中国南方灯影峡期海洋碳酸盐岩原始δ13C和δ18O组成及海水温度

中国南方灯影峡期(晚前寒武纪)是白云岩广泛发育的海洋碳酸盐沉积时期,在灯影组中部发育从海水直接沉积沉淀的原生白云岩,目前仍保留其原始组构特征。从40个原生白云石(岩)中测得:泥晶白云石的δ¹³C值为3.64‰,δ¹⁸O值为-1.17‰(n=6);白云岩的13C值为3.52‰,δ¹⁸O值为-1.86‰(n=15);海水纤状白云石胶结物δ¹³C值为2.90‰,δ¹⁸O值2.65‰(n=8);海水刃状白云石胶结物的δ¹³C值为2.96‰,δ¹⁸O值为-2.41‰(n=8);晶纹层和海水纤状白云石胶结物的δ¹³C值为2.79‰,δ¹⁸O值为-3.13‰。40个岩样的δ¹³C平均值为3.25‰±0.44‰,δ¹⁸O平均值为-2.12‰±0.98‰(均以PDB标准)。对于灯影峡期海相云岩的原始δ¹³C和δ¹⁸O值,不采用所有样品的平均值,而是采用原生白云石沉积物与海水白云石结物δ¹³C值和δ¹⁸O值两个图示分布区重叠部分的最重同位素值,即：δ¹C值为4.43‰(PDB标准),δ¹⁸O值为-0.62‰(PDB标准),将其作为灯影峡期海洋碳酸盐岩的原始同位素组成。对海水原生白云石胶结物包裹体盐度进行了测定,海水δ¹⁸O计算值为2.90(SMOW标准),用原始δ¹⁸O值计算的原生白云石形成时的海水温度为40.8 ℃。这说明中国南方灯影峡的海洋为炎热的较高的海水温度环境。     

河北省邢台白涧铁矿床成矿作用研究

白涧铁矿床赋存于燕山期闪长岩和中奥陶统灰岩接触带中,空间上与矽卡岩密切相关; SIMS锆石U-Pb定年结果表明,含矿闪长岩加权平均年龄为128.47±1.2 Ma(MSWD=0.65, 95%置信度),代表白涧铁矿床形成的上限年龄;闪长岩Fe同位素组成的变化范围为δ⁵⁶Fe=+0.043‰~+0.166‰,平均值为0.0915‰±0.019(2SD, n=8);矽卡岩Fe同位素的变化范围为δ⁵⁶Fe=+0.058‰~+0.083‰,平均值为0.0707‰±0.019(2SD, n=3);灰岩Fe同位素的变化范围为δ⁵⁶Fe=-0.157‰~+0.042‰,平均值为-0.0575‰±0.019(2SD, n=2);磁铁矿Fe同位素的变化范围为δ⁵⁶Fe=+0.114‰~+0.146‰,平均值为0.1334‰±0.019(2SD, n=5);黄铁矿-磁黄铁矿Fe同位素的变化范围为δ⁵⁶Fe=+0.242‰~+0.270‰,平均值为0.2617‰±0.023(2SD, n=3)。闪长岩、矿石和矽卡岩Fe同位素组成的时空演化特征表明它们为同一流体体系演化的产物,具有相同的物质来源,来自于岩浆流体;白涧铁矿矽卡岩型矿体为燕山期华北克拉通破坏过程中岩浆流体成矿作用的产物。     

MC-ICP-MS准确测定地质样品中锂同位素组成

以一根阳离子交换树脂填充的石英交换柱,使用1 mol/L HNO_3/80%(V/V)CH_3OH作为淋洗液可实现对不同性质标样中Li元素的化学分离与富集;讨论了Li淋洗曲线与样品岩性和Mg︰Li值的关系,建立了可靠的岩石样品的Li化学分离流程。研究发现,化学分离得到的Li接收液中残余离子不同对Li同位素准确测定的影响不同,但将残余离子浓度控制在一定范围内时(~10),可以忽略残余离子的影响。使用5%NaCl溶液消除Li的记忆效应后,样品和标样中Li浓度和HNO_3浓度不匹配对Li同位素准确测定的影响大大降低。因此,该方法无须严格基体匹配即可进行Li同位素比值的准确测定。     

