利用MC-ICPMS精确测定143Nd/144Nd和Sm/Nd比值

多收集器等离子体质谱(MCICPMS)用于分析SmNd同位素时,质量分馏系数(β)与同位素的质量数呈线性关系.可以采用两种方法进行质量分馏校正:双分馏系数内部校正法(DFIC)和单分馏系数外部校正法(SFEC).采用DFIC法,对国际标样ShinEtsuJNdi1和实验室标样NdGIG进行了为期五个月的143Nd/144Nd比值测量统计,结果分别为0.512120±0.000012(2σSD)、0.511532±0.000013(2σSD).采用SFEC法,对NdGIG标样的测量统计结果为0.511525±0.000015(2σSD).两种方法的测量结果在分析误差范围内与其推荐值或TIMS测量值完全一致.对加Ce和Sm的NdGIG混合溶液分别进行了Ce和Sm对143Nd/144Nd比值分析的干扰校正研究和Sm/Nd比值测量,结果显示,143Nd/144Nd比值分别与Ce/Nd、Sm/Nd测量值呈线性关系,Sm/Nd测量值与其质量比值亦呈很好的线性关系.这表明利用MCICPMS可以快速精确地测定存在Ce、Sm干扰的样品的143Nd/144Nd比值,同时可获得精确的Sm/Nd比值,而无需加入稀释剂.这就使直接测定地质样品的SmNd等时线年龄成为可能.     

激光原位LA-MC-ICP-MS测定地质样品Sm-Nd同位素方法新进展

本文综述了近10年来激光原位LA-MC-ICP-MS测定地质样品Sm-Nd同位素测试技术的最新进展,着重介绍了同质异位素干扰校正的关键技术难点及校正方案。LA-MC-ICP-MS技术对轻稀土富集矿物可以获得可靠的~(147)Sm /~(144)Nd and~(143)Nd /~(144)Nd值,是当前进行地质样品激光原位Sm-Nd同位素测定的主要技术,配合矿物微区U-Th-Pb年龄测定和微量元素分析,可以对矿物的成因演化提供重要的制约参数。多元同位素体系(Sr-Nd-Hf同位素、U-Th-Pb年龄和微量元素)的原位微区联合测定,低含量地质样品(小于500μg/g)和高Sm/Nd值矿物(如磷钇矿Sm/Nd远远大于1,有时甚至达到10)的Sm-Nd同位素组成的准确测定是未来LA-MC-ICP-MS激光原位Sm-Nd同位素测定的主要发展方向之一,具有广阔的应用前景。     

岩石铷-锶和钐-钕同位素标准物质的研制

通常样品的⁸⁷Sr/⁸⁶Sr和¹⁴³Nd/¹⁴⁴Nd同位素比值分析采用SRM9⁸⁷、JNdi-1作为标准物质,它们分别是纯的碳酸盐和氧化物,适用于监控质谱测试过程。中国现有的钐-钕地质和铷-锶年龄标准物质,分别为玄武岩和钾长石,它们与很多地质样品的基质存在差别。仅有这两种基质的标准物质不能有效地监控不同地质样品Rb-Sr、Sm-Nd同位素分析过程,因此研制不同岩性的Rb-Sr、Sm-Nd同位素标准物质具有重要现实意义。本文采集中国典型地区的橄榄岩、榴辉岩和花岗岩作为候选物,严格按照《一级标准物质技术规范》(JJF 1006-1994)和《标准物质定值的通用原则及统计学原理》(JJF 1343-2012)等相关标准物质国家计量技术规范和国家标准,研制了橄榄岩、榴辉岩和花岗岩铷-锶、钐-钕同位素标准物质(编号为GBW04139、GBW04140、GBW04141),其中橄榄岩标准物质适用于高Mg、Fe,低Rb、Nd含量样品的分析,榴辉岩和花岗岩标准物质适用于含有难溶副矿物的岩石样品的分析。每个标准物质具有6个特性量值,Rb、Sr、Sm和Nd含量分布分别为0.16~64μg/g、12~560μg/g、0.1~3.2μg/g和0.3~15.3μg/g,⁸⁷Sr/⁸⁶Sr比值分布为0.70446~0.71309,¹⁴³Nd/¹⁴⁴Nd比值分布为0.51115~0.51267,同位素比值精度达到或优于同类标准物质。这些特性量值更接近实际样品,使用时将更加有效和方便。该系列标准物质可用于校准仪器和评价方法,并能有效监控实验室此类样品的铷-锶、钐-钕同位素分析过程。     

