钕同位素比值~(143)Nd/~(144)Nd标准溶液研制

钕同位素比值(~(143)Nd/~(144)Nd)是Sm-Nd同位素方法的关键量值,由于被测样品的~(143)Nd/~(144)Nd比值变化范围很小,所以对~(143)Nd/~(144)Nd比值测试的精准度要求很高(精度优于0.005%)。为了获得高精度和高准确度的测试数据,分析过程中所用Nd同位素标准物质起着重要作用。以往的Nd同位素标准物质都是氧化钕,经过近三十年有的已消耗殆尽。本文阐述了钕同位素比值~(143)Nd/~(144)Nd标准溶液的研制,经检验标准溶液的均匀性和稳定性良好,由11家实验室协同定值,采用MC-TIMS和MC-ICP-MS方法测定~(143)Nd/~(144)Nd,确定了Nd同位素标准溶液的特性值~(143)Nd/~(144)Nd=0.512438,不确定度为5×10-6。此标准溶液于2015年5月获得国家标准样品证书(批号为GSB 04-3258—2015),可被用于地质、资源、海洋、环境、考古等多种样品~(143)Nd/~(144)Nd比值测定时的仪器校准和分析过程的质量监控。     

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.     

高精度质谱计在同位素地球化学的应用前景

微量地质样品的高精度同位素比值测试已经成为地质和环境科学等领域极其重要的研究手段.新型固体热电离质谱计以其高精度和高灵敏度, 将在同位素年代学和地球化学领域有广阔的应用前景.报道采用IsoProbeT质谱计测量标准物质溶液的结果.测量锶标准物质NBS987和钕标准物质Ames分别获得平均87Sr/86Sr比值0.710 241 8±0.000 005 1和平均143Nd/144Nd比值0.512 148 4±0.000 002 9, 内部精度可达0.000 3%.微量锶标准物质(0.3~1 ng) 的同位素比值测量内部精度可以优于0.003%.结合低本底化学流程, 实现了微量地质样品的高精度同位素比值测试.这一结合将有效地促进单颗粒矿物年代学和同位素示踪在岩浆岩、变质岩、矿床、构造岩研究的应用.      

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).     

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。     

T_(CHUR)~(Nd)年龄计算公式的推导

通过对地球早期所形成岩石的研究,人们认定原始地幔具有与球粒陨石相同的~(147)Sm/~(144)Nd和~(143)Nd/~(144)Nd比值,并用缩写CHUR表示“球粒陨石均一源区”。T_(CHUR)~(Nd)是指各种岩石源区的稀土比值与CHUR产生差异的年龄。从T_(CHUR)~(Nd)年前到现代,CHUR和岩石样品(S)的演化可分别用下述两方程表示:     

采用氧化物方式高精度测量微量样品钕同位素比值

微量样品Nd同位素比值的高精度测定在地球科学和环境科学研究中具有重要的意义,同时也是同位素测定的难点.对1ng以下的国际标准样品进行了高精度质谱测试.采用新一代高精度热电离质谱计(IsoProbe-T)分别运用Nd 和NdO 测试方法,多次测量常量(≥200ng)和超微量(0.25ng、0.5ng和1ng)Nd标准物质(Ames、JMC和Jndi-1)和实验室内部标准LRIG-Nd溶液.质谱计同位素比值测量均采用静态多接收模式.143Nd/144Nd比值测量的内部精度均优于0.003%.与传统的Nd 测量方式相比,NdO 测量方式具有显著的优势,即有极高的灵敏度,是Nd 分析灵敏度的100倍左右.     

大别山麻粒岩和TTG片麻岩的Sr,Nd,Pb同位素地球化学

北大别4个麻粒岩和4个TTG片麻岩样品的Sr,Nd同位素分析结果表明，样品普遍具有较高的锶同位素比值（^87Sr/^86Sr=0.7066-0.7461)，较低的Nd同位素比值（^143Nd/^144Nd=0.5108-0.5124)，表现出明显的壳源特征，结合铅同位素的组成来看，北大别麻粒岩及TTG片麻岩的同位素成分相当于－下地壳。岩石的特源为古老的地壳，大约在2－3Ga之间，少数样品的同位素特征可能暗示源区有年轻地壳物质的加入。     

