 21 ppt ¹⁸⁷Os (MSWD = 1.1). It appears that the Re-Os isotopic system in pyrite has been reset on the millimeter scale and that the 21 ppt ¹⁸⁷Os intercept reflects the in situ decay of ¹⁸⁷Re during the ∼160 to 170 m.y. interval from ∼2778 Ma (time of molybdenite ± pyrite deposition) to ∼2607 Ma (time of pyrite resetting). When the Re-Os data for molybdenites from the nearby Kivisuo prospect are plotted together with the Kuittila molybdenite and pyrite data, a well-constrained five-point isochron with an age of 2780 ± 8 Ma and a ¹⁸⁷Os intercept (−2.4 ± 3.8 ppt) of essentially zero results (MSWD = 1.5). We suggest that the pyrite isochron age records a regional metamorphic and/or hydrothermal event, possibly the time of Au mineralization. A proposed Re-Os age of ∼2607 Ma for Au mineralization is in good agreement with radiometric ages by other methods that address the timing of Archean Au mineralization in deposits worldwide (so-called “late Au model”). Molybdenite, in contrast, provides a robust Re-Os chronometer, retaining its original formation age of ∼2780 Ma, despite subsequent metamorphic disturbances in Archean and Proterozoic time. Received: 25 September 1996 / Accepted: 27 August 1997