山东济南下寒武统朱砂洞组软沉积变形中燧石的Sm-Nd年龄测定及其意义

在济南南部下寒武统朱砂洞组丁家庄段硅质白云岩中,发育地震引起的硅质触变脉、硅质触变沉陷构造和触变楔等软沉积变形构造。从同一地震触变沉陷构造中,采得一组灰黑色燧石样品。使用英国VG354同位素质谱仪和同位素质谱分析方法,测得每个样品的 ¹⁴⁷Sm/¹⁴⁴Nd 和 ¹⁴³Nd/¹⁴⁴Nd 同位素值。采用Sm-Nd 等时线法,对燧石进行了测年。获得燧石的成岩年龄为530.8±6.1 Ma,由于软燧石(硅胶体)成岩至少经历了0.1 Ma的时间,所以,地震沉积事件发生在530.7±6.1 Ma,属早寒武世早期。由于测年结果与沧浪铺阶的下界年龄接近,山东朱砂洞组丁家庄段无化石且河南省标准地层剖面中的整个朱砂洞组属沧浪铺阶,这暗示济南地区朱砂洞组丁家庄段属沧浪铺阶。本次测年得到了鲁西地区第1个下寒武统的同位素年龄值,这对确定该地区早寒武世地震沉积事件发生的时间具有参考价值和意义,也为深入研究鲁西地区寒武纪地层提供了新资料。     

多接收器等离子体质谱(MC-ICPMS)高精度测定Nd同位素方法

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一,通过用等离子体质谱测量Nd国际标准材料La Jolla和JMC Nd203以及实际样品GBW04419,研究MC-ICPMS测量Nd的质量分馏特点,解决MC-ICPMS测量的关键所在质量分馏校正.通过修正分馏系数,可以实现理想的分馏校正.结果显示出所得到的分析精度达到热电离质谱的测量水平.具有实际地质样品代表性的实验室内部标准CAGS-Nd-1重现性长期分析结果为:143Nd/144Nd=0.512072±0.000008(2σ,n=140).     

多接收器等离子体质谱仪测钕同位素比值的质量歧视校正初探

利用国内首次引进的Nu Plasma型MC-ICPMS,对Nd同位素测试过程的质量歧视效应特征进行了研究.发现该类仪器测试过程的质量歧视效应并不完全符合指数函数,也不符合幂函数.质量歧视引起的同位素分馏随同位素对的平均质量数变化,但不严格遵从线性关系.只是在较小质量范围内呈近似线性关系.据此,用双分馏系数校正法可以获得143Nd/144Nd的校正系数,并用来校正143Nd/144Nd值.用此方法获得的JNdi-1的143Nd/144Nd值为O.512 107±O.OOO 008(2RSD),在测量误差范围内与TIMS测定值完全吻合.     