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。     

利用套柱法快速分离提纯Sr和Nd元素

样品放射性成因Sr-Nd同位素比值受控于源区初始同位素组成、放射性元素母体与子体相对丰度,以及衰变时间等因素。它们具有极强的示踪能力,因而在地质学领域有广泛的应用。传统的Sr-Nd同位素分析使用的是阳离子树脂,提纯Nd元素时往往涉及有机试剂以及调节pH值等操作,其分析效率较低。近年来特效树脂的出现使得分离这些元素变得简单,但是受硫酸根等因素影响,特效树脂使用次数有限。为了提高分析效率,缩短分析时间,本文开发了一种套柱法,该方法结合阳离子树脂和特效树脂,实现了Sr-Nd元素的快速分离,并且能延长特效树脂的使用寿命。实验采用阳离子树脂、Sr特效树脂和LN稀土特效树脂对玄武岩BCR-2标样进行了分析。Sr-Nd回收率均90%,BCR-2玄武岩~(87)Sr/~(86)Sr比值为0.705016±0.000016(n=36,1SD),~(143)Nd/~(144)Nd比值为0.512624±0.000012(n=39,1SD),与前人TIMS法获得的结果吻合(~(87)Sr/~(86)Sr:0.705000～0.705023;~(143)Nd/~(144)Nd:0.512630～0.512650)。最终分离提纯的溶液中~(85)Rb/~(86)Sr值小于0.01,~(147)Sm/~(144)Nd值小于0.001,表明该方法可以高效分离Rb-Sr和Sm-Nd,实现Sr、Nd同位素的准确分析。     

Nd/Nd and Sm/Nd stratigraphy of Upper Ordovician epeiric sea carbonates

Stratigraphic changes in the ε_Nd of epeiric sea carbonates from central North America track the submergence history of the interior craton during the Late Ordovician. Fluctuations in sea level changed the Nd isotope balance of the epeiric sea by modifying the flux of Nd weathered from the highlands of the Taconic Orogen (ε_Nd = −6 to −9) and from the low relief Precambrian basement (ε_Nd = −22 to −15) of the Transcontinental Arch and Canadian Shield. Transgressions over the Arch and Shield, which diminished the weathering flux of Nd from the Precambrian basement, are recorded as positive shifts in the ε_Nd profiles of carbonates. Negative ε_Nd shifts reflect regression and reexposure of the Precambrian basement to erosion. Correlation of Upper Ordovician carbonates by use of the ε_Nd profiles demonstrates the potential for Nd isotope stratigraphy. Comparison of stratigraphic variations in carbonate Sm/Nd ratios with sea level curves, conodont paleoecology, and the ε_Nd profiles suggest that our observed variations in Sm/Nd ratios are related to changes in depth. Increasing Sm/Nd ratios correlate with increasing depth, whereas decreasing Sm/Nd ratios correlate with decreasing depth. This relationship between Sm/Nd ratios and depth suggests Sm/Nd profiles have potentially wide applications in understanding the paleoceanography of ancient epeiric seas.     

钕易解石

易解石为含稀土钛铌钽的复杂氧化物,钕易解石为化学组分中富含钕的易解石。即钛铌钽酸盐类矿物。钕易解石是比较罕见的矿物,它的发现和研究在理论和实用方面均具重要意义。 谢苗诺夫等最先确定出富钕的易解石,而列文星最早指出了命名的原则,谢苗诺夫则认为碱性花岗岩热液脉中或花岗伟晶岩中的易解石富钕。 本文对产自我国内蒙白云鄂博热液交代矿床中的钕易解石进行了分析、研究。     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

High-precision Measurements of the 143Nd/144Nd Isotope Ratio in Certified Reference Materials without Nd and Sm Separation by MC-ICP-MS

A precise and accurate method for the determination of 143 Nd/144 Nd isotope ratio without Nd and Sm separation by multiple collector inductively coupled plasma mass spectrometry is demonstrated in this paper.     

β—钕褐钇铌矿(Fergusonite-beta-Nd)

至今,吐界上已经发现的褐钇铌矿族矿物中仅有钛褐钇铌矿、铈褐钇铌矿、铈-钇-褐钇铌矿……等,而未见有矿物中稀土元素以钕为最富的单斜钕褐钇铌矿的报道^[1,4,5]。     

In search of a hidden long-term isolated sub-chondritic Nd/Nd reservoir in the deep mantle: Implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic ¹⁴²Nd/¹⁴⁴Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic ¹⁴³Nd/¹⁴⁴Nd and high ²⁰⁷Pb/²⁰⁶Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic ¹⁴²Nd/¹⁴⁴Nd.High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable ¹⁴²Nd/¹⁴⁴Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle.We then evaluate mass balance in the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε¹⁴³Nd estimates of the reservoirs in the μ¹⁴²Nd = 0 Earth, where μ¹⁴²Nd is ((measured ¹⁴²Nd/¹⁴⁴Nd/terrestrial standard ¹⁴²Nd/¹⁴⁴Nd)−1 * 10⁻⁶) and the μ¹⁴²Nd = 0 Earth is the proportion of the silicate Earth with ¹⁴²Nd/¹⁴⁴Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd unless the μ¹⁴²Nd = 0 Earth has a ε¹⁴³Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age ¹⁴²Nd-¹⁴³Nd isochron for the Earth intersects μ¹⁴²Nd = 0 at ε¹⁴³Nd of +8 ± 2 providing a minimum ε¹⁴³Nd for the μ¹⁴²Nd = 0 Earth. The high ε¹⁴³Nd of the μ¹⁴²Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε¹⁴³Nd.If the EER formed early after solar system formation (0-70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ¹⁴²Nd = 0 Earth must have a bulk ε¹⁴³Nd more radiogenic than DMM and additional high ε¹⁴³Nd material is required to balance the Nd isotope systematics of the Earth.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

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.