AG MP-1M阴离子分离Cu、Fe、Zn及其在Fe同位素测定上的应用

采用新型阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF、4 mol/L HCl、2 mol/L HCI和0.5 mol/L HNO,可以有效分离地质样品中Cu、Co、Fe和Zn,克服了AG MP-1阴离子交换树脂分离Cu时Co随Cu同时淋洗下来,以及在分离Co含量较高的地质样品时Co和Cu需过二次柱分离的弊端.对花岗闪长岩等地质标样的研究结果表明,AG MP-1M阴离子交换树脂能有效分离Cu、Fe和Zn,并且它们的回收率均大于99%.标准样品经过离子交换分离后Fe同位素未发生分馏,可满足多接收器电感耦合等离子体质谱(MC-ICPMS)的同位素测定要求.     

胶北荆山群张舍石墨矿碳同位素特征及其地质意义

中国的石墨矿床广泛发育于华北克拉通周边的孔兹岩系内,其碳质具有多来源特征,碳质的大量沉积集聚对古环境具有指示意义。文中总结前人同位素年代数据,将荆山群的形成时代限定在2.1~1.9 Ga,同时报道了胶北张舍矿区荆山群陡崖组石墨矿床的12件岩石样品主量元素数据、10件石墨δ13Cgrap数据、4件透辉石大理岩δ13Ccarb与δ18Ocarb数据和15个石墨晶体的拉曼光谱数据。8件片麻岩样品的δ13Cgrap为-21.7‰～-18.6‰,平均值(-20.5±0.9)‰,2件透辉石大理岩样品δ13Cgrap分别为-16.3‰和-19.3‰,均略高于全球有机质平均水平((-26±7)‰),4件透辉石大理岩样品的δ13Ccarb和δ18Ocarb值分别为-8.9‰~0.2‰和12.5‰~16.6‰。拉曼光谱谱峰数据计算出石墨经历的最高温度为700~800 ℃。碳同位素数据显示石墨碳质来源以有机质为主,主要为生物成因,并与无机碳混合,产生了均一化,导致碳同位素变重。高温变质作用以及流体的影响是石墨碳发生均一化的重要因素。古元古代生物成因石墨矿床的大量产出,伴随同时代的叠层石爆发、磷块岩沉积、海洋碳循环扰动等现象,指示了古元古代晚期具有很高的生物产率,并发生大规模的有机质埋藏。     

用于多接收器等离子体质谱铜铁锌同位素测定的离子交换分离方法

采用AGMP-1阴离子交换树脂，分别以7mol／L HCl、2mol／L HCl、0．5mol／L HNO3作为淋洗剂，可有效分离Cu、Fe、Zn。介绍了方法的基本原理、化学分离过程及混合标准溶液与地质标样的分离结果。结果表明，Cu、Fe、Zn回收率均接近100％，标准溶液在离子交换分离前后同位素组成一致，可以满足多接收器等离子体质谱对Cu、Fe、Zn同位素高精度分析的要求。     

石油碳、氢同位素组成的研究

通过对我国18个含油气区、385个石油样品进行碳、氢同位素和部分馏份碳同位素分析,将所获数据对两种不同性质的石油如正常原油和轻质（凝析）油分别研究其碳、氢同位素地球化学特征,提出轻质（凝析）油的碳同位素值（δ13C为-32.5‰～ -24.3‰）比正常原油δ13C为-34.4‰～ -24.6 ‰．6‰）相对偏高;石油馏份中芳烃碳同位素组成的变化受母质继承效应更为明显。因此,用芳烃碳同位值可以判识不同母质来源的石油。与海相有关的轻质（凝析）油的氢同位素值大于-15.0‰,而非海相轻质（凝析）油的δD值( δD为-21.0‰～-1.05‰）基本覆盖了海相轻质油的分布范围,从淡水－微咸水－半咸水和海水环境其氢同位素有明显变重趋势,表明氢同位素主要与沉积环境密切相关。     