Sr-Nd同位素初始比值和Nd模式年龄的误差估算

SrNd同位素参数广泛应用于岩石物质来源及其成因研究,但绝大多数研究者在应用这些参数时并未说明它们的误差大小,这种做法并不科学。作者首次利用误差传播定律推导出了有关参数的误差估算公式,这些参数包括Sr同位素的初始比值(87Sr/86Sr)t、Nd同位素的初始比值(143Nd/144Nd)t、εSr(t)、εNd(t)、Nd同位素模式年龄等。Rb、Sr含量的高低及其测定误差决定着(87Rb/86Sr)s的误差,Sm、Nd含量的高低及其测定误差决定着 (147Sm/144Nd)s的误差,(87Rb/86Sr)s的大小及其误差、(87Sr/86Sr)s误差、年龄值大小及其误差共同影响着(87Sr/86Sr)t的误差。同样,(147Sm/144Nd)s的大小及其误差、(143Nd/144Nd)s 的误差、年龄值大小及其误差共同影响着(143Nd/144Nd)t的误差。Nd同位素球粒陨石模式年龄TCHUR和单阶段亏损地幔模式年龄TDM的误差影响因素主要包括(147Sm/144Nd)s的大小、(143Nd/144Nd)s 的大小及这两个比值的误差,而Nd同位素两阶段亏损地幔模式年龄TDM2的误差除上述影响因素之外,还包括年龄值大小及其误差。通过对广西姑婆山4个花岗岩样品SrNd同位素参数及其误差的计算,作者对各个影响因素进行了详细分析,认为采用同位素稀释质谱法测试数据和高精度的年龄数据是获得理想示踪参数的保证,Rb、Sr、Sm、Nd含量沿用微量（包括稀土）元素测试结果的做法是不可取的,对高Rb样品更应该谨慎从事。建议研究者在使用SrNd同位素参数时能够估算这些参数的误差,并在文章中有所说明。     

电感耦合等离子体质谱法测定地质样品中锗和镉的干扰及校正

采用HF-HClO₄-HNO₃分解样品,8 mol/L HNO₃提取剂,外标法校准,电感耦合等离子体质谱法同时测定地球化学样品中锗和镉。选择¹⁰³Rh为内标,确定了最佳仪器参数,研究了Zn、Zr、Sn、Ce、Nd、Sm对Ge和Cd的干扰,试验选择质量数⁷⁴Ge和¹¹⁴Cd作为测定同位素,采用数学公式校正法校正了来自Nd和Sm的二次电离离子对Ge的干扰、Sn对Cd的同质异位素干扰。方法检出限（10s）分别为Ge 30 ng/L、Cd 15 ng/L,精密度（RSD,n=15）为Ge 1.35%、Cd 1.47%。对多种国家一级标准物质进行分析验证,结果与标准值相符。方法适用于地质样品中微量锗和镉的测定。     

Sm-Nd同位素准确测定的影响因素分析

通过对Sm-Nd同位素测定的流程分析,探讨了对Sm-Nd同位素分析的影响因素。采用HF+HNO3+H3BO3溶解样品,可有效地消除氟化物对REE回收率的影响;样品容器和分离柱的本底是全流程本底的主要来源;根据同位素稀释法误差倍增曲线,合理加入稀释剂的量可有效提高147Sm/144 Nd测定的准确度;稀释剂加入量对稀释法同位素比值测定的影响主要来源于稀释剂同位素组成测定的不确定度,通过数学迭代法,可对稀释剂同位素组成测定的质量分馏效应进行有效校正,提高稀释剂同位素组成的准确性。     

玄武岩分相Sm-Nd内部等时线定年方法流程

长期以来,对玄武岩精确测年一直是困扰地质学家的重大科学问题。玄武岩结构和组成特殊,岩石中矿物组成单一、锆石十分稀少,颗粒很细,采用物理方法挑选单矿物和锆石十分困难,很难应用内部等时线法和锆石U-Pb法研究其成岩时代。而全岩样品间因岩浆分异产生的147Sm/144Nd比值差别很小,等时线年龄相对误差较大;Rb含量很低,Rb/Sr比值很小,全岩Sm-Nd法、Rb-Sr法常常不能给出正确可信的年龄。根据内部等时线法原理,本文通过化学方法,采用王水和氢氟酸-硝酸对玄武岩样品进行分步溶解,分别对同一件样品的王水溶解相、王水不溶相和全岩开展Sm-Nd同位素组成分析。结果表明:通过不同酸介质分步溶解,可提取玄武岩中石英、透辉石、长石等矿物组合,该组合与其全岩具有相同的εNd(t)和一致的Nd同位素模式年龄;矿物与全岩构筑的内部等时线中,147Sm/144Nd比值的变化由全岩之间的0.005扩大到0.11,143Nd/144Nd值的变化由全岩的0.512500~0.512547扩大到0.512500~0.513145。通过该方法获得了与已有锆石U-Pb年龄在误差范围内一致的Sm-Nd等时线年龄:t=(991±21)Ma(MSWD=2.1)。通过对比研究,本文认为:玄武岩分相Sm-Nd内部等时线定年方法,适用于前寒武纪及更古老的玄武岩样品的年龄测定。该方法的建立不仅有效提高玄武岩Sm-Nd等时线定年成功率,也为其他隐晶质且不易挑出单矿物样品的年龄测定提供了新的思路。     

Non-chondritic Sm/Nd ratio in the terrestrial planets: Consequences for the geochemical evolution of the mantle-crust system

Super-chondritic ¹⁴²Nd signatures are ubiquitous in terrestrial, Martian and lunar samples, and indicate that the terrestrial planets may have accreted from material with Sm/Nd ratio higher than chondritic. This contradicts the long-held view that chondrites represent a reference composition for the ¹⁴⁷Sm-¹⁴³Nd system. Using coupled ¹⁴⁶Sm-¹⁴²Nd and ¹⁴⁷Sm-¹⁴³Nd systematics in planetary samples, we have proposed a new set of values for the ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios of the bulk silicate Earth (Caro et al., 2008). Here, we revise the Bulk Silicate Earth estimates for the ⁸⁷Rb-⁸⁷Sr and ¹⁷⁶Lu-¹⁷⁶Hf systems using coupled Sr-Nd-Hf systematics in terrestrial rocks. These estimates are consistent with Hf-Nd systematics in lunar samples. The implications of a slightly non-chondritic silicate Earth with respect to the geochemical evolution of the mantle-crust system are then examined. We show that the Archean mantle has evolved with a composition indistinguishable from that of the primitive mantle until about 2 Gyr. Positive ε¹⁴³Nd and ε¹⁷⁶Hf values ubiquitous in the Archean mantle are thus accounted for by the non-chondritic Sm/Nd and Lu/Hf composition of the primitive mantle rather than by massive early crustal formation, which solves the paradox that early Archean domains only have a limited extension in the present-day continents. The Sm-Nd and Lu-Hf evolution of the depleted mantle for the past 3.5 Gyr can be entirely explained by continuous extraction of the continents from a well-mixed mantle. Thus, in contrast to the chondritic Earth model, Sm-Nd mass balance relationships can be satisfied without the need to call upon hidden reservoirs or layered mantle convection. This new Sm-Nd mass balance yields a scenario of mantle evolution consistent with trace element and noble gas systematics. The high ³He/⁴He mantle component is associated with ¹⁴³Nd/¹⁴⁴Nd compositions indistinguishable from the bulk silicate Earth, suggesting that the less degassed mantle sources did not experience significant fractionation for moderately incompatible elements.     

Determination of Sm‐Nd Isotopic Compositions in Fifteen Geological Materials Using Laser Ablation MC‐ICP‐MS and Application to Monazite Geochronology of Metasedimentary Rock in the North China Craton

In this study, we report both ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured β_Sm and β_Nd (r² = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min^?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. ¹⁴³Nd/¹⁴⁴Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g^?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a ¹⁴⁷Sm‐¹⁴³Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.     