铝土矿中锂同位素分离提纯方法的建立

铝土矿是极端风化作用的产物,也是锂的重要载体,由于其资源量巨大,对铝土矿中锂的富集机制和分布规律的研究将有利于找矿预测。锂同位素的高效准确分析是深入认识矿物中锂的富集机制和分布规律的基础。铝土矿样品由于化学稳定性较强,溶样过程较为复杂,且Al、Na、Ca、K等基体元素含量远高于锂,给锂的纯化增加不少难度。本文采用内径5mm、柱长190mm的聚四氟乙烯离子交换柱和AG50W-X12阳离子交换树脂,以0.5mol/L硝酸为淋洗液淋洗34mL,收集最后的12mL,即可完成对铝土矿中锂的完全纯化回收。该纯化方法减少了淋洗液的使用量,提高了实验效率。采用该方法对国际标样L-SVEC、RGM-2、GSP-2进行锂的纯化,通过多接收电感耦合等离子体质谱仪(MC-ICP-MS)测试锂同位素组成,得到的δ~7Li测试值分别为-0.26‰±0.09‰(2SD,n=3)、3.19‰±0.37‰(2SD,n=3)、-0.78‰±0.22‰(2SD,n=3),与前人报道一致,验证了该方法的可靠性。此外,采用本方案对铝土矿国家标样(GBW07182)进行锂的纯化,δ~7Li测定值为10.16‰±0.21‰(2SD,n=3)。     

安徽省铜陵桂山铜铅锌矿C-H-O-S-Pb 同位素地球化学特征及其意义

安徽铜陵桂山铜铅锌矿床是铜陵矿集区沙滩脚矿田内近年来新发现的以铜矿为主,伴生铅锌矿的中小型多金属矿床,该矿床的矿体主要赋存于三叠系南陵湖组灰岩与青山花岗闪长斑岩体接触带附近及花岗闪长斑岩体内。本文在对该矿床地质特征的研究基础上,对代表性（岩）矿石进行碳、氢、氧、硫、铅同位素研究分析,据此约束该矿床的成矿流体和成矿物质来源。研究成果显示, 桂山铜铅锌矿床中方解石样品中δ¹³C_V-PDB 值为−3.2‰～2.0‰ 间,δ¹⁸O_V-SMOW 为8.3‰～15.2‰ 间,石英流体包裹体水的δD_V-SMOW 为−112.6‰～−6.8‰,δ¹⁸O_V-SMOW 为10.5‰～14.7‰,矿石中硫化物δ³⁴S值变化范围为−0.9‰～4.1‰,具塔式分布特征,矿石铅中的²⁰⁶Pb /²⁰⁴Pb 比值为18.409～18.585,²⁰⁷Pb /²⁰⁴Pb 比值为15.588～15.703,²⁰⁸Pb /²⁰⁴Pb 比值为38.483～38.843,以上指示了桂山铜铅锌矿床的成矿流体主要来源于岩浆水,并有大气降水的加入。分异成矿流体的岩浆可能来源于地幔,且伴有上地壳物质混入的特点。岩浆-地幔的溶解作用,伴有地层中碳质的混入。     

内蒙古甲乌拉大型Pb-Zn-Ag矿床稳定同位素地球化学研究

内蒙古甲乌拉银多金属矿床位于大兴安岭成矿带北段,为近年来发现的大型银铅锌多金属矿床。矿床矿体分布完全受到断裂构造的控制,金属矿物组成主要为方铅矿、闪锌矿、黄铜矿、黄铁矿、磁黄铁矿、毒砂、辉钼矿及磁铁矿等。文中重点分析了矿床的硫、氢、氧、碳和铅稳定同位素地球化学特征。研究结果表明：金属硫化物δ34S集中为1.37‰~4.10‰,平均为3.10‰(n=13),极差为2.73‰;石英和方解石δ18Owater的变化范围较大(-18.96‰~+1.08‰) (n=9),均值为-11.36‰;δDV SMOW的变化范围比较集中(-133.6‰~-103.4‰) (n=9);27件样品的铅同位素组成为：206Pb/204Pb=18.228 3~18.758 7、207Pb/204Pb=15.457~15.880和208Pb/204Pb=37.841~39.049,矿床的铅组成基本为正常的放射性成因铅;方解石δ13CV PDB变化范围为-5.2‰~-8.4‰,平均为-6.8‰(n=2)。矿石硫化物的硫同位素及方解石的碳同位素均指示成矿物质可能来源于深部的岩浆活动;石英和方解石的氢氧同位素组成表明成矿流体早期以岩浆流体为主,成矿晚期加入了大量加热补给的大气降水;铅同位素组成表明成矿流体中铅的来源主要为幔源,矿床形成过程中混入少量的壳源铅。矿床稳定同位素组成显示成矿流体主要来源于深部的岩浆热液,特别与燕山晚期的火山次火山热液有较为密切的联系,在流体演化过程中大气降水的加入对矿床成矿元素的聚集和沉淀也起到有利作用。成矿作用的发生是在一种总硫浓度比较低、中等氧化环境、相对开放的非平衡体系中进行的。矿床形成的地球动力学背景为一种岩石圈大规模快速减薄的过程。甲乌拉大型Pb Zn Ag矿床的成因类型属于火山次火山热液脉状银多金属矿床。     

Separation and Precise Measurement of Lithium Isotopes in Three Reference Materials Using Multi Collector‐Inductively Coupled Plasma Mass Spectrometry

Lithium separation technique for three reference materials has been established together with precise determination of lithium isotope using a Neptune multi collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The solutions of lithium element standard reference materials, potassium, calcium, sodium, magnesium and iron single element, were used to evaluate analytical methods applied. Three separate stages of ion-exchange chromatography were carried out using organic cation-exchange resin (AG 50W-X8). Lithium was enriched for the three stages using different eluants, which are 2.8 M HCl, 0.15 M HCl and 0.5 M HCl in 30% ethanol, respectively. The columns for the first and second stages are made of polypropylene, and those for the third stage are made of quartz. Total reagent volume for the entire chemical process was 35 mL for three reference materials. The recovery yielded for the three stages is 98.9–101.2% with an average of 100.0%, 97.6–101.9% with an average of 99.9%, and 99.8–103.3% with an average of 100.6%, respectively. The precision of this technique is conservatively estimated to be ±0.72–1.04‰ (2σ population), which is similar to the precision obtained by different authors in different laboratories with MC-ICP-MS. The δ7Li values (7Li/6Li relative to the IRMM-016 standard) determined for andesite (AGV-2) and basalt (BHVO-2) are 5.68‰ (n=18), 4.33‰ (n=18), respectively. The δ7Li value (7Li/6Li relative to the L-SVEC standard) determined for IRMM-016 is –0.01‰ (n=15). All these analytical results are in good agreement with those previously reported. In addition, the results for the same kinds of samples analyzed at the MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, are consistent with those obtained at the Plasma Laboratory, University of Maryland, within analytical uncertainty. According to these experiment results, it is concluded that this proposed procedure is a suitable method for determining the lithium isotopic composition of natural samples.     

Accurate and High-Precision Measurement of Lithium Isotopes in Two Reference Materials by MC-ICP-MS

We report here a newly developed method for measurement of Li isotopes by use of multi-collector ICP-MS (Neptune) allowing rapid and high precision determination of Li isotope ratios at low levels of lithium (15–20 ng). The lithium reference sample solution IRMM-016 was analysed over a period of ten months with an external reproducibility of 0.24% (2s, n = 52). Chemical separation of Li from matrix was performed on the seawater sample IRMM BCR-403, for which a mean δ⁷Li value of + 31.0 ± 0.1 % (2s/√n, n = 31) was obtained. This mean value is in good agreement with those previously published for other seawater samples. BCR-403 seawater being readily available, we propose that this seawater sample be used as a reference sample for Li isotope measurements.     

长江流域河水和悬浮物的锂同位素地球化学研究

深入理解流域侵蚀过程中的锂同位素分馏对于运用锂同位素来示踪化学循环和气候变化是十分必要的。研究集中在长江干流和主要支流的水体和悬浮物的锂及锂同位素组成。长江流域水体的锂及锂同位素组成（δ⁷Li）分别为150~4 570 nmol/L和+7.6‰~+28.1‰,两者沿上游至下游的变化趋势相反。悬浮物锂同位素组成（δ⁷Li）变化比较稳定,分别为41~92 μg/g和-4.7‰~+0.7‰,而且总是低于相应水体的锂同位素组成。悬浮物和流体之间的锂同位素分馏系数在0.977和0.992之间,与悬浮物的量及组成存在明显相关性,反映了粘土矿物的吸附和化学风化的程度。锂含量与锂同位素组成之间良好的负相关性表明流域水体的锂来自2个端元混合：其一可能是蒸发盐岩,并伴有深部热泉水;其二可能是硅酸岩。     