Trace element systematics and Sm-Nd and Lu-Hf ages of Larkman Nunatak 06319: Closed-system fractional crystallization of an enriched shergottite magma

Combined ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf chronology of the martian meteorite Larkman Nunatak (LAR) 06319 indicates an igneous crystallization age of 193 ± 20 Ma (2σ weighted mean). The individual ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf internal isochron ages are 183 ± 12 Ma and 197 ± 29 Ma, respectively, and are concordant with two previously determined ¹⁴⁷Sm-¹⁴³Nd and ⁸⁷Rb-⁸⁷Sr internal isochron ages of 190 ± 26 Ma and 207 ± 14 Ma, respectively (Shih et al., 2009). With respect to the ¹⁴⁷Sm-¹⁴³Nd isotope systematics, maskelynite lies above the isochron defined by primary igneous phases and is therefore not in isotopic equilibrium with the other phases in the rock. Non-isochronous maskelynite is interpreted to result from shock-induced reaction between plagioclase and partial melts of pyroxene and phosphate during transformation to maskelynite, which resulted in it having unsupported ¹⁴³Nd relative to its measured ¹⁴⁷Sm/¹⁴⁴Nd ratio. The rare earth element (REE) and high field strength element (HFSE) compositions of major constituent minerals can be modeled as the result of progressive crystallization of a single magma with no addition of secondary components. The concordant ages, combined with igneous textures, mineralogy, and trace element systematics indicate that the weighted average of the radiometric ages records the true crystallization age of this rock. The young igneous age for LAR 06319 and other shergottites are in conflict with models that advocate for circa 4.1 Ga crystallization ages of shergottites from Pb isotope compositions, however, they are consistent with updated crater counting statistics indicating that young volcanic activity on Mars is more widespread than previously realized (Neukum et al., 2010).     

Sm-Nd age of the Stillwater complex and the mantle evolution curve for neodymium

An internal isochron determined for a gabbro from the Stillwater complex by the Sm-Nd method yields a precise age of 2701 ± 8 Myr and initial ¹⁴³Nd/¹⁴⁴Nd = 0.508248 ± 12. The initial is close to the CHUR evolution curve but clearly displaced below it by ?_Nd = ?2.8 ± 0.2. A spectrum of total rocks in the Stillwater complex ranging from anorthosite to pyroxenite were found to lie on the same isochron to within experimental error indicating the same age and initial. These data demonstrate that some ancient mantle-derived rocks have initial ¹⁴³Nd/¹⁴⁴Nd which deviate substantially from the CHUR evolution curve at the time of their formation. This implies that there was early layering in the mantle with substantial REE fractionation (~6–12% Nd/Sm enrichment) or that the Stillwater complex was highly contaminated with REE from much older continental crust during emplacement. The results show the necessity of high-precision ages and initial ¹⁴³Nd/¹⁴⁴Nd values in order to properly describe REE fractionation in the mantle. While the Sm-Nd age results show no indication of any irregularities, we have confirmed that the Rb-Sr data for the Stillwater are highly disturbed. This comparison indicates that the Sm-Nd parent-daughter system may be much less susceptible to element redistribution during metamorphism, therefore permitting wide application of this technique to rocks of complex histories.     

High-precision Nd/Nd measurements in terrestrial rocks: Constraints on the early differentiation of the Earth’s mantle

We present new ultra-high precision ¹⁴²Nd/¹⁴⁴Nd measurements of early Archaean rocks using the new generation thermal ionization mass spectrometer Triton. Repeated measurements of the Ames Nd standard demonstrate that the ¹⁴²Nd/¹⁴⁴Nd ratio can be determined with external precision of 2 ppm (2σ), allowing confident resolution of anomalies as small as 5 ppm. A major analytical improvement lies in the elimination of the double normalization procedure required to correct our former measurements from a secondary mass fractionation effect. Our new results indicate that metasediments, metabasalts, and orthogneisses from the 3.6 to 3.8 Ga West Greenland craton display positive ¹⁴²Nd anomalies ranging from 8 to 15 ppm. Using a simple two-stage model with an initial ε¹⁴³Nd value of 1.9 ± 0.6 ε-units, coupled ¹⁴⁷Sm-¹⁴³Nd and ¹⁴⁶Sm-¹⁴²Nd chronometry constrains mantle differentiation to 50-200 Ma after formation of the solar system. This chronological constraint is consistent with differentiation of the Earth’s mantle during the late stage of crystallization of a magma ocean. We have developed a two-box model describing ¹⁴²Nd and ¹⁴³Nd isotopic evolution of depleted mantle during the subsequent evolution of the crust-mantle system. Our results indicate that early terrestrial protocrust had a lifetime of ca. 0.7-1 Ga in order to produce the observed Nd isotope signature of Archaean rocks. In the context of this two box mantle-crust system, we model the evolution of isotopic and chemical heterogeneity of depleted mantle as a function of the mantle stirring time. Using the dispersion of ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios observed in early Archaean rocks, we constrain the stirring time of early Earth’s mantle to 100-250 Ma, a factor of 5 shorter than the stirring time inferred from modern oceanic basalts.     

Production and Certification of the Reference Material GSB 04‐3258‐2015 as a 143Nd/144Nd Isotope Ratio Reference

A new certified reference material, labelled GSB 04‐3258‐2015, for use as a ¹⁴³Nd/¹⁴⁴Nd isotope ratio reference has been prepared by the Institute of Geology, Chinese Academy of Geological Sciences, Beijing. Standardization Administration of the People's Republic of China provided the certification for this reference material. This report presents the reference ¹⁴³Nd/¹⁴⁴Nd isotope ratio and supporting production and certification procedures. The reference value was determined by an interlaboratory comparison of results from eleven participating laboratories using MC‐TIMS or MC‐ICP‐MS. The calibration of mass fractionation was conducted by using the exponential law, and the ¹⁴³Nd/¹⁴⁴Nd isotope ratios were normalised to the ¹⁴⁶Nd/¹⁴⁴Nd isotope ratio value of 0.7219. Isobaric interference of ¹⁴⁴Sm on ¹⁴⁴Nd was corrected using an interference‐free ¹⁴⁷Sm/¹⁴⁹Sm isotope ratio value for mass fractionation. GSB 04‐3258‐2015 shows sufficient homogeneity and stability for use as an international isotopic reference material. The certified value was calculated from the unweighted means of the results submitted by the participating laboratories. The ¹⁴³Nd/¹⁴⁴Nd isotope ratio value for GSB 04‐3258‐2015 is 0.512438, with a combined expanded uncertainty (k = 2) of 5 × 10^?6. Reference material GSB 04‐3258‐2015 is available upon request from the Institute of Geology, Chinese Academy of Geological Sciences, and may be used for accurate interlaboratory calibration of Nd isotope analysis.     

Sm-Nd isotope systematics in garnet from different lithologies (Eastern Alps): age results, and an evaluation of potential problems for garnet Sm-Nd chronometry [Chem. Geol. 185 (2002) 255-281]

Interpretation of Sm-Nd garnet ages is frequently impaired by one of the following restrictions: (a) high-LREE inclusions, (b) isotopic disequilibrium, and (c) the uncertainty about the closure temperature. These issues are addressed by way of an evaluation of garnet Sm-Nd data from different rock types of the Austroalpine basement units, Eastern Alps, including metabasic eclogites, mica schist and paragneiss, metapegmatite and metagranite.Nd concentration in handpicked garnet varies between 0.021 and 23.1 ppm in metabasites, 0.49 and 17.4 ppm in metapelites and between 0.024 and 4.6 ppm in metapegmatites and metagranites. The overall range of ¹⁴⁷Sm/¹⁴⁴Nd is 0.15-2.5 in garnet from metabasites, 0.12-3.03 in metapelite garnet and 0.66-7.21 in Mn-rich garnet from metapegmatites and metagranites. A clear negative correlation between Nd concentration and Sm/Nd is observed in garnets from all these lithologies. Therefrom, it is concluded that even optically “clean” garnet separates may contain high-LREE microinclusions, such as epidote-allanite, zoisite, apatite, sphene, monazite or zircon. However, very low Nd concentrations correlated with low Sm/Nd as well as high Nd concentrations (>5 ppm) correlated with fairly high Sm/Nd ratios (0.8) have also been observed. Apart from replicate analyses within as well as between samples with a common PT-history, leaching experiments are a useful technique to elucidate any distorting influence of unequilibrated inclusions on the garnet age, especially if the observed Sm/Nd ratio is low (<0.5). Leaching of garnet separates with HCl (2.5, 5.8 M) produces no obvious element fractionation, but may improve Sm/Nd, and hence age precision, considerably. Isotopic disequilibrium between garnet and other matrix minerals is observed preferentially in basic eclogites, derived from gabbroic precursors.Sm-Nd garnet analysis allows the recognition of several distinct garnet-forming events in the Eastern Alps.(a) A Variscan high-P event is documented in metabasites from the northern-central Ötztal basement around 360-350 Ma, whereas garnet from sillimanite-bearing gneisses dates the Variscan thermal peak in the western part of the same subunit around 345-330 Ma.(b) A long-lived, Permian to Triassic event (285-225 Ma), correlated with crustal extension and low-P metamorphism, is documented by spessartine-rich garnet from metapegmatites as well as almandine-rich garnet cores from mica schist.(c) Age data of garnet from eo-Alpine (Cretaceous) deeply subducted rocks of the southern/eastern Austroalpine units are related to near-peak PT, eclogite- to amphibolite-facies metamorphic conditions (peak: 2 GPa/685 °C), and/or incipient isothermal decompression, due to fast, tectonically driven exhumation (110/100-85 Ma). At cooling rates of 20-30 °C/Ma (exhumation rates: 3-5 km/Ma), the Sm-Nd closure temperature (T_c) for mm-sized garnet in these rocks is estimated at 650-680 °C.     

火成碳酸岩Sm-Nd等时线定年技术

选取庙垭铌-稀土矿床中5件新鲜的碳酸岩样品,依据内部等时线法原理,依次采用醋酸、王水、氢氟酸对其进行分步溶解,并分别对其醋酸溶解相、王水溶解相、氢氟酸溶解相和全岩进行了Sm-Nd 同位素组成分析。结果显示不同溶解相之间147Sm/144Nd同位素比值变化全岩之间由0.02 扩大为0.09,5件样品共计17个点拟合获得的等时线年龄为233±12 Ma (MSWD=2.7),其中单件样品的分相Sm-Nd等时线定年结果为235±17 Ma (MSWD=1.4)。这些结果与在该套碳酸岩中的独居石SHRIMP U-Th-Pb 年龄(233.6±1.7 Ma)(Geochimica et Cosmochimica Acta, 2014,143: 189 - 206.)、独居石LA-ICP-MS Th-Pb年龄(~240 Ma)以及铌铁矿LA-ICP-MS U-Pb年龄(232.8±4.5 Ma)(Lithos, 2017, 290 - 291:159 - 171.)在误差范围内基本一致,表明火成碳酸岩分相Sm-Nd定年结果可靠。     

Fluorite as an Sm–Nd geochronometer of hydrothermal processes: Dating of mineralization hosted in the Strel’tsovka uranium ore field,eastern Baikal region

The possibility of using hydrothermal fluorite as an Sm–Nd geochronometer is based on the results of an REE pattern study of this mineral (Chernyshev et al., 1986). As a result of REE fractionation, in many cases, the Sm/Nd ratio achieves a multifold increase compared with its level in terrestrial rocks, and the radiogenic shift of the ¹⁴³Nd/¹⁴⁴Nd isotope ratio reaches 10–20 ε_Nd units over a short time interval (as soon as tens of Ma). This is a necessary prerequisite for Sm–Nd isochron dating of fluorite. Zonal polychrome fluorite from a vein referred to the final stage of large-scale uranium mineralization at the Sterl’tsovka deposit in the ore field of the same name located in the eastern Transbaikal region has been dated using the ¹⁴³Nd/¹⁴⁴Nd method. To optimize isochron construction, local probes with high and contrasting Sm/Nd ratios have been sampled from the polished surfaces of two samples, taking into account the REE pattern of zonal fluorite. Sm–Nd isochron dating has been carried out separately for each sample. The ¹⁴⁷Sm/¹⁴⁴Nd и ¹⁴³Nd/¹⁴⁴Nd ratios vary within the intervals 0.5359–2.037 and 0.512799–0.514105, respectively. Two isochrons, each based on six fluorite probes, have been obtained with the following parameters, which coincide within 2σ uncertainty limits: (1) t = 134.8 ± 1.3 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512310 ± 13, MWSD = 0.43 and (2) t = 135.8 ± 1.6 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512318 ± 10, MWSD = 1.5. The mean age of fluorite based on two isochron datings is 135.3 ± 1 Ma. Comparison of this value with the most precise dating of pitchblende related to the ore stage in the Strel’tsovka ore field (135.5 ± 1 Ma) shows that four mineralization stages, distinguished by geological and mineralogical data, that were completed with the formation of polychrome fluorite veins 135.3 ± 1 Ma ago, represent a single and indivisible hydrothermal process whose duration does not exceed 1 Ma.     

Petrogenesis of 3.15 Ga old Banasandra komatiites from the Dharwar craton,India: Implications for early mantle heterogeneity

Spinifex-textured.magnesian(MgO 25 wt.%) komatiites from Mesoarchean Banasandra greenstone belt of the Sargur Group in the Dharwar craton,India were analysed for major and trace elements and~(147,146)Sm-~(143,142)Nd systematics to constrain age,petrogenesis and to understand the evolution of Archean mantle.Major and trace element ratios such as CaO/Al_2O_3.Al_2O_3/TiO_2,Gd/Yb,La/Nb and Nb/Y suggest aluminium undepleted to enriched compositional range for these komatiites.The depth of melting is estimated to be varying from 120 to 240 km and trace-element modelling indicates that the mantle source would have undergone multiple episodes of melting prior to the generation of magmas parental to these komatiites.Ten samples of these komatiites together with the published results of four samples from the same belt yield ~(147)Sm-~(143)Nd isochron age of ca.3.14 Ga with an initial ε_(Nd)(f) value of+3.5.High precision measurements of ~(142)Nd/~(144)Nd ratios were carried out for six komatiite samples along with standards AMES and La Jolla.All results are within uncertainties of the terrestrial samples.The absence of~(142)Nd/~(144)Nd anomaly indicates that the source of these komatiites formed after the extinction of ~(146)Sm,i.e.4.3 Ga ago.In order to evolve to the high ε_(Nd)(t) value of +3.5 by 3.14 Ga the time-integrated ratio of~(147)Sm/~(144)Nd should be 0.2178 at the minimum.This is higher than the ratios estimated,so far,for mantle during that time.These results indicate at least two events of mantle differentiation starting with the chondritic composition of the mantle.The first event occurred very early at ~4.53 Ga to create a global early depleted reservoir with superchondritic Sm/Nd ratio.The source of Isua greenstone rocks with positive ~(142)Nd anomaly was depleted during a second differentiation within the life time of ~(146)Sm,i.e.prior to 4.46 Ga.The source mantle of the Banasandra komatiite was a result of a differentiation event that occurred after the extinction of the ~(146)Sm,i.e.at 4.3 Ga and prior to 3.14 Ga.Banasandra komatiites therefore provide evidence for preservation of heterogeneities generated during mantle differentiation at4.3 Ga.