Three Secondary Reference Materials for Lithium Isotope Measurements: Li7-N, Li6-N and LiCl-N Solutions

The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing ⁷Li or ⁶Li spikes and either L-SVEC or IRMM-016 certified reference materials to produce solutions having a known Li concentration and isotopic composition. The Li7-N and Li6-N solution samples (1.5 mol l⁻¹ HNO₃) have nominal δ⁷Li isotopic compositions of 30.1‰ and -9.7‰ respectively relative to L-SVEC and concentrations of 100 mg l⁻¹. Repeated measurement of these samples using the QUAD-ICP-MS at the CRPG yielded δ⁷Li of 30.4 ± 1.1‰ (n = 13) and -8.9 ± 0.9‰ (n = 9) at the 2s level of confidence. An additional LiCl-N solution was measured and yielded a delta value of 9.5 ± 0.6‰ (n = 3). Identical results were obtained at the BRGM (Orléans, France) from determinations performed with a Neptune MC-ICP-MS (30.2 ± 0.3‰, n = 89 for the Li7-N, -8.0 ± 0.3‰, n = 38 for the Li6-N and 10.1 ± 0.2‰, n = 46 for LiCl-N at the 2s level of confidence). The deviation of measured composition relative to the nominal value for the Li6-N solution might be explained by either contamination during preparation or an error during sample weighing. These secondary reference materials, previously passed through ion exchange resin or directly analysed, may be used for checking the accuracy of Li isotopic measurements over a range of almost 40‰ and will be available to the scientific community upon request to J. Carignan or N. Vigier, CRPG.     

锂同位素及其地质应用研究进展

锂同位素示踪是近几年发展起来的一门新兴的稳定同位素地球化学方法,锂有两个稳定同位素：^6Li和^7Li。自在界锂同位素的组成变化很大,其δ^6Li值变化幅度超过60‰,现代大洋水的δ^6Li值为－31．0‰,洋中脊玄武岩（BORB）的δ^6Li值为－4．7‰--3.7‰,由于锂同位素存在大的分馏和不同地质体中在截然不同的δ^6Li值,因此锂同位素地质应用前景十分广泛。目前,锂同位素在研究星云形成过程和宇宙事件,洋壳蚀变和海底热液活动,壳－幔物质循环和板块俯冲作用过程,判断卤水起源和演化等方面的研究中成效显著。     

锂同位素及其在四川甲基卡伟晶岩型锂多金属矿床研究中的应用

锂同位素在地质学、地球化学研究中有着广阔的应用前景。简单介绍了锂同位素研究已取得的进展,并在四川甲基卡伟晶岩型锂多金属矿床研究中开展应用。研究表明,四川甲基卡锂矿床中2件锂辉石的锂含量非常高,分别为33 592×10-6和34 264×10-6,相应的δ7Li值分别为-0.6‰和-0.4‰,平均值为-0.5‰,而二云母花岗岩中黑云母的锂含量为7 350×10-6,δ7Li值为+0.6‰,两者在误差范围内具有非常好的一致性,证明锂辉石来源于二云母花岗岩,这与其他包裹体、同位素地球化学和年代学证据等相一致。     

A Revisited Purification of Li for ‘Na Breakthrough’ and its Isotopic Determination by MC‐ICP‐MS

The accurate and precise determination of Li isotopic composition by MC‐ICP‐MS suffers from the poor performance of traditional column chromatography. Previously established chromatographic processes cannot completely remove Na in complex geological samples, which is currently interpreted to be a result of Na breakthrough. In this study, Na breakthrough during single‐column purification was found to differ between simply artificial Na‐containing sample solutions, where a little Na residue was found, and silicate rocks, where a large amount of breakthrough occurred. A revised two‐step column purification for Li using 0.5 and 0.3 mol l^?1 HCl as eluents was designed to remove the Na. This modified method achieves high‐efficiency Li purification from Na and consequently avoiding high Na/Li ratio interference for subsequent MC‐ICP‐MS analyses. The proposed method was validated by the analysis of a series of reference materials, including Li₂CO₃ (IRMM‐016, ‐0.10‰), basalt (BCR‐2: 2.68‰; BHVO‐2: 4.39‰), andesite (AGV‐2: 6.46‰; RGM‐2: 2.59‰), granodiorite (GSP‐2: ?0.87‰) and seawater (CASS‐5, 30.88‰). This work reports early Na appearance prior to the elution curves in chromatography and emphasises its influence for subsequent Li isotope measurement. Based on the findings, the established two‐step method would be more secure than single‐column chemistry for Li purification.     

Lithium Isotope Composition of Marine Biogenic Carbonates and Related Reference Materials

In this study, the accuracy and the precision corresponding to Li isotopic measurements of low level samples such as marine and coastal carbonates are estimated. To this end, a total of fifty‐four analyses of a Li‐pure reference material (Li7‐N) at concentrations ranging from 1 to 6 ng ml^?1 were first performed. The average δ⁷Li values obtained for solutions with and without chemical purification were 30.3 ± 0.4‰ (2s, n = 19) and 30.2 ± 0.4‰ (2s, n = 36), respectively. These results show that the chosen Li chemical extraction and purification procedure did not induce any significant isotope bias. Two available carbonate reference materials (JCt‐1 and JCp‐1) were analysed, yielding mean δ⁷Li values of 18.0 ± 0.27‰ (2s, n = 6) and 18.8 ± 1.8‰ (2s, n = 9), respectively. Small powder aliquots (< 15 mg) of JCp‐1 displayed significant isotope heterogeneity and we therefore advise favouring JCt‐1 for interlaboratory comparisons. The second part of this study concerns the determination of δ⁷Li value for biogenic carbonate samples. We performed a total of twenty‐nine analyses of seven different tropical coral species grown under controlled and similar conditions (24.0 ± 0.1 °C). Our sample treatment prior to Li extraction involved removal of organic matter before complete dissolution in diluted HCl. Our results show (a) a constant δ⁷Li within each skeleton and between the different species (δ⁷Li = 17.3 ± 0.7‰), and (b) a Li isotope fractionation of ?2‰ compared with inorganic aragonite grown under similar conditions. Comparison with literature data suggests a significant difference between samples living in aquaria and those grown in natural conditions. Finally, we investigate ancient (fossil) carbonate material and foraminifera extracted from marine sedimentary records. Different leaching procedures were tested using various HCl molarities. Results indicate that carbonate preferential dissolution must be carried out at an acid molarity < 0.18 mol l^?1. Possible contamination from silicate minerals can be verified using the Al/Ca ratio, but the threshold value strongly depends on the carbonate δ⁷Li value. When the silicate/carbonate ratio is high in the sediment sample (typically > 2), contamination from silicates cannot be avoided, even at low HCl molarity (? 0.1 mol l^?1). Finally, bulk carbonate and foraminifera extracted from the same core sample exhibited significant discrepancies: δ⁷Li values of foraminifera were more reproducible but were significantly lower. They were also associated with lower Sr/Ca and higher Mn/Ca ratios, suggesting a higher sensitivity to diagenesis, although specific vital effects cannot be fully ruled out.     

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Optimisation of Lithium Chromatography for Isotopic Analysis in Geological Reference Materials by MC‐ICP‐MS

The lithium isotope system can be an important tracer for various geological processes, especially tracing continental weathering. The key to this application is the accurate and precise determination of lithium isotopic composition. However, some of the previously established column separation methods are not well behaved when applied to chemically diverse materials, due to the significant variations in matrix/lithium ratios in some materials. Here, we report a new dual‐column system for lithium purification to achieve accurate and precise analysis of lithium isotopic compositions using a multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS). Compared with single‐column systems, our dual‐column system yielded a consistent elution range of the lithium‐bearing fraction (7–16 ml) for samples with a large range of lithium loads and matrix compositions, so that column re‐calibration is not required. In addition, this method achieved complete lithium recovery and low matrix interference (e.g., Na/Li ≤ 1) with a short elution time (~ 6 h, excluding evaporation), with the entire procedure completed in 1.5 days. We report high precision Li isotopic compositions in twelve chemically diverse materials including seawater, silicates, carbonates, manganese nodules and clays. New recommended Li isotopic values and associated uncertainties are presented as reference values for quality control and inter‐laboratory calibration for future research and were consistent with previously published data. However, significant lithium isotopic variances (~ 1‰) in BHVO‐2 from different batches suggest Li isotopic heterogeneity in this reference material and that Li isotopic studies using this reference material should be treated with